United States Environmental Protection Agency · Ai ASEA BROWN BOVERI January 21, 1993 PN: 7054.01 012193.LTR Barr Engineering Company ATTN: Mr. John Borovsky 8300 Norman Center Drive

BIOLOGICAL TREATABILITY STUDYARROWHEAD

SOIL, FILTER CAKE, AND SLUDGEDRAFT REPORT

JANUARYS, 1993

ABBASEA BROWN BOVERt


SOIL, FILTER CAKE, AND SLUDGEDRAFT REPORT

JANUARY 8, 1993

ABBASEA BROWN BOVERI

AiASEA BROWN BOVERI

January 21, 1993 PN: 7054.01012193.LTR

Barr Engineering CompanyATTN: Mr. John Borovsky8300 Norman Center DriveMinneapolis, MN 55437-1026

SUBJECT: Treatability Study

Dear Mr. Borovsky:

It is a pleasure to provide Barr Engineering Co. with a draft copyof our treatability report entitled "TREATABILITY STUDY, ARROWHEAD,SOIL, FILTER CAKE AND SLUDGE". The report contains seven sectionsand two appendices and was prepared in accordance with theNovember 25, 1991 draft Work Plan and subsequent discussionsbetween Barr and ABB-ES.

The results contained in this report strongly support thefeasibility of biological treatment of soil, filter cake andsludge. GC fingerprint analysis indicated that the bulkcontaminant is qualitatively the same in the three matrix types.Duplicate treatability studies, using composting treatmentsimulations, were carried out with soil, two with filter cake, andone with a 4:1 mix of soil and cake, which demonstrated that thisbulk contaminant is readily biodegradable, and determined thetreatment times and amendment requirements. The results wereconfirmed with several other experiments, including three withabiotic controls, documenting the biological nature of the process.Filter cake was shown to be biodegradable both with and withoutpretreatment, and pretreated sludge was biodegraded both bycomposting and by slurry treatment.

GC/MS analysis of initial samples and of treated material providedpositive identification and quantitation of compounds of concern.Data for 2- to 4-ring PAH and phenolics indicated 67 percent to98 percent biodegradation of these compounds. In addition, severaltoxic metals were shown to have reductions in leachability by 30 to64 percent. Volatile compounds were generally not present in thetreated material with detection limits of 18 ppb and 47 ppb forsoil and filter cake respectively.

ABB Environmental Services Inc.

Bioremediation Systems Corporate Plaoa 126 Telephone (617) 245-6606107 Audutoon Road Fax (617) 246-5060WakeWd, Massachusetts 01880

Mr. John BorovskyJanuary 21, 1993 PN: 7054.01Page 2

ABB-ES is currently preparing cost estimates for full scale composttreatment of Arrowhead soil and filter cake.

Yours truly,

ABB ENVIRONMENTAL SERVICES, INC.

Sam Fogel, Ph.D.Project Manager

Enclosure

cc: Margaret Findlay,Treatability Coordinator

SL KK Bloremediation SystemsASEA MOWN 1OV1PH


SOIL, FILTER CAKE, AND SLUDGE

DRAFT REPORT

JANUARY 8,1993

Prepared for:Barr Engineering Company8300 Norman Center Drive

Minneapolis, MN 55437

Prepared by:

ABB Environmental ServicesBioremediation Systems Division

Wakefield, MA



DRAFT REPORT

TABLE OF CONTENTS

Section_________________litlfi_______________ Page No.

1. EXECUTIVE SUMMARY . . . . . . . . . . . . . . . . . . l-l

2. APPROACH . . . . . . . . . . . . . . . . . . . . . . 2-1

3. METHODS . . . . . . . . . . . . . . . . . . . . . . . 3-1

4. MATRIX CHARACTERIZATION . . . . . . . . . . . . . . 4-1

5. SOIL TREATMENT . . . . . . . . . . . . . . . . . . 5-1

5.A Introduction and Summary, Soil Experiments . 5-15.B Soil Preliminary Test . . . . . . . . . . . . 5-25.C Soil Compost Treatment Simulations . . . . . 5-45.D Soil Compost with Abiotic Control . . . . . .5-125.E Conclusions, Soil Treatment . . . . . . . . . 5-145.F Conceptual Design for Full Scale Treatment . 5-14

6. FILTER CAKE TREATMENT . . . . . . . . . . . . . . . 6-1

6 .A Introduction and Summary of Filter CakeExperiments . . . . . . . . . . . . . . . . . 6-1

6.B Filter Cake Pretreatment with Kiln Dust ... 6-26.C Filter Cake Compost #1 (Preliminary) ... . 6-36.D Filter Cake Compost #2 . . . . . . . . . . . 6-76.E Soil:Filter Cake 4:1 Compost . . . . . . . . 6-146.F Filter Cake Compost with Abiotic Control . . 6-206.G Summary and Conclusions, Filter Cake

Treatment . . . . . . . . . . . . . . . . . . 6 - 2 26.H Conceptual Design for Filter Cake Treatment . 6-24

7. SLUDGE TREATMENT . . . . . . . . . . . . . . . . . 7-1

7. A Introduction and iSummary . . . . . . . . . . 7-17.B Sludge Compost #1 (Preliminary) . . . . . . . 7-27.C Sludge Pretreatment . . . . . . . . . . . . . 7-47.D Sludge Compost #2 . . . . . . . . . . . . . . 7-57.E K-Sludge Slurry Treatment with Killed

Control . . . . . . . . . . . . . . . . . . . 7-87.F Discussion, Sludge Treatment . . . . . . . . 7-13



DRAFT REPORT

LIST OF FIGURES

Figure__________________Iltlfi________________Page No.

4-1 Soil, Filter Cake, and Sludge Fingerprints .... 4-2

5-1 Soil Compost TPH-IR and Bacteria . . . . . . . . . 5-6

5-2 Soil Compost #1 Fingerprints . . . . . . . . . . . 5-8

6-1 Filter Cake Compost TPH-IR, and Bacteria . . . . . 6-9

6-2 Filter Cake Compost Fingerprints . . . . . . . . . 6-10

6-3 Soil:Cake 4:1 Compost TPH-IR, and Bacteria . . . . 6-16

6-4 Soil:Cake 4:1 Compost Fingerprints . . . . . . . . 6 - 1 7

7-1 K-Sludge Compost TPH-IR and Bacteria . . . . . . . 7-7

7-2 Sludge Slurry Treatment TPH-IR and Bacteria . . . 7-10

Al Soil Compost #2 Fingerprints . . . . . . . . . . . Al-8

A2 Kiln Dust Treated Filter Cake Compared to OriginalAl-10



DRAFT REPORT

LIST OF TABLES

Table__________________Title________________Page No.

1-1 Chemical Data for Soil, Filter Cake, and Sludge . 1-21-2 Compost Treatment Process Results . . . . . . . . 1-41-3 Compost Treatment Parameters . . . . . . . . . . . 1-51-4 RMAL Detection Limits in Finished Compost . . . . 1-51-5 PAH and Phenolics Biodegradation . . . . . . . . . 1-61-6 Reduction of Metal Reachability . . . . . . . . . 1-74-1 Matrix Physical Properties . . . . . . . . . . . . 4-14-2 TPH-IR, ABB and RMAL, Percent Dry weight . . . . 4-14-3 Inorganic Fraction of Soil, Filter Cake, and Sludge 4-24-4 Total GC Hydrocarbons, Arrowhead Matrices . . . . 4-34-4a Volatiles Decane and Lighter . . . . . . . . . . . 4-34-5 Particle Size Distribution in Matrix Material . . 4-44-6 Bacterial Population in Arrowhead Matrices .... 4-45-1 Bacterial Growth in Soil Microcosm . . . . . . . . 5-35-2 Soil Composts #1 and #2, Amendment Weight Ratios . 5-45-3 Bacterial Growth in Soil Composts ftl and #2 ... 5-65-4 TPH-IR Reduction during Soil Compost Treatment . . 5-75-5 GC Total Hydrocarbon Reduction During Soil Compost

Treatment . . . . . . . . . . . . . . . . . . . . 5-95-6 GC/MS Data for PAH and Phenolics . . . . . . . . . 5-105-7 TCLP Lead and Arsenic, Soil and Finished Soil

Compost . . . . . . . . . . . . . . . . . . . . . 5 - 1 05-8 Summary of VOA Analysis, Soil and Soil Compost . . 5-115-9 Summary Comparison of Compost #1 and Compost #2 .5-115-10 CO, Production, 02 Use, and TPH Reduction during

Soil Composting . . . . . . . . . . . . . . . . . 5-136-1 Hydrocarbon Analysis of "K-Cake" Pretreated with

Kiln Dust . . . . . . . . . . . . . . . . . . . . 6-26-2 Filter Cake Compost #1 Amendment Weight Ratio . . 6-36-3 Filter Cake Compost #1 Process Data Summary ... 6-56-4 Filter Cake Compost #1 Bacterial Numbers and TPH-IR

Reduction . . . . . . . . . . . . . . . . . . . . 6-66-5 Filter Cake Compost #2 Amendment Ratios ..... 6-76-6 Bacterial Growth in Filter Cake Compost #2 .... 6-86-7 Reduction of TPH-IR, Filter Cake Compost #2 ... 6-96-8 GC Total Hydrocarbons, Filter Cake Compost #2 . . 6-106-9 GC/MS Data for PAH and Phenolics Starting Filter

Cake and Finished Filter Cake Compost . . . . . . 6-116-10 TCLP Heavy Metals, Filter Cake and Filter Cake

Compost . . . . . . . . . . . . . . . . . . . . . 6 -126-10a Summary of VOA Analysis, Filter Cake Compost . . 6-136-11 Soil:Cake 4:1 Compost Treatment Amendment Weight

Ratios . . . . . . . . . . . . . . . . . . . . . . 6-14



DRAFT REPORT

LIST OF TABLES(continued)

Table__________________Title_______________Page No

6-12 Bacterial Growth in Soil:Cake 4:1 Compost . . . . 6-166-13 Reduction of TPH-IR, Soil:Cake 4:1 Compost . . . . 6-176-14 GC Total Hydrocarbons, Soil:Cake 4:1 Compost . . . 6-176-15a GC/MS cPAH in Finished Soil:Cake 4:1 Compost . . 6-186-15b Biodegradation of 2 Compounds in Soil:Cake Compost6-186-16 TCLP Lead: Soil, Cake, and Finished Soil:Cake

Compost . . . . . . . . . . . . . . . . . . . . . 6-196-17 CO, Production, 02 Use, and TPH Reduction During

Filter Cake Composting . . . . . . . . . . . . . . 6-217-1 Sludge Compost #1 Amendment Ratios . . . . . . . . 7-27-2 Bacterial Growth in Sludge Compost #1 . . . . . . 7-37-3 TPH-IR Values, Sludge Compost #1 . . . . . . . . . 7-47-4 Sludge Compost #2 Amendment Ratios . . . . . . . . 7-67-5 Bacterial Growth, K-Sludge Compost #2 . . . . . . 7-77-6 TPH-IR Reduction, Sludge Compost #2 . . . . . . . 7-87-7 Flask Contents for K-Sludge Slurry Test . . . . . 7-97-9 Bacterial Growth during K-Sludge Slurry Treatment 7-107-10 TPH-IR Reduction during K-Sludge Slurry Treatment 7-11A-l Determination of Necessary Extraction Volume for

TPH-IR . . . . . . . . . . . . . . . . . . . . . . Al-5A-2 GC Volatiles Compounds, Decane and Lighter, Percent of GC

Total Soil, Filter Cake, and Sludge . . . . . . . Al-6A-3 Soil Compost #1, Process Monitoring Log . . . . . Al-7A-4 Soil Compost #1, Process Adjustment Log . . . . .Al-7A-5 Soil Compost #2, Process Monitoring Log . . . . . Al-8A-6 Soil Compost #1, Process Adjustment Log . . . . .Al-8A-7 TPH-IR Changes in Soil at Different pH using KOH and

Lime . . . . . . . . . . . . . . . . . . . . . . . Al-9A-8 TPH-IR and GC Total for Kiln Dust Treated Filter CAfcelOA-9 Filter Cake Compost #1, Process Monitoring Log . Al-llA-10 Filter Cake Compost #1, Process Adjustment Log . Al-llA-11 Filter Cake Compost #2, Process Monitoring Log . Al-12A-12 Filter Cake Compost #2, Process Adjustment Log . Al-12A-13 Soil:Cake 4:1 Compost, Process Monitoring Log . Al-13A-14 Soil:Cake 4:1 Compost, Process Adjustment Log . Al-13A-15 Filter Cake Abiotic Test Duplicate Values . . . Al-14

BarrEngineering Company8300 Norman Center DriveMinneapolis, MN 55437-1026Phone: (612)832-2600Fax: (612)835-0186 January 21, 1993

Mr. Ted SmithRemedial Project ManagerHaste Management DivisionOffice of Superfund (HSRM-J5)U.S. Environmental Protection Agency77 West Jackson BoulevardChicago, IL 60604-3590

Re: Draft Arrowhead Refinery SiteBiotreatability Study Report

Dear Mr. Smith:

Please find enclosed Volume II of the Draft Arrowhead Refinery SiteBiotreatability Study Report, Volume I of this report is being forwarded to youtoday by Sam Fogel of ABB. We expect to be able to provide EPA with costestimates for alternative conceptual designs involving bioremediation ofArrowhead site contamination by February 3, 1993.

If you or your review team (see distribution list) have questions regardingthe Draft Report, please call me at (612) 832-2620.

Best regards,

'John P. Borovsky/vice President

JPB:plsEnclosurec: Tom Kelley

Gina BayerDon DraperPhilip Brick

23\69\065\TS.I.TR

1* EXECUTIVE SUMMARY

Arrowhead soil, filter cake and sludge have been shown to betreatable by biodegradation, with reductions of bulk contaminant ofaround 85 percent. The final product is odor-free, not oily innature, and has excellent handling properties. Volatile organiccontaminants were not detected at detection limits less than 50PPB, and most carcinogenic PAH not detected at a limit of l PPM.Two or more tests were carried out for each media and the resultswere highly reproducible. Since the bulk contaminant was shown tobe the same by GC fingerprint for all three media, the collectivedata is strong evidence of its biodegradability. Data from killedcontrols supported the biotic nature of the process.

Site Description

The Arrowhead Refinery Site in Hermantown MN is contaminated as aresult of the reprocessing of waste crankcase oils. The processinvolved recovery of a light fraction of oil for re-use, and thedisposal of sulfuric acid contaminated heavy hydrocarbons as asludge and as a clay-containing filter cake. Based on a report byCH2M Hill (Field Design Investigation Vols 1, 2, & 3, ArrowheadRefinery site, Hermantown, MN, EPA WA 129-5NH8, Apr 30 1990), the10 acre site contains approximately 40,000 cu yd of contaminatedsoil and sediment, 2,300 cu yd of sludge, 1,700 cu yd of filtercake, and 600 cu yd of oil-saturated peat.

Matrix Texture. Bulk Contaminant. oH

Site matrix samples were collected by Barr Engineering and sent toRocky Mountain Analytical Laboratories for chemicalcharacterization, and to ABB Environmental Services for biologicaltreatability testing. ABB found that the soil has an easily-workedstructure and contains about 50,000 PPM (5 %) petroleumhydrocarbons as measured by TPH-IR, dry weight basis, EPA Method418.1. The soil contains a wide range of particle sizes, from finesand to cobbles. The filter cake is a dense black hydrophobicmaterial having a hydrocarbon content of about 400,000 ppm TPH-IR,a pH of 3.5, and a high clay content. Sludae is a blackhydrophobic sticky fluid with a high viscosity, pH of 2, and TPH-IRof about 690,000 ppm.

Matrix Chemical Characterization

Gas chromatographic analysis of the three matrix types demonstratedthat the bulk hydrocarbon contaminant is essentially the same in

1-1

ABB Bkxemediation Systems

soil, filter cake, and sludge. The GC fingerprint (Section 4)demonstrated that about 99 % of the material is represented by abroad band of unseparated hydrocarbon compounds, containing from 19to 35 carbons, and that a much smaller fraction of the materialappears as a series of small peaks, representing the linear alkanesand related compounds, from octane to CIS. Of these, several peaksrepresenting volatile compounds having fewer than 10 carbons, makeup 0.3 % or less of the GC total.

Samples were analyzed in triplicate by RMAL for semivolatiles,including six carcinogenic PAH (cPAH). These were not detected inmost of the matrix samples (with the exception of chrysene reportedin all matrices, and benzo(b)fluoranthene reported in soil samples.Any cPAH, if present at half the detection limit, would make upless than 0.04 % of the GC total for each matrix, and as thesewould appear at the same fingerprint location as C25 to C32alkanes, would not be visible on the broad band of unseparatedhydrocarbons. These data .are summarized in Table 1*1. Lead, incontrast to the organic contaminants of concern, was reported inhigh concentrations: 0.1 % for soil, 1.1 % for filter cake, and 1.2% for sludge.

Tabl* 1-1

Chemical Data for Soil, Filter Cak«, & Sludge

Volatiles & GC Tot, ABB: cPAH & Benzene, RMAL

Benzene Sum of volatiles Each c-PAH GC TotalPPM PPM % GC Tot PPM % GC Tot PPM

SOIL ND< 4 45 0.2 % ND < 3 0.005 % 22,700

CAKE J 0.4 190 0.1 % ND < 130 0.030 % 214,100

SLUDGE ND<16 850 0.2 % ND < 300 0.035 % 405,200

Treatabilitv Study Approach

The purpose of the treatability research was to determine whetherbiological treatment is possible for any of the Arrowhead matrices,develop a process, and assess its feasibility. Because somecompounds of concern such as some of the cPAH are not detectable inthe site material, it was necessary to study the progress ofbiodegradation in terms of the bulk petroleum contaminant. This is

1-2

ABB Bioremediation Systems

reasonable, since the bacterial population that is expected tobiodegrade the contaminants of concern will first metabolize mostthe bulk contaminant before attacking cPAH. Furthermore, since PAHare initially dissolved in the petroleum compounds, elimination ofthese compounds will reduce the mobility of the cPAH allowing themto bind strongly to soil organic matter* For these reasons, thebiodegradation process was studied in terms of TPH-IR and GCtotals.

Selection of Compost Treatment

The Arrowhead site soil has a population of acclimated hydrocarbon-degrading bacteria that responded to soil texture modification, pHadjustment, and addition of mineral nutrients by multiplying100,000 fold in 7 days. Since the soil required the addition ofbulking agent to prevent compaction and provide air permeabilityfor bacterial metabolism, soil composting was tested and found tobe successful. It was thus demonstrated that the petroleumcompounds in the Arrowhead bulk contaminant are readilybiodegradable. Since these are the same compounds in filter cakeand sludge, it followed that composting, texture modification withbulking agent to insure aeration, together with the addition offertilizer and site bacteria, might allow biological treatment ofthese matrices, if the bacteria could acclimate to the high leadconcentrations. This apparently occurred, as composting of cakeand sludge was successful.

Treatability Procedure

For soil composting, soil was mixed with 20 % by weight bulkingagent of shredded branches, to improve permeability, and organicmatter (manure) to improve moisture holding ability. A completemineral fertilizer containing 9 elements in the proportion neededby bacteria was added, and aeration was provided by frequentmixing. The soil compost was analyzed frequently for pH, moisturecontent, and the availability of nitrogen and phosphate fertilizerelements, and adjustments were made* immediately to assure optimalpH, moisture and mineral availability. Samples were also analyzedfrequently to determine bacterial growth rates, and TPH-IRreduction, GC fingerprint changes. The biodegradation process wasjudged to be complete when no further decrease in TPH-IR occurred.Final samples were sent to Rocky Mountain Analytical Laboratory(RMAL) for analysis of total and TCLP volatile and semi-volatileorganics, and total and TCLP metals, according to an EPA-approvedQAPP.

Since filter cake and sludge were acidic, hydrophobic, sticky, andgenerally difficult to work with, physical modification was animportant first step to treatment. It was found that pretreatmentwith kiln dust produced a stable emulsion with neutral pH and good

1-3


handling properties. The compost testing procedure was otherwisesimilar to that carried out with soil, except that much morebulking agent was needed, and involved the addition of bulkingagent and fertilizer,'frequent aeration by mixing, and maintenanceof proper pH, moisture, and available minerals. Full treatmentsimulations were carried out for filter cake and for a 4:1 mixtureof soil and filter cake. For sludge, the experiments did notinclude sending samples to RMAL, but an additional slurry treatmentwas carried out.

Treatabilitv Results

For all three matrices, after initiation of compost treatment, thebacterial population increased to over 100 million per gram ofcompost, and the TPH-IR gradually decreased by about 85 % in about40 days. GC fingerprint, analysis of starting, mid-point andfinished compost illustrated a dramatic decrease in all hydrocarbonconstituents of the bulk contaminant. GC total hydrocarbons alsodecreased about 85 % during treatment. These data are given inTable 1-2. and process information, such as treatment times,percent bulking agent, and fertilizer use are given in Table 1-3.The high phosphate requirements for soil and filter cake are due toconstituents present in these matrices which react with phosphate.

Table 1-2Compost Treatment Process Results

Million (max)Bacteria per TPH-IR , GC Totalgram compost Reduction Reduction

SOIL 200 85 % 84 %FILTER CAKE 170 86 % 77 %SLUDGE 130 82 %4:1 SOIL:CAKE 170 88 % 84 %

1-4

AMI Bkwemediation Systems

Table 1-3

Compost Treatment Parameters* vet weight matrix

time for Total Kg/Kg* grams grams50 % TPH Treat Added PO4 N perReduction Time Drv bulk per KQ* Ka*

SOILFILTER CAKESLUDGE4:1 SOIL:CAKE

7 days23 days35 days14 days

30 days50 days64 days30 days

0.150.801.350.22

614.51.51.8

0.94.42.23.5

Volatiles Reductions

Comparison of RMAL analysis of finished compost with those forstarting matrix samples indicated that the detection limit forvolatile organic compounds and PAH had been greatly reduced due tothe removal of bulk contaminant. These are given in Table 1-4.

Table 1-4

RMAL Detection Limits in Finished Compost

Dry weight matrix basis

Matrix Each VOA Most cPAH

SOIL ND < 18 PPBFILTER CAKE ND < 47 PPB4:1 SOIL:CAKE ND< 22 PPB

ND < 1.4 PPMND < 1 PPMND < 2 PPM

1-5


Biodearadation of Semi Volatiles

PAH were not detected in all samples, but based on limited data,significant biodegradation rates were found for 4 PAH. Values werealso available for some phenolics. These are given in Table 1-5.

1-5

PAH and Phenolics Biodtgradation - Boil

PercentInitial Soil Treated Soil Degraded

naphthalene 2 ppm 0.07 ppm 97 %phenanthrene 1.1 ppm 0.08 ppm 92 %fluoranthene 0.53 ppm 0.1 ppm 78 %chrysene 1.2 ppm 0.33 ppm 67 %phenol 0.27 ppm 0.13 ppm 52 %2/4dimethylphenol 0.82 ppm 0.28 ppm 66 %

PAH and Phenoliea BiodUgradation - Filter cake

Initial Cake Treated Cake Degraded

naphthalene 14.5 ppm 0.13 ppm 98 %2methylnaphth 13.5 ppm 0.11 ppm 98 %phenanthrene 16.7 ppm 0.47 ppm 97 %fluoranthene 7.5 ppm 0.16 ppm 95 %chrysene 11 ppm 1.0 ppm 81 %phenol 24 ppm 1.6 ppm 93 %2,4 dimethylphenol 22 ppm 2.2 ppm 90 %mp cresol 19 ppm 2.1 ppm 89 %

PAH and PHenolics Degradation, 4:1 soil:CaX«

Initial mix Treated mix Degraded

chrysene 1.94 ppm 0.57 71 %phenol 2.6 ppm 0.19 93 %

1-6


Reduction in Leachabilitv of Metals

Comparison of the TCLP metals data of initial and treated samplesindicated that the leachability of several metals had been reducedby the biological process. This data is summarized in Table 1-6.

Table 1-6

Reduction of Metal Leachability - Soil

ug/L ug/L PercentInitial Soil Treated Soil Reduction

Lead 267 187 30 %Arsenic 6.3 ND<2.4 62%

Reduction of Metal Leachability - Filter Cake

ug/L • ug/L PercentInitial Cake Treated Cake Reduction

lead 25,400 10,720 57 %Chromium 148 ND < 53 64 %Cadmium 63 34 46 %

Reduction of Metal Leachability -4:1 Soil:Cake

ug/L ug/LInitial mix Treated mix Reduction

lead 2,700 840 69 %

The Biotic Nature of the Treatment Process

Several observations support the contention that the treatmentprocess presented here is the result of biological action, ratherthan of abiotic processes. Primarily, treatment initiation wasalways accompanied by rapid increases in the numbers of bacteria,and TPH-IR reductions always occurred in the presence of highpopulations of bacteria. Volatilization is ruled out as a possibleexplanation for the reduction in hydrocarbons, since only 0.2 % ofthese were volatile compounds.

Experiments with killed controls were carried out for each matrix.Soil and filter cake composts were tested in sealed containers,with controls heat treated to inactivate bacteria. TPH reduction,C02 production, and oxygen use were greatly reduced in the heattreated samples compared to identical samples not heated. Forsludge, a slurry experiment with a HgC12-killed control showed no

1-7

AIM Bioremediation Systems

TPH reduction, while degradation was observed in live samples.

Additional evidence for the biotic nature of the composting processis provided by the GC fingerprints produced at the beginning, mid-point and end of the treatment. Examining the fingerprints forsoil compost, for example, it can be seen that the broad band ofunseparated hydrocarbons is centered on the position of C26 (26carbon straight chain alkane) on day 0, on C 27 on day 21, and onC28 on day 41. This means that the lower molecular weight,compounds are being preferentially biodegraded, which is typicalof bacterial attack on hydrocarbon mixtures. If an abiotic processsuch as adsorption to bulking agent were involved, the shift wouldprobably be in the other direction, since this process wouldprobably preferentially effect higher molecular weight molecules.Another item of evidence that adsorption to bulking agent is not aprimary cause for TPH reduction, is .the sludge slurry test, inwhich TPH reduction was observed but bulking agent was not present.

Reproducibility of Treatability Results

Two entirely separate soil compost treatment simulations werecarried out during this project, at different times, using aboutthe same concentration of bulking agent. The results were closelysimilar with respect to the TPH-IR reduction, the treatment times,bacterial numbers and amount of lime and fertilizer required. Athird soil compost experiment involving the heat treated control,again showed a similar treatment time and TPH reduction. Theseresults indicate that the process is reproducible and the data canbe used to calculate requirements for full scale remediation.

Two entirely separate filter caJce compost treatment simulationswere also carried out, one for the full treatment time and one onlyuntil 50 % degradation occurred. Data from these two experimentsis also closely similar, regarding the rate and extent of TPHreduction and bacterial numbers. The third filter cake experiment,involving the heat-killed control, exhibited the same rate of TPHreduction as the first two experiments.

The sludge was shown to be biodegradable both in compost treatmentand in slurry treatment experiments. For composting, both kiln-dust -pretreated sludge and CaO-pretreated sludge demonstratedbiodegradation. Therefore, the feasibility biological treatment ofsludge is considered to be well documented.

1-8


Conclusions

Arrowhead soil, filter cake and sludge have been shown to betreatable by biodegradation, with reductions of bulk contaminant ofaround 85 percent. The final product is odor-free, not oily innature, and has excellent handling properties. Carcinogenic PAH(cPAH) were generally not detectable in the starting samples, butthe detection limits were high due to analytical interference fromthe bulk hydrocarbon contaminant. Biological treatment reduced thebulk contaminant so that detection limits were lowered. Treatedsoil and treated filter cake contained no volatile organiccontaminants at detection limits of 18 PPB and 47 PPB respectively,and both treated soil and treated filter cake contained no cPAH atdetection limits of 1 PPM each PAH. Comparison of leachability ofmetals in starting samples and compost-treated samples demonstratedthat the leachability of several metals was significantly reducedby biological treatment.

Composting is a relatively simple and trouble-free biologicalprocess, as compost mixtures do not require constant attention, arerelatively stable to fluctuations in environmental temperatures andmoisture conditions, and are not significantly effected byequipment mal- functions or delays. Furthermore, the finishedcompost can be easily dried.

For Arrowhead soil, sufficient process information is provided inthis report to support full scale design. For sludge and filtercake, additional experiments are needed to determine the extent ofcompost volume reduction that can be achieved by drying, screeningto recover bulking agent, and compacting the finished compost.

1-9

J& B&I& Bioremediation Systems

2. APPROACH

Purpose

The purpose of this study was to determine whether biologicaltreatment could be applied to any of the Arrowhead matrices, and ifso, to develop a process for this biological treatment. Theresearch involved developing specific cost-effective procedures tooptimize conditions for bacterial activity in each matrix type(soil, filter cake, and sludge), and documenting the processparameters by fast turn-around analysis during the treatabilitytesting, as well as demonstrating effectiveness by the analysis oftreated samples by an EPA certified laboratory (RMAL) forcontaminants of concern.

Treatabi1itv Approach

Many species of ordinary soil bacteria will break down petroleumhydrocarbons, using them as their only source of food, producingmore bacteria and C02. In order to bring about this process, thebacteria must be supplied with (1) oxygen, (2) water, and (3) asupply of readily available (dissolved) minerals. These bacterialrequirements can be met in either a solid matrix treatment system,or in an aqueous system. __

Selection of Solid Matrix Treatment.

Because Arrowhead bulk contaminant and target compounds arerelatively insoluble compounds, and because of the highconcentrations of bulk contaminant present, Arrowhead material ismore efficiently treated in a solid matrix system. The texture ofArrowhead materials could be easily modified to make them suitablefor treatment by soil and sludge composting methods. These areexplained in detail below.

Texture modification for air permeability using bulking agents.

The general approach in the biological treatment of solid matricessuch as contaminated soil and chemical sludges, is to modify thetexture of the material so that it can be handled by ordinary fieldequipment, and so that it will have pore spaces to trap air whichwill supply oxygen to the bacteria. Porosity can readily beincreased by the addition of bulking agents such as wood chips orshredded branches, which have the structural features necessary tomaintain pore spaces under the weight of a foot or more oftreatment mixture.

2-1


Addition of moisture-holding agents.

Oily sludges and oil-contaminated soil are generally hydrophobicmaterials which do not hold sufficient water to support bacterialgrowth. The addition of a few percent of fine particles of organicmatter, such as finely chopped straw or manure, can improve themoisture-holding ability of an oily matrix.

Addition of a supply of dissolved minerals.

Bacteria which are expected to convert high concentrations ofhydrocarbon into biomass require large amounts of nitrogen-containing compounds and phosphate, as well as lessor quantities ofsulfur, potassium, sodium, calcium, magnesium, chloride, iron andtrace elements. A mixture of these elements was provided in theproportions required by bacteria (ACT fertilizer).

Use of Site-Acclimated bacteria.

Since petroleum hydrocarbons are natural products, many species ofsoil bacteria are able to biodegrade these compounds. Best resultsin treatment, however, are likely to be obtained by the bacterialpopulation from the actual site, since these are already acclimatedto site-specific conditions. For the Arrowhead matrices it wasparticularly important to use the native bacteria, since thesewould be acclimated to high concentrations of lead.

Filter cake and sludge did not have significant populations ofbacteria, since these materials were impermeable to air and wereprobably lacking critical mineral elements. For experimentsinvolving these matrices, a small amount of Arrowhead soil wasadded to provide an inoculum of acclimated bacteria.

Maintenance of Mineral Nutrient Supply:

The concentration of dissolved nitrogen, (as NH3) was monitored atintervals. When the nitrogen was depleted by the bacteria, theentire mixture of elements was again added to the experimentalsystem. Monitoring was also carried out for available phosphate,since it is reactive in soils, tending to bind to clays orprecipitate with common cations and mineralize, becomingunavailable to bacteria. Supplementary phosphate was added asneeded to maintain a supply of this element in the dissolved state.Since fast-turn-around analysis of available minerals is essentialfor biological treatability investigations, these analyses werecarried out by test kit.

2-2


Maintenance of pH and moisture content.

pH and moisture content were measured frequently and adjustedimmediately during treatment simulations. pH control wasparticularly important, since the Arrowhead matrices were quiteacidic, and tended to revert to acid pH within a few days ofinitial adjustment.

Bacterial Enumeration.

The enumeration of the bacterial population during treatmentsimulations provided an index of the all-over success inmaintaining conditions optimal for biodegradation. A drop inbacterial numbers, or failure to attain high numbers, signaled aneed to initiate trouble-shooting procedures. Bacterialenumeration data are reproducible within only about 50 %, that is,100 million and 150 million per gram are not significantlydifferent.

The Importance of biodearadina the bulk contaminant.

Over 99 percent of the hydrocarbons present in the Arrowheadmatrices do not constitute "contaminants of concern", but are heavyhydrocarbons, primarily alkanes, that are considered relativelyharmless as individual compounds. As an oily matrix, however, theyprovide mobility to the compounds of concern, such as polynucleararomatic hydrocarbons (PAH). When the oily matrix is extensivelydegraded, the remaining compounds, which may include PAH, are morelikely to be immobilized by binding to soil.

A second reason for concern with treatment of the bulk contaminantis that the PAH are relatively high molecular weight compounds,which bacteria do not generally attack until the lighter moleculesin the bulk contaminant have been degraded. Finally, the organiccontaminants of concern can only be analyzed with low detectionlimits when the bulk contaminant is reduced.

The Use of TPH-IR Analyses

TPH-IR measurements are useful to indicate the progress and theendpoint of a treatment simulation, as well as for comparisons,such as live test vs killed control. TPH-IR is a non-specificanalytical method that responds to carbon-hydrogen bonds in anyfreon-extractable material, and is calibrated against an arbitraryEPA standard composed of a mixture of 25 % chlorobenzene, 37 % iso-octane, and 37 % n-hexadecane. It is unlikely that "pure"Arrowhead hydrocarbons would measure exactly 100 % using thisstandard.

2-3


TPH-IR measurements are used in treatability studies because it ispossible to obtain the data on a rush basis in a few hours, and ona routine basis in two days, and fast turn-around analyses arecritical for maintaining a real time understanding of the progressof a treatability experiment. GC analysis, if performed in thetreatability laboratory generally require about one week for dataturn-around, and GC/MS analysis carried out by a separatelaboratory typically require at least one month. Another importantconsideration in the use of TPH-IR measurements is cost, which ismuch lower than either GC or GC/MS.

TPH-IR measurements on samples having relatively large particlesize, such as compost containing wood pieces up to 0.5 inches, aregenerally reproducible only to within 15 %. The portion of theerror is due to obtaining representative samples for extraction, aswell as for the dry weight determination.

Use of GC hydrocarbon analysis.

The gas chromatographic method is a more specific method forhydrocarbons, producing a visual display (GC Fingerprint) of theseparated hydrocarbons, as well as allowing quantitation of totalhydrocarbons. During treatability testing, when TPH-IR dataindicated a significant reduction in bulk contaminant, selectedfrozen freon extracts that had been prepared for the TPH analysiswere then analyzed by GC. Although GC analyses are usuallyperformed on methylene chloride/acetone extracts, this procedurereduced cost and insured that the TPH and GC data were performed onthe same extract.

Quantitation for GC hydrocarbons was based on orthoterphenyl (OTP)as internal standard. This is an aromatic compound which does notnecessarily have the same response factor in the gas chromatographas "pure" Arrowhead hydrocarbons. Thus, the GC totals may notrelate quantitatively to the Arrowhead hydrocarbons, but relativechanges in GC totals should reflect changes in Arrowheadhydrocarbons.

The method of quantitating the GC total also involves manualintegration of the unseparated hydrocarbon "hump", by cutting andweighing a fingerprint tracing. This method is therefore anestimate, and is probably reproducible only to within 20 %.

2-4


3. METHODS

Petroleum Hydrocarbons bv Infra Red Analysis

The TPH-IR was determined by EPA method 418.1, modified as follows:For each matrix, the amount of solvent required to extract 95 % ofthe hydrocarbon was determined experimentally, by repeatedextractions of the same sample. This ratio of solvent volume tomatrix weight was then maintained during the entire project.

Routinely, soil and compost samples were extracted twice with atotal volume of freon equal to 10, 15, and 20 ml per gram of soil,filter cake and sludge respectively. The extractions were carriedout in sealed containers by shaking 20 minutes in a reciprocalshaker. Silica gel clean-up was employed carefully according tomethod 418.1 until a clear extract was obtained. Infra redabsorption was determined using the method 418.1 standard solutionfor calibration. Freon extracts were stored at -20 deg for laterfingerprint analysis.

Petroleum hydrocarbon oas chromatoaraphic fingerprints

GC Method. Hydrocarbon fingerprints were prepared by analyzingthe freon extracts by gas chromatography according to EPA method #8100. Major hydrocarbon constituents were tentatively identifiedby retention time comparison with known compounds. While freon isnot always as efficient as methylene chloride in extractingpetroleum hydrocarbons from various matrices, the procedure isreproducible and gives a valid representation of changes in theamount of bulk contaminant during a given treatment simulation. Adetailed experiment demonstrating recovery of spiked compounds fromArrowhead soil compost by freon extraction is presented inAppendix #1.

Typical GC Fingerprint. Typically the fingerprints of Arrowheadmaterial show a broad band of instrument response representingnumerous compounds present in approximately the same concentration,thereby not showing separate "peaks'* on the fingerprint. Risingabove this band, are individual peaks of a few individual compoundsthat are present in higher concentrations. All GC fingerprintspresented in this report contain one full-scale peak at 23 minuteswhich is orthoterphenyl, the internal standard added forquantitation.

GC quantitation method. As an alternative to the IR method ofestimating the amount of bulk contaminant, a procedure was

3-1


developed to quantitate the hydrocarbons that were analyzable bygas chromatography. This involved summing two quantities: the GCinstrument integration of the "peaks", and the manually integratedarea of the broad band of hydrocarbons. For "peak*1 integration,the GC baseline was set to follow the broad band, and the peakswere quantitated by the internal standard method using OTP. Todetermine the amount of hydrocarbon in the broad band, thefingerprint was xeroxed and the band ("hump") was cut and weighed,and quantitated by comparison to the weight of an area of paperobtained by analyzing the standard separately. Further detailsare presented in Appendix #1.

Process Monitoring Methods

Available Nitrogen and Phosphate. Compost samples were extractedwith 5 volumes of deionized water by shaking for 20 minutes. Theextract was separated from the compost by centrifugation andfurther clarified by passing through a 0.45 micron filter, thenanalyzed for pH and for NH3, N03 and PO4 according to modificationsof Standard Methods (17 th ed) # 4500 NH3 C, NO3 E, and P D. Theconcentrations of these substances in the test compost wereobtained by multiplying these values by 5.

Moisture Content. Moisture content was calculated from weight lossupon drying at 100 deg C.

Enumeration of Bacteria. Total bacteria were enumerated bystandard plate counting technique, using nutrient agar, incubatedat room temperature, and counted after 7 days of growth. Bacteriacapable of growing on volatile sludge hydrocarbons as their solecarbon source were enumerated by a modification of Standard method9215C (17 th ed.). Colonies were grown on nobel agar mineral mediaplates incubated in an atmosphere of volatile hydrocarbons, andcounted after 10 days of growth.

3-2


4. MATRIX CHARACTERIZATION

Sampling and Description of Matrix Physical Properties.

Sampling was conducted by Barr Engineering at the Arrowheadrefinery site in November 1991. Each media was sampled randomly inthree different locations. Each backhoe bucket of material wasmixed on a plywood sheet, and about 1.6 gallons placed in a 5gallon pail, resulting in samples having 3 layers. A descriptionof the sampling procedure is given in Appendix #1, together withABB's detailed description of the appearance of the matrix samplesand of the compositing procedure carried out in the laboratory. Asummary of matrix properties is given in Table 4-1.

Table 4-1Matrix Physical Properties.

Viscosity • Stickv hvdrophobic TextureSOIL - no no tillCAKE not fluid yes yes fineSLUDGE fluid yes yes fine

TPH-IR (Total Petroleum Hydrocarbons bv Infrared Analysis)

A sample of each matrix was subjected to four successiveextractions with freon and the TPH recovered with each extractionwas recorded. From this data, the volumes of freon per gram wetmatrix required to extract 95 % of the TPH were determined to be10, 15, and 20 ml for soil, cake, and sludge respectively.

The TPH-IR values determined for each matrix type on a dry weightbasis are listed in Table 4-2. in comparison with TPH valuesobtained by RMAL. (ABB soil TPH is for 12 mm sieved sample.) TheTPH values obtained by ABB for filter cake and sludge aresignificantly higher than those determined by RMAL. This resultmay be explained by the fact that ABB uses a larger extractionvolume than the 5 ml/gram required by EPA method 418.1, and mayrecover a higher fraction of the TPH from highly contaminatedsamples.

Table 4-2TFH-ZR , ABB and RMAL, Percent Dry weight

Soil Cake Sludae

TPH, ABB 5 % 43 % 69 %TPH, RMAL 6 % 19 % 38 %

4-1

Ailll Btoremediation Systems

Inorganic Fraction

The percent water was determined by drying at 100 deg C. This isan acceptable method of estimation because the fraction of volatilehydrocarbons is relatively low in these samples. The inorganicfraction was determined by extracting the samples with 1:1dichloromethane:acetone, without the presence of the usual dryingagent sodium sulfate, to remove the petroleum, then drying. (Soildata is in terms of 12 mm sieved soil) The data are presented inTable 4-3. The percent inorganic content can be compared with ashcontents determined for Barr Engineering, of 30% for filter cake(average of 8 samples) and 7 % for sludge (average of 12 samples).While the agreement is not good, the trend is similar: filter cakehas more inorganic content than sludge, reflecting is content ofclay filter material.

, Table 4-3

Inorganic Fraction of Soil, Filter Cake and sludgeSoil Cake Sludae

% water 25 25 36% inorganic solids 75 49 21

GC Fingerprint and GC Total Hydrocarbons.

The fingerprints for the 3 matrices are presented in Ficrure 4-1 andare qualitatively similar. Eluting prior to the standard is aregularly spaced series of compounds having the same retentiontimes as the linear alkanes, up to C19. Immediately to the rightof the standard is a large "hump" of undifferentiated compounds,with an indication of the remaining -linear alkanes extending abovethe hump.

The total hydrocarbon content of the peaks and the broad band("hump") were determined as described in the Method section, andthe data are presented in Table 4-4. The sum of these values forchromatographable hydrocarbons are 2.3 % for soil, 21% for cake,and 41 % for sludge.

4-2

Jk ft R Bkwemediation Systems

GC FINGERPRINT ARROWHEAD SOIL. FILTER CAKE & SLUDGE

v ••

SOIL X 1 *

i

I. J, J. .1. .l...l..l.jJuJIfcl1* —

-•* **•

*!«« (A

* U!

~+«i

FILTER CAKE X .1 *

v

.!. . I -I .1*

* to

SLUDGE X .05 *

^LU. .1, .1 . l . l iUt

3 S = fta 3« is

O)o otoo

00o

t

I

Q.->o

CMCMO

t•i

^>CMa

00CMo

CMtoO

ALKANESTANDARD

• r«lotiv« dilution, dry vtight Bioremediation Systems

Table 4-4

Total GC Hydrocarbons/ Arrowhead MatricesPercent, Dry Weight Basis

Matrix Peaks Hump Total

SOIL 0.1 2.2 2.3

CAKE 1.5 20.0 21.5

SLUDGE 2.3 38.3 40.6

Fraction of volatile compounds

As illustrated in the GC Fingerprints, Ficrure 4-1, the volatileconstituents of the Arrowhead matrix samples are well separatedfrom each other and can be individually quantitated. The GCanalysis quantitated several volatile compounds lighter thandecane, ranging from relatively volatile substances such asxylenes, to slightly volatile compounds such as trimethyIbenzene.This data is given in Appendix /I. The sum of these compounds wasdetermined for each matrix and is given in Table 4-5. These sumsrepresent 0.3 % or less of the GC totals. Thus, volatile losseswould not account for any measurable reduction in bulk contaminantduring a biodegradation experiment.

Table 4-4

Volatile*, Decane and Lighter, as % of GC Totaldry weight

VolatilesPercent of

Volatiles -GC Total Total

SOIL 45 ppm 22,700 ppm 0.2 %CAKE 139 ppm 214,000 ppm 0.06 %SLUDGE 1287 ppm 405,200 ppm 0.3 %

4-3


Matrix Particle Size Distribution.

The organic portion of each matrix was removed by extraction withorganic solvent and the remaining inorganic material was sized onstandard sieves. For soil, stones greater than 12 mm, had beenpreviously removed. The results are given in Table 4-5. For soil,45 % of the particles were greater than 1 mm. For cake, 75 % aresmaller than 0.1 mm, and for sludge, 55 % are smaller than 0.1 mm.

Table 4-5

Particle size Distribution in Matrix Materialpercent of total

4 mm -1 mm -. 5 mm —,25mm -.1 mm -.05mm -

12 mm4 mm1 mm.5 mm.25mm.1 mm

<.05mm

2322111512108

CAKE

321192649

SLUDGE

1521181540

Bacterial Enumeration

Bacterial content of the soil composite sample was about 0.13million per gram wet weight. This would be considered a lowaverage for fertile soil, and is a sufficient population forremediation. Furthermore, it should be noted that these bacteriaare acclimated to site contaminants. Bacteria were not detected inArrowhead sludge and filter cake. This is typical of dense sludgematerial which has no porosity and therefore no oxygen to supportthe growth of microorganisms.

Table 4-6

Bacterial population in Arrowhead Matrices

Total Bacteria per gram wet SampleSOIL 150,000SOIL (dup) 120,000CAKE not detected, < 1000SLUDGE not detected, < 1000

4-4

ABB Bloremediation Systems

5. SOIL TREATMENT

5-A. INTRODUCTION AND SUMMARY, SOIL EXPERIMENTS

Contaminated soil from the Arrowhead site has a population ofacclimated hydrocarbon-degrading bacteria, an easily-workedstructure, and about 5 % petroleum hydrocarbon contamination, ofwhich over 99.6 % are non-volatile compounds. The preliminary soiltest demonstrated that site hydrocarbon-degrading bacteria wouldrespond to soil texture modification, pH adjustment and mineralnutrient availability by multiplying 100,000 fold in 7 days.

Soil treatment by composting was carried out, since the soilrequired the addition of a bulking agent to prevent compaction andto provide air permeability needed by the biological process. Twoseparate soil composting experiments demonstrated that the bulkcontaminant can be 50 % biodegraded in about 7 days, and about 85% biodegraded in about a month. The experiments also determinedthat about 5 grams of lime are needed per Kg dry soil to maintaina pH of 6.3, and about 6 grams of phosphate per Kg dry soil areneeded to maintain available phosphate.

An experiment with heat treated soil compost demonstrated that TPHreduction, oxygen use and C02 production were greatly reduced inthat sample, compared to an identical compost not heated,indicating that the process is biological.

Based on limited GC/MS data, it was determined that the 2-ring PAHnaphthalene biodegraded 97 %, and the 4-ring PAH fluoranthene andchrysene biodegraded 78 % and 67 % respectively. Chrysene, theonly carcinogenic PAH detected in the finished compost, was presentat 0.33 PPM. Benzene was not detected in the finished compost ata detection limit of 15 PPB. TCLP data on metals indicated thatthe leachability of lead in soil was reduced by about 30 %, andarsenic by 60 %, by biological treatment.

The proposed strategy for full scale remediation is influenced bythe very limited space on the site for treatment. The approachinvolves the excavation of contaminated soil, screening to removedebris and rocks, and backfilling of this material. The screenedsoil would be treated in two stages, the first being one week ofmechanically mixed composting on a treatment pad, during which timethe required amendments would be gradually added. The second stagewould be a compact treatment by forced aeration composting in largepiles 6 to 8 feet tall. After treatment, some of the bulking agentwould be recovered by screening, and the treated soil would bereturned to the site.

5-1

ABB Btoremediation Systems

5-B. SOIL PRELIMINARY TEST

Purpose: Pretreatment Requirements and Bacterial Growth.

The purpose of this experiment was to determine the requirementsfor raising the pH from 4.5 to 7, to investigate the interaction ofthe soil with the mineral nutrient amendment, and to determinewhether the population of bacteria could be stimulated to multiply.The results of this test would be used to design the larger scalesoil treatment simulation.

Procedure: Preliminary Soil Test.

Arrowhead Soil ( 4 mm sieved) was amended with ACT completefertilizer ( 9 elements, as described in Section 2) to give 145 ragnitrogen and 60 mg phosphate / Kg wet weight soil, and the pH wasadjusted from 5 tcr 7 using KOH. Then 1 percent organic matter(horse manure) was added to improve soil moisture-holding abilityand structure. Aeration was provided by mixing two times per day,and the moisture was maintained as high as possible withoutreducing porosity.

Process Monitoring and Adjustment, Preliminary Soil Test.

pH adjustment. On days 3 and 10 the pH had again dropped to 5, andadditional alkali (K2HPO4) was added, stabilizing the pH at 7 byday 10 with a total of 185 milliequivalents of alkali per Kg wetsoil.

Nitrogen and phosphate use. On day 3, a soil sample was analyzedfor available (water soluble) nitrogen and phosphate. Nitrogen was20 ppm so additional ACT was added.- Phosphate was not detectableso extra excess phosphate was added. Similar additions were madeon day 10. By the end of the test on Day 14, 260 ppm nitrogen hadbeen used. Since bacteria use about 4 grams of phosphate for 10grams of nitrogen, this would account for only 65 ppm of phosphateused by bacteria. During this time, however, 3769 ppm of phosphatewas required. Therefore, 3,700 ppm phosphate had reacted with thesoil, becoming unavailable to water extraction, and presumably alsounavailable to bacteria.

5-2

A.HI* Bioremediation Systems

Bacterial growth. Hydrocarbon-degrading bacteria increased 100,000fold from 1000 per gram to over 100 million per gram in 7 days.These data are listed in Table 5-1.

Table 5-1.

Bacterial Growth in Soil MicrocosmPetroleum Degraders per Gram Wet Soil

Day 0 0.001 millionDay 7 200 millionDay 7 duplicate 130 million

Conclusions, Preliminary Soil Test.

The rapid bacterial growth in response to a treatment involvingonly aeration, pH adjustment, and the addition of complete mineralfertilizer (with excess phosphate), indicate that direct treatmentof the soil is possible.

The fact that the bacterial population increased to very highnumbers without the addition of an emulsifier, indicated that suchan additive would not be needed for soil treatment.

It was observed that a slight excess of water caused the soil tobecome muddy and compacted and to lose porosity. Therefore, thesoil will require a bulking agent for full scale treatment.

The decision was made to use this test soil as a culture ofacclimated bacteria for other experiments, rather than to developa liquid culture.

5-3


5-C. SOIL COMPOST TREATMENT SIMULATIONS

Purpose. Approach, and Compost Constituents.

Two Experiments. The simulation of soil treatment by compostingwas carried out in two separate experiments, which demonstrated thereproducability of the process. The data from both experiments arepresented here. The second experiment, Soil Compost # 2, was alarge batch prepared to provide samples to Rocky MountainAnalytical Laboratory (RMAL) for analysis of volatiles, semi-volatiles, metals, TCLP metals, and general parameters.

Simulation of Mechanically Aerated Composting. The work plandiscussed the simulation of closed-system forced aerationcomposting process. However, since GC fingerprint data indicatedvery low volatiles in soil (Section 4) , open system composting, inwhich aeration is accomplished by mechanical mixing, was performedin the laboratory. The data generated are applicable to eithermixed soil composting or forced aeration composting.

Requirements for pH adi ustment and phosphate binding. Since thepreliminary experiment showed that these factors require gradualadjustment, it was decided to determine these parameters during thetreatment simulation. A separate experiment was carried out whichdetermined that the optimal range of pH for soil composting isbetween 6 and 7, using either KOH or hydrated lime. The data isgiven in Appendix #1.

Method of Determining Compost Bulking Agent Ratios. The bulkingagent, shredded branches, and the moisture-holding agent, manure,were added gradually with water to Arrowhead soil until a mixturewas obtained which had high moisture content but would not compactunder pressure, and had high porosity and good drainagecharacteristics. The ratios determined are given in Table 5-2.

Tabl« 5-2

soil composts #1 and #2, Amendment weight Ratios

Soil (25 % water) 100Shredded Tree Waste (dry) 13Manure (dry) 2Bulk per dry soil « 0.2Dry soil/Tot dry compost =0.83

5-4

• Bioremediation Systems

Process Initiation. Moisture and Aeration, Soil Composts.

Water was added to the mixture of soil and bulking agents to givea moisture content of about 38 %. Compost samples were analyzedevery 7 to 10 days to determine the moisture content, and water wasadded as necessary to maintain 38 % moisture . The composts wereaerated daily by mixing for the first week, then 3 times per week.Biodegradation was initiated by the addition of ACT fertilizer togive a concentration of 200 ppm nitrogen (wet weight) in thecompost. Extra buffered phosphate solution, over 600 ppm, was alsoadded initially, in an attempt to correct the soil phosphatebinding problem. Bacteria used were those already present in thesoil.

Process Monitorina and Process Adjustment.

Treatment of Acidity. Compost samples were analyzed for pHapproximately at weekly intervals, and adjusted immediately. Soilcompost #1 was maintained at pH=7 and required 6.3 grams ofhydrated lime per Kg wet compost added over 4 days to stabilize thepH at the desired level. Compost #2 was maintained at pH = 6.4 ,and therefore required only 2.3 g lime per Kg compost, and only 1day to adjust the pH.

Available N and P04. At approximately weekly intervals, sampleswere removed for analysis of available nitrogen and phosphate, andadditional ACT fertilizer and extra phosphate were added tomaintain an average concentration of available N and PO4 of about100 ppm each. The averages were estimated based on the amountspresent at analysis and the amounts added immediately afteranalysis.

The total amount of N and PO4 required in 40 days of composting wasabout 900 ppm and 3,200 ppm respectively, wet weight compost.

Phosphate binding. Bacteria incorporate about 4 grams phosphatefor 10 grams nitrogen. Therefore, 360 ppm PO4 would be needed for900 ppm N. Thus the phosphate that reacted with the soil andbecame unavailable for bacteria amounted to about 2,800 ppm wetweight compost (5,600 ppm dry soil).

The details of process monitoring and process adjustment forcompost #1 and #2 are given in the Appendix #1.

5-5

AMI Bkxemediation Systems

Bacterial Growth. Soil Composts # 1 & # 2.

Samples of Soil Compost # 1 were analyzed at 5 time points forbacterial numbers. Total plate count bacteria increased rapidlyfrom 2 million per gram wet compost to 300 million in 18 days, andremained high during the active treatment period of 41 days. Totalplate counts over 100 million carried out in the ABB laboratoryhave been associated with successful field and laboratory petroleumcompost treatment. Therefore the number obtained for Soil Compost#1 was taken to indicate the successful initiation of treatment.

Hydrocarbon degraders were counted by a method that reports onlythose bacteria capable of growth on volatile (less than 12 carbons)hydrocarbons. Since the Arrowhead contaminant is mainly heavyhydrocarbons, the volatile degraders are not expected topredominate. The volatile hydrocarbon degraders increased slowlyfrom 2 million to 15 million per gram by Day 21, a number less thanthat achieved in the soil preliminary test, and in other compostsreported in this study, but nevertheless sufficient to indicate asatisfactory population.

Enumeration of the bacteria in Soil Compost # 2 was not carried outroutinely, since good bacterial growth had already beendemonstrated in the first experiment. However, one count was madeon day 21 which confirmed that a similar population had developed.The bacterial enumeration data for both soil compost experimentsare listed in Table 5*3. and are plotted in Figure 5-1. Thedifference between 100 million for compost # 2 and 300 million forcompost # 1 may not be significant, since bacterial enumerationdata is considered to be reproducible only within a factor of 2.

T*bX« 5-3

Bacterial Growth in Soil Composts # 1 and # 2

million bacteria per.gram wet compostCompost * 1 Compost * 2

Total Hydrocarbon Total HydrocarbonBacteria Deoraders Bacteria Dearaders

Day 0 2 2Day 7 140 6Day 18 300 8Day 21 - 15 100 37Day 41 100

5-6


FIGURE 5-1

SOIL COMPOSTTPH-IR

compost f 1 A compost # 2

4*

g:I£ 2

10 20 30

DAYS

40 50 60

1000

100«**O

SOIL COMPOSTBACTERIA (total)

compost f 1 A compost # 2

Bioremediation Systems

TPH-IR Hydrocarbon Reduction. Soil Composts # 1 and # 2.

Rate and Treatment Time. Samples were removed from the soilcomposts at intervals and analyzed for bulk hydrocarbon content byTPH-IR. The data for both compost experiments is presented inTable 5-4. and plotted in Figure 5-1. The data indicate that thebulk contaminant is about 50 percent degraded in about 7 days, and70 % degraded by day 20. After one month the rate of decrease wasvery slow, and it therefore appears that the active treatmentperiod at 68 degrees F is one month.

Kinetics. Other than stating that the initial half-life of thisprocess is about 7 days, a kinetic analysis is not appropriate,since the catalyst (bacteria) is increasing in concentration, andthe reagents (hydrocarbon molecules) are changing. The fact thatthe apparent half-life of the process increases from 7 days for thefirst 50%, to 10 days for the second 50% is explained by theassumption that readily-degraded compounds are degraded first,followed by degradation of less-readily-degraded compounds.

QA. Quality assurance within this experiment was provided by theanalysis of duplicate samples on several occasions, with excellentagreement, as evident in Table 5-4. In addition to these duplicateanalyses, a spike recovery experiment was carried out on Day 53 ofexperiment #2, in which an 8000 ppm (dry weight) spike of EPAmethod 418.1 TPH calibration standard was spiked into the finishedcompost and 98 % was recovered. Details of this analysis are givenin Appendix #1. The percent decrease in TPH-IR for Soil Composts# 1 and # 2 was 89% and 83% respectively, which is good agreement,given that TPH-IR measurements are usually reproducible in compostmatrices only to within 15 percent.

Tabl« 5-4

TPH-IR Reduction during Soil Compost Tr«ata«nt

Percent, EPA Method 418.1 on Dry Height Basis

Soil compost # 1____ Soil Compost / 2

Dav TPH dup Day TPH duo

0 4.2 4.5 0 4.07 1.8 2,0 7 2.721 1.3 1.3 20 1.228 0.9 32 0.641 0.5 0.5 46 0.8 0.8

74 0.7

% Reduction 89 % 83 %

5-7

AMI Bloremediation Systems

TPH-IR Reduction, Soil Composting, Comparison with RMAL Data.RMAL reported an initial soil TPH-IR (triplicate) value of 6.2 % ,which is similar to ABBs initial soil TPH of 6 % . (ABB sievedsoil to remove stones larger than 12 mm, but it is not knownwhether RMAL carried out a similar procedure.) The soil compostswere 83 % dry soil to dry compost so this would be a calculatedinitial TPH of 5.1 % in the compost. A sample of Soil Compost # 2was analyzed by RMAL in triplicate and reported to contain 0.5 %TPH-IR, a value similar to that obtained at ABB, and indicating areduction of 90 % of the soil TPH-IR. The RMAL data report is inVolume 2.

GC Hydrocarbon Reduction. Soil Composts # 1 & # 2.

Fingerprints. The GC fingerprints for the freon extracts of day 0,7, 21, and 41 for Soil Compost # 1 are presented in Figure 5-2.Those for Compost # 2 are in Appendix *i. These illustrate thatthe more volatile compounds (less than about 16 carbons, to theleft of the added standard in Figure 5-2) are degraded in the firstweek, and that thereafter the heavier compounds are degraded,resulting in a dramatic reduction in the fingerprint height.

Preferential Loss of Lower M.W. Compounds. A close inspection ofthe fingerprints reveals that the "hump" has shifted to the right,Day 0 being centered on the position of C-26 (26 carbon straightchain alkane) , Day 21 on C-27, and Day 41 on C-28. ( Refer toFigure 4-1 for locations of alkanes.) A similar shift is evidentfor Soil Compost # 2. This shift is consistent with thepreferential biodegradation of lighter compounds that is usuallyobserved with hydrocarbons. It should be noted that if"humification11 were the primary factor in the disappearance of thehydrocarbons, the shift would probably be in the other direction,since this process would probably preferentially effect the heavierhydrocarbons. Humification is a little-understood process thatinvolves the irreversible chemical modification of organiccompounds and their integration into soil humic material.

GC Tota1 Hydrocarbon. The reduction in GC chromatographablematerial during composting was quantitated by the area estimationprocedure described under Methods in Section 3, and the data arepresented in Table 5-5. The numbers shown include the instrumentintegration of the small separated peaks plus the manual "hump"area determination. The results indicate hydrocarbon reductions of91 % and 77 % for soil composts # 1 and # 2, respectively. Thesevalues do not differ significantly, since this method ofquantitation is an estimation.

5-8


SOIL COMPOST # 1

il

DAY 0

£-

DAY 21

""*£z Z * 2

O o

DAY 41

Btoremecliation Systems

Table 5-5

GC Total Hydrocarbon Reduction During Soil Compost TreatmentPercent hydrocarbon, Dry Weight Basis

Soil Compost # 1 Soil Compost # 2

Day TPH J>3y_ TPH0 2.62 0 2.167 1.39 721 0.85 20 0.9841 0.24 47 0.50

Reduction 91 % 77 %

GC/MS Data for PAH and pheholics. Soil Compost # 2.

GCMS Data from RMAL on PAH in the final compost and starting soilare listed in Table 5-6. The complete RMAL data are in Volume 2.In an effort to maximize the use of the available data, all values,labled "J" were used to calculate the extent of biodegradation.The values for treated soil were calculated by dividing the valuefor compost by 83 % soil in the compost.

(The EPA J qualifier can be applied for two reasons. One is toindicate that an analyte is detected below the contract requireddetection level, and the other is to indicate that the data has notmet criteria for a quality control element such as calibration,spikes, standards, lab control samples, and intereference checks.J data are considered usable. The J-qualified data were used asreported estimated concentrations and did not affect the achievmentof the project goals or completeness.)

The data indicate that the 2-ring PAH naphthalene degraded 97 %,the 3-ring PAH pnenanthrene degraded 92 %, the 4-ring PAHfluoranthene and chrysene degraded -78% amd 67 % respectively. Twophenolics, phenol and 2,4-dimethylpheonl, degraded 52 % and 66 %,but a related compound benzenethiol, appeared not to have degraded.

TCLP Semi volatiles. Semi volatiles were generally not found inthe TCLP extract of finished soil compost, with a detection limitof 50 ug/L. Since this is a 20 fold extract, this represents adetection limit of 1 ppm in the compost.

5-9

Ann Bioremediation Systems

Table 5-6

GC/MS Data for PAH and Phenolics

RMAL, mg/Kg dry weight, U = not detected

StartingSoil

2J, 2J, 2J2 ringNaphthalIC-Napth3 ringanthracphenanth4 ringfluoranBaAnthrachrysene5 ringBaPyreneBbFluorBkFluorDbAnthphenolicsphenol .27J 2.6U 224dmp .81J .95J .benzenethiol 1.1J .

2.5U,2.6U,.75J .96J

.53J,.53J,2.5U,2.6J,2.5U,2.6U,

2.5U,2.6U,.43J,.34J,

2.5U,2.6UJ,2.5U,2.6UJ,

FinishedCompost

1U,.06J,1.2U1U, .5U, 1.2U

2.9U 1U, .5U, 1.2U1.2J 1U, .07J 1.2U

.53J 1U, 0.1J,1.2U2.9U 1U, .5U, 1.2U1.2J . .31J, .35J,1.2U

2.9U 1U, .5U, 1.2U.43J 1U, .5U, 1.2U2.9U 1U, .5U, 1.2U2.9U 1U, .50, 1.2U

.9U 1U .075J .14J70J .21J -3J .19J72J .73J 1.1J -22J

Treatedsoil

0.07

0.08

0.12

0.4

.13,28.82

PercentDegraded

97 %

92 %

78 %

67 %

52 %66 %0

Heavy Metal Analysis. Soil Compost #2

RMAL analyzed triplicate samples of starting soil and finished soilcompost for metals. The complete report is in Volume 2.Sufficient TCLP data for comparison is available for two metals,which is listed in Table 5-7. The data indicate a reduction inleachability of 30 % for lead and 62 % for arsenic. Other toxicmetals, Cd, Cr, and Hg, were not detected at limits of 15, 25, and0.2 ug/L.

Table 5-7

TCLF Lead and Arsenic, Soil and Finished Soil Compost

Analyzed by RMAL, averages of triplicates, ul/L

LeadArsenic

Soil

267 J6.3

FinishedCompost

156ND < 2

SoilBasis

187< 2.4

PercentReduced

30 %62 %

5-10

ABR Bioremediation Systems

Volatile Organic Compounds. Soil Compost *2

Volatile organic compounds were analyzed by RMAL, and data is inVolume 2. Twenty-five compounds were not detected in eitherstarting soil or finished soil compost, with detection limits of3,800 ppb and 15 ppb respectively. The reduction in detectionlimit of 250 fold is probably due to the removal of bulkcontaminant by the biodegradation process. Four other compoundsrelated to petroleum products are listed in Table 5-8. For threeof these there is sufficient data to calcultae removal percents,which are over 99 %.

Tabl* 5-8

Summary of VOA Analysis/ soil and Soil compostRMAL, tripliicates, ug/Kg dry weight

25 compoundsPetroleum-related

BenzeneTolueneEthylbenzeneXylenes

NO < 3800

ND < 38001200 J1800 J12000

FinishedSoil Compost

ND < 15

ND < 153 JND < 15ND < 15

Comparison of soil Composts * 1 and # 2.

A comparison of data for Compost #1 and # 2 is given in Table 5-9.The similarities indicate that the compost treatment process isreproducible.

Tabl« 5-9

summary Comparison of Compost # 1 and Compost i 2

Ave percent moistureAverage pHlime / Kg wet compost

Compost # 1

39 %7.06.3 g

Compost

Total N required (wet comp)Total PO4 required "P04 "bound" "

0.9 g/Kg3.2 g/Kg2.8 g/Kg

highest bacteria/gm% TPH-IR reduction

300 million89 %

5-11

38 %6.42.3 g

0.9 g/Kg3.1 g/Kg2.8 g/Kg

100 million83 %

ABU Bioremediation Systems

5-D. SOIL COMPOST WITH ABIOTIC CONTROL

Purpose.

The purpose of this experiment was to demonstrate that bioticprocesses were responsible for TPH-IR reduction in the Arrowheadsoil, rather than abiotic processes.

Experimental Design.

The experiment was designed to measure oxygen use, C02 production,and TPH reduction on the same sample of soil compost, and tocompare the results with those from three control conditions asfollows:

Live Starting Compost . live bacteria. contaminated soil. bulking agent and fertilizer

Killed Starting Compost . bacteria killed by sterilization. contaminated soil. bulking agent and fertilizer

Live Finished Compost . live bacteria. contaminant already biodegraded. bulking agent and fertilizer

Live Unamended Soil . live bacteria. contaminated soil. no bulking agent, no fertilizer

Procedure. Soil Compost with Abiotic Control.

Fresh compost, 120 grams, was prepared using the same proportionsof contaminated soil, bulking agents, lime and fertilizer asreported for the soil compost experiments above, except the soiland bulk were 4 mm sieved. The fresh compost and the sieved soilwere analyzed in duplicate for TPH-IR.

Five grams of test material were placed in duplicate bottles foreach test condition, and the bottles were tightly sealed.Oxygen for bacterial metabolism was provided by the air in thetrapped headspace, and C02 produced by biodegradation wouldaccumulate in the bottle. Control #1 was then "killed11 by 20minutes heat sterilization of the sealed bottles. (Thesterilization time should have been 30 minutes, and it is possiblethat the bacterial population was not completely eliminated.)

5-12

ABil Bioremediation Systems

At 6 days, 0.2 ml samples of headspace were withdrawn by syringeand analyzed by gas chromatography with thermal conductivitydetection (GC/TDC) for O2 and C02. The values were recorded, andbottles having low oxygen content were flushed with air and re-sealed. This procedure was repeated as necessary. At 15 days, thetest bottles were extracted with freon for TPH-IR analysis.

Results. Abiotic Experiment

Tabl« 5-10

CO2 Production/ O2 Use, and TPH Reductionduring Soil Composting

Averages of Duplicate AnalysesTPH, Percent dry weight sample

C02 and 02 as volume % in headspace

Live Killed Live LiveStarting Starting Finished SoilCompost Compost Compost Only

TPH start 5.4 % 5.4 % 0.7 % 6.0 %TPH 15 days 2.7 % 4.3 % 0.7 % 5.3 %

O2 Use 10.4 1.1 0.9 2.4

C02 produced 7.4 0.9 0.9 1.6

Conclusion. Abiotic Experiment

The live starting compost biodegraded 50 % of the TPH-IR in 15days, but the "killed" starting compost biodegraded only 13 % ofthe TPH, while using significantly less 02 and producingsignificantly less C02. This result indicates that thedisappearance of TPH is linked to the production of CO2 and is abiotic process.

The live finished compost, which contained bacteria but did notcontain readily degradable "food" for the bacteria, did not show adecrease in TPH, and used very little O2, probably in the slowbiodegradation of bulking agent. The unamended soil, which hadlive bacteria and was well aerated, but had no fertilizer orbulking agent, achieved only 12 % TPH degradation, indicating thatthese compost amendments provide a significant stimulus tobiodegradation.

5-13

ABB Bioremedtation Systems

5-E CONCLUSIONS, SOIL TREATMENT

The contaminated soil composite from the Arrowhead site was treatedby a composting process which involved the addition of 15 percentbulking material, correction of the soil phosphate binding problemand acidity, frequent aeration, and maintenance of a supply ofwater-soluble mineral nutrients. The extent of treatment of bulkcontaminant hydrocarbon achieved was estimated to be about 85 %based on TPH-IR and GC data. The final material was odor-free, andeasily worked. Also, lead in TCLP leachate was only 160 ppb, andwas slightly reduced compared to starting soil. Thus, it can beconcluded that the treatment is satisfactory and that the treatedsoil is suitable for replacement on site.

5-F CONCEPTUAL DESIGN FOR FULL SCALE TREATMENT

Treatment Strategy

It is proposed that Arrowhead soil be treated by composting, byincorporating roughly 15 % bulking agent consisting mainly ofchipped or shredded tree material and a smaller amount of manure.The amounts of nitrogen (urea), phosphate (superphosphate) andhydrated lime will be approximately those listed in Table 5-9. Theamounts of other elements required will be determined by analysisof the soil and selected bulking agent. The exact amount ofbulking agent will be a function of the bulking material that isactually obtained, and will be determined during mixing of thefirst batch.

Selection of forced-aeration composting as part of the treatmentstrategy is dictated by the very limited area available fortreatment on this site. The working plan is as follows:

. Excavate soil from a staging area.

. Screen out stones larger than 2 inches and backfill stones.

. Add fill as necessary to create a solid working space.

. Construct a pad, sloped to drain.

. Use an auger mixer, either truck or tractor-mounted to mixsoil with bulking agent, fertilizer and lime.

. Operate windrow composting on the pad for one week, mixingdaily, and adjusting pH and mineral content.

. Move the compost to 8 foot forced aeration piles, cover toprotect from rain and to retain heat. Treat for 3 weeks

. Screen out large pieces of bulking agent

. Backfill with treated soil compost.

5-14

AIM Btoremediation Systems

Detailed Consideration of Design Items

Screening

Successful treatment was obtained in the laboratory by adding 15 %by weight bulking agents (13 % shredded branches and 2 % manure) toArrowhead soil which had been sieved to remove all stones largerthan 0.5 inches and which had a 25 % moisture content. This is 20% on a dry weight basis of 0.5" sieved soil. Half inch sieving wasrequired in the laboratory to assure reproducibility in analysisusing reasonable sample sizes, but would not be required in fullscale remediation.

For field work, the screening requirement is a function of thefield equipment and the treatment requirements for the oversizematerial, as well as considerations of compost compression due tothe presence of stones. The critical choice in field equipment isrelated to the decision to use mechanical aeration or forcedaeration composting. In the forced aeration process, the initialmixing is usually carried out in a truck-mounted auger mixer, andthese usually have a size limit for stones of 2 inches. Formechanically aerated row composting, the mixing is usually carriedout by a tractor-mounted auger mixer. This equipment can handle 2inch stones, but a high percentage of these will probablycontribute significantly to compost compaction, causing anincreased requirement for bulking agent and/or a decreasedallowable pile height. The decision is waste-specific and site-specific. It would be reasonable to plan to screen 2 inches.

Bulking Agent Requirement

The bulking agent requirement for field remediation will depend onthe screen size selected as well as on the properties of the actualbulking agent obtained. If the bulking agent is closely similar tothat used in the laboratory treatability, then the percent willprobably have to be increased slightly for the presence of 0.5 to2 inch rocks, perhaps 15 % shredded branches instead of 13 %. Ifthe locally available bulking agent is significantly different inproperties from the shredded branches, such as 2 inch wood chips,a few percent more or less will be needed, and the amount of manuremay have to be increased. These decisions are "fine tuning" andare best done during the first batch of compost, which serves as afield "pilot" test in this regard. The laboratory treatabilitytest, then, gives only an approximation that is useful in makingcost estimates.

5-15


Forced Aeration vs Mixed Pile Treatment

The decision to use either forced aeration or mechanically mixedpiles is based on space and time considerations, and the possibleneed to provide a covered process. Mechanically mixed rowcomposting is simple, flexible, and relatively trouble-free.For the smaller Brown Bear auger mixer, the piles are triangular-shaped and are generally about 4 feet high and 6 feet wide, and canbe laid out on 6 to 7 foot centers, giving an average coverage of18" on the treatment area. As the Bear mixes, it shifts the row toone side, so the treatment area must have a free space 15 feet widealong the length, as well as a 20 foot turning space at each end ofthe rows. Typically, the Bear can aerate and mix 100 feet of rowin about 30 minutes.

Forced-aeration composting involves an initial mixing step whichcan be accomplished using the tractor-mounted auger ( about$140,000) mixer or a truck-mounted auger mixer (about $ 110,000).The truck mixer can prepare a 20 cubic yard batch of compost with15 minutes of mixing time, but the total mixing process alsoincludes loading and unloading time and is dependent on convenientlayout of the staging area. After mixing, the compost is laid outon perforated PVC ducts which are connected to half horsepowerblowers. The compost should be supported on a drainage materialand the ducts should be protected from equipment damage. The pilescan be 6 to 10 feet high. Higher piles may require a higherproportion of bulking agent and/ or a second layer of aerationpipes. Although forced-aeration composting requires lesscomposting area, space must be planned for the initial mixing step.If the treatment area is to be covered to provide better moisturecontrol or enclosed to provide a longer treatment season, forcedaeration is less area intense, but it should be remembered thatstructural supports may interfere with equipment movement.

Treatment Pad

Mixed composting is more trouble-free when carried out on atreatment pad sloped to provide for drainage, since auger mixerstend to dig into soft ground, and good drainage is important foravoiding delays due to rain.

Fertilizer

The ACT fertilizer used in the treatment simulation contained nineelements needed by bacteria, mixed in the correct proportions withminimal salt content. We need to add 0.9 grams nitrogen and 3.2grams PO4 per KG wet soil compost. That is 1.75 grams N per and6.22 Kg dry soil. The nitrogen in ACT was urea, and this is theleast expensive form of nitrogen, available for $.15 per pound ifpurchased by the truckload. Urea is 46 % nitrogen. Superphosphate

5-16


is a good source of phosphate. Typical bags are 20 % P2O5 whichare equal to 26.7 % P04.

For treatment of Arrowhead soil which contains only 4 to 5 %hydrocarbons, it would be most economical to analyze the soil foravailable minor nutrients and to add only what is needed tosupplement these. Magnesium and calcium would be added by the limeused to adjust pH, and the soil probably has high sulfur from thecontaminant, so we probably need to add only potassium and iron andtrace elements which will not be a significant portion offertilizer costs.

The above information is currently being considered by the ABBdesign team for preparation of a cost estimate.

5-17

ABB Bloremediation Systems

ABB6. FILTER CAKE TREATMENT

6-A INTRODUCTION AND SUMMARY OF FILTER CAKE EXPERIMENTS

Filter cake material from the Arrowhead site is a dense blacksludge having a hydrocarbon content of about 400,000 ppm (dryweight) as measured by TPH-IR, and about 220,000 pm as measured bygas chromatography. It also contains the clay filter material usedin the oil reprocessing activities and has a pH of 3.5. Filtercake is a hydrophobia substance which is difficult to disperse inwater. It was, however, possible to spread the filter cake onbulking agent to form a compost, allowing conditions to beoptimized for biotreatment.

Due to the difficulty in handling, pretreatment was investigated,and mixing with 10 % kiln dust on a dry weight basis was found toproduce a neutralized material with excellent handling properties.This material was used for the second two compost experimentsdescribed in this section. All four experiments indicate that thebulk hydrocarbon contaminant in filter cake is readily degradable,with the extent of treatment being about 86 % based on TPH-IR.

Filter Cake Compost # 1 was a brief preliminary experiment whichdemonstrated that when filter cake was neutralized, provided withfertilizer, and texture modified by the addition of bulking agents,hydrocarbon-degrading bacteria multiplied 1000-fold in 7 days andTPH-IR could be significantly reduced. About 430 meq of alkaliwere needed to neutralize the pH, and at least 5.4 g phosphate /Kgwet cake were needed to correct a phosphate binding problem.

Filter Cake Compost # 2 was a treatment simulation, using bulkingagent to wet cake weight ratio of 0.8 to l. Phosphate binding was12.8 g/Kg wet cake. The bulk contaminant was reduced 50 % in thefirst 26 days, and treatment was complete in about 42 days, with areduction in TPH-IR of 86 % and in GC hydrocarbons of 77 %. GC/MSanalysis of the finished compost showed that 2-ring PAH biodegraded98 %, the 3-ring PAH phenanthrene 97 % and 4-ring PAH fluorantheneand chrysene biodegraded 95* and 81 % respectively. Threephenolics, phenol, 2,4-dimethyl phenol, and mp cresol biodegraded93%, 90 % and 89 %. TCLP metal analysis indicated reductions inleachability for lead of 57%, chromium 64%, and cadmium 46%

An additional full scale treatment simulation was carried out witha mixture of 4 parts soil and 1 part kiln-dust pretreated filtercake, with 88 % treatment in 30 days. Chrysene and phenol degraded71 % and 93 %, and lead leachability by reduced 69 %. The filtercake abiotic experiment demonstrated that O2 use, CO2 production,and TPH reduction were greatly reduced in a compost heated to killbacteria, compared to an identical mixture not heated, indicatingthat the treatment is a biological process.

6-1

ABB6-B. FILTER CAKE PRETREATMENT WITH KILN DUST

Kiln Dust Pretreatment of Filter Cake bv Hazen.

Hazen Research, Inc. treated a 1000 gram wet weight (25 % water)sample of Arrowhead filter cake composite with 74 grams kiln dustand 500 ml water to produce a smooth material with neutral pH andgood spreading properties. This procedure resulted in only 1degree C increase in temperature, and therefore was not expected tohave caused any chemical change in the filter cake. The Hazenreport is presented in Appendix #1. While this material possessedimproved properties for composting, when added to water, it tendedto coalesce and not disperse, and become sticky. As a result, thekiln dust pretreated filter cake was tested in a compost system,but not in an aqueous system.

Analysis of Kiln Dust Pretreated Filter Cake. "K-Cake".

In order to determine whether any chemical changes had occurredduring the pretreatment process, the K-Cake was analyzed intriplicate for TPH-IR, and for GC total hydrocarbons andfingerprint characteristics. The results for hydrocarbon contentwere very close to those expected based on the values for un-pretreated filter cake (Section 4), corrected for the addition ofkiln dust. These data are presented in Table 6-1.

The GC fingerprints of the pretreated filter cake are closelysimilar to those of the un-pretreated filter cake. These arepresented in the Appendix #1. Specifically, the small peaks on theleft of the fingerprint representing the volatile compounds appearto represent the same concentrations as those in the un-pretreatedfilter cake. Based on the similarities in the hydrocarbon contentand the fingerprint, it was concluded that changes in the filtercake were only of a physical nature.

Tabl« 6-1

Hydrocarbon Analysis of "K-Cake11Pretr«at«d with Kiln Dust

Percent, dry weight basis

TPH-IR GC Total

Original Filter Cake # 43.0 21.5Calculated, Pretreated Cake 39.1 19.6Actual, Pretreated Cake (*) 38.8 21.0

# Single analysis * Within 5 % , average of triplicates

6-2

6-C. FILTER CAKE COMPOST #1 (PRELIMINARY)

Purpose: Pretreatment Requirements and Toxicitv test.

The purpose of this experiment was to obtain preliminaryinformation relative to the pretreatment of the filter cake, whichcould not be obtained under aqueous conditions because of thehydrophobic nature of the material. This included measuringthe amount of alkali necessary to raise the pH of the filter cakefrom 3.5 to 7, and measuring the binding of phosphate by the filtercake. After correcting the acidity and phosphate availabilityproblems, toxicity was assessed by determining whether bacteriawould multiply in the compost, and whether biodegradation could beinitiated.

This was a small batch of compost and was operated only to 40 %degradation. Since this was not a treatment simulation but only apretreatment investigation, Gas chromatographic data was notobtained, kinetic data was not collected, and samples were not sentto RMAL.

Filter Cake Compost *l; Constituents

Filter cake was mixed directly with bulking agent and texturingagent (manure) to form a compost. In order to minimize hydrophobicinteractions, it was noted that filter cake should be addeddirectly to the dry bulking agent, before adding water. Thebulking agent in this experiment was "saw chips", and was differentfrom the bulking agent used in most of the other experiments inthis report. The material is coarse sawdust from rough sawingoperations, having a size of about 0.2" x 0.2" x 0.1". Theconstituents of the compost are given in Table 6-2.

Tabl« 6-2Filter Cak« Compost #1Amendment Weight Ratio

Filter Cake (25 % water) 100Dry Saw Chips 51Dry Manure 22Water (initial) 59Soil (bacterial inoculum) 2

6-3

ABBInitiation. Aeration, and Moisture (Cake Compost

Composting was initiated by the addition of 2 % soil from the soilmicrocosm bacterial culture (Section 5-A), ACT mineral fertilizerat the rate of 290 mg nitrogen per Kg wet compost, and aeration bysimulated tilling. Aeration was continued on a daily basis for thefirst week and 3 times per week thereafter. The moisture contentinitially was 36 % water, but as the wood chips absorbed water,more water was added, resulting in 55 % water as the optimalmaintained moisture content.

Process Monitoring and Adjustment (Cake Compost

Samples were removed from the compost mixture frequently foranalysis of pH (every 2 days), available phosphate (every 2 to 3days), available nitrogen (every 3 days). Details of processmonitoring and process adjustment activities are given in Appendix£1. Mineral nutrient adjustments were made by adding ACTferti1izer approximately every 3 days to maintain about 50 ppmavailable nitrogen, and by adding ACT and extra buffered phosphatesolution to maintain at least 15 ppm available phosphate. (Theaverage available N and PO4 concentrations are higher than thosereported in the Process Monitoring Tables in the Appendix, becausefertilizer was usually added immediately after analysis.)pH wasadjusted with KOH. Samples were also removed at 3 time points forbacterial enumeration and TPH-IR measurement.

Treatment of Acidity (Cake Compost

The pH of the filter cake compost was initially 7, because of thebuffering action of the ACT fertilizer. Subsequently, the pHdropped as the acid constituents of the filter cake began todissolve in the aqueous phase of the compost. When the pH droppedto 5, it was adjusted with KOH to 7. In 11 days, the pH wasstabilized at 7 with the total addition of 425 milliequivalents perKg wet filter cake. This value is slightly less than the 666 megreported by RMAL for wet filter cake (33 g CaC03 / Kg) , probablybecause of the buffering activity of the bulking agents and mineralsupplement. ( The pretreatment requirements for filter cake aregiven in terms of wet weight filter cake because it is believedthat filter cake is a stable emulsion having uniform moisturecontent and this data will be readily applicable to planning forfield scale operations.)

Treatment of Phosphate Binding fCake Compost #11

Initially, 120 ppm phosphate was added to the filter cake compostas a major constituent of the bacterial mineral supplement.However, analysis for water-soluble phosphate, carried out

6-4

ABBimmediately following addition, showed that no phosphate wasavailable to bacteria. Repeated additions of buffered phosphatesolutions resulted in a measurable soluble phosphate concentrationof 15 ppm by day 3, after a total addition of 720 ppm phosphate.Phosphate continued to be "bound" throughout the 24 days of theexperiment, with a total application of 2,600 mg per Kg compostwhich is 6,100 mg per Kg original filter cake.

Bacteria use about 0.4 grams of phosphate for every gram ofnitrogen, so based on the nitrogen addition of 1,690 mg per Kg wetfilter cake, the phosphate that reacted with the filter cake was5.4 grams per Kg wet filter cake. This is not unexpected, since itis known that the Arrowhead filter cake contains clay used in theoil re-processing procedure, and that clays bind phosphate.(According to the particle size distribution reported in Table 4-6.50 % of the inorganic material in filter cake is smaller than 0.05mm).

The process data are summarized in Table 6-3. This data was usedin the design of the second filter cake compost experiment.

Table 6-3Filter Cak« Compost #1Process Data Summarywet filter cake basis

Treatment of Acidity (to pH 7) 425 meq / KgPhosphate Binding (21 days) 5.4 grams P04 / kg

Bacterial Growth and TPH-IR Reduction: Filter Cake Compost *1

Hydrocarbon-degrading bacteria increased 1000-fold from 0.3 millionper gram wet compost to 300 million in the first 7 days, andmaintained high numbers. The rate of bacterial growth and the highnumbers achieved indicate that the filter cake compost was nottoxic toward the bacteria.

The TPH-IR decreased from an average of 23 % on a dry weight basisto 14 % in 24 days, indicating that filter cake hydrocarbons arebiodegradable. This rate of biodegradation was consideredsufficient to justify starting a larger filter cake compostexperiment to prepare samples for CLP analysis. The bacteria andTPH-IR data are summarized in Table 6-4. These data are alsoplotted in Figure 6-1. in comparison to the data obtained forFilter Cake Compost #2.

6-5

ABB

Table 6-4

Filter Cake Compost # 1Bacterial Numbers and TPH-IR Reduction

Hydrocarbon Degraders per Kg wet compostTPH-IR on dry weight basis

Bacteria TPH-IR

Day 0 0.3 million 22.4 % 23.7 %

Day 7 300 million

Day 14 - 13.8 % 16.6 %

Day 17 100 million

Day 24 - 14.0 % 14.4 %

6-6

ABB6-D. FILTER CAKE COMPOST # 2

Purpose. Approach, and Constituents.

The purpose of this experiment was to simulate the proposed filtercake compost treatment procedure as defined by the preliminaryexperiments described above, to carry out the biodegradation for alonger period, and to prepare a large batch of finished compost forCLP analysis. The approach was to mix un-pretreated filter cakecomposite into dry bulking agent and texturing agent (manure),adding water last, then adjust the pH and phosphate, and finallyadd soil inoculum containing bacteria to initiate the process.

One of the important changes made for this experiment was thereplacement of saw chip bulking agent with shredded branches, whichcontains some readily degradable material and possibly would be asource of slow-release minerals and naturally chaelated traceelements. The other important change was the use of commercially-available hydrated lime (instead of KOH) to adjust the pH, whichwould be a more economical amendment. The constituents of thecompost are given in Table 6-5.

Tabl* 6-5

Filter Cake Compost #2 Amendment Ratios

Weight. Ka vn|iijng, fr

Filter Cake (25 % water) 100 59Dry Shredded Branches 58 344Dry Manure 23 122Soil Compost Inoculum 5 5Dry Bulk Agents Per Wet Cake 0.8 7.9Dry Cake / Dry Total 0.47

Process Initiation. Moisture, and Aeration.

Water was added to the mixture of filter cake and bulking agents togive an initial moisture content of 43 % water. During the next 7days as the bulking agent absorbed water, the moisture content wasgradually increased to 55 %, which was then maintained during theremaining composting period. Even at this high water content thecompost did not compact or lose porosity.

The biodegradation process was initiated by adding ACT completemineral formula at the rate of 300 mg nitrogen per Kg wet compost,and by adding a 5 % bacterial inoculum of soil compost. Aerationwas accomplished by mixing daily for the first two weeks and 3times per week thereafter.

6-7

ABBProcess Monitoring and Process Adjustment. Cake Compost #2.

Treatment of Acidity. The pH was raised from 3.5 to 6.3 by theaddition of dry powdered hydrated lime. Because the acidity of thefilter cake was released slowly during composting, it was notpossible to add all of the lime at one initial application. Everythree days during the first three weeks of composting, samples wereremoved for pH analysis and the pH was brought up to 6.3 with lime.pH was adjusted less frequently during the last three weeks. Thetotal hydrated lime addition was 11 grams per Kg (wet) filter cake,which was 320 milliequivalents per Kg. The pH of 6.3 was selectedfor this experiment, rather than 7.0 which was used for thepreliminary experiment, because data was available from the soilbiodegradation experiment indicating that any pH between 6.0 and7.0 is satisfactory for site bacteria.

Available N and PO4. At approximately one week intervals, sampleswere removed from the compost and analyzed for available nitrogenand phosphate. After each analysis, ACT fertilizer and extrabuffered phosphate were added to maintain an average concentrationof 170 ppm available nitrogen and 100 ppm available phosphate.During the 60 day composting period, total nitrogen required was4.4 grams per Kg wet filter cake, and total phosphate required was14.5 grams P04 per Kg wet filter cake. Assuming 0.4 grams P04incorporated into bacteria per 1 gram nitrogen incorporated,phosphate "binding" was 12.8 grams / Kg wet cake. Details ofprocess monitoring and process adjustment data are given inAppendix #1.

Bacterial Growth ; Filter Cake Compost #2

Samples were removed from the compost at intervals and analyzed fortotal plate count bacteria and hydrocarbon degraders. By day 1,total bacteria had increased 240-fold and hydrocarbon degradersincreased 330-fold. Total bacteria counts in excess of 100 millionper gram wet compost were attained. The bacterial growth data aregiven in Table 6-6 and plotted in Figure 6-1.

Tabl* 6-6Bacterial Growth in Filter Cake Compost #2

million bacteria per gram wet compost

Total Hydrocarbon DeoradersDay 0 0.7 0.1Day 7 170 33Day 22 150 73Day 41 90 so

6-8

ABBTPH-IR Hydrocarbon Reduction; Filter Cake Compost #2

ABB Data. Samples were removed from the compost at intervals foranalysis of bulk hydrocarbon content by TPH-IR and GC methods. TheTPH-IR data is presented in Table 6-7. and plotted in Figure 6-1.The values decreased from about 230,000 ppm to about 34,000 ppm in54 days, a reduction of 86 %.

RMAL Data. The finished compost was also analyzed by RMAL for TPH-IR, and the reported value was 14,000 ppm, significantly less thanthe ABB value. The RMAL data is given in Volume 2. Thisdifference underscores the fact that the TPH-IR method is carriedout differently in different laboratories, and that comparisonsshould be limited to data produced by one laboratory within a givenexperiment. (Refer to Section 2, TPH Discussion).

RMAL reported a value of -19 % TPH-IR for starting filter cake(compared to ABBs 43 %). As the ratio of dry filter cake to drystarting compost was 0.47, this would be equivalent to 8.93 % TPH-IR in starting compost, and a treatment of 84 %. Thus, in terms ofABB data or RMAL data, significant removal of TPH-IR occurredduring composting of filter cake.

Table 6-7

Reduction of TPH-IR, Filter Cake Compost # 2

Percent dry weight

TPH-IR Pup

Day 0 21.8 % 22.3 %Day 7 23.1 %Day 21 13.5 % 17.5 %Day 34 7.1 %Day 41 4.7 .%Day 54 3.4 %Day 104 3.5 % 3.2 %

Percent Removed = 86 %

6-9

ABBFIGURE 6-1

FILTER CAKE COMPOSTTPH-IR

• CAKE COMP |1 A CAKE COMP |2

1000 F

E

ô*c«+sO

toO

100 r

FILTER CAKE COMPOSTBACTERIA (TOTAL)

CAKE. COfcP * CAKE COMP #2

ABBGC Hydrocarbon Reduction. Filter Cake Compost

The GC fingerprints of Day 0, Day 34, and Day 104 freon extractsare compared in Figure 6-2 . Since the compost extracts wereprepared and analyzed under the same conditions, the decrease inheight of the trace represents the decrease in analyzablehydrocarbons. The fingerprint changes indicate an extensivereduction in all hyrocarbon constituents, as well as completeremoval of lighter compounds by Day 34. These lighter hydrocarbonsare represented by the individual peaks to the left of the Day 0fingerprint, which do not appear in later fingerprints.

The GC total hydrocarbon analysis is reported in Table 6-8. Thevalues decreased from about 122,400 ppm to 28,700 ppm, a reductionof 77 percent.

6-8GC Total Hydrocarbons/ Filter Cake Compost # 2

Percent Dry Weight

Peaks Plimp Total

Day 0 0.85 11.39 12.24Day 34 0.12 5.09 5.21Day 104 0.09 2.78 2.87

Percent Removed = 77 %

GC/MS Data for PAH and Phenolics. Filter Cake Compost *2

A sample of finished filter cake compost was analyzed by RMAL. Thecomplete report is in Volume 2. Data on PAH is presented in Table6-9. in comparison with that reported for filter cake. Thedetection limit achieved for finished compost is 1.1 ppm, 120-foldlower than that obtained for starting filter cake, due to thereduction in bulk contaminant which allowed GC/HS analysis of amore concentrated extract. In terms of starting filter cake (47 %of the compost), this is a detection limit of 2.3 ppm.

While most of the PAH were not detected in most of the samples,there is data reported as J values (less than the nominal detectionlimit) for 4 of the PAH, and these have been used to calculatepercent reductions. The 2-ring PAH naphthalene and 1-methylnaphthalene have been biodegraded 98 %, the 3-ring PAHphenanthracene was biodegraded 97 %, and 4-ring PAH fluorantheneand chrysene have biodegradaded 95 and 81 %, respectively.

6-10

RUM i SM am. iwSTART FILTER CAnt

•Hlf PKEON t)LftNhI _ . ____ nTT »

g;Q

SIftRTFiLfEdcXMe ComflMTDflY lOWI KID piLjJTicw A'fl - 3

D/1VRUN to I AUG IH-

M 22. « mlo t>iL.»J nc«M AtT = 3

o>

o

r

o>

if iff/7 mi FREOMX6Mwo DILUTION -ATT* a

-IImisM

O Ô A

ABBData was also available for 3 phenolic compounds and are listed inTable 6-9. Phenol was degraded 97 %, 2,4-dimethyl phenol 90 % andnip cresol 89 %. Thus it appears that extensive degradation ofaromatic organic compounds occurred.

Table 6-9

GC/MS Data for PAH and PhenolicsStarting Filter Cak« and Finished Filter Cake Compost

2-ringnaphthaleneIC-naphthal3-ringanthracenephenanthrene4-ringfluoranthBaAnthracchrysenepyrene5-ringBaPyreneBbFluoranBkFluoranDbAnthracEhe.no liesphenol24dmphenolmp cresol

RMAL, U=not detected, rag/Kg dry weight

StartingFilter Cake_

120U 15J 14J120U 14J 13J

120U 64U 130U15J 17J 15J

120U 7.5J 130U120U 64U 130U120U 11J 130U120U 64U 130U

120U 64U 130U120U 64U 130U120U 64U 130U120U 64U 130U

23J 19J 30J29J 18J 19J25J 13J 13OU

FinishedCompost

1.1U1.1U

1.1U1.1U

0.13J0.11J

l .OU0.22J

1.1U .16J1.1U l .OU1.1U l.OJ1.1U ,67J

1.1U l.OU1.1U l.OU1.10 l.OU1.10 l .OU

.75J 1.01.1 l.OJ1.1 0.9J

TreatedCake

0.280.23

2.23U0.47

0.342.23U2.11.4U

2.23U2.23U2.23U2.23U

1.62.22.1

PercentReduction

98 %98 %

97 %

95 %

81 %

93 %90 %89 %

TCLP analysis of PAH

TCLP analysis of finished filter cake compost by RMAL for each ofthese PAH resulted in non-detection at a limit of 0.05 mg/L. Sincethis is a 20-fold volume extract, this is equivalent to a detectionlimit of 1 mg/kg in compost, and 2.1 on treated cake basis.

6-11

ABBMetal Analysis. Filter Cake Compost.

RMAL analyzed filter cake and finished filter cake compost fortotal and TCLP metals. The complete report is in Volume 2.Total Pb. The values for total lead appear to be higher forfinished compost (1.3 %), than for starting filter cake (1.12 %).Since it is unlikely that bulking agent or fertilizer introducedlead into the compost, the low value for original filter cake isprobably explained by interference by a matrix constituent whichwas removed during treatment.

TCLP Metals. The TCLP data for lead indicated a value of 25 mg/Lfor starting filter cake, and a lower value of 5 mg/L for finishedcompost. This would be about (S/.47) = 10.7 mg/L in terms oftreated filter cake, and represents a 57 % reduction in leachablelead as a result of biological treatment. Similar results wereobtained for Cd and Cr. ( Other metals which were not detected inboth samples, are not included.)

Table 6-10

TCLP Heavy Metals, Filter Cake and Filter cake compostReported by RMAL, ug/L, Av of triplicates

Treated PercentCake Compost Cake Basis Reduction

Pb 25,400(J) 5,040 10,720 57 %Cr 148 ND < 25 ND < 53 64 %Cd 63 (J) 16 34 46 %

Volatile Organic Compounds, Filter Cake Compost.

yolatile organic analysis was carried out my RMAL for 33 compoundsin the starting filter cake and the finished compost. Most ofthese were not detected at a limit of 3,000 ppb in filter cake, andalso not detected, but at a much lower limit of 22 ppb, in thefinished compost. The RMAL data is given in Volume 2,

Significant reductions in petroleum-related compounds werereported. The data are listed in Table 6-10a as well as reductionscalculated assuming the detection limit, which are greater than 89% for benzene, and at least 99.6 % for ethylbenzene and xylenes,and 99.9 % for toluene.

6-12

ABBTypical laboratory solvents, methylene chloride and acetone, werealso greatly reduced in finished compost compared to startingfilter cake. TCE, a subject of extensive research activities inthe ABB lab, was detected at 8 ppb in the finished compost and mayrepresent lab contamination. HEK, a natural bacterial metabolicintermediate, was also detected in the finished compost.

Table 6-10a

Summary of VGA Analysis/ Filter Cake compost

RMAL, Av of Triplicates, ug/Kg Dry weight, U=not detected

Finished Treated PercentFilter Cake Compost Cake Reduced

25 compounds U < 3000 U < 22 U < 47

Petroleum-RelatedBenzene 420 (J) U < 22 U < 47 > 89 %Toluene 7,900 (J) 4 (J) 8.5 99.9 %Ethyl Benzene 21,000 (J) U < 22 U < 47 > 99.8 %Xylenes 11,000 U < 22 U < 47 > 99.6 %

Laboratory-RelatedMethylene Chloride 1730 (J) 12 (J)Acetone 9500 (J) ND < 34MEK ND < 3000 8.5 (J)TCE ND < 3000 10.5 (J)

6-13

ABB6-E. SOIL:FILTER CAKE 4:1 COMPOST

Purpose. Approach, and Constituents

This experiment involved treating a mixture of 4 parts Arrowheadsoil and one part filter cake, and was initiated at a time duringthe project when it was not certain that "pure" filter cake wouldbe sufficiently non-toxic to bacteria to allow complete treatment(at the completion of Filter Cake Compost #1, but before initiationof Filter Cake Compost # 2) . As it turned out, Filter Cake Compost#2 was successful in treating "pure11 filter cake. The 4:1 mixtureexperiment is important, however, because it demonstrates thetreatment of kiln dustpretreated filter cake, which was nottested in the previous experiments.

The kiln dust pre-treated filter cake spread easily over thebulking agent and mixed readily with the soil. The compost wasassembled with the ratios listed in Table 6*11. The resultingmixture was 69 % soil and 10 % filter cake, and 21 % bulk on a dryweight basis.

Tabl* 6-11

Soil:Cake 4:1 Compost TreatmentAmendment Weight Ratios

Soil , wet weight 100, dry weight 86.5

Kiln dust pretreated filter cake 25original filter cake, wet 16.3original filter cake, dry 12.3kiln dust 1.2

Shredded branches, dry weight 20.8manure, dry weight 5.3dry soil/dry total « 69.%dry orig cake / dry total = 10 %

Process Initiation. Moisture, and Aeration.

Water was added to the mixture of soil, pretreated filter cake andbulking agents to bring the moisture content to 42 %. This wasincreased to an optimal of about 45 % water , the highest watercontent that would not produce compaction or loss of porosity, andmaintained at that level for the duration of the study. Aeration

6-14

ABBwas provided by mixing daily for the first week, 3 times for thenext 3 weeks, and twice per week thereafter.Biodegradation was initiated by the addition of ACT completefertilizer to provide an initial concentration of 300 ppra nitrogen.In an attempt at initial correction of the phosphate bindingproblem, 1180 ppm of extra buffered phosphate solution was added onDay 0. An initial correction of acidity was not necessary, sincethe filter cake was pretreated with kiln dust to pH = 7, and theslight acidity of the soil was apparently corrected by the additionof buffered phosphate. The bacteria active in this compost werethose already present in the Arrowhead contaminated soil.

Process Monitoring and Process Adjustment. Soil:Cake 4:1.

Treatment of Acidity. pH was easily maintained at 6.5 by additionof only 23 meg of hydrated lime. pH was measured approximatelyonce per week during the first 60 days of treatment, and adjustedon two occasions.

Available N and PO4. At approximately one week intervals, sampleswere removed from the compost and analyzed for available nitrogenand phosphate. After each analysis, additions of ACT mineralfertilizer and extra buffered phosphate were made. The averageconcentration of available nitrogen and phosphate maintained wereabout 190 mg and 100 mg per Kg wet compost.

The total amounts of nitrogen and phosphate used were was 1.84 and3.5 grams per Kg wet compost, respectively. Allowing 0.4 gramsphosphate for bacterial use for each gram nitrogen used, thisleaves about 2.7 grams phosphate "bound" per Kg wet compost. Basedon the phosphate binding reported for soil ( 5.4 grams / Kg drysoil. Sect 5-B), and for Cake, (17.1 g / Kg dry cake. Sect 6-D),and the percents soil and cake in this compost, the expectedphosphate binding is 3 g/Kg wet compost, which agrees well with themeasured value.

Details of process monitoring and process adjustment data are givenin Appendix #1.

6-15

ABBBacterial Growth. Soil:Cake 4:1 Compost

Samples were removed from the compost for bacterial enumerationduring the first three weeks of treatment. The total bacteriaincreased rapidly from 33 million per gram wet compost on day 2 to370 million on day 19. Similarly, the hydrocarbon degradersincreased from 4 million to 67 million. The bacteria enumerationdata is presented in Table 6-12, and the total bacteria are plottedin Figure 6-3.

Tabl« 6-12

Bacterial Growth in Soil:Cake 4:1 Compost

Million bacteria per gram wet compost

HydrocarbonTotal Deoraders

Day 2 33 4Day 5 170 124Day 19 370 67

TPH-IR Hydrocarbon Reduction. Soil:Cake 4:1 Compost

Samples were removed from the compost at intervals for analysis ofbulk hydrocarbon content by TPH-IR and GC methods. The TPH-IR datais presented in Table 6-13. and are plotted in Figure 6-3 • Thevalues decreased from about 80,000 ppm to about 10,000 ppm in about75 days, a reduction of 88 % RMAL reported a TPH-IR a value of4,000 ppm for this finished compost, significantly less than theABB value, but nevertheless consistent with a significant extent oftreatment of bulk contaminant in this soil-filter cake mixture.

On day 53, analysis of a spike of this compost with TPH standardsolution (EPA method 418.1) resulted in 100 % recovery of the spikehydrocarbons. This data is presented in Appendix /I.

The material treated in this experiment was an artificial mixtureof soil and filter cake, and therefore no matrix sample wasanalyzed by RMAL. Also, starting compost was not submitted toRMAL. In the case of filter cake compost #2 TPH-IR, discussedearlier, RMAL TPH data on starting material and treated materialindicated slightly better degree of treatment than did ABB data.It should be mentioned again that TPH-IR data is not highlyreproducible between laboratories.

6-16

AilFIGURE 6-3

SOIL : K-CAKE 4:1 COMPOSTTPH-IR %

kiln dualpretreated

«

10 20 30 40

DAYS

50 60

SOIL : K-CAKE 4:1 COMPOSTBACTERIA (TOTAL)

kiln dustpretreated

1000

oo

o

100

10

10 20 30

DAYS

40 50 60

Table 6-13

Reduction of TPH-IR, Soil:Cake 4:1 Compost

Percent dry weight

TPH-IR

Day 0Day 5Day 18Day 41Day 53Day 75

7.98.52.41.31.71.0

8.2

1.52.11.0

Percent Reduction « 88 %

GC Hydrocarbon Reduction, Soil;Cake 4:1 Compost

The GC fingerprints of Day 0, Day 18, and Day 75 freon extracts arecompared in Figure 6*4. The fingerprint changes indicate anextensive reduction in all hydrocarbon constituents, as well ascomplete removal of lighter compounds (< C 18, those to the left ofthe internal standard marker in Figure 6-4) by Day 18.

GC total hydrocarbon analysis is reported in Table 6-14. Thevalues decreased from about 26,000 ppm to about 4,100 ppm, areduction of 84 %.

Table 6-14

GC Total Hydrocarbon*, Soil:Cake 4:1 Compost

Percent, dry Weight

Peaks Hump Total

Day 0 0.24 2.36 2.60Day 18 0.04 .75 .79Day 75 0.02 .39 .41

Percent Reduction = 84 %

6-17

KUH I 'V: filif. |j. i-V-;-1 l:. CuftP W

Kl'H 1 J.S:* HtJ:- ! i. 1 -n't 11:t MySOIL/CAKE t':i

.-I ml

»tondard

CTQ

i; i > 3 <i rr - 1 A-TT» 1

edd«d ttondard oddvd stondard

O>

*-Jcn

>-<

00

t-'UH i M.' mi', in. ffx i j ' . - ' i H i ' /MftRibOlL/CAKE'J:! COM? DAXO

~1if ii-* ml FftCoN _. .I DILiUCD Z-^J flit » ,1

GC/MS Data for Carcinogenic PAH. Soil;Cake 4:1 Compost

A sample of soil:cake 4:1 compost was analyzed by RMAL. Thecomplete report is in Volume 2. Selected data on carcinogenic PAHare presented in Table 6-15A . Most were not detected with adetection limit of about 1.5 ppm in finished compost.

Chrysene and phenol are the only compounds detected in both soiland cake starting materials as well as in finished compost.Chrusene was present in initial cake at 11 ppm, and in initial soilat 1.2 ppm. calculating the amount in Soil:Cake compost (69% soiland 10 % cake, dry weight basis), gives a biodegradation of 71 %.Calculations for both compounds are given in Table 6-15B.

Table 6-15A

GC/MS cFAH in Finished Soil:Cake 4:1 Compost

RMAL, U=not detected, mg/Kg dry weight

benzo a anthracene 1 U 2.1 Ubenzo b fluoranthene l U 1.4 Jbenzo k fluoranthene 1 U 2.1 Ubenzo a pyrene 1 U 2.1 Udibenzo anthracene 1 U 2.1 Uchrysene 1 U 0.57 J

Table 6-15B

Bi©degradation of 2 Compounds in Soil:Cake compostmg/Kg dry weight

CalculatedInitial Initial Initial finished percentSoil Cake Compost Compost Degraded

chrysene 1.2 J 11 J 1.94 .57 J 71%phenol 0.27 J 24 J 2.6 .19 J 93 %

TCLP Semivolatiles

TCLP analysis of finished Soil:Cake 4:1 Compost was also carriedout by RMAL. None of the carcinogenic compounds was detected, witha detection limit of 0.05 mg/L. The TCLP data represents a 20-foldextract, indicating a detection limit of l mg/Kg in terms ofcompost.

6-18

ABB Btoremediatton Systems

Lead Analysis

RMAL analyzed finished Soil:Cake 4:1 compost for Total and TCLPmetals, and the complete report is in Volume 2. Selected data forlead is listed in Table 6-16. The TCLP value for lead that wouldbe expected for soil:cake compost, based on the values reported fororiginal filter cake and original soil, and on the dry weightpercentages (70 % and 10 %) of those materials in soil:cake mix, is2.7 mg/L. The value reported for TCLP lead for finished soil:cakecompost is 0.84 mg/L, representing a 3-fold decrease in theleachability of lead in the treated material.

Table 6-16

TCLP Lead: Soil/ Cake, and Finished Soil: Cake Compost

RMAL, ave of triplicates,.

TCLP TCLP Calculate ReportedSoil Cake Soil : Cake Soil : Cake Percent

Matrix Matrix Compost Compost Reduction

0.27 (J) 25.4 (J) 2.7 0.84 69 %

6-19


6-F. FILTER CAKE COMPOST WITH ABIOTIC CONTROL

Purpose

The purpose of this experiment was to demonstrate that bioticprocesses were responsible for TPH-IR reduction in the ArrowheadFilter Cake, rather than abiotic processes.

Experimental Design

The experiment was designed to measure oxygen use, C02 production,and TPH-IR reduction on the same sample of filter cake compost, andto compare the results with those from two control conditions asfollows:

Live Compost . live bacteria. -filter cake. bulking agent and fertilizer

Killed Compost . bacteria killed by sterilization. filter cake. bulking agent and fertilizer

Unamended Filter Cake. filter cake. no added bacteria. no bulking agent, no fertilizer

Procedure, Filter Cake Compost with Abiotic Control

Compost orenaration. A new batch of filter cake compost wasprepared using kiln dust pretreated filter cake and was maintainedin an open container for 4 days for the purpose of adjusting thenutrient concentrations, demonstrating that the pH was stabilized,and demonstrating that TPH-IR analyses were reproducible (Anapparent lag or increase in TPH values had previously been observedfor filter cake biodegradation).

The compost was prepared by mixing 135 g kiln dust-pretreatedfilter cake (TPH-IR « 38.8 % +/- 1.2 %), 53 g 4 mm-sieved shreddedbranches, 21 g 2 mm sieved manure, 75 ml water, ACT completefertilizer at the level of 300 ppm nitrogen, and extra phosphatefor a total of 425 ppm phosphate (wet weight basis). A bacterialinoculum was provided by adding 2 g 2 mm-sieved finished FilterCake Compost #2. On day 0, duplicate TPH analysis gave 20.7% and18.2%. On day 1, pH was 7.2 and phosphate was 225 ppm. On day 4,duplicate TPH was 20.9% and 20.5%. On Day 5, pH was 6.7, nitrogenwas down to 10 ppm, and phosphate was 225 ppm. Nitrogen wasincreased to 500 ppm and phosphate to 425 ppm.

6-20

Bkwemediation Systems

Test Set-Uo and Data Collection, Cake Compost Abiotic Experiment.On Day 5, two grams of compost were placed in each of four 160 mlserum bottles and sealed with teflon-lined septa and crimpedaluminum caps. Two of the bottles were sterilized by heating for30 minutes. Two additional sealed bottles were prepared containing0.9 grams of un-amended kiln-dust neutralized filter cake.

After 8 days, the headspace in the bottles containing the live cakecompost was sampled and analyzed by gas chromatography with thermalconductivity detection (GC/TCD) for C02 and 02, and the values wererecorded. Then the headspace in those two bottles was flushed andreplaced with ambient air. After 6 additional days the headspacein all 6 bottles was analyzed. For the Live bottles, cumulativeCO2 produced and O2 used were calculated. Then all bottles wereextracted with freon and the extracts analyzed for TPH-IR.

Results, Filter Cake Compost Abiotic Experiment.

Table 6-17

CO2 Production, O2 Use, and TFH ReductionDuring Filter Cake composting

Averages of Duplicate Analyses.TPH-IR, Percent dry weight +/- 10%.C02 and 02 as Volume % in Headspace.

Live Ki1led K-CakeCake Cake no bulkCompost Compost no fertilizer

TPH Start 20.7 % 20.7 % 38.8 %

TPH Finish 11.3 % 19.1 % 32.4 %

O2 used 30.1 0.1 1.6

CO2 produced 25.1 1.5 2.8

TPH. Live vs Killed. The results of the Filter Cake AbioticExperiment are presented in Table 6-17 as average values. Detaileddata are presented in Appendix #1. The live filter cake compostbiodegraded 46 % of the TPH-IR in 16 days. In contrast, the killedcake compost showed a TPH-IR reduction of only 8 %, and theuntreated filter cake only 16 % , values which are within thereproducability of the TPH method, and can therefore not beconsidered to represent significant biodegradation.

6-21

AMI Bioremediation Systems

02 and C02. Filter Cake Abiotic Experiment. The killed filter cakecompost used only 0.3 % as much oxygen and produced only 6 % asmuch C02 as the live compost, and some of the C02 may have beenpresent in the compost moisture before it was heat sterilized. Inany case, there is a significant correlation between the lack ofTPH reduction and the lack of biological activity.

The un-treated filter cake, which had been pre-neutralized withkiIn dust but not amended with bulking agent, ferti 1 izer orbacterial inoculum, showed only 5 % as much oxygen use, and 11 % asmuch C02 production as the filter cake compost. The measured oxygenuse, a change of 1.5 % 02 in the bottle headspace, is barelysignificant with respect to the accuracy of the method, but mayrepresent a very slow biodegradation of TPH in the un-amendedfilter cake, carried out by a bacterial population initiallyundetected in filter cake by the enumeration procedure, < 1000/gmof filter cake (Section 4).

Conclusions. Filter Cake Abiotic Experiment. The correlationbetween significant TPH-IR reduction with O2 use and CO2production, in contrast to low TPH-IR reduction and low O2 use inthe killed control and un-treated filter cake, indicate that TPHreduction in filter cake compost is a biological process.

6-6 SUMMARY AND CONCLUSIONS, FILTER CAKE TREATMENT

Bulking Aaent Requirement. For the filter cake composts describedin this section, one weight of filter cake (original, wet weight)was mixed with 0.8 weights of dry bulking agent (tree waste plusmanure). However, because the density of filter cake is 1.7 g/cc,and that of the dry bulking agents is around 0.17 g/cc, this ratioamounted to about 8 volumes of bulking agent per volume of filtercake. Since the moisture content of the compost does not greatlyeffect its volume, this amounts to about a 9-fold volume increasefor filter cake during treatment.

Volume Increase. Several factors relating to this 9-fold volumeincrease should be stressed: (1) Generous amounts of bulking agentwere added to the filter cake in order to assure the success ofthese initial experiments, and no attempt was made to determine theminimal amount of bulking agent that would support biodegradation.Therefore the amount of bulk actually needed may be less than thatreported here. (2) Some of the bulking agent can be recovered fromthe finished compost by screening. (3) The volume increase is onlytemporary, since the bulking agent is ultimately biodegradable toC02. (4) During treatment, compost has a high fraction of airspaces, but finished compost can probably be compressed, tosignificantly reduce its volume before backfilling.

6-22

•••••• Bioremediation Systems

Treatment of Acidity. Data obtained from operation of Filter CakeComposts # 1 and # 2 indicate that 320 meq of alkali per Kg wetcake are needed to raise the pH of the compost from 3.5 to 6.3, andan additional 100 meq to raise the pH to 7.0. For pH 6.3, thisamounted to 11 grams of hydrated lime per Kg wet filter cake.

Kiln Dust Pretreatment. Neutralization with kiln dust required 75grams of kiln dust per Kg wet filter cake to raise the pH to 7, andproduced a material that was easy to handle and mix with bulkingagent, in contrast to the untreated filter cake which could bemanipulated in the laboratory only in a manner that probably couldnot be scaled up to field application. Two of the compostexperiments reported in this section were carried out with kiln-dust-pretreated filter cake and two with original filter cake.Those containing kiln dust achieved the same degree of treatmentand treatment times, within the accuracy of the measurements.

Treatment Times. The compost assembled with original filter cakerequired 26 days for the first 50 % reduction in TPH-IR, and anadditional 16 days to "complete" the treatment, that is until nofurther reduction in TPH-IR occurred. The compost containing 4parts soil to i part K-cake was 50 % treated in 15 days andfinished in about 30 days, according to TPH-IR. This is betweenthe rate for soil compost (first 50 % in 7 days) and cake compost(first 50 % in 26 days). The compost containing only K-cake(killed control experiment) was 40 % treated in 21 days, notsignificantly different from the compost with original cake.

Extent of Treatment. Filter cake compost # 2 reduction of bulkcontaminant was 86 % based on TPH-IR reduction, and 77 % treatedbased on GC total hydrocarbon estimates. Soil:Cake 4:1 compostreduction of bulk contaminant was 86 % based on TPH-IR reduction,and 84 % based on GC Totals. GC/HS analysis was able to achievea much lower detection limit in finished compost (1 PPM) comparedwith initial filter cake (100 PPM). Although most of thecarcinogenic PAH were not detected in either the initial filtercake or the finished compost, data was available for chrysene,which biodegraded 81 %. Other PAH detected in both starting andtreated material were naphthalene and l-methyl naphthalene, each 98% biodegraded, and fluoranthere, 95 % biodegraded. For soil/cake4:1 compost, chrysene was 71 % biodegraded, and phenol 93%.

Lead analysis indicated 57 % and 69 % reductions in leachable leadin filter cake compost # 2, and Soil/Cake compost, respectively.The finished compost product was easy to handle and was free of thecharacteristic unpleasant odor of filter cake.

Biological Nature of the Process. The killed control experimentdemonstrated that the TPH reduction, oxygen use, and carbon dioxideproduction in heat treated compost was greatly reduced compared toan identical mixture containing live bacteria, indicating that theprocess described here is mainly biological.

6-23

Jk HK Bioremediation SystemsA SEA SHOWN BOVEMI

6-H CONCEPTUAL DESIGN FOR FILTER CAKE TREATMENT

The Arrowhead Filter cake could be treated by composting in amanner similar to that employed for the soil, except that kiln dustpretreatment should be done, a higher percentage- of bulking agentis needed, and screening to recover bulking agent should be carriedout after composting.

The amendment ratios are as follows:

1000 g filter cake74 g kiln dust580 g dry shredded branches230 g dry manure4.4 g nitrogen

14.5 g phosphate

Treatment time at 68 degrees F will be about 6 weeks. Becausethere is a high percentage of bulking agent, forced aerationcomposting using piles 6 to 10 feet high should be considered. Airpermeabi1ity and compaction testing can be carried out for thefirst batch to determine the allowable height.

A water extract of kiln dust pretreated filter cake should beanalyzed to confirm that sufficient Ca, Mg, S04 are provided forthe bacteria by the cake and kiln dust, and to determine how muchK, Na, Cl, Fe and trace elements will be needed.

6-24

Bioremediation Systems*SF* anowu •owtm

7. SLUDGE TREATMENT

7-A. INTRODUCTION AND SUMMARY

Arrowhead sludge is a black hydrophobia sticky fluid having highviscosity and strong odor, and a TPH-IR measured according to EPAmethod 418.1 of 69% on a dry weight basis. Of the total material,moisture content is 36% , and particulates, most less than .25 mm,.make up 21 %. RMAL reported 1.2 % lead, dry weight basis. SludgepH is 2 and requires at least 2.7 equivalents of alkali per Kg forneutralization.

Pretreatment of sludge with 15 weight percent kiln dust and 67weight percent water, created a stable emulsion with neutral pH andgood handling properties. This kiln dust pretreated sludge ("K-sludge") was found to be biodegradable by both composting andslurry methods. Kiln dust .pretreatment may also be necessary forsludge handling for alternative treatments such as incineration.

Sludge treatment by composting resulted in 82 % biodegradation ofbulk contaminant as measured by TPH-IR. K-sludge was mixed with 75% weight of bulking agents, which resulted in a volume increase ofabout 7 fold, due partly to introduction of air pore spaces.Arrowhead site bacteria and complete mineral fertilizer were added,aeration was provided by mixing, and a high moisture content wasmaintained. Within 19 days the bacterial population had increasedto 130 million per gram of compost, and within 64 days the TPH-IRdecreased from about 200,000 ppm to about 35,000 ppm.

Slurry treatment of K-sludge for 33 days resulted in 77 %biodegradation in a 5 % slurry, 31 % biodegradation in a 17 %slurry, and none in a 50 % slurry, as measured by TPH-IR. Theexperiment also included slurries in which the bacteria were killedwith HgC12. The bacterial population increased rapidly by day 7 toaround 200 million per ml of slurry in the 5% and 17 % slurries,and less rapidly to 50 million in the 50 % slurry. The TPH-IR inthe killed controls did not change in 14 days, indicating that novolatilization occurred and that the TPH-IR decreased were due toblotic processes.

The sludge compost and slurry experiments demonstrate that thehydrocarbons in Arrowhead sludge are readily biodegradable. Whilecomposting is a simpler and more trouble-free process, it willresult in a significant temporary volume increase. Volumereduction can be obtained by screening dry finished compost torecover bulking material, followed by compacting. Slurry treatmentwould be more complex and costly, and would generate large volumesof process water requiring treatment.

7-1

Jk HK Bioremediation SystemsDBOWM BOVf »

7-B. PRELIMINARY EXPERIMENTS WITH UN-PRETREATED SLUDGESLUDGE COMPOST #1

Introduction and Approach. Since Arrowhead sludge is extremelyhydrophobic and can not be directly dispersed in water, thedecision was made to initiate the investigation of this material bya composting approach. The experiment allowed the measurement ofsludge acidity and phosphate binding, and demonstrated that sludgeis not highly toxic to acclimated site bacteria. Although datacollection in this experiment was not carried out long enough todemonstrate biodegradability of sludge, such data was obtained inlater experiments, reported in Sections 7-D and 7-E.

Sludae Compost #1 Constituents, Sludge was mixed with saw chips asbulking agent and manure in the ratios given in Table 7-1. This isthe same bulking agent as used in Filter Cake Compost / 1 (Section6) . During mixing water was added to provide maximum moisturewithout causing compaction and loss of pore spaces. The resultingcompost contained 0.8 Kg dry bulking agents per Kg wet sludge,having a volume ratio of 7.2 cc of amendments to cc wet sludge, andwas about 35 % wet sludge per wet compost. The ratios areexpressed in terms of wet sludge because this material isconsidered to be a stable emulsion, and design will be done interms of wet weight of sludge.

Table 7-1

Sludge Compost i 1 Amendment Ratios

Weight VolumeRatios Ratios

Sludge (35 % water) 100 Kg 50 Litersdry saw chips 65 300dry manure 12 64Bulk Per Wet Sludge -0.8 7.2water, approx 107

Treatment of Acidity. Since the initial pH of the compost mixturewas 2.0, it was decided to adjust the pH to 7 before adding thebacteria. This was accomplished over a three day period by addinga total of 34 grams of hydrated lime per Kg of original wet sludge,which is 2740 meg of alkali. Subsequently, the pH remained between6.7 and 7.0 without additional lime.

7-2

Jk IK IK Btoremediation Systems

Process Initiation. Moisture. and Aeration. Treatment wasinitiated by the addition of a bacterial inoculum of 1 % soil fromthe Preliminary Soil Test (Section 5). ACT complete mineralfertilizer was added to provide 360 ppm N and 150 ppm P04 on a wetcompost basis, and aeration was provided by mixing daily for thefirst week and 3 times per week thereafter. The initial moisturecontent was 54 %. This was increased to 64 % water by day 7 andmaintained at about that level for the remainder of the test.

Available Nitrogen and Phosphate. Samples of compost were analyzedfor available nitrogen and phosphate approximately every 5 days,and ACT was added immediately to maintain an average of 65 ppm Nand 75 ppm PO4 on a wet compost basis. Total N and PO4 used in 26days were 660 ppm and 490 ppm, respectively. Assuming that 0.4grams PO4 are used by bacteria for 1 gram N, 225 ppm P04 were"bound". This is 0.64 grams P04 per Kg wet sludge, and is very lowcompared to wet soil (4.2 g/Kg) and wet filter cake (12.8 g/Kg).

Bacterial Growth. Sludae Compost *l. Samples were removed from thecompost on Day 0 and Day 7 and analyzed for total plate countbacteria and hydrocarbon-specific degraders. The data arepresented in Table 7-2. The total bacteria increased 80 fold, andthe hydrocarbon degraders 200 fold.

Table 7-2

Bacterial Growth in Sludge Compost #1

Million Bacteria per gram wet compost

Total Hydrocarbon Dearaders

Day 0 0.4 0.1 0.3 (dup)Day 7 30 30 50 (dup)

TPH-IR Hydrocarbon Analyses. Sludae Compost *1. The TPH-IR wasdetermined at intervals during the 26 day treatment period. Thesevalues are presented in Table 7*3. Based on the ratio of drysludge to dry compost of 0.446, and the TPH of dry sludge of 69 %,the TPH of starting compost was calculated to be around 31 %, whilethe measured was significantly lower. According to the measuredvalues, no significant treatment of the sludge occurred. However,if there was an error in the Day 0 measured value, then degradationfrom 31 % TPH to 23 % TPH might have occurred. Sludge Compost #2(Section 7-D), did demonstrate TPH biodegradation.

7-3


Tabl« 7-3TFH-IR Valuta/ Sludge Compost #1

Percent Dry Weight

Day 0 Calculated 31.0Day 0 Measured 24.1 23.5 (dup)Day 7 26.7 27.4 (dup)Day 26 23.7

Conclusions, Sludae Compost *1. A compost of wet sludge with 80 %added dry bulking agents, was neutralized with 2.7 eq/Kg wetsludge, and demonstrated only 0.64 g phosphate binding /Kg wetsludge. Based on the rapid increase in bacteria in the sludgecompost during the first 7 days of composting, it can be statedthat the sludge compost was not highly toxic to the bacteria. Therelatively high population achieved would normally indicate thattreatment was occurring, but the experiment was not extendedsufficiently to demonstrate this. To further optimize conditionsfor bacteria, a second compost was planned (Section 7-D) usingkiln-dust pre-neutralized sludge (Sect 7-C), and a more degradablebulking agent such as shredded branches.

7-C. SLUDGE PRETREATMEKT

Rationale and Introduction. Since the sticky and rubberyproperties of sludge would make direct handling costly, developmentof a pretreatment step was an important consideration. Successfulpretreatment of the filter cake with kiln dust to produce aneutralized easy-to-handle product suggested that the same processbe tried with sludge. Three processes were tested: (1)Emulsification with hydrated lime,' (2) Emulsification with kilndust, and (3) Treatment by the OCR process (described below). Thekiln dust process proved to be the most cost-effective.

OCR Pretreatment. The OCR process is a proprietary pretreatmentfor hydrocarbon-contaminated soils provided by Sound Engineering ofSacramento CA, which uses high temperature CaO addition andproduces pelleted/dried material having residual CaOH and high pH.Several DCR-pretreated Arrowhead sludge samples were evaluated byABB. The procedures and results are reported in the Appendix onpage A-7-1. While some of the DCR-pretreated sludge samples provedto be amenable to composting and to support high bacterialpopulations, none was better than kiln-dust-pretreated sludge to be

7-4


discussed below. Due to the high cost of the OCR treatmentcompared to the cost of kiln dust pretreatment, the latter processis the preferred pretreatment of sludge.

Lime Pretreatment for Sludae. 150 g wet weight sludge and 75 mlwater were placed in a Waring blender and 16 grams of hydrated limewere added gradually with 5 minutes of blending to produce anemulsion with improved spreadability and a pH of 6.2. The emulsionwas not stable, however, as by the next day 32 ml of water haddissociated from the sludge and the sludge had regained somerubbery and sticky properties. When the lime-pretreated sludge wasadded to bulking agent to form a compost, it did not show improvedmaterial handling properties compared to original sludge.

Kiln Dust Pretreatment for Sludae. The properties of kiln dust aregiven in the Appendix #1. -A 150 gram portion of sludge was placedin a Waring blender and mixed for 3 minutes, with gradual additionof 22.5 grams of kiln dust and 100 ml of water, to form a fine-grained (2 mm) emulsion having neutral pH. Some of this materialwas used within 2 hours to form a compost, and it demonstratedmixing properties that were better than original sludge. Within afew days, the compost assumed a homogeneous texture, with sludgespread evenly over the bulking agent. Another portion of the kiln-dust-pretreated sludge was stored at room temperature for 22 daysduring which time it was stable, then used in a slurry experiment,to be described in Section 7-E.

7-D. SLUDGE COMPOST #2

Purpose. Approach, and Constituents.

The initial purpose of this sludge compost experiment was todetermine whether kiln dust treated sludge (K-sludge) was amenableto composting in terms of wet ability, pH stability, and ability tosupport bacterial growth. After initial data indicated that theserequirements had been met, the decision was made to monitor theTPH-IR as well, thus the initial TPH value was not measured, butwas calculated based on the fraction of sludge in the compost.Although data from this experiment provides evidence that sludge isreadily biodegradable, this was not a full scale treatmentsimulation designed to provide samples for analysis of PAH by RHAL.The constituents of the compost, based on 100 grams of originalsludge, are listed in Table 7*4. (Sludge volume is calculatedbased on density of 1.65.)

7-5

ARB Bioremediation Systems

Tabl« 7-4

Sludge Compost #2 Amendment Ratios

Weiaht

Kiln Dust Treated Sludge 181(original wet sludge) (100)(kiln dust) ( 15)(water) ( 66)

Dry Shredded Branches 97Dry Manure 39

Dry Additives/Original wet sludge 1.5Dry orig sludge/Tot dry compost - 0.3

Kg

Volume

135 Liters(61)

570195

12.5

Process Initiation. Moisture and Aeration. Sludae Compost #2.

During mixing of the bulking agents with the K-sludge, water wasadded to 53 % (calculated) which produced a mixture with high watercontent without reducing porosity. Moisture was graduallyincreased to 60 % and maintained at that level for the remainder ofthe study. Treatment was initiated on Day l by the addition of 4% wet weight 2 mm sieved finished Arrowhead soil compost as abacterial inoculum, and the addition of ACT complete fertilizer atthe level of 290 ppm nitrogen and 115 ppm PO4, wet weight basis.Aeration was provided by mixing daily for the first two weeks, then3 times per week. After the first few days, compost homogenietywas judged to be excellent.

Treatment of Acidity. Sludae Compost #2.

Compost pH was measured on days 1, 9, and 16, and found to beconstant at pH 7. Thus, it was concluded that sludge acidityeffectively was neutralized by the kiln dust pretreatment.

Available N and P04. Sludae Compost #2.

Available N and PO4 were determined on day 9 and found to be 25 ppmN and 25 ppm PO4 (spike recovery only 50 % for PO4). ACT was addedto provide 125 ppm N and 50 ppm PO4, and buffered phosphate wasused to provide 125 additional PO4. Subsequently, available N andP04 were not analyzed or amended.

7-6


Total N added was 415 ppm on a wet weight total compost basis,which was 2.18 grams per Kg original sludge. P04 use was 1.53grams per Kg original sludge. Assuming that all added N and PO4were utilized, and that bacteria use 0.4 g P04 per g N, phosphatebinding was 0.65 grams per Kg original sludge. Although only anestimate, this is the same binding found for sludge compost #1.

Bacterial Growth. Sludae Compost #2.

The limited bacteria data are given in Table 7-5. Bacteria werenot enumerated initially, but starting bacteria counts aregenerally under 1 million per gram for both total and specificdegraders for sludge and cake composts (Filter cake compost #1 &#2,Sludge Compost #1). Counts of 17 million per gram on Day 8 and130 million on Day 19 represent a rapid increase and a populationequal to those developed in.the soil and filter cake composts. Thevalues are also plotted in Figure 7.1. The 19 day time required toattain a total bacteria count of 130 million, is about twice thetime required to reach that population in filter cake compost #2.

Table 7-5Bacterial Growth, K-Sludge compost #2

Million bacteria per gram wet compost

VolatileTotal HydrocarbonBacteria Dearaders

Day 8 17 -Day 19 130 27

TPH-IR Hydrocarbon Reduction. Sludae Compost #2

The initial TPH-IR of sludge compost #2 was not measured, but canbe calculated from the percent dry original sludge per dry compost(100 g orig sludge times .64 percent dry weight / 215 g dry totalcompost) times the percent TPH dry weight in original sludge, 69 %,giving 20.8 % on Day 0. Adjusting for the 5% inoculum (dry wtbasis) , the TPH on Day 1 would have been 19.8 %. TPH was measuredat intervals thereafter, and the values are listed in Table 7-6.and plotted in Figure 7-1. The data indicate biodegradation ofbulk contaminant of 82 % in 64 days. The apparent time for thefirst 50 % reduction of TPH was about 35 days, somewhat slower thanfilter Cake Compost which was 50 % degraded in about 25 days.

7-7


FIGURE 7-1

K-SLUDGE COMPOSTTPH-IR %

kiln dustpr«1r«ttt»d

20

15

I 10a.

1OOO

I5I

O 10 20 30 4O SO 6O

DAYS

K-SLUDGE COMPOSTBACTERIA (TOTAL)

kiln dustpretreated

O 1O 20 3O 40 50 60

DAYS

ARB Bkxemedtation Systems

Table 7-6

TPH-IR Reduction/ Sludge compost #2

Percent Dry Weight

Day 1 (calculated) 19.8Day 20 14.0Day 30 11.1Day 55 4.2Day 64 3.5

Percent Reduction = 82 %

Conclusions, Sludae Compost *2

Compost treatment of kiln-dust-pretreated sludge is a relativelysimple process, requiring minimal pH and phosphate adjustments.The bacterial inoculum (from soil compost) grew more slowly insludge compost than in filter cake compost having about the sameinitial TPH-IR, indicating that a slightly longer acclimation timeis required for sludge. Nevertheless, extensive treatment wasachieved in a reasonable time. The initial volume increase isabout 15 fold, however the volume of the finisned compost could bereduced by drying, screening, and compacting.

7-E. K-SLUDGE SLURRY TREATMENT WITH KILLED CONTROL

Purpose and Approach.

Slurry Properties of Kiln Dust Pretreated Sludae fK-Sludael. Theoriginal Arrowhead sludge has a hydrophobia nature that precludesslurry treatment, since it forms into rubbery balls that resistdispersion. Kiln dust pretreatment of sludge, however, produced astable emulsion that appeared to have potential for slurrytreatment. When this material was shaken with an equal volume ofwater, it dispersed into 1 mm granules that were stable during twodays of continuous stirring, and settled rapidly when stirringstopped. Because of these excellent dispersive properties, anexperiment was planned to determine sludge toxicity andbiodegradability under slurry conditions. Toxicity was to beassessed by measuring bacterial growth, and biodegradabilitymeasured in terms of TPH-IR changes in live versus killed testflasks.

7-8

Jft HH Bioremediation Systems

Experimental Design. The experiment involved the preparation ofmultiple identical flasks of K-sludge slurry. Three sets of flaskswere set up, representing 50 %, 16 %, and 5 % K-sludge in water.Open flasks were aerated by rotary shaking. Each set contained oneflask (#1) in which the bacteria were killed using 2 % HgC12, fourflasks for TPH-IR analysis at different time points, and one flask(#6) for bacterial and mineral nutrient analysis. The bacterialinoculum was 2mm sieved DCR(e)-sludge compost (day 32), which hadabout 30 million hydrocarbon degraders per gram.

For TPH-IR analysis, the entire contents of a flask were extractedwith freon. The ("live") bacteria counts were done on 1 ml samplesremoved from the same flask at three time points, and dilutedappropriately before plating. The "killed" bacteria counts wereperformed on 0.3 ml samples taken from the killed flask and plateddirectly.

Details of the flask contents are given in Table 7-7.

An alternative design for this experiment, involving a single largeslurry bioreactor, was rejected because of the difficulty ofobtaining representative samples, due to the rapid settling of theK-sludge granules during sampling.

Table 7-7

Flask contents for K-sludge slurry Test

FertilizerK-Sludae Solutions Inoculum

Set 1 10.0 g 10 ml 0.5 gSet 2 3.3g 13.4 ml 0.5gSet 3 1.0 g 17.9 ml 0.5g

Fertilizer Formulation for K-Sludae Slurry Test.

Consideration was given to the high concentration of electrolytesthat would be present in the 50 % K-sludge slurry as a result ofthe presence of kiln dust (8.3 % wet weight K-sludge) as well asthe high concentration of ACT fertilizer needed. In order tominimize the redundant addition of salts, a fertilizer without S,Ca, or Hg, was formulated, based on test kit analysis of thedissolved salts in a 50 % K-sludge slurry.

7-9


PH. and available N and PO4. K-Sludae Slurrv Treatment.

On Day 14, Flask # 6 from each set was analyzed for pH andavailable N and P04. Phosphate was found to be 5 ppm in each setand additional buffered PO4 solution was added to bring the PO4concentration to 3000, 1000, and 300 ppm in sets 1, 2, and 3respectively. pH was neutral in sets 2 & 3, but 9 in the 50%slurry, which was then adjusted to 7. Available nitrogen was 2000,1400 and 500 ppm in sets 1,2, and 3 respectively. Water lost dueto evaporation was replaced.

Bacterial Growth during K-Sludae Slurrv Treatment

The bacterial enumeration data for the K-sludge slurry experimentare given in Table 7-9. and plotted in Figure 7-2. On Day 0 the"killed" flask in each set was sampled for bacteria. Bacteria werenot detected at a detection limit of 3 cfu per ml of slurry,indicating that the HgC12 had successfully killed the bacterialpopulation and that flask #1 in each set was a satisfactory abioticcontrol.

Table 7-9

Bacterial Growth during K-Sludge Slurry Treatment

Million Bacteria per ml of Slurry

VolatileK-Sludge Day 0 Live. Total Bacteria HydrocarbonWeight (total) Degraders

Set Percent Killed Day 0 Dav 4 Day 7 Live Dav 7

#1 50 % ND * .02 " 0.2 53 45

#2 17 % ND .05 6.7 190 36

#3 5 % ND .001* 41 240 30

* Detection Limit for Killed flasks, 3 cfu/ml# Did not meet QC standards.

7-10

AIW Bioremediation Systems

FIGURE 7-2

SLUDGE SLURRY TREATMENTTPH-IR

50 % • 17 % V 5 % o KILLEDSLURRY SLURRY SLURRY CONTRL

o<CD(£>

1OOO

100

SLUDGE SLURRY TREATMENTBACTERIA (TOTAL)

5 0 % • 1 7 X V 5 %SLURRY SLURRY SLURRY

0.0110 20

DAYS

30


On Days 0, 4, and 7, Flask # 6 in each set was sampled for totalbacteria. The data for Set #3 did not meet QC requirements, andsince all flasks received the same inoculum, the average of set #1ad #2, 35,000 bacteria per ml, is taken to be the startingpopulation. By day 7, the bacterial populations had increased 1500fold in the 50 % slurry, 5400 fold in the 17 % slurry, and 6900fold in the 5 % slurry.

The bacterial enumeration data indicates that none of the slurrymixtures is severely toxic to bacteria, but that conditions in the50 % slurry are not optimal, causing slower growth. Although thepopulation in the 50 % slurry is 30 fold lower than that in the 17% slurry on Day 4, the difference decreased to 4 fold by Day 7.Also, in the 50 % slurry, the fraction of volatile hydrocarbondegraders (which would be present during the initial degradationwhen volatile hydrocarbons are present) , is high, indicating earlystage of biodegradation. The fraction of volatile hydrocarbondegraders is lower in Sets #2 and #3, indicating that the volatilehydrocarbons have been degraded and heavier hydrocarbons are beingdegraded. (Bacterial enumeration data are reproducible only towithin 50 %, so that the difference between 50 million and 200million is significant, but the difference between 30 and 45 maynot be significant.)

TPH-IR Reduction Purina K-sludae Slurry Treatment

The TPH-IR data are presented in Table 7-10. and plotted in Figure7-2. Although the three concentrations of K-sludge slurriescontained different amounts of sludge, the TPH-IR values arereported in terms of the percent TPH, wet weight of K-sludge basis,facilitating comparison of the data.

Table 7-10

TPH-IR Reduction during K-Sludge slurry Treatment

Percent on Wet Sludge Basis

K-Sludge Day 14Weight Killed

Set Percent Day 0 Dav 8 Dav 14 Day 33 Control

#1 50 % 43 39 44 41 44

#2 17 % 47 36.5 27 31 46

#3 5% 46 27 30.5 10.5 48

7-11


Killed control. K-Sludae Slurrv Treatment. The three day 0 valuesfrom set #1, #2, and #3, represent triplicate analyses of thestarting sludge (45% TPH), and agree within 4 % of each other.Similarly, the three Day 14 Killed Control values representtriplicate analyses of the killed condition (46 % TPH), and agreewithin 4 % of each other. Thus, it can be concluded that thehydrocarbon concentration in the killed condition did not changeduring the test, and since the killed and live conditions had thesame amendments, any change in the live flasks was due tobiological processes.

No Volatilization. It should be noted that the killed control dataindicates that there were no significant losses of hydrocarbons dueto volatilization. This in consistent with the fact that GCanalysis showed that less than 1 % of the total hydrocarbons inArrowhead sludge are volatile compounds. (Section 3).

Live Condition. 50 % Slurrv> Data for the 50 % slurry show that nosignificant decrease in TPH occurred. Although there was asignificant population of hydrocarbon degraders on Day 7, the pH of9 measured on Day 14 may have impaired degradation. Although thepH was adjusted once, it may have continued to increase. Beforeconcluding that 50 % slurry is too concentrated, a more carefullycontrolled experiment should be carried out.

17 % and 5 % Slurries. Based on the TPH values reported for thelast time point, Day 33, degradation was 31 % for the 17 % slurry,and 77 % for the 5 % slurry. However, considering the lack ofinternal consistency for both of these slurrys in the three timepoints, it must be stated that these reductions, althoughsignificant, are only rough approximations. Because the 17 %slurry contained more total sludge, the total quantity of TPHdegraded is greater in that test condition than in the 5 % slurry(460 mg vs 350 mg).

ConclusJ9ns' K-Sludae Slurrv Treatment.

The K-Sludge slurry treatment discussed above represents a"preliminary" experiment, in that duplicate analyses were not doneat time points, limited time points were analyzed, and limitedprocess monitoring and process adjustment were carried ut. It istherefore appropriate to make only the general conclusion that theprocess shows promise. The optimal slurry concentration is probablybetween 17 % and 5 %, expected to produce about 50 % degradation in33 days.

7-12


7-F. DISCUSSION, SLUDGE TREATMENT

Biodegradabilitv of Sludae. Pretreated Arrowhead sludge was shownto be biodegradable both by composting and by slurry treatment.Compost. containing 30 % dry weight original sludge to dry totalcompost, biodegraded 82 % in 64 days, and theslurry of 5 % kiln dust pretreated sludge (1.8 % dry originalsludge) biodegraded 77 % in 33 days.Based on dilution requirements, composting appears to be the morefeasible treatment.

Kiln Dust Pretreatment. The kiln dust pretreatment using 15 weight% kiln dust and 66 weight percent water to original sludge resultedin a product having a volume of about 2.2 times the original sludge(calculated assuming a density of 1.65 for sludge and 1 for kilndust) . This material is stable and would be easy to handle withtraditional earth moving equipment.

Volume Increases: Composting Vs Slurrv Treatment. Both methods ofbiological treatment of sludge involved significant volumeincreases, in addition to that caused by the kiln dustpretreatment. For composting, 136 grams of dry bulking agents wereadded to 181 grams of K-sludge, but since the bulking agents had avolume of 765 cc and the K-sludge had a volume of about 135 cc, theinitial volume increase due to bulking agent addition was around 7fold, largely due to the introduction of air pore spaces. Aportion of this initial volume increase is temporary, as thefinished compost can be compressed about 2 fold. Eventually, ifthe finished compost is kept aerobic, the bulking agent willbiodegrade and the volume will be further reduced.

For slurry treatment, if we assume that a 10 % slurry of K-sludgein water will give optimal treatment, then there is a volumeincrease of about 10 fold during the aqueous treatment. Since theK-sludge granules settle readily, it will probably be relativelyeasy to recover this water. However, the water may requiretreatment, as discussed below.

Treatment of Slurrv Process Water. Slurry reactors frequentlyrecycle process water, but for the Arrowhead sludge, this water maybe high in salts introduced by the sludge and kiln dust, and willhave to be replaced frequently. The process water may also containa significant amount of lead, since it is known that bacteriaprotect themselves against toxic lead by producing extracellularcolloidal lead granules covered by organic material (L. Barton,Dept of Biology, Univ of New Mexico, Albuquerque).

7-13

AMI Bioremediation Systems

Conclusion, Sludge Treatment. Sludge handling properties can beimproved, and acidity can be neutralized, by pretreatment with kilndust. Preliminary experiments indicated that both composting andslurry treatment have potential for biological treatment of sludge.The composting process achieved an 82 % reduction in TPH-IR in 64days, while treatment of a 5 % slurry resulted in 77 % TPH-IRreduction in 33 days.

While composting is a simpler and more trouble-free process, itwill result in a significant temporary volume increase due tobulking agent. Volume reductions could be achieved after treatmentby drying then screening to recover bulking agent, and compactingthe treated material. An advantage of the high fraction of bulkingagent required in sludge compost, is that the initial compostmixture can probably be treated by forced aeration composting,using extensive piles 10 feet high. Under these conditions, heatgenerated by biodegradation could be conserved in the piles,raising the temperature, and speeding treatment. Slurry treatmentwould be more complex and costly than composting, and wouldgenerate large volumes of process water requiring treatment.

Because of the preliminary nature of the experiments, GC/HSanalyses were not carried out on finished sludge compost or slurrytreated sludge. However, since the hydrocarbon content if thesludge is qualitatively the same as that in Arrowhead soil andfilter cake, it is expected that most of the carcinogenic PAH wouldalso be not detectable in the sludge matrix, and that theleachability of lead would be reduced by composting.

7-14


A»BASEA BROWN BOVERI

APPENDIX # 1

Al-l Site Background Information Al-l

Al-2 Site Sampling by Barr Engineering Al-3

Al-3 Matrix Characterization, Supplementary Al-4

Matrix Composite Preparation Al-4Extraction Volumes for TPH-IR Al-5GC Volatile Compounds, soil, cake, sludge Al-5

Al-4 Soil Composts, Supplementary Al-7

Soil Compost #!/ Process Monitoring & Adjustment Al-7Soil Compost #2, GC Fingerprints Al-8Soil Compost #2, Process monitoring & Adjustment Al-8Routine Spike of TPH solution, Soil Compost #2 Al-9Experiment, Optimal pH for Soil Treatment Al-9

Al-5 Kiln Dust Pre-Treated Filter Cake Al-10

Kiln Dust Properties, Pretreatment by Hazen Al-10Triplicate TPH-IR, GC totals, & fingerprints Al-10

Al-6 Filter Cake Compost, Supplementary Al-ll

Cake Compost #1, Process Monitoring & Adjustment Al-llCake Compost £2, Process Monitoring & Adjustment Al-12Soil:Cake 4:1 Compost, Process Monit.S Adjust. Al-13Routine Spike of TPH solution. Soil:Cake Compost Al-14Filter Cake Abiotic Test Duplicate Values Al-14

Al-7 Sludge Treatment, Supplementary Al-15DCR Pretreated Sludge Evaluation Al-15

Al-8 ABB Treatability Standard Operating Procedures Al-16Sample GC Manual Integration Calculation Al-29

Al-9 ABB Laboratory Quality Control Documentation Al-30

Al-10 Soil Compost Spiked with PAH and Alkanes Al-45

Al-ll Raw Treatability Data Al-81

A II IIASEA MOWN BOVERi

APPENDIX # 1

Al-1. SITE BACKGROUND INFORMATION

The Arrowhead Refinery site is located in Hermantown, Minnesota,about 7 miles from Duluth, and consists of 10 acres of relativelyflat land containing scattered wetlands. Prior to 1945, the sitewas used to retin milk cans. An underground storage tank removedin 1985 may indicate the existence of a gas station. From 1945 to1977, used oils were reclaimed by the acid/clay process, and wasteswere deposited on site.

The acid/clay process involved four steps: First the waste oilswere dewatered by heating to 320 degrees F. The generated steam,which contained some oil, was condensed and discharged to a ditch.The dewatered oil was then treated with concentrated sulfuric acidand allowed to settle overnight. The sludge that accumulated atthe bottom of the reactor contained sulfuric acid, water andpetroleum, as well as motor oil additives such as detergents andacryloids. This sludge was deposited in a 2 acre wetland, referredto afterwards as the sludge lagoon.

The third step in the oil reclamation process involved refluxingthe acid-treated oil with clay at about 560 degrees F, while addingsteam. The steam condensate was neutralized with sodium carbonateand discharged to the ditch. Then the oil/clay mixture was cooledand pumped through a filter press, producing a filter cake that waspiled in two mounds in the sludge lagoon.

In addition to approximately 4,600 cu yd of sludge and filter cakein the lagoon, soil in the process area is contaminated. Thisarea, together with the wastewater ditch, contains approximately36,000 cu yd of contaminated soil.

The Arrowhead Refinery Company was ordered by the MPCA todiscontinue the dumping of sludgein 1976. Early in 1977, thecompany informed the MPCA that operations ar the site had beenterminated. In 1979, the MPCA requested the assistance of the EPAin evaluating the environmental effects resulting from wastedisposal activities at the site, and the EPA conducted apreliminary surface water quality and hydrogeologic investigationof the site in 1980, which determined that the site was inviolation of the Clean Hater Act. The EPA constructed a ditch todivert surface water flow around the sludge lagoon to help controlsite runoff.

According to EPA reports, the main hazards of the sludge are thecorrosivity, high concentrations of metals, and the potentialpresence of toxic and carcinogenic volatile organic andpolyaromatic hydrocarbons. Off-site exposures were not found, but

Al-1

Jl ItIIASEA BROWN BOVERt

the potential was identified for contaminant migration through thegroundwater above the bedrock.

A feasibility study of possible remedial actions for the site wascompleted in 1986. The volumes of contaminated soil and sludge onthe site were estimated by defining the areal extent ofcontamination using remedial action levels and field data. Arecord of decision for the site was signed by the EPA in Septemberof 1986. the ROD defined the appropriate remedial actions for thesite to involve incineration of sludge and contaminated soil,extraction and treatment of contaminated groundwater, extension ofthe municipal water system, and implementation of groundwatermonitoring.

Remedial actions at the site have been divided into four operableunits: (1) furnishing municipal water, (2) contaminatedgroundwater, (3) source material, and (4) contaminated soilcovering 3 to 4 acres. The first two operable units are thesubject of the April 1990 CERCLA Section 106 Order issued by theEPA. The third is the subject of a May 1990 Special Notice ofLiability Letter and a May 1991 CERCLA Section 106 order. All fourare the subject of a May 1990 Request for Response Action (RFRA)issued by the MPCA.

In 1990 the Minnesota Arrowhead site Committee (MASC) completedaction on furnishing municipal water. A workplan was submitted tothe EPA/MPCA for the groundwater extraction system, which wasdesigned in 1991, and was planned to be constructed in 1992.

Parties making up the MASC agreed in 1991 to initiate the predesigninvestigations included in the May 1991 Section 106 Order for thesource material. On a parallel track, MASC members are proceedingwith predesign investigations of biotreatment and solidification-stabilization technologies for the source materials andcontaminated soil at the site.

Al-2

A It IIf\nnASEAMOWNBOVERI

Al-2 SITE SAMPLING BY BARR ENGINEERING

Barr Engineering conducted a sampling exercise at the Arrowheadrefinery site in November 1991 to provide source material fortreatability studies. Samples of sludge, filter cake, and soilwere collected in accordance with the field sampling plan and thequality assurance plan prepared and approved prior to the sitevisit, which is presented in Volume 2D. A more detaileddescription of site sampling is provided in Volume 2E.

The depth of sampling varied with the media. The depth of sludgein the lagoon is about 2 feet. Thus, a grab sample of sludgecontained the complete vertical profile for sludge at that samplinglocation. Filter cake is located in mounds along the south edge ofthe sludge lagoon and was sampled to a depth of 2-3 feet.

A clamshell dredge was used for sludge and filter cake, while abackhoe was used to dig the test trenches for soil sampling. Eachmedia was sampled randomly in three different locations. Theexcavator placed one bucket of material from one location on aplywood sheet. After removing large debris, the material was mixedwith hand tools to make it as uniform as possible. Approximatelyone-third of a 5 gallon sample container was taken from the handmixed material from each location, resulting in a container havingthree layers. These were later composited at the laboratoriesdoing treatability studies.

Al-3

n iiASEARflOWNBOVERl

Al-3. MATRIX CHARACTERIZATION, SUPPLEMENTARY INFORMATION

Matrix Composite Preparation. Procedures and Observations.

Soil Matrix

Observations. Three 5-gallon buckets labeled FTT-1, -2 and -3, werereceived . In general , the top layer had a strong odor , andappeared to be black and brown organic soil of friable texture, nothydrophobia, containing some gravel and stones. The middle layerappeared to be brown sand or clay. FTT-3 had water on top, andmany 3 inch rocks.

Compositing. Only FTT-1 was composited. All layers were easilyworked and did not stick to a spatula. The top layer was darkbrown and appeared to contain silt, sand, gravel and 3" stones,glass and twigs. The middle layer was medium brown and appeared tohave a finer texture and higher moisture content. The bottom layerwas similar to the top layer and contained glass, sand, gravel,silty clumps and cakes of woody fiber, with a strong odor.

Each layer was transferred temporarily to a separate bucket. Then,a scoop from each layer was placed into a 18 inch diameter .5 inchmesh sieve, and the material from each layer was sieved together.This procedure was repeated until all of the material had beensieved. The sieved material was then placed in a 2 foot by 3 foottray and mixed thoroughly with a spade. The composited soil wasthen placed in glass jars and in the original bucket. StonesRemoved amounted to 25 percant of the total by weight.

Filter Cake Matrix.

Observations. One bucket of filter cake matrix, labeled 7-FC, wasreceived in good condition. The filter cake had a black cilysludge appearance, but was stiff and did not flow. The material issticky and hydrophobic, and did not contain stones.

compositing. A layer of water was removed from the top of thefilter cake and stored in the refrigerator. For compositing, avertical pie-shaped section weighing 33 Ib was removed from thebucket. No changes in the nature of the material were observed forthe three layers. The section of cake was placed in a largestainless steel bowl and stirred until homogeneous, then stored inglass jars.

Sludge Matrix

Observations . Three buckets of sludge, 7-SL-l, -2, and -3, werereceived. The contents of the three containers appeared similar,

Al-4

II II IIASEA BROWN BOVERI

having a layer of black oil on to of very black sludge. The sludgeflows readily and is easy to stir, although it sticks to a spatula.The material was hydrophobic, had a strong odor, and appeared tohave a fibrous material throughout, but no rocks. The three layersin the bucket did not appear to differ in composition.

Compositing. The contents of 7-SL-3 were poured into a 2 foot x 3foot tray and stirred with a spade. The composited sludge was thenpoured back into its original bucket to be stored at roomtemperature .

Table A-i

Determination of Necessary Extraction Volumes for TPH-IREach sample extracted 4 times

Freonper wet gm Percent of total TPH. each extracteach extract first second third forth

'SOIL(4mm) 5 ml 79 % 16 % 4.0 % 1.0 %CAKE 10 ml 93 % 6 % 0.5 % 0.1 %SLUDGE 12.5 ml 90 % 9 % 1.0 % 0.1 %

GO Volatile Compounds for Soil, Filter Cak« and Sludg*

The GC analyses of soil, filter cake and sludge reported in Section4, provided information on the concentration of those compoundswhich were relatively lower in molecular weight and which were wellseparated by the GC process. For the purpose of this calculation,decane (CIO) and lighter compounds are considered to be volatile.The concentrations of all peaks guantitated by the GC analysis arelisted in Table A-2 for soil, filter cake and sludge. For eachmatrix, the "volatiles1' are summed and divided by the GC Totalreported in Section 4, to obtain the fraction of volatiles present,(soil analysis originally on 4 mm sieved sample, corrected to 12mm)

Al-5

tentativename

mp-xyleneo-xylene

C9

ik»»f\mmASE* MOWN BOVERt

Table A-2GC Volatile Compounds, Decane and Lighter,

Percent of GC TotalSoil, Filter Cake, and Sludge

trimethylbenzCIO

TOTAL VOLATILESCG TOTALS (Sect 4)Percent Volatiles

GC R.T.min

3.2053.7164.1605.3265.7625.8666.6776.9357.0257.0827.2247.2587.5447.7357.835

SOILPPM

1.0

FILTERCAKE.PPM

SLUDGEPPM

-2.55.02.04.41.31.91.85.22.6--7.110.745.5

22,7000.2 %

19.7-19.6-11.7---25.9---18.044.4139.3

214,0000.06%

35.933.796.0-95.528.060.942.2

129.058.861.742.4

139.5367.21,287.4405,200

0.32%

Al-6

A II II»SE* BHOWN BOVEftl

Al-4 SOIL COMPOST EXPERIMENTS, SUPPLEMENTARY INFORMATION

Table A-3

Soil Compost #1, Process Monitoring LogNH3 & PO4, PPM wet compost

Available Available PercentDav PH fNH3)N PO4 Drv

10 .677535

.628252575

.631515

.58152010

Table A-4Soil Compost #!/ Process Maintenance Log

Per Kg wet compost(1 mg N «• 3 mg ACT)

Add . Add Tot addedDay mea lime mg N ma PO4

0 554 1206111214182128344863

Al-7

04671113182021283441424863

4.5, 7.04.5, 7.0

7.0-7.0--6.5-6.87.2---7.0

_5050-13255050-100120-9085

14590579090145603060-9030

730450590280404203808

100804012

A IIII*\IPIPASEA MOWN BOVERI

Soil Compost # 2: GC Fingerprints next page Figure A-l

Table A-5

Soil Compost #2, Process Monitoring Log

N and P04, mg per Kg wet compost

Dav

0371220273235475370779198108

Soil

mg perLime:

PH

6.36.5-6.56.46.4-6.26.3-6.56.36.06.36.3

Compost

Kg wetDay 0

Day

0312202735474963708294

Available

«50-< 513175-12560-1002001257535

Table A-6

i 2f process

AvailableP04

< 5< 5-5

< 510-1220-1323352335

Adjustment Log

PercentDrv

.64-.65

.59

.66

.62

.62

.65

.68

compost (1 mg N = 3 mg ACT)add 7.5 gram, Day 94 add 1 g

Add N

200603002003075-60300200--

Add P04

1,50084012032010030100120220180120100

Al-8

FIGURE A -1f

ASEA SHOWN BOVER t

DAY 20

DAY 47

blank

««te* i

* &lar-

AASEA BROWN BOVEWl

Al-4 CONTINUED: SOIL COMPOST SUPPLEMENTARY INFORMATION

Routine Spike of TPH Standard Solution into Soil Compost # 2

On day 53, two 14.2 g soil compost # 2 samples were analyzed forTPH=IR and a third was spiked with 90 ul of EPA method 418.1 TPHstandard solution and then analyzed. The TPH standard contains 25% chlorobenzene, 37.5% isooctane and 37.5% n hexadecane, density =0.82 mg/ul. The ppm added by the spike was (90 ul)(.82 mg/ul)divided by (14.2 g)(.622 compost dry weight) = 8,390. Spikerecovery was within 2 % of expected, as detailed below:

soil compost duplicates 8,100 ppm, 10,200 ppmsoil compost av 9,150 ppmspike calculated " 8,390 ppmspiked compost calc 17,540 ppmspiked compost report 17,700 ppmdifference 160 ppmrelative percent diff 2 %

Experiment to Determine optimal pH for Soil Treatment

The purpose of this experiment was to determine the optimal pH forsoil treatment, and to determine whether lime or KOH was better asa source of alkali. Six small soil microcosms were set up using 4mm sieved soil which had been amended with 1 % manure to improvetexture and moisture retention, and supplemented with ACT and extraphosphate. These were maintained at pH 5, 6, or 7 with eitherlime or KOH, and analyzed for TPH after one month. The data, givenin Table A-7. showed no obvious trends, and it was concluded thatany pH between 6 and 7 is suitable for biodegradation of TPH inArrowhead soil. This is reasonable, since these bacteria werepreviously surviving in this soil at pH 4.5.

Table A-7

TPH-IR changes in Soil at Different pH using KOH and LimaPercent dry weight

Day 0 7.0 % Day 0 dup 6.5 % Day 0 Av * 6.75 %

Dav 34 TPH-IR Percent Degraded

pH 5, KOH 2.2pH 5, lime 1.8pH 6, KOH 2.3pH 6, lime 0.9pH 7, KOH 1.4

67 %73 %66 %87 %79 %

pH 7, lime 1.8 % 73 %

Al-9

A II II»SE* BROWN BOVEBI

Al-5 KILN DUST PR E- TREAT ED FILTER CAKE

Kiln Dust Properties and Pretreatment of Filter Cake by Hazen

Hazen Research of Golden, Colorado, pretreated 1000 grams of wetweight (750 g dry) Arrowhead filter cake by mixing with 74 gramskiln dust and 500 grams water. The rotary kiln fines sample wasprovided by Cutler-Magner and was from the dust collectionequipment of their limestone calciner. The Hazen report, and theirchemical analysis of kiln dust are included here, immediatelyfollowing this page.

ABB analyzed the kiln dust pretreated filter cake (K-cake) , intriplicate for TPH-IR , GC fingerprint, and GC total hydrocarbons.The hydrocarbon data is presented in Table A-8. and show that theTPH-IR and GC totals are within the accuracy of the methods, thesame as those calculated for original filter cake mixed with 10 %dry weight kiln dust. The GC fingerprints are presented in FigureA-2 (next page) in comparison to that of original filter cake andshow that there are no qualitative differences in hydrocarbondistribution. It was concluded that filter cake hydrocarbonproperties were not changed as a result of kiln dust addition.

Table A-e

TPH-IR and GC Total for Kiln Dust Treated Filter Cakeppm dry

TPH-IR GC totaloriginal filter cake 430,000 214,000orig w 10 % Kiln dust, calc 387.000 193.000Kiln dust treated cake 405,000 205,800

dup 382,000 202,400trip 376,000 221,000ave 388.000 210.000

Al-10

KILN DUST TREATEAi|-i|R CAKE COMPARED TO ORIGINAL

a oif

ORIGINAL CAKE

X .014

lfHsuen Research, Inc.4601 Indiana StreetGolden, Colorado 80403Tel: (303) 279-4501

ASEA BROWN BOVEfii

May 7. 1992

Mr. Sam FogeiABB Environmental ServicesCorporate Place107 Audobon RoadWakefleldMA 01880

Re: Arrowhead Refinery Site •Neutralized FUter Cake SamplesHRI Project No. 7606*02

Dear Mr. Fogel:

Mr. George Pruchnofski of Ban- Engineering Company requested we send you two pint samples ofArrowhead Refinery Site filter cake which have been neutralized; one with hydnted lime and the O'herwith rotary kiln fines. Also enclosed in the Federal Express package are pint samples of the hydrated limeand rotary kiln fines neutralizing agents.

We have blended 1000 grams of filter cake with 500 grams of tap water and added 18.5 grams of hydratedlime to one sample which resulted in a sample pH of 5.9. The other sample (of 1000 grams of filter cakeand 500 grams of tap water) we added 74 grams of rotary kiln fines which resulted in a pH of 7.2.

Attached are data sheets.

If you have any questions, please can.

HAZEN RESEARCH. INC.

Steven D. WillResearch Engineer

cc: R.C. HodgsonG. Pruchnofski. Barr Engineering

ProjectASEA MOWN BOVEHl

DettnnmatfcttS

Rotary K3n flats (utw cample)Ssaple Assay Results:

Ca.%Mg.%

CO2.%H2O. %LOL3LOI.ft

44,000.686.10

21.07041ZS4223 <g>900-C

Asst&BoiCalcolattdCompostBon (1}

Bulk Density:Loose, Ib^cfP2Cit4lb/ef

CaO.% .Ca(OH)2,%CaC03.«MgO,%Mt(OH)2,%MgC03,%c»%H20,%

Total. %

AvsDabk Calemm as % CaO

35090.00

47.15OS*0^0O620350X11

15.84loaoo

2S.251.767J

RoOur Kta Sines <from previom nork)Sample Assay Results;

Ca.%Mg.%

C02.%H20,%LOLft

Baflc Density:Loose.ni/bfPacked. Uwfcf

44.60

0.401.13

54,74 J

MgO.*M((OB)2.%

AssumedOdCBlated

Compotfft'nn (1J4i970X0

34.76055OJOO

@9oo : c*B20.4

0^7040

19 7Tot** 10000

36.4

Tlw mnltt of the loss on ignition (LOI) test it'tfOCTC fcficate the rwaiy kirn fines sampledid not lose roach wiser of hydtatioa from cdeisn hyditsudt but t high amoimc ovcarbon dixwide from calcium carbonate wulottatÔO'C, ihns this ample is usar-* tobe primarily calciom carboOTtt. SomeoftlWweigfatk)s«tttfOQ*CisearboBdiono«6oi&tffr fiw«li»n

** TOTAL PflSE.002 **

Job Site

A IIIIHRI Project N*MPNb6-02

ASE* BROWN BOVERi

Barr Engineering CompanyMaterlala Handling Laboratory Pretreatment

Teet Data Sheet Test No.

Arrowhwead Refinery Stte Date:

Purpose of Test:

Sample Treated:

Procedure:

Test Data:

Testing of Neutralizing Agents Rotary Kiln Fines

Arrowhead Filter Cake HRI No. 48864 -2

Prepare 1000 prams of sample, add 500 g water and measure Initial pH.Add neutralizing agent to adiust pH to about 6 to 7.Measure the final pH.

InitialFinal

SampleWeight

0

10001574

PH

3.587.19

WaterAdded

0-

500

Temperature Weight of AgentChange Added«C g.

20 7421

Test Observations: GaseousEmissions

none

Odors

oflysmeH

Immisctolrty

wiU not mix withwater untilneutralized

General Observationsand Comments:

Sample mixed easily and did not stick to mixer.

JobStt*

Purpose of Tast:

Sample Treated:

Procedure:

Test Data:

AIII!IIMI i» • ,ASE* WOWN BOVEBHfll Project No. 760M2

Barr Engineering CompanyMaterials Handling Laboratory Pretrsatment

TeetData3heet

Arrowhwead Refinery SKe

Testing of Neutralizing Agents

Test No.

Date; 5/7/92

Hydrated Lime

Arrowhead Fitter Cake HRINo. 46864 -2

Prepare 1000 grams of sample, add 500 a water and measure initial pH.Arid neutralizing agent to adjust pH to about 6 to 7.Measure the final pH.

InitialFinal

SampleWeight

g.10001518

PH

3.585.94

WaterAdded

g.500

Temperature Weight of AgentChange Added°C g.

2021

18.5

Test Observations: GaseousEmissions

none

Odors

oHvsmefl

Immisciblity

wiN not mix withwater untilneutralized

General Observationsand Comments:

Sample mixes well in water and is smooth and soupy

A IIIIr\nnASEA SHOWN BOVERl

Al-6. FILTER CAKE COMPOST, SUPPLEMENTARY INFORMATION

Table A-9

Filter Cake Compost i 1, Process Monitoring Log

N and P04, ing/Kg wet compost

available available PercentDav

02357111214181921

_E]

75,5,5,5,6,-777-

3_

77777

fNH3)N

—

--—50157520510-

PO4

0-1520301515131025-

Dry

.46

.38

.45

Table A-10Filter Cake Compost i 1, Process Adjustment Log

meg or mg per Kg wet compost (1 mg N = 3 mg ACT)

Dav

0235711141819

megKOH

—

3434404332---

addN

290--90-90903030

addP04

240-480400-280280210210

Al-11

A II IIASEA MOWN BOVERI

Table A-ll

Filter Cake Compost #2, Process Monitoring Log

N and PO4, mg per Kg wet compost

Available Available PercentDav pH rNH31N PO4 Drv

0 6.3 - .571 6.3 - 84/5 4.9, 6.37 5.9 10 < 5 .4514 5.4 60 < 515 6.3 - 818/19 5.3/5.422 6.5 100 8 .4434 6.0 ' 100 35 .4140 - .4243 6.3 175 4050 6.3 250 , 3554 - .4564 - 250 3571 6.3 300 10085 6.3 375 10088 6,5 500 100

Table A-12Filter Cake Compost #2, Process Adjustment Logmeq or mg per Kg wet compost. 1 mg N = 3 mg ACT

Dav meq lime Add N Add P04

0 2 300 15201 7 3004 208 8 210 56014 10 90 33015/18 2019 10 200 56022 - 200 28026 1036 10 200 23043 - 120 15064 - 100 7076 - 100 14088 5 100 100

Al-12

\

AvailablefNH3)N

^

60-< 5-75200"250300150125100

AvailablePO4—

0-8-51081523< 535

PercentDrv

.58

.52

.56

.57

.55

.55

ASEA BROWN BOVEfti

Table A-13

Soil:cake 4:1 Compost, Process Monitoring Log

N and P04, mg per Kg wet compost

Dav PH

03 7512 61821 6.528 6.335 6.542 7.056 6.363 6.573 6.375 - .61

Table A-14

Soil:cake 4:1 Compost, Process Adjustment Log

meg or mg per Kg wet compost (1 mg N = 3 mg ACT)

Dav mea lime add N add PO4

0 - 300 13003 - 240 3907 90 19014 10 300 12027 - 220 19028 - 90 15035 - .100 19042 17047 - 100 24056 - 200 28059 13 200 28066 - 200 100

Al-13

A IIIIfMPIPASCAWtOWNBOVERi

Routine Spike with TPH standard solution into soil:Cake compost

On day 53, Soil:Cake 4:1 compost was analyzed in duplicate and athird sample was spiked with 102.5 mg of EPA method 418.1 standardsolution. Samples were 15.0 grams wet, • 8.28 g dry weight.Therefore the spike was expected to add 12,380 ppm to the sample.The data listed below indicate that 100 % of the spike wasrecovered.

soil cake compost TPH (dry) • 17,400 ppmduplicate 20,500 ppmaverage 19,000 ppm

spike 12,400 ppmcompost plus spike, calculated 31,400 ppmcompost plus spike, measured 31,100 ppmdifference 300 ppmrelative percent difference" 1 %

Table Al-15

Filter Cake Abiotic Test Duplicate Values

Live Cake Killed Cake K-Cake, noCompost Compost amendments

TPH % start 20.9, 20.5 20.9, 20.5 40.5, 38.2, 37.6

TPH % finish 11.3, 11.3 19.1, 19.0 33.7, 31.1

O2 used 23.8, 36.4 0.2, 0.0 1.5, 1.6

C02 produced 22.2, 28.1 1.6, 1.3 2.7, 2.7

Al-14

Jl IIIIfMPIPASEA BROWN BOVERI

Al-7 SLUDGE TREATMENT, SUPPLEMENTARY INFORMATION

DCR Pretreated sludge Evaluation.

Several samples of DCR pretreated sludge were received from SoundEngineering and evaluated at ABB. The two which gave the bestresults, (b) and (e), will be discussed. Both were reported tohave been amended with "15 % CaCO3 and 40 % CaO", and had pH of 12and 10. Sample (b) had also been treated with detergent, and (e)with detergent plus moist C02 to lower the pH. The TPH-IR wasdetermined for a sample similar to (b) and found to be 28 % on adry weight basis, in contrast to original sludge which is 69 % TPH.Sample (e) had a TPH-IR of 23 %. Thus, the DCR process resulted ina significant weight increase of the sludge. GC fingerprintanalysis indicated that the sludge hydrocarbons had not beenaltered by the DCR process.

Sound Engineering stated that the extremely high pH could bebrought to neutral, simply by aerating. Therefore, these sludgeswere mixed with bulking agent and water to form a compost whichcould be easily kept aerated. Both DCR treated sludge samplesdemonstrated good mixing and wetting properties. After 2 days thepH of (e) compost fell to 8.0, while the pH of (b) compost required3 weeks.

Additional experiments were carried out to test the ability of thepretreated sludge compost to support bacterial growth andbiodegradation of the bulk contaminant. The (e) compost wassupplied with bacteria and fertilizer, and within 5 days had apopulation of total plate count bacteria of 100 million per gramwet compost. The (b) compost was also supplied with bacteria andfertilizer, and during the subsequent 35 days the TPH-IR of thecompost decreased from 12.4 % to 3.9 % (dry weight), a change of 69percent. These data indicate that DCR pretreated sludge willsupport bacterial growth and the biodegradation of the bulkcontaminant in sludge. Thus, the DCR pretreatment would besatisfactory for preparing Arrowhead sludge for biotreatment.

At the same time, Arrowhead sludge was pretreated at ABB with Kilndust to produce a stable emulsion having neutral pH and good mixingproperties. After the addition of a bacterial inoculum, 130million bacteria per gram compost were measured on day 19, and adecrease in TPH-IR of 79 % was observed in 55 days. Since the kilndust pretreatment would be very much less costly than the DCRprocess, it was decided to proceed with experiments with kiln dustpretreated sludge. Experiments with DCR treated sludge werediscontinued.

Al-15

SECTION A1-8

Standard Operating Procedure

Nitrate Nitrogen: In Water

Method: Based on Cadmium Reduction Method(4500- NO3 E., Standard Methods, 1989)LaMotte Chemical Test Kits for Nitrate (CODE 3110)

Principle:

Nitrate is reduced almost quantitatively to nitrite in the presence of cadmium. Thenitrite produced thus is determined by diazotizing with sulfanilamine and coupling withN-(1-naphthyl)-ethyienediamine dihydrochloride to-form a highly colored and dye thatis measured colorimetrically.

Range: 0.25-10 ppm nitrate nitrogen (N)

Spike: 0.1 ml 600 ppm NaNO3 in 2.5 ml (= 4 ppm nitrate nitrogen)

Validation: Analyze: (1) Dl water, (2) Dl plus spike, (3) Sample, (4) Sample plusspike. If the difference between spiked and non-spiked sample isnot within 20% of the difference between spiked and non-spikedwater, then the analyses is not valid.

Procedure:

1. Rl! the sample bottle (0688) to the first line (2.5 ml) with the sample.

2. Add the Acid Reagent (V-6278) to the second line (5.0 ml total). Cap and mix.Wait 2 minutes.

3. Use the 0.1 g spoon to add one level measure of Nitrate Reducing Reagent (V-6279) to the tube.

4. Cap and invert the tube 50-60 times in one minute.

5. Let stand 10 minutes. Mix before inserting the Color Comparator (3109).Match the color with the standards to obtain the test result expressed in ppmNitrate Nitrogen (N).

6. If the sample is too concentrated, dilute the sample with the Ol water andrepeat test.

A1-16

mm mmmm Biorerrwdiation Systems


Orthophosphate: PO4 In Water

Method: Based on Stannous Chloride Method(4500- P D., Standard Methods, 1989)

. LaM'otte Chemical Test Kits for Phosphate (CODE 4408)

Principle:

Orthophosphate reacts in acid conditions with ammonium vanadomolybdate to formvanadomolybdophosphoric acid. Vanadomolybdophosphoric acid is reduced bystannous chloride to intensely colored molybdenum blue.

Range: 1.0 • 10.0 ppm Orthophosphate (PO4)

Spike: 0.1 ml 290 ppm KH2PO4 in 5 ml (4 ppm PO4)


Procedure:

1. Fill the test tube to the 5 ml line with water sample.

2. Add 1.0 ml of VM-Phosphate Reagent (4410) to the test sample and mix byinverting the tube several times.

3. Let stand for 5 minutes. Then use the plain pipet to add 3 drops of ReductionReagent (6405) and mix. A blue color will develop in 10 seconds.

4. Insert the test tube into Color Comparator (4414), read the test result within 30seconds.

5. If sample is too concentrated, dilute the sample with Dl water.

By Spectrophotometer: Read at 650 nm -690 nm

Preparation of standard curve: Prepare at least 4 standards. Make up standardsadding the following volumes of spike solution and diluting to 5 ml Dl water; 0, 25 ul,50 ul, 75 ul, 100 ul (= 0,1, 2, 3, 4 ppm). Read in spectrophotometer and determinethe phosphate concentration from the calibration curve.

A1-17

Bioremedtation Systems


Ammonia Nitrogen: In Water

Method: based on Nesslerization Method(4500-NH3 C.. Standard Methods, 1989)LaMotte Chemical Test Kits for Ammonia (CODE 4795)

Principle:

Ammonia, under alkaline conditions, reacts with mercuric iodide to form a yellow toyellow-orange complex. Iron will also react with alkaline mercuric iodide to form aprecipitate. Pretreatment of sample with sodium potassium tartrate (Rochelle' salt) willminimize interferences.

Range: 1-9 ppm ammonia nitrogen (N)

Spike: 0.1 ml 775 ppm NH4CI in 5.0 ml (= 4 ppm ammonia nitrogen)

Note: The test sample must be neutralized before proceeding with the test. Ifsolids are present or are formed, remove by filtration or centrifugation.


Procedure:

1. Fill the test tube to the 5 ml line with water sample to be tested.

2. Add 4 drops of Ammonia Nitrogen Reagent No. I (4797) and mix.

3. Add 8 drops of Ammonia Nitrogen Reagent No. 2 (4798) and mix.

4. Allow 5 minutes for maximum color development Inserting the test tube intoColor Comparater (4796). Match the color with the standard to obtain the testresult expressed in ppm ammonia nitrogen (N).

5. If sample is too concentrated, dilute the sample with Dl water and repeat step1-4.

By Spectrophotometer: Read at 400 nm -425 nm

Preparation of standard curve: Prepare at least 4 standards. Make up standardsadding the following volumes of spike solution and diluting to 5.0 ml Dl water; 0, 25 ul,50 ul, 75 ul. 100 ul (= 0, 1. 2, 3, 4 ppm).

A1-18


Bioremediation Systems Standard Operating Procedure, 1/15/91

CO2 In Headspace by GC/TCD

Principle: This method is designed to estimate CO2 production in sealed microcosms.The procedure is wfthout reference in ERA or Standard Methods. The typical applicationis for serum bottles having 110 ml headspace and 50 ml liquid. The method does notaccount for CO2 dissolved in the liquid.

Instrumentation: A Hewlett Packard 5890" Gas Chromatograph with ThermalConductivity Detector (GC/TCD).having a chromatographic column 6 feet in lengthpacked with Carbosieve 80/100 support

Temperature Program: Initial 35°C 10 minutesIncrease 30°C per minuteFinal 220°C 20 minutes

Detection Limit: 2 micrograms

Linear Range: 0 to 200 micrograms for any constituent of a gas mixturei

Sample Handling: Withdraw with Gas-tite syringe, inject immediately into GC.

Quality Control: Analyze a 175 microliters air blank and duplicate 175 microliters 10%CO2 in N2. CO2 standards are obtained from Scott Specialty Gases,Inc.

For Unknown Sample A sample, 175 microlrters, is withdrawn from a serum bottle butthe pressure may not be 1 atm, so the volume at 1 atm is not known. Therefore, the datamust be normalized for N2 which is considered to remain constant.

A1-19


Total Petrftl m*?\vi Hydrocarbon by ISWith Shake Extraction

Modified from EPA Method 418.1 for Soil and SludgeABB-ES BRS January 20, 1991

Principle: Freon is used to extract hydrocarbons from soil or todissolve hydrocarbons in sludge. The silica gel adsorption stepremoves polar compounds such as humic acid. Detection is byInfra red absorbtion.

Extraction/Dissolution: The sample must be mixed with sufficientfreon to solubilize the hydrocarbon. 'For moderately contaminatedsoil two extractions with 10 ml each for a 2 gram sample may besufficient. For petroleum refinery sludge the sample size—shouldbe reduced to 0.5 ml.

* Place sample in a test tube. Record exact weight of sample.Prepare an extra tube for a blank extraction (Method Blank).Add one to two weights Na2S04 to the tube. Immediately add 10mis Freon. Shake vigorously to break up clumps. If anyclumps of soil remain, break them up with a glass rod. If theNa2SO4 forms a lump, add more Na2S04.

* Shake on shaker for 20 minutes in horizontal position.Centrifuge the extract in the tabletop centrifuge for 5minutes. Pour off solvent into a new test tube. Add 10 moremis of Freon to the sample and repeat shake andcentrifugation.

* Pour off solvent and combine with first extraction into newtest tube. Add a spatula of silica gel to the extract andshake. If the gel turns yellow/brown, add more silica gel.Shake on reciprocal shaker for 5 minutes. Centrifuge theextract in the table top centrifuge for 5 minutes. Store theextract in freezer until ready to analyze.

Analysis of Extracts. The calibration standard is made accordingto EPA Method 418.1 (15 ml n-hexadecane, 15 ml isooctane, 10 mlchlorobenzene) . This is diluted 20 fold with freon, then 5working standards are prepared having 0.25 to 4.0 mg per 10 mlfreon.

The standard solutions are analyzed by recording infra redspectrophotometer at 2920 cm* and a standard curve forabsorbance (neg log of % transmission) is prepared. The samplesare then analyzed, diluting any sample having a % transmissionless than that of the 4 mg/ml standard. Percent transmission ofthe sample is corrected by adding (1 - % T of method blank) .

2737.SOPA1-20

Btoremediation Systems

Bioremedlation Systems Standard Operating Procedure, 11/1/90

Modified EPA Method 3550 and 3510For Extraction of Organic Compounds

from Soil, Sludge, Compost and Slurries

Modified Method 3550 for Soil. Sludge, or Compost

Organic compounds are extracted from moderately contaminated soil with 10 volumesof methylene chloride:acetone (1:1). The sample size must be large enough relative tothe matrix particle size to assure reproducible results. Sludge will probably require 20volumes of solvent for adequate extraction. One to two weights of Na2SO4 is added to"dry" the sample. The extraction is carried out in a closed container by shaking 15minutes on a reciprocal shaker, followed by centnfugation.

Modified Method 3510 for Slurries

Slurries are prepared from soil or sludge mixed with 40 ml water in a glass serum bottlesealed with teflon-lined septa and crimped aluminum caps. The entire contents of thebottle are extracted by injecting 15 ml of methylene chloride through the septa into thesealed bottle using a glass syringe, and venting the bottle through the syringe. The bottleis then shaken on a reciprocal shaker for 20 minutes. The phases are allowed toseparate and the soil to settle, centrifuging the bottle if necessary. A portion of thesolvent is then removed by glass syringe.

3550/3510.SOP

Al-21

A!*!* Bkxemediation Systems

Bioremediation Systems Standard Operating Procedure November 1,1990

Heterotrophlc Plate Counting

Modified Standard Method . <?215 C

Analyte: Heterotrophic bacteria

Matrix: Aqueous (fresh and saline) or soil

Summary of Method

Water samples or soil extracts are serially diluted. Aliquots of the diluted sample arespread on agar plates. Individual cells multiply and form colonies on the agar surface.The colonies are counted and an estimate of the number of live bacteria present in thesoil or water sample can be made.

Apparatus:

1. Incubator2. Glass rod3. Turntable4. Disposable glass pipettes

Reagents and Media:

1. Plate Count Agar (American Scientific #0479-01 or equivalent)

Nutrient Agar 0.8 gDistilled Water 1 L

Agar is autoclaved for 15 minutes and poured into sterile disposable petri plates.

2. Stock Phosphate Buffer solution:

5 g NH4CI5 g NaHP305500 ml distilled waterCheck pH. Adjust to between 6.8 and 7.2, if necessary.Dilute to 1 L with distilled water

Al-22HPC.SOP


A II II

3. Dilute Solution:

10 ml Stock phosphate buffer1 L Distilled water

Place 9 ml (± 0.2 ml) dilution solution into test tube or bottle (or 99 m! ± 2 ml in alarge bottle). Autoclave for 15 minutes.

Procedure:

1. Soil samples are extracted by adding 5 g soil to 45 ml dilute buffer. Samples areshaken for 20 minutes.

2. Water samples and soil extracts are serially diluted, 1 to 10. Water samples arediluted to 1 x 10"6 and soil extracts are diluted 10*7.

3. Pipet 0.3 ml of diluted sample onto the surface of a nutrient agar plate. Distributeinoculum over surface on the plate using a sterile bent glass rod and rotating the dishon a turntable. Let the inoculum be adsorbed completely into the medium beforeplacing in the incubator.

4. Incubate plates in an inverted position at 22°C ± 5°C for one week.

5. Count all colonies on dilution plates that have between approximately 30 to 300colonies each. Calculate the number of bacteria in the sample by multiplying thecount per plate by the reciprocal of the dilution used. Report counts as colonyforming units (CPU) per ml of water or per gram of soil.

6. If all plates have greater than 300 colonies, use the dilution piate having a countnearest to 300 colonies. Compute the count as above and report as Estimated CPUper ml or gram.

7. If all plates have less than 30 colonies, report the count as Less than one (< 1) timesthe reciprocal of the lowest dilution.

To Enumerate special classes of bacteria (eg. fuel degraders, toluene degraders),the following amendments to the procedure are made.

1. Nobel (organic free agar) is used instead of nutrient agar} plus a, comple-kmineral SupbUment.

2. The carbon source is made available by either incorporating it into the agar or byincubating the agar plates in a dessicator that contains the target compound as avapor phase.

Reference: Adapted from Standard Method 907B, 1985 Edition.

HPC.SOP A1-23

Modified BPA Method 8100 for Extractable oroanicsStandard Operating Procedure

November 1, 1990

Scope of Application. £PA Method 8100 has three levels ofapplication at BRS:

1. Hydrocarbon Fingerprint, which gives information on therelative distribution of constituents by molecular weight(retention time) and the extent of weathering.

2. Estimation of the total hydrocarbon content of a sample byintegration of the resolved peaks plus undifferentiatedmaterial.

3. Quantitation of project-specific target compounds. Forexample, for coal tar, 25 aroma tics from toluene to 6-ringPAH, are guantitated. For un-weathered petroleum products 21linear and 3 branched alkanes are guantitated.

Analytical Procedure

The instrument to be used is a Hewlett-Packard (HP) model 5880gas chromatograph fitted with a DB-5 (J. and W. Scientific)capillary column and equipped with a flame ionization detector.Samples are introduced to the GC by autoinjection using an HP7673A automatic sampler. The instrument detection limit is 500ng/ml of extract. Separation of compounds is achieved by .atemperature program beginning at 40 C then increasing by 8 C perminute to 290 C and holding for 30 minutes.

Calibration Standard Preparation

Mono- and Polyaromatic Hydrocarbons

A calibration standard solution, containing the target compounds,is prepared every two weeks. The calibration standards are madeto a final concentration of 50 ug/ml. The standard compounds areobtained from a referenced source and prepared in methylenechloride in a mini-inert vial. This procedure is repealed everytwo weeks. All calibration standards are stored at -20 C.

Internal standard Preparation

The internal standard that is used for 8100 analysis isorthoterphenyl (OTP) for mono- and polyaromatic hydrocarbons andparaterphenyl (PTP) for fuel oils. The internal standard isprepared to a concentration of 50 ug/ml in a mini-inert vial.The standard is stored at -20 C.

GC/FID.SOP


Ji II IIASU MOWN BOVERI

Check standard Preparation

A check standard is prepared from standards that have beenobtained from a different referenced source than what was usedfor calibration standards. The check standard contains allcompounds in calibration standard and is made in the same manner.The concentration of check standard is 50 ng/ul.

Calibration Procedures for Mono- and Polyaromatic Hydrocarbons

The instrument is calibrated and results obtained using theinternal standard method. Relative response factors for eachcompound are calculated from the multicomponent standard mixwhich is also used for compound identification by retention timematching.

The calibration procedure is performed weekly. Daily, a mid-level standard (50 ppm) is analyzed. The value must be within ±15% of the standard value. If the standard is outside the rangea check standard is analyzed. If this fails to fall within therange, the instrument is recalibrated. A continuing calibrationstandard is run 10 samples or per batch.

Calibration Procedures for Fuel Oil Hydrocarbons

The instrument is calibrated and results obtained using theinternal standard method. A response factor is calculated fromthe internal standard and used for the target list compounds.Compound identification is by retention time match with knownstandards.

Pro-Analysis

Set up the GC with the following conditions:

Column: 0.25 m x 30. m DB-5 Fused Silica Signal: Attn: 2Oven: Temp 1 40 C Area Reject: 0

Time 1 0.1 min Threshold: lRate 8*C/min Peak Width: 0.04Time 2 30 min

Run Table: 0.00 Valve 5 on0.50 valve 5 off0.1 Int. 0 off3.0 Int. on

GC/FID.SOPA1-25

Als/o;

IIIUEABftOWNBOVERl

If the capillary column needs to be changed or maintenanceperformed, the oven should be brought to room temperature. Theinjection port nut, once removed, allows replacement of septa, 0-rings and cleaning of the injection port liner. The columnshould be checked to be sure both ends are cut evenly and arefitted with fresh ferrules such that both the injection andetector ends are secured properly. All nuts should be tightened .and the carrier gas flow should be checked for leaks. Thecolumn, if time allows, can be held at its maximum temperature(290 C) for 30 minutes. The carrier gas flow of 20 psi should beused.

Routine Analysis

For routine analysis, samples are loaded into the autosampler. Afinal volume of 1 ml is always used and 1 ul is injected into theGC. Each sample must have 10 ul of Internal Standard/ExternalStandard solution added to it just prior to loading on theautosampler. All samples are quantified using Internal StandardMethod.

Internal Standard Calculations

For Mono- and polyaromatic hydrocarbons:

_____Area of Component_____ ua of IS ____1 1Cone. = Area of Internal Standards (IS) x Fraction used x Sample Amt. x KRF

Area of Component Amt IS____RRF « Area of IS x Amt. Component

For fuel oil hydrocarbons:

_____Area of Component_____ - ua of IS ____1Cone. «= Area of Internal Standards (IS) x Fraction used x Sample Amt.

A solution of standard PAH should be analyzed and used tocalibrate the instrument (see Calibration). After this hasoccurred and the analyst has checked the runs for quality,samples can be analyzed. Consult.the manufacturers operationsnotebook for program run commands for the autosampler.

After samples have been chromatographed by GC/FID, the analystmust once again visually check for quality of chromatography,consistency in internal standard area and proper instrumentidentification of compound peaks. Once this is assured, theamount of each compound of interest (ug/ml) is transposed to adata sheet and calculations performed.

GC/FID.SOPA1-26

Ik II IIASEAMOWNBOVERI

% Solids

To determine the moisture content of each sample, tare the weightof an aluminum boat. Then add approximately 10 g of sample andreweigh. Let the sample dry overnight in an oven at 100 C. Thedry mass is then determined by recording the new (dry) mass ofsample and boat and subtracting the mass of the boat.

% Solids « Mass Dry Sample x 100/mass wet sample

Compound concentration calculations

Concentration in Extract fug/mil x Volume fmls^ extract * ug PAH/g dry wtdry wt sample (g) x concentration factor or ppm

Quality Control

Quality control procedures for the modified 8100 method includecalibration standards, calibration check standards, blanks, andinternal standard, as well as laboratory control samples andreagent blanks. A reagent blank shall be run each time a newreagent lot is used. A method blank shall be analyzed dailyafter calibration or calibration check runs, when samples are tobe analyzed, and after the analysis of any high concentrationsample.

Data Recording

Analytical -results (raw data) are collected using an IBMcompatible computer system to measure peak height/area andinterpret results in concentrations (ppm). Documentation of

^ analyses will appear in a laboratory log. Results are reportedas a data print-out from the computerized system.

References

(1) U.S. EPA. 1979. Methods for Chemical Analysis of Water andWastes- EPA 600/4-79-020 (Revised, March 1983). EPA/EMSL,Cincinnati, Ohio.

(2) U.S. EPA. 1986. Test Methods for Evaluating Solid Waste-Phvsical/Chemlcal Methods- SW-846 Third Edition. Office ofSolid Waste, U.S. EPA, Washington, D.C.

GC/FID.SOP AA1_27

A II IIASEA BROWN BOVERi

SAMPLE CALCULATION FOR OC HUMP BY MANUAL INTEGRATION

soil compost #2, day 0

SAMPLE freonwet weight % drv volume dilution14.06 g .639 100 ml none

Therefore, 11.13 ml freon per gram dry sample.

STANDARDorthoterphenyl (OTP) 50 ug/ml

GO fingerprint conditions:InstrumentAttenuation

sample 2*1OTP 2A4

chartspeed

0.515.0

Area by"cut & Weigh"

21 mg206 mg

If OTP had been analyzed at the same chart speed and attenuation asthe sample :

50 ug OTP = 21 mg paper (2*4) (0.5) = 5.6 mg paper(2-1) (15.0)

1 mg paper at chart.5 and Attl = 8.93 ug OTP/ml

Let 8.93 ug OTP/ml represent 8.93 ug hydrocarbon/ml

Sample: 206 mg paper X 8.93 ug hydrocarbon /ml per mg paper- 1840 ug hydrocarbon/ml analyzed.

sample 1840 ug/ml extract X 11.13 ml extract/gram dry= 20,500 ug/g ~ 20.500 ppm dry weight

(2-1) (15.0)

A1-29

f\nwASEA SHOWN BOVERt

Arrowhead Project # 7054-01ABB-ES Laboratory Data Quality Control Review for Laboratory Treatability Studies

performed for the Arrowhead/Barr Engineering.Date: 9/15/92

All data reported by an analyst was quality control (QC) checked by a second analyst andsigned. This QC check involves reviewing all raw data calculations, data reports, extractionand instrument logs for consistency with data reports, and the initial and continuingcalibrations for the instruments used are checked for performance.

In addition, the ABB Quality Control Officer (QCO) for this project is responsible forreviewing 10% of all data. The Arrowhead laboratory data is filed in three-ring bindernotebooks in sections according to sample matrix or experiment. Each matrix or experimentwill be considered a "batch" and 10% of each type of analysis (ie- Total PetroleumHydrocarbon, Nutrients, GC/FED, etc.) per batch will be reviewed. In general, the QCOreview process will entail checking all raw data calculations, data reports, extraction andinstrument logs, and initial and continuing calibrations for the instruments used. A detailedreview list for the QCO is provided with each analysis type. The QCO will initial all datareports, calculations, extraction logs, etc. as they are checked. A list of all analysisperformed, listed by analysis type and batch, are listed from which the QCO will select 10%for review. The analysis reviewed will be checked of in the" QC1 column corresponding tothat particular sample.

1.0 Total Petroleum Hydrocarbons (TPH) (Modified EPA Method 418.1)

TPH QCO Review List

• TPH Calibration Log: initial calibration curve correlation > 0.980.

• Extraction Log: extraction dates, extraction volumes, analyst initials, and sample IDagree with data report.

• Dry Weight: calculations and corresponding sample IDs consistent with data report.

• Instrument Log/Spectra Printouts: calculations and corresponding sample IDsconsistent with data reports.

• Raw Calculations and Data Reports: all calculations.

• Check to ensure all data in TPH and % Moisture logbooks have been previously QCchecked and signed off by a second analyst.

A1-30

A II IIASEA BROWN flOVERi

Notebook#1

1

1

1

1

1

1

1

11

1

1

11

1

Section name

InitialAnalysis

Cake comp2/14/92

Soil Micro2/20/92

sludge Comp3/4/92

Soil comppH/alkali

optimization

extractiondate

1/23/92

2/14/92

2/28/92

3/9/92

2/21/92

2/28/92

3/9/92

3/13/92

3/20/92

4/2/92

3/6/92

3/13/92

3/24/92

3/31/92

3/18/92

QC

T%/

xW<rff

$Li •

$k&i

Sample ID

C^Soil composite extr 1-37}Filter cake composite extr~~M

Sludge composite extr 1-3

Cake Comp t = 0Dup

Cake Comp t=14Dup

Cake comp t=24Dup

Soil Compost t=0Dup

Soil comp t=7Dup

Soil Comp t = 17Dup

Soil Comp before wash t = 21Soil comp after wash t = 21

Soil Comp t= 28

Soil Comp t=4lDup

Sludge Comp t = 0Dup

Sludge comp t~7Dup

Sludge comp washed t= 18Sludge comp washed

Sludge comp unwashedSoil micro t=0

Dup

A1-31

A II IIIASEAIKOWNBOVERi

Notebook#1

1

2

2

2

2

2

2

2

2

2

2

2

Section name

Soil pH/alkalioptimization

Soil Comp4/10/92

Filter cakeComp #2

extractiondate

4/2/92

4/21/92

4/10/92

4/17/92

4/29/92

5/12/92

5/27/92

6/2/92

6/23/92

7/29/92

4/23/92

4/30/92

5/15/925/14/92

QC

/*/4</h.

Mty

/»

Sample ID

Soil micro pH 5 KOHpH 5 LimepH 6 KOHpH 6 LimepH 7 KOHpH 7 Lime

Soil micro pH 5 KOHpH 5 Lime<^JHJLKQH-^pH 6 LimepH 7 KOHpH 7 Lime

Soil comp tÔ

Soil comp t=7

Soil comp t = 19

#> Soil comp t=32Soil comp t=47

DupSoil comp + spike t=47

Soil comp t=53Dup

Soil comp + spike t=53Soil comp t=74

Soil comp t=110Dup

Filter cake comp t=0Dup

K Filter cake comp t =7Rotary Kiln Fines Filter Cake

Filter Cake t=21Dup

A1-32

n iiASEA MOWN BOVEfii

Notebook#2

22

2

2

2

2

2

2

2

2

2

2

2

2

2

2

Section name

Filter cakeComp #2

Soil/Cakecomp

Abiotic Test

extractiondate

5/27/92

6/2/92

6/9/92

6/16/926/16/927/29/92

8/11/92

5/15/92

5/21/92

6/2/92

6/11/92

6/23/92re-analy6/25/92

7/7/92

6/25/92

6/25/92

QC

,

ffi

Sample ID

Filter Cake comp t=34

Filter cake comp t=40

Hazen Kiln Dust

Filter cake comp t=56Rotary Kiln Fines Filter Cake

Filter cake comp t = 99Dup

Filter cake compost t = 112after wash

Soil/Cake comp t = 0Dup

Soil/Cake comp t=6Soil/Cake comp t=18

Soil/Cake comp t=27Dup

Soil/Cake comp t=0, Dup

Soil/Cake Comp t=41Dup

Soil/Cake Comp t=53Dup

Soil/Cake Comp t=53 + spikeSoil/Cake Comp t=75

Dup

Test Soil comp t=0Dup

Unamended Soil t=0Dup

Test Cake Comp t=0Dup

A1-33

A II IIASE* BROWN BOVERi

Notebook#2

2

2

2

3

3

3

Section name

Abiotic Test

TreatedSludge

'extractiondate

6/29/92

7/7/92sampled6/30/92

7/10/92

7/16/92

11/6/92

10/29/92

11/12/92

QC

/tA/r«/0>

AV#p>

.

Sample ID

Test Cake comp t = 4Dup

Test Soil Comp t =5Unamended Soil t=5

Soil Abiotic Test t= 15bottle #1

<5Qtite_£2~Jbottle #3bottle #4bottle #5bottle #6bottle #7bottle #8

Cake Abiotic Test t=21bottle #1bottle #2bottle #3

C^jSttjejB^bottle #5bottle #6

Shiny Bottle #3 Set #1Slurry Bottle #3 Set #2Slurry Bottle #3 Set #3

K-Sludge CompostDCR "B" Compost

OCR "c,d,f&g"

Slurry Bottle #5 Set #1Slurry Bottle #5 Set #2Slurry Bottle #5 Set #3Slurry Bottle #1 Set #1Slurry Bottle #1 Set #2Slurry Bottle #1 Set #3Slurry Bottle #4 Set #1Slurry Bottle #4 Set #2Slurry Bottle #4 Set #3

A1-34

AB»AKA MOWN BOVERl

Notebook

3

Section name

TreatedSludge

Analysisdate

12/1/92

QC Sample ID

Slurry Bottle #3 Set #1Slurry Bottle #3 Set #2Slurry Bottle #3 Set #3

K-Sludge CompostDCR Compost VDCR "b" Compost

DCR "c,d,f&g"

A1-35

AirASEA BROWN BOVER!

2.0 Nutrient Analysis

Nutrient OCO Review List

• Nutrient Data Reports : all calculations.

• Blank values < detection limit: Ammoinia nitrogen < 1 ppm, nitrate notrogen <0.25 ppm, total and orthophosphate < Ippm.

• Check to see if matrix spikes and blank + spikes were done. One per sample ofsimiliar matrix. % Recovery should be 100 + /- 30% or data should be flagged as"Estimated Values".

• Check to ensure all data in nutrient logbook has been previously QC checked andsigned off by a second analyst.

A1-36

AIillASEAIAOWNBOVERl

Notebook#

1

1

11

1

1

1

1

1

1

1

1

1

1

1

1

1

1

1

1

1

1

1

Section name

SoilMicrocosm

CakeCompost

Preliminarybiodeg of

Cake

Soil Micromade 2/20/92

extractiondate

2/10/92

2/11/92

2/17/92

2/21/92

2/19/92

2/21/92

2/25/92

2/26/92

3/3/92 &3/4/92

2/17/92

2/26/92

2/21/92

2/25/92

2/28/92

3/3/92

3/5/92

3/10/92

3/12/92

3/13/923/20/923/26/924/3/924/9/92

QC

^l|»|»

Hi<

Sample ID

Soil Microcosm t=3 days

" " t=4davs

t= 10 days

" " t = 14 days

Cake Compost t=5 days

Cake Compost t=7 days

Cake Compost t = ll daysCake Compost t=12 days

Cake Compost

APSC-1 & NPSC-1 t=3 days

APSC & NPSC

Soil Compost #2

Soil Compost #2

Soil Compost #211 n

ir rt

II it

M II

v Soil Compost #2 first washSoil Compost #2

ti n

n iiii n

A1-37

A IIIIAIPIPAKA BROWN BOVERI

Notebook#1

11

111111111111

111111111

Section name

Soil Micromade 2/20/92

SludgeCompost

made 3/4/92

Soil Comp pHand alkalioptimiz.

extractiondate

4/16/92

4/24/92

3/4/92

3/5/92

3/9/92

3/12/92

3/24/92

3/24/92

3/24/92

3/30/92

3/30/92

3/31/92

3/31/92

4/6/92

3/18/92

3/20/92

3/20/92

3/21/92

3/21/92

3/21/92

3/21/92

3/26/92

4/3/92

4/3/92

QC

/44il/ltftP'

%(

•

Sample ID

Soil Compost #2

ii it

Sludge Compost

•I it

ii ii

n H

Sludge Compost Wash #1

" " #2

" " #3

Washed Sludege Compost

Unwashed Sludge Compost

Washed Sludge CompostUnwashed Sludge Compost

Sludge Compost WashSoil Compost for pH and alkali

study

pH 6 KOH CompostpH 6 Lime CompostpH 5 KOH CompostpH 5 Lime Compost

pH 7 KOH Compost

pH 7 Lime CompostpH 6 Lime CompostpH 7 KOH CompostpH 7 Lime Compost

A1-38

A II IIASEA MOWN flOVERl

Notebook#1

1

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

22

Section name

Soil Comp pHand alkalioptimiz.

Soil CompLarge Batch

,

Filter CakeComp Batch 2

extractiondate

4/9/92

4/16/92

4/10/92

4/13/92

4/16/92

4/24/92

4/30/92

5/7/92

5/15/925/27/92

6/19/92

6/26/92

7/10/92

7/17/92

7/27/92

4/24/92

4/30/92

5/7/92

5/15/92

5/27/926/5/92

6/12/92

6/19/926/26/92

QC

wiv|HtL

VfliltJ4J|l

ifjV

Sample ID

pH 6 Lime Compost

pH 6 KOH CompostSoil Comp 4/10/92

H H

H II

H II

H H

n ii

H II

k n n

fi M

n »

n n

N II

N II

Cake Compost

n n

H It

H It

H n

M II

n n

tt H

n n

A1-39

Jk •» IIf\nnASEA BROWN BOVER<

Notebook#2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

3

Section name

Filter CakeComp Batch 2

Soil/CakeCompost

AbioticExperiment

TreatedSludge

extractiondate

7/10/92

7/17/92

7/27/92

8/10/92

5/19/92

5/27/92

6/5/92

6/12/92

6/19/92

6/26/92

7/10/92

7/17/92

7/27/92

6/25/92

6/26/92

6/30/92

11/12/92

QC

/vîiW*»' '

W

•

Sample ID

Cake Compost

H n

H n

Cake Compost WashedSoil/Cake Compost

n n» nn nii itti nn n•ii tiII H

Soil Compost (abiotic)

Cake compost (abiotic)

Test Cake Comp


A1-40

A II II•SEA BROWN BOVERi

3.0 Bacterial Enumerations

Bacterial Enumeration OCO Review List

• Raw calculations on bacterial enumeration data sheets.

• Data Reports: all calculations.

• Check to ensure all data in bacterial enumeration logbook has been previously OCchecked and signed off by a second analyst.

—-- • —iA1-41

A II IIASEA BROWN BOVER

Notebook#

1

1

1

1

1

1

1

1

1

1

1

1

1

1

1

1

Section name

InitialAnalysis

Soil Micro2/7/92

CakeCompost2/14/92

Cake/SlurryTest

Soil Compost2/20/92

Analysisdate

2/4/92

1/29/92

2/7/92

2/24/92

2/14/92

2/20/92

2/20/92

3/2/92

2/14/92

2/19/92

2/27/92

2/20/92

2/28/92

3/10/923/13/92

4/2/92

QC

i*H*

AV ,i\>T|l:

Sample ID

Sludge CompositeFilter Cake Composite

Soil CompositeDuplicate

Soil MicrocosmDuplicate


Cake CompostDuplicate

L Cake Compost

Cake CompostDuplicate

Cake CompostAPSC-1

APSC-1

ASC-1NPSCNFS

APSC-1APSNSC

Soil Compost

^ Soil CompostSoil Compost

Soil Compost Before washSoil Compost after wash

Soil Compost

A1-42

Jl IIIIf\nnASEAIROWNBOVERl

Notebook#1

1

11

2

2

2

2

2

2

2

22

2

2

2

3

Section name

SludgeCompost

Soil CompostpH and alkalioptimization

Soil Compost4/10/92

CakeCompostBatch #2

Soil/CakeCompost

SpikingExperiment

TreatedSludge

Analysisdate

3/6/92

3/13/92

3/24/92

3/17/92

5/1/92

4/23/92

5/1/92

5/15/92

6/3/925/19/92

5/20/92

6/3/928/19/92

8/25/92

9/22/92

10/15/9210/16/92

QC

^ u*P#

**

Sample ID

Sludge CompostDuplicate

Sludge CompostDuplicate

Sludge compost after washSoil Microcosm

Duplicate

Soil Compost

Filter Cake Compost

Filter Cake Compost

Filter Cake CompostFilter Cake CompostSoil/Cake Compost

Soil/Cake Compost

Soil/Cake CompostSoil Compost with alkanes

Soil Compost with alkanes

Soil CompostSoil Microcosm

* Kiln Sludge CompostDCR Compost 0.01% NaAzide

0.03%0.1%0.3%

A1-43

Jk » IIASEA BROWN BOVERi

Notebook#3

3

3

3

3

Section name

TreatedSludge

Analysisdate

10/20/92

11/9/92

10/30/92

11/5/92

11/3/92

QC

ttti*H^

SI Inf\J .

flfUw

Sample ID

DCR Compost 0.01% NaAzide

0.1%0.3%

DCR Compost "c,d,f&g"DCR Compost "e"DCR Compost "a"DCR Compost VK Sludge Compost

Slurry Bottle #6 Set #1Slurry Bottle #6 Set #2Slurry Bottle #6 Set #3Slurry Bottle #1 Set #1

^Slurry Bottle #1 Set WZ?Slurry Bottle #1 Set #3


Slurry Bottle #6 Set #1Slurry Bottle #6 Set #2

(flurry Bottle #6 Set WpSlurry Bottle #1 Set #1Slurry Bottle #1 Set #2Slurry Bottle #1 Set #3

SECTION A1-10

ABBASEA BROWN BOVERI

ARROWHEAD SOIL COMPOST SPIKED WITH PAH AND ALKAKES

October 6, 1992

PURPOSE

Arrowhead soil contaminated with oil reprocessing wastes wastreated by biodegradation to reduce the bulk contaminant ofhydrocarbons, with analyses being carried out with freon extractsof the compost mixture. It .was desired to determine whether spikedadditions representing the bulk contaminant (alkanes) and compoundsof concern (PAH) could be recovered using this extraction solvent,and whether the hydrocarbons were gradually binding to the treewaste, becoming unavailable to this particular solvent with time.

The experiment was designed to spike finished Arrowhead soilcompost with a mixture of PAH and determine the percent of PAHrecoverable after 1 hour and 1 week, and to spike a separate sampleof compost with a mixture of alkanes and determine the percentrecoverable after one week. The one week incubation was carriedout in the presence of mercuric chloride which killed the bacteria,so that only abiotic processes were observed.

RESULT

PAH Recovery. The freon extract of compost recovered 58 percent ofthe spiked PAH after one hour, and 43 percent after one week.The data are consistent with the idea that reduction of PAHrecovery which occurred between 1 hour and 1 week may have takenplace within the first day. No difference in PAH availability wasobserved for PAH of different molecular size.

Alkane Recovery. The freon extract of compost recovered 83 percentof the spiked alkanes after 7 days (17 % loss). The actualbiological treatability study (live bacteria) reported 45 percentreduction of the bulk contaminant (alkanes) after 7 days. Thisdata is consistent with the idea that the majority of the reductionin bulk contaminant during the treatability study was due to actualbiodegradation.

A1-45

ABB Environmental Services Inc.

BiorwnMJtaton System* Corporate Place 126 Telephone (617) 2454606107 Audubon Road Fax (617) 246-5060W«ktMd. MMMchutfOi 01880

IB!

METHOD

soil composting Procedure. 2.5 Kg of arrowhead soil composite weremixed with 335 grams of shredded tree waste to improve permeabilityand 55 grams of horse manure to improve moisture retention and addtrace elements. The compost mixture was maintained at about 38percent moisture, and a fertilizer mix containing nitrogen andphosphate as well as 7 other elements required by bacteria, wasadded at intervals to maintain the available N above 50 ppm and theavailable PO4 above 10 ppm. Hydrocarbon-degrading bacteriaincreased from 2 million per gram wet compost to 37 million by day20. The biodegradation process was monitored by EPA method 418.1,TPH-IR. This value decreased by 82 % in 47 days. GC fingerprintsobtained according to EPA Method 8100 using the freon extractsshowed 80 percent decrease in hydrocarbons over the same period.

PAH SPIKING PROCEDURE

Analysis of spike mixture added to freon solvent. Table 1. Thisprocedure was carried out for the purpose of checking the statedconcentration of the spike mix and determining the reproducabilityof pipetting and analysis. The spike mix contained 2 mg/ml each of16 PAH (Supelco cat / 4-9805). Of this, 34 ul were added to 10 mlfreon in duplicate for an expected concentration of 6.8 ppm eachPAH, and 10 ul to 10 ml for an expected concentration of 2 ppmeach. These dilutions were analyzed in runs / 645, / 646, and /647. The concentrations reported in the extracts are listed inTable 1 on a per ul basis and averaged for each compound, thensummed for each run to calculate the RPD (relative percentdifference), which was 6.5 %. The average values were multipliedby 34. The average value for the 16 compounds was 110 % of theexpected 6.8 ug/ml.

Solvent Extraction Method for Compost Samples. Compost sampleswere extracted according to a modification of EPA Method 3550,which involves shaking for 20 minutes rather than soxhletextraction. Samples of 15 grams wet weight were extracted twicewith a total of 100 ml freon, using sodium sulfate as drying agentand silica cleanup. Because the compost samples were of identicalweight within 0.5% of the average, the data for spiked compost arenot corrected for sample size, but are presented as concentrationsin the extract.

GC Method for ouantitation of PAH peaks appearing on a broad bandof undifferentiated material. A reference standard of 29 PAH andaromatic compounds was analyzed in Run 644 to determine theinstrument response factors for the compounds of concern. The

A1-46

AIM Btownediation Systems

standard fingerprint and data is included. Quantitation was by theinternal standard method using OTP as internal standard. Toquantitate the peaks appearing on the "hump** of undifferentiatedmaterial, the instrument was programmed when necessary to force thebaseline to follow the curve of the "hump".

Unspiked Compost Analysis. Table 2. 90 grams wet weight offinished soil compost were removed from the large batch and mixedthoroughly. Two 15 gram samples were removed from this andextracted twice each with a total of 100 ml of freon according tothe modification of EPA method 4.18.1 used throughout thebiodegradation study (extraction by shaking 20 min on a reciprocalshaker). These two samples were analyzed by EPA method 8100 (Runf 649 and # 668), and produced broad "humps11 of undifferentiatedmaterial showing only two very small peaks having the sameretention times as the PAH to be spiked. The results are given inTable 2.

Zero Time Contact of PAH with Compost. Spike added to Extract.Table 3.

The spiking mix, 34 ul, was added to 10 ml of compost extract induplicate, in order to produce an extract representing Zero timecontact between the PAH and the compost. These spiked extractswere analyzed in runs / 773 and #651, and the concentrations of PAHare reported in Table 3. For two compounds the values of the smallpeaks having the same retention times found in un-spiked compostwere subtracted. These values amounted to only 5 % of the zero timePAH concentrations. The concentrations of each PAH for theduplicates were averaged and these values used to calculate anaverage RPD for the duplicates, which was 3 percent. The averageconcentration for each PAH was compared to the expected 6.8 ug/mland found to be 98.6 % for 12 of the compounds, but only 67 % forfour of the compounds. These four were the 5 and 6 ring PAHlocated on the "hump", which did not have corresponding small peaksin the unspiked compost extract.

1 Hour Contact of PAH with Compost. Table 4.

The remaining 60 grams of compost were spiked with 1.33 ml of PAHmix by applying a fine stream from a fine syringe needle directedonto a .5 inch layer of compost, followed by mixing thoroughly.(The amount added should have been 1.36 ml.) After one hour, twosamples were removed and extracted with freon as described above.These extracts were analyzed in runs # 652 and # 653, and the datais presented in Table 4. The RPD, based on the average of 16 PAH

A1-47

ABE* Btorwnediation Systems

for each run, was 7 percent. For each compound and average wasdetermined and this number compared to the value for that compoundobtained in the spiked extract (Zero time). The average recoverywas 57 percent, with a range from 51 to 63 percent. The averagerecoveries for 2 & 3 ring, 4 ring, and 5 & 6 ring PAH were alsocalculated. These did not differ significantly from each other.

1 Week Contact of PAH with Compost. Table 5.

The 30 grams of remaining compost were treated with 0.6 grams offinely powdered and sieved mercuric chloride and mixed thoroughly.The compost was then placed in a closed jar to prevent moistureloss, and aerated briefly by mixing twice during the week toprovide oxygen. In part II of this experiment, bacteria insimilarly treated one day and one. week killed compost wereenumerated and found to be below the method detection limit,<1000/gm, indicating that the bacteria were successfully killed bythe addition of mercuric chloride.

At the end of one week, two samples were extracted with freon andanalyzed in Run # 654 and 655. The values for each are listed inTable 5, and two compounds corrected by subtracting values forsmall peaks in unspiked extract. The RPD, based on the averagerecoveries for 16 PAH was 3 percent. The average concentration ofeach PAH was listed and the recovery calculated based on the valuein the spiked extract (Time 0). The average recovery was 42percent. The average recoveries for the three size groups of PAHwere also calculated, and these did not differ significantly.

ALKANE SPIKING EXPERIMENT

The Alkane mix used was a Sulpelco Mix of C22, C24, C28, and C32,labled 50 mg/ml. It was initially assumed that this meant 50 mg/mlof each alkane, but it was actually 50 mg/ml total of 4 alkanes.Although the concentrations spiked -were 1/4 that intended, it waspossible to obtain useful data.

Unsoiked compost extract. The GC data for the freon extract ofunspiked soil ( Run 668) was was re-processed by the GC integrationsystem to print out the data in terms of alkanes rather than PAH.The GC was programmed for retention times of alkanes based on astandard of #4 fuel. The data is presented in Table 6. Theanalysis found that there was a small peak in the un-spiked compostcorresponding to C28. The duplicate was not analyzed, however, itwas demonstrated in the PAH part of this experiment that theduplicates of unspiked compost extract showed good agreement.

A1-48

ARB Bkwnwdiation Systems

Alkane spike added to compost extract. Zero time contact betweenalkanes and compost•

A 10 ml portion of the unspiked compost extract was spiked with34ul of 25-fold diluted aIkane mix, giving a calculatedconcentration of each alkane in the extract of about 1.7 ug/ml.The extract was analyzed in Run / 665. The data are presented inTable 6, and the value for the small peak of C28 present in un-spiked compost is subtracted from that in the spiked extract. Thisanalysis was not done in duplicate. The recoveries of the 4alkanes in the spiked extract were calculated in terms of theexpected 1.7 ug/ml and ranged from 80 to 99 percent, average 87 %

7 Dav contact between Alkanes and Compost.

60 grams of compost were spiked with 1.3 ml of diluted alkane stockto give an expected 1.625 ug/ml in the extract if 15 grams wereextracted with 100 of freon. (The amount of spike should have been1.36 ml to be equivalent to the 1.7 ug/ml in the spiked extractdiscussed above. For comparison, the concentrations in the extractwill be multiplied by 1.36/1.30.) The compost was then treatedwith 2 % mercuric chloride and stored in a closed container. Thecompost was aerated briefly every 2 to 3 days.

After 7 days, duplicate 15 gram samples were extracted with 100 mlfreon each and analyzed in Runs 663 and 838. The data arepresented in Table 6. For C28, the value of the small peak in un-spiked compost is subtracted. The concentrations of the 4 alkanesin each analysis were averaged and the average RPD of theduplicates was calculated to be 7 %. The average values for eachalkane were compared to those obtained for "zero time contact" inthe spiked extract.

Corrections: The recoveries were corrected for incorrect amount ofspike (1.36/1.30), and for the weight of mercuric chloride (correctsample size/actual sample size - 15.3/15.07), total correction *1.06. The 7 day recoveries ranged from 80 % to 84 %, with anaverage of 83 %.

BACTERIAL ENUMERATIONS

Samples of compost were removed from the experimental batch andenumerated for total bacteria 1 day and 7 days after the additionof the alkane spike and mercuric chloride* Both samples had fewerthan the detection limit, 1000 per gram, whereas prior to mercuricchloride treatment the numbers had been between 10 and 100 millionper gram.

A1-49

ABB Biownadiation Systems

Table 1PAH SPIKE ADDED TO SOLVENT

concentration, ug/ml

Expect 6.8 ug/nl each PAH

Run 645 Run 646 Run 647 Average X 3434ul/iOml 34ul/10al loul/iomlper ul per ul per ul per ul

.224 7.62

.229 7.79

.228 7.75

.222 7.55

.227 7.72

.224 7.62

.221 7.51

.220 7.48

.212 7.21

.229 7.79

.214 7.28

.224 7.62

.216 7.36

.198 6.73

.223 7.58

.216 7.34

Ave .203 .242 .216 .220 7.50

diff .017 .022 .004

RPD = ave diff / av - .014 / .220 = 6.5 percent

Average Recovery = 7.50 / 6.8 = 110 %

napanaaneflupneantflapyrbaachrbbfbkfbapinpdbabpe

.208

.199

.209

.208

.209

.206

.200

.201

.194

.209

.198

.203

.201

.190

.216

.204

.242

.253

.245

.241

.246 •-

.243

.241 '

.238

.236

.251

.235

.243

.240

.225

.254

.240

.223

.253

.231

.218

.227

.223

.223

.221

.206

.227

.208

.225

.208

.180

.200

.204

A1-50

ARB Btomrwdiation Systems

Table 2

DN8PZKED COMPOST

Concentrations in ug/ml in the extract

Two samples of compost, 15.06 and 15.08 grams, were extracted with100 ml freon and analyzed according to EPA method 8100.

Run * 668 Run * 662

nap <. 1 <. 1ana <. 1 <. 1ane <. 1 <. 1flu <.l <.lphe <. 1 <. 1ant <.l .. <.lfla <.l <.lpyr <.l <.lbaa <.15 <.15chr <,15 <.15bbf <.2 <.2bap 0.30 0.304inp <. 2 <. 2dba <.2 <.2bpe 0.373 0.417

A1-51

ABB Biorwwdiation Systems

Table 3PAH SPIKE ADDED TO COMPOST EXTRACT

"0 time contact of PAH with compost"

15.08 and 15.06 grams compost extracted with 100 ml freon each, 10ml spiked with 34 ul PAH mix, and analyzed by EPA Method 8100.

Concentration ug/ml in the extract

Two PAH have been corrected for peaks found in un-spiked compostextract: 0.302 ug/ml subtracted from bap, and 0.395 ug/ml from bpe)

Run 773 Run 651 - Average Percent ofspiked solvent

nap 6.572 6.917 6.75 99ana 7.014 7.187 7.10 104ane 6.827 6.964 6.90 101flu 6.593 6.919 6.76 99phe 6.810 7.034 6.92 102ant 6.645 6.940 6.79 100fla 6.641 6.858 6.75 99pyr 6.687 6.923 6.81 100baa 6.175 6.448 6.31 93Chr 6.666 7.055 6.86 101bbf 4.624 4.759 4.69 69bkf 4.658 4.999 4.83 71bap 6.203 6.600 6.40 94inp 3.821 4.388 4.10 60dba 4.001 5.083 4.54 67bpe 5.569 6.644 6.11 90

AVE 5.97 6.36 6.16 *

RPD 3 % 3 %

* Percent of expected concentrations: 12 compounds = 98.6 %4 compounds = 67 %

A1-52

Jt I)IE Btonrmdlatfon Systems

Table 4

COMPOST SPIKED WITH PAH - 1 HOUR CONTACT

Compost spiked with 22.5 ul spike solution per gran wet compost,and after one hour 15.10 and 15.06 g of compost extracted with 100ml freon, and analyzed by EFA method 8100.

Concentration ug/ml in extract

Two PAH have been corrected for peaks found in un-spiked compostextract: 0.302 ug/ml subracted from bap, 0.395 ug/ml from bpe.

Average2/3 ring4 ring5/6 ringdiffRPD

Run 652

2/3 rinanapanaaneflupheant4 rinaflapyrbaachr5/6 rinabbfbapinpdbabpe

4.1314.2954.3133.8903.9934.030

3.6933.9243.5954.066

3.4343.7463.0253.3833.166

3.76

Run 653

3.9094.0244.0183.6743.7373.776

3.4723.6553.2493.635

2.0193.1192.1672.1763.037

3.25

Average

4.024.164.173.783.873.90

3.583.793.423.85

2.733.432.602.783.10

3.51

3.983.662.93

Percent ofzaro time

605960565657

53565456

5854636151

57

585557

.257 %

.267 %

correction for incorrect apifca voluma = 1.36/1.33 = 1.022Corractad avaraga recovery = 57 % x 1.022 = 58 %

A1-5 3

ABB Bioranwdiation Systems

Table 5COMPOST SPIKED WITH PAH - 7 DAY CONTACT

Compost spiked with 22.5 ul of PAH spike mix per gram of compostplus 2 % mercuric chloride, and after one week, 15.13 and 15.18grams extracted with 100 ml freon each, analyzed by EPA Method 8100

Concentration ug/ml in extract

Two PAH have been corrected for peaks in un-spiked compost extract:0.302 mg/ml subtracted from bap, 0.395 ug/ml from bpe.

Average

2/3 ring4 ring5/6 ringdiffRPD

Run 654

2/3 ringnapaneanaflupheant4 rinaflapyrbaachr5/6 rinabbfbkfbapinpdbabpe

3.3032.4453.2122.9492.9182.841

2.6242.8562.5522.843

2.4332.4972.7851.8612.2452.008

2.65

Run 655

3.4172.5213.4213.0623.0302.955

2.7562.9572.4512.756

1.7591.6292.4541.4381.3072.056

2.50

Average

3.362.483.323.012.972.90

2.692.912.502.80

1006

222.621.651.782.03

2.57

3*012.732.04

Percent ofZero time

503548454343

40434041

454341403933

42

444140

.0783 %

.0723 %

Correction for incorrect spike amount = 1.36/1.33Correction for weight of mercuric chloride =

desired sample / actual sample = 15.3/15*16Total correction = 103 %corrected average recovery = 42 x 1.03 = 43.3 %

A1-54

Btownediation Systems

Table 6ALKANE SPIKE EXPERIMENT

Values for C 28 listed for spiked extract and spiked compost havebeen corrected by subtracting the concentration of the small peakfound in unspiked compost extract, 0.145 ug/ml.

C22C24C28C32Ave

Run 668UnspikedCompost

<0.05<0.050.145

<0.10

Run 665"0 time"Spiked Extract1.3371.3371.6831^497

Percent ofExpected1.7 ug/ml

80 %80 %99 %88 %87 %

C22C24C28C32AveragediffRPD

Run 6637 DaysSpikedCompost15.08 g

1.0981.0621.3521.3691.2200.0787 %

Run 8387 Daysspikedcompost15.06 g

1.0170.9561.2890.9921.064

Average

1.0581.0091.3211.1811.142

% of "0 time"corrected

(1.36/1.30)(15.3/15.07)

83.9 %80.0 %83.2 %83.6 %82.7 %

A1-55

Btorwrwdiatkxi Systems

REF ': RTU: 2.886 HON-REF '4 RTW: 2.068

LEVEL: i RECHLIBRATIONS: iCALI

123

' 45691811121314151617IS*

, 19282122232425

' 26272829

RT3.6265.8825.1345.5547.4728.32311.38913.44813.77116.21216.81117.35318.41521.42521.56822.98825.24225.93826.73829.81329.93933.27933.36234.43239.63539.79641.883

LV AHT1 5.0000E+*!1 5.8080E+811 5.0060E+011 5.8008E+011 5.0088E+811 5.8860E+811 5.8868E+811 5.0800E+011 5.0868E+011 5.8000E+811 5.8068E+811 5.0088E+811 5.8080E+011 5,0088E+011 5.8880E dl1 5.8008E+811 5.8888E+811 5.8888E+811 5.0e68£+611 5.0888EH011 5.080«E+8t1 5.8600E+011 5.8000E+811 5.8888E+811 5.8980E+811 5.8088E+811 5.8d68E>01

AMT/AREA2.6795E-842.7428E-842.7281E-842.7174E-842.7501E-843.8587E-042.4237E-842.5621E-842.3694E-842.4282E-042.3326E-842.3182E-842.3775E-W2.3987E-942.3922E-842.4986E-842.3414E-842.3281E-042.4982£r«42.3291E-642.4981E-042.2886E-842.3755E-842.3956E-042.4338E-842.8591£-»42.4725E-W

CALt NAME1 TOLUENE2 ETHYL BENZEN

. 3 H'P-XYLEN4 P-XYLENE5 TRINETHYLBENZEN6 INDAN9 NAPHTHALENE18 2-CH3-NAPHTH11 1-CH3-NAPHTH12 ACENAPHTHALENE13 ACENAPHTHENE14 DIBEN20FURAH15 FLUORENE16 PHENANTHRENE17 ANTHRACENE18 OTP/ISTD19 FLUORANTHENE20 PYRENE21 FTP22 BENZOANTHRACENE23 CHRYSENE24 BENZ-B-FLUOORAN25 BEHZ-K-FLUORAN26 BEN20-A-PYRENE

.27 INDENOPYRENE28 D1BENZOANTHRACEN29 BENZOPERYLENE

CALIBRATION OPTIONSRF of uncalibrated peaks ..Calibration fit ...........Disable post-run RT updateISTD Peak I ...............'ISTO A«T ..................SAMPLE A«T ................NIL FACTOR ................

1.0088E+88PYES185.8880E+01

PAH GC CALIBRATION MIX

/IT

6.113

A4/7

11.32712.1K

j.uj«

14.95J

18.845

* t O1O

i/'2w18.447

ii.ti*

2^.835

27.296

T 31.591

29.9*5

a.tti34.524

'35.513

37.142

tt.91341.316

END OF SIGNALiClosim sianal file H:C514C275.BNAStoring report to H:Q514C275.RPA

RUN* 644

A1-56

AUG 26, 1992 15:36:21

SAHPLEi il.B888E+0e

SIGNAL FILE: WQ514C275.BNA

Closing signal file H!ft514CE£E.BHAStorin* report to H:95l4CEE£.RPA.

RUNI AUG .?6, 1992 16:29:34

SAMPLE! 2

SIGNAL FILE: H:Q514CEEE.BNAREPORT FILE: H:ti514CEEE.RPflISTD

RT2.9823.53211.38916.21216.81117.17518.41521.42521.56822.98825.24225.93829.81329.93933.27933.36234.43239.63599.79641.883

RT2.9623.33211.38916.212

, 16.81117.17518.41521.42521.36822.98825.24225.93829.81329.93933.2/933.36234.43239.63539.79641.883

TYPEPB86PBPSPBPBPBPBB6PBPBPBPVV8BVveBBPVVBBB

CALI

912131415161718119282223242526272829

AREA44B1893295363868036869693

38846308602953228295329367296992855828866298812948328875268222593228298

AMOUNT.188.269

7.8817.3587,122.1937.8667.1886.988j^« WW6.8816.8396.5797.1186.7416.9896.8426.4557.3346.921

yjOTH HEIGHT.817 425.819 942.832 15483.836 14186.837 13991.834 338.836 13/49.838 13381.839 12775.843 79408.838 12771.848 12365.848 U828.842 11369.954 9218.852 9913.861 784ft.896 4642.895 4569.189 4312

NAME

NAPHTHALENEACENAPHTHALENEACENAPHTHENEDI6ENZOFURANFLUORENEPHENANTHRENEANTHRACENEOTP/ISTDFLUORAHTHENEPYRENEBENZOANTHRACENECHRYSENE6EHZ-B-FLUOORANBENZ-K-FLUORANBENZO-A-PYREMEINDENOPYRENEOIBENZOANTHRACENBENZOPERYLEHE

TOTAL AREA* 671523WJL FACTOR-1.8888E*8eISTD AHT*5.8888£+81

RUN PARAMETERSZERO - 8ATT 2* = 1CHT SP = 8.5AR REJ = 8THRSH = 1

Run 64534 ul PAH Spike in 10 ml FraonRUN I 645START

rAUG 26, 1992 It:2?:34

A1-57

3.532

17.175. 16.21?

16.811I

13.415

25.24325.938

34.432

41.683

22.

signal til* H:85140861.SNAStoring report to H:&514DB61.RPA

RUN! 646 AUG 26, 1992 17:22:41

SAMPLED 3

SIGNAL FILE: H: 85140861. BNAREPORT FILE: H:Q5i4M6i.RpftISTD

RT2.9813.53011.36816.21016.31818.41521.42421.56722.98825.24225.92929.81429.939

" 33.23133.36634.43639.64239.86241.896

RT2.9013.53811.38816.21816.81018.41521.42421.56722.96625.242

25.92929.81429.93933.28133.36634.43639.64239.86241.898

TYPEPB86PBPBPBPB6886PBPBPBPVVBPVVBB6BVV9BB

CALi

9121315161713419 .262223242526272829

HREA34i

1301*35181367143695535788362933575220880S36213360653566135494362263597735223325393128634172

AHQUHT.882.3128.2388.6648.3288.2168.3748.25450.6868.1838.1938.8168.5367.9748.2488.1447.6418.6338.154

WIDTH HEIGHT.818 313.819 U17.833 13015.837 16611.037 16639.037 16155.037 16452.039 15291.043 30839.040 15170.041 14634,.042 1429fr..042 H958.855 10537.051 11346.061 9626.995 5681.694 5535.189 5211

HAKE

NAPHTHALENEACEHAPHTHALENE ,ACEHAPHTHEHEFLUGREHEPHENANTHREHEANTHRACENEOTP/ISTDFLUORAHTHEHEPYRENEBENZOANTHRACENECHRYSEHEBENZ-B-FLUOORANBENZ-K-FLUORANBEHZO-A-PYREHE ,IHDENOPYREHEOIBENZOAHTHRACEHBEHZOPERYLENE

TOTAL AREA* 775188MUL FACTOR*1.0080E+06'ISTD AMT-5.6686E+61

RUN PARAMETERSZEROATT 2ACHT SPAR REJTHRSHPK UD

616.5818.64

RUH 64634 ul PAH Spika 10 ml Fr«on

RUN I 646START

AUG 26,'1992 17*22:41

3.538

A1-58

n.388

16.21816.81*

18.415

25.24225,92?

34.4%

Closing signal fil* H:Q514E7E1.BNAStoring report to H:Q514E?E1.RPA

RUNf 647 ) AUG 26, 1992 18:16:86

SAMPLE! 4

SIGNAL FILE: H:Q5l4E7Ei.3NftREPORT FILE: H:tt5l4E?El.RPft•ISTD

RT2.9623.53311.38816.21016.86318.41521.42121.56522.966

• 25.23925.92529,88929.93433.26333.35i34.42339.66739.77541.646

RT2.9623.53311.36816.21616.868

- 18.41521.42121.56522.98825.23925.92529.88929.93433.26833.35134.42339.68739.77541.846

TYPEPBB8PBPBPBB8PB68PBPBBBPVVBPVVBPBPVVBVB

CALt

9121315161718119262223242526272829

AREA27?378936697929981926596839414

2927899640958589519222921495618769747478638316

AMOUNT.669.891

2.2312.3542.3852.1812.2732.229

Oo.otro2.2342.2892.8642.2732.6882.2482.8861.8662.8812.835

WIDTH HEIGHT.313 265.321 294.833 4648.936 4595.938 4466.837 4228.036 4395,041 3846.642 88719.939 4161.341 3864.939 3796.644 3569.652 2951.854 2924.662 2362.691 1372.694 1257.112 1243

NAME

NAPHTHALENEACEHAPHTHALENE .ACENAPHTHEHEFLUOREHEPHENANTHREHEANTHRACENEOTP/ISTOFLUORAHTHENEPYRENEBEHZOAHTHRACENECHRYSENEBENZ-B-FLUOORAN •BEHZ-tC-FLUORANBENZO-A-PYREMEINDEHOPYREHEDIBENZOANTHRACENBENZOPERYLEHE

Run 64710 ul PAH Spike is 10 ml Freon

RUN I 647 AUG 26, 1992 18:'16:66START

1"___ ____

3.533

11.388

" 16.21816. SW

18.415

added standard, otp'22.9W

25.925

TOTAL AREA= 348593MUL FACTOR=1.6688E+eeISTD

RUN PARAMETERSZERO =ATT 2^ =CHT SP =AR REJ =THRSH =PK yo =

ei6.56I6.84

I3.36t34.423

41.646

A1-59..

Run 773PAH Spike add«d to Compost Extract

RUN * 773 SEP 4, 1992 16: 11:21START

Closing signal fil* H:Q52053C9.BNAStoring report to H:Q52853C9.RPA

RUM*

SIGNAL FILE: H:flS2053C9.BNAREPORT FILE: H:Q5£953C9.RPfiI3TD

RT3.53811.321316.22316.82318.42821.43621.58022.91325.25525.73125.94823.87728.67229.82729.952

. 31.75631.83832.71033.18733.29533.38833.63534.14234.45134.78535.25836.81536.299

. 37.34538.92639.66839.82141.167

TYPEBBPBPBPBPBPBPBPBPBPBPBP6PBPBBBPBBBPBPBBBBBPBPBPBBBVBPBPBPBPBPBBBBB

AREA111823619384883089429278308682932121189729936435

383161889747

2793328255554641592777

21399286953884285623661153529872182128521844179165751477125459

MIDTH.828.832.836.837.836.836.839.642.839.037.846.666.847.041.042.848.841.041.063.846.045.073.075.663.352.091.883.052.065.080.079.078.106

SEP 4, 1992 10:11:21

SAMPLE! 1

HEIGHT923

1491914269140451367113901124868439912955197

12521275267

113121132323326223829578667644373633

7611496547428385557869

351931494616

nr3.53«

11.329

16.22316.823

IF

21.511-22.913

25.25525.948

A1-60

Run 651PAH Spike added to Compost Extract

RUN*

SIGNAL FILE: H:QSi51?9E.BNAREPORT FILE: H:fl515199ii.RPfiISTD

RT3.5316.38211.36616.29816.38718.41221.42121.56322.96825.23925.71925.92727.15623.97328.66929.81529.93938.82631.74431.82732.76232.96733.16933.28133.36633.616

' 34.12934.43634.68635.24736.66336.28237.33238.91439.64239.79741.087

TYPEPBPBSBPBPBPBPBBBPBPBPBBBPBVBPBP3BBPBPBB8PBPBPBBBBBPBPBPBPBVBPBPBBBPBPBBBPB

AREA1119545

36343314713174636944312833884621345931146569

316191286692948

294383612516647346594751389677

22189223753631296236626196727632165112620195135191771898236273

yiDTH.620.625.032.835.037.036.037.938.042.939.041.940.078.641.861.641.042.966.951.640.039.078.658.647.043.975.684.662.955.085.082.052.062.096.078.076.108

AUG 26, 1992 21:48:13

SAMPLE* 8

HEIGHT956370

1560614916142761416814239136918406713285248

13623276278258

11833126122S5238275202295196793086158045858234666532428357545895

489141294691

RUN i 651 AUG 26, 19?2 21:43:13START

IF

11.386

A1-61

22.908

Closing signal fil* H:Q5161F44.BHAStoring report to H:Q5161F44.RPA

RUN* 668 AUG 27, 1992 16:24:35

SAMPLE* 26

SIGNAL FILE: H:Q5161F44.BNAREPORT FILE: H:Q5l61F44.(?PftISTD

RT22.96227.15828.97128.66931.83132.69133. 17233.46733.62534. 14634.42134.68835.23835.99836.28437.33438. 91841.853

RT22.98227.15828.87123.66931.33132.69133.17233.46733.62534.14634.42134.68835.23835.99836.28437.33438.91841.858

TYPEPBPBPBPBVBPBPBPBBBPBPBPBVBPBBBPBBBBB

CALftm21

2425

26

2729

AREA289113

248191975365866278613963523288613241992259428961144314849941756

AMOUNT58.866.859,244.186.157.158.155.317.842.696.384.476.628.566,274.7511.166.417

U10TH HEIGHT.842 82489.026 156.857 296.047 2fc?.038 296.038 293.061 -.194.079 292.064 • 916.086 599.072 365.056 591.883 521.085 489.051 372.079 661.889 938.095 389

NAMEOTP/ISTDFTP

BENZ^-FLUOORANBEHZ-R^FLUORAN

BF-NZO-A-PYREME

INDEhSPYRENEBENZOPERYLEHE

TOTAL AREA= 239992 -FACTOR=1.8008E+88

Un-spiked compost/ Praon ExtractRUN I 668 AUC "2771992 16:24:35START1IF

IF

27.J5B.28.67128.W9

31.831

'&!*37.334

A1-62

22.982

649 AUC 26, 1992 28:82:04

SAMPLE* 6

SIGNAL FILE: H:Q51500BC.BNAREPORT FILE: H:fl51580eC.RPAISTD

RT6.38222.89827. 17823.86328.65531.73931.82132.78133. 16433.46733.62134.14534.43134.63135.23535.99836.28337.32933.98641.854

RT6.38222.89827.17823.86828.65531.73931.82132.78133. 16433.46733.62134. J4534.43134.68135.23535.99836.28337.32938.98641.854

TYPEPBSBPBPSPBVBBBVBPBVBBBPBPBPBVBPBPBPBPBBB

CALt

m21

2425

26

2729

AREA553

21 65797810598726436821848224710123668389713881871268218681872225239501581

AMOUNT.131

58.083.238.251.287.153.162.249.488.229.871.735.297.444.618.443.254.535.916.373

yiDTH.025.044.875.868.056.040.839.863.106.855.075.889.077.857.033.079.049.067.073.087

NAME

HEIGHT374

79284216292258276288279352384814581281549528392364561841384

OTP/ISTOPTP

BtNZ -FLUOORAHBENZ-KXfLUORAH

BENZO-A-PYREHE

INDEfofiPYREHEBENZOPERYLEHE

TOTAL AREA= 243884MUL FACTOR=1.8888E+0eISTD AMT=5.8688£+81

RUN PARAMETERSZERO = 8AH 2* = 1CHT SP = 8.5AR REJ = 8THRSH

Un-spiked compost, Freon Extract

RUN I 649 ~AWT26rT992^28:82:04START

6.382

PK UD= 1= 8.84 A1-63

added standard, otp

.27.179,28.1*326.655

RT3,5316.36211.36616.20816.80713.41221.42121.56322.90625.23925.71925.92727.15028.07328.66929.81529.93930.82631.74431.82732.70232.96733. 16933.28133.36633.61634. 12934.43634.68635.24736.66336.28237.33238.91439.64239.79741.087

CAL*

9121315161718&19

2021

2223

2425

26

Z?2829

AMOUNT.262.128

6.9177.1876.9646.9197.9346.94656.0666.858.1386.923.361.162.2226.4487.055.235.172.154-111.325.1594.7594.999.851.6946.968.461.633.493.262.4731.2634.3885.8837.039

UAUP *r* i \ 1 1 / ^**nrinc u I n 1 I *Ni\U J\J Lff-J

NAPHTHALENEACENAPHTHALENEACENAPHTHEHEFLUORENEPHENANTHRENEANTHRACENEOTP/ISTDFLUORANTHENE

PYRENEPTP

BENZOANTHRACEHECHRYSENE

BENZ-B-FLUOORANBENZ-K-FLUORAN

BENZO-A-PYRENE .

1HOENOPYRENEDIBENZOANTHRACEHBENZOPERYLEHE

TOTAL AREA= 697721MUL FACTORS.0000E+00ISTD AMT=5.00eeE+81

RUN PARAMETERSZERO =ATT 2* =CHT SP =AR REJ =THRSH =PK UD =

616.5016.04

RT3.53811.32816.22316.82318.42821.43621.58622.91325.25525.73125.94828.877-28.67229.82729.95231.75631.83832.71833.18733.29533.38933.63534.14234.45134.79535.25836.81536.29937.34538.92639.66839.82141.107

CAL*

91213151617ISi19

20

2223

2425

26

272829

AMOUNT.2626.5727.8146.8276.5936.8106.64556.0806.641.1836.667,257.176

6.1756.666.131.151.140.1334.6244.658.898.67+6.505.362.705.496.284.515.986

3,8214.0015.964

TOTAL AREA= 661484MIL FACTORS.06edE+60ISTD AHT=5.0006E+ei

RUN PARAMETERS2ERO = 8AH 2* = 1CHT SP = 0.5AR REJ = 6THRSH = 1PK UD = 6.64

NAPHTHALENEACENAPHTHALENEACENAPHTHENEFLUORENEPHENANTHREHEANTHRACENEOTP/ISTDFUUQRAHTHENE

PYRENE

BENZOflNTHRACENECHRYSENt

BEMZ-B-FLUGORANBENZ-JC-FLUORAN

BENZO-A-PYRENE

INOENQPYRENEDIBENZQANTHRftCENBENZOPERtLENE

A1-64

1 hour Contact, PAH Spike in Compostsignal file H:85153274.BHA

Storing report to WQ5153274.RPA

RUN* 60*3

SIGNAL FILE: H: 65153274. BNAR£?'J3T FILE: H:Qb 153274. SPAISTD

RT11.38716.2*816.38818.41221.42921.56422.98625.23825.92627.15228.67829.81829.93538.87131.83533.15533.27333.35733.61634.14234.42834.68835.24536.88636.28837.33838.91839.62239.78141.868

TYPtPBPBPBPBPBB8PBBBPBPBVBPBBBPBVBPBBBBBPBPBPBPBVBPBPBPBPBPBBB88

AREA1?61713181188151638117875172432192881619717149115518431523915947166668318696681867434182584155991778227218959172438371297388312

15161

U1DTH*o3o.837.636.936.836.833.942,939.848.976.972.848.841.889.848.923.943.843.874.878.968.955.888.988.842.972.878.982.973.118

AUG 26, 1992 23:34:12

SAMPLES 18

HEIGHT988682558719774578977524

8655369887154253242

63646412

18928472

37754699773535

4312534472396368568797

198417772387

KUH • 653START

IF

AUG 26, 1992 23:34:12

IF

11.387

J6.2M16.888

13,412

2f>fti'

4UM

22.9W

A1-65

RTC.53-511.30716.20916.88918.41421.42921.56422.89925,23825.92527.15828.87828.67829.81829.93538.82531.83132.69433.15133.27333.35533.62334.13634.43834.68835.24536*89436.28837.32638.99939.62339.78841.858

CAlft

91213151617181192821

2223

2425

26

272829

AMOUNT-8784.1314.2954.3133.8983.9934.83858.8683.6933.924.243.163.1%3.5954.866.395.669.426.3513.4343.543.855.9894.648.738.796.4%.635.6661.2293.62S3.3833.561

TOTAL AREA* 562419KUL FACTOR*!.9668E+60ISTD ANT=5.6669£+91

RUN PARAMETERSZERO * 6ftTT 2* * 1CHT SP » 6.5AR REJ = 8THRSH = 1PK UO = 6.94

NAPHTHALENEACEMAHHTHALENEACENAPHTHEHEFLUOREHEPHENANTHRENEANTHRACENEOTP/JSTDFLUORANTHENEPYRENEFTP

BENZOAHTHRACENECHRYSENE

BENZ-B-FLUOORMBCNZHC-FLUORAN

BENZO-A-PYKEHE

INOENOPYRENEOIBENZOAMTHRACENBENZOPERYLENE

RT11.38716.28316.86818.41221.42821.56422.96825.23825.92627. 15228.67829.31929.93539.87131.83533.15533.27333.35733.61634.14234.42834.68835.24536.88636.28837.33638.91839.62239.78141.666

CAL*9121315161718&192621

2223

2425

26

272829

AMOUNT3.9694.9244.6183.6743.7373.77656.8663.4723.655.ass.2383.2493*t>3«>.225.156.623

2.81S2.321.779.5713.421.464.518.432.269.554.8462.1672.1763.432

TOTAL AREA* 481681HUL FACTOR=1.8668E+68ISTD AMT=5.6668E+61

RUN PARAMETERSZERO =AH 2* =CHT SP =AR REJ =THRSH =PK UD =

816.5616.64

NAME L53NAPHTHALENEACENAPHTHALENEACENAPHTHEHEFLUORhHEPHENANTHRENEANTHRACENEOTP/ISTDFLUORANrHENEPYRENEPIP

BENZOANTHRftCENECHRYSENE

BEHZ-B-FLUOORANBENZ-K-aUORAN

BEN20-A-PYRENE

INOEHOPYRENEDIBENZOAHTHRACEHBENZOPEftYLENE

A1-66

Run 6521 hour Contact, PAH Spike in Compost

tfttj 3IGHHL

WW I 652START

IF

AUG 26, 1992

Closirn signal f i l e Hsa5I52685.BNflStorms report to H:Q5152665.RPA

1

RUHI 652

SIGNAL FILE: H:REPORT FILE: H!ISTD

RT TYPfc3.533 BB

11.387 PB16.289 PB16.869 PB18.414 PB21.428 PB21.564 PB

, 22.899 P825.238 BB25.925 P827.158 BP28.878 W28.678 PV29.818 PV29.935 VB38.825 W31.831 VV32.694 W33.151 VV33.273 W33.355 W33.623 VP34.138 W34.438 W34.688 W35.245 VV

WWPPVVVPBB

HUG 26, 1992 22:41:89

SAKfLEi

Qbl52665.BNA

36.28637.32638.96939.62339.78641.658

AREA322

174981816618985168601714S1729b28612716194173641861673866

158471676516ZS27661755144815462153123526407717352366832552945261824745667127651215614789

WIDTH.826.632.035,«37.836,837.838.943.838.641.668.846.648.642.843.664.886.059.679.854.853.669.696.666.673.091.686.673.067.695.695.102.183

HEIGHT266

928195328524784776767551

7974976297619247281282

63486429426574495386

47494887856709

4364690599396

618

224119852481

22.89*

A1-67

Closint ftisnal fil? HSQ5153EE4.BNAStorin» report to HJQ5133EE4.RPA

RUN* 654 AUG 27, 1992

SAMPLE*

7 Day Contact, PAH Spike in CompostRUN I 654 AUG 27, 1992 66.-27:i6STARTHIP

U

SIGNAL FILE: H:fi5153EE4.8HAREPORT FILE: H:Q5153EE4.RPnISTD

RT TYPE11.366 PB11.536 B815.196 PB16.218 PB16.868 PB18.413 8821.421 PB

. 21.565 PB22.899 BB25.239 PB25.925 PB27.148 W28.678 VV28.662 PV29.816 (£p29.935 W36.827 VV31.745 VV31.825 VV .33.163 <JV/>33.272 VV33.357 W33.625 VV &34.136 W 34.436 W34.696 W35.246 WL35.999 c»-36.286 W37.329 PV38.914 PV39.619 0V39.785 VB41.060 BP

AREA1401980S656

1035714165127581255312216266493115221261917011194867

112691174517801935169012431697218811

. 5257537513257355136262140286924324964786980789997

WIDTH.033.034.637.036.037.837.036.639.843.846.041.695.666.051.643.046.075.071.054.660.057.055.088.113.073.077.101.096.676.869.898.098.106.104

HEIGHT7686393294

47756458571456695201

8669548575142297382281

43714272393494522343

32313260996791

3632770599398632596830

133713491664

11.386

15.1M

added standard, otp22.899

.27.14325.925

H.3S234.438

38.91499.UI

A1-68

Ciosins «i»al file H:B5154B5e.BWStarlfH rwrt to H>85154B58.RPfl

Run 6557 Day Contact, PAH Spike in Compost

RUN* 65S 27, 1W2 81:28115RUN I 655START

AUG 27* 1992 81:28:'l5

SIGHAl F1L£: W85154B58.BNAREPORT FILE! ^85154836, KPflISTO

RT11.38711.33713.191I6,2»916.88918.41221.420

, 21.36422.9*625.23325.92327.14728.87228.66629.81029.95533.16933.27133.35533.62534.137

. 34.42834.6*835.122

' 35.24836.886

* 36.28837,33233.56339.61539.77941.851

TYPEPBPBPBPBPBP8PBPBPBP8PBPBysP8PBeePB88BBPB?BPBBBPSBePBPBpePBPBBBBB

ftREfl14628

82tf665

1876615210133561314312011

28819812289131711243666812

19913U477

5417»7487sr&3839

1193316374b6

16221928H862124437?39*95578

18281

U10TH.833.834.636.636.*37.837.937.838.842,83d.848.877.946.949.841.044.839.944* OTO.874.886,967.854,636• 800,888.852.966,688.988.878.195

HEJGHI7344487385sear

6927682859395569

8339693165443278241277

44144316154

S792683838598

29W582218 .399362368338

. 82S —124111971628

IF

11.53?

15.191

16.899

25.23825.925

41.051

A1-69

22.988

H H It H M H

•ui xiv>

â -HgSoa> **•nr- •

*§i £M omCfl*»• M M rproro

§Si—

CP fTlNIt— +s

s

ig jgliiiSi3^l522-*O mi m-i-i£ Z9O X Xm rnm ni 2>ffi W ni nis

R

3*m

S " B

^* -H3FSernPM OlCJI»• H

£» —m*D

01

w tj

ui 01 -ro roro MM

15 f*B*

**

STOP

Closing signal file H:Q5158B£A.BNCStorins report to H:ft5158BEA.RPT

RUN* 668 AUG 27. 1992 85:55:54

SAMPLEf 17

HEIGHT651168

8194528532835

Run 660Alkanes added to Freon Solvent"RUN f 668 "*UG ^7,^1992 85:55:54SMRT

IF1SIGNAL FILE: H:Q5158BEA.BHCREPORT FILE: H:Q5158BEft.RPrISTD

RT17.17522.79422.981-26.528"28.77831.588-32.915<39.849

RT17.17522.78422.981

" 26.52828.77631.53832.91539.849

TYPEPBPPPBPBPBVVPBBP

CALt131923*22252829 .

AREA1383365

2846815578*5559*23767811*7865 •

AMOUNT.338.889

58.8881.3611.358.581

1.7131.922

WIDTH.835.836.642.833.833.396.848.875

NAMECISC19OTP/ISTDC22C24C27C23C32.

h

29211744

TOTAL AREA= 234738MUL FACTOR=1.8688E+8813TD

17.175

RUN PARAMETERSZERO =ATT 2A =-'T SP =^ REJ =THRSH =PK UD =

818.58e8.84

added stahdard, otp22.981

26.528 C22

28.7/8 C24

31.581

32.915 C28

39.M9 C32

A1-71

RT CALi AMOUNT2.835

11.543 922.982 23* 5824.413 2924.56124.33925.624 2125.96626.84826.21726.427 2226.95227.15827.43327.665 2427.89428.87123.43428.677 2529.88529.24929.983 2638. 17938,322 2731.18931.39231.75131.831

; 32. 128, 32,173 28

32.34832.69332.91333. 172 2933.46733.62533.79334.93834.14634.421 3834.68835.81135. 12535.23835.62335.99436.28536.51937.85537,33437.45238.918 141.86141.34342.19843.833

TOTAL AREA= 258981MUL FACTORS. 8888E+91STD AMT=5.9988E+91

.936

.181

.868

.857,854.979.135.994.876.999.953,184.857.975.968,969.223.17?.188 ..948.888.376.253.962.916.984.154.155.869.988.122.168.145*.188 \.332.839.838.839.784.337.479.187.891.332.127.587.278.128.419.752.267 ,.886-<.428.337.381,246

8

NAME

C12 IBOTP/ISTDC26

C21

C2?" *»

C23

c&r*nt>

C25

C26

C27

C28

C29

W^H-X

Run 668Freoa Extract of Soil compost(GC programmed for Alfcane analysis)RUN I 668START

AUG 27, 1992 16:24:35

rff.835

r 11.543

RUN PARAMETERSZERO - 8AH 2A = -1CHT SP = 8.5AR REJ = 8THRSH = 8DK un = 0 04

A1-72

added standard, otp

'«.#42.1H43.133

22.992

RT2.8354.2656.3857.55411.53815.19422.96824.416£4.56225.338£5.61825.73625.96226.84426.21926.52626.95427.14627.53827.66527.98927.97528.87228.42528.66528.77129.25529.35329.44829.77529.88729.98638. 14738.82631.13231.42731.73431.83332.12332.37832.69432.91833. 17833.39333.46733.62233.78934.14134.42534.68934.88834.99835.12135.24736.83636.28537.85837.33237.44838.98839.85339.72341.85741.33943.825

CALf

69n23*28

21

22

24

25

26

27

28

29

38

AMOUNT.838.843.993.870.179.138

58.986.862.858.996.135.825.181.868.897

1.898.144.311.887.886.114.853.183.116.233

1.962.198.877.964.963.913.274.814.977.934.312.157.2+5.978.885.2731.497*.633 >.968.215.872.866• DOC*.368.492.111.926.119.363.519.387.467.627.261.873

HAM

TR1IC12C14DTP-C29

C21

C22

C23

C24

C25

C26

C27

C28

C29

_.«i

RUN ISTART

TR1METHYLBENZEH

663 AJG 27, 1992 6857:48Alkan« SpiXed Soil Compost7 Day Contact, Freon Extract

,122,459,425,242

TOTAL AREA= 274844*UL FACTOR=1.8986E+8eISTD AMT=5.8888E+ei

RUN PARAMETERSZERO = 6AH 2*CHT SPAR REJTHRSHPK UD =

-18.5888.84 A1-74

11.538

15.134

added standard, otp

26.526 C22

C24

I32.9J8 C28

39.723

43.125

C32

22.9W

'- Run 838RUN 1 S33 SEF 16.. !*»? 13:36:35 "

RT CAL*2.843

6*335?!S85 7

'9.67411.566 915.225 112!. 833 Id':2.948 23*:3.898 28_4.454^4.599

4.671.4.92825.175?5.368 21

• .:5,78226.88126.238••b.4366.568 22

. j.756^6.988

1:7.188:?.48527.575:?7.783 24•7.93428.18528.293

Js! 473^8.78523.382 2579.956.9.28629.47229.584!9.852

938 26bvi 21738.438;0.533Jd.862'38.988 27

- ;!292^1.43231.465

1.781t.873

oi.93572.9622.155 28

, 2.48132.735^2.956^.285 29

^3.46533.665"i.825J.932

J4.185M.463 384.7424.925

15.078

AMOUNT NAME

:S KM.989 332.998 C18.962.285 C12,136 CH.487 PHYTANE

56,898 OfP/ISTD.376 C28.182.965.988.993.182:.125 C21.315.995,175.985

1.817 C22.858.142.932.353.874.988 C23.189.172•858 35.179

•JS 35'255•188 35.674•289 36.855.956 C24 36.336•386 36.417•112 37.116.18/ 37 2*8•875 37/484 K/0— »-112 38.262.178 C25 38.971• 175 -M IIA r* "2 Q s,-. O7il iw V,, d^L J•J24 39.781•?£6 48.221•185 41.131.182 C26 41.421.872 43.188' ^t& 43 503-938 43;8ie

!l84 48'466

—f Alkane Spiked soil compost

.885

.888

.137 '

.685

.292

.152

.585 !

.8551.528.912.936 i449 -• 77£.

.158

.626

.488

.395

.33214fl• iTW

.579 ,

.688 '

• l l6 TOTAL AREA= 318657•4« MUL FACTOR=1.9888E+88.998 ISTO AMT=5.8ee8E+81.898 C27.121.155

1,434^QfC$ ^^9Q* EvO CtO

•*™ RUN PARAMETERS1.98/ 2ERO = 8.872 An 2A = -1•255 CHT sp = e.5-8*6 AR REJ = 8.328 C29 THRSH = 8•514 PK UD = 8.84.121.253

1

A 1-75

7 Day contact/ Frson Extract

'K843

' 4.285

'6.335' 7.535

18.6/4"11.563

iI\f 15.225IfIj) 19.261Ipi. 333 adA«d standard

V.&JJ 8w\5£(wv&xs1j&£38

hte

01&656S C22

%5lOH r"5 A

iH5Mr SSSfe?LtfjiBE^J .956 C28

-«SwPMwTtoP

f ^* •*•» iv-i

£38.262f^*"3fc.Wh r^^ -j vnvn \fj&kaii

C j* 13JA «•'«

1 43.J88^9;W8

M8.466I

22.948

663

3NAL FILE: H:Q515668C.BNA S£?ORT FILE: H:C513B68C.RPft

.-TORT

2.8354.2656.3857.55411.53815.19422.96824.41624.56225.33625.61325.73625.96226.844>6.2i826.52626.95427.14627.5367.665

•27.99627.97528.87228.42528.66528.77129.25529.35329.44629.77529.88729.9660.147<8.82631.13231.42731,734- 833x_12332.376T2.694:2.91833.17833.393

- 3.4673.62233.78974.1414.425J4.68934.886'4.996:5,121"35.24736.666.2857.65837.332\4480.988.9.0539.7231.0571.3393.025

TYPEBVPBBB86PBWPBPBPBVBVBBBPBBBVBVBPBBBVBVBVBBBB8PBPBBBPB88BBPBBBPBPBPBPBPBPB8BPBPBBBBBPBBBBBVBBBPBPBPBVBBBP8BBBBPBPBVB86PBBBPBPBBBBB

AREAJ55176378284728528

282965252237388546162416277393445658b1264352351464217744446944431343731125327753

111255313148126563899528434611166077257627687135382692692146619964511674461473266912451895254711413545555949718641727982

UIDTH.016.625.625.031.034.633.642.649.639.059.066.046.837.033.638.034.047.072.041.039.049.932.044.648.056.033.847.648.645.866.016.877.616.631.022.697.644.656.643.648.664.842.123.662.847.669.648.871.678.656.836.656.644.659.679.655.161.869.666.871.871.679.692.184.892

AUG 27, 1992 88:57:4S

SAMPLE! 26

HEIGHT159119253151358233

886928616216913743184138173

2165267291142151158112282155288215415618896775624257167164218243296169121291242934774312857936333475982673217644643?3783126122878361313165339276178

SIGNAL FILE: H:Q52S6Ci-3.8HA $<REPORT FILE: H:Q5236CE3.RPA'ISTD

RT2.8434.2856.3357.58516.67411.56315.22521.83322.94623.89824.45424.59924.67124.92025,17525.36025.78226.66126.23826.43626.56626.75626.98827.18827.48527.57527.79327.93428.16528.29328.37628.47328.78528.86229.85629.28629.47229.58429.85229.93838.21738.43838.53338.86238.98831.15231.28231.43231.46531.781

• 31.87331.93532.86232.15532.48132.73532.95633.28533.46533.66533.82533.93234.18534.46334.74234.925

TYPEPVPBPBVPBBPBVBVBPBPBPBBBBBPBVBBBPBPBPBBBBGPBPBPBPBBBBBPBVBPBBBBBPBBBPBBBPB86PBBBPBVB

- 86PB8BPBBBPBBBPBBBBBBBBBPBPBPBPBPBVBBBBBBBPBPBVB

ftREA1454543774122618655722854

210766156443127236939342V526132348173S357428524359813614833123694617232462257578864629129847245136904737157365211585443431364265126389775491177841337858865266463492859424336418753566'.381!167A1-76 512

WIDTH.015.025.825.632.933.036.332.084.041.638.653.946.856.949.654.986.639.644.661.952.633.986.047.616.638.944,848.853.633.033.634.673.651.632.634.838.047.033.075.656.959.649.038.634.635.636.832.622.636.646.834.041.041.636.852.638.043.647.062.874.642.072.086,072.057.837

in T •*• CM — IN.rs, in co -* oy LI

HEIGHT161304247217136475295487

8469869713511312213313211657115326111421644721614664811915314631512511117228720786462661611646105238239179695215285139148941792782447291691761642832323124769951122249688321629228

OS ijv Os — 00 —

co •«• oo — <s c-j ——« Cs( sO * &> " •*SO "3D '-O V 'J"> -V T-CM CM — — Al "-

CO J3 30 CO CD CQ CC> Q_ CO > CD CO i-<

.-, — — co en -s soOJ CO C\l« <T- —• sDCM — •*• ** (O 00 *TCD — -ÔO CO CO OC

^ -V -T

1-- IS. <S) —»•

CO CM tft S » '-O CO0> * CO OJ IS. ••& >7*

iS 9 '33 i~

OQ OQ CQ> 00 (39 i. 00 u-

•& f*, —GO— CJ CSJ <?• ~+ N.

IO -Wn r» oo so IT)CM -~ rs. « irt

oo co^^ fft CO CO

in

\O •«• 4D 9r^ o ooCD

00 00 •* ON ^M OD ODu> 10 ^r rs. \n co irOD CO N. in Iff CM vC~* oo eg —«

CD CD CD JQ 00 00 COoo ao m x o- a. m

OD ONiv is.CP -*to **in ooOD co

i/o in m uo vo o sococo co oo co oo co

RUN* 665 AUG 27, 1992 14:15:88

SAMPLES 22 RUN! 663

SIGNAL FitE: H:Q51666EC.BNAREPORT FILE: H:fl5166«EC.»PAISTD

RT TYPE2.8296.29811.53622.89124.55524.87825.61425.95326.84826.26326.51826.75226.93927.14627.66328.86823.24628.41628.65928.76228.90529.23329.86936.16738.39538.81831.13131.38431.73331.81832.16932.34832.51632.68232.96733.14633.35633.45633.61133.76334.12434.41334.67634.86534.96835.11735.23235.61335.99636.27037.63737.31737.43238.89539.63341.64641.32342.99943.485

BVPBPBPBPBPBPBPBBBVBVBPBPBVBPBVBPBVBPBBBBBPBPBPBPBPBPBPBVBBBP6PBPBPBPBPBP8VBBB6BPBPBPBVBBBBBBBPBVBPBVBVBBBPBBBPBVBVBVB

AREA145336447

2121782163534443452824445674285463186521768623774376756725143604942416416338528655567873735633553477566722461672365615727841386191155895762126246291757167613682225163935216354182516581196841

VIDTH.815.825.643.843.634.055.054.038.037.943.034.079.049.066.031.045.030.669.658.834.869.852

.'046

.825

.821

.842

.832

.839

.843

.676

.837

.056

.835

.042

.054

.035

.057

.671

.625

.873

.675

.855

.646 -

.896

.053

.067

.076

.871

.847

.681

.665

.878

.674

.072

.895

.898

.188

.182

HEIGHT163221174

81866187187136152128172

281766158278115251131186256

281112411675152116129153

23726516116111225736542691143128611036323675782631771945861504153312795742497911466319282183138

5*

SIGNAL FILE: H:Q5161F44.£NAREPORT FILE: H:C5161F44.RPflISTD

RT2.33511.54322.98224.41324.56124.88925.62425.96626.84326.21726.42726.95227.15827.43327.66527.89428.07128.43428.67729.88529.24929.96338.17936.82231.16931.39231.75131.83132.12832.17332.34832.69332.91333.17233.46733.62533.79334.63634. 146

, 34.42134.68835.81135.12535.23835.62335.99436.28536.51937.85537.334

' 37.45238.91641.66141.343

. 42.19043.833

TYPEBVPPPBPBPBP8VBPBBBVBBBPBPBPBPBPBVBVBPBPBPBVBVBPBPBPBPBBBPB68PBPBPBPBPBBBBBPBBBPBPBPBBBBBPBPBPBPBVBBBBBPBBBBBPBBB

AREA149421

28906Z23822b'32956339431S41b223434239314233287931738753199336154718562686735364364628733656967166775113873567127165294214882664788386159952921191164588175631441117426S17881469125S1629

UIDTH.616.043.842.046.036.056.061.641.646.844.876.843.626.842.841.048.852.884.645.048.046.091.081.036.021.056.053.037.037.033.061.038.653.863.988.664.831.635.081.075.056.088.845.665.669.886.852.664.691.879.665.678.695.893.142.693

AUG 27, 1992 16:24:35

SAMPLE* 2&

HEIGHT157165

S2485981859815316013415949169155124115188296H727869121282218144541182832951311691392931922082969146879665314592148142489128469375136319661287964313253148184

A1-77

HUM LOADING HiTOMBALUMET

for SYS tea ReadinessRUN I 659 AUG 27, 1992 84:55:12START

K834

4.265

39.946

A1-78

RUN < 656 AUG 27, 1992 02:13:99 tX/»START

1**M.

36.389

»- A1-79 f -SIGNAL

22.89?

WN I 648STARTHlF

AUG 26, 19$2 19:69:63

1IF

22. W7

A1-80

AVAILABLE NITROGEN, PHOSPHATE AND PH

ANALYZED ON 1:5 WATER EXTRACT, REPORTED ON WET SAMPLE BASIS

PROJECT: ARROWHEAD

Name of Sample

Soil Micro pH 5 KOH

Soil Micro pH 5 Lime

Soil Micro pH 6 KOH


Soil Micro pH 7 KOHSoil Micro pH 7 Lime

Soil Micro pH 5 KOH


Soil Micro pH 6 KOH

Soil Micro pH 6 LimeSoil Micro pH 7 KOHSoil Micro pH 7 Lime

Soil Micro pH 7 KOH

Soil Micro pH 7 LimeSoil Micro pH 6 Lime

Soil Micro pH 6 KOH

K-Sludge Slurry TestBottle 6 Set #1

K-Sludge Slurry TestBottle #6 Set #2K-Sludge Slurry TestBottle #6 Set #3

K-Sludge Slurry TestBottle #5 Set #1

DateSampled

3/26/923/26/92

3/26/92

3/26/92

3/26/92

3/26/923/23/92

3/23/92

3/23/92

3/23/923/23/923/23/92

4/3/924/3/924/9/924/16/92

11/12/92

11/12/92

11/12/92

11/19/92

(mg/kg)

(N)NH3

NA

NA

NA

-NA

NA

NA

NA

NA

NA

NA

NA

NA

15

512.5163

2,000

1,300

450

NA

P04

NA

NA

NA

NA

NA

NA

NA

NA

NA

NA

NA

NA

2.5105<54

4

3

NA

pH

5.2

5.1

6,3

6.5

7.2

7.1

5.6

5.3

6.3

6.6

7.3

7.3

6.9

7.1

5.95.9

9

7.5

7.0

7.5

NA - not analyzedE - Estimated

Signature:

A1-81

yb019310.W7



PROJECT: ARROWHEAD

Name of Sample


Soil Micro pH 7 KOHSoil Micro Compost

Soil Micro pH 6 LimeSoil Micro pH 6 KOH


Soil Micro pH 5 KOH


Soil Micro pH 6 KOH


Soil Micro pH 7 KOH


Soil Micro pH 6 LimeSoil Micro pH 6 Lime

DateSampled

3/19/92

3/19/92

3/20/92

3/20/92

3/20/92

3/20/92

3/21/92

3/21/92

3/21/92

3/21/92

3/21/92

3/21/92

3/26/92

3/26/92

(mg/kg)(N)NH3

NA

NA

2.5

- 2.5

12.5

12.5

125

125

125

100

63

63

<5

50

P04

NA

NA

<1

<1

<5

<55.0

5.0

5.0

5.0

12.5

12.5

<5

17.5

pH

7.27

6.76NA

NA

NA

NA

5.0

5.3

6.3

6.2

7.1

6.9

NA

NANA - not analyzedE - Estimated

Signature:

A1-82

yb019310.W7



PROJECT: ARROWHEAD

Name of Sample

Soil Compost Batch #1 firstwash water

Soil Compost Batch #1


Soil Compost Batch #1Soil Compost Batch #1



Sludge Compost

Sludge Compost

Sludge Compost

Sludge CompostSludge CompostSludge Compost (washed)

Sludge Compost (unwashed)Sludge Compost (unwashed)Sludge Compost (washed)Soil CompostSoil Micro pH 5 Lime

Soil Micro pH 5 KOHSoil Micro pH 6 Lime

Soil Micro pH 6 KOH

;^V-:DateV:::0Sampled

3/13/92

3/20/92

3/26/92

4/3/92

4/9/92

4/16/92

4/24/92

3/4/92

3/5/92

3/6/92

3/9/923/12/923/30/923/30/923/31/923/31/923/18/923/19/923/19/923/19/923/19/92

(mg/kg)

(N)NH3

100(mg/1)

100

118

87.5

7.5

<55

NA

40

NA

5040

12.5

12.512.5

125NA

NA

NA

NA

NA

P04

13(mg/1)

15

15

15

20

22.5

10

62.5

37.5

NA

7.5

35

75

7575

752.5

NA

NA

NA

NA

pH

NA

6.757.2

7.1

7.2

6.9

7.0

NA

6.3

7.5

7.0

6.5

7.0

7.07.0

7.0

NA

5.3

5.25

6.21

5.96A - not analyzed ./

E - Estimated Is ^^/ 4 ^~-Signature:

A1-83

yb019310.W7

AVAILABLE NITROGEN, PHOSPHATE AND pH


PROJECT: ARROWHEAD

Name of Sample

APSC-2

ASC-1ASC-2

APS-1

APS-2

APSC-1

APSC-2

ASC-1

ASC-2

NPS

NPSC

NSC




Soil Compost Batch #1Soil Compost Batch #1Soil Compost Batch #1Soil Compost Batch #1

DateSampled

2/21/92

2/21/92

2/21/92

3/5/92

.3/5/92

3/5/92

3/5/92

3/5/923/5/923/5/923/5/923/5/922/21/922/25/922/26/92

2/28/923/3/92

3/4/92

3/5/92

3/10/92

3/12/92

(nig/kg)

(N)NH3

NA

NA

NA

-NA

NA

NA

NA

NA

NA

NA

NA

NA

50

550

50

12.5

12.5

25

50

50

P04

NA

NA

NA

NA

NA

NA

NA

NA

NA

NA

NA

NA

10

<57.5

7.5

7.5

1025

25

75

pH

5.75.75.7

6.8

6.8

5.5

5.5

5.8

5.8

7.0

7.0

7.0

6.5

4.57.0

7.0

6.86.8

7.0

7.0

6.54A - not analyzed .X" .E- Estimated /^ // / /7v

Signature:

A1-84

yb019310.W7



PROJECT: ARROWHEAD

Name of Sample

Soil Microcosm (2/7/92)

Cake Compost Batch #1

Cake Compost Batch #1

Cake Compost Batch #1Cake Compost Batch #1

Cake Compost Batch #1Cake Compost Batch #1

Cake Compost Batch #1Cake Compost Batch #1APSC-1

NPSC

APSC

NPSC

APSC

NPSC

APSC-1

NPSC-1

NFS

NSC

APS-1

APS-2

^Date"14Sampled

2/21/922/17/92

2/19/92

2/21/92

2/25/92

2/26/92

2/28/92

3/3/923/4/922/17/922/17/922/19/922/19/922/21/922/21/92

2/26/922/26/92

2/21/92

2/21/92

2/21/922/21/92

(mg/kg)

(N)NH3

150100

10

- 50

1550

20

5

10

125

<1

NA

NA

NA

NA250

25

NA

NA

NA

NA

P04

1500<1100

12.5

15

1512.5

10

25

200

150

NA

NA

NA

NA

150175

NA

NA

NA

NA

pH

7.0

5.0

NA

5.5

6.0

7.0

7.0

6.8

6.8

5.0

5.5

6.3

6.6

5.76.3

NA

NA6.6

6.0

6.6

6.6NA - not analyzed£ - Estimated

yb019310.W7



PROJECT: ARROWHEAD

Name of Sample

Filter Cake Compost Batch #2



Filter Cake Compost Batch #2(Following washing)

Soil/Cake Compost

Soil/Cake Compost

Soil/Cake CompostSoil/Cake Compost


Soil/Cake Compost

Soil/Cake CompostSoil/Cake CompostAbiotic Experiment: SoilCompost

Abiotic Experiment: CakeCompostAbiotic Experiment: CakeCompost

Abiotic Experiment: SoilCompostDCR Treated SludgeSoil Microcosm (2/7/92)



DateSampled

7/10/92

7/17/92

7/27/92

8/10/92

5/19/92

5/27/926/5/926/12/92

6/19/92

6/26/92

7/10/92

7/17/927/27/926/25/92

6/26/92

6/30/92

6/30/92

10/16/922/10/922/11/922/17/92

(mg/kg)(N)NH3

375

500

500-375

62.5

<575

200

250

300

150

125

100

NA

- NA

2

10

25

20

NA

20

P04

100

100

100100

<5

7.5510

7.5

15

22.5

<53515

225

45

225

25E

<1

>10

50

PH

6.25

6.50

6.256.25

7.00

6.00

6.50

6.25

6.50

7.00

6.25

6.5

6.25

6.70

7.20

6.70

NA

7.00

4.5

7.0

5.5fNA - not analyzed /^ ^Ê- Estimated Ai-86 /^> /^ -

Signature:

yb019310.W7



PROJECT: ARROWHEAD

Name of Sample





Soil Compost Batch #2Soil Compost Batch #2Soil Compost Batch #2


Soil Compost Batch #2Soil Compost Batch #2Soil Compost Batch #2

Filter Cake Compost Batch #2Filter Cake Compost Batch #2

Filter Cake Compost Batch #2Filter Cake Compost Batch #2

Filter Cake Compost Batch #2Filter Cake Compost Batch #2Filter Cake Compost Batch #2Filter Cake Compost Batch #2Filter Cake Compost Batch #2


DateSampled

4/10/92

4/13/92

4/16/924/24/92

.4/30/92

5/7/92

5/15/925/27/92

6/19/926/26/92

7/7/92

7/10/92

7/27/92

4/24/924/30/92

5/7/92

5/8/92

5/15/925/27/926/5/926/12/926/19/92

6/26/92

(rag/kg)(N)NH3

NA

50

<5

- - <563

175175

62.5

100

200

75125

35

NA

12.5

62.5

NA

100100175250250

300

P04

<5

<5

5

55

10

12.5

20

13

22.5

22.5

35

35

7.5

<5<57.5

7.535

37.5

35

35

100

pH

6.3

6.56.4

6.5

6.4

6.4

6.25

6.25

6.5

6.25

6.25

6.0

6.25

NA

5.9

5.4

NA

6.56.06.256.25

6.25

6.25NA • not analyzedE - Estimated A 1-87 , ^

Signature

yb019310.W7

BACTERIA ENUMERATION

PROJECT: ARROWHEAD

Name of Sample

Sludge Composite

Filter Cake Composite

Soil Composite

Soil CompositeDuplicate

Soil Microcosm


Soil Microcosm


Filter Cake CompostBatch #1

Filter Cake CompostBatch #1 Duplicate


Soil CompositeBatch #2

Filter Cake CompostBatch n

Filter Cake CompostBatch #2 Duplicate


Soil Compost Batch #\



Type of Degraders

Total

////

//

/

/

/

/

/

/

/

///

Specific

//

//

/

/

/

/

/

/

/

////

DatePlated

2/4/92

2/4/92

1/28/92

1/28/92

2/7/92

2/7/92

2/14/92

2/14/92

2/14/92

2/14/92

2/20/92

2/20/92

2/21/92

2/21/92

3/2/92

2/20/92

2/28/92

3/10/92

3/13/92

WetWeight(gms)

5

5

5

5

5

5

5

5

5

5

5

5

5

5

5

5

5

5

5,/

MillionBacteria/Gram

<1.0x lO'5

<1.0xlO-5

.15

.12

> . l / .67

>.!/ .17

> 1,000

> 1,000

.21 /.33

.19/.20

60 / >100

1 / 1

67 / > 1,000

50 / > 1,000

230 / 100

1.9/2.4

140/6

330/8

13•^

Signature:


PROJECT: ARROWHEAD

Name of Sample

Soil Compost withalkane, kill


Soil Composite

Kiln Sludge

DCR Compost 0.01%Na Azide






DCR Compost 0.1%Na AzideDCR Compost 0.3 %Na Azide

K-Sludge Compost

DCR Compost "a"DCR Compost "b"

DCR Compost "cdfq"

DCR Compost "e"

DCR Compost "cdfq"

DCR Compost VK-SIudge Compost

DCR "e" inoculum

K-Sludge Compost

Type of Degraders

Total

/

/

/

/

/

/

/

/

/

/

/

/

/

/

/

/

/

/

/

Specific

•.

///

/

DatePlated

8/25/92

9/22/92

9/22/92

10/15/92

10/16/92

10/16/92

10/16/92

10/16/92

10/20/92

10/20/92

10/20/92

10/20/92

10/26/92

10/26/92

10/26/92

10/26/92

10/26/92

11/9/92

11/9/92

11/9/92

10/30/92

12/21/92

WetWeight(gins)

10

10

1010

10

10

10

10

10

10

10

10

10

10

10

10

10

10

10

10

10

/ 10


<1.0x 10-3

.43

.0417

>.l

>.l

>.l

>.l

>.l

>.l

>.l

>.l

130

4.3

53

5

42

45

33

27

.17

^•W/>3Signature:.


PROJECT: ARROWHEAD

Name of Sample

APSC-1

APSC-5

ASC-1

NPSC

NFS

ASPC-1

APS

NSC

Slurry Test Bottle 6Set#l

Slurry Test Bottle 6Set #2


Slurry Test Bottle 1Set # 1 Kill


Slurry Test Bottle 1Set # 3 KillSlurry Test Bottle 6Set#lSlurry Test Bottle 6Set #2



Slurry Test Bottle 1Set #2 KiU

Slurry Test Bottle 1Set #3 Kill

Type of Degraders

Total

/

/

/

/

/

/

/

/

/

/

/

/

/

Specific

/

/

/

/

/

/

/

/

DatePlated

2/14/92

2/19/92

2/27/92

2/27/92

2/27/92

2/27/92

2/27/92

2/27/92

10/30/92

10/30/92

10/30/92

10/30/92

10/30/92

10/30/92

11/3/92

11/3/92

11/3/92

11/3/92

11/3/92

11/3/92X,

SampleVolume

(ml)

0.5

0.5

0.5

0.5

0.5

0.5

0.5

0.5

0.5

0.5

0.5

0.5

0.5

0.5

0.5

0.5

0.5

0.5

0.5

0.5


3.9

57/15

1

12

9.7

1.7

1.7

6

.017

.05

.0013

<1.0x 10-3

<1.0xlO-5

<1.0xlO-5

.2

6.7

41

<1.0

<

<1.0xlO^

Signature:/


PROJECT: ARROWHEAD

Name of Sample

Slurry Test Bottle 6Set#l



Type of Degraders

Total

^

/

/

Specific

/

/

/

DatePlated

11/5/92

11/5/92

11/5/92

SampleVolume

(ml)0.5

0.5

0.5


53/45

190 / 19

240/30

Signature:/

TPH-IR MODIFIED EPA METHOD 418.1

PROJECT: ARROWHEAD

Name of Sample

Soil Compost

Soil Compost Duplicate

Soil Compost

Soil Compost Duplicate

Soil Compost

Soil Compost

Soil CompostBefore Wash

Soil CompostAfter Wash

Soil CompostSoil CompostSoil Compost Duplicate

Sludge CompostSludge Compost Duplicate

Sludge CompostSludge Compost Duplicate

Sludge Compost WashedSludge Compost WashedSludge Compost Washed

DateExtracted

2/20/92

2/20/92

2/28/92

2/28/92

3/9/92

3/9/92

3/13/92

3/13/92

3/20/92

4/2/92

4/2/92

3/6/92

3/6/92

3/13/92

3/13/92

3/24/92

3/31/92

3/31/92

Vol. ofFreon in

ml

505050505050100

100

10010010050505050505050

WetWeight(gins)

7.19

7.087.15

6.99

' 7.12

7.14

13.97

13.95

14.24

14.09

14.03

7.16

7.12

7.04

7.06

6.93

7.34

6.92

% Diy Wtof Sample

67.1

67.1

61.961.9

61.2

61262.8

58.9

573

58.0

58.0

47.9

47.9

363

363

38.1

36.639.7j — ^

TPHppm

(dry Wt)

42,000'

45,000

18,000

19,000

22,000

20,000

13,000

13,000

9,000

5,000

5,000

241,000

235,000

266,000

275,000

312,000

224,000

' /Signature:


PROJECT: ARROWHEAD

Name of Sample

Soil Micro

Soil Micro Duplicate

Soil Micro PH5 KOH

Soil Micro PH5 Lime

Soil Micro PH6 KOH

Soil Micro PH6 Lime

Soil Micro PH7 KOH

Soil Micro PH7 Lime

Soil Micro PH5 KOH

Soil Micro PH5 LimeSoil Micro PH6 KOH

Soil Micro PH6 LimeSoil Micro PH7 KOH

Soil Micro PH7 Lime

K-Sludge Slurry Test Set #1K-Sludge Slurry Test Set #2

K-Sludge Slurry Test Set #3K-Sludge Slurry Test Set #1

K-sludge Slurry Test Set #2

DateExtracted

3/18/92

3/18/92

4/2/92

4/2/92

4/2/92

4/2/92

4/2/92

4/2/92

4/21/92

4/21/92

4/21/92

4/21/92

4/21/92

4/21/92

10/29/9210/29/92

10/29/92

11/6/92

11/6/92

Vol. ofFreon in

ml

50

50

50

50

50

50

50

50

50

50

50

50

50

50140

46

14

140

46

WetWeight(gms)

5.04

5.154.99

5.07

5.08

5.03

5.07

5.05

4.98

5.13

5.06

5.00

5.14

5.07

10.03.3

1.0

10.0

33 ,

% Dry Wtof Sample

67.8

67.8

75.2

72.2

74.1

73.4

71.1

71.6

71.8

73.2

72.4

72.4

73.0

71.2

47.8

47.8

47.8

47.8

47.8

TPHppm

(dry Wt)

70,000

65,000

52,000

70,000

55,000

54,000

59,000

55,000

2,000

2,000

23,000

9,000

14,000

18,000

431,000

472,000

459,000

388,000

365,000Signature:

/


PROJECT: ARROWHEAD

Name of Sample

K-SIudge Slurry Test Set #3

K-Sludge Slurry Test Set #1



K-Sludge CompostFilter Cake #7cf

DateExtracted

11/6/9212/1/9212/1/9212/1/92

12/10/92

12/21/92

Vol. ofFreon in

ml

14

140

46

14

50

100

WetWeight(gins)

1.0

10.0

3.3

1.0

7.01

4.06

% Diy Wtof Sample

47.8

47.8

47.8

47.8

39.5

75.2

TPHppm

(diy Wt)

271,000

407,000

309,000

105,000

35,000

345,000

Signature:


PROJECT: ARROWHEAD

Name of Sample

Filter Cake Compost Batch #2DuplicateFilter Cake Batch #2 Compost

Soil/Cake Compost

Soil/Cake Compost Duplicate

Soil/Cake Compost

Soil/Cake CompostSoil/Cake Compost Duplicate


Soil/Cake Compost DuplicateSoil/Cake Compost

Soil/Cake Compost

Soil/Cake Compost DuplicateSoil/Cake CompostSoil/Cake Compost DuplicateSoil/Cake Compost

Soil/Cake Compost DuplicateAbiotic ExperimentAbiotic Test Soil Compost

DateExtracted

7/29/92

8/11/92

5/15/92

5/15/925/21/92

5/15/925/15/926/2/926/11/926/11/92

6/23/92

6/25/92

6/25/92

7/7/927/7/927/29/92

7/29/926/25/926/25/92

Vol. ofFreon in

ml

140

90

120

120

120

120

120

120

120

120

120

120

120

120

120120

120

50

WetWeight(gms)

15.14

10.01

15.00

15.00

15.05

15.00

15.00

15.4

14.99

15.00

15.10

15.05

15.08

15.01

14.9515.17

15.13

5.04

% Diy Wtof Sample

43.3

42.3

57.9

57.9

51.6

57.9

57.9

55.5

56.9

56.9

59.3

55.4

55.4

55.2

55.261.4

61.4

6.06

TPHppm

(dry Wt)

32,000

29,000

78,00084,000

85,000

74,000

79,000

24,000

26,000

8,000

78,000

13,000

15,000

21,000

17,0009,900

10,400

60,000

Signature:


PROJECT: ARROWHEAD

Name of Sample

Abiotic Test Soil Compost DuplicateAbiotic Test Unamended SoilAbiotic Test Unamended Soil Duplicate

Abiotic Test Cake CompostAbiotic Test Cake Compost Duplicate

Abiotic Test Cake CompostAbiotic Test Cake Compost Duplicate

Cake Compost Abiotic Test Bottle #1

Cake Compost Abiotic Test Bottle #2Cake Compost Abiotic Test Bottle #3Cake Compost Abiotic Test Bottle #4Cake Compost Abiotic Test Bottle #5

Cake Compost Abiotic Test Bottle #6Cake Compost Abiotic Test Bottle #1

Cake Compost Abiotic Test Bottle #2



DateExtracted

6/25/926/25/926/25/92

6/29/92• 6/29/92

6/29/926/29/927/10/927/10/927/10/927/10/927/10/927/10/927/16/927/16/927/16/927/16/927/16/927/16/92

Vol. ofFreonin ml

5050

50

-30

30

30

30

50

50

50

50

50

50

30

30

30

30

30

30

WetWeight(gins)

5.06

3.94

3.95

2.5

2.02

2.13

2.21

5.00

4.95

5.01

5.07

5.03

5.11

2.00

2.03

2.04

2.02

0.94

0.92

% DryWtof

Sample

6.0669.0

69.0

47.3

47.3

51.3

51.3

60.7

60.7

60.7

60.7

62.7

62.7

48.0

48.0

48.0

48.0

56.5

56.5

TPHppm

(dry Wt)

56,00044,00058,000

207,000182,000

209,000

205,000

29,000

25,00042,000

44,000

6,000

8,000113,000113,000

191,000

190,000

337,000311,000

Signature:


PROJECT: ARROWHEAD

Name of Sample

DRC Treated Sludge "a"DCR Treated Sludge "c"

DCR Treated Sludge "e"

DCR Treated Sludge "q"

DCR Treated CompostSludge "a"DCR Treated CompostSludge "h"

DCR Treated CompostSludge "cdfq"

DCR Treated CompostSludge "e"K-Sludge CompostSoil CompositeFilter Cake Composite

Sludge Composite

Sludge Composite Duplicate

Filter Cake Compost

Filter Cake CompostDuplicate

Filter Cake CompostFilter Cake CompostDuplicate

Filter Cake Compost

Filter Cake CompostDuplicate

DateExtracted

9/21/92

9/21/92

9/21/92

9/21/92

10/27/92

10/27/92 '

10/27/92

10/27/92

10/27/92

1/23/92

1/23/92

1/23/92

1/23/92

2/14/92

2/14/92

2/28/922/28/92

3/9/92

3/9/92

Vol. ofFreon in

ml

3034

50

50

50

50

504012090902828

2828

2828

WetWeight(gms)

2.00

2.04

2.04

2.05

7.19

6.96

7.10

7.03

7.03

4.19

4.39

239

2.335.97

6.13

6.02

6.10

5.95

6.05

% Dry Wtof Sample

85.180.880.0

85.7

46.1

38.7

37.4

41.6

33.5

66.974.5

64.6

64.6

45.7

45.7

37.637.6

453

453/ .

TPHppm

(dry Wt)

277,000

332,000

234,000299,000

101,000

124,000

134,000

96,000

140,000

60,000

427,000

717,000

660,000237,000

224.000

138,000

166,000

144,000

140,000^s s

Signature:

GC/FID FINGERPRINT MANUAL HUMP INTEGRATION

PROJECT: ARROWHEAD

[SAMPLE CHART SPEED 0.5][OTP = SOjiG/ML, CHART = 15 ATT = 4]

[SEE GC/FID PEAK REPORT FOR EXTRACTION DETAILS]

Name of Sample

Sludge Composite

Soil Composite



Soil Compost Batch #1Soil Compost Batch #1Soil Compost Before Wash


Filter Cake CompostBatch #2Soil Compost Batch #2

fl Soil/Cake Compost


Soil Compost Batch #2Soil/Cake Compost

Filter Cake Hazen-Kiln

Filter Cake Hazen-KilnFilter Cake Hazen-Kiln

Soil/Cake CompostFilter Cake CompostBatch #2

DateExtracted

1/23/92

1/23/92

1/23/92 .

2/21/92

2/28/92

2/28/92

3/31/92

4/2/92

4/10/92

4/23/92

4/30/92

5/15/92

5/27/92

5/27/92

6/2/92

6/9/92

6/9/92 -6/16/927/29/92

7/29/92

SampleAttenuation

1

1

2

1

1

1

1

1

1

3

113

1

1

2

2

2

1

3

"Cut & Weigh" Results •

mgOTPStandard

20.0020.00

20.00

22.8

22.8

22.8

26.5

25.8

21.0

20.0

21.0

20.0

20.0

21.0

20.0

21.0

21.0

21.0

20.0

20.0/

mg Sample

15.0

20.8

14.5

293.0

146.1

152.2

103.3

27.8206.0

193.5

90.0

213.559.5

48.6

67.0

199.0

197.0

215

34.0

34.5s

Signature:

HEADSPACE OXYGEN AND CARBON DIOXIDEGC/TCD ANALYSIS

PROJECT: ARROWHEAD

Name of Sample

1% CO2 Standard

Air Blank

Soil Abiotic TestTest

Soil Abiotic TestTest Duplicate

1% CO2 Standard

Air Blank



Soil Abiotic TestTest KillSoil Abiotic TestTest Kill Duplicate

Soil Abiotic TestFinished Compost

Soil Abiotic TestFinished CompostDuplicate

Soil Abiotic TestUnamended SoilSoil Abiotic TestUnamended SoilDuplicate

Date Sampled

6/29/92

6/29/92

6/29/92

6/29/92

7/1/92

7/1/92

7/1/92

7/1/92

7/1/92

7/1/92

7/1/92

7/1/92

7/1/92

7/1/92

Area Count

Oxygen

38,284

708,495

545,422

454,451

33,000

696,800

450,000

299,000

682,000

684,000

688,000

692,000

632,000

646,000

Nitrogen

2,333,950

2,787,432

2,816,640

2,823,942

2,281,000

2,737,300

2,860,000

2,917,000

2,828,000

2,815,000

2,814,000

2,827,000

2,811,000

2,839,000

Carbon Dioxide

29,008

NA

189,570

264,931

33,920

4,800

291,000

432,000

44,000

39,000

42,000

40,000

73,000

82,000

Signature:

A1-88


PROJECT: ARROWHEAD

Name of Sample

1% CO2 StandardAir Blank


Filter Cake AbioticTest Test

Filter Cake AbioticTest Test DuplicateFilter Cake AbioticTest Test Kill

Filter Cake AbioticKill Test Duplicate

Filter Cake AbioticTest UnamendedFilter Cake AbioticTest UnamendedDuplicate


Filter Cake AbioticTest TestFilter Cake AbioticTest TestSoil Abiotic TestTest


Date Sampled

7/1/92

7/1/92

7/6/92

7/6/92

7/6/92 -

7/6/92

7/6/92

7/6/92

7/6/92

7/6/92

7/9/92

7/9/92

7/9/92

7/9/92

7/9/92

7/9/92

Area CountsOxygen

33,600

696,500

35,000

NA

406,000

210,000

684,000

699,000

700,000

670,000

35,700

699,900399,000

77,000

14,000

122,200

Nitrogen

2,180,203

2,737,300NA

2,729,792

2,764,000

2,815,000

2,701,000

2,727,000

2,730,000

2,692,000

3,138,200

2,717,500

2,744,000

2,851,000

3,049,000

2,863,000

Carbon Dioxide57,4004,800

50,500NA

352,000

352,000

40,000

13,000

3,000

31,000

45,100NA

347,000

649,000

204,000

521,000

A1-89Signature:


PROJECT: ARROWHEAD

Name of Sample

1% CO2 Standard

Air Blank



1% CO2 Standard

Air Blank

Filter Cake AbioticTest Test

Date Sampled

7/10/927/10/92

7/10/92

7/10/92 '•

7/14/92

7/14/92

7/14/92

Area CountsOxygen

651,400

29,900

481,000

476,000

32,000

663,000286,000

Nitrogen

2,534,800

2,929,300

2,643,000

2,542,000

3,030,900

2,593,600

2,660,000

Carbon DioxideNA

45,804

161,000

241,000

51,100

8,000

417,000

Signature:

A1-90

GC/FID FINGERPRINT PEAK TOTALS,EPA METHOD 8100

PROJECT: ARROWHEADSOLVENT: FREON

Name of Sample

Filter Cake Hazen-KilnNeutralized

Soil/Cake CompostFilter Cake CompostBatch #2Soil Compost + PAHSpikePAH Spiking Test FreonT = 0

PAH Spiking Test FreonT = 0 DuplicatePAH Spiking Test FreonT = IhrPAH Spiking Test FreonT = 1 hr Duplicate

r PAH Spiking Test DCM/T = 0

PAH Spiking Test DCM/T = 0 Duplicate

PAH Spiking Test FreonT = 7

PAH Spiking Test FreonT = 7 DuplicateAlkane Spiking TestFreon

Alkane Spiking TestFreon Duplicate

DateExtracted

6/15/92

7/29/92

7/29/92

8/10/92

8/19/92

8/19/92

8/19/92

8/19/92

8/19/92

8/19/92

8/26/92

8/26/92

8/26/92

8/26/92

SolventVolume

in ml

80

120• 140

100

100

100

100

100

100

100

100

100

100

100

WetWeight

4.17

15.15

15.16

15.19

15.08

15.06

15.10

15.06

15.06

" 15.08

15.13

15.18

15.00

15.08

%DryWeight

54.6

61.4

43.3

66.8

58.6

58.6

58.6

58.6

58.6

58.6

58.6

58.6

58.6

58.6

DilutionAnalyzed

1:1.5

1:1.5

1

1

1

1

1

1

1

1

1

1

1

1

GCPeakTotal

(mg/kg)15279

184

911

1352

152

119

NA

NA

1104

1424

NA

NA

NA

NA

N/A = Not Analyzed " 7X ^^ //Â1-91 Signature: ^T^^^^l / &£fr

- *" y //



Name of Sample

Sludge CompositeSoil Composite



Soil Compost Batch #1Soil Compost Batch #1before wash


Filter Cake CompostBatch #2Soil Compost Batch #2Soil/Cake Compost

Soil Compost Batch #2Filter Cake CompostBatch #2

Soil/Cake Compost

Filter Cake Hazen-KilnNeutralizedFilter Cake Hazen-KilnNeutralized Duplicate

DateExtracted

1/23/92

1/23/92

1/23/92

2/21/92

2/28/92

3/9/92

3/13/92

4/2/92

4/10/92

4/23/92

4/30/92

5/15/92

5/27/92

5/27/92

6/2/92

6/9/92

6/9/92

SolventVolume

in ml

604080505050100

10010090

100120100140

12080

80

WetWeight

2.39

4.19

4.39

7.14

7.07

7.13

13.97

14.06

14.06

10.04

14.09

15.0

- 14.01

15.35

15.40

4.05

4.18

% DryWeight

64.6

66.9

74.5

67.1

6.19

61.2

62.8

58.0

63.9

45.0

58.9

57.9

62.4

41.5

55.054.1

54.1

DilutionAnalyzed

1:71

1:3

1

1

1

1

1

1

1

1

1:1.5

1

1

1:1.51:1.5

1:1.5

GCPeakTotal

(mg/kg)22525

1455

14533

1114

206

309224

33.3

1048.5

10806

116.5

15279

56.7

1233

400

15401

13860

A1-92 Signature:/



Name of Sample

DCR Treated Sludge"a"DCR Treated Sludge"c"DCR Treated Sludge"e"DCR Treated Sludge"g"

DateExtracted

9/21/92

9/21/92

9/21/92

9/21/92

SolventVolume

in ml30

3?

30

34

WetWeight

2.00

2.04

2.04

2.05

%DryWeight

85.1

80.8

80.0

85.7

DilutionAnalyzed

1:7

1:7

1:7

1:7

GCPeakTotal

(mg/kg)

10727

12793

8136

11343? f

Signature:

A1-93


PROJECT: ARROWHEAD

Name of Sample

1% CO2 StandardAir BlankSoil Abiotic TestTest

Soil Abiotic TestTest Duplicate1% CO2 StandardAir BlankFilter Cake AbioticTest TestFilter Cake AbioticTest Test Duplicate1% CO2 StandardAir BlankFilter Cake AbioticTest TestFilter Cake AbioticTest Test DuplicateFilter Cake AbioticTest B011Filter Cake AbioticTest Kill DuplicateFilter Cake AbioticTest UnamendedFilter Cake AbioticTest UnamendedDuplicate

Date Sampled

7/10/927/10/927/10/92

7/10/92

7/14/92

7/14/92

7/14/92

7/14/92

7/15/92

7/15/927/15/92

7/15/92

7/15/92

7/15/92

7/15/92

7/15/92

Area CountsOxygen

651,400

29,900

481,000

476,000

32,000

663,000286,000

175,000

33,000665,000200,000

113,000

639,000

646,000

601,000

602,000

Nitrogen2,534,800

2,929,300

2,643,000

2,542,000

3,030,900

2,593,600

2,660,000

2,658,000

3,005,200

2,581,400

2,610,000

2,658,000

2,522,000

2,526,000

2,535,000

2,548,000

Carbon DioxideNA

45,804

161,000

241,000

51,100

8,000

417,000

518,000

49,700

1,100

580,000

656,000

69,000

55,000

117,000

121,000

A1-94Signature:

Documents

United States Environmental Protection Agency · Ai ASEA BROWN BOVERI January 21, 1993 PN: 7054.01 012193.LTR Barr Engineering Company ATTN: Mr. John Borovsky 8300 Norman Center Drive