The Florida Institute of Phosphate Research was created in 1978 by the Florida Legislature (Chapter 378.101, Florida Statutes) and empowered to conduct research supportive to the responsible development of the state’s phosphate resources. The Institute has targeted areas of research responsibility. These are: reclamation alternatives in mining and processing, including wetlands reclamation, phosphogypsum storage areas and phosphatic clay containment areas; methods for more efficient, economical and environmentally balanced phosphate recovery and processing; disposal and utilization of phosphatic clay; and environmental effects involving the health and welfare of the people, including those effects related to radiation and water consumption.

FIPR is located in Polk County, in the heart of the central Florida phosphate district. The Institute seeks to serve as an information center on phosphate-related topics and welcomes infomration requests made in person, or by mail, email, or telephone.

Executive Director Paul R. Clifford

Research Directors

G. Michael Lloyd, Jr. -Chemical Processing J. Patrick Zhang -Mining & Beneficiation Steven G. Richardson -Reclamation Brian K. Birky -Public Health

Publications Editor Karen J. Stewart

Florida Institute of Phosphate Research 1855 West Main Street Bartow, Florida 33830

(863) 534-7 160 Fax: (863) 534-7165

http://www.fipr.state.fl.us

EVALUATION OF THE EFFECTIVENESS OF NEUTRALIZING ACCIDENTAL

SPILLS OF ACIDIC WASTE WATER FROM HOLDING PONDS

FINAL REPORT

Daniel P. Foley and Allan L. Pollock Principal Investigators

with

Samuel V. Houghtaling and James W. Cox

HiTech Solutions, Inc. 129 South Kentucky Avenue, Suite 301

Lakeland, Florida 33801

Prepared for

FLORIDA INSTITUTE OF PHOSPHATE RESEARCH 1855 West Main Street

Bartow, Florida 33830 USA

Contract Manager: G. Michael Lloyd, Jr. FIPR Project Number: 98-01-155

December 2000

DISCLAIMER

The contents of this report are reproduced herein as received from the contractor. The opinions, findings and conclusions expressed herein are not necessarily those of the Florida Institute of Phosphate Research, nor does mention of company names or products constitute endorsement by the Florida Institute of Phosphate Research.

iii

PERSPECTIVE

This study is for the Florida Institute of Phosphate Research (FIPR). It is a generic plan to treat a specific accidental acidic waste water spill, hereafter called the SPILL, that enters a tributary or river around the active phosphate complexes in Central Florida. This generic plan can be used with modifications, dependent on the local geography and neutralization chemicals available, at other locations in Florida and in other parts of the United States. The plan will entail a recommendation of treatment, selection of equipment, staffing, training of manpower, and development of the most effective procedures to act promptly in the event of an accidental spill. The study recommends the on site storage of hydrated lime slurry at all active phosphate complexes in Florida. The study requires close cooperation among all active phosphate complexes, local lime suppliers, and trucking companies. Through proper industry-wide preplanning, the effect of a future spill can be held to a minimum.

Any accidental discharge of acidic waste water from holding ponds and gypsum stacks is damaging to the environment and expensive to remediate. These uncontrolled accidental discharges have been so infrequent that there has been no investigation by the phosphate industry to determine how they were treated in the past, any effects on the river systems and weather spills can be neutralized.

The Florida Department of Environmental Protection (FDEP) has set standards on new gypsum stacks and cooling ponds that include lining the bottom and shallower slopes on the sides. These changes will reduce the chances of spills. However, the possibility of future spills still exists.

An evaluation of how some of these spills were treated in the past and the effects on the river systems are important to what future action can be taken. By studying the past reactions of the rivers and river life systems to these spills, a generic plan has been prepared to assist the phosphate industry in effectively treating future uncontrolled accidental discharges of acidic waste water. A proper Emergency Neutralization Plan (ENP) based on cooperation between phosphate complexes, lime suppliers, trucking companies, and portable equipment leases can minimize the environmental and economic impact on the river system.

This study outlines a general ENP and recommends an additional site-specific study for each individual plant to develop an ENP. The site specific study should, as much as possible, focus on keeping the SPILL on plant property and minimizing the amount reaching the local tributary or river system. Any accidental wastewater spill is too costly to the environment. Also, the P2O5 that is in the pond water is a large economic loss to the plant.

v

ABSTRACT

This study was done to develop a generic plan to treat an accidental multi-million gallon spill of less than 2 pH water from an active phosphate complex into a central Florida fresh water tributary. The effects on the environment resulting from a spill of low pH water can be reduced by prompt neutralization of the spill. This study has resulted in the general outline of an industry-wide plan of action. The plan outlines how to treat a large accidental spill of acidic water with hydrated lime in time to significantly increase the pH of the water within the first 36 hours of the spill. The plan will require cooperation from all phosphate complexes in central Florida in conjunction with the lime supplier, Chemical Lime Company, and the trucking company, Commercial Carrier Corporation.

vii

TABLE OF CONTENTS PERSPECTIVE.................................................................................................................. iii ABSTRACT.........................................................................................................................v EXECUTIVE SUMMARY..................................................................................................1 Review ...........................................................................................................................1 Study ..............................................................................................................................1 Treatment Plan ...............................................................................................................1 Recommendations..........................................................................................................2 Justification for Recommendations................................................................................2 INTRODUCTION................................................................................................................5 Phosphate Industry Plant Description ............................................................................5 The American Cyanamid Spill in 1962..........................................................................5 Historic River Treatment ...............................................................................................5 The 1962 Action Plan ....................................................................................................5 The 1962 Results............................................................................................................6 The 1997 Occurrence .....................................................................................................6 Future Emergency Neutralization Plan ..........................................................................6 GENERIC SPILL.................................................................................................................9 Definition of a Generic Spill..........................................................................................9 Treatment of a Generic Spill..........................................................................................9 The Emergency Neutralization Plan ............................................................................10 Spill Alert System ...............................................................................................11 Spill Treatment Team .........................................................................................11 Neutralization Data .............................................................................................11 Quicklime Supplier .............................................................................................13 Trucking Company .............................................................................................14 Quicklime Hydrating Slurry System ...................................................................14 Hydrated Lime Slurry Truck Deployment ..........................................................15

viii

TABLE OF CONTENTS (CONT.) Treatment Site.....................................................................................................15 pH Monitoring System...............................................................................16 Slurry Distribution System.........................................................................16 River Mixing Equipment ...........................................................................16 Neutralization of Spill Area .......................................................................17 Ammonia Injection ......................................................................................................17 COST ESTIMATE.............................................................................................................19 REFERENCES ..................................................................................................................21 APPENDIX A Remediation of Areas Affected by Spill................................................ A-1 Pond and Swamp Remediation ................................................................................. A-1 Manpower Requirements ................................................................................. A-1 Spill Remnant Remediation of Tributaries ............................................................... A-1 Manpower Requirements ................................................................................. A-2 APPENDIX B Treatment Stations Details......................................................................B-1 Location .....................................................................................................................B-1 Size and Layout..........................................................................................................B-1 Utilities.......................................................................................................................B-1 Preliminary Sketches..................................................................................................B-1 Equipment List per Treatment Station .......................................................................B-2 Manpower Requirements per Shift per Station..........................................................B-2 Sketch 1309-1 (Treatment Site) .................................................................................B-3 Sketch 1309-2 (Slurry Distributor) ............................................................................B-4 Sketch 1309-3 (Air Spargers) ....................................................................................B-5 APPENDIX C River Data...............................................................................................C-1

ix

TABLE OF CONTENTS (CONT.) APPENDIX D Hydrated Lime Slurry Treatment Rates................................................. D-1 Proposed Treatment Rates at the Selected Sites ....................................................... D-1 Lime Consumption Rate Calculations ............................................................. D-2 Graph of Lime Quantity vs. % P2O5 in the Waste Water................................. D-3 APPENDIX E Pond Water Analysis...............................................................................E-1 APPENDIX F Lime/Limestone Suppliers for Neutralizing Acidic Waste Water Spills from Holding Ponds......................................................................F-1 Quicklime Supplier ....................................................................................................F-1 Hydrated Lime Supplier.............................................................................................F-1 Pulverized Limestone Supplier ..................................................................................F-2 Limestone Supplier ....................................................................................................F-3 APPENDIX G NLA Member Lime Plants, U.S. & Canada .......................................... G-1 APPENDIX H Maps ...................................................................................................... H-1 IMC-Agrico

• Central Florida Phosphate Area .......................................................................... H-1 • Central Florida .................................................................................................... H-2

APPENDIX I Chemical Lime Co. Information ............................................................... I-1 APPENDIX J Report on “Evaluation of the Effectiveness of Neutralizing Spills of Acid Waste Water from Holding Ponds” by PBS&J......................................................................................................J-1

xi

LIST OF TABLES Table Page 1. Comparison of Amounts of Compounds to Treat a Generic Spill ..............................12 2. Required Equipment and Cost .....................................................................................19 3. Manpower Requirements for Large Ponds ............................................................... A-1 4. Manpower Requirements for Spill Remediation ..................................................... A-2 5. Equipment List per Treatment Station .......................................................................B-2 6. Monthly Mean Flow Rates from October 1996 to September 1997 .........................C-1 7. Daily Mean Peak and Low Flow & Site Location ....................................................C-2 8. Site Information ....................................................................................................... D-1 9. Treatment Rate in Tons of Dry Quicklime per Hour ............................................... D-1 10. Quicklime ............................................................................................................... D-2 11. Hydrated Lime ....................................................................................................... D-2 12. Pond Water Analysis ...............................................................................................E-1

1

EXECUTIVE SUMMARY REVIEW

A review of the American Cyanamid spill in 1962 at Hookers Prairie includes the action taken and a discussion of the results. A short description of the accidental spill at Mulberry Phosphates in Mulberry, Florida is also included. STUDY

A study of how the industry could successfully treat a possible future accidental acidic waste water discharge from a holding or cooling pond was conducted. A generic spill of 50 million gallons of typical central Florida acidic waste water was defined to provide a basis for design and treatment The design was for the spill to discharge in six hours and to flow into the nearest tributary or river as a continuous concentrated unit flow. Treating the generic spill will require site-specific studies to establish an ENP for the individual plant, whether it is in central Florida or in other parts of Florida or the country. TREATMENT PLAN

Using this generic spill as a basis, the general requirements of an ENP were developed. The ENP includes continuous monitoring of possible discharge points to alarm if a discharge occurs, prearranged and predesigned treatment stations at predesignated locations on the river, cleanup plans, and preliminary cost estimate. The ENP would require each plant to develop and staff a Spill Treatment Team, hereafter called the Team. The Team must include assigned personnel and have quarterly training. Chemical Lime Company, the recommended central Florida lime supplier, recommends using hydrated lime slurry based on actual neutralization tests and past experience with slaking using water with sulfate levels above 2,000 ppm. In water with more than 2,000 ppm, the slaking reaction rate is too slow to be practical for hydrating pulverized quick lime in the river. Unlike the old mechanical lime transport equipment used during the 1962 American Cyanamid spill, the modern lime transports are pneumatic. Lime treatment equipment is recommended at each phosphate complex and a supply of quicklime and hydrated lime slurry will be needed to neutralize the accidental spill. The recommendation of this study is to deliver quicklime to the phosphate complexes, slake it into hydrated lime slurry, and then truck the hydrated lime slurry to the treatment sites. The information on lime and equipment suppliers should be reviewed and upgraded annually to reflect any changes that could affect the ENP. A preplanned quick response is the key to success.

2

RECOMMENDATIONS

This study recommends the following actions be taken:

1. Installation of a continuous pH monitoring system to alert company personnel to an accidental spill from an acidic waste water holding pond.

2. Development of an ENP. This must be a joint plan with all the other phosphate complexes, lime suppliers, trucking companies, and suppliers of rental equipment in the surrounding area.

3. Establish slaking sites at each phosphate complex as described in Generic Spill - Item 6. Quicklime Hydrating Systems.

4. Establishment of treatment sites for each active phosphate complex. 5. Use of the PermaBatch® or PortaBatch® slaker to make maximum use of

available pulverized or pebble quicklime. 6. Use of low sulfate water (less than 2,000 ppm SO4) for the slaking. 7. Quarterly training for the TEAM with all equipment. 8. Small-scale testing of the equipment used at the spill treatment sites, i.e., in

plant water treatment. 9. Training on leased diesel-driven air compressors and generators.

JUSTIFICATION FOR RECOMMENDATIONS

The economics were based on actual neutralization tests. Based on past experience, Chemical Lime Company recommends using hydrated lime slurry rather than slaking with water having sulfate levels above 2,000 ppm. This confirmed HiTech Solutions’ design of hydrated lime slurry treatment stations.

1. As stated in the section on Treatment of a Generic Spill, the long- and short-term effects on the river system can be reduced by a quick preplanned remediation response. Also, see the section on pH Monitoring System.

2. As stated in the section on the Emergency Neutralization Plan, we recommend an ongoing industry-wide ENP that requires the corrective action to begin as soon as possible.

3. As stated in the section on Treatment Plan, unlike the old mechanical lime transport equipment used during the 1962 American Cyanamid spill, the modern lime transports are pneumatic. Lime treatment equipment is recommended at each phosphate complex and a supply of quicklime and hydrated lime slurry will be needed to neutralize the accidental spill. The recommendation of this study is to deliver quicklime to the phosphate complexes, slake it into hydrated lime slurry, and then truck the hydrated lime slurry to the treatment sites.

4. As stated in the section on Treatment Site, preplanned and preestablished treatment sites are critical for the successful and timely delivery of the hydrated lime slurry.

3

5. As stated in the section on Quicklime Hydrating Slurry System, this study recommended that future slakers be the PortaBatch® type. If a spill occurred outside of Central Florida (White Springs), the PortaBatch® slakers could be moved to the area where the hydrated lime slurry is needed. As stated in the cost estimate note, this equipment can be used for the normal plant water discharge treatment on an as-needed basis.

6. As stated in the section on generic spill, based on actual neutralization tests and past experience with slaking, using water with sulfate levels above 2,000 ppm, Chemical Lime Company recommends using hydrated lime slurry.

7. As stated in the section on Spill Treatment Team, the Team would have quarterly training sessions with the equipment to ensure proper training and equipment readiness.

8. As stated in the section on River Mixing Equipment, we recommend testing improved mixing system by putting perforated hoses (like soaking hoses) along the bottom of the river for 100 feet.

9. As stated in the section on Future Emergency Neutralization Plan, the Team would have quarterly training sessions with the equipment to ensure proper training and equipment readiness.

5

INTRODUCTION PHOSPHATE INDUSTRY PLANT DESCRIPTION Ground phosphate rock is reacted with sulfuric acid to produce phosphoric acid and precipitate gypsum, calcium sulfate dihydrate (CaSO4·2H2O). The gypsum is separated from the phosphoric acid by filtration. The phosphoric acid is used to make granular fertilizers such as DAP or TSP. The gypsum is slurried with recycled water and pumped to a holding pond on the top of a large gypsum stack. This results in the containment of millions of gallons of acidic process water on top of a continuously growing gypsum stack. Around the base of the gypsum stack is a seepage collection ditch. Some phosphate complexes have separate cooling water ponds. Typical process water contains about 1.3% phosphoric acid with an average pH of 1.75. The other major components are fluorine and sulfate. THE AMERICAN CYANAMID SPILL IN 1962

In 1962, the American Cyanamid Phosphate Complex at Brewster, Florida, had an uncontrolled discharge of acidic water from a new gypsum stack. The cause of the spill was a break in the dike around their new gypsum stack/cooling pond. The first indication of the spill was a call received about some cows standing in stomach-deep acidic water. The plant was using the old stack and cooling pond, so there was no effect on the plant operation. A quick check of the pond system revealed that a 100-foot wide section of the north dike in the new gypsum stack had washed away. The amount of water released was estimated at 3,000,000,000 gallons. Hookers Prairie received the full onslaught of the spill and diluted it to around 2000 ppm SO4. The outlet of Hookers Prairie was restricted before it discharged into the South Prong of the Alafia River. This provided time for treatment with lime in the tributary before the spill reached the main river. HISTORIC RIVER TREATMENT

The American Cyanamid plant discharge was handled by dumping lime at seven treatment stations along the river and hydrating it in the river. Air compressors with air lances were used to mix the lime in the river. A plan to put hydrated lime slurry in the river wherever possible after the spill will reduce the severity, but is less effective than a full emergency neutralization plan. THE 1962 ACTION PLAN

All regulatory agencies were notified immediately. Within hours a plan of action was

outlined and put into effect. Lime trucks were ordered and local and county officials were asked to help control traffic in the spill area. Seven liming stations were set up at different

6

points along the river. Several stations were set up on private property with the owners’ permission. Due to the dryness of the season, the river water flow was low and slow. This slowed the velocity of the discharge from Hookers Prairie and allowed time to set up the liming stations. The stations were manned around the clock for weeks and at each station, lime was brought in by trucks and discharged into the river. After the lime had been added to the river, additional mixing was done with air compressors and air lances. THE 1962 RESULTS

As a result of the American Cyanamid treatment team’s quick action, no low pH water got beyond the bridge over the South Prong of the Alafia at Bethlehem Road, which is approximately 6 miles from the start of the stream. The around-the-clock action at the seven stations was continued for weeks. Then the liming at the station farthest downstream was discontinued because the pH was satisfactory. As the pH of the water in the river returned to acceptable levels, the downstream liming stations were discontinued one at a time. At the outlet of Hookers Prairie, the treatment was continued for several more weeks. One man was assigned to pick up the dead fish at each station. The fish kill was low, with only two bushels of fish collected. As this study will show, the ENP implemented after the spill by the American Cyanamid’s team was very close to the final recommendations of this study. A 1997 OCCURRENCE

Another unexpected pond water dam break occurred in December 1997 at Mulberry Phosphates in Mulberry, Florida. This spill was estimated at about 50,000,000 gallons. The discharge from the gypsum stack was very rapid and was complete in about an hour. The vast majority of the spill went south of the phosphate complex and into a marsh and ponds belonging to CF Industries. Only a small part of the spill discharged into the North Prong of the Alafia River. Mulberry Phosphates made an attempt to treat the discharge in the river with lime, but was stopped by the Florida Department of Environmental Protection (FDEP). The estimated fish kill was reported to the Ledger to be between 50,000 and 3,000,000 (fish, blue crab, and shrimp) depending on the source of the report. The continuous stream of acid wastewater traveled at about 0.4 mph down the Alafia River to Tampa Bay. A study completed in 1999 by PBS&J on the effectiveness of spill treatment in rivers is included as Appendix J. FUTURE EMERGENCY NEUTRALIZATION PLAN

The gypsum stacks and holding ponds that are being built now and in the future will meet improved standards of lined bottoms and safer setbacks on the slopes. This will reduce the probability of an accidental wastewater discharge in the future.

7

To contend with an accidental wastewater discharge will require an ENP. This plan will cover the preplanning of treatment stations, complete with required equipment and neutralization material. It will describe a plan of action that will include continuous monitoring of possible discharge points, the location for preestablished treatment sites, equipment required, and staffing needed for quick response. The plan will recommend equipment and the development of a Team. The Team would have quarterly training sessions with the equipment to ensure proper training and equipment readiness. The plan will recommend a preagreed joint effort among the phosphate operating plants to supply the required labor for the treatment sites and prearranged agreements with vendors and suppliers of leased equipment, lime, and trucks.

9

GENERIC SPILL

DEFINITION OF A GENERIC SPILL

This report will cover the problem of a sudden/accidental discharge of acidic waste water from a cooling pond or gypsum stack into a river. Because all of the parameters can vary so much, the generic spill will be defined by the following parameters:

1. A spill of 50,000,000 gallons of acidic waste water 2. The spill will have the following analysis

P2O5 = 13,236 ppm F = 6,185 ppm

SO4 * = 7,087 ppm pH = 1.75

3. Estimated time of discharge is six hours unless the flow is restricted 4. The spill will enter a tributary of the primary river for that area 5. Estimated river speed between 0.3 and 0.5 miles per hour with 0.5 mph used

for the time allowed for the location of the treatment stations

There is an undefined cost to the operation of the plant associated with the loss of the P2O5 in the acidic waste water spill. If fresh makeup water is required to operate the process water system, there is a loss of P2O5 from the plant operations to the makeup water. This will continue until a new equilibrium level of P2O5 in the acidic waste water is established. TREATMENT OF A GENERIC SPILL

Treatment of a spill into a tributary will require preplanned treatment sites for treatment with hydrated lime slurry. The reasons for this approach as opposed to adding quicklime straight into the tributary are based on the efficiency of reaction with acidic waste water and the availability and deliverability of the lime solution. The factors that affect the efficiency of the reaction are:

1. The distribution of the hydrated lime slurry across the tributary 2. Contact time between reactants which is based on

1) Pre-hydrated lime slurry 2) Suspension of hydrated lime slurry in water for improved contact

3) Agitation of the treated water ______________

*Based on actual neutralization tests and past experience with slaking using water with sulfate levels above 2,000 ppm, Chemical Lime Company recommends using hydrated lime slurry. This confirmed HiTech Solutions’ design of hydrated lime slurry treatment stations.

10

3. Speed of the river 4. Greater than 2,000 ppm of SO4 in the tributary. In water with more than 2,000

ppm, the reaction rate is too slow to be practical for hydrating pulverized quick lime in the river.

There may be occurrences that arise where regardless of preplanning, a spill the size

of the defined generic spill or larger will occur. If this happens there is no way with present operating conditions that the surge of water can be treated at the point of discharge. To remediate the spill, quick action is required to inject a hydrated lime slurry at several points down the river. To be ready for such an occurrence, an ENP should be developed for the initial response. After the spill has occurred, and the initial response completed, the neutralization of the residual acidic waste water in the spill area will be addressed. The faster the remediation response to such a spill, the less severe the long- and short-term effects on the river system will be.

If the generic spill is below 5,000,000 gallons of acidic waste water and the sulfate levels in the wastewater-contaminated river stay low (less than 2,000 ppm SO4), quicklime (fine fraction of CaO) can be slaked directly in the river until the hydrated lime slurry arrives. If the hydrated slurry systems break down for any reason, quicklime can also be used while they are being fixed. During these emergency periods, agitation must be maximized and pH monitored more frequently. THE EMERGENCY NEUTRALIZATION PLAN

The treatment of a massive spill reaching the river requires the corrective action to begin as soon as possible. This will require an ongoing industry-wide ENP. We recommend the following plan. This plan would consist of each phosphate complex having a Spill Alert System. The System would continuously monitor the locations where an accidental spill, based on the site-specific study, would flow. It would alarm when an accidental spill has occurred. A trained, local-plant Spill Treatment Team would respond to the alert. A communication system could be used to inform the teams at the other plants, regulatory agencies, recommended lime supplier (Chemical Lime Company), and recommended trucking company (Commercial Carrier Corporation). A quicklime hydration station would be started to prepare the hydrated lime slurry at several phosphate complexes. Prepared treatment sites on the river that include slurry distribution systems, river-mixing systems and a pH measurement program would be activated. This study recommends the ENP contain, but not be limited to, the following:

1. Spill Alert System 2. Spill Treatment Team 3. Neutralization Data 4. Quicklime Supplier 5. Trucking Company

11

6. Quicklime Hydrating Slurry System 7. Hydrated Lime Slurry Truck Deployment 8. Treatment Site

1) pH Monitoring System 2) Slurry Distribution System 3) River Mixing System

9. Neutralization of Spill Area

Spill Alert System At the present time, all plants are required by FDEP to continually monitor their water discharge as it leaves the plant property. However, the present system does not take into account an accidental spill that could leave the plant property at a different location from their normal water discharge. To improve the present system in relation to an accidental spill, the integrity of the acidic holding ponds can be monitored at all times by a continuous warning system located in the central control room of the phosphoric acid plant. This monitoring can be done with a series of pH meters located in various points around the area of pond water containment. During the site-specific study, the location of the pH meters will be determined relative to where an accidental spill would flow. The readings would be continuously transmitted back to the plant control room by radio telemetry. These pH meters should have the same standard maintenance as provided to the meters on the plant fresh water discharge streams. Spill Treatment Team The future ENP would require a team of personnel at each plant to handle a spill correctly and expeditiously. During the site-specific study a spill treatment plan would be developed and procedures written for each phosphate complex. There would be a team for each shift. The Team would consist of plant personnel from operations, instrumentation, and maintenance. People would be assigned to fill all the requirements for the various duties. The Team would have quarterly training sessions with the equipment to ensure proper training and equipment readiness. Each plant Team would be coordinated with the Team at the other phosphate complexes. The ENP should be reviewed yearly for changes in requirements, treatment location, equipment maintenance, technology changes, and manpower requirements. Neutralization Data The neutralization requirements for this spill will be based on the stoichiometric amount of the neutralization compound required to react with the P2O5 and fluorine in the pond water. Three readily available compounds are commonly used to neutralize acidic water. The compounds are limestone (calcium carbonate -- CaCO3), hydrated lime (calcium

12

hydroxide -- Ca(OH)2) and quicklime (calcium oxide -- CaO). Quicklime is recommended, as it is the most efficient of the three forms of lime and is readily available where it is required in Florida. It can easily be slaked to a hydrated lime slurry with PermaBatch® or PortaBatch® lime slakers and transported in available trucks in the quantities necessary to treat the generic spill. The amount of water that these compounds can treat is relative to the compound and its purity.

Commercial quicklime (calcium oxide -- CaO) contains about 92% Ca, while

hydrated lime (calcium hydroxide -- Ca(OH)2) contains about 94% Ca(OH)2. Based on the analysis of the generic pond water in a spill, the amounts of the different compounds that are necessary to treat the generic spill are: Table 1. Comparison of Amounts of Compounds to Treat a Generic Spill.

Compound Estimated Tons of Compound as Solids Lb./1000 gal. Efficiency per Million Gal.

Quicklime 177 85% 104 (92% CaO) Hydrated Lime 229 85% 135

25% Slurry (94% Ca(OH)2)

Limestone neutralization was not considered for central Florida because of three

factors:

(1) Pebble or pulverized quicklime is readily available that can be quickly slaked into a hydrated lime slurry, which can be transported to treatment sites in locally supplied, fresh pulverized quicklime was selected.

2) Limestone would only bring up the pH to a maximum of 4.0, while hydrated lime slurry can complete the neutralization to a normal pH of 7.0 to 8.0. (The State of Florida surface water standards require that the discharge be above 6.0 pH.)

(3) Use of limestone to neutralize the generic spill would require 9,700 tons, compared to 5,200 tons of quicklime.

However, in other areas they may look at limestone for primary treatment or storage considerations, with hydrated lime slurry as the final treatment. Quicklime and hydrated lime, supplied in bags, both have a short storage life of only about three months. After this time, H2O and CO2 intrusion will start to convert the materials to limestone. Therefore, locally supplied, fresh pulverized quicklime was selected.

13

Warning. Unslaked quicklime (CaO) or caustic (NaOH) should be added directly to the river only under emergency conditions when other materials are not available, for several reasons.

1. It can result in a layer or pockets of high-pH material on the bottom of the river. This layer or pocket of lime or caustic is harmful to the organisms on the bottom of the river.

2. It needs extra safety precautions and special equipment in handling to readily minimize burns to the personnel handling the material.

3. Any spillage would be harmful to the environment and would require its own cleanup procedure.

Quicklime Supplier After researching the central Florida area for the availability of different neutralization material from local suppliers, pulverized or pebble quicklime supplied by Chemical Lime Company was selected. Pneumatic tanker trucks from Commercial Carrier Corporation can deliver it to the PermaBatch® or PortaBatch® slakers located at each phosphate complex as determined by the study for the specific site future spill. The selected slakers can efficiently slake either pulverized or pebble quicklime.

For central Florida, with ten active fertilizer complexes, quicklime would be delivered to the quicklime hydrating slurry system at each complex. Chemical Lime Company currently has 500 tons of pulverized quicklime storage at their Nichols plant that they will increase to 1,000 tons within a year. Loaded rail cars at this site provide an additional 800 tons for a total supply of 1,800 tons. The Fort Lauderdale plant site has 2,400 tons of pebble quicklime storage capacity plus up to 1,600 tons in rail cars, for a total of 4,000 tons. Trucks can haul the quicklime to central Florida plant sites in five to six hours. The Nichols plant can currently load 24 trucks for 600 tons within 24 hours. Additional loading capacity to provide 1,200 tons within 20 hours, 2.4 trucks per hour, requires consideration. The Fort Lauderdale plant can currently load 100 trucks per day for a 2,500 ton supply. The combined total required is 5,200 tons of quicklime with 4,000 tons from Fort Lauderdale. In order to meet the schedule requirements of the lime slakers, the loading capability at Fort Lauderdale would have to be increased from four to eight trucks per hour. This capacity increase would permit Fort Lauderdale to load the required quicklime in 20 hours. Chemical Lime Company can also supply quicklime from Montevallo, Alabama in 14 hours. A weekend pager will initiate emergency supply on weekends and after 5:00 P.M. on weekdays. Additional storage of available quicklime in existing Florida Phosphate Council member silos in central Florida should be considered.

The Potash Corporation of Saskatchewan (PCS) plants at White Springs, Florida can be supplied with quicklime from the Chemical Lime Co. plant in Montevallo, Alabama, with a delivery time of eight hours. Slaking quicklime at the sites in central Florida and trucking

14

the slurry to White Springs should be considered. Another alternative, that of hauling the PortaBatch® slakers from central Florida to the site, should be considered in the site-specific program at White Springs.

Trucking Company The number, location, and availability on short notice of the large number of trucks required for the dry pulverized quicklime and the different trucks required for the hydrated slurry that will be required for a spill of this size could be a major problem. However, discussions with Commercial Carrier Corporation have removed this problem. Commercial Carrier Corporation has more than a sufficient number of trucks to meet any need. Since Commercial Carrier Corporation is the trucking company that Chemical Lime Company already uses to carry its lime, it would reduce the planning difficulties required for a project of this size and with this project’s time constraints. For these reasons, Commercial Carrier Corporation is recommended as the trucking company to utilize for spill planning. Quicklime Hydrating Slurry System All the quicklime will be shipped to the phosphate complexes and slaked to form a hydrated lime slurry that can be transported and utilized quickly with a high reaction efficiency at each treatment site. To accomplish the large amount of slaking of quicklime necessary for effective treatment of a generic spill, there are several things required at each of the active phosphate complexes:

1. Two lime unloading/storage silos 2. A PortaBatch® or PermaBatch® lime slaker 3. Fresh water - 1,200 gpm 4. Electrical power

5. A slurry storage tank (approximately 20' diameter x 12' high) 6. Trained personnel (Team)

The system would be designed to receive a truck of pulverized lime into one silo while discharging from the other silo into a PortaBatch® slaker. The PortaBatch® would be modified to receive 17,000 gallons of water in 15 minutes and then the addition of 25 tons of quicklime in 15 minutes. The mixture would slake for 10 minutes and then be pumped into a slurry storage tank. The trucks would load out of the slurry storage tank while the slaker would be preparing another batch of hydrated lime slurry. With a PortaBatch® at each phosphate complex, it would give a combined total of 250 tons of slaked lime per hour, which would meet the projected requirements. There are two types of slakers, the portable one (PortaBatch®) and the permanent one (PermaBatch®). Both types are being used in the phosphate industry but this study recommended that future slakers be the PortaBatch® type. If a spill occurred outside of central Florida (White Springs), the PortaBatch® slakers could be moved to the area where the hydrated lime slurry is needed.

15

Hydrated Lime Slurry Truck Deployment The total amount of hydrated lime slurry required to raise the pH from 1.75 to 6 of 50,000,000 gallons of pond water is about 6,750 tons made from 5,200 tons of quicklime. Each phosphate complex, with an active waste water system, will be assigned an emergency response number by the Florida Phosphate Council, which coordinates the industry emergency spill treatment plan. To neutralize the generic spill, five sites are required with a treatment period of six hours per site, which is the time expected for the spill to pass each site. Each site will be assigned slurry trucks for a six-hour treatment period. The trucks will pick up hydrated lime slurry from the slakers at the pre-designated phosphate complexes. Two sites will be in service at one time, with an overlap of two hours. Ten phosphate complexes are currently in operation in central Florida. Treatment Site There would be five preplanned treatment stations along the river. Preplanned and preestablished treatment sites are critical for the successful and timely delivery of the hydrated lime slurry. If during the site-specific study, sites with existing private or public access to the river are located in the right place and emergency access can be guaranteed, these should be considered. If none exist, these sites should be owned or leased, with emergency right-of-way access, so that permanent site improvements can be made. These sites must be easily accessible by trucks and have sufficient area for working and temporary storage of equipment. Each individual site would need to be about an acre in size with a strip of land 1,250 feet long bordering the river (see Sketch 1309–1, Appendix B).

At each treatment site, when the spill has reached that location, hydrated lime slurry

from the nearest six slakers will be hauled by trucks to the site and pumped to slurry distributors each hour, for a total of 225 tons per hour of hydrated lime for approximately 6 hours at each treatment site. On this basis the total time required for slaking and distribution of the 6,750 tons of hydrated lime at the five treatment sites is 30 hours.

The locations of the five treatment sites will be determined during the site-specific study. The first treatment site should be located 1½ to 2 miles downstream from the spill site on the tributary or river to allow up to 4 hours to transfer the first truckloads of hydrated lime slurry to the first site. This time is also required to transport leased equipment and distribution troughs to the site, set up the equipment and be ready for hydrated lime slurry treatment of the acidic waste water in the tributary or river. The other sites should be spaced 2 to 2½ miles downstream from each other. Upstream pH monitoring at each site will indicate when to start lime treatment. The continuous pH monitoring downstream of each site will provide a guide for operation of the system and indicate when the slurry trucks should be moved to another downstream treatment site. After the major spill has passed the first treatment station, there is expected to be continuing drainage of acidic waste water into the stream that would require one discharge system with trucks to remain in service at the first location for some days.

16

pH Monitoring System. To aid in determining the effect of a spill and when recovery has occurred, a weekly pH reading could be taken and a historical record compiled. This historical record of the pH at each location will be necessary since the only published record of the pH of the river may be at some location too far downstream to have relevancy to the individual treatment sites. The records from the U.S. Geological Survey report for the North and South Prong of the Alafia River are some distance from anticipated treatment stations (see Appendix C).

Once a spill has occurred, additional pH measurement systems would be taken to the predetermined spill treatment locations on the river. With this information, you could monitor the spill as it flowed down the river. This would allow maximum utilization of the treatment stations. These pH systems would also provide information on the effectiveness of the treatment stations.

Slurry Distribution System. The distribution of the neutralization slurry into the river is very important. The proposed method is to use a slurry pipe and distribution trough at four places 500 feet apart at each site. A pre-engineered slurry system would include a series of four distribution troughs that are designed to have permanent anchor points and should be preinstalled on the river bank, otherwise they can be stored at the phosphate complex. The troughs would be swung out over the river when the treatment site is operating (see Sketch 1309–2, Appendix B). At each slurry distribution trough, a portable pump on a trailer or skid with an inlet manifold to handle two trucks at once would be brought in from the plants by the Team. The pump would be designed to discharge at a rate of 615 gpm of hydrated lime slurry. At this rate, each treatment site would be capable of handling the equivalent of 174 tons per hour of quicklime. River Mixing Equipment. After the hydrated lime slurry is originally distributed across the river, it may start to settle depending on the velocity of the river at that location and the amount of slurry added. (At the generic spill river speed of 0.5 miles per hour, the velocity is 0.75 feet per second. For proper treatment, a design flow of 6 feet per second would be required to maintain solids in suspension). To increase the utilization of the neutralization slurry, air lances were found to be very effective during the American Cyanamid spill in 1962. Based on this experience, air lances are acceptable for mixing but, we recommend testing an improved mixing system by putting perforated hoses (like soaking hoses) along the bottom of the river for 100 feet. These can be used to mix the solids that have settled on the bottom of the river and will give an effect similar to a fluid bed. An air header for each set of hoses will be installed just in front of each slurry distribution trough (see Sketch 1309–3, Appendix B). A diesel-driven air compressor would be required to supply the agitation air for each set of hoses. Four air compressors would be required for each active treatment site for six hours and could then be relocated to another downstream treatment site.

17

Neutralization of Spill Area. Immediately after the initial spill from the acidic water holding pond has been contained and treated, the cleanup of the area that the water went through to reach the river should begin. To minimize the effect on the environment, the channel where most of the acid water flowed from the settling area to the stream or river should be cleaned first. The plan could include, but is not limited to, rinsing the channel with a hydrated lime solution to bring the surface of the channel, along with any small pools of acid water, back to a 6-8 pH. The design parameters will be detailed in Appendix A. AMMONIA INJECTION

The possibility of using liquid ammonia as an additional source of material to neutralize large quantities of acidic waste water was investigated. The question about the use of ammonia is whether it would cause more harm to the environment than the acidic water. The reason for this concern is the amount of nitrogen that would be added to Tampa Bay. FDEP was asked the question, “Which is worse, low pH water or a large concentration of nitrogen?” The response was that a study would have to be done to determine whether it would be beneficial or harmful if ammonia were used to neutralize the acidic waste water. Our recommendation, at this time, is to not include the use of ammonia in the Emergency Neutralization Plan. If an ammonia study is done, and the ammonia would be beneficial, the method of injection must be carefully designed.

If injection of liquid ammonia is an accepted alternative source of neutralization material, it could be used for spills from certain phosphate complexes. The Tampa Bay Ammonia Pipeline crosses the Alafia River at two locations. At a point about one mile above Lithia Springs on SR 640, and on the South Prong of the Alafia River about 2 miles east of SR 39 on SR 640. A large amount of liquid ammonia could be utilized by construction of a delivery station from the ammonia pipeline, complete with a meter at each location: A pumping system for river water at 50 psi would be required to supply water for mixing with the ammonia in a pipe before being fed into a distribution pipe system and discharged into the river. The premixing of the ammonia and water (70% water and 30% ammonia) in a pipe would prevent a cloud of ammonia vapor from forming. This could put up to 75 tons per hour of ammonia in the river to neutralize the acidic waste water.

19

COST ESTIMATE

The following is an estimate of the equipment cost for each Phosphate Complex if five independent sites are required (no shared sites). Table 2. Required Equipment and Cost.

Equipment Number Required Cost

Slaker 1 $120,000 Silos, 35 ton 2 @$45,000 90,000 Feeders and bag house 2 @$30,000 60,000 Slurry tank with agitator 1 55,000 Slurry pumps, 4 on trailers 4 @$20,000 80,000 Slurry pump at plant 1 60,000 Air compressors 4 (RENT) 0 Generators for lights 4 (RENT) 0 Site prep (does not include land) 5 @$20,000 100,000

Sub total $565,000 Note: This equipment can be used for the normal plant water discharge treatment on an as-needed basis.

21

REFERENCES Cardinale, T. 1998. Mulberry Phosphates Incorporated. December 1997 acid spill. Water quality impacts on Alafia River and Tampa Bay. A Water Management Division Report. Environmental Protection Commission of Hillsborough County, Florida. Coffin JE, Fletcher, WL. 1998. Water resources data for Florida, water year 1997, volume 3A: Southwest Florida surface water. Report No. FL-97-3A. Tallahassee, FL: U.S. Geological Survey, Water Resources Division. p 202-203, 206. Mulberry Phosphates, Incorporated. 1998. Consultant report. Key findings. Mulberry Phosphates, Incorporated. 1998. Department of Environmental Protection, Florida Marine Research Institute. Assessment of fish, blue crab, and pink shrimp mortality in the tidal portion of the Alafia River following the December 1997 acid spill, with a preliminary assessment of faunal recovery. May 27, 1998. Williges K, Neugebauer V, Cook C. 1998. An initial assessment of the impacts to vegetation resulting from the Alafia River acid spill. Florida Department of Environmental Protection Bureau of Mine Reclamation.

APPENDIX A

REMEDIATION OF AREAS AFFECTED BY THE SPILL

A-1

REMEDIATION OF AREAS AFFECTED BY THE SPILL

POND AND SWAMP REMEDIATION

The design requirements for remediation of large ponds and swamp areas are standard. The area is treated with bag hydrated lime spread across the surface of the water. Manpower Requirements Table 3. Manpower Requirements for Large Ponds.

Duty No. of People

Handle bagged hydrated lime 2 Boat crew to spread the lime 2 pH sampling * Supervision 1

Total 5 * The pH sampling would be done by the boat crew with a portable meter.

Each additional crew would require four people. All personnel for this cleanup will be supplied by the phosphate complex that incurred the spill. SPILL REMNANT REMEDIATION OF TRIBUTARIES

The cleanup of the remnants of the spill where it entered the tributary and/or river may necessitate a different approach. One possible scenario is to send in teams of men and equipment to spray the approaches, small channels, and banks with a lime slurry to neutralize the remaining pockets of acid water. The equipment needed for this operation is quite different.

• PortaBatch® Slaker at the phosphate complex to prepare the hydrated lime slurry

• Several long hoses hooked up to a pump on the hydrated lime slurry truck • Hand-held pH equipment • Acid-protective suits and proper protective equipment for the handling of

lime

A-2

Manpower Requirements To fully man a single system would require: Table 4. Manpower Requirements for Spill Remediation.

Duty No. of People

Personnel for the hoses & slaking 3 Truck driver 1 Supervisor 1

Total 5 Each additional team would require four people.

APPENDIX B

TREATMENT STATIONS DETAILS

B-1

TREATMENT STATIONS DETAILS LOCATION

The proposed Treatment Stations require prepared sites along the river. Based on an estimated speed of the river of between 0.3 to 0.5 miles per hour (it is beyond the scope of this paper to accurately calculate the river speed at different levels of water flow and at different locations along the river) it is proposed that the stations be located at about 2, 4, 6, 9, and 12 miles from the expected entry point of the discharge. This will allow time for the stations to be manned before the discharge has passed them. SIZE AND LAYOUT

The site should be fronting the river with access for heavy equipment to install

distribution headers and air mixing systems 750 feet upstream and 1300 feet downstream from the center of the site. The site must offer easy access to heavy equipment and 20-ton slurry trucks. At each slurry header there will be room for a diesel-powered 615 gpm low-head pump on a trailer and room for two hydrated lime slurry trucks to hook up to the pump inlet manifold. Space should be available for two additional trucks to prepare to fill the positions at the pump header. At each air mixing site there should be room for a truck and air compressor. About an acre should be adequate to accomplish these requirements. The area should be fenced for security. UTILITIES

The utilities required for each site will be minimum: Portable lights for night operations and portable sanitation facilities. PRELIMINARY SKETCHES Site Sketch 1309-1

This is the basic layout of a site showing the three treatment sites and their relative location.

Slurry Distribution Trough Sketch 1309-2 The slurry distribution trough can be installed once the site has been picked. This

trough will be installed on a steel post with a swivel so that when it is needed it can be swung into position. Each trough will need to be made for the exact location where it is to be installed.

B-2

River Mixing System Sketch 1309-3

The air mixing system is composed of a boom which has an air manifold with several flexible hose connections to attach 100 feet of ½” stainless steel tubing. This will provide an aerated area to improve the mixing of the lime slurry for improved utilization of the hydrated lime slurry. The boom will be installed on a steel post with a swivel so that when it is needed it can be swung into position. It will be installed after the site is selected and the flexible hose and tubes will be installed when required. The exact design for each station will be determined by the site-specific study. With this type of installation a boom truck or cherry picker would not be required. Each air mixing system will require its own air compressor.

EQUIPMENT LIST PER TREATMENT STATION

The equipment required for each treatment station is listed below in Table 5.

Table 5. Equipment List per Treatment Station.

Equip. No. Number Reqd. Description

1101 4 Lime Slurry Pump with Trailer (1 per plant) 1301 4 Air Compressor (rented) 1302 4 Air Mixing System (2 sets of flexibles per plant) 2102 4 Slurry Distributor (installed where possible) 3100 1 Portable lights (rented)

MANPOWER REQUIREMENTS PER SHIFT PER STATION

Eight men will be required per shift at each treatment station: an instrument man, three truck drivers, three labors, and a supervisor. An additional supervisor will be required to coordinate the lime from other plants and suppliers.

For two treatment stations the manpower requirement will be 16, plus a coordinator for a total of 17 people. The manpower and equipment will be supplied by ten or more different phosphate complexes. The complex that has the spill will use their Team to supply eight men and a coordinator to man and supply equipment for one treatment site. The second through fifth treatment sites will be supplied with Teams from other companies.

B-3

B-4

B-5

APPENDIX C

RIVER DATA

C-1

RIVER DATA U.S. Geological Survey Water-Data Report FL-97-3A Southwest Florida Surface Water

• Site Data Points

• Alafia River

• North Prong at Keysville, • South Prong near Lithia • Lithia

• Peace River

• Bartow • Fort Meade • Zolfo Springs • Arcadia

Table 6. Monthly Mean Flow Rates from October 1996 to September 1997. Avg. Minimum Maximum Site CFS* MMGPD CFS MMGPD CFS MMGPD Alafia River N.P. at Keysville 72 46 25 16 201 130 S.P. Near Lithia 52 33 8 5 184 119 Lithia 138 89 38 25 441 285 Peace River Bartow 115 75 18 11 564 365 Fort Meade 134 87 13 9 739 478 Zolfo Springs 293 189 80 52 1221 789 Arcadia 491 317 107 69 1970 1273

* CFS – Cubic Feet Per Second MMGPD – Million Gallons Per Day

C-2

USGS Water Resources Data Florida, Water Year 1997

• Site Data Points

• Alafia River • North Prong at Keysville, • South Prong near Lithia • Lithia

• Peace River

• Bartow • Fort Meade • Zolfo Springs • Arcadia

• Data from USGS Water Resources Data, Florida, Water Year 1997

• Site – Distance Upstream from River Mouth • 1997 Daily Mean Low Flow • 1997 Daily Mean Peak Flow

Table 7. Daily Mean Peak and Low Flow & Site Location. Upstream from 1997 Mean Peak Flow 1997 Mean Low Flow Site River Mouth – Miles CFS* MMGPD Date CFS MMGPD Date North Prong at Keysville 29 1880 1215 9/28 14 9 6/8 South Prong near Lithia 24 700 452 9/28 3 2 4/23 Lithia 16 3430 2217 9/29 19 12 6/8 Bartow 105 792 512 8/14 6 4 6/9 Fort Meade 92 1070 692 8/14 1 0.6 4/11 Zolfo Springs 69 2620 1693 8/14 42 27 6/6 Arcadia 36 3550 2294 9/29 59 38 3/13

* CFS – Cubic Feet Per Second MMGPD – Million Gallons Per Day

APPENDIX D

HYDRATED LIME SLURRY TREATMENT RATES

D-1

HYDRATED LIME SLURRY TREATMENT RATES

PROPOSED TREATMENT RATES AT THE SELECTED SITES

River flow rate 0.5 miles per hour Plug flow for 6 hours

Table 8. Site Information.

Site number 1 2 3 4 5 Site location (in miles from entry) 2 4 6 9 12 Time after spill that Treatment starts 4 8 12 18 24 Time after spill that Treatment stops 10 14 18 24 30

Table 9. Treatment Rate in Tons of Dry Quicklime per Hour. Site No. Time, Hrs 1 2 3 4 5 Average Rate Tons Added

4-6 174 174 348 6-8 174 174 696 8-10 174 174 348 1392 10-12 174 174 1740 12-14 174 174 348 2436 14-16 174 174 2784 16-18 174 174 3132

18-20 174 174 3480 20-22 174 174 3828 22-24 174 174 4176 24-26 174 174 4524 26-28 174 174 4872 28-30 174 174 5220

Total Tons per site 1044 1044 1044 1044 1044 5220

Hydrated Lime Slurry Flow Rate

Solids, TPH 225 Slurry, TPH 643

S.G. 1.26 GPM 2450 at each treatment site for 50 minutes each hour.

D-2

Pump Capacity - 4 pumps with a design rate of 615 gpm. Each pump would pump from two slurry trucks at the same time for 50 minutes per hour.

Lime Consumption Rate Calculations

Comp. Conc.(mg/l)

P2O5 13,236 F 6185 SO4 7087

pH 1.75

Table 10. Quicklime.

Total Pond Water Component P2O5 F Total 85% Efficiency Theoretical CaO, factor 0.789 1.47 Theoretical CaO, mg/l 10443 9092 Quicklime (92% CaO), mg/l 11351 9883 Quicklime, Lb/1000 gal 94.7 82.5 177 208 Quicklime, tons/million gal 47.3 41.2 88.5 104 Quicklime, tons/50 million gal 2368 2063 4431 5213 Table 11. Hydrated Lime.

Total Pond Water Component P2O5 F Total 85% Efficiency Theoretical CaO, factor 0.789 1.47 Theoretical CaO, mg/l 10443 9092 Hydrated Lime (94% Ca(OH)2), mg/l 14676 12777 Hydrated Lime, Lb/1000 gal 122 107 229 269 Hydrated Lime, tons/million gal 61.0 53.5 115 135 Hydrated Lime, tons/50 million gal 3050 2675 5725 6735

APPENDIX E

POND WATER ANALYSIS

E-1

POND WATER ANALYSIS

The phosphate complexes of central Florida were asked to submit an analysis of their acidic waste water (commonly referred to as pond water). The compiled results of the analysis show that the contents of the acidic waste water vary tremendously from plant to plant. These factors will greatly affect the neutralization requirements for an individual accidental spill. Some of the reasons for these variances are:

• Time of year the samples were analyzed • Production rates • Production efficiencies • Location of samples • Time since last production run (in some cases this has been in excess of a

year) Table 12. Pond Water Analysis.

Parts per Million

Plant pH P2O5 F SO4

1 1.24 21,031 12,011 9,956 2 2.05 8,102 1,294 5,233 3 1.11 16,927 12,183 5,970 4 2.20 9,207 634 10,989 5 1.50 16,896 8,400 8,613 6 1.90 12,139 5,100 5,100 7 1.80 11,325 5,825 4,325 8 1.98 12,500 5,520 8,500 9 2.00 11,000 4,700 5,100

Avg. 1.75 13,236 6,185 7,087

Low 1.11 8,102 634 4,325

High 2.20 21,031 12,183 10,989

APPENDIX F

LIME/LIMESTONE SUPPLIERS FOR NEUTRALIZING ACIDIC WASTE WATER SPILLS FROM HOLDING PONDS

F-1

LIME/LIMESTONE SUPPLIERS FOR NEUTRALIZING ACIDIC WASTE WATER SPILLS FROM HOLDING PONDS

Quicklime Supplier:

Firm - Chemical Lime Co. Phone - 863-425-1544 Location - Nichols Road, Mulberry Contact - John Thompson

- Elaine Thompson - Carl Anderson

Supply Delivery Rate $/Ton Freight

Trucks

Quicklime (92 to 94 % CaO) 60/day 95 $5 to $7/ton (Local plants)

Storage Capacity, tons 600 + 800 in rail cars - Supplied by Chemical Lime Co.

Montevallo, Alabama Phone - 1-800-388-8550

Truck Capacity, tons (bulk) 25

Particle Size Granular lime, 100% - # 8 mesh, 100% + # 80 mesh

Notice Time 1 to 2 days Delivery Time Mon. to Fri. @ 8:00 A.M. to 5:00 P.M.

Weekend pager for emergency supply

Truck firms for bulk supply with pneumatic tankers:

• Commercial Carrier Corp. 1-800-524-1101 - Contract Hauler • Walpole Trucking, Tampa 1-800-741-6800

Hydrated Lime Supplier:

Firm - Florida Crushed Stone Phone - 352-793-5151 Location - Brooksville Contact - Camile Beyerl Phone - 800-531-9044 Sales - Leesburg Phone - 352-787-0608 Contacts - Larry Korzon

- Caroline Orme

Supply Delivery Rate $/Ton Freight Trucks

F-2

Hydrated Lime 12/day Bulk @ 115 $ 0.13 / ton mile (94% Ca(OH)2) 50 Lb Bags @ 130 $ 0.08 / ton mile

Super Sacks @ 145 $ 0.14 / ton mile

Quick Lime (92 % CaO) - Supplied from Alabama firms to plant site

Truck Capacity, tons - bulk @ 23 - 50 Lb bags @ 24 - 3/4 ton super sacks (18) @ 14

Notice Time 20 to 24 hours Delivery Time Mon. to Fri. @ 7:00 A.M. to 3:30 P.M.

Truck firms for bulk supply with pneumatic tankers:

• Commercial Carrier Corp. 800-524-1101 • Walpole Trucking, Tampa 800-741-6800

Truck firms for transport with bags - Refer to limestone hauling

Pulverized Limestone Supplier: (for Ag Lime and Lime Rock Supply)

Mills Mine, E.R. Jahna Industries, Dade City Phone - 352-583-3080

1. Agricultural Lime

Firm - Ag Lime Sales, Inc. Phone - 863-638-1481 Sales Office - Babson Park Contact - Ray Bassett

- Vicki Gailey

2. Lime Rock

Firm - E.R. Jahna Industries, Inc. Phone - 863-676-9431 Sales Office - Lake Wales Contact - Pete Gall

F-3

Supply Delivery Rate $/Ton Freight Trucks

Ag Lime (90% CaCO3) 60/day normal 8.50 $ 0.08/ton mile Lime Rock (93% CaCO3) 120/day max. 3.50 - 4.00 $ 0.08/ton mile Truck Capacity, tons 21 mini - wheeler

23-24 semi - trailer

Particle Size - Ag Lime 90% -8 mesh, 80% -20 mesh, 50% -50 mesh - Lime Rock 1-1/2" & 3-1/2"

Notice Time 20 to 24 hours Delivery Time Mon. to Fri. @ 6:00 A.M. to 4:00 P.M.

Truck firms for transport:

• S&R Transport, Haines City 863-422-5985 • Florida Transport Service, Bartow 863-533-0565 • Trans-Phos Inc., Bartow 863-534-1575

Limestone Supplier:

Firm - Florida Crushed Stone Phone - 352-793-5151 Location - Brooksville Sales - Leesburg Phone - 352-787-0608 Contacts - Caroline Orme

- Larry Korzon

Supply Delivery Rate $/Ton Freight Trucks

Lime Rock 100/day 3.00 $0.08/ton mile

Truck Capacity, tons 24

Particle Size 3/8" min. to 1-1/2" max.

Notice Time 20 to 24 hours Delivery Time Mon. to Fri. @ 4:00 A.M. to 9:00 P.M. Truck firms for transport:

• Tri-State, Brooksville 800-883-0345 • Eagle Rock, Tampa 800-692-2996 • Montgomery, Coleman 800-725-3482

APPENDIX G

NLA MEMBER LIME PLANTS IN THE U.S. & CANADA (1998)

G-1

G-2

APPENDIX H

MAPS

H-1

H-2

APPENDIX I

CHEMICAL LIME COMPANY INFORMATION

I-1

I-2

I-3

I-4

I-5

APPENDIX J

“EVALUATION OF THE EFFECTIVENESS OF NEUTRALIZING SPILLS OF ACID WASTE WATER FROM HOLDING PONDS”

BY PBS&J

Prepared For:

HiTech Solutions, Inc. 129 S. Kentucky Avenue, Suite 3 01

Lakeland, FL 3 3 80 1

Prepared By:

PBS&J 5300 W. Cypress Street,

Suite 300 Tampa, FL 33607

March, 1999

Evaluation of the Effectiveness of Neutralizing Spills of

Acid Waste Water from Holding Ponds

Table of Contents

1 .O Introduction and Objective ................................................ 1

2.0 ScopeofWork ......................................................... 1

3 .O Task 1 - Recommendation of Potential Neutralizing Agent ......................... 3

3.1 Carbonates ....................................................... .

3.2 Oxides......................................................~ . ...4

3.3 Hydroxides ....................................................... .

3.4 Silicates ....................................................... ...5

3.5 Recommendations ................................................. 5

4.0 Task 2 - Design and Conduct of Acute Toxicity Bioassay Tests ..................... 6

5.0 Literature Cited ........................................................ .7

Appendix 1 - Acid Pond Waste Toxicity Tests

1.0 Introduction and Objective

The mining and processing of phosphate rock is a complex series of operations that requires the storage of acidic waste water. The storage is accomplished within large holding ponds. Accidental breaches in these ponds have resulted in acidic waste water reaching surface waters such as the Alafia River. Such spills can have serious impacts due to the rapid changes in pH that can occur. This report is part of an investigation into the efficacy of neutralizing acidic waste water spills to minimize the effects of low pH in the surface waters receiving accidental spills.

The neutralization of acidic surface waters to improve survival of aquatic biota has been practiced over the years in waters aff’ected by acid mine drainage and most recently waters affected by acid deposition (Olem, 1991; Brocksen et al., 1992). High concentrations of IT and Al” ions in acidic waters adversely tiect ion regulation in aquatic organisms, resulting in osmoregulatory failure. The principal detrimental effect on fish and other aquatic organisms is the leaching of sodium chloride from body fluids. Also, elevated H” and M concentrations can disrupt gas-transfer and lead to asphyxiation.

There are many alkaline materials that have been used for neutralizing acidic waters. They can be placed into four groups: carbonates, oxides, hydroxides, and silicates. Calcium carbonate is the neutralizing ?gent most commonly used to treat mildly acidic waters. This material is relatively inexpensive, is widely available, has a relatively low dissolution rate which results in a gradual pH increase, presents low risk associated with overdosage, and has low causticity.

Prior to the 197Os, calcium hydroxide was the primary neutralizing agent used in the U.S. for treating drinking water, sewage, and industrial wastewaters. Hydrated lime [Ca(OH)J is less caustic than quicklime but much more so than calcium carbonate. It is more reactive and water soluble than calcium carbonate, therefore, less hydrated lime is necessary to generate the same amount of acid neutralizing capacity. However, the higher dissolution rate also poses a hazard when the material is added directly to surface waters since overdosage could result in excessively high pH.

The accidental spills or releases of acidic waste water from holding ponds have caused mortality of aquatic oi&nisms in the receiving water bodies. It has recently been suggested that means could be taken to reduce the toxicity of the acid spills by the addition of neutralizing agents. The objective of this work was to evaluate the potential impact of neutralizing acidic waste water to reduce the acute toxicity caused by the accidental spills.

2.0 Scope of Work

Task 1. Recommendation of potential neutraliig agents

This task included providing a summary of potential neutralizing agents and the advantages and disadvantages of their application to reduce toxicity in surface waters. This technical memorandum summarizes these findings.

Task 2. Design and conduct acute toxicity bioassay tests

The basic design of the recommended acute bioassay tests to satisfy the objective of determining whether neutralization of acidic waste water from a holding pond can significantly reduce the toxic effects of low pH was as follows.

. Field collection of acidic waste water samples were taken f?om a holding pond and from the upper Al&a River. These samples were shipped to the bioassay lab for processing.

. Test concentrations of 100, 50, 25, 12.5, 6.25, and 0% (control) of the acidic waste waters . were prepared in the laboratory with the river water being used as dilution water for the original rangefinder tests. Concentrations for the definitive tests were 5 4 3 2 and 1% for the > > , , fish species and 50,25, 12,6, and 3% for amphipods.

. The bioassay tests were 96 hours in duration. Ten (10) animals per test cell were exposed: Five (5) replicate test cells per concentration were run for the rangefinder tests. Three replicate treatments were used in the final definitive toxicity tests.

. Four test organisms, 2 fish and 2 macroinvertebrate taxonomy were chosen: C’rineZZa lee& (banner-fin shiner), Menidia beryllina (inland silverside), HyaleIIa azteca (freshwater amphipod), and LeptocheiruspZumuZoms (estuarine amphipod). These are test organisms with well-documented responses to laboratory exposures to potential toxicants and include both freshwater and estuarine species.

0 The effect measured was the LC,, (the concentration at which 50% mortality of the test organisms is observed).

2

3.0 Task 1. Recommendation of Potential Neutralizing Agent

Many alkaline materials have been used or proposed for neutralizing acidic waters. These materials can be placed into four groups:

. carbonates,

. oxides,

. hydroxides, and

. silicates.

There are several criteria that are typically used to rank potential neutralizing agents, including:

. dissolution efficiency,

. application method,

. availability of material,

. safety/ease of handling,

. effects of water chemistry and biota, and

. cost.

3.1 Carbonates

The carbonate group of neutralizing agents includes:

. calcium carbonate (calcite, limestone), l calcium-magnesium carbonate (dolomite), . sodium carbonate (soda ash), and . sodium bicarbonate (baking soda).

Calcium carbonate has typically been the neutralizing agent of choice when treating mildly acidic waters. The dissolution rate is relatively slow, thus guarding against very rapid pH shifts. Despite the slow dissolution rate, the dissolution efficiency can be relatively high. The dissolution of calcium carbonate is a function of a number of factors, including:

. particle size - smaller particles have a higher dissolution efficiency;

. the chemistry of the mineral - trace amounts of magnesium reduce the dissolution efficiency;

. the chemistry of the receiving water body - low pH, low dissolved organic carbon, and low calcium concentrations improve the dissolution efficiency;

. water temperature - dissolution effkiency increase with water temperature; and

3

l water turbulence - particles stay in suspension longer in more turbulent waters, thus increasing dissolution efficiency.

Given its widespread agricultural use, calcium carbonate is readily available and relatively inexpensive. The maximum theoretical pH attainable after application of calcium carbonate is--8.3. Therefore, the risk associated with overestimating the amount of calcium carbonate needed is relatively low.

Dolomite (calcium-magnesium carbonate) is also readily available and inexpensive. However, given its lower dissolution efficiency, more material is needed to attain the same level of neutralization thereby increasing costs.

Soda ash (sodium carbonate) has a very rapid dissolution rate and efficiency. The maximum potential pH following application of soda ash is approximately pH 1 l-12. Given these properties, the potential risk for unacceptably high pH conditions is higher than expected for calcium carbonate. Soda ash is commonly used in industrial applications, thus availability is high. However, the cost of soda ash is much higher than that of calcium carbonate.

Baking soda (sodium bicarbonate), like soda ash is readily available but at a higher cost than for calcium carbonate. The potential for over-application of baking soda is nonexistent since the maximum theoretical pH is about pH 8.0. The dissolution efficiency of baking soda is high, it is easy to handle, and is relatively safe.

3.2 Oxides

There are two basic oxide materials used for neutralizing acidic waters: calcium oxide (quicklime) and calcium-magnesium oxide (dolomitic quicklime). Quicklime has a very high dissolution rate and can potentially raise the pH of the receiving water body to levels approaching pH 13. Quicklime, in comparison to the carbonate neutralizing agents, is highly caustic and therefore more difficult to handle, store, and apply safely and effectively. Also in contrast to the carbonates, quicklime is not as readily available and more costly. There is very little difference in dissolution efficiency, availability, and cost between quicklime and dolomitic quicklime.

3.3 Hydroxides

The hydroxides that have commonly been used to neutralize acidic water include:

. hydrated lime (calcium hydroxide),

4

. dolomitic hydrated lime (calcium-magnesium hydroxide), and

. caustic soda (sodium hydroxide).

Hydrated lime is considerably easier to handle than quicklime, given the reduced likelihood of reacting with moisture in the atmosphere. In contrast to calcium carbonate, hydrated lime is more reactive, has a higher dissolution efficiency, and is more difficult to handle safely. Rapid pH shifts are also more likely with the application of hydrated lime as compared to calcium carbonate. However, the availability of hydrated lime, the equipment capable of handling a hydrated lime slurry, and the overall familiarity of the industry in using a hydrated lime slurry tend to support the choice of hydrated lime in situations similar to the desired neutralization of acidic waste waters.

Dolomitic hydrated lime is less readily available than is hydrated lime and its cost is somewhat higher. Caustic soda (sodium hydroxide) is commonly used in industrial and water and wastewater treatment processes. It has an extremely high dissolution rate and the pH of the receiving waters can reach as high as pH 14. Given its extreme causticity, caustic soda is extremely difficult to handle and thereby poses safety risks.

3.4 Silicates

Basic slag, composed of calcium oxides and silicon dioxides, and olivine, a naturally occurring silicate material, have the potential for neutralization of acidic water. Slag is an industrial by- product and is readily available in some areas. Given the uncertainty in the trace metal content of basic slag, there are higher risks associated with its use as compared to other agents such as calcium carbonate and quicklime. While olivine is a naturally occurring material with relatively low cost, its potential for use as an acid neutralizing agent is untested.

3.5 Recommendations

Given the simple goal of neutralizing acidic waste water spills fi-om clay settling and holding ponds, two potential neutralizing agents stand out. Calcium carbonate and hydrated lime both offer advantages with regard to dissolution rate and efficiency, availability, and cost when compared to the other potential neutralizing agents discussed above. The use of a slurry form of either of these agents would be more effective than the application of dry material.

The eventual choice of a neutralizing agent should also be depend upon local conditions. Based on discussions with Mr. Dan Foley of HiTech Solutions, Inc. and the results of this analysis, hydrated lime is the agent that offers the greatest overall benefit for neutralizing acidic waste water spills from the holding ponds. The purchase cost of the neutralizing agent is but one component of the overall

5

neutralization system cost. The costs and availability of equipment to transport and slurry hydrated lime are much in favor of its use as compared to calcium carbonate. The use of hydrated lime slurry is also more familiar to industry personnel than is the use of calcium carbonate slurry. These factors outweigh concerns regarding the differences in the ease of use of the two potential neutralizing agents; and given the increased dissolution efficiency and reaction rate of hydrated lime, its use to neutralize acidic waste water spills is desirable.

4.0 Task 2. Design and Conduct of Acute Toxicity Bioassay Tests

The fmal report from the PBS&J Environmental Toxicology Laboratory, which contains the results and conclusions from the biological effects tests conducted as prescribed in Task 2, is provided in Appendix 1.

The results from the biological effects tests demonstrate that neutralization of acidic waste waters does reduce the toxicity of the waste water for all four species tested: Cyprinella Zeedsi (bannerfin shiner), Menidia bevyllina (inland silverside), HyaZeZZa azteca (freshwater amphipod), and Leptocheirusplumulosus (estuarine amphipod). The amphipods were less sensitive to exposure to the neutralized acidic waste water. The reduction in toxicity to each of four species tested was greater when the final pH achieved was greater @H 6.5 vs. pH 5.0). The dilution series tests results demonstrate that the effectiveness of neutralization of the acidic waste waters to decrease toxicity in the four species tested increases with dilution of the waste waters.

7

APPENDIX 1

Acid Waste Pond Toxicity Tests

5.0 Literature Cited

Brocksen, R.W., M.D. Marcus, and H. Olem. 1992. Practical Guide to Managing Acidic Waters and Their Fisheries. Lewis Publishers, Inc. Chelsea, Michigan. 190 pp.

Olem, H. 1991. Liming Acidic Surface Waters. Lewis Publishers, Inc. Chelsea, Michigan. 33 1 PP.

8

_.,_ -_ ._.__ .~ .,,, ._. . . _. _ -.” . “_

PBS&J Document No. 990156

Acid Pond Waste Toxicity Tests

Document No. 990156 Job No. 1 O-004.00

ACUTE TOXICITY OF A WET-PROCESS PHOSPHORIC ACID FACILITY

ACID POND WASTE

Prepared for:

PBS&J CORPORATION Tampa, Florida

Prepared by:

PBS&J Environmental Toxicology Laboratory 888 West Sam Houston Parkway South, Suite 110

Houston, Texas 77042-I 917

February 1999

SUMMARY

The PBS&J Environmental Toxicology Laboratory (Houston, TX) conducted a series of biological effects tests of an acid pond waste (APW) sample collected from a wet process phosphoric acid facility located within the Alafia River (FL) drainage basin. The work consisted of 96-hr acute toxicity bioassays of the APW sample following neutralization, by addition of calcium carbonate (CaCO,), to both pH 5.0 and pH 6.5. The toxicity tests were conducted wiIh freshwater organisms -- CypMella lee&i (bannerfin shiner) and Hyaleila azteca (amphipod), and saltwater organisms -- Menidia beryllina (inland silverside) and Leptocheinrs piumulosus (amphipod).

The partially-neutralized acid pond waste demonstrated acute toxicity to freshwater and saltwater fish; LCs, confidence intervals ranged from cl % to about 2% APW for the pH 5.0 aliquot and from about 1.5% to 5.1% APW for the pH 6.5 aliquot. Sediment-dwelling freshwater and saltwater amphipods were about one order of magnitude less sensitive than fish; LC, confidence intervals ranged from about 12.1% to 17.8% APW for the pH 5.0 aliquot and from 13.5% to 39% APW for the pH 6.5 aliquot. In general saltwater organisms were somewhat less sensitive to partially- neutralized APW than were the freshwater organisms.

Job No. 10-004.00 i PBsg ;

STATEMENT OF COMPLIANCE

The test procedures, original records, and the report for this study comply with the general requirements of Methods for Measurinq the Acute Toxicitv of Effluents and Receivina Waters to Freshwater and Marine Orqanisms (EPA 600/4-90/027F) and PBS&J Standard Operating Procedures. This report is an accurate reflection of the original data. Original data from this study are archived at the PBS&J Environmental Toxicology Laboratories in Houston, TX.

James D. Home Date Director, Special Projects

a-l6-4cr Date

Job No. 10-004.00 ii

TABLE OF CONTENTS

Section Paae

SUMMARY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . i

STATEMENT OF COMPLIANCE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . , . . . . . . . . ii

TABLE OF CONTENTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii

LIST OF TABLES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iv

1.0 lNTRODUCTlON......................................................l

2.0 MATERIALS AND METHODS ........................................... 1 2.1 Laboratory Facilities .............................................. 1 2.2 TestOrganisms ................................................. . 2.3 Acid Pond Waste ................................................ 1 2.4 Receiving Water (Diluent & Control) ................................ .2 2.5 Laboratory Water Controls ........................................ .2 2.6 Experimental Design .. ; ......................................... .2 2.7 Statistical Analyses ............................................. .3 2.8 Reference Toxicant Tests ........................ : ............... .3

3.0 RESULTS AND DISCUSSION .......................................... .3 3.1 Water Quality Characteristics ...................................... .4

3.1 .I Cvmhella leedsi Tests ..................................... .4 3.1.2 Menidia bewlha Tests ..................................... .4 3.1 .I Hvalella azfeca Tests ...................................... .4 3.1.2 Leotocheirus olumulosus Tests ............................... 5

3.2 Acute Toxicity Test Results ....................................... .5 3.2.1 Cvorinella leedsi Tests ..................................... .5 3.2.2 Menidia bervha ......................................... .5 3.2.3 Hvalella azteca ........................................... .6 3.2.4 Ledocheim Mmulosus ................................... .6

3.3 Reference Toxicant Test Results ................................... .7

4.0 CONCLUSION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...7

5.0 REFERENCE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...7

APPENDIX A: SAMPLE CUSTODY RECORDS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .24

APPENDIX B: TEST ORGANISM RECORDS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .27

APPENDIX C: LABORATORY DATA . . . . . . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . s .33

APPENDIX D: STATISTICAL ANALYSIS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .50

Job No. 10-004.00 . . . 111 PBzg i

LIST OF TABLES

Table Pase

Table I.

Table 2.

Table 3.

Table 4.

Table 5.

Table 6.

Table 7.

Table 8.

Table 9.

Table 10.

Table 11.

Table 12.

Table 13.

Table 14.

Table 15.

Table 16.

Water quality parameters measured during a 96-hr static renewal toxicity test of pH 5.0 acid pond waste (APW) with Cyprinella leedsi . . . . . . . . . . . . . . .8 Water quality parameters measured during a 96-hr static renewal toxicity test of pH 6.5 acid pond waste (APW) with Cyprinella leedsi . . . . . . . . . . . . . . . 9

Water quality parameters measured during a 96-hr static renewal toxicity test of pH 5.0 acid pond waste (APVV) with Menidia beryllina . . . . . . . . . . . . . . 10 Water quality parameters measured during a 96-hr static renewal toxicity test of pH 6.5 acid pond waste (APW) with Menidia beryllina . . . . . . . . . . . . . . 11 Water quality parameters measured during a 96-hr static renewal toxicity test of pH 5.0 acid pond waste (APW) with Hyalella azfeca . . . . . . . . . . . . . . . 12 Water quality parameters measured during a 96-hr static renewal toxicity test of pH 6.5 acid pond waste (APW) with Hyalelia azteca . . . . . . . . . . : . . . . 13 Water quality parameters measured during a 96-hr static renewal toxicity test of pH 5.0 acid pond waste (APW) with Lepfocheirus plumulosus . . . . . . . 14 Water quality parameters measured during a 96-hr static renewal toxicity test of pH 6.5 acid pond waste (APW) with Lepfocheirus p/umu/osus . . . . . . . 15 Survival of bannerfin shiner, Cyprinella leedsi, exposed in a 96-hr static renewal toxicity test to pH 5.0 acid pond waste (APW) . . . . , . . . . . . . . . . . . . 16 Survival of bannerfin shiner, Cyprinella leedsi, exposed in a 96-hr static renewal toxicity test to pH 6.5 acid pond waste (APW) . . . . . . . . . . . . . . . . . . 17

Survival of inland silverside, Menidia berylha, exposed in a 96-hr static renewal toxicity test to pH 5.0 acid pond waste (APW) . . . . . . . . . . . . . . . . . . 18 Survival of inland silverside, Menidia beryllina, exposed in a 96-hr static renewal toxicity test to pH 6.5 acid pond waste (APW) . . . . . . . . . . . . . . . . . . 19

Survival of amphipod, Hyalella azteca, exposed in a 96-hr static non- renewal toxicity test to pH 5.0 acid pond waste (APW) . . . . . . . . . . . . . . . . . .20 Survival of amphipod, Hyalella azfeca, exposed in a 96-hr static non- renewal toxicity test to pH 6.5 acid pond waste (APW) . . , . . . . . . . . . . . . . . . 21

Survival of amphipod, Lepfocheirus p/umu/osus, exposed in a 96-hr static non-renewal toxicity test to pH 5.0 acid pond waste (APW) . . . . . . . . . . . . . . . 22 Survival of amphipod, Lepfocheims p/umulosus, exposed in a 96hr static non-renewal toxicity test to pH 6.5 acid pond waste (APW) . . . . . . . . . . . . . . . 23

Job No. 10-004.00 iv , PBq

q.0 INTRODUCTION

In January 1999, the PBS&J Environmental Toxicology Laboratory (Houston, TX) commenced work on a series of biological effects tests of an acid pond waste (APW) sample collected from a wet process phosphoric acid facility located within the Alafia River (FL) drainage basin. Analysis of this sample has been completed and is the subject of this report.

The work consisted of 96-hr acute toxicity bioassays of the APW sample following neutralization with calcium carbonate (CaCO,) to pH 5.0 and pH 6.5. The toxicity tests were conducted with freshwater organisms -- Cyprinella lee&i (bannerfin shiner) and /-/Yale//a azteca (amphipod), and saltwater organisms (amphipod).

-- Menidia bety//ih (inland silverside) and Leptoche/rus- p/&~.~/osus

2.0 MATERIALS AND METHODS

Materials and methods forwork reported herein followed guidelines given in Methods for Measurinq the Acute Toxicitv of Effluents and Receivinq Waters to Freshwater and Marine Orqanisms (EPA/600/4-90/027F), U.S. Environmental Protection Agency, 1993.

2.1 Laboratory Facilities

The acute toxicity tests were performed at the PBS&J Corporation, Environmental Toxicology Laboratory, 888 West Sam Houston Parkway S. - Suite 1 IO, Houston, Texas 77042-1917. This laboratory is certified by the State of Florida Department of Health (Lab # E87.587) and operates under Comprehensive Quality Assurance Plan (No. 980176) approved by the Florida Department of Environmental Protection.

2.2 Test Organisms

Menidia bery//ina and f-/Yale//a azfeca specimens used in these tests were obtained from cultures maintained at the PBS&J laboratory. Cyprinella lee&i (6 day-old specimens) were purchased from Sachs’ System Aquaculture, St. Augustine, FL. Leptocheirus plumulosus (2-4 mm juvenile specimens) were obtained from Chesapeake Cultures, Hayes, VA.

2.3 Acid Pond Waste Sample

A 20-gal acid pond waste (APW) sample was collected by PBS&J-Tampa personnel on 6 January 1999. The sample was placed in four 5-gal polyethylene CubitainersO, packaged in insulated coolers at ambient temperature, and shipped to the PBS&J Environmental Toxicology Laboratory by ground transport (UPS) on the same day. Upon receipt at the laboratory on 11 January 1999, the samples were cornposited into a clean 30-gal polyethylene vat and stored in a walk-in cooler maintained at I-4 “C. APW chemical properties are summarized below.

Job No. 10-004.00 1

The APW was neutralized to pH 5.0 or 6.5 by addition of calcium carbonate powder (USP, Fisher Lot No. 985333). Neutralization to pH 5.0 required about 104 g CaCO, per liter of APW; 365 g CaCO, per liter APW was required to raise the pH to 6.5. Calcium carbonate addition produced copious amounts of precipitate which was filtered and discarded. The neutralized, filtered APW was used to prepare bioassay test solutions. An aliquot of each pH-adjusted APW samples was salted to 20%0 by addition of a dry, commercial seasalt mix (HW Marinemix@); this aliquot was used in tests with Menidia beryllina and Lepfocheirus plumulosus.

2.4 Receiving Water (Diluent & Control)

Receiving water (RW) used as the diluent for APW test solutions and as a control was collected from the Alafia River on 6 January 1999 by PBS&J-Tampa personnel. A 40-gal RW sa-mple, contained in eight 5-gal polyethylene Cubitainers@ was shipped to the PBS&J Environmental Toxicology Laboratory by ground transport (UPS) on the same day. Upon receipt at the laboratory, the RW samples were stored, un-opened until used, in a walk-in cooler maintained at I-4 “C. Chemical properties of the RW are summarized below.

.: .(., . . . . :. ..::.:: -:..::I:~.~-;':.:'.:. .; :...:::j-':j::::':.:; :...:. :,.,.,.,:,:, .,:,:,. :: . . . . . . -:::.. .:.:. .;f$ .,:.: z,Z~mmonlajl':I~:~,~~~.~~ tj$,:: : ;y$:::.::.>:f :.y '.?$? : .;gii':ijz$; :::::: ,.i,,,&y r &.,, y)j:/:L;: .:z:;.ii

7.1 11,460 . '. 0' 2,200 1.25 ‘I Alkalinity measurement is qtiestionable, possibly due to matrix interference

An aliquot of the RW sample was salted to 20%0 by addition of a dry, commercial seasalt mix (HW Marinemix@); this aliquot was used as the diluent and control in tests conducted with Menidia beryllina and Leptocheirus p/umu/osus.

2.5 Laboratory Water Controls

Reconstituted moderately-hard freshwater and 20 %O saltwater, produced at the laboratory using reagent grade chemicals or a commercial seasalt mix (HW Marinemix@) and deionized water, was used as a negative control in each test. Properties of the reconstituted laboratory waters are summarized below.

Freshwater, MH 7.4 350 80 100 eo.02

Saltwater, 20 Oh0 8.1 28,500 40 4,000 co.02

2.6 Experimental Design

The tests were g&hour static, acute toxicity tests; the fish tests were renewed once (after 48 hours), however, the amphipod tests were not renewed. The fish were fed a small amount of Artemia nauplii for about two hours just before test solution renewal; amphipods were not fed during the tests. Exposure containers were disposable plastic beakers (fish: -350 cc; amphipods:

Job No. 10-004.00 2

-130 cc). Test solution volume was 250 mL in fish tests; 100 mL test solution and a thin (2-3 mm) layer of sand (Hyalella) or culture sediment (Leptocheirus) was used in the amphipod tests. The tests were not aerated. The tests were performed in a temperature-controlled room maintained at 20 f 1 “C; a 16L:8D hour photoperiod was maintained with cool-white fluorescent lighting (50 - 100 ft-c).

Test solutions comprised pH-adjusted (to 5.0 and 6.5) APW, diluted to selected concentrations with RW. Two controls were used in each test: 100% RW and either reconstituted fresh or saline laboratory water (to provide a basis for evaluating potential RW toxicity). Five replicate treatments were used for each control solution; five replicates were also used for each test concentration in preliminary rangefinder tests, however, three replicate treatments were used in the final, definitive toxicity tests due to the small, remaining volume of RW. Concentrations used in the definitive tests with fish species were 5, 4, 3, 2, and 1% APW (v/v), diluted with RW; concentrations used in the amphipod tests were 50, 25, 12, 6, and 3% APW (v/v), diluted with RW.

In fish test, the number of surviving organisms was determined after48-hours exposure and at test termination. The number of surviving amphipods was determined at test termination only, because the organisms remained partially burrowed in the substrate throughout most of the test. The test acceptability criterion was 290% survival among control organisms.

Water quality characteristics (pH, temperature, dissolved oxygen, and specific conductance (or salinity for tests with marine organisms) were measured in each test concentration at the beginning of the test, after 48-hours exposure, and at test termination.

2.7 Statistical Analyses

Survival data from the Cyprinella, Menidia, Hyalella, and Leptocheirus acute toxcity tests were analyzed by the trimmed Spearman-Karber procedure (a non-parametric test) using software distributed by the U.S. EPA. This regression model provides a median lethal concentration (LC,,) estimate, with 95% confidence interval (Cl), for data which demonstrates a dose response.

2.8 Reference Toxicant Tests

Reference toxicant tests, positive controls which contain a substance that is expected to elicit a defined and measurable response in a test organism population, are conducted once each month with organisms produced from cultures maintained at the PBS&J laboratory. Reference toxicant tests are conducted at least once per month with organisms procured from each primary external source, or with each batch of organisms, if the test species is not used frequently.

3.0 RESULTS AND DISCUSSION

Sample chain-of custody records are located in Appendix A. Organism receipt records and supplier information are provided in Appendix B. Copies of original laboratory data sheets are provided in Appendix C. Statistical analysis of survival and growth data is given in Appendix D.

Job No. 10-004.00

3.1 Water Quality Characteristics

3.1.1 Cvminella lee&i Tests

Water quality characteristics measured in pH 5.0 and pH 6.5 APW tests using Cyprinella lee&/are presented in Tables 1 and 2. Dissolved oxygen concentrations in test solutions prepared from neutralized APW (to pH 5.0 and pH 6.5) decreased slightly from 8.2-8.3 mg/L (8.6 and 8.8 in the controls) at the beginning of the test and stabilized at 7.8 to 8.0 mg/L (2 90% saturation). Solution pH values in both tests demonstrated a concentration effect, with lower pH values being observed in the higher APW concentrations. In the pH 5.0 APW test, values ranged from 5.9-6.5 (7.3 and 7.7 in the controls) at the beginning of the tests, but increased slightly and stabilized at 6.9-7.8. In the pH 6.5 APW test, initial values ranged from 6.7-7.1 (7.3 and 7.7 in the controls); pH values increased to and stabilized at 7.6-8.0 after 48 hours. Specific conductance of test solutions increased slightly from 12100-l 2200 pmhoscm-’ at the beginning of the tests to a range of 12500- 12900 pmhoscm-’ at the end of the tests. Temperature remained stable at 20 “C in both tests.

3.1.2 Menidia berviiha Tests

Water quality characteristics measured in pH 5.0 and pH 6.5 APW tests using Menidia beryiiha are presented in Tables 3 and 4. Dissolved oxygen concentrations in test solutions prepared from neutralized APW (to pH 5.0 and pH 6.5) decreased slightly from 7.8-8.3 mg/L (8.3 and 8.4 in the controls) at the beginning of the test to 7.3-8.0 mg/L at the end of the test (290% saturation).

5 Solution pH values in both tests demonstrated a concentration effect, with lower pH values being observed in the higher APW concentrations. In the pH 5.0 APW test, values ranged from 6.0-6.8 (7.8 and 7.9 in the controls) at the beginning of the tests, but increased slightly and stabilized at 6.7-8.0. In the pH 6.5 APW test, initial values ranged from 7.0-7.6 (7.8 and 7.9 in the controls); pH values increased to 7.7-8.0 after 48 hours, then increased further to 8.0-9.0 by the end of the test. Test solution salinity remained stable at 20 %O in both tests. Temperature remained stable at 20 “C in both tests.

3.1.1 Hvaieiia azteca Tests

Water quality characteristics measured in pH 5.0 and pH 6.5 APW tests using Hyaleiia azteca are presented in Tables 5 and 6. Dissolved oxygen concentrations in test solutions prepared from neutralized APW (to pH 5.0 and pH 6.5) decreased slightly from 8.0-8.3 mg/L at the beginning of the test to 6.9-7.4 mg/L (r80% saturation) at the end of the test. Solution pH values in both tests demonstrated a concentration effect, with lowest pH values being observed in the highest APW concentrations. In the pH 5.0 APW test, values ranged from 5.3-6.2 (7.3 and 7.7 in the controls) at the beginning of the tests; by the end of the the test, pH values had increased to 5.7-7.5. In the pH 6.5 APW test, initial values ranged from 6.7-6.9 (7.3 and 7.7 in the controls); pH values increased to 7.9-8.1 at test termination. Specific conductance of test solutions increased slightly from about 11300-12300 pmhoscm“ at the beginning of the tests to a range of 12000-13700 pmhoscm-’ at the end of the tests. Temperature remained stable at 20 “C in both tests.

Job No. 10-004.00 4

/ . . _ / , . . . . . L. ^ ) ,‘/ . _ . S . “ . . : . . . . . . . . . . . . . . . _,

3.1.2 Leptocheifus ~lumulosus Tests

Water quality characteristics measured in pH 5.0 and pH 6.5 APW tests using Lepfocheirus plumulosus are presented in Tables 7 and 8. Dissolved oxygen concentrations in test solutions prepared from neutralized APW (to pH 5.0 and pH 6.5) decreased slightly from a range of 8.0-8.4 at the beginning of the test to a range of 6.2-7.3 mg/L (~75% saturation) at the end of the test. Solution pH values in both tests demonstrated a concentration effect, with lower pH values being observed in the higher APW concentrations. In the pH 5.0 APW test, values ranged from 5.1-6.2 at the beginning of the tests, but increased slightly to 5.5-7.0 at the end of the test. In the pl-l 6.5 APW test, initial test solution pH values ranged from 6.6-6.7, but increased to 6.8-7.7 by the end of the test. Test solution salinity increased slightly from 20 %O to about 24 %O in both tests. Temperature remained stable at 20 “C in both tests.

3.2 Acute Toxicity Test Results

3.2.1 Cwinella leedsi Tests

Banner-fin shiners were exposed to APW neutralized to pH 5.0 and 6.5 in 96-hour static renewal bioassays. Preliminary rangefinder tests showed that both APW’s (pH 5.0 and 6.5, diluted in RW) at concentrations 26% produced total mortality; all specimens exposed to 1% solutions survived a 96-hour exposure. Accordingly, test solutions of 5, 4, 3, 2, and 1% APW, along with RW and labwater controls, were used in the definitive bioassays.

Banner-fin shiner test results are summarized in Tables 9 and IO. Survival was 90% in the receiving water control and 92% in the laboratory water control; both controls met the acceptability criterion. Survival of fish exposed to the pH 5.0 APW ranged from 0% in the two highest concentrations (4% and 5% APW) to 63% in the 1% APW. Survival of fish exposed to the pH 6.5 APW ranged from 0% in the two highest concentrations (4% and 5% APW) to 73% in the 1% APW. There was a strong, concentration-related dose response observed in both Cyphella leedsi tests. The 96-hour median lethal concentration (LC,,) for pH 5.0 APW was 1.29% (95% Cl: 1 .I 2-1.49%); for pH 6.5 APW, the L&, was 1.78% (95% Cl: 1.50-2.12%). Although there was little separation between the LC,, estimates (in fact, the 95% confidence intervals very nearly overlap), the bannerfin shiner was slightly more sensitive to pH 5.0 APW test solutions than to pH 6.5 APW test solutions.

3.2.2 Menidia bervliina Tests

Inland silversides were exposed to APW neutralized to pH 5.0 and 6.5 in 96-hour static renewal bioassays. Preliminary rangefinder tests showed that both APW’s (pH 5.0 and 6.5, diluted in RW) at concentrations 26% produced total mortality, while most specimens exposed to a 1% solution survived a 96-hour exposure. Accordingly, test solutions of 5,4,3,2, and 1% APW, along with RW and labwater controls, were used in the definitive bioassays.

Inland silverside test results are summarized in Tables 11 and 12. Survival was 100% in the receiving water control and 96% in the laboratory water control; both controls met the acceptability criterion. Survival of fish exposed to the pH 5.0 APW was 0% in all but the lowest concentration; 90% of the fish survived the g&hour exposure to I % pH 5.0 APW solution. Survival of fish exposed to the pH 6.5 APW ranged from 40% in the highest concentration (5% APW) to 100% in the 2%

Job No. 10-004.00 m i

APW and 90% in the 1% APW. There was a strong, concentration-related dose response observed in both Menidia beryllina tests. The 96-hour median lethal concentration (LC,,) for pH 5.0 APW was 1.36% (95% Cl: <l-2%); for pH 6.5 APW, the LCs, was 4.75% (95% Cl: 4.42~5.11%). Although there was little separation between the L& estimates, the inland silverside was slightly more sensitive to pH 5.0 APW test solutions than to pH 6.5 APW test solutions.

3.2.3 Hvalella azfeca Tests

Freshwater amphipods were exposed to APW neutralized to pH 5.0 and 6.5 in 96-hour static renewal bioassays. Preliminary rangefinder tests showed that both APWs (pH 5.0 and 6.5, diluted in RW) at concentrations ~50% produced total mortality, while most specimens exposed to a 3% solution survived a 96-hour exposure. Accordingly, test solutions of 50, 25, 12, 6, and 3% APW, along with RW and labwater controls, were used in the definitive bioassays.

Hyalella test results are summarized in Tables 13 and 14. Survival was 100% in the receiving water control and 98% in the laboratory water control; both controls met the acceptability criterion. Survival of amphipods exposed to the pH 5.0 APW ranged from 0% in the highest concentration (50% APW) to 97% in the lowest concentration (3% APW). In the pH 6.5 PW, survival of amphipods ranged from 0% in the highest concentration (50% APW) to 93% in the 3% APW. A strong, monotonic dose response was observed in both Hyalella tests. The 96-hour median lethal concentration (LC,,) for pH 5.0 APW w&s 14.73% (95% Cl: 12.17-17.84%); for pH 6.5 APW; the LC5, was 17.00% (95% Cl: 13.5521.33%). Although there was little separation between the LCsO estimates (for both tests, the 95% confidence interval of one included the LC50 from the other), the freshwater amphipod was slightly more sensitive to pH 5.0 APW test solutions than to pH 6.5 APW test solutions.

3.2.4 Lepfocheifus dumulosus Tests

Marine amphipods were exposed to APW neutralized to pH 5.0 and 6.5 in 96-hour static renewal bioassays. Preliminary rangefinder tests showed that both APWs (pH 5.0 and 6.5, diluted in RW) at concentrations ~50% produced total mortality, while most specimens exposed to a 3% solution survived a 96-hour exposure. Accordingly, test solutions of 50, 25, 12,6, and 3% APW, along with RW and labwater controls, were used in the definitive bioassays.

Leptocheirus test results are summarized in Tables 15 and 16. Survival was 100% in the receiving water and in the laboratory water controls; both controls met the acceptability criterion. Survival of amphipods exposed to the pH 5.0 APW ranged from 0% in the highest concentration (50% APW) to 100% in the 6% APW and 97% in the 3% APW. In the pH 6.5 PW, survival of amphipods ranged from 17% in the highest concentration (50% APW) to 100% in the 3% APW. A strong, monotonic dose response was observed in both Leptocheirus tests. The 96-hour median lethal concentration (LC,,) for pH 5.0 APW was 13.81% (95% Cl: 11.74-16.24%); for pH 6.5 APW, the LC,, was 31.63% (95% Cl: 25.67-38.99%). The saltwater amphipod was clearly more sensitive to pH 5.0 APW test solutions than to pH 6.5 APW test solutions.

Job No. 10-004.00

3.3 Reference Toxicant Test Results

Reference toxicant tests results for the period in which the subject tests were conducted are summarized below. Reference toxicant LC,,‘s for Menidia and /iyale//? conducted in this time- frame were within the respective control limits (2 2 standard deviation, sd) of historical mean LC, values for PBS&J laboratory-reared specimens; the potential for organism batch-related bias is small. The PBS&J laboratory does not have a historical basis for evaluating the responses of Cyprinella and Leptocheirus to the reference toxicants employed. The LC, values summarized below, however, compare favorably to values determined and reported by other testing facilities.

Menidia berylha, 48-hr

Hyalella azteca, 9%hr KCI 1 01/12/99 1 (;;.;;-;y;) 1 297.28

Cyprinella leedsi, 48-hr NaCl I 12/30/98 I (;::::‘6, I - / -

Leptocheirus piumuiosus, Cadmium, 96-hr Cd+2 02iOll99 1.86 mg/L

(1.47-2.36) - -

. . . . . . . . . . . i:~:::.: ‘.~::~:~::::~:::::: ‘:::::::::::::::.:.:.:.:...:...:.~.: . . . . , . . , . , . :.:;~~.::i: : . : . : . :.:z: : . : . : ::::~~-::::::.: ‘ . : . :...:.: . . , . . . : h:.:.‘... .v.. . . . . . . : . . : .?-. . . . . . . . . : : i:::,:::::“:“::;:: ‘:::..:.:::: ‘:::::::~~:.:.~:.~:... .:.:.:.:.:::::.::::~,::::~:~~:~:,:~:~:::,:~’:.~, ; : . ‘:L’..2.‘.i’

. ; : . : . ._.: , . , . , , . / , . , . . , . , . , , . . , ( : : : . : : . . . . . . . : : , . , . : ; . , . : . : . . . . . . ::::“):::.~...‘:. . . . . . : . : . : . : . : . : . : . : . : . : . : . : . : . . . : : . : . . . : . ‘ : . :~:; : : : : : : : ::.,._ ‘, >:.::

: : . : : “ . ‘ . “ : : . : : . . : . : . : . - . , : . : , ; : : : : : ::z.::,::.;-:i:y . : . . . . . . . ; . : . . . . . . . . . . . . . y:.. : : . : - \ . , . : . , : . . :q:.. : . , : : . : . : . : . : :j

. . . : .._.. : , .._ , . . . . sii~~f~:~~~~~liiiii ~~~~ ~~~~;~: ::.$‘~~:‘B~ Lqy . : .~~~~~~ ~~~~:8’i;$; ,,:+

. . , . : . : . . : _.. . . . . . . f f , $ tonca f Data . . : . . :<:‘::j:: :

. . / . . . : . . .

~ , . , : ,..~ : , . : .,~ : ~, , , ,

.‘._......, . . . . . .._.. j.:. . / : . . . / . . . . .:::.q+.&&&$ . : :

~~~~~~:~~~~;lk ii(ili:i:~B$H:~~~~~~“i:I g:::&j:,

: . : : : :p j i;::<:i’:::::.:..: . . . M. . . . . : . : : : : : . : : : : : : , : : :~: : :

$;;.~:~

. . , . ::i::::.::::::::::::::::~~~.:~:: : . : . : . I’. . : . : . . . : ..y : . :i::i’; .j:‘$jyJ~y$j Cl:~iiil::j~~: . , , : : : : : , . , . : . : : . ; : , . : . : . : . : :‘: : :

&;:::g; 3 i:::‘::+...:i ..:.::-‘i.g;

Mean t...s...:. . . ;““i~,ip.‘yy?:~:. -iii:.;: J;

. . . . . . . . . . . . . . . . . . . . . . . , . . . . . : i:..:.: . . ,.... . . ..s.. ‘:::‘.‘.‘::.~:i;.~:.:::(.~::.:~:.: :/ ,.. _. ,. . . . . ._ :..:i..i,1:~‘l:~:i:l:~:::;1’: . . : : . : ..‘-.:‘: : ‘. :.7: :...A: :.:::: ,,,: .:.1’: :.::.: ..:. ..:: . ...,... ,.. :::.. . . :f.2 sd: . . . . . : ,. ,,(/ ,..::, . . ,,,, ..: . . . . :.:y :,. :. .:. . . . :: . . ..,::. . .

Chromium, Crffi 32.29

44.25 20.33

351.22 243.33

4.0 CONCLUSION

Static acute toxicity tests of partially-neutralized acid pond waste demonstrated acute toxicity to freshwater and saltwater fish, with LC,, confidence intervals ranging from ~1% to about 2% APW for the pH 5.0 aliquot and from about 1.5% to 5.1% for the pH 6.5 aliquot. Sediment-dwelling freshwater and saltwater amphipods were about one order of magnitude less sensitive than fish; LCs, confidence intervals ranged from about 12.1% to 17.8% APW for the pH 5.0 aliquot and from 13.5% to 39% for the pH 6.5 aliquot. In general saltwater organisms were somewhat less sensitive to partially-neutralized APW than were the freshwater organisms.

5.0 REFERENCE

EPA. 1993. Methods for Measuring the Acute Toxicity of Effluents and Receiving Waters to Freshwater and Marine Organisms, EPA/600/4-90/027F. U.S Environmental Protection Agency, Washington, D.C.

Job No. 10-004.00

Table 1. Water quality parameters measured during a 96-hr static renewal toxicity test of pH 5.0 acid pond waste (APW) with Cyprinella lee&i

LW Control 8.8 8.0 7.9 RW Control 8.6 8.0 7.9

1 a.3 8.0 8.0 Dissolved Oxygen (mg/L) 2 8.3 7.9 7.9

3 8.3 7.9 7.8 4 8.3 7.9 NM*

-- LW Control 7.7 8.0 7.6 RW Control 7.3 7.8 ,7.8

.I 6.5 7.7 7.8 PH 2 6.2 7.6 7.6

3 6.1 7.4 7.5 4 6.0 7.0 NM 5 5.9 6.9 6.9

LW Control 20 20 20 RW Control 20 20 20

1 20 20 20 Temperature (“C) 2 20 20 20

3 20 20 20

4 20 20 NM 5 20 20 20

LW Control 360 400 430 RW Control 11600 12120 12850

1 12160 12540 12920 Conductivity (pmhoskm) 2 12110 12580 12810

3 12190 12660 12820 4 12170 12600 NM

5 12070 12610 12640

’ Water quality parameters were measured at time 0 prior to the introduction of test organisms, before renewal of test solutions at 48 hours, and at test termination. 2 NM = not measured

Job No. 10-004.00 8

Table 2. Water quality parameters measured during a 96-hr static renewal toxicity test of pH 6.5 acid pond waste (APW) with Cyprinek lee&i

Dissolved Oxygen (mg/L)

LW Control 8.8 8.0 7.9

RW Control 8.6 8.0 7.9

1 8.3 8.0 8.0

2 8.2 7.8 8.1

3 8.2 7.9 7.8

4 8.0 8.0 7.8

PH

LW Control 7.7 8.0 7.6

RW Control 7.3 7.8 ,7.8

1 7.1 7.8 7.6

2 6.9 7.9 7.9

3 6.8 7.9 8.0

4 6.8 7.9 8.0

LW Control 20 20 20

RW Control 20 20 20

1 20 20 20

Temperature (“C) 2 20 20 20

3 20 20 20

4 20 20 20

LW Control 360 400 430

RW Control 11600 12120 12850

1 12220 12400 12770

Conductivity (gmhoskm) 2 12210 12630 12770

3 12190 12630 12640

4 12120 12640 12880

5 12080 12630 NM

’ Water quality parameters were measured at time 0 prior to the introduction of test organisms, before renewal of test solutions at 48 hours, and at test termination. ’ NM = not measured

Job No. 10-004.00 9

Table 3. Water quality parameters measured during a 96-hr static renewal toxicity test of pH 5.0 acid pond waste (APW) with Menidia beryllina

LW Control 8.3 7.5 7.6

RW Control 8.4 7.5 7.6

1 8.0 7.4 7.3

Dissolved Oxygen (mg/L) 2 8.0 7.6 NM’

3 8.0 7.5 NM

4 8.0 7.7 NM

5 7.8 7.5 NM

LW Control 7.9 7.3 7.6

RW Control 7.8 8.0 .9.1

1 6.8 7.7 8.0

PH 2 6.5 7.4 NM

3 6.3 7.2 NM

4 6.2 6.9 NM

5 6.0 6.7 NM

LW Control 20 20 20

RW Control 20 20 20

1 20 20 20

2 20 20 NM

3 20 20 NM

4 20 20 NM

Temperature (“C)

Salinity (%a)

LW Control 20 20 20

RW Control 20 20 20

1 20 20 20

2 20 20 NM

3 20 20 NM

4 20 20 NM

5 20 20 NM

’ Water quality parameters were measured at time 0 prior to the introduction of test organisms, before renewai of test solutions at 48 hours, and at test termination. * NM = not measured

Job No. 10-004.00 10

Table 4. Water quality parameters measured during a 96-hr static renewal toxicity test of pH 6.5 acid pond waste (APW) with Menidia beryllina

Dissolved Oxygen (mg/L)

LW Control 8.3 7.5 7.6

RW Control 8.4 7.5 7.6

1 8.3 7.6 8.0

2 8.2 7.4 8.0

3 8.2 7.4 7.9

4 8.0 7.4 7.9

5 8.3 7.4 7.6 LW Control 7.9 7.3 7.6 RW Control 7.8 8.0 ,9.1

1 7.6 8.0 9.0

2 7.4 7.9 8.6

3 7.3 7.9 8.2

4 7.2 7.9 8.1

5 7.0 7.7 8.0

LW Control 20 20 20 RW Control 20 20 20

1 20 20 20

2 20 20 20

3 20 20 20

4 20 20 20

5 20 20 20

LW Control 20 20 20

RW Control 20 20 20

1 20 20 20

2 20 20 20

3 20 20 20

4 20 20 20

5 20 20 20

PH

Temperature (“C)

Salinity (%0)

’ Water quality parameters were measured at time 0 prior to the introduction of test organisms, before renewal of test solutions at 48 hours, and at test termination. ’ NM = not measured

Job No. 10-004.00

Table 5. Water quality parameters measured during a 96-hr static renewal toxicity test of pH 5.0 acid pond waste (APW) with Hyaiella azfeca

LW Control 8.3 7.4

RW Control 8.0 7.4

3 8.3 7.4 Dissolved Oxygen (mg/L) 6 8.3 7.3

12 8.3 7.4

25 8.1 7.4

50 8.0 7.2

LW Control 7.7 8.0

RW Control 7.3 8.0

3 6.2 7.5 PH 6 5.9 6.7

12 5.7 6.2

25 5.4 5.9

50 5.3 5.7

LW Control 20 20

RW Control 20 20

3 20 20 Temperature (“C) 6 20 20

12 20 20

25 20 20

50 20 20

LW Control 360 470

RW Control 11600 13680

3 12070 13740 Conductivity (pmhoskm) 6 12050 13770

12 11970 13510

25 11790 13370

50 11420 13140

’ Water quality Pm?Mers were measured at time 0 prior to the introduction of test organisms and at test termination. * NM = not measured

Job No. 10-004.00 12

Table 6. Water quality parameters measured during a 96-hr static renewal toxicity test of pH 6.5 acid pond waste (APW) with Hyalella azteca

LW Control 8.3 7.4

RW Control 8.0 7.4

3 8.0 7.3 Dissolved Oxygen (mg/L) 6 8.1 7.2

12 8.2 7.3

25 8.0 7.2

PH

LW Control 7.7 8.0

RW Control 7.3 8.0

3 6.9 7.9

6 6.8 8.1

12 6.7 8.1

25 6.7 8.1

LW Control 20 20

RW Control 20 20

3 20 20

Temperature (“C) 6 20 20

12 20 20

25 20 20

50 20 20

LW Control 360 470

RW Control 11600 13680

3 12220 13510

Conductivity (pmhoskm) 6 12060 13450

12 12030 13400

25 11790 12890

50 11290 12000

’ Water quality parameters were measured at time 0 prior to the introduction of test organisms and at test termination. * NM = not measured

Job No. 10-004.00 13 I-Y i

Table 7. Water quality parameters measured during a 96-hr static renewal toxicity test of pH 5.0 acid pond waste (APW) with Lepfocheirus plumulosus

LW Control 8.3 6.3

RW Control 8.4 7.2

3 8.3 7.3 Dissolved Oxygen (mg/L) 6 8.3 6.5

12 8.3 6.2

25 8.0 6.7

PH

LW Control 7.9 6.3

RW Control 7.8 7.0

3 6.2 7.0

6 5.9 7.0 12 5.6 6.0

25 5.4 5.7

50 5.1 5.5

LW Control 20 20

RW Control 20 20

3 20 20

6 20 20

12 20 20

25 20 20

50 20 20

LW Control 20 24

RW Control 20 24

3 20 24

6 20 22

12 20 22

25 20 20

50 20 16

Temperature (“C)

Salinity (%o)

’ Water quality parameters were measured at time 0 prior to the introduction of test organisms and at test termination. * NM = not measured

Job No. 10-004.00 14

Table 8. Water quality parameters measured during a 96-hr static renewal toxicity test of pH 6.5 acid pond waste (APVV) with Lepfocheirusplumulosus

Dissolved Oxygen (mg/L)

LW Control 8.3 6.3

RW Control 8.4 7.2

3 8.4 6.7

6 8.4 6.5

12 8.2 6.4

25 8.3 6.4

50 8.2 6.6

LW Control 7.9 6.3

RW Control 7.8 7.0

3 6.7 6.8 PH 6 6.7 7.6

12 6.7 7.8

25 6.6 7.7

50 6.6 7.7

LW Control 20 20

RW Control 20 20

3 20 20

Temperature (“C) 6 20 20

12 20 20

25 20 20

LW Control 20 24

RW Control 20 24

3 20 23

Salinity(%o) 6 20 22

12 20 22

25 20 20

50 20 16

’ Water quality parameters were measured at time 0 prior to the introduction of test organisms and at test termination. 2 NM = not measured

Job No. IO-004.00 15

Table 9. Survival of bannerfin shiner, Cyprinella lee&i, exposed in a 96-hr static renewal toxicity test to pH 5.0 acid pond waste (APW)

4 0 0

3 10 7

2 27 13

1 83 63

RW Control’

LW Control2 ’ RW Control = Receiving Water control 2 LW Control = Labwater control

100 90

94 92

Job No. 10-004.00 16

Table 10. Survival of bannerfin shiner, Cyprinella leedsi, exposed in a 96-hr static renewal toxicity test to pH 6.5 acid pond waste (APW)

3 20 7

2 77

1 93 73

RW Control’ 100 90 LW Control2

’ RW Control = Receiving Water control 2 LW Control = Labwater control

94 92

Job No. 1 O-004.00 17

Table Il. Survival of inland silverside, Menidia beryllina, exposed in a 96-hr static renewal toxicity test to pH 5.0 acid pond waste (APW)

4 0 0

3 0 0

2 0 0

1 90 90

RW Control’

LW Control2 ’ RW Control = Receiving Water control 2 LW Control = Labwater control

100 100

100 96

Job No. 10-004.00 18

Table 12. Survival of inland silverside, Menidia beryllna, exposed in a 96-hr static renewal toxicity test to pH 6.5 acid pond waste (APW)

,: :.:, .:...:, ,.,. :.: 2;:. .::::.,: ::::.: :,:.: ::.,,. .,. . . . . . . . :...:.:::::/ ‘-:.::,‘..;:::j.:..:.:~ .::.::::::.:‘.:::y::.+:+> .,.,.,... :;.:.:.>::.:...;..:. . . ‘:.., si::i,-i:~:z::-::rh;;i::I.::::. >. .,.,..../.,.... ::~.-.~:..v.~:: . . . . . . . . . . . ,. \.... .,‘,‘,...,,.:.:. ~ . . . . . . . . . . . . . . . . . . . (..... . . . . . . ,....... . _.........._ ._.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .._...__..__. ,...... . . . . . ..y.:: :.:. :I . . . . . . ,.. .._ .:;.:.: ,,,,..,, : ,:. :.:.: . . ,)“> ,::::, 4 ~~:;~i::;~~:ii::::r:_i:::.~ :.‘:’ :,>.:,: :::.:i: ..: :. :.,.:,: ._ ..,

~‘.‘~.~...~............_.:: .A..):.: .:.::.: ~ .:,:... ;::. . . . . . . . .,..__ _. .....i ./.. ,......_....

..:“:~reatmen~~(,~:,~p,~~~~~~~~~~~~~~~~~~~~~~~~.~~~~. I: ~~~.~~~~~~:~~:~~~~:~~~~~~~: :i::: ..:. :::.....:. .:._ ., j$l, L:,.;,, : j ~:~:::l’:~.i:-:~::~~~~~~~~~~:~~~.~:~~~~~~~~~~~~~~~~~~~ .‘,‘:’ ‘.“~:~::il;;:i;i,i~~~~~~~:~~~~~~ ; .:1--~~..;:l-:~~~~~:ai~~:~~~:~~~~~~.~~~~~~~~~~~~~~~~~~~~~:~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~:~

.‘:i:::;:;:z:I:I ::.,,., :.,. :::l:::::::.:.j::::..::::::j. :$:> .:. 2. i:.:_ .:.... ,.( .,...: . . . .,., . ..‘.‘.‘... .\. . . . .,.,. .,.,.,.:,..); “. . . ._. . . . . . . . \.... :.:.:.:,::;:y :.:... :.:.:‘:.:i::,~;::‘:..::.:... . . . . . /:::: ..:. ,‘. ..,. ‘.‘.‘..‘.I

.,.,. :. .:.i(.:..,:-.‘.:.:.~. >::.:.:;.::;y:: :.:...... .:.,.:.: .,:.. .,.,.,,,. ~ ,.,. : :.: .:.. ., : :.“>j:.:;; /.....,.......,......,.i., . . . ..._I...,.., ,_ ,, ,... :,‘,..:.:,:::::j:.:‘: :.::;:; ,...: :‘:,:::::l’;ji:~:‘i:~::jp; . . . . . .‘.‘.‘i .‘. .’ .‘.. .‘. .A’.‘.‘.’ ..-.a>::+:.:-.: ,.:..., . . . ..y. :..>j:,:.:.:.:::...:,.:.: . . . .._.... .:: ..,...\,.(.... ,.:. . . . ..:: ._,.;.... ,. .. .. .‘. .,...,

. . . . . .i. . . . . . . . /),. . . . . .._.. .,.,, .,., .:: ..yy:.:: ;.:. ).. .,, :,: i .., .,: . . . . .,.~:::.;‘,.,,,. :.:.... :.: P,($ . . . . . . . ., ,, ,,, :i:.....:,:,:,.:.:....,.: ,;:....: ..,.,.... :.:..:r:-,~y~:~~:i::‘~.~. ,_,,,, . . . . . . . ,..............,.: . . . . . . . . . . .._. .‘..:.::.:.“.‘..““.“- ,, ,, ..:. ,,, :,,,, ,, :,: :‘;; ii: ::,. ~~lh~~i:~:~i~~~~~~~~~~~~~~~~~~~~~~~~~~~

,. . . .: . .A. . . . . . .,._ ‘.....‘. :.: . ..., j :.:,., +::; . . . . . . . . . . . . ,. ,..,,,,,. .::::>:.: . . . . . . . . . . . . . :.. __.,,.,. .,., ..- . . . . . . . . . . 1,. . . . . . . . . . . _. ;.: . . . . . . . . . . . . . .._...._ . ::::>: . ..i :.:-.;::.:::::.:.::-;:::,$~.~~~::~:i,i:~1.:::::,::l:::.::.:::.:::::a-::.:.::.::.:,:; ‘.>‘.(.‘. .:, ..- .,,,...: .:.:.. ., i .:...,..:..,:: :;.,; . . . . . . . . . ..:.::.:: .::..,..:.. :::, ::::.:,. .,‘.::“.‘:::.‘:.::,::

5 57 40

4 100 83

3 100 83

2 100 100

1

RW Control’ 90 90

100 100 LW Control2

’ RW Control = Receiving Water control 2 LW Control = Labwater control

100 96

Job No. 10-004.00 19

Table 13. Survival of amphipod, Uyalella azfeca, exposed in a 96-hr static non- renewal toxicity test to pH 5.0 acid pond waste (APW)

,,. :::.:..:...>, .;::.:. ..;.,,. ..:...::.:... .:.

25 20

12 67

6 90

3 97

RW Control’ 100

LW Control2 l RW Control = Receiving Water control 2 LW Control = Labwater control

98

Job No. 10-004.00 20

I

Table 14. Survival of amphipod, Hyalella azteca, exposed in a 96-hr static non- renewal toxicity test to pH 6.5 acid pond waste (APW)

12 77 6

3

RW Control’

LW Control* 98 ’ RW Control = Receiving Water control ’ LW Control = Labwater control

Job No. 10-004.00 21

Table 15. Survival of amphipod, Lepfocheirus plumulosus, exposed in a 96-hr static non-renewal toxicity test to pH 5.0 acid pond waste (APW)

25 17

12

6 100

57

3

RW Control’

LW Control2 ’ RW Control = Receiving Water control 2 LW Control = Labwater control

97

100

100

Job No. 10-004.00 22

Table 16. Survival of amphipod, Leptocheirus plumulosus, exposed in a 96-hr static non-renewal toxicity test to pH 6.5 acid pond waste (APW)

12

3

RW Control’

LW Control* ’ RW Control = Receiving Water control 2 LW Control = Labwater control

100

Job No. 10-004.00 23

Job No. 1 O-004.00

APPENDIX A: SAMPLE CUSTODY RECORDS

24

An employee-owned company

Jawary 6,1999

Mr. Jim Horn PBSJ Toxicofogy Lab 888 W. Sam Houston Pkwy s. suite 110 Houston, Texas 77042019 17

Re: Chain of Custody - Water Samp

Dear Jim,

As discussed, we did not receive a cl

You will be receiving 12 coolers, 8 i from the process pond.

Each of the containers are approxixni January 6,1999 by Mr. Jerry Reeves 1999. They should arrive to your of

Please let me lcnow if you have any f

Sincerely, :

Melisa L. Reitex Senior Scienfist

cc: 10-004.00 1

riththeco

eceiving s

2. Thesa ia ground lesday, Jeu

‘hone: 813.87

I

rssenttotls. !

i

am and 4 of w”; I I

~p.Ecec;$ .

Lry 13th. I I ! i

;

i ;’ i, I I I I. I I I :. !.. I’

!75 l www.pbrj.cor$ I I i. : .

iare

PRGE. 02

Jer vices

CHAIN OF CUSTODY RECORD

PBS&J JOB NO. i3 - 00 J( lo0

bnemcai resriilg Feld Services

SAMPLE INFO. DESCRIPTION OR NOTES

Relinquished By:

S./l PS Signature

Received By: I- WV Date

Signature

Rev. 10/16/98 BLANKCC.Doc

Organization

Tie

Organization

ETOX laboratory 888 W. Sam tkmon Pkwy. S.. Suite 110 l Houston. Texas 77042-1917 l Telephone: 713.977.1500 l Fax: 711977.9233 l www.pbsi.com

APPENDIX B: TEST ORGANISM RECORDS

Job No. 1 O-004.00 27

i.

PO :Verbd

SPECIES : C.leedsi

GUANTITY : 700

HATCH DATE ‘: 012199 -

AGE :4DavsGld

BROOD MJM-BER : SScL92-98

BATC-X NUMBER : CLO12WI

pR : 8.0

HARDNESS : 12OMGAL

COMMENTS : Thanks Kristine. houe vou have a meat week.@

i .

SHIPPING DATE : l/18/99

CCNPADW :PBS&J

PO : VerbaI

SPFCTES : C.1eeb.i

ar4Nq--rn I .

HATCflDATE :011399

0 Packi@ I

0 P&ckedaY I I

0 shipping bfetiod I

0 Endosuru: SRT BRO t CERT SW- 1 PRI UXi !

0 checkdb~~ I !

AGE! :5d2vs

BRCOD INUMBI~? : CL,OI 1399

BATCH ~N-JMWm : ssag2-gg

pH : 8.0

coMMENTs : Thank.3 C&tine, eniw the week?. . ..O

- .__---. . -- -- - --.- --- -- __ __ _. - - .-- - .- --. _ --- .-- _-- _ __. _. . . , - 4

/

ST.AU~WTINE,FLCNDA,32095 (304}824-s308

!ElI.?PING DATE : l/11/99

OT!rn?I’ : 800

FL4TCH DATE : 010799

BROOD NLJ%BER : CL010799 . .

BATCH IVJ’;;MBER : SSf=T,92-99 ’

C .,

. . . , ‘\ 5,

L. ‘.

. . . - -- - . . __,. _ ,_ _ _ . - . - - - -’ - -

___ - -.- _

Chesapeake. Cultures P.O.Box507 H;lycs,Vaz3cJ7z (804) 693-4046

Shipment Information

Species LePtocheirus plurmlosus

Age 2-YA%h,

Quanky &jr

No res Sediment is from pristine York River Marsh, passed through .*

. a 250 micron sieve and subsequently frozen. No water is

- added during processing. Sediment provided by Chesapeake

Cultures is from the same source as sediment used at our

facility for culturing L. plumulosus. It is the responsibility . . of the recipient to determine its suitability for testing.

Bioiogisr 3c m- Please inspect shipmenr carefiIIy upon arrival a& report any problem inuneGrti!y.

Chesapeake- Cultures P.O.Bax507 H~ycs,kZ3072 (KM) 693-4046

Shipment Information .

Species Leptocheirus ~L~U~OSUS

Age d-Cihm

QWlriry 6SCJ:,t

Dare //W 15’9

P.O. No.

Invoice No. z0 13 .

Notes . . Sediment is from pristine York River Marsh, passed through

a 250 micron sieve and subsequently frozen. No water is

- added during processing. Sediment provided by Chesapeake

Cultures is from the same source as sediment used at our

facility for culturing L. plumulosus. It is the resoonsibilitv . - -_ of the recipient to determine its suitability for testing.

Biologist ST J)3-

Please inspect shipmenr carefirlly upon arrival a& report any problem immediare!y.

APPENDIX C: LABORATORY DATA

Job No. 10-004.00 33

APPENDIX D: STATISTICAL ANALYSIS

Job No. 10-004.00 50

TRIMMED SPEARMAN- KARBER METHOD. VERSION 1.5

.DATE: l/27/99 TEST NUMBER: 1 TOXICANT : APW @ pH 5.0 SPECIES: Cyprinella leedsi

RAW DATA: Concentration Number __- ---- (%I Exposed

.oo 50 1.00 30 2.00 30 3.00 30 4.00 30 5.00 30

SPEARMAN-KARBER TRIM: 29.63%

SPEARMAN-KARBER ESTIMATES: LC50: 95% LOWER CONFIDENCE: 95% UPPER CONFIDENCE:

DURATION: 96 h

Mortalities

5 11 26 28 30 30

1.29 1.12 1.49

NOTE: MORTALITY PROPORTIONS WERE NOT MONOTONICAI,LY INCR.EASING. ADJUSTMENTS WERE MADE PRIOR TO SPEARMAN- KARBER ESTIMATION.

____________________------------------------- ----we _________-_____-__---------

TRIMMED SPEARMAN- KARBER METHOD. VERSION 1.5

DATE: l/27/99 TEST NUMBER: 2 TOXICANT : APW @ pH 6.5 SPECIES: Cyprinella leedsi

RAW DATA: Concentration Number m-w ---- (%I Exposed

. 00 50 1.00 30 2.00 30 3.00 30 4.00 30 5.00 30

SPEARMAN-KARBER TRIM: 18.52%

SPEARMAN-KARBER ESTIMATES: LCSO: 1.78 95% LOWER CONFIDENCE: 1.50 95% UPPER CONFIDENCE: 2.12

DURATION: 96 h

Mortalities

5 8

17 28 30 30

NOTE: MORTALITY PROPORTIONS WERE NOT MONOTONICALLY INCREASING. ADJUSTMENTS WERE MADE PRIOR TO SPm- KARBER ESTIMATION.

----_____- __________________________________^_____-------------- ---_--- -------

TRIMMED SPEARMAN -KARBER METHOD. VERSION 1.5

DATE: l/28/99 TEST NUMBER: 5 TOXICF'dT : APW @ pH 5.0 SPECIES: Menidia beryllina

RAW DATA: Concentration Number --- s-w- (%) Exposed coo 00 50

30 2.00 30 3.00 30 4.00 30 5.00 30

SPEARMAN-KARBER TRIM: 10.00%

DURATION: 96 h

Mortalities

0 3

30 30 30 30

SPEARMAN-KARBER ESTIMATES: LCSO: 1.36 95% CONFIDENCE LIMITS ARE NOT RELIABLE. ------------------------------------------------------------------------------

TRIMMED SPEARMAN -KARBER METHOD. VERSION 1.5

DATE: l/28/99 TOXICANT : APW @ SPECIES: Menidia

TEST NUMBER: 6 pH 6.5 beryllina

RAW DATA: Concentration --- ---- (%I

1:oo 00

2.00 3.00 4.00 5.00

Number Exposed

50 30 30 30 30 30

SPEARMAN-KARBER TRIM: 40.00%

DURATION: 96 h

Mortalities

0 3 0 5 5

la

SPEARMAN-KARBER ESTIMATES: LCSO: 4.75 95% LOWER CONFIDENCE: 4.42 95% UPPER CONFIDENCE: 5.11

NOTE: MORTALITY PROPORTIONS WERE NOT MONOTONICALLY INCREASING. ADJUSTMENTS WERE MADE PRIOR TO SPEARMAN- KARBER ESTIMATION. ------------------------------------------------------------------------------

TRIMMED SPEARMAN- KARBER METHOD. VERSION 1.5

r- s DATE: l/27/99 TEST NUMBER: 3

TOXICANT : APW @ pH 5.0 SPECIES: Hyalella azteca

RAW DATA: Concentration Number __- ---- (%) Exposed

.oo 50 3.00 30 6.00 30

12.00 30 25.00 30 50.00 30

SPEARMAN-KARBER TRIM: 3.33%

DURATION: 96 h

Mortalities

0 1 3

10 24 30

a+- 4 %! \p ‘L

SPEARMAN-KARBER ESTIMATES: LC50: 14.73 95% LOWER CONFIDENCE: 12.17 95% UPPER CONFIDENCE: 17.84

------------------------------------------ ____________________----------------

TRIMMED SPEARMAN- FARBER METHOD. VERSION 1.5

DATE: l/27/99 TOXICANT : APW @ pH 6.5 SPECIES: Hyalella azteca

RAW DATA: Concentration --- ---- (%I

.oo 3.00 6.00

12.00 25.00 50.00

TEST NUMBER: 4 DWTION: 96 h

Number Exposed

50 30 30 30 30 30

SPEARMAN-KARBER TRIM: 6.67%

SPEARMAN-KARBER ESTIMATES: LC50: 17.00 95% LOWER CONFIDENCE: 13.55 95% UPPER CONFIDENCE: 21.33

Mortalities

0 2 6 7

19 30

----___________-___------------------ ---w-w - - - -em - - - - - - - - - - - - - - - - - ____---^----

TRIMMED SPEARMAN- KARBER METHOD. VERSION 1.5

DATE: l/28/98 TEST NUMBER: 5 TOXICANT : APW @I pH 5.0 SPECIES: Leptocheirus plumulosu

RAW DATA: Concentration Number _-- ---- (%I Exposed

.oo 50 3.00 30 6.00 30

12.00 30 25.00 30 50.00 30

DURATION: 96 h

Mortalities

0 1 0

13 26 30

SPEARMAN-KARBER TRIM: 1.67%

StiEARMAN-KARBER ESTIMATES: LCSO: 13.81 95% LOWER CONFIDENCE: 11.74 95% UPPER CONFIDENCE: 16,24

NOTE: MORTALITY PROPORTIONS WERE'NOT MONOTONICALLY INCREASING. ADJUSTMENTS WERE MADE PRIOR TO SPEARMAN-KARBER ESTIMATION.

----- ________________________________________---------------------------------

TRIMMED SPEARMAN- KARBER METHOD. VERSION 1.5

DATE: l/28/98 TEST NUMBER: 8 TOXICANT : APW @ pH 6.5 SPECIES: Leptocheirus plumulosu

RAW DATA: Concentration Number --- --w- (%I Exposed

.oo 50 3.00 30 6.00 30

12.00 30 25.00 30 5cj.00 30

SPEARMAN-KARBER TRIM: 16.67%

SPEAR&TAN-KARBER ESTIMATES: LCSO: 31.63 95% LOWER CONFIDENCE: 25.67 95% UPPER CONFIDENCE: 38.99

DWTION: 96 h

Mortalities

0 0 2 2 9

25