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Nick BastaProfessor of Soil and Environmental ChemistrySchool of Environment and Natural Resources
Ohio State University
Ecological Effects of Land Application of Biosolids
Workshop on Microconstituents and Ecological Impacts of Biosolids and Effluent Reuse; June 26, 2008
Environmental Science / Ecosystem ScienceTerrestrial Wildlife and Ecology
mammals, avian (including migratory birds)reptiles,
Soil Science (including soil ecology)Carbon Management and Sequestration Center
Wetland Science / ecosystemsOlentangy River Wetland Research Park
Forest EcosystemsStream, Lake Ecosystems and FisheriesEnvironmental Social Science
School of Environment and Natural ResourcesOhio State University
ORWRP
Research programSoil/Environmental contaminant chemistry; ecotoxicologyDevelopment and evaluation of remediation technologiesof contaminated landBeneficial use of industrial by-products via land applicationBiogeochemical cycling of trace elements in soils
School of Environment and Natural ResourcesSoil Environmental Chemistry Program
Today’s Presentation
Contaminant Exposure (bioavailability)in Contaminated Soil Systems and Ecological Effects
Use of Soil Amendments and Biosolids to ReduceContaminant Exposure / Ecological Effects
Long-term Ecological Effects of Biosolids Applicationto Agricultural Land
Soil Environmental Chemistry,Contaminant Bioavailability, and Toxicity
Soil / contaminant chemistry affects availability,contaminant transmission, and human and ecological risk
Total ContaminantContent in Soil
Soluble / Available Soil Contaminant
Insoluble / UnavailableSoil Contaminant
High LowPotential Bioavailability / Toxicity
Potential Human/Ecological Risk
Soil Chemistry affects Contaminant Partitioning and Availability
Soil Chemical PropertiespH, OC, Clay, etc
Soil Chemical Properties and Solid Phases affect Contaminant Solubility / Bioavailability
Surface Chemistry - Adsorption Reactions in Soil
Pb2+
Soluble Pb
SOM
Fe
Fe
O
OH
OH2+
+ H2AsO4-
Fe
Fe
O
OH
O OH
OH
O
AsSoluble
Insoluble
Insoluble
O
CO
OSOM
OH
CO
O +
Ca10(PO4)6(OH)2 + xPb2+ Ca10-xPbx(PO4)6(OH)2 + xCa2+
Precipitation Reactions in Soil
Soluble Insoluble
Soil / contaminant chemistry affects availability,contaminant transmission, and ecological risk
Contaminant Exposure in Soil Systemsand Ecological Effects
Low pHLow OCLow Clay
High pHHigh OCMod Clay
High pHHigh OCMod Clay
Mod pHLow OCMod Clay
Low pHHigh OCMod Clay
Soil Chemical Properties / Solid Phase Components affect Solubility, Bioavailability, and Toxicity
5 pots of the same Zn contaminated soil
All pots have same total soil Zn but different bioavailable Zn
Soil ContaminantSoil Contaminant
Herbivore PathwayHerbivore Pathway
Carnivore PathwayCarnivore Pathway
Plant
Invertebrate Shrew
How Do We Adjust for the Effect of Soil on Contaminant Transmission to Ecological Receptors?
Environmental Security and Technology Certification ProgramStrategic Environment Resource Development Program(DOD, DOE, USEPA consortium)USEPA National Center for Ecological Assessment
Ohio State University; US Army Edgewood Chem. Biol. Ctr; Oak Ridge National Laboratory; Stanford Univ.; Univ. of Missouri; USEPA National Risk Management Lab; USEPA National Exposure Research Lab; Auburn Univ.;
Quantifying the Effect of Soil Chemical Propertieson Soil Ecotoxicity for Ecological Risk Assessment
contaminated soil research (not biosolids)
Research Projects
CAl + Fe oxide (FEAL, mol/kg)
0.00
0.05
0.10
0.15
0.20
BCation Exchange Capacity (CEC, cmolc/kg)
0
15
30
45
AOrganic Carbon (% OC)
0
1
2
3
DpH
Soil1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
0
2
4
6
8
U.S. EPA NCEA StudyU.S. EPA NCEA Study
22 soils with wide range of properties / constituents
soils spiked with one level ofAs, Pb, Zn, or Cd
ecotoxicological endpointslettuce, earthworms
Bradham et al. 2006. Environ. Tox. Chem. 25(3):769-775
Dayton et al. 2006. Environ. Tox. Chem 25(3):719-725
Soil Chemical Properties affected Phytotoxicity
0
10
20
30
40
50
60
70
80
Bernow B
Canis
teo
Dennis
ADen
nis B
Doughtery
AEfa
w AHan
lon A
Haske
llKirk
land A
Luton A
Mansi
c A
Mansi
c BOsa
ge A
Osage B
Perkin
s
Pond Cre
ek A
Pond Cre
ek B
Pratt
APra
tt B
Richfie
ld B
Summ
it A
Summ
it B
% G
row
th R
elat
ive
to C
on
tro
l
Lettuce grown in soil spiked with 250 mg/kg As
22 soils with a wide range of properties
Similar results for Pb, Cd, Zn
Soil
Soil Chemical Properties affect Pb BioaccumulationEarthworm Bioassay
0
100
200
300
400
500
600
700
800
900
Luto
nOsa
ge B
Osage
AKirk
land
Canist
eoSum
mit B
Man
sic A
Summ
it ADen
nis B
Dennis
AHan
lonM
ansic
BNor
geRich
field
Taloka
Dough
tery
Pond
Creek
B
Pond
Creek
ATell
erPra
tt B
Pratt
ABer
now
Soil
Inte
rnal
Con
cent
ratio
n (m
g P
b kg
-1dr
y w
t.)
Earthworms in soil spiked with 2000 mg/kg Pb
22 soils with a wide range of properties
Similar results for Cd, Zn, As
Remedial Techniques for Soil Property Multicollinearity
Many soil properties are inherently strongly intercorrelated(soil pH, CEC, organic carbon, clay content, etc)
Usual Multiple Regression Techniques will produce highly inaccurate ecotoxicological endpoints
Solution: specialized methodsStructural equation modelingPath analysisMultiple Regression ModelsRidge regression
Ridge Regression
Using Soil Chemical Properties toAdjust/Predict Soil Ecotoxicological Endpoints
Advanced Statistical ApproachesAdvanced Statistical Approaches
Prediction Equations used to Model Food Chain and Contaminant Transmission
Soil AvailableContaminant
Earthworm ShrewContaminant
SolubilityBioavailabilityto earthworm
Oral or GastrointestinalBioavailability
to ShrewDermal bioavailabilityand/or Oral Bioavailability
How do you measure effects from ingestionof contaminated soil?
Soil Contaminant Oral Bioavailability Soil Ingestion Exposure Pathway
Risk = [Soil]Risk = [Soil](BW) (AT)(BW) (AT)
(EF) (ED) (IR)(EF) (ED) (IR) (BIO)
How do we measure BIO for children?
for other ecological receptors ?
OSU In Vitro Gastrointestinal MethodAn Inexpensive, Fast, Accessible Alternative
in vitro “(bio)availability” = dissolved contaminant= bioaccessible contaminant
stomach phaseintestinal phase
Sequential extraction, 3737ooCC
U.S. EPA, Guidance for Evaluating the Oral Bioavailability of Metals in Soils for Use in Human Health Risk AssessmentOSWER 9285.7-80, May 2007; RBALP IVG accepted for Pb, others under consideration for Pb and As.
Rodriguez et al. 1999. ES&T 33:642-649
OSU IVG correlation with in vivoAs with dosing vehicle
As without dosing vehicleBasta et al., 2007. J. Environ.Health Sci. Part A 42:1275-1181.
Pb with/out dosing vehicleSchroder et al., 2004
J. Environ. Qual., 33:513-521.
Cd with/out dosing vehicleSchroder et al., 2003.
ES&T 37:1365-1370.
Rel
ativ
e B
ioav
aila
ble
As,
%
% Bioaccessible As
0 10 20 30 400
10
20
30
40
50
60
RBA As = 0.942 IVG RBA As = 0.942 IVG --7.11 r = 0.91**7.11 r = 0.91**
Basta et al. 2003. Grant R825410 Final Report. submitted to U.S. EPA ORD
OSU IVG Bioaccessibility Method
Ecotoxicological Risks Associated with Land Treatment of Petrochemical Wastesfrom Petrochemical-Contaminated Soils
Prior Use of in vitro methods for estimatingecotoxicological risks from ingestion of contaminated soil
Landfarming of Petrochemical WasteResulted in Soil Contamination
Oily/acid petrochemical sludge pit
Heavily vegetated landfarmcreates an attractive
“ecological nuisance”
Organic chemical wastesHF- octane productionPb - tetraethylleadcatalysts (Zn, Cr, V, other metals)
Contaminant Indicator SpeciesContaminant Indicator SpeciesCotton Rats (Cotton Rats (Sigmodon hispidusSigmodon hispidus))
small mammal with a critical functional role small mammal with a critical functional role in terrestrial food chainin terrestrial food chain
19.92 μg day -1
146.7 μg day-1
11.4%. .
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F exposure from incidental ingestion of soil associated with dietary (soiled food) and non-dietary pathways
88.6%88.6%
DietarypathwayDietary
pathway
Non-dietary pathwayNon-dietary pathway
Incidental ingestion of soil is a major contaminantexposure pathway for cotton rats
Soil Remediation by in situ Soil Amendments
Pb2+
Available
Unavailable
Pb
BiosolidsBiosolids Biosolids
O
O
OH
Treat soil to reduce contaminant solubility/availability to ecological and human receptors
adjust soil pHincrease clay/oxide contentadd organic matter, etc.
In Situ Chemical Immobilization of Pb
Immobilization of Pb Contaminated SoilPhosphates / P Fertilizer
Hydroxyapatite + available Pb
Ca10(PO4)6(OH)2 + xPb2+
Lead pyromorphiteLow bioavailability
Ca10-xPbx(PO4)6(OH)2 + xCa2+
Hydroxyapatite (Ma et al., 1995; Laperche et al., 1997)
Soluble phosphate fertilizerBasta and McGowen, 2004; McGowen et al., 2000
Before AfterBunker Hill, ID; Joplin, MO; Leadville, CO; othersBunker Hill, ID; Joplin, MO; Leadville, CO; othershttp://faculty.washington.edu/slb/Brown, Chaney, et al. 2004. J. Environ. Qual. 33:522-531.
Large-Scale Ecological Restoration Using BiosolidsUniversity of Washington, USDA-ARS, USEPA
Soil Remediation Using ByproductsLarge-Scale Field Studies
Palmerton, PA, 1980; Dead Ecosystem on Blue Mountain.
Palmerton, PA, 1999: Looking down revegetated Blue Mountain.
Soil Remediation in Picher, OK using ByproductsUniv. of Washington, USEPA ERT, OSU
72 plots on Pb, Zn, Cd contaminated landAlkaline BiosolidsBiosolids CompostCommercial phosphorus fertilizerAl-Drinking water residualsFe-Drinking water residuals
Seeded with Bermudagrass
Soil Remediation in Picher, OK using ByproductsUniv. of Washington, USEPA ERT, OSU
Soil Remediation and Ecological Restoration
“Ecological Revitalization” of contaminated Superfund sites
http://www.cluin.org/ecotools/
Ecological RestorationSoil Amendments
•biosolids•manures•compost•pulp sludges•yard /wood waste•lime•wood ash•coal combustion products•sugar beet lime•foundry sand•steel slag•FGD•water treatment residuals•etc
http://www.cluin.org/products/tpm/
Ecological RestorationEvaluating Contaminant Remediation
Technology Performance MeasuresStep 1 – Selecting the Goal of the Soil Amendment Application
Step 2 – Selecting the Exposure Pathway of ConcernStep 3 – Select the Performance EndpointStep 4 – Select What You Want To MeasureStep 5 – Select the Performance Measurement
TPM to Evaluate Amended SoilTPM to Evaluate Amended SoilReductions in Bioavailability and Ecological ExposureReductions in Bioavailability and Ecological Exposure
TPM for herbivore pathway: plant bioassay / metal bioaccumulationTPM for carnivore: earthworm bioassay / bioaccumulationTPM for both pathways: plant/worm ingestion- in vitro GI methods
Soil ContaminantSoil Contaminant
Herbivore Pathway
Carnivore Pathway
Shrew
Remediated Site
AlkalineBiosolids
Control N-ViroSoil
RockPhosphate
Non-alkalineBiosolids
Zn
Fra
ctio
n, m
g k
g-1
2000
4000
6000
Ca(NO3)2NaOAcEDTA HNO3
Chemical Immobilization and Phytotoxicityin Treated Pb/Zn Smelter-Contaminated Soils
Chemical Immobilization and PhytotoxicityChemical Immobilization and Phytotoxicityin Treated Pb/Zn Smelterin Treated Pb/Zn Smelter--Contaminated SoilsContaminated Soils
Basta, Gradwohl, Snethen, and Schroder. 2001. J. Environ. Qual. 30:1222-1230.
0
20
40
60
80
100
0 48 96 144 192 240 288 336
Time (h)
Cu
mu
lati
ve M
ort
alit
y (%
)
Alkaline Biosolids (LSB)
Control
Rock Phosphate (RP)
Non-Alkaline Biosolids (BS)
Condor, Lanno, and Basta. 2001. J. Environ. Qual. 30:1231Condor, Lanno, and Basta. 2001. J. Environ. Qual. 30:1231--1237.1237.
Earthworm Toxicity TestingZn, Pb, Cd Contaminated Smelter Soil
0
10
20
30
40
50
None LSB RP BSZn-smelter treated soils
Ca(NO3)2- extractable Zn, mmol/kg
No toxicity to Eisenia fetida in alkaline biosolids treated soil !
Quantifying Efficacy of In Situ Remediation Treatments:Treatment Effects on Ecological Risk
r2 = 0.61P < 0.01
0
10
20
30
40
50
60
70
80
90
100
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Soil organic carbon (%)
Co
coo
n p
rod
uct
ion
(%
)
Organic Matter Amendments Increase Earthworm Cocoon Production
More Earthworms!
0.0
0.5
1.0
1.5
2.0
2.5
In-VitroPb
aa
b
c
b
Did the Amendments Decrease Soil Ingestion Risk? in-vitro Pb GI Bioavailability
in Amended Soil
Control Alk.Biosolids
NViro PO4 BiosolidsBasta et al., 2001. J. Environ. Qual. 30:1222-1230
Soil Contaminant
Soluble
Released In Gut
Bioaccumulated in Organism
Drinking Water
Ingestion of Soil
Food Chain
Combination Amendment
Biosolids + Phosphorus Fertilizer (for Zn / Pb / Cd)
Best Amendment to Reduce Bioavailability / Mobility and Transmission via Exposure Pathways
Brown, S.L., H. Compton, and N.T. Basta. 2007. Field Test of In Situ Soil Amendments at the Tar Creek National Priorities List Superfund Site J. Environ. Qual. 36:1627-1634.
Nick Basta, Shane Whitacre, SENRRoman Lanno, Dept. of Entomology
Plots established by Dr. Terry Logan in 1992 One time application of biosolids. 10 application rates ranging from 0 to 300 Mg/ha
Long-Term Ecological and Environmental Benefitsfrom Land Application of Biosolids
Plots established by Dr. Terry Logan in 1992 One time application of biosolids10 application rates ranging from 0 to 300 Mg/ha
Experimental Design
Percent MortalityReproduction (cocoons, juveniles)Contaminant Bioaccumulation
Dry matter growthbioaccumulationgermination
Earthworms
Eisenia andrei
Ecological Test Species
Perennial Ryegrass
Lolium perenne L.
Ecological Test Species
6630.2792.735.58300
*Mehlich 3 Extraction
4560.2091.986.67150
630.1151.207.000
P* (mg/kg)Total N (%)Organic C (%)pHBiosolids, Mg/ha
Soil Properties / Nutrients
Long Term Improvement in Soil Quality and Fertility
Biosolid Plots
Zn
50
100
150
200
250
300
350
400
As
12.0
12.5
13.0
13.5
14.0
14.5
15.0
Cd
0
1
2
3
4
5
6
Cr
15
20
25
30
35
40
Cu
20
30
40
50
60
70
80
90
Mo
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
Ni
Biosolid application rate (Mg/ha)
0 50 100 150 200 250 30019
20
21
22
23
24
25
26
Pb
0 50 100 150 200 250 30040
45
50
55
60
65
70
Soil Metal Content for OSU Logan Biosolids Study, all in mg/kg
Soil Metal Contents
Zn Cd
As Cr
Cu Mo
Ni Pb
Increase in Zn, Cu, Pb, Cd
Mg/ha Zn Cu Pb Cd
0 109 24 43 0.60
300 374 85 67 4.90
metal in mg/kg soil
0 Mg/ha 150 Mg/ha 300 Mg/ha
Large increase in dry matter growth with Biosolids Application Rate
Effect of Biosolids on Ryegrass Dry Matter Growth
Metal Bioaccumulation in Perennial Ryegrass
Concentrations of two metals increased in Ryegrass grown on plots amended with biosolids:Zn: 36 mg/kg for 0 Mg/ha
111 mg/kg for 300 Mg/ha
Cu: 3.7 mg/kg for 0 Mg/ha4.7 mg/kg for 300 Mg/ha
Cu sufficiency for Ryegrassis 5 mg/kg
Biosolids improved micronutrient status of soil and improved soil and plant nutrition for Cu and Zn
Cocoon production of Eisenia andrei in reproduction test
05
10
15202530
35
0 0* 60 150 300 300*
Application rate
To
tal c
oco
on
s / 1
0 w
orm
s
Cocoons Day 14
Cocoons Day 28
Cocoons Total
* No food
Soil Ecotoxicity- Invertebrates
Biosolids had no effect on cocoon production
Hatchling production of Eisenia andrei in reproduction test
0
20
40
60
80
0 0* 60 150 300 300*
Application rate
To
tal h
atch
ling
s / 1
0 w
orm
s
Hatchlings Day 14
Hatchlings Day 28
Hatchlings Total
* No food
Biosolids had no effect on hatchling production
Soil Ecotoxicity- Invertebrates
• Biosolids increased concentrations of several metals in amended soil
• Biosolids improved soil quality and fertility
• Long term increase in ryegrass dry matter growth
• Improved Cu and Zn in ryegrass (removed deficiency)
• No effect on reproduction in E. andrei
Summary
Kottman Hall
Thank you for your attentionMore information? Please contact:
Nick Basta, SENR OSU [email protected]