Appendix A. Quality Assurance Project Plan, Technical Background Document: Mercury Wastes, Evaluation of Treatment of Bulk Elemental Mercury, Final Report February 8, 2002 Submitted to:

U. S. Environmental Protection Agency Ariel Rios Building Office of Solid Waste 1200 Pennsylvania Avenue, N. W. Washington, D. C. 20460 Submitted by:

Science Applications International Corporation Engineering and Environmental Management Group 11251 Roger Bacon Drive Reston, Virginia 20190 EPA Contract No. 68 W 98 025 Work Assignment No. 3 8 SAIC Project No. 06 0758 08 1373 000 QUALITY ASSURANCE PROJECT PLAN TECHNICAL SUPPORT FOR AMENDMENT OF LAND DISPOSAL RESTRICTIONS FOR MERCURY WASTES SAIC/ EPA Prime Contract No. 68 W 98 025 Work Assignment WA# 2 15 Submitted to: Mary Cunningham, EPA Task Order Manager Office of Solid Waste U. S. Environmental Protection Agency Submitted by:

ALTER Corporation December 2000 TABLE OF CONTENTS Section Name Page Revision Date 1.0 Project Description 1 0 12/ 20/ 00 2.0 Project Organization and Responsibility 3 0 12/ 20/ 00 3.0 Experimental Approach 7 0 12/ 20/ 00 4.0 Sampling Procedures 13 0 12/ 20/ 00 5.0 Testing and Measurement Protocols 17 0 12/ 20/ 00 6.0 QA/ QC Checks 25 0 12/ 20/ 00 7.0 Data Reduction, Validation and Reporting 33 0 12/ 20/ 00 8.0 Assessments 36 0 12/ 20/ 00 Appendices A Acidity/ Alkalinity B University of Cincinnati's Constant pH Leaching Procedure Project Specific   Untreated Surrogate C University of Cincinnati's Constant pH Leaching Procedure Project Specific   Treated Surrogate D Chain of Custody E Standard Operating Procedures for Agvise Laboratories F Project Schedule List of Illustrations Figures Page 2 1 Project Organization 6 3 1 Experimental Design 10 Tables Page 3 1 Surrogate Sludge Composition 7 5 1 Test Procedures Used by Agvise Laboratories 18 5 2 Test Procedures Used by Environmental Enterprises 18 5 3 Test Procedures Used by ALTER 19 5 4 Sample Handling and Storage Conditions 20 6 1 Quality Assurance Objectives for MDL Precision and 27 Accuracy of Chemical Analyses 6 2 Quality Control Checks 32 6 3 QC Standards 32 Distribution List Mary Cunningham and Josh Lewis, OSW Linda Rieser, Project Manager, ALTER Corporation Rich Abitz, SAIC, Quality Assurance Officer for ALTER Jian Zhang, ALTER Corporation ( Staff Laboratory Copy) Debbie Jones, Environmental Enterprises Mary Thingelstad, Agvise Laboratories Mike Morris, Oak Ridge National Laboratory / UT Battelle Sara Hartwell, SAIC EPA QA Section No. 1.0 Revision No. 0 Date: December 20, 2000 Page 1 of 38 1.0 Project Description 1.1 Purpose There are concerns about incineration of mercury containing wastes since incineration does not destroy, extract, or immobilize mercury. It may actually increase rather than minimize mercury movement into the environment by releasing mercury vapor and mercury salts into the atmosphere. The Environmental Protection Agency Office of Solid Waste ( EPA OSW) in collaboration with the Accelerated Life Testing and Environmental Research Corporation ( ALTER) is investigating alternative non combustion technologies for the disposal of mercurycontaining wastes.

The purpose of this project is to create a surrogate mercury sludge and to investigate a range of commercial remediation technologies using a surrogate mercury sludge.

1.2 Process Description A laboratory scale surrogate mercury sludge will be assembled by ALTER. The sludge will be characterized and subjected to leaching tests to provide baseline information.

Following analysis of the baseline data , the surrogate mercury sludge components will be shipped to commercial treatment vendors selected by Oak Ridge National Laboratory ( ORNL)

and EPA. The commercial vendors will mix and treat the surrogate sludge and return the treated material to ALTER for testing.

The vendor treated materials will be characterized and subjected to leaching tests to determine the applicability of the treatment processes. EPA QA Section No. 1.0 Revision No. 0 Date December 20, 2000 Page 2 of 38 1.3 Objectives The objective of this investigation is to provide reliable information on the applicability of non thermal alternative treatment technologies to treat mercury containing wastes.

Primary objectives:

· Prepare a surrogate mercury sludge · Characterize and determine the leachability of a surrogate mercury sludge under controlled laboratory conditions.

· Characterize and determine leachability of the treated surrogate mercury sludge. EPA QA Section No. 2.0 Revision No. 0 Date: December 20, 2000 Page 3 of 38 2.0 Project Organization and Responsibility 2.1 Organizations Involved in the Project 1. Office of Solid Waste U. S. Environmental Protection Agency Washington D. C.

Mary Cunningham Telephone ( 703) 308 8453 Fax ( 703) 308 8433 email cunningham. mary@ epa. gov Josh Lewis Telephone ( 703) 308 7877 Fax ( 703) 308 8433 email lewis. josh@ epa. gov 2. ALTER Corporation 7852 State Rd 62, Dillsbord, IN 47018 Linda Rieser Telephone ( 513) 556 2060 Fax ( 513) 556 3148 email lrieser@ uceng. uc. edu Graduate Students Telephone ( 513) 556 1029 Fax ( 513) 556 3148 Jian Zhang email zhanjn@ email. uc. edu Haishan Piao email piaoh@ email. uc. edu Li Meng email mengli@ email. uc. edu 3. Oak Ridge National Lab( ORNL) PO Box 2008, Oak Ridge, TN37831 6180 Mike Morris Telephone ( 865) 574 0559 Fax ( 865) 574 5912 email morrismi@ ornl. gov 4. Environmental Enterprises Inc. 10163 Cincinnati   Dayton Rd., Cincinnati, Ohio 45241 Debbe Jones and Jyoti Desai Telephone ( 513) 772 2818 Fax ( 513) 782 8970 EPA QA Section No. 2.0 Revision No. 0 Date: December 20, 2000 Page 4 of 38 5. Agvise Laboratories, Northwood P. O. Box 510, Highway 15, Northwood, ND. 58267 Julie M. Johnson and Mary L. Thingelstad Telephone ( 701) 587 6010 Fax ( 701) 587 6013 6. Science Applications International Corporation ( SAIC) 1710 Goodridge Dr. Mclean, VA22102 Sara Hartwell Telephone ( 703) 318 4662 Fax ( 703) 318 4682 Email hartwell@ saic. com Richard Abitz Telephone ( 513) 226 5329 Fax ( 513) 556 3148 email rabitz@ att. net 2.2 Quality Assurance Managers 1. Charles Sellers, Quality Assurance Officer, OSW, U. S. EPA 2. Rich Abitz, SAIC, Quality Assurance Officer for ALTER Corporation The ALTER Quality Assurance officer will be responsible for data validation,

investigation of " out of control" situations and the assurance that data quality checks are being made. Charles Sellers ( EPA OSW) will be responsible for reviewing the QAPP and providing comments to the project manager. The ALTER QA officer will review QA data from all contributing organizations. The ALTER QA officer is an essential link between all research members as data is developed, analyzed, reviewed and checked prior to reporting said work.

These responsibilities are more specifically outlined in sections 6.0 and 8.0 of this document.

2.3 Responsibilities of Project Participants Project organization and reporting relationships are depicted on the following chart. Josh Lewis ( OSW), Mary Cunningham ( OSW Task Order Manager), Charles Sellers ( OSW QA Officer) and Sara Hartwell ( SAIC) will be responsible for providing technical direction, project coordination and communication along with reviewing and approving the QAPP. Mike Morris, ORNL will be responsible for the statement of work for stabilization vendors, evaluation of vendor test plans and coordination of surrogate and vendor treated EPA QA Section No. 2.0 Revision No. 0 Date: December 20, 2000 Page 5 of 38 surrogate transfer between vendors and ALTER. Linda Rieser ( ALTER, Subcontractor to SAIC)

will serve as Project Manager and shall have responsibility for supervision and monitoring of all aspects of this project, including the collection of samples, sample custody, project planning,

QAPP development, daily operations oversight, data analysis and will assist SAIC with final reports. Rich Abitz ( SAIC) will serve as ALTER QA officer. Student research assistants and professional technicians will participate in the research under the guidance of the project manager. Student research assistants will primarily be involved in the laboratory work associated with leaching tests and will be responsible for monthly reports. Sara Hartwell, SAIC will be responsible for the final report.

Agvise Laboratory will provide support for characterization ( Table 5.1). Environmental Enterprises will provide mercury analysis of surrogate, treated surrogate and leachates. The QA/ QC control functions have been organized to allow independent review of project activities.

The objective of the QA/ QC efforts is to assess and document the precision, accuracy, and adequacy of the data derived from the investigation. Figure 2.1 shows project authority lines. EPA QA Section No. 2.0 Revision No. 0 Date: December 20, 2000 Page 6 of 38 Figure 2.1 Project Organization Linda Rieser Project Manager ALTER Corporation Subcontractor to SAIC Responsibitlites   Project Planning, QAPP development, daily operations oversight, data reduction and analysis, final report preparation, sample collection, and sample custody ALTER Graduate Students Jian Zhang Haishan Piao Li Meng Responsibilities   Execution of experiments and monthly progress report generation Agvise Laboratories Julie M. Johnson   Analytical Manager Mary L. Thingelstad   QA Manager Responsibilities   characterization testing Environmental Enterprises Debbe Jones   Lab Manager Jyoti Desai   QA Manager Responsibilities   Mercury analysis of waste and leachates Rich Abitz SAIC Quality Assurance Officer for ALTER Mary Cunningham Josh Lewis EPA OSW Work Assignment Mgr.

Mike Morris ORNL Charles Sellers EPA Quality Assurance Officer ( OSW) Sara Hartwell SAIC Contractor to OSW Final Report EPA QA Section No. 3.0 Revision No. 0 Date: December 20, 2000 Page 7 of 38 3.0 Experimental Approach A surrogate mercury sludge will be constructed by ALTER for use in this evaluation. The surrogate will be subjected to physical and chemical characterization and leaching tests to determine leachability of the surrogate after treatment. The surrogate will be treated by vendors selected by ORNL and EPA's Office of Solid Waste. ALTER will ship two one hundred pound samples to selected vendors for treatment and residuals return to ALTER. The surrogate will be shipped as pre measured components to be blended by the vendors. Additional surrogate will be made available to the vendors upon request for pre treatment treatability testing. ALTER will observe the mixing and treatment. Following successful treatment of the two one hundred pound surrogate batches by the selected vendors, the entire 200 pounds of treated surrogate will be shipped to ALTER for sampling and evaluation. Physical and chemical characterization and leaching tests identical to those performed on the baseline surrogate will be performed on the vendor stabilized materials. Figure 3.1 details the experimental design for this project. Appendix F provides the project schedule.

3.1 Construction of Surrogate Sludge A surrogate sludge will be constructed for use in this study. The sludge composition is outlined in Table 3.1.

Table 3.1 Surrogate Sludge Composition Sludge Constituent Weight Percentage % Mercury Concentration ppm Phenyl Mercury 0.08 500 Mercury Nitrate 0.17 1000 Elemental Mercury 0.15 1500 Mercury Oxide 0.11 1000 Mercury Chloride 0.14 1000 Diatomaceous Earth 20 Aluminum Hydroxide 10 Ferric Chloride 10 Sodium Chloride 10 Motor Oil ( new) 1 Water 48.35 Total 100 5000 EPA QA Section No. 3.0 Revision No. 0 Date: December 20, 2000 Page 8 of 38 Sludge will be mixed in 3 liter batches in a 5 quart Hobart mixer. Mercury species as listed in Table 3.1 will be added only after the major constituents have been well blended. Three random samples will be analyzed to assess total mercury variability and three TCLP tests will be performed to assess leachability. The laboratory scale surrogate will be characterized and leached as described in sections 3.2 and 3.3.

3.2 Characterization Samples of the baseline surrogate, the vendor mixed surrogate before treatment and the treated surrogate will be analyzed for total mercury and subjected to the Toxicity Characteristics Leaching Procedure ( TCLP). Samples of the sludge and leachate will be submitted to Environmental Enterprises Inc. for mercury analysis. Samples of the baseline surrogate and treated surrogate will also be sent to Agvise for physical and chemical measurements, including bulk density, moisture content, percent organic matter, cation exchange capacity, and particle size distribution. The Agvise testing uses standard methods for soils, established by the USDA and the Soil Society of America.

Additional characterization of the baseline surrogate and vendor stabilized materials by ALTER will include alkalinity and acidity testing, and pH analysis on all samples. All characterization testing will be performed in duplicate.

3.3 Leaching In order to assess the stability of the wastes, several leaching procedures will be performed on the baseline surrogate and vendor treated surrogate. Leaching tests to be performed by ALTER include TCLP, and UC constant pH. Upon completion of each leaching test, the pH values will be taken by ALTER and the leachate mercury concentration will be determined by Environmental Enterprises Inc. All leaching tests will be performed with a minimum of 50%

duplicates and will include an experimental blank. The following paragraphs discuss the leaching tests. EPA QA Section No. 3.0 Revision No. 0 Date: December 20, 2000 Page 9 of 38 Toxicity Characteristic Leaching Procedure1 This is a standard regulatory test intended to determine the potential mobility of contaminants in a liquid or solid under simulated landfill conditions. Tests are run in duplicate and analyzed for mercury content.

UC Constant pH Based Leaching Constant pH leaching tests are a means to determine the effect pH has on the stability of a waste. The constant pH procedure was developed at the University of Cincinnati and is attached as Appendix B. Separate project specific pH leaching procedures are provided for untreated and treated surrogate to accommodate QC specific to the number of samples leached. Samples are leached in a constant pH solution that is adjusted to the desired pH end point. The constant pH leaching test will be run on the 6 pH values of 2, 4, 6, 8, 10 and 12. The pH will be maintained by automated systems for a 10 day period prior to leachate sampling. Three pH values 2, 8 and 12 experiments will be duplicated. The test shall include an experimental blank. All extracted samples are filtered and analyzed for mercury content.

1 Federal Register Volume 51 EPA QA Section No. 3.0 Revision No. 0 Date: December 20, 2000 Page 10 of 38 Agvise Characterization Table 5.1 ALTER Characterization Table 5.3 Data Collection and Interpretation at ALTER TCLP Performed by ALTER on Baseline Surrogate Conduct Leaching Experiments Table 5.3 Leachate Sent to Environmental Enterprises for Mercury Analysis Table 5.2 Results to ALTER for Data Analysis ALTER Analysis for Acidity and Alkalinity Construct Baseline Surrogate pH Measurements Taken on All Leachates by ALTER Vendor Test Plans evaluated to meet Statement of Work by Mike Morris, ORNL Leachate and Surrogate Sent to Environmental Enterprises for Mercury Analysis EPA QA Section No. 3.0 Revision No. 0 Date: December 20, 2000 Page 11 of 38 Vendor Mixes and Treats Surrogate, TCLP to Outside Lab, Ships Stabilized Materials Passing LDR Treatment ALTER Ships Surrogate Components to Vendors TCLP and Total Mercury Performed on Vendor Mixed Surrogate and Stabilized Materials Agvise Characterization Table 5.1 Data Collection and Interpretation at ALTER Conduct Leaching Experiments Table 5.3 ALTER Analysis for Acidity and Alkalinity pH Measurements Taken on All Leachates by ALTER ALTER Characterization Table 5.3 EPA QA Section No. 3.0 Revision No. 0 Date: December 20, 2000 Page 12 of 38 Figure 3.1 Experimental Design Leachate Sent to Environmental Enterprises for Mercury Analysis Table 5.2 Reporting SAIC/ ALTER Results to ALTER for Data Analysis EPA QA Section No. 4.0 Revision No. 0 Date: December 20, 2000 Page 13 of 38 4.0 Sampling Procedures 4.1 Laboratory Scale Surrogate Sludge Preparation and sampling of the laboratory scale surrogate sludge will be performed by ALTER. The sludge will be mixed using a Hobart 5 quart mixer. The sub samples will then be transferred to the appropriate sample containers for each test. Observations and judgements about sample homogeneity ( e. g. color, texture, etc.) will be recorded in the lab notebook.

4.2 Vendor Sampling Vendors selected by ORNL and EPA ( OSW) will receive two surrogate pre measured 100 lb. samples. Vendors will be responsible for mixing the surrogate from the components shipped by ALTER. When mixing is complete, a composite sample of approximately 1 kg will be removed from the mixed surrogate as 10 approximately 100 g random grab samples to be shipped with the treated surrogate. After treatment of the two 100 lb. surrogate batches, vendors will submit a sample of each batch to an outside lab for TCLP testing, then will return the successfully treated surrogate to ALTER for evaluation.

Each vendor will submit, for review by Mike Morris ORNL, a plan for treatment of the surrogate batches. The plan will include the following:

· Mixing method · Sample containerization and preservation · Process design and operating data collection.

· Total mass of treatment additives.

4.3 Sampling for Treatment Tests All treated surrogate will be returned to ALTER for testing. The treated surrogate will be crushed if necessary to pass a 9.5 mm sieve. Crushed treated material, or material passing the 9.5 mm sieve will then be blended and sub sampled, using a sample splitter, for each test to be performed. EPA QA Section No. 4.0 Revision No. 0 Date: December 20, 2000 Page 14 of 38 4.4 Field Sample Custody Sample custody will begin, in all cases, at the time of sample collection by placing the sample in a sealed container, or other appropriate container, in the possession of the designated laboratory or field sample custodian. A line item on the chain of custody record form ( Appendix D) will be immediately filled out and signed by the field or laboratory sample custodian. The following information will be included when the chain of custody record is filled out:

Project Number Enter the complete project number.

Project Name Enter the project name Samplers Enter signature and print name of person or persons who participated in the collection of the samples listed and who should be contacted if questions arise during sample log in.

If the field sample custodian is not listed as a sampler,

receipt of documentation is to be indicated.

Field Sample No. Enter the sample numbers for each of the two 100 lb samples collected.

Date Enter date of sample collection.

Time Enter time of actual sample collection.

Sample Location Enter the number of containers to be shipped for the two samples.

Remarks Indicate special considerations for a sample ( i. e.,

preservatives used and mass of additives).

Upon completion of all line items, or upon sample pickup, the custodian will sign, date,

enter the time, and confirm completeness of all information written on the chain of custody record. Each individual who subsequently assumes responsibility for the sample will sign the chain of custody record and indicate the reason for assuming custody.

4.5 Sample Transport Samples prepared for shipment will be packaged and labeled in compliance with current U. S. Department of Transportation ( DOT) and International Air Transport Association ( IATA)

dangerous goods regulations. Any additional requirements stipulated by the overnight carrier will be followed. EPA QA Section No. 4.0 Revision No. 0 Date: December 20, 2000 Page 15 of 38 Only a metal or plastic ice chest will be used as the outside shipping container for samples, unless otherwise specified by the shipping regulations. The outside container must be able to withstand a 4 foot drop on solid concrete in the position most likely to cause damage.

Each ice chest will be lined with a 6 mil thick plastic bag. Styrofoam or bubble wrap will be used to absorb shock. When more than one set can fit into an ice chest, each of the sets will be placed in separate plastic bags to prevent cross contamination if breakage occurs.

After sample containers are sufficiently packaged, the 6 mil thick plastic bag will be sealed around the samples by twisting the top and securely taping the bag closed to prevent leakage.

Chain of custody records and any other shipping/ sample documentation accompanying the shipment will be enclosed in a waterproof plastic bag and taped to the underside of the ice chest lid.

Each ice chest prepared for shipment will be securely taped shut. This can be accomplished with reinforced or other suitable tape ( i. e., strapping tape) wrapped at least twice around the ice chest near each end where the hinges are located. A label, or a business card,

identifying the name and address of the responsible party will be affixed on the top of each ice chest prepared for shipment.

Sample shipping containers will be marked in accordance with DOT Regulations for Shipping Hazardous Materials ( 49 CFR 172) and/ or IATA Dangerous Goods Regulations, 28th Edition, January 1, 1987. In addition to the complete mailing address, each ice chest must be clearly marked with " this end up" arrows on all four sides.

At the time of shipment, the sampling crew chief is to supply the following information to the ALTER Project Manager: the date on which the samples were shipped, the name of the commercial carrier, the carrier invoice number, the number of shipping containers shipped, and the expected time of arrival at the laboratory.

4.6 Laboratory Sample Custody After the ice chests are checked for damage, the samples will be unpacked and the information on the accompanying chain of custody records will be examined. If the samples shipped match those described on the chain of custody record, the ALTER Project Manager will sign the form and assume responsibility for the samples. If problems are noted with the EPA QA Section No. 4.0 Revision No. 0 Date: December 20, 2000 Page 16 of 38 sample shipment, the Project Manager will sign the form and record the problems in the " Remarks" box, and notify the ALTER QA officer.

All samples will then be logged into a sample logbook. The following information will be documented in the logbook:

· Date and time of sample receipt · Project number · Field sample number · Laboratory sample number ( assigned during log in procedure)

· Sample matrix · Sample parameters · Storage location · Log in person's initials All information relevant to the samples will be secured at the end of each business day.

All samples will be stored in a designated sample storage area, access to which will be limited to laboratory employees.

Samples ( baseline surrogate, vendor mixed surrogate, vendor treated surrogate and leachates) will be delivered to Environmental Enterprises by the Project Manager for mercury analysis. Chain of custody records will be generated and maintained by ALTER for these samples. EPA QA Section No. 5.0 Revision No. 0 Date: December 20, 2000 Page 17of 38 5.0 Testing and Measurement Protocols Tables 5.1 thru 5.3 list all of the methods that may be used by Agvise Laboratories,

Environmental Enterprises, and the Accelerated Life Testing and Environmental Research ( ALTER) Corporation in this research. Most of these are standard EPA or ASTM procedures and are referenced. Non   standard procedures are provided as appendices. Standard operating procedures for Agvise laboratories are located in Appendix E.

Samples are immediately placed in a refrigerator for storage after sampling unless a refrigerator is not required. The parameters for sample preparation and storage are listed in Table 5.4 for various matrices and analyses. EPA QA Section No. 5.0 Revision No. 0 Date: December 20, 2000 Page 18 of 38 Table 5.1 Test Procedures Used by Agvise Laboratories PROCEDURE PRIMARY REFERENCE1 PHYSICAL( 2)

Density Water Content Particle size Cation Ion Exchange Capacity Percent Organic Matter Cations ( Magnesium, Potassium, Calcium, Sodium) NUT. 02.10 NUT. 02.36 NUT. 02.32 NUT. 02.03 NUT. 02.04 NUT. 02.12 Notes: ( 1) These procedures are based on Standard Methods for Soils established by the USDA and the Soil Society of America. NUT refers to Agvise's nutrient laboratory where the testing is conducted and the numerical reference refers to their standard operating procedures.

( 2) A total of 250 g of raw waste is submitted for the 6 analyses. A duplicate ( 250g) is also submitted.

Table 5.2 Test Procedures Used By Environmental Enterprises PROCEDURE PRIMARY REFERENCE Mercury ( aqueous)( 1) SW 846 Method 7470A Mercury ( solid)( 2) SW 846 Method 7470A Notes: ( 1) Volume of sample available varies with test performed. Where possible, 250 ml is submitted for analysis. Test duplicates for 50% of the data points are also submitted. ( 2) A total of 100 g is submitted for analysis. A duplicate is also submitted. EPA QA Section No. 5.0 Revision No. 0 Date: December 20, 2000 Page 19 of 38 Table 5.3 Test Procedures Used by ALTER PROCEDURE PRIMARY REFERENCE SAMPLE VOLUME/ TEST Characterization Leachates and Wastes Alkalinity 2320( 1) 200g( 2) / 40 ml( 3)

Acidity( Variable Mass Only) 2330( 1) 200g( 2) / 40 ml( 3)

pH ( All Leachates) 4500( 1) 5g( 2) / Performed on gross leachate before filtration Wastes Moisture Content ASTM D 2216 80 100g( 4)( 5)

Particle Size ASTM D 422 63 150g( 2)

Leaching Experiments TCLP Federal Register Volume 51 200g( 2)

UC Constant pH Leaching Appendix B 250g( 2)

Notes:

( 1) Standard Methods for the Examination of Water and Wastewater, 18th ed. 1992 ( 2) Minimum Dry Solids Required.

( 3) Minimum Leachate Required ( 4) Minimum Raw Waste Required ( 5) Procedure Modified   for all wastes dry in hood at room temperature, 72 ° F. EPA QA Section No. 5.0 Revision No. 0 Date: December 20, 2000 Page 20 of 38 Table 5.4 Sample Handling and Storage Conditions ANALYTE SAMPLE CONTAINER SAMPLE CONTAINER PREPARATION SAMPLE CONTAINER PRESERVATION SAMPLE HOLDING TIME Acidity 400 ml polyethylene beakers One Time Use N/ A( 1) N/ A( 1)

Alkalinity 400 ml polyethylene beakers One Time Use N/ A( 1) N/ A( 1)

Mercury Waste for Analysis 250 ml or larger polyethylene with screw cap One Time Use N/ A( 1) Indefinite Mercury Waste Stored 2 liter HDPE Jars with Teflon lids One Time Use None Indefinite Mercury Leachates 250 ml or larger polyethylene with screw cap One Time Use Acidify filtered aqueous samples with HNO3 to obtain a pH < 2. Keep cool ( 4 ° C) 28 days pH 100 ml polyethylene with screw cap One Time Use N/ A( 1) N/ A( 1)

Notes:

( 1) N/ A   Samples consist of leachates generated or wastes with DI water added which are measured immediately. EPA QA Section No. 5.0 Revision No. 0 Date: December 20, 2000 Page 21 of 38 5.1 Calibration Procedures and Frequency Equipment that will require periodic calibration or servicing falls into two general categories:

1. Facility support equipment 2. Laboratory testing equipment The following paragraphs describe the types of equipment in each category and the proposed method and frequency of calibration.

Facility Support Equipment in this category includes the Department's water deionization system,

compressed air system, constant humidity moisture room ( for sample storage and curing), and fume hood. All of these systems are operational and are maintained/ serviced under ALTER service contracts.

Laboratory Testing Equipment Calibration Calibration will be performed by trained personnel, or approved vendors, using the approved procedures. Identification records will be assigned and affixed to the devices and entered into supporting calibration records. The calibration frequency of each instrument will be defined within the calibration procedure. When the integrity of a product, process or sample is in question because of an out of calibration device, the Project Manager will be notified. Based on the evaluation performed, the extent of any non conforming situation will be reported to the Co

PI who may specify the disposition, including re measurement or re test. Section 8.2 of this document discusses the corrective action scheme. EPA QA Section No. 5.0 Revision No. 0 Date: December 20, 2000 Page 22 of 38 Analytical Balances Instrument   Mettler PM 4600 Mettler B303 Calibration The balances are calibrated daily when in use, or when moved.

Standards Standard metric weights are used for calibration. Weights used for calibration should bracket the expected range of the sample. Calibration must be within +/ 0.01g. If variation from standard exceeds +/ 0.01 g, balance will be tagged " out of service" and will not be used. It will then be reported to Project Manager.

Cold Vapor Mercury Analysis   Environmental Enterprises, Inc.

Instrument   Varian SpectrAA20 Atomic Absorption Spectrophotometer with VGA 76 Vapor Generation Accessory Calibration Prior to daily calibration and analysis, the instrument is turned on and allowed to thermally stabilize. After the lamps and optical pathway is optimized, five standards ( 0.5, 2, 5,

10, 40 ug/ L) and a blank are analyzed in order to generate a calibration curve. The correlation coefficient (" r") is calculated and must be greater than or equal to 0.995. Immediately after calibration, the Initial Calibration Verification ( ICV) secondary source check standard is analyzed. ICV acceptance criteria is +/ 10% of the true value ( 5 ug/ L). The Initial Calibration Blank ( ICB) check standard is then analyzed. ICB value must be less than the reporting limit ( 0.5 ug/ L). The Low Detection Limit ( LDL) secondary source check standard is then analyzed.

LDL acceptance criteria is +/ 30% of the true value ( 0.5 ug/ L). Method Blanks ( MB) and Laboratory Control Samples ( LCS) are then analyzed. MB value must be less than the reporting limit ( 0.5 ug/ L). LCS acceptance criteria is +/ 15% of the true value or within the suppliers certified acceptance limits for purchased soil/ solid reference standards. Continuing Calibration Verification ( CCV) secondary source check standards are analyzed after every 10th analysis.

CCV acceptance criteria is +/ 20% of the true value ( 5 ug/ L). All analytical runs must end with a CCV and CCB. EPA QA Section No. 5.0 Revision No. 0 Date: December 20, 2000 Page 23 of 38 Standards Atomic absorption standards and reference solution are ACS grade. Mercury calibration standards are purchased from Fisher Scientific. Secondary check standards are purchased from EM Science. To ensure optimum stability, each solution has a concentration of 1000 ppm. All dilutions are prepared volumetrically. EPA QA Section No. 5.0 Revision No. 0 Date: December 20, 2000 Page 24 of 38 pH Meter Instrument   Fisher Scientific Accumet pH meter 915 Fisher Scientific Accumet research AR50 Calibration Calibration procedures for the pH meter are described in Standard Methods, 4500   H+ B1.

The meter will be calibrated using a two point calibration with certified calibration standards.

Standards for calibration are pH 4 and pH 10. A pH 7 standard will be used as the check standard. The meter will be calibrated not less than twice daily, at the beginning and end of experiments, using a two point calibration protocol. Based upon comparison of pH standards with actual pH, a range of +/ 0.05 pH units is acceptable. If accuracy is not in this range, the unit will be tagged " out of service" and will not be used. It will then be reported to the Project Manger.

Standards All calibration standards certified and are purchased from Fisher Scientific. Fresh standards are used for each calibration.

1 Standard Methods for the Examination of Water and Wastewater, 19th ed. 1995. EPA QA Section No. 6.0 Revision No. 0 Date: December 20, 2000 Page 25 of 38 6.0 QA/ QC Checks The parameters routinely used to gauge data quality are precision and accuracy. Precision is defined as the reproducibility of data upon repeated analysis. Precision is monitored by comparing the results of duplicate samples. Precision objectives for all the measurements listed in Table 6.1 are presented as relative percent difference ( RPD) for duplicate samples. In addition to duplicate extract and test samples, Environmental Enterprises performs a batch duplicate sample digestion and analysis at a rate of 1 for every 20 ( or less) mercury samples submitted.

Accuracy is defined as the agreement of a measurement with the true value of a known traceable standard. The goal is to maintain results within the specified limits. In the study of earth or sludge materials, where numerous physical measurements are required, there are no standards of known true value against which accuracy can be estimated. Furthermore, it is clearly not feasible to " spike" a physical measurement. Therefore, accuracy for physical measurements related to percent moisture and particle size will be determined by checking the analytical balance with standard weights and bracketing the anticipated weights of the samples.

Upon the development of a new method, spiked samples are analyzed and the percent recovery calculated for the analyses. This will then be an estimate of the recoveries that can be expected for the specific test system. Environmental Enterprises performs a batch spiked sample digestion and analysis at a rate of 1 for every 20 ( or less) mercury samples submitted. Accuracy is further shown by the evaluation of a laboratory control sample of known value that is digested and analyzed in the same manner as the samples submitted.

This project incorporates the use of two non standard tests for leaching of mercurycontaining wastes. Procedures for these tests are provided as Appendices B & C. EPA QA Section No. 6.0 Revision No. 0 Date: December 20, 2000 Page 26 of 38 Quality control with these techniques is addressed in the individual procedures.

Wherever possible, reference to standards promulgated by EPA, ASTM ( American Society for Testing and Materials), or COE ( Corps of Engineers) will be followed. Limits of accuracy are yet to be determined and will be addressed in addenda to the Quality Assurance Project Plan as the techniques are developed.

A summary of the estimated QA objectives for precision and accuracy are presented in Table 6.1. EPA QA Section No. 6.0 Revision No. 0 Date: December 20, 2000 Page 27 of 38 Table 6.1 Quality Assurance Objectives for MDL Precision and Accuracy of Chemical Analyses Performed at ALTER Chemical / Process Method MDL( 1) Precision( 2 ) Accuracy( 3)

Alkalinity 2320( 4) 5 mg/ l 20 75 125% Acidity 2330( 4) 5 mg/ l 20 75 125% pH 4500H+ B ( 4)  0.02( 6) 0.05( 5)

Quality Assurance Objectives for MDL Precision and Accuracy of Chemical Analyses and Performed at Environmental Enterprises Chemical / Process Method Reporting Limit Precision( 2) Accuracy( 3)

Mercury ( aqueous) 7470A( 7) 0.0005 mg/ l 25 75 125%

Mercury ( solids) 7470A( 7) 0.05 mg/ kg 25 75 125%

Notes:

( 1) Method detection limit ( 2) As relative percent difference ( RPD) of analytical duplicates ( 3) As percent recovery range ( 4) Standard Methods for the Examination of Water and Wastewater, 18th ed. 1992 ( 5) As bias limits ( 6) Expressed in pH units as limits for deviation of check standards from true value ( 7) Test methods for evaluating solid waste use SW 846 EPA QA Section No. 6.0 Revision No. 0 Date: December 20, 2000 Page 28 of 38 6.1 Calculations of Data Quality Indicators Precision Precision is measured by running two or three replicate analyses. When duplicates are analyzed the precision will be expressed in terms of the Relative Percent Difference ( RPD).

( ) 100 x 2 / 2 1 2 1 D D D D RPD + - = where: RPD = Relative Percent Difference D1 = Duplicate result 1 D2 = Duplicate result 2 When three samples are analyzed, precision will be reported in terms of the standard deviation and/ or the coefficient of variation ( relative standard deviation).

where: s = Standard deviation n = Number of replicates X1= Replicate result X = Mean of the replicate measurements ( ) X s CV 100 x = where: CV = Coefficient of variation s = Standard deviation X = Mean of replicate results ( ) ( ) 2 1 1 - - = å = n X X s n i i EPA QA Section No. 6.0 Revision No. 0 Date: December 20, 2000 Page 29 of 38 Accuracy Accuracy is the defined as the degree of agreement between a measurement and an accepted reference value. For some parameters, accuracy will be gauged through analysis of reference standards. This of course depends on whether or not a reference standard exists for a given analysis. Wet chemical waste analyses have reference standards for most common parameters. Reference standards have a known true value and an acceptable range of values ( usually three standard deviations established from interlaboratory testing of the standards). When accuracy is based on reference standards, it is the accuracy objective to be within this acceptable range of values. Since analysis of reference standards estimates the accuracy of the measurement process, they may or may not truly evaluate the accuracy of the unknown sample data. When applicable, spiked samples will be analyzed to estimate unknown accuracy. In these cases, the accuracy objective is expressed in terms of maximum acceptable deviation from 100 % recovery.

Percent recovery is defined as follows:

% R Sp s C = - x100 where: % R = Percent recovery Sp = Spiked sample concentration S = Unspiked sample concentration C = Concentration of spike added EPA QA Section No. 6.0 Revision No. 0 Date: December 20, 2000 Page 30 of 38 6.2 Internal Quality Control Checks, Performance, and System Audits The internal quality control checks ( Table 6.2) routinely implemented with analytical testing are method blanks, replicate samples, and QC standards. The following discussions describe each type of QC that is applied to the testing.

Experimental test blanks pertain only to the leaching or chemical characterization tests.

These blanks are deionized water or a standard leachant, as outlined in a specific test protocol,

taken through the entire equipment cleaning/ sample leaching procedure or sample preparation and analysis routine. When steps in the leaching procedure call for re use of a piece of equipment during the procedure cleaning between samples is required and blanks are collected to determine if any cross contamination has occurred. Should test blank results indicate any amount of detectable contamination, samples will be re analyzed if possible. If this is not possible,

results of the blank will be reported along with the results from the samples. Test blanks are run at a frequency of 1 for every 10 samples analyzed. If a set of tests is run on less than 10 samples,

then at least 1 blank is run for each test. Each Environmental Enterprises, Inc. analytical batch consists of 1 test blank, 1 laboratory control sample and up to 20 samples. One of these samples in each batch is duplicated and spiked.

A minimum of 50% duplicate samples are run on all leaching tests. These are individual samples that are tested in parallel. The replicate analyses provide a measure of the variability ( precision) of the entire testing and measurement process. Table 6.2 indicates the type and frequency of QC checks. EPA QA Section No. 6.0 Revision No. 0 Date: December 20, 2000 Page 31 of 38 QC standards are samples of a known concentration which have been prepared from an independent source. This type of analysis is useful for verifying calibration of a particular system. QC Standards are analyzed on several of the chemical characterization tests. Table 6.3 indicates those tests where QC Standards are applicable and the frequency required.

Other internal quality control considerations include the following:

( 1) All chemicals used in leaching procedures are reagent grade or higher purity ( e. g.

samples for metals analyses from leachate are acidified with re distilled nitric acid).

These chemicals are dated when received.

( 2) Water used in all leaching tests is ASTM Type I or II as appropriate to the specific test.

The QA officer will participate throughout the testing and analysis cycles as was noted in Section 2. Performance and system audits will be handled by external means. ALTER will participate as required by EPA. As of now, no audits are scheduled. EPA QA Section No. 6.0 Revision No. 0 Date: December 20, 2000 Page 32 of 38 Table 6.2 Quality Control Checks QUALITY CONTROL CHECKS FREQUENCY Analytical Method Blanks 1 for every 10 samples( 1)

Experimental Test Blanks Leachant used in Specific Test Calibration Standards Daily Analytical Duplicate 1 duplicate for every 10 samples( 1)

Test Duplicate ( pH Based Leaching) Required for 50% of data points Test Duplicate ( TCLP) Each sample duplicated Spiked Samples 1 for every 10 samples( 1)

( 1) Note: If less than 10 samples are analyzed in any grouping, 1 blank, 1 duplicate, and 1 spike are required.

Table 6.3 QC Standards TEST STANDARD USED FREQUENCY Alkalinity Na2CO3 1 time/ test day prior to analysis Acidity NaOH 1 time/ test day prior to analysis pH pH 10.0 Calibration Standard pH 7.0 Check Standard pH 4.0 Calibration Standard Beginning and end of each operating day Mercury HgNO3 After every 10 samples EPA QA Section No. 7.0 Revision No. 0 Date: December 20, 2000 Page 33 of 38 7.0 Data Reduction, Validation and Reporting All results will be reduced to the appropriate reporting units ( designated in the Standard Procedures) by the analyst performing the test. Calculations are prepared by computer and are checked by the analyst for gross error and miscalculation. Results are averaged and the mean and the standard deviation or range are calculated. All data is reviewed by the Project Manager prior to reporting. All data points are reported along with the mean and appropriate estimations of variability. All data generated by ALTER will be retained for five years.

Raw data is collected from the instruments and entered into spreadsheets for final data calculations. The ALTER QA officer determines whether or not data have met QA objectives.

Spot recalculation will be made by the QA officer to check for incorrect calculations.

Approximately 10 % of the data will be checked for calculation error by the QA officer. Any data not meeting stated objectives are brought to the attention of the appropriate Project Manager. The Project Manager determines whether results are indicative of a problem or if it is simply a statistical outlier. Suspect data will be excluded from the mean and reported individually as a suspect data point. At no time will data be discarded. A data report will be reviewed by the Project Manager for overall technical review. Other validation procedures executed by the QA officer and/ or Project Manager include making sure proper testing procedures are followed, adequate documentation is maintained and spot checks of calculations.

The Project Manager and the QA officer review QA/ QC data generated to determine whether objectives are being met and if trends in the data are indicating potential problems. If necessary,

they will specify new tests based on available data  should this need be indicated from the data collected. EPA QA Section No. 7.0 Revision No. 0 Date: December 20, 2000 Page 34 of 38 ALTER uses the EPA definition of Method Detection Limit ( MDL) as stated in 40CFR pt136, App. B. pg. 554 ( 7 1 91Ed): " The method detection limit is defined as the minimum concentration of a substance that can be measured and reported with 99% confidence that the analyte concentration is greater than zero.

7.1 Project Output Environmental Enterprises will maintain all analytical data for ten years. The following QA/ QC data will be provided by Environmental Enterprises Inc. as an appendix for all project analytical data:

Sample Description of ID Number Laboratory sample ID Number Analyses Performed Method Reference Analyst report Chain of Custody Date Prepared and Analyzed Blank Report Laboratory Control Sample Report Initial Calibration Curve Copies of Analyst Bench Sheets Case Narrative Monthly reports will be prepared by graduate students, reviewed by the project manager and submitted to the EPA on the 15th of every month. Distribution of the monthly report to other agencies will be at the discretion of the EPA project manager. A final report will be prepared by SAIC with input from the ALTER project manager. The final report format will be structured as follows:

1.0 Introduction 2.0 Background Data from waste generators Vendor process descriptions 3.0 Characterization Data Generated by ALTER, Agvise and Environmental Enterprises as outlined in Section 3.0 of the QAPP. Characterization data will be presented in tables which will provide the parameter measured, the result and the organization responsible for the data. 4.0 Leaching Detailed methods and results for each test will be provided as follows: EPA QA Section No. 7.0 Revision No. 0 Date: December 20, 2000 Page 35 of 38 · TCLP   will be presented in a table providing mercury analysis results. · UC Constant pH Leaching   will be presented in a table providing pH results with the corresponding mercury analysis of the leachate. The data will also be presented graphically, plotting leachate mercury concentration against pH. 5.0 Data Quality Discussion 6.0 Conclusions · Data Interpretation · Data based assessment of the applicability of vendor processes to treat the mercury containing surrogate.

Modifications or deviations to standard procedures will be documented and presented in the final project report. EPA QA Section No. 8.0 Revision No. 0 Date: December 20, 2000 Page 36 of 38 8.0 Assessments 8.1 Quality Assurance Reports to Management Quality Assurance reports will be compiled by the analyst computing data, then reviewed by the Project Manager and the QA officer. Review of data quality is a continuous process. All key project personnel will meet on a weekly basis while experimental work is in progress to assure that all QA/ QC practices are being followed.

Any problems and/ or recommended solutions will be reported as they are encountered. It is important that all data anomalies be examined in a timely fashion in order to minimize unusable data. All QA activities will be documented in appropriate logbooks at the time of any action for later review at the routine QA meetings.

Requests for amendments of the QA Project Plan will occur only after agreement by the Project Manager and the QA officer. The Project Manager will notify EPA when a change is required and the change will be documented in writing and a copy included in the monthly report of the project. This documentation will describe the necessary changes and present the reason for the amendment request.

All principal project participants on the distribution list will receive a copy of the approved QA Project Plan. Any subsequent revisions will be distributed to these individuals as the revisions are documented. The document control format in the upper right hand corner of the page will reflect the new date and revision number. EPA QA Section No. 8.0 Revision No. 0 Date: December 20, 2000 Page 37 of 38 8.2 Corrective Action Scheme A corrective action implies the identification of a problem and subsequent elimination of the problem. Occasionally, a problem can be immediately identified by the research assistants and eliminated prior to any data collection. More often, the problem has been in existence for some time and, therefore, the need for corrective action is indicated by an out of control situation or unacceptable levels of completeness. In these situations, it is the responsibility of the project manager to document and oversee the corrective action process. Appropriate authorities in the problem area are contacted for assistance in the identification and elimination steps when necessary.

The corrective process is basically divided into four units:

1. Identification of the problem 2. Elimination of the problem 3. Documentation of the problem 4. Verification of the correction In all cases, problems encountered will be dealt with immediately and eliminated as quickly as possible. No data will be generated after a problem is identified until the problem has been eliminated. If possible, suspect results generated during the existence of problem will be discarded and reanalyzed. When this is not possible or practical, suspect results will be flagged.

Final disposition of such flagged, suspect results will be decided by the Project Manager in conjunction with the Co PI or the QA officer.

Potential problems that occur and corrective action taken is outlined below: EPA QA Section No. 8.0 Revision No. 0 Date: November 15, 1999 Page 38 of 38 Problem Area Action( s)*

· Analytical Methods 1) If the operator disagrees with any b procedure or part of the analytical method · Instrumental Analysis 1) If blanks produce an erratic baseline b, c and/ or noise 2) If multiple analyses of standard( s) b, c yield inconsistent results 3) If the calibration curve is nonlinear b, c 4) Loss of greater than 10 % of instrument b, c sensitivity during any given test day 5) Instruments out of calibration a, c · Data Review 1) If the data is contrary to that expected a, b 2) If the data review has not been performed a, b within one day of analytical measurement 3) If precision and accuracy calculations are a, b discovered to be incorrect after data has been reported * Action Codes:

a = Notify the Project Manager; discuss with the Co PI over that area b = Notify the QA officer; discuss with the Co PI c = Adjust, repair or return the instrument to the manufacturer for repair APPENDIX A Acidity/ Alkalinity ALTER LABORATORY Standard Methods for the Examination of Water and Wastewater, 1992  2310 ACIDITY Acidity of a water is its quantitative capacity to react with a strong base to a designated pH. The measured value may vary significantly with the end point pH used in the determination. Acidity is a measure of an aggregate property of water and can be interpreted in terms of specific substances only when the chemical composition of the sample is known. Strong mineral acids, weak acids such as carbonic and acetic, and hydrolyzing salts such as ferrous or aluminum sulfates may contribute to the measured acidity according to the method of determination.

Acids contribute to corrosiveness and influence chemical reaction rates, chemical speciation, and biological processes. The measurement also reflects a change in the quality of the source water.

1. General Discussion a. Principle: Hydrogen ions present in a sample as a result of dissociation or hydrolysis of solutes react with additions of standard alkali. Acidity thus depends on the end point pH or indicator used. The construction of a titration curve by recording sample pH after successive small measured additions of titrant permits identification of inflection points and buffering capacity, if any, and allows the acidity to be determined with respect to any pH of interest.

In the titration of a single acidic species, as in the standardization of reagents, the most accurate end point is obtained from the inflection point of a titration curve. The inflection point is the pH at which curvature changes from convex to concave or vice versa. Because accurate identification of inflection points may be difficult or impossible in buffered or complex mixtures, the titration in such cases is carried to an arbitrary end point pH based on practical considerations. For routine control titrations or rapid preliminary estimates of acidity, the color change of an indicator may be used for an end point. Samples of industrial wastes, acid mine drainage, or other solutions that contain appreciable amounts of hydrolyzable metal ions such as iron, aluminum, or manganese are treated with hydrogen peroxide to ensure oxidation of any reduced forms of polyvalent cations, and boiled to hasten hydrolysis. Acidity results may be highly variable if this procedure is not followed exactly. b. End points: Ideally the end point of the acidity titration should correspond to the stoichiometric equivalence point for neutralization of acids present. The pH at the equivalence point will depend on the sample, the choice among multiple inflection points, and the intended use of the data. Dissolved carbon dioxide ( CO2) usually is the major component of unpolluted surface waters; handle samples from such sources carefully to minimize the loss of dissolved gasses. In a sample containing only carbon dioxide bicarbonates carbonates, titration to pH 8.3 at 25  C corresponds to stoichiometric neutralization of carbonic acid to bicarbonate. Because the color change of phenolphthalein indicator is close to pH 8.3, this value generally is accepted as a standard end point for titration of total acidity, including CO2 and most weak acids. Metacresol purple also has an end point at pH 8.3 and gives a sharper color change. For more complex mixtures or buffered solutions selection of an inflection point may be subjective. Consequently, use fixed points of pH 3.7 and pH 8.3 for standard acidity determinations in waste waters and neutral waters where the simple carbonate equilibria discussed above cannot be assumed. Bromphenol blue has a sharp color change at its end point of 3.7. The resulting titrations are identified, traditionally, as " methyl orange acidity" ( pH 3.7) and " phenolphthalein" or total acidity ( pH 8.3) regardless of the actual method of measurement. c. Interferences: Dissolved gasses contributing to acidity or alkalinity, such as CO2, hydrogen sulfide, or ammonia, may be lost or gained during sampling, storage, or titration. Minimize such effects by titrating to the end point promptly after opening sample container, avoiding vigorous shaking or mixing, and protecting sample form the atmosphere during titration, and letting sample become no warmer than it was at collection. In the potentiometric titration, oily matter, suspended solids, precipitates, or other waste matter may coat the glass electrode and cause sluggish response. Difficulty from this source is likely to be revealed in an erratic titration curve. Do not remove interferences from sample because they may contribute to its acidity. Briefly pause between titrant additions to let electrode come to equilibrium or clean the electrodes occasionally. In samples containing oxidizable or hydrolyzable ions such as ferrous or ferric iron, aluminum, and manganese, the rates of these reactions may be slow enough at room temperature to cause drifting end points. Do not use indicator titrations with colored or turbid samples that may obscure the color change at the end point. Residual free available chlorine in the sample may bleach the indicator. Eliminate this source of interference by adding 1 drop of 0.1N sodium thiosulfate ( Na2S2O3). d. Selection of method: Determine sample acidity from the volume of standard alkali required to titrate a portion to a pH of 8.3 ( phenolphthalein acidity) or pH 3.7 ( methyl orange acidity of waste waters and grossly polluted waters). Titrate at room temperature using a properly calibrated pH meter, electrically operated titrator, or color indicators. Construct a titration curve for a standardization of reagents. Use the hot peroxide procedure to pretreat samples known or suspected to contain hydrolyzable metal ions or reduced forms of polyvalent cation, such as iron pickle liquors, acid mine drainage, and other industrial wastes. Cool to room temperature before titration. Color indicators may be used for routine and control titrations in the absence of interfering color and turbidity and for preliminary titrations to select sample size and strength of titrant (  4b). e. Sample size: The range of acidities found in waste waters is so large that a single sample size and normality of base used as titrant cannot be specified. Use a sufficiently large volume of titrant ( 20 mL or more from a 50 mL buret) to obtain relatively good volumetric precision while keeping sample volume sufficiently small to permit sharp end points. For samples having acidities less than about 1,000 mg as calcium carbonate ( CaCO3)/ L, select a volume with less than 50 mg CaCO3 equivalent acidity and titrate with 0.02N sodium hydroxide ( NaOH). For acidities greater than about 1,000 mg as CaCO3/ L, use a portion containing acidity equivalent to less than 250 mg CaCO3 and titrate with 0.1N NaOH. If necessary, make a preliminary titration to determine optimum sample size and/ or normality of titrant. f. Sampling and storage: Collect samples in polyethylene or borosilicate glass bottles and store at low temperature. Fill bottles completely and cap tightly. Because waste samples may be subject to microbial action and to loss or gain of carbon dioxide ( CO2) or other gasses when exposed to air, analyze samples without delay, preferably within 1 day. If biological activity is evident analyze within 6 hr. Avoid sample agitation and prolonged exposure to air.

2. Apparatus a. Electrometric titrator: Use any commercial pH meter or electrometrically operated titrator that uses a glass electrode and can be read to 0.05 pH unit. Standardize and calibrate according to the manufacturer's instructions. Pay special attention to temperature compensation and electrode care. If automatic temperature compensation is not provided, titrate at 25  C,  2  C. b. Titration vessel: The size and form will depend on the electrodes and the sample size. Keep the free space above the sample as small as practicable, but allow room for titrant and full immersion of the indicating portions of electrodes. For conventional sized electrodes, use a 200 mL, tall form Berzelius beaker without a spout. Fit beaker with a stopper having three holes, to accommodate the two electrodes and the buret. With a miniature combination glass reference electrode use a 125 mL or 250 mL erlenmeyer flask with a two hole stopper. c. Magnetic stirrer. d. Pipets, volumetric. e. Flasks, volumetric, 1,000, 200, 100 mL. f. Burets, borosilicate glass, 50, 25, 10 mL. g. Polyolefin bottle.

3. Reagents a. Carbon dioxide free water: Prepare all stock and standard solutions and dilution water for the standardization procedure with distilled or deionized water that has been freshly boiled for 15 min and cooled to room temperature. The final pH of the water should be  6.0 and its conductivity should be < 2 m mhos/ cm. b. Potassium hydrogen phthalate solution, approximately 0.05N: Crush 15 to 20 g primary standard KHC8H4O4 to about 100 mesh and dry at 120  C for 2 hrs. Cools in a desiccator. Weigh 10.0  0.5 g ( to the nearest mg), transfer to a 1 L volumetric flask, and dilute to 1,000 mL. c. Standard sodium hydroxide titrant, 0.1N: Prepare solution approximately 0.1N as indicated under Preparation of Desk Reagents as indicated in Table B.

TABLE B: PREPARATION OF UNIFORM SODIUM HYDROXIDE SOLUTIONS Required Required Weight of Volume of Normality NaOH to Prepare 15N NaOH to of 1,000 mL of Prepare 1,000 NaOH Solution mL of Solution Solution g mL 6 240 400 1 40 67 0.1 4 6.7 Standardize by titrating 40.00 mL KHC8H4O4 solution ( 3b), using a 25 mL buret. Titrate to the inflection point (  1a), which should be close to pH 8.7. Calculate normality of NaOH:

where: A = g KHC8H4O4 weighed into 1 L flask, B = mL KHC8H4O4 solution taken for titration, and C = mL NaOH solution used.

Use the measured normality in further calculations or adjust to 0.1000N; 1 mL = 5.00 mg CaCO3. d. Standard sodium hydroxide titrant, 0.02N: Dilute 200 mL 0.1N NaOH to 1,000 mL and store in a polyolefin bottle protected from atmospheric C) 2 by a soda lime tube or tight cap. Standardize against KHC8H4O4 as directed in  3c, using 15.00 mL KHC8H4O4 solution and a 50 mL buret. Calculate normality as above (  3c); 1 mL = 1.00 mg CaCO3. e. Hydrogen peroxide, H2O2, 30%. f. Bromphenol blue indicator solution, pH 3.7 indicator: Dissolve 100mg bromphenol blue, sodium salt, in 100 mL water. g. Metacresol purple indicator solution, pH 8.3 indicator: Dissolve 100 mg metacresol purple in 100 mL water. h. Phenolphthalein indicator solution, alcoholic, pH 8.3 indicator. i. Sodium thiosulfate, 0.1M: Dissolve 25 g Na2S2O3  5H2O and dilute to 1,000 mL with distilled water.

4. Procedure If sample is free from hydrolyzable metal ions and reduced forms of polyvalent cations, proceed with analysis according to b, c, or d. If sample is known or suspected to contain such substances, pretreat according to a. a. Hot peroxide treatment: Pipet a suitable sample ( see  1e) into titration flasks. Measure pH. If pH is above 4.0 add 5 mL increments of 0.02N sulfuric acid ( H2SO4)( Section 2320B. 3c) to reduce pH to 4 or less. Remove electrodes. Add 5 drops 30% H2O2 and boil for 2 to 5 min. Cool to room temperature and titrate with standard alkali to pH 8.3 according to the procedure of 4d. b. Color change: Select a sample size and normality of titrant according to criteria of  1e. Adjust sample to room temperature, if necessary, and with a pipet discharge sample into an erlenmeyer flask, while keeping pipet tip near flask bottom. If free residual chlorine is present add 0.05 mL ( 1 drop) 0.1N Na2S2O3 solution, or destroy with ultraviolet radiation. Add 0.2 mL ( 5 drops) indicator solution and titrate over a white surface to a persistent color change characteristic of the equivalence point. Commercial indicator solutions or solids designated for the appropriate pH range ( 3.7 or 8.3) may be used. Check color at end point by adding the same concentration of indicator used with sample to a buffer solution at the designated pH. c. Potentiometric titration curve: C x 204.2 B x A = Normality 1) Rinse electrodes and titration vessel with distilled water and drain. Select sample size and normality of titrant according to the criteria of  1e. Adjust sample to room temperature, if necessary, and with a pipet discharge sample while keeping pipet tip near the vessel bottom. 2) Measure sample pH. Add standard alkali in increments of 0.5 mL or less, such that a change of less than 0.2 pH units occurs per increment. After each addition, mix thoroughly but gently with a magnetic stirrer. Avoid splashing. Record pH when a constant reading is obtained. Continue adding titrant and measure pH until pH 9 is reached. Construct the titration curve by plotting observed pH values versus cumulative milliliters titrant added. A smooth curve showing one or more inflections should be obtained. A ragged or erratic curve may indicate that equilibrium was not reached between successive alkali additions. Determine acidity relative to a particular pH from the curve. d. Potentiometric titration to pH 3.7 or 8.3: Prepare sample and titration assembly as specified in  4c1. Titrate to preselected end point pH (  1d) without recording intermediate pH values. As the end point is approached make smaller additions of alkali and be sure that pH equilibrium is reached before making the next addition.

5. Calculation Acidity, as mg CaCO3/ L where: A = mL NaOH titrant used, B = normality of NaOH, C = mL H2SO4 used (  4d), and D = normality of H2SO4.

Report pH of the end point used, as follows: " The acidity to pH = mg CaCO3/ L." A negative value signifies alkalinity.

6. Precision No general statement can be made about precision because of the great variation in sample characteristics. The precision of the titration is likely to be much greater than the uncertainties involved in sampling and sample handling before analysis. Forty analysts in 17 laboratories analyzed synthetic water samples containing increments of bicarbonate equivalent to 20 mg CaCO3/ L. Titration according to the procedure of  4d gave a standard deviation of 1.8 mg CaCO3/ L, with negligible bias. Five laboratories analyzed two samples containing sulfuric, acetic, and formic acids and aluminum chloride by the procedures of  s 4b and 4d. The mean acidity of one sample ( to pH 3.7) was 487 mg CaCO3/ L, with a standard deviation of 11 mg/ L. The bromphenol blue titration of the same sample was 90 mg/ L greater, with a standard deviation of 110 mg/ L. The other sample had a potentiometric titration of 547 mg/ L with a standard deviation of 54 mg/ L, while the corresponding indicator result was 85 mg/ L greater sample mL 50,000 x D)] x ( C  B) x [( A = with a standard deviation of 56 mg/ L. The major difference between the samples was the substitution of ferric ammonium citrate, in the second sample, for part of the aluminum chloride. ALTER LABORATORY Standard Methods for the Examination of Water and Wastewater, 1992  2320 ALKALINITY Alkalinity of a water is its quantitative capacity to react with a strong acid to a designated pH. The measured value may vary significantly with the end point pH used. Alkalinity is a measure of an aggregate property of water and can be interpreted in terms of specific substances only when the chemical composition of the sample is known.

Alkalinity is significant in many uses and treatments of natural and waste waters. Because the alkalinity of many surface waters is primarily a function of carbonate, bicarbonate, and hydroxide content, it is taken as an indication of the concentration of these constituents. The measured values may include contributions from borates, phosphates, or silicates if these are present. Alkalinity in excess of alkaline earth metal concentrations is significant in determining the suitability of a water for irrigation. Alkalinity measurements are used in the interpretation and control of water and waste water treatment process. Raw domestic waste water has an alkalinity less than or only slightly greater than that of the water supply. Properly operating anaerobic digesters typically have supernatant alkalinities in the range of 2,000 to 4,000 mg calcium carbonate ( CaCO3)/ L.

1. General Discussion a. Principle: Hydroxyl ions present in a sample as a result of dissociation or hydrolysis of solutes react with additions of standard acid. Alkalinity thus depends on the end point pH used. For methods of determining inflection points from titration curves and the rationale for titrating to fixed pH end points, see Section LPC# 301.1a. For samples of low alkalinity ( less than 20 mg CaCO3/ L) use an extrapolation technic based on the near proportionality of concentration of hydrogen ions to excess of titrant beyond the equivalence point. The amount of standard acid required to reduce pH exactly 0.30 pH unit is measured carefully. Because this change in pH corresponds to an exact doubling of the hydrogen ion concentration, a simple extrapolation can be made to the equivalence point. b. End points: When alkalinity is due entirely to hydroxide, carbonate, or bicarbonate content, the pH at the equivalence point of the titration is determined by the concentration of carbon dioxide ( CO2) at that stage. CO2 concentration depends, in turn, on the total carbonate species originally present and any losses that may have occurred during titration. The following pH values are suggested as the equivalence points for the corresponding alkalinity concentrations as milligrams CaCO3 per liter: Table 1. End Point pH Values End Point pH Total Alkalinity Phenolphthalein Alkalinity Alkalinity, mg CaC03/ L:

30 4.9 8.3 150 4.6 8.3 500 4.3 8.3 Silicates, phosphates known or suspected 4.5 8.3 Routine or automated analyses 4.5 8.3 Industrial waste or complex system 4.5 8.3 c. Interferences: Soaps, oily matter, suspended solids, or particulates may coat the glass electrode and cause a sluggish response. Allow additional time between titrant additions to let electrode come to equilibrium. Do not filter, dilute, concentrate, or alter sample. d. Selection of method: Determine sample alkalinity from volume of standard acid required to titrate a portion to a designated pH taken from  1b. Titrate at room temperature with a properly calibrated pH meter or electrically operated titrator, or use color indicators. Report alkalinity less than 20 mg CaCO3/ L only if it has been determined by the lowalkalinity method of  4d. Construct a titration curve for standardization of reagents. Color indicators may be used for routine and control titrations in the absence of interfering color and turbidity and for preliminary titrations to select sample size and strength of titrant ( see below). e. Sample size: See Section LPC# 301.1e for selection of size sample to be titrated and normality of titrant, substituting 0.02N or 0.1N sulfuric ( H2SO4) or hydrochloric ( HCl) acid for the standard alkali of that method. For the low alkalinity method, titrate a 200 mL sample with 0.02N H2SO4 from a 10 mL buret. f. Sampling and storage: See Section LPC# 301.1f.

2. Apparatus See Section LPC# 301.2.

3. Reagents a. Sodium carbonate solution, approximately 0.05N: Dry 3 to 5 g primary standard Na2CO3 at 250  C for 4 hrs and cool in a desiccator. Weigh 2.5g,  0.2 g ( to the nearest mg), transfer to a 1 L volumetric flask, fill flask to the mark with distilled water, and dissolve and mix reagent. Do not keep longer than 1 week. b. Standard sulfuric acid or hydrochloric acid, 0.1N: Dilute 3.0 mL conc H2SO4 or 8.3 mL conc HCl to 1 L with distilled or deionized water. Standardize against 40.00 mL 0.05N Na2CO3 solution, with about 60 mL water, in a beaker by titrating potentiometrically to pH of about 5. Lift out electrodes, rinse into the same beaker, and boil gently for 3 to 5 min under a watchglass cover. Cool to room temperature, rinse cover glass into beaker, and finish titrating to the pH inflection point. Calculate normality:

where: A = g Na2CO3 weighed into 1 L flask, B = mL Na2CO3 solution taken for titration, and C = mL acid used.

Use measured normality in calculations or adjust to 0.1000N; 1 mL 0.1000N solution = 5.00 mg CaCO3. c. Standard sulfuric acid or hydrochloric acid, 0.02N: Dilute 200.00 mL 0.1000N standard acid to 1,000 mL with distilled or deionized water. Standardize by potentiometric titration of 15.00 mL 0.05N Na2CO3 according to the procedure of  3b; 1 mL = 1.00 mg CaCO3. d. Bromcresol green indicator solution, pH 4.5 indicator: Dissolve 100 mg bromcresol green, sodium salt, in 100 mL distilled water. e. Mixed bromcresol green methyl red indicator solution: Use either the aqueous or the alcoholic solution: 1) Dissolve 100 mg bromcresol green sodium salt and 20 mg methyl red sodium salt in 100 mL distilled water. 2) Dissolve 100 mg bromcresol green and 20 mg methyl red in 100 mL 95% ethyl alcohol or isopropyl alcohol. f. Methyl orange solution. g. Phenolphthalein solution, alcoholic. h. Sodium thiosulfate, 0.1M: See Section LPC# 301.3i.

4. Procedure a. Color change: See Section LPC# 301.4a. The color response of the mixed bromcresol green methyl red indicator is approximately as follows: above pH 5.2, greenish blue; pH 5.0, light blue with lavender gray; pH 4.8, light pink gray with bluish cast; and pH 4.6, light pink. Check color changes against reading of a pH meter under the conditions of the titration. Because colors are difficult to distinguish, the method is subject to relatively large operator error. b. Potentiometric titration curve: Follow the procedure for determining acidity ( LPC# 301.4b), substituting the appropriate normality of standard acid solution for standard NaOH, and continue titration to pH 4.5 or lower. Do not filter, dilute, concentrate, or alter the sample. C x 53.00 B x A = N Normality, c. Potentiometric titration to pre selected pH: Determine the appropriate end point pH according to  1b. Prepare sample and titration assembly ( LPC# 301.4b). Titrate to the end point pH without recording intermediate pH values and without undue delay. As the end point is approached make smaller additions of acid and be sure that pH equilibrium is reached before adding more titrant. d. Potentiometric titration of low alkalinity: For alkalinities less than 20 mg/ L titrate 100 to 200 mL according to the procedure of  4c above, using a 10 mL microburet and 0.2N standard acid solution. Stop the titration at a pH in the range 4.3 to 4.7 and record volume and exact pH. Carefully add additional titrant to reduce the pH exactly 0.30 pH unit and again record volume.

5. Calculations a. Potentiometric titration to end point pH:

where: A = mL standard acid used and, N = normality of standard acid.

or where: t = titer of standard acid, mg CaCO3/ mL.

Report pH end point used as follows: " The alkalinity to pH = mg CaCO3/ L" and indicate clearly if this pH corresponds to an inflection point of the titration curve. b. Potentiometric titration of low alkalinity: Total alkalinity, mg CaCO3/ L where: B = mL titrant to first recorded pH, C = total mL titrant to reach pH 0.3 unit lower, and N = normality of acid.

c. Calculation of alkalinity relationships: The results obtained from the phenolphthalein and total alkalinity determinations offer a means for stoichiometric classification of the three principle forms of alkalinity present in many waters. The classification ascribes the entire alkalinity to bicarbonate, carbonate, and hydroxide, and assumes the absence of other ( weak) inorganic or sample mL 50,000 x N x A = / L CaCO mg , Alkalinity 3 sample mL 1,000 x t x A = / L CaCO mg , Alkalinity 3 sample mL 50,000 x N x C)  B ( 2 = organic acids, such as silicic, phosphoric, and boric acids. It further presupposes the incompatibility of hydroxide and bicarbonate alkalinities. Because the calculations are made on a stoichiometric basis, ion concentrations in the strictest sense are not represented in the results, which may differ significantly from actual concentrations especially at pH > 10. According to this scheme: 1) Carbonate ( CO3 2) alkalinity is present when phenolphthalein alkalinity is not zero but is less than total alkalinity. 2) Hydroxide ( OH) alkalinity is present if phenolphthalein alkalinity is more than half the total alkalinity. 3) Bicarbonate ( HCO3 ) ions are present if phenolphthalein alkalinity is less than half the total alkalinity. These relationships may be calculated by the following scheme, where P is phenolphthalein alkalinity and T is total alkalinity (  1b): Select the smaller alkalinity value of P or ( T P). Then, carbonate alkalinity equals twice the smaller value. When the smaller value is P, the balance ( T 2P) is bicarbonate. When the smaller value is ( T P), the balance ( 2P T) is hydroxide. All results are expressed as CaCO3. The mathematical conversion of the results is shown in the following table:

Result of Titration Hydroxide Alkalinity Carbonate Alkalinity Bicarbonate Concentration P = 0 0 0 T P <  T 0 2P T  2P P =  T 0 2P 0 P >  T 2P  T 2( T  P) 0 P = T T 0 0 Key: P  phenolphthalein alkalinity; T  total alkalinity.

Alkalinity relationships also may be computed nomographically ( see Carbon Dioxide, LPC# 316). Accurately measure pH, calculate OH concentration as milligrams CaCO3 per liter, and calculate concentrations of CO3 2 and HCO3  as mg CaCO3/ L from the OH concentration, and the phenolphthalein and total alkalinities by the following equations:

Similarly, if difficultly is experienced with the phenolphthalein end point, or if a check on the phenolphthalein titration is desired, calculate phenolphthalein alkalinity as CaCO3 from the results of the nomographic determinations of carbonate and hydroxide ion concentrations: ] OH 2[  2P = CO   2 3 ] OH [ + 2P  T = HCO   3 6. Precision and Bias No general statement can be made about precision because of the great variation in sample characteristics. The precision of the titration is likely to be much greater than the uncertainties involved in sampling and sample handling before the analysis. In the range of 10 to 500 mg/ L, when the alkalinity is due entirely to carbonates or bicarbonates, a standard deviation of 1 mg CaCO3/ L can be achieved. Forty analysts in 17 laboratories analyzed samples containing increments of bicarbonate equivalent to 120 mg CaCO3/ L. The titration procedure of  4b was used, with an end point pH of 4.5 The standard deviation was 5 mg/ L and the average bias ( lower than the true value) was 9 mg/ L. Sodium carbonate solutions equivalent to 80 and 65 mg CaCO3/ L were analyzed by 12 laboratories according to the procedure of  4c. The standard deviations were 8 and 5 mg/ L, respectively, with negligible bias. Four laboratories analyzed six samples having total alkalinities of about 1000 mg CaCO3/ L and containing various ratios of carbonate/ bicarbonate by the procedures of both  4a and  4c. The pooled standard deviation was 40 mg/ L, with negligible difference between the procedures. ] OH [ + ] CO 1/ 2[ = P   2 3 APPENDIX B University of Cincinnati's Constant pH Leaching Procedure Project Specific   Untreated Surrogate University of Cincinnati ALTER Facility Constant pH Leaching Procedure Project Specific   Untreated Surrogate Summary The constant pH test is a static leach test that is conducted to assess the chemical integrity of a waste form at the pH, temperature, and pressure of interest. A series of tests is commonly run to provide data on contaminant concentration as a function of pH ( e. g., six tests at pH values of 2, 4, 6, 8, 10, and 12). This information is used to determine the optimum pH condition for immobilizing the contaminant.

For the mercury LDR project, two sets of pH profiles ( pH 2, 4, 6, 8, 10, and 12) will be performed on untreated surrogate made at ALTER. The tests will be conducted using automated pH controllers. The specified pH will be held constant for ten days ± one hour. The leachant will be continuously stirred during the contact period with the waste form. Automated adjustments will be made with 0.1N nitric acid or 0.1N sodium hydroxide to maintain the specified pH. Prior to collection of the analytical sample at ten days, the leachate will be filtered.

Materials Waste form Beakers for leach tests ( teflon, HDPE, or glass; 800 mL) Magnetic stir bars Stir plates Constant pH controllers Parafilm Reagent grade nitric acid ( ACS or equivalent) Reagent grade sodium hydroxide ( ACS or equivalent) Deionized water ( ASTM Type 2) 3 liter vessels for preparing leachant ( HDPE or glass) pH meter ( accurate to within ± 0.1 pH units) Filters ( borosilicate glass fiber; pore size of 0.7 m m) Filter holders ( teflon, HDPE, or glass; Nuclepore Corp. 425910 or 410400, or equivalent) Polyethylene sample bottles Laboratory balance ( accurate to within ± 0.01 g) Laboratory hood or oven Sieves ( if needed)

Procedure Prepare the waste sample: If needed, reduce the particle size of the waste sample to less than 9.5 mm in diameter. Determine the moisture content of the sample using modified ASTM D 2216 ( Drying temperature is modified to 60 ° C). The moisture content will be used to calculate the weight of waste sample for each pH test. 25 g of waste sample on dry basis is needed for each data point.

Prepare the leachant: Using reagent grade nitric acid and sodium hydroxide, prepare stock solutions of 0.1 N nitric acid and 0.1 N sodium hydroxide. Prepare 2 liters of leachant for each pH test by adjusting the pH of deionized water using the 0.1 N nitric acid or 0.1 N sodium hydroxide. Leachant pH values are 2, 4, 6, 8, 10, and 12.

Prepare the leach test beakers, filter holders, and filters: Prepare a stock solution of 1.0 N nitric acid. Place the test beakers and filter holders in a bath of 1.0 N nitric acid for one hour. Remove each beaker and filter holder and rinse with 1.0 N nitric acid followed by three consecutive rinses with deionized water ( minimum of 500 mL per rinse). Place the beakers and filter holders upside down on a clean, absorbent material ( e. g., kimwipes) until needed. Rinse the borosilicate glass fibers with 1.0 N nitric acid followed by three consecutive rinses with deionized water ( minimum of 500 mL per rinse). Assemble the filter apparatus using the filter holders and glass filters.

Prepare leach tests: Set up 11 acid washed 800 ml beakers under a hood and label them as follows: pH 2 1 - pH 2 sample 1 pH 4 1 - pH 4 sample 1 pH 6 1 - pH 6 sample 1 pH 8 1 - pH 8 sample 1 pH 10 1 - pH 10 sample 1 pH 12 1 - pH 12 sample 1 Duplicates: pH 2 D - pH 2 sample 2 pH 8 D - pH 8 sample 2 pH 12 D - pH 12 sample 2 Blanks: pH 2 B - pH 2 method blank pH 12 B - pH 12 method blank Record the information in the log book.

Weigh out 25 ± 0.01g of dry waste sample ( as calculated using the waste moisture content) for each of the 3 test beakers for each pH. Add 500mL of the appropriate pH leachant to each of the 3 test beakers for each pH and the blank beaker. Measure the leachant pH in each beaker to the nearest 0.1 pH unit and record the initial value in the log book. Place a stir bar in each beaker, cover each with parafilm and place the beakers on a stir plate. Connect constant pH controllers to each beaker and adjust for hourly pH correction. Begin stirring all beakers simultaneously, and maintain rapid stirring throughout the experiment. Monitor and maintain pH value: The pH shall be checked manually using a pH meter on days 1, 2, 7 and 10. Record this information in the log book.

Filtration: At the conclusion of each test, the sample will be filtered prior to placing the leachate in the sample container. The leachate from each 500 mL test will be filtered through a separate 0.7 m m glass filter and collected in a polyethylene bottle. A minimum of 200 mL of filtrate must be collected for each sample. The filtrate will be acidified with nitric acid to a pH of less than 2 and stored at 4o C until analyzed.

Analysis: The leachate will be analyzed for mercury content using the cold vapor atomic absorption method ( SW 846 Method 7470 or Standard Method 3112B). The maximum allowable detection limit is 0.001 mg/ L.

Quality Assurance Requirements: All data, including log books and analytical results, should be maintained and available for reference and inspection. Duplicates and blank sample will be analyzed for each pH value tested. Analytical work will follow all quality control measures listed in the method ant the QAPP. APPENDIX C University of Cincinnati's Constant pH Leaching Procedure Project Specific   Treated Surrogate University of Cincinnati ALTER Facility Constant pH Leaching Procedure Project Specific   Treated Surrogate Summary The constant pH test is a static leach test that is conducted to assess the chemical integrity of a waste form at the pH, temperature, and pressure of interest. A series of tests is commonly run to provide data on contaminant concentration as a function of pH ( e. g., six tests at pH values of 2, 4, 6, 8, 10, and 12). This information is used to determine the optimum pH condition for immobilizing the contaminant.

For the mercury LDR project, two sets of pH profiles will be performed on the two 100 lb samples of treated surrogate returned to ALTER from the vendors. Two pH profiles ( pH 2, 4, 6, 8, 10, and 12) will be generated from batch 1 and one pH profile will be generated from batch 2. The tests will be conducted using automated pH controllers. The specified pH will be held constant for ten days ± one hour. The leachant will be continuously stirred during the contact period with the waste form. Automated adjustments will be made with 0.1N nitric acid or 0.1N sodium hydroxide to maintain the specified pH. Prior to collection of the analytical sample at ten days, the leachate will be filtered.

Materials Waste form Beakers for leach tests ( teflon, HDPE, or glass; 800 mL) Magnetic stir bars Stir plates Constant pH controllers Parafilm Reagent grade nitric acid ( ACS or equivalent) Reagent grade sodium hydroxide ( ACS or equivalent) Deionized water ( ASTM Type 2) 3 liter vessels for preparing leachant ( HDPE or glass) pH meter ( accurate to within ± 0.1 pH units) Filters ( borosilicate glass fiber; pore size of 0.7 m m) Filter holders ( teflon, HDPE, or glass; Nuclepore Corp. 425910 or 410400, or equivalent) Polyethylene sample bottles Laboratory balance ( accurate to within ± 0.01 g) Laboratory hood or oven Sieves ( if needed) Procedure Prepare the waste sample: If needed, reduce the particle size of the waste sample to less than 9.5 mm in diameter. Determine the moisture content of the sample using modified ASTM D 2216 ( Drying temperature is modified to 60 ° C). The moisture content will be used to calculate the weight of waste sample for each pH test. 25 g of waste sample on dry basis is needed for each data point.

Prepare the leachant: Using reagent grade nitric acid and sodium hydroxide, prepare stock solutions of 0.1 N nitric acid and 0.1 N sodium hydroxide. Prepare 2 liters of leachant for each pH test by adjusting the pH of deionized water using the 0.1 N nitric acid or 0.1 N sodium hydroxide. Leachant pH values are 2, 4, 6, 8 10, and 12.

Prepare the leach test beakers, filter holders, and filters: Prepare a stock solution of 1.0 N nitric acid. Place the test beakers and filter holders in a bath of 1.0 N nitric acid for one hour. Remove each beaker and filter holder and rinse with 1.0 N nitric acid followed by three consecutive rinses with deionized water ( minimum of 500 mL per rinse). Place the beakers and filter holders upside down on a clean, absorbent material ( e. g., kimwipes) until needed. Rinse the borosilicate glass fibers with 1.0 N nitric acid followed by three consecutive rinses with deionized water ( minimum of 500 mL per rinse). Assemble the filter apparatus using the filter holders and glass filters.

Prepare leach tests: Set up 20 acid washed 800 ml beakers under a hood and label them as follows:

pH 2 1 - pH 2 sample 1 Batch 1 pH 2 2 - pH 2 sample 1 Batch 2 pH 4 1 - pH 4 sample 1 Batch 1 pH 4 2 - pH 4 sample 1 Batch 2 pH 6 1 - pH 6 sample 1 Batch 1 pH 6 2 - pH 6 sample 1 Batch 2 pH 8 1 - pH 8 sample 1 Batch 1 pH 8 2 - pH 8 sample 1 Batch 2 pH 10 1 - pH 10 sample 1 Batch 1 pH 10 2 - pH 10 sample 1 Batch 2 pH 12 1 - pH 12 sample 1 Batch 1 pH 12 2 - pH 12 sample 1 Batch 2 Duplicates: pH 2 D1 - pH 2 sample 2 Batch 1 pH 2 D2 - pH 2 sample 2 Batch 2 pH 8 D1 - pH 8 sample 2 Batch 1 pH 8 D2 - pH 8 sample 2 Batch 2 pH 12 D1 - pH 12 sample 2 Batch 1 pH 12 D2 - pH 12 sample 2 Batch 2 Blanks: pH 2 B - pH 2 method blank pH 12 B - pH 12 method blank Record the information in the log book.

Weigh out 25 ± 0.01g of dry waste sample ( as calculated using the waste moisture content) for each of the 3 test beakers for each pH. Add 500mL of the appropriate pH leachant to each of the 3 test beakers for each pH and the blank beaker. Measure the leachant pH in each beaker to the nearest 0.1 pH unit and record the initial value in the log book. Place a stir bar in each beaker, cover each with parafilm and place the beakers on a stir plate. Connect constant pH controllers to each beaker and adjust for hourly pH correction. Begin stirring all beakers simultaneously, and maintain rapid stirring throughout the experiment.

Monitor and maintain pH value: The pH shall be checked manually using a pH meter on days 1, 2, 7 and 10. Record this information in the log book.

Filtration: At the conclusion of each test, the sample will be filtered prior to placing the leachate in the sample container. The leachate from each 500 mL test will be filtered through a separate 0.7 m m glass filter and collected in a polyethylene bottle. A minimum of 200 mL of filtrate must be collected for each sample. The filtrate will be acidified with nitric acid to a pH of less than 2 and stored at 4o C until analyzed.

Analysis: The leachate will be analyzed for mercury content using the cold vapor atomic absorption method ( SW 846 Method 7470 or Standard Method 3112B). The maximum allowable detection limit is 0.001 mg/ L.

Quality Assurance Requirements: All data, including log books and analytical results, should be maintained and available for reference and inspection. Duplicates and blank sample will be analyzed for each pH value tested. Analytical work will follow all quality control measures listed in the method and the QAPP. APPENDIX D Chain of Custody APPENDIX E Standard Operating Procedures for Agvise Laboratories METHOD SUMMARY FOR SOIL ANALYSIS TESTING LABORATORY: AGVISE LABORATORIES, INC. P. O. BOX 510; Highway 15 Northwood, ND 58267 ( 701) 587 6010 The following is a summary of analytical methods used by AGVISE Laboratories in the determination of soil characteristics and nutrient content. Analytical data of some or all of these analytical methods are presented based upon the testing requested by the firm submitting the soil specimens.

Chemical Properties Carbonates  Determined by gravimetric loss of carbon dioxide ( NUT. 02.14).

Cation Exchange Capacity   Determined by summing the cations with hydrogen ( NUT. 02.03). The cations of Magnesium, Potassium, Calcium, and Sodium are determined by extraction with 1.0 N ammonium acetate ( NUT. 02.12). Hydrogen is determined by measuring the pH of the soil in Adams Evans Buffer Solution ( NUT. 02.11).

Nitrogen, % Total   Determined by the Kjeldahl method ( NUT. 02.15).

Organic Carbon %  Determined by the Walkley Black Procedure ( NUT. 02.20).

Organic Matter %  Determined by the Walkley Black Procedure ( NUT. 02.09) in soils with less than 10% organic matter. Determined by the loss of weight on ignition procedure ( NUT. 02.04) in soils with a 10% or more organic matter.

pH   Determined with a pH electrode in a 1: 1 soil: water suspension ( NUT. 02.05) except when specified by state regulations to use a saturated paste ( NUT. 02.39).

Phosphorus   Determined by the Olsen method ( NUT. 02.07).

Soluble Salts   Determined using a conductivity meter in a 1: 1 soil: water suspension ( NUT. 02.19).

Physical Properties % Gravel   Determined by dry sieving and weighing the fraction over 2 mm ( NUT. 02.16).

% Sand, Silt, and Clay   Determined by hydrometer method ( NUT. 02.06) or by pipette method ( NUT. 02.56). Sand Particle Size   Determined by weighing fractions obtained by wet sieving ( NUT. 02.32). Bulk Density   Disturbed bulk density is determined by weighing a known volume of dried and ground soil ( NUT. 02.10). Core or non disturbed bulk density is determined by weighing a known volume of an intact, dried soil core ( NUT. 02.02).

Water Holding Capacity and Water Relations Moisture %  Determined by gravimetric loss upon drying ( NUT. 02.36).

Saturated Hydraulic Conductivity   Determined by using the constant head method and measuring the rate of flow of water through a saturated soil column ( NUT. 02.34).

Water Infiltration Rate   Determined by using the constant head method and measuring the length of time from water application to production of a leachate from a soil column ( NUT. 02.35).

Water Holding Capacity   Determined by measuring the moisture remaining when saturated soil is placed under 1/ 3 or 0.10 bar pressure ( NUT. 02.08).

Water Holding Capacity   Determined by measuring the moisture remaining when saturated soil is placed under 15 bar pressure ( NUT. 02.13).

All of the above methods are detailed in the current analytical SOPs used by AGVISE Laboratories' Characterization testing laboratory.

NUT. 05.01. Long Term Storage of Soil and Water Characterization Specimens: According to this Sop, soil characterization samples will be retained by AGVISE Laboratories for at least two years before disposal and water characterization samples will be retained for a period of 60 days before disposal.

Adm. 05.01. Archivist Duties and Archiving Procedures: This SOP states that copies of soil and water characterization reports, original COC's and original raw data will be archived within 60days after the signature by the analytical investigator. Hard copies generated by computer will be archived weekly, and supplemental data will be archived annually.

QAU. 08.01. Quality Assurance Inspections of Facilities, Studies, and Processes for GLP Compliance: Method inspections will be performed on a regular basis at AGVISE Laboratories, Inc. For soil characterization, two methods will be inspected per month and one water characterization inspection will be conducted per month. An annual facility audit will be performed by AGVISE Laboratories, Inc. Quality Assurance Unit.

All of the above methods are detailed in the current analytical SOP's used in AGVISE Laboratories' characterization laboratory. APPROVED BY ANALYTICAL INVESTIGATOR: ___________________________________________ Robert L. Deutsch, Soil Scientist Date APPENDIX F Project Schedule Mercury > 260 ppm Surrogate Sludge Testing Program Schedule Date: 10/ 18/ 00, Revision 0, Page 1 of 2 ID Task Name Duration Start Finish Responsible 1 Start 0 days Mon 10/ 2/ 00 Mon 10/ 2/ 00 2 Kick Off Meeting 2 days Tue 10/ 10/ 00 Wed 10/ 11/ 00 3 QA Task 55 days Thu 10/ 12/ 00 Wed 1/ 3/ 01 LR 4 Revise Draft QA plan 5 days Thu 10/ 12/ 00 Wed 10/ 18/ 00 LR 5 Review Draft QA plan 5 days Thu 10/ 19/ 00 Wed 10/ 25/ 00 All 6 Phone Call Meeting 1 day Thu 10/ 26/ 00 Thu 10/ 26/ 00 LR, Vega, MC 7 Revise Draft QA plan 5 days Fri 10/ 27/ 00 Thu 11/ 2/ 00 LR 8 Submit Draft plan to EPA 0 days Thu 11/ 2/ 00 Thu 11/ 2/ 00 LR 9 EPA Revise & Comment plan 19 days Fri 11/ 3/ 00 Fri 12/ 1/ 00 EPA, LR 10 Revise/ Settle Comments to plan 10 days Mon 12/ 4/ 00 Fri 12/ 15/ 00 LR 11 Submit Plan for Final Approval to EPA 0 days Fri 12/ 15/ 00 Fri 12/ 15/ 00 LR 12 Plan Reviewed/ Approved by EPA 10 days Mon 12/ 18/ 00 Wed 1/ 3/ 01 EPA, LR 13 QA Plan Approved 0 days Wed 1/ 3/ 01 Wed 1/ 3/ 01 LR 14 Surrogate Testing 113 days Mon 11/ 6/ 00 Thu 4/ 19/ 01 LR 15 Purchase bench scale testing materials 30 days Mon 11/ 6/ 00 Tue 12/ 19/ 00 LR 16 Go/ No Go Surrogate test 10 days Thu 1/ 4/ 01 Thu 1/ 18/ 01 LR 17 Reformulate surrogate ( if necessary) 10 days Fri 1/ 19/ 01 Thu 2/ 1/ 01 LR 18 Extended surrogate testing 50 days Fri 2/ 2/ 01 Thu 4/ 12/ 01 LR 19 Complete Extended Surrogate Testing 0 days Thu 4/ 12/ 01 Thu 4/ 12/ 01 LR 20 Purchase raw materials for vendor kits 20 days Fri 3/ 16/ 01 Thu 4/ 12/ 01 LR 21 Make up vendor surrogate waste kits 5 days Fri 4/ 13/ 01 Thu 4/ 19/ 01 LR 22 Ship Surrogate Waste Kits to Vendors 0 days Thu 4/ 19/ 01 Thu 4/ 19/ 01 LR 23 Procurement Process 107 days Thu 10/ 12/ 00 Mon 3/ 19/ 01 MM 24 Prepare CBD announcement 15 days Thu 10/ 12/ 00 Wed 11/ 1/ 00 MM 25 Review & Comment CBD announcement 10 days Thu 11/ 2/ 00 Wed 11/ 15/ 00 All 26 Revise CBD announcement 5 days Thu 11/ 16/ 00 Wed 11/ 22/ 00 MM 27 Issue CBD Announcement 1 day Mon 11/ 27/ 00 Mon 11/ 27/ 00 MM 28 Vendor responses to CBD 30 days Tue 11/ 28/ 00 Thu 1/ 11/ 01 Vendors 29 Prepare draft SOW & RFP 10 days Thu 11/ 2/ 00 Wed 11/ 15/ 00 MM 30 Review & Comment SOW & RFP 15 days Thu 11/ 16/ 00 Fri 12/ 8/ 00 All 31 Revise SOW & RFP 10 days Mon 12/ 11/ 00 Tue 12/ 26/ 00 MM 32 Issue SOW & RFP to Vendors 0 days Wed 1/ 3/ 01 Wed 1/ 3/ 01 MM 33 Vendor Response 22 days Thu 1/ 4/ 01 Mon 2/ 5/ 01 Vendor 34 Review Proposals 15 days Tue 2/ 6/ 01 Mon 2/ 26/ 01 All 35 Vendor best & final proposal 5 days Tue 2/ 27/ 01 Mon 3/ 5/ 01 Vendor 36 Contract awards to vendors 10 days Tue 3/ 6/ 01 Mon 3/ 19/ 01 MM 37 Contracts Awarded to Vendors 0 days Mon 3/ 19/ 01 Mon 3/ 19/ 01 MM 10/ 2 11/ 2 12/ 15 1/ 3 4/ 12 4/ 19 1/ 3 3/ 19 Q1 Q2 Q3 Q4 Q5 2001 Mercury > 260 ppm Surrogate Sludge Testing Program Schedule Date: 10/ 18/ 00, Revision 0, Page 2 of 2 ID Task Name Duration Start Finish Responsible 38 Vendor Testing 105 days Tue 3/ 20/ 01 Fri 8/ 17/ 01 MM 39 Prepare test plans 20 days Tue 3/ 20/ 01 Mon 4/ 16/ 01 Vendor 40 Review & comment test plans 5 days Tue 4/ 17/ 01 Tue 4/ 24/ 01 all 41 Test Plans Approved 0 days Tue 4/ 24/ 01 Tue 4/ 24/ 01 MM 42 Receive surrogate waste kits 5 days Wed 4/ 25/ 01 Tue 5/ 1/ 01 LR 43 Begin Vendor Testing 0 days Tue 5/ 1/ 01 Tue 5/ 1/ 01 Vendor 44 Bench scale testing 20 days Wed 5/ 2/ 01 Wed 5/ 30/ 01 Vendor 45 Two 100 lb batch scale testing 10 days Thu 5/ 31/ 01 Wed 6/ 13/ 01 Vendor 46 Complete Vendor Testing 0 days Wed 6/ 13/ 01 Wed 6/ 13/ 01 Vendor 47 Waste form ( WF) analysis 10 days Thu 6/ 14/ 01 Wed 6/ 27/ 01 Outside lab 48 Package & ship WF to U of C 5 days Thu 6/ 28/ 01 Fri 7/ 6/ 01 Vendor 49 Prepare draft report 30 days Mon 7/ 9/ 01 Fri 8/ 17/ 01 Vendor 50 Vendor Report to DOE 0 days Fri 8/ 17/ 01 Fri 8/ 17/ 01 Vendor 51 Waste Form ( WF) Evaluation 75 days Fri 7/ 6/ 01 Mon 10/ 22/ 01 LR 52 Receive Waste Forms From Vendors 0 days Fri 7/ 6/ 01 Fri 7/ 6/ 01 LR 53 Sample preparation 5 days Mon 7/ 9/ 01 Fri 7/ 13/ 01 LR 54 WF TCLP testing 3 vendors 15 days Mon 7/ 16/ 01 Fri 8/ 3/ 01 LR 55 WF pH testing for 3 vendors 70 days Mon 7/ 16/ 01 Mon 10/ 22/ 01 LR 56 WF variable mass testing for 3 vendors 15 days Mon 7/ 16/ 01 Fri 8/ 3/ 01 LR 57 Complete WF Testing 0 days Mon 10/ 22/ 01 Mon 10/ 22/ 01 LR 58 Final Report 40 days Tue 10/ 23/ 01 Wed 12/ 19/ 01 SAIC 59 Prepare Final Draft Report 20 days Tue 10/ 23/ 01 Mon 11/ 19/ 01 SAIC 60 Review & Comment Draft Report 10 days Tue 11/ 20/ 01 Wed 12/ 5/ 01 All 61 Revise & issue final report 10 days Thu 12/ 6/ 01 Wed 12/ 19/ 01 62 Issue Final Report 0 days Wed 12/ 19/ 01 Wed 12/ 19/ 01 4/ 24 5/ 1 6/ 13 8/ 17 7/ 6 10/ 22 12/ 19 Q2 Q3 Q4 Q5 Q6 2001 2002