Table of Contents

Section Page

Title Page 1 Table of Contents 2 1 Project Management 3 1.1 Project Description 3 1.2 Distribution List 3 1.3 Project Organization 4 1.4 Problem Definition/Background 4 1.4.1 Constituents for which EPA Listing is based 4 1.4.2 Waste Generation Process/Treatment Process 5 1.4.3 Constituents of Concern and Quantification Methods 6 1.4.4 Information on Waste Variability over Time 6 1.4.4.1 Chemical Authorization Process 6 1.4.4.2 Environmental Impact Assessment Process 7 1.4.5 Proposed Waste Disposal Location, if Delisted: 7 1.5 Project Description and Schedule 7 1.6 Quality Objectives and Criteria for Measurement Data 7 1.6.1 Objectives and Project Decisions 7 1.6.2 Action Limits/Levels 8 1.6.3 Measurement Performance Criteria/Acceptance Criteria 8 1.7 Special Training Requirements/Certification 8 1.8 Documents and Records 8 2 Data Generation and Acquisition 9 2.1 Sampling Design 9 2.2 Sampling Methods 9 2.3 Sample Handling and Custody 10 2.4 Analytical Methods 10 2.5 Quality Control Requirements 10 2.6 Instrument/Equipment Testing, Inspection, and Maintenance 10 2.7 Data Management 10 3 Assessment and Oversight 12 3.1 Assessment/Oversight and Response Actions 12 3.2 Reports to Management 12 4 Data Review and Usability 12 4.1 Data Review, Verification, and Validation Requirements 12 4.2 Verification and Validation Methods 12 Attachments 1 Wastewater Treatment Process Overviews 2 Table 1 - IBM Essex Junction, VT Sludge Delisting Constituents of Concern 3 Chemical Management Process Overview 4 Laboratory (Endyne) Quality Systems Manual 5 Laboratory (Endyne) Method SOPs (9) and associated QC tables (3) 1311, 6010, 8260, 8270, 3060A, 7196A, 7471A, 9012A
6 Endyne QA/QC Elemental Analysis of Water and Sludge Samples1 PROJECT MANAGEMENT

1.1 Project Description

The waste consists of industrial wastewater treatment sludge generated from the treatment of wastewaters from semiconductor manufacturing operati ons. The applicable RCRA waste code for this waste is F006 (wastewater treatment sludges from elect roplating operations). However, the sludge is a functionally nonhazardous waste stream and as generated meets the treatment standards outlined in 40 CFR Part 268 Subpart D for F006 nonwastewaters. It is proposed to collect representative samples of sludge for laboratory analysis, and provide new sludge characterization data that will lead to delisting the sludge to a nonhazardous classification.

1.2 Distribution List

Name: David Kost Title: Chief Industrial Wastewater Treatment Operator Organization: IBM Corporation Contact Information: 1000 River Street Mailstop 966A Essex Junction, VT 05452 (802) 769-2761 dlkost@us.ibm.com

Name: Candice Callahan Title: Hazardous Waste Program Manager Organization: IBM Corporation Contact Information: 1000 River Street Mailstop 966A Essex Junction, VT 05452 (802) 769-0579 ccallaha@us.ibm.com

Name: Tim Baechle Title: Manager of Energy, Environmental and Chemical Programs Organization: IBM Corporation Contact Information: 1000 River Street Mailstop 966A Essex Junction, VT 05452 (802) 769-4153 tbaechle@us.ibm.com

Name: Roland Luxenberg, P.E. Title: Consulting Engineer, Field Sampling Organization: Aquaterra Contact Information: 255 Flynn Avenue Burlington, VT 05401 (802) 238-0071 roland@luxenberg.us

Name: Harry Locker Title: Chemist Organization: Endyne, Inc. Contact Information 160 James Brown Drive Williston, VT 05445 (802) 879-4333 hlocker@endyne.comName: Sharon Leitch Title: EPA Project Manager Organization: EPA New England Region 1 Contact Information: 5 Post Office Square Suite 100 (OSRR07-1) Boston, MA 02109-3912 (617) 918-1647 leitch.sharon@epa.gov

1.3 Project Organization

Project Manager David Kost ( IBM, Chief Industrial Wastewater Treatment Operator) will be the responsible official for this project overseeing the overall project and budget, as well as tasking contractors with work required to complete this project. He will communicate project needs to the contractor’s project managers.

QA Manager Candice Callahan (IBM, Hazardous Waste Program Manager) will be responsible for reviewing and approving the QA Project Plan. She may provide technical input on proposed sampling design, analytical methodologies, and data review. She may assist with coordinating laboratory services.

Contractor Project Manager Roland Luxenberg (Aquaterra, Field Sampling) and Mark Fausel (Endyne, Laboratory Analysis) will have overall responsibility for assigning appropriate personnel to complete the tasks included in this plan. They will ensure that the project budget is adhered to. They will communicate with the Project Manager on work accomplished in this plan and any problems or deviations that need to be resolved. Roland will be responsible for collecting sludge samples in accordance with this document. Mark will be responsible for assigning appropriate laboratory staff to perform the analyses specified in this plan.

EPA Project Manager Sharon Leitch (EPA, Project Manager) will have the responsibility to see that the final report is reviewed, to inform IBM of any repor ting deficiencies and assist in their resolution, and will inform IBM if sludge is delisted (or if not, reason(s) why not).

1.4 Problem Definition/Background

The waste proposed for delisting consists of industria l wastewater treatment sludge generated from the treatment of wastewaters from semiconductor manufact uring operations. The sludge is primarily made up of lime added during the wastewater treatment pr ocess. The sludge is typically 40% solids (ranging from 20 to 55%), with a pH of 12 (range of 5 to just under 12.5). The applicable RCRA waste code for this waste is F006 (wastewater treatment sludges from electroplating operations).

1.4.1 Constituents for which EPA Listing is based

The hazardous constituents that were the basis for the F006 listing are found in 40 CFR 261, Appendix VII (cadmium, hexavalent chromium, nickel, and complexed cyanide). These constituents are not present in the sludge at concentrations that would impact human health or the environment. The sludge is a functionally nonhazardous waste stream and as generated meets the treatment standards outlined in 40 CFR Part 268 Subpart D for F006 nonwastewaters. The sludge is not regulated for any hazardous characteristics, such as a toxicity characteristic metal (40 CFR 261.24).1.4.2 Waste Generation Process/Treatment Process

The sludge is generated from the combination of three separate wastewater treatment processes. The sludge from each process is combined, thickened/conditioned, and pressed to generate this waste stream. The majority of sludge mass is from the industrial wastewater treatment plant (IWTP) process. The smaller contributors are the biological wastewater treatment (BWTP) process and the chemical mechanical polishing (CMP) microfiltration process.

Sludge is generated on a continual basis, as the IBM Essex Junction manufacturing facility operates 365 days per year 24 hours per day. Approximate average waste generation annually (over previous 5 years) is 7 million pounds per year, with an approximate maximum waste generation rate (over previous 5 years) of 10 million pounds per year (these values include sludge generated from periodic cleaning and maintenance of the two 7.5 million gallon IWTP process water storage tanks).

Chemical Mechanical Polishing (CMP) Pretreatment Waste

The CMP process is used to smooth the surface of the wafer using a combination of chemical etching and mechanical polishing. The CMP waste tr eatment system receives wastewater from chemical/mechanical polishing tools (CMP) used in semiconductor manufacturing. This system filters ferric nitrate solids, copper particles, silica solids, copper sulfate plating bath solutions (30-50 gallons per day), and tungsten solids. The CMP treatment system also filters some organics present in the polishing slurries (polyacrylic acid, sodium octy lsulfate, benzotriazole, and tetramethylammonium hydroxide). The filters are backflushed after each approximately 20 minute cycle, producing sludge with a pH of 7.5 to 8. Periodic cleaning of the filters with sulfuric acid may temporarily drop the pH of the sludge in the CMP thickener to around 5. The CMP process treats approximately 100,000 gallons of water per day.

Biological Wastewater Treatment Plant (BWTP)

The three major waste streams treated at the BWTP are concentrated waste (CW), dilute organic waste (DOW), and sanitary waste. All three wastes are mixed and equalized prior to treatment in Sequential Batch Reactors (SBR). The BWTP process treat s approximately 120,000 gallons of water per day.

Concentrated Waste (CW)

The concentrated waste stream consists of waste from semiconductor and mask manufacturing photolithography develop steps, chemical wafer cl eaning, etching, and stripping operations, and parts decontamination. The major chemical constituents in the waste stream are tetramethylammonium hydroxide (TMAH), hydrofluoric acid, phosphoric acid, glacial acetic acid, ammonium hydroxide, and hydrogen peroxide. The fluoride in the CW waste is treated by flash mixing with lime slurry to produce calcium fluoride, a solid which precipitates in the treatment system and is accumulated in the sludge. These inorganic wastes are biodegradable and treated by the microorganisms in the BWTP process. The CW process contributes approximately 40,000 gallons of water per day to the BWTP process.

Dilute Organic Waste (DOW)

The DOW waste stream receives discharges from chemical wafer cleaning and stripping, Deep UltraViolet (DUV) photolithography waste, air abatement adsorber decant waters, and facility chilled waterand boiler maintenance operations. The major chemical constituents in the DOW waste stream are isopropyl alcohol (IPA), propylene glycol monomethyl ether acetate (PGMEA), gamma-butyrolactone (GBL), n-butyl acetate (NBA), and propylene and ethylene glycols. These organic wastes are biodegradable and treated and consumed by the microorganisms in the BWTP process. The DOW process contributes approximately 5,000 gallons of water per day to the BWTP process.

Sanitary Waste

The sanitary waste stream consists of discharges from the site cafeterias and restrooms. These typical sanitary wastes are biodegradable and treated by the microorganisms in the BWTP process.

Industrial Wastewater Treatment Plant (IWTP)

The IWTP waste stream receives discharges from chemical wafer and mask manufacturing cleaning, etching, and stripping, photolithography waste, chem ical etching and mechanical polishing, air abatement scrubbers, effluent from the CMP and BW TP treatment systems, wafer rinse, and facility maintenance operations. The major chemical constituents in the IWTP waste stream are acids, bases, deionized water rinses, metals (Cu, Fe, Pt, etc.), and deionized water system reject water. The wastewaters also include rinse waters from copper electroplating manufacturing operations (1000 gallons per day) and wastewaters from acid etching of a thin platinum film and the subsequent rinse step (800 gallons per day). The IWTP treatment process cons ists of a sodium bisulfite pretreatment step to reduce hydrogen peroxide and chlorine. This is followed by acid and base neutralization, solids precipitation, and a final pH adjustment step. The IWTP process treats approximately 3 million gallons of water per day.

See Attachment 1 for the wastewater treatment process overviews.

1.4.3 Constituents of Concern and Quantification Methods

The constituents of concern are listed in Table 1 (Attachment 2). Also included in this table is the selection basis for each constituent.

1.4.4 Information on Waste Variability over Time

Potential variability is identified and managed through the following review processes.

1.4.4.1 Chemical Authorization Process

Before any chemical is brought onto the IBM campus for use by IBM personnel, contractors, or tenants, the chemical is identified and authorized through the company’s on-line chemical information and authorization management system. This review process identifies hazards and environmental issues associated with the use of a particular chemical. In addition, the expanded use of any existing chemical in a new process at the facility is also reviewed.

This system also provides access to supplier Mate rial Safety Data Sheets (MSDS), which contain information about the chemical’s health and safety hazards, storage compatibility, and handling characteristics. The authorization review process includes consideration of how any waste to be generated will be managed. Additional information may be obtained from the requester or the chemicalsupplier when necessary to properly characterize the waste expected to be generated.

1.4.4.2 Environmental Impact Assessment Process

The objectives of conducting a process environmental impact assessment are to identify potential significant impacts to the environment from IBM processes; to consider feasible alternatives for avoiding potential impacts; and to ensure compliance with applicable legal and regulatory requirements. Installation, modification, or relocation of chemical-u sing equipment proposed to discharge waste to any drains leading to the wastewater treatment facility is managed via an on-line environmental impact assessment system. The hazardous waste engineer or coordinator must review and approve all such waste discharges. These reviews are conducted on an ongoing, real-time basis to insure that compatibility and impacts are assessed.

See Attachment 3 for the chemical management process overview.

1.4.5 Proposed Waste Disposal Location, if Delisted:

The existing disposal locations (Stablex Canada in Blainville, Quebec or Chemical Waste Management in Model City, NY) could continue to be used, in addition to potential new opportunities. The preferred future use for the delisted sludge would be as a raw material in a cement kiln.

1.5 Project Description and Schedule

Field sampling will commence within 2 weeks of QA PP approval. Four (4) sampling events will be equally spaced out over a 4 week period. Each sampli ng event will be completed within two days, with samples delivered to the laboratory within the sampling week. Analysis for each sample event will be completed within 3 weeks. A summary table and brief narrative, along with laboratory reports, will be submitted within 4 weeks following receipt of the final laboratory results.

The following is a timetable summary, with elapsed time from QAPP approval:

Field sampling commences: 2 weeks Field sampling completed: 6 weeks Lab analysis commences: 3 weeks Lab analysis completed: 9 weeks Report submittal: 13 weeks

1.6 Quality Objectives and Criteria for Measurement Data

1.6.1 Objectives and Project Decisions The objective of this study is to demonstrate that the industrial wastewater treatment sludge currently regulated as hazardous can be delisted to a nonhazardous waste. Samples will be collected and results compared to target levels to be determined by EPA from an EPA model, in addition to already stated toxicity characteristic concentrations. If all sludge concentrations are below target levels and toxicity characteristic concentrations, then enough information will exist to allow for delisting of the sludge.1.6.2 Action Limits/Levels

The EPA will determine target levels through the use of their internal model.

1.6.3 Measurement Performance Criteria/Acceptance Criteria

The constituents of concern are identified in Table 1 (Attachment 2). Table 1 shows each constituent, holding times, extraction and analysis methods, the expected method reporting limit, and quality control (QC) criteria. In their reporting, the laboratory will identify which QC criteria, if any, were not initially satisfied, and what steps were taken to insure that overall accuracy was maintained.

1.7 Special Training Requirements/Certification

Field sampling and laboratory analysis will follow standard techniques, so no special training or laboratory certifications are required. The laborat ories will have National Environmental Laboratory Accreditation Conference (NELAC) certifica tion (if applicable) for all analysis.

1.8 Documents and Records

The approved QAPP will be distributed to key personnel by email. Field sampling documentation will be contained on the chain-of-custody, which will be included in the laboratory data package. The data package will consist of the results, along with appropriate QC data. This will be transmitted as a pdf file to the IBM project manager. The final report, with appropriate narrative, summary table, and laboratory data package, will be emailed to EPA New England Region 1.

All files (both electronic and hardcopy) will be part of IBM Corporation Records Retention Program. A hardcopy of the QAPP and final report will be kept in on-site files for a minimum of 3 years.2 DATA GENERATION AND ACQUISITION

2.1 Sampling Design

Wastewater has at least one day hydraulic residence time before and during treatment (3 million gallons per day (MGD) passing through one or two 7.5 million gallon (MG) process water storage tanks and a 1 MG equalization basin prior to treatment in a 0.3 MG cl arifier). There is estimated to be just over four days of solids residence time within the process tanks, based on 3000 mg/l total suspended solids (TSS) in the 0.3 MG clarifier, 30,000 mg/l TSS in the 0.109 MG gravity thickeners, and eight thousand pounds of sludge solids (dry weight) generated per day. Sludge is generated in stirred (biological, sequential batch reactor) or raked (industrial, clarifiers and thickeners) tanks, so sludge resulting from a filter press cycle is expected to be uniform. Pressed sludge drops into a wheeled trailer, with about five to six filter press cycles required to fill a trailer over the course of three to four days.

It is relatively easy to obtain a systematic random grid sample of the pressed sludge in a trailer by collecting samples of pressed sludge at the end of a filter press cycle before it drops into the trailer. In addition, the primary contaminants of concern are stable, so multiple filter press cycles can be composited over time. It is proposed that during each filter press cycle, samples be obtained from a random filter press plate towards each end, and in the middle of a filter press (three samples). During the next filter press cycle, another three random filter press plates would be sampled, and again for a third filter press cycle, for a total of nine samples to make one composite sample. This sample technique will be repeated every week, so that four composite samples are collected over a four week period.

2.2 Sampling Methods

Prior to sampling, a glass bottle will be labeled with a filter press location, date, and time. Each sample from a random filter press plate will be collected by pressing a thin walled plastic cylinder into the pressed sludge, then removing the cylinder. A total of three (3) locations at one filter plate will be sampled, so that the 12 grams of sludge per sample tube (using a 2.5 cm diameter sample tube pressed 5 cm into the sludge, and using a sludge density of 0.5 grams per cubic centimeter) will accumulate the 300 grams of required sludge (3 plates/cycle x 3 sample tubes per plate x 3 cycles x 12 grams per sample tube). The retained sludge will be extruded into the sample bottle with a plastic ram. After sampling is completed for a filter press cycle, the sampling equipment will be placed in another glass bottle, and all bottles (samples, sampling device) will be stored in a refrigerator, with a partially completed chain-of-custody. The chain-of-custody fo rm will be used to document the filter plates sampled, along with date and time, for each filter press cycle.

Additional bottles will be filled for the second and thir d filter press cycle. The sample bottles will then be placed in the sample refrigerator along with the completed chain-of-custody prior to laboratory courier pick-up. Prior to the next sample collection, the sampling equipment will be cleaned with soap and tap water.2.3 Sample Handling and Custody

Once picked up by the laboratory their general sample handling procedures will be followed. These procedures can be found in their Quality Systems Manual (Attachment 4). For TCLP VOC and SVOC analysis, one sample core from each sample bottle will be used (1 core/bottles x 9 bottles x 12 grams/core). For VOC/SVOC analysis, a 1/4 section from a sample core will be collected from each sample bottles (taking one core, cutting it in half, then cutting it in half again). All remaining sample core material from all bottles will be placed together, manually disaggregated using plastic tools until all sample fragments are less than 1 cm, then placed into a glass bottle and manually agitated for 1 minute to insure complete mixing prior to aliquots removed for all other sample analyses.

2.4 Analytical Methods

Each sample will be analyzed for a variety of metals (TCLP and total), cyanide (total and amenable to chlorination), semi-volatile organic compounds (TCLP and total), and volatile organic compounds (TCLP and total); see Table 1 (Attachment 2). Analytical procedures will follow general analysis guidelines found in the laboratory's Quality Systems Manual (Attachment 4), and those found in the method Standard Operating Procedures (SOPs) (Attachment 5).

The sub-contracted laboratory (VHG Labs, Inc of Manc hester, NH) that will analyze for total content of two metals (platinum and tin) will use the same extraction and analysis methods (listed in Attachment 2) as Endyne for total metals analysis, and will meet or exceed Endyne's quality control criteria for total metals analysis. Endyne is the contracted lab (by IBM) and will be ultimately responsible for the QA/QC of any sub-contracted analysis. Attachme nt 6 (Endyne QA/QC Elemental Analysis of Water and Sludge Samples) describes Endyne's method associ ated with the analysis of the sub-contracted metals.

2.5 Quality Control Requirements

Quality Control requirements are found in the method SOPs and associated QC criteria tables (Attachment 5). These include laboratory reagen t blanks, laboratory fortified blanks, calibration check/verification, calibration blank, interelement check standard, matrix spike, matrix spike duplicate, duplicate analysis, internal standards, and surrogate standards. The acceptance criteria are summarized in Table 1 (Attachment 2). In addition, a field duplicate will be collected during the first sampling event. Sampling will involve collecting an additional three (3) sample tubes at the same filter press plate used for the regular sample.

2.6 Instrument/Equipment Testing, Inspection, and Maintenance

Laboratory equipment testing, inspection, and maintenance will follow those contained in the laboratory's Quality Systems Manual and method SOPs (Attachments 4 and 5).

2.7 Data Management

The IBM Project Manager will receive the laboratory data package. The IBM Project Manager will review the package with assistance from IBM's Hazardous Waste Program Manager. The IBM Project Manager will enter the data into a summary spreadsheet, stored on both an office computer and on acompany-wide accessible electronic data storage area. The IBM Project Manager’s data entry will be checked by the Hazardous Waste Program Manager. The IBM Project Manager will communicate with the laboratory if any deviation from the QC criteria is found that has not already been addressed by the laboratory.

Once the laboratory data is considered complete, the IBM Project Manager will prepare the summary narrative, and then distribute the draft summary narrative, results summary spreadsheet, and laboratory data package for IBM internal review. Once all reviewers have responded with comments or concerns, the IBM Project Manager will resolve these issues as needed. The IBM Project Manager will send out final documents to EPA New England Region 1.3 ASSESSMENT AND OVERSIGHT

3.1 Assessment/Oversight and Response Actions

The IBM Project Manager will oversee sampling procedures on one or more of the four sample collection efforts. He will inform field sampli ng personnel of deviations from proposed sampling methods, and with assistance from Aquaterra will determine if these deviations are significant. After review of the first laboratory data package, the IBM Project Manager will contact Endyne if reporting times are not met, if insufficient documentation is received, or if quality control deviations are not adequately explained in the reporting narrative. If QC criteria are not met or adequately explained, the IBM Project Manager will delay further field sampling or stop additional laboratory analysis until QC deviations are resolved. The IBM Project Manager will contact the IBM Environmental Programs and Operations Manager and the EPA Project Manager if the timetable will be exceeded by more than one month, or if changes need to be made in the QC criteria as the result of matrix peculiarities.

3.2 Reports to Management

The IBM Project Manager will prepare an interim memorandum if there are quality control issues in field sampling or laboratory analysis, with assist ance from IBM's Hazardous Waste Program Manager. This will be sent to the IBM Environmental Programs and Operations Manager and discussed with the relevant Contractor Project Manager.

4 DATA REVIEW AND USABILITY

4.1 Data Review, Verification, and Validation Requirements

The field inspection of sampling events and comparison of the laboratory data package to QC criteria in Table 1 (Attachment 2) will be used to determine the validity of the final results.

4.2 Verification and Validation Methods

In their results narrative, the laboratory will identify analyses not meeting QC criteria, and corrective steps they used to try and resolve QC issues. The IBM Project Manager will review the laboratory data package to insure that no other QC criteria were not met, and will identify these unmet QC criteria, and/or those identified in the narrative, in the summary report. The IBM Project Manager will consult with EPA to determine if these QC deficiencies are significant when compared to target levels.ATTACHMENT 1WASTE TREATMENT FACILITYProcess OverviewLIME PRETREATMENTCHEMICAL PROCESSCALCIUM HYDROXIDE + FLUORIDES =CALCIUM FLUORIDE PRECIPITATECONCENTRATEDWASTE (CW)- AMMONIA- FLUORIDE- PHOSPHORUS- PEROXIDEBIOLOGICAL WASTE TREATMENTBIOLOGICAL PROCESS- SEQUENTIAL BATCH REACTORS(SBRs)- TREATS: ORGANICS, PHOSPHORUS,AMMONIA, PEROXIDESANITARYWASTEDILUTE ORGANICWASTE (DOW)- ADSORBER DECANT WATER- IPA < 24%- NBA/GBL- GLYCOL SOLUTIONS- DUV PGMEA WASTEINDUSTRIAL WASTE TREATMENT- CHEMICAL PROCESS- SOLIDS CONTACT AND REACTOR TYPECLARIFIERS- TREATS: ACIDS, BASES, METALS,PHOSPHORUS, pH- DOES NOT TREAT: ORGANICS, AMMONIAINDUSTRIALWASTE (IW)- ACIDS/ BASES- RINSEWATERS- REJECTWATER- METALSCMP PRETREATMENTCHEMICAL PROCESSPRECIPITATION, COAGULATION, FLOCCULATION,FILTRATION, METAL AND PARTICULATE REMOVALCMP WASTES WINOOSKI RIVER-POLISHING SLURRIES- SURFACTANTS,DISPERSANTS, SOAPS- METALS (Cu, Fe, Al)- SOLIDSChemicalMechanicalPolishing (CMP)Photolithography DevelopClean, Etch, & StripParts DecontaminationWafer Cleaning and StrippingPhotolithographyAir AbatementFacilities MaintenanceWafer and Mask ManufacturingCleaning, Etching, and StrippingPhotolithographyChemical PolishingRinsewatersAir Abatement ScrubbersPre-treated Waste (CMP & BWTP)DI Water SystemDrainKeyContributorsWastesCafateriaBathrooms-TYPICAL SANITARY WASTEINDUSTRIAL WASTE TREATMENT SYSTEMPROCESS FLOW SCHEMATICSLUDGECONDITIONINGTANK9'DX7'SWDFILTER PRESS1FSDFILTER PRESS 2JWISOLIDS TO LANDFILLCLAR 4MAX CAP5.0 MGD65'DX12'D1 MGALEQUALIZATIONBASIN70'LX95'WX25'DFORWARDINGPUMPSRECIRCULATION/WASTING PUMPS21'DX10'SWD25KGALTHICK.2THICK.330'DX16'SWD84KGAL3.3KGALPROCESS WATER BASINSTILLINGCHAMBER,FLUME &OUTFALLWINOOSKI RIVERFORWARDINGPUMPSRECIRCULATION/WASTING PUMPSPROCESSWATERSTORAGETANK #27.5 MGPROCESSWATERSTORAGETANK #17.5 MGCLAR 2MAX CAP2.0 MGD46'DX12'DCLAR 3MAX CAP2.3 MGD46'DX14.5'D- RO REJECT- TREATED GROUNDWATER- GROUNDWATER FIRETRAINING AREAINDUSTRIAL WASTE TREATMENT SYSTEMProcess FlowEQUALIZATIONCLARIFICATIONNaHSO3H2SO4pH ADJUST TO 2.5 to 3REDUCTION OF H2O2REDUCTION OF Cr6+ TO Cr 3+KILLS ORGANISMS FROM BWTPLIMEPOLYMERFINAL pH ADJUSTH2SO4pH ADJUST TO 6.5 TO8.5pH ADJUST TO 9 TO 10LIME HYDROXIDE PRECIPITATIONOF METALSINFLUENTTO IWTPEFFLUENTTO RIVERFILTER PRESS OF SLUDGESLUDGE TO OFF SITE DISPOSALBIOLOGICAL WASTEWATER TREATMENT PLANTPROCESS FLOW SCHEMATICDILUTE ORGANICWASTE 10 KGDAMMONIA-FLUORIDEWASTE50 KGDHIGH BOD ORGANICFROM CDC(Intermittent to 0.5 KGD)SANITARYWASTE:WILLISTON,900, 963, 964,965, 966, 986,& 974, CMPSBR #1SBR #2SBR #3EFFLUENTTO IWTPPROCESS WATERSTORAGEWETWELLS1993SEWAGEPUMPSRECIRCULATION/FEED PUMPSLIMEBLENDTANKABLENDTANKBAIRBLOWERSSEWAGEGRINDERSFLASHMIXTANK60GALLIME25KGalWASTEDSOLIDSTO IWTPTHICKENERHIGH STRENGTHORGANICFEED/RECIRC PUMPSSITE SANITARYBACKBONEFORCEMAINSANITARYLOAD100K GPD25KGalCMP WASTE TREATMENT SYSTEMPROCESS FLOW SCHEMATICFILTER PRESSProcess WaterStorage &EqualizationMicrobar EnChemTreatmentFILTER PRESSCMP DRAIN SYSTEMBWTPORGANICS/AMMONIAEQUALIZATIONCLARIFICATIONPROCESSWATERFINAL pHADJUSTPROCESSWATERSTORAGESITE IWFLOWSIWTPSOLIDS/METALSCMPSOLIDS/METALSEQUALIZATIONSEQUENTIAL BATCHREACTORSSANITARYDOWCMP stream conditioning(pH, polymer, coagulant)Thickener 2Storage TankFILTER PRESSAFThickener 2 & 3Acid,Caustic,MetclearAcid,Caustic,Metclear,Coagulant,PolymerAcid,Caustic,Coagulant,PolymerTo BWTP or IWBackflushCMP FILTRATION PROCESS FLOW SCHEMATICDesign Capacity 310 KGDTo SludgeHandlingTo SludgeHandlingTo SludgeHandlingTo BWTP or IWTo BWTP or IWChemicaladditioncapabilities:ProcessespHadjustmentflocculationcoagulationMixingATTACHMENT 2Table 1 IBM Essex Junction, VT Industrial Wastewater Treatment Sludge De-Listing Constituents of ConcernSelection BasisHold time US EPA Method Detection LimitAnalysis Quality Control CriteriaConstituentCAS No.EM HC LDR PC TC Ext/An.,dExtractionAnalysisug/l ug/KgLRB LFB CCV Dup LFM ISAluminum7429-90-5Y180/180 3050B 6010 na 2500 <RL 70% R 10% 20% 70% RArsenic7440-38-2Y180/180 1311 3050B 6010 2 2000 <RL 70% R 10% 20% 70% RBarium7440-39-3Y180/180 1311 3050B 6010 20 500 <RL 70% R 10% 20% 70% RCadmium7440-43-9YYYY180/180 1311 3050B 6010 3 500 <RL 70% R 10% 20% 70% RChromium7440-47-3YYY180/180 1311 3050B 6010 20 1000 <RL 70% R 10% 20% 70% RChromium, hexavalen 18540-29-9Y30/2 3060A 7196A na 5000 <RL 80% R 20% 20% 70% RCopper7440-50-8YY180/180 3050B 6010 na 1000 <RL 70% R 10% 20% 70% RIron 7439-89-6Y180/180 3050B 6010 20 5000 <RL 70% R 10% 20% 70% RLead7439-92-1YYY180/180 1311 3050B 6010 2 2000 <RL 70% R 10% 20% 70% RMercury7439-97-6Y28/28 1311 7471A 7471A 1 600 <10% 90% R 10% 20% 70% RNickel 7440-02-0YYY180/180 1311 3050B 6010 20 1500 <RL 70% R 10% 20% 70% RPlatinum7440-06-4YY180/180 3050B 6010 na 5000 <RL 70% R 10% 20% 70% RSelenium7782-49-2Y180/180 1311 3050B 7010 5 3000 <10% 85% R 10% 20% 70% RSilver7440-22-4YYY180/180 1311 3050B 6010 20 2000 <RL 70% R 10% 20% 70% RTin 7440-31-5Y180/180 3050B 6010 na 5000 <RL 70% R 10% 20% 70% RZinc 7440-66-6Y180/180 3050B 6010 na 1500 <RL 70% R 10% 20% 70% RCyanides - Tota 57-12-5YY14 9010B 9012A na 710 <RL 80% R 10% 20% 80% RCyanides - Amenable57-12-5Y14 9010B 9012A na 710 <RL 80% R 10% 20% 80% RCresols, Tota N/AY14/7/40 14/40 1311 3550B 8270C 5 100 <RL 20% 30%2,4-Dinitrotoluene121-14-2Y14/7/40 14/40 1311 3550B 8270C 5 100 <RL 48-106%R 20% 30% 36-101%RyesHexachlorobenzene118-74-1Y14/7/40 14/40 1311 3550B 8270C 5 100 <RL 20% 30%Hexachlorobutadiene87-68-3Y14/7/40 14/40 1311 3550B 8270C 5 100 <RL 20% 30%Hexachloroethane67-72-1Y14/7/40 14/40 1311 3550B 8270C 5 100 <RL 20% 30%Nitrobenzene98-95-3Y14/7/40 14/40 1311 3550B 8270C 2 40 <RL 20% 30%Pentachloropheno 87-86-5Y14/7/40 14/40 1311 3550B 8270C 15 300 <RL 32-120%R 20% 30% 41-118%RyesPyridine110-86-1Y14/7/40 14/40 1311 3550B 8270C 10 200 <RL 20% 30%2,4,5-Trichloropheno 95-95-4Y14/7/40 14/40 1311 3550B 8270C 10 200 <RL 20% 30%2,4,6-Trichloropheno 88-06-2Y14/7/40 14/40 1311 3550B 8270C 10 200 <RL 20% 30%Benzene71-43-2Y14/14 14 1311 5035 8260B 1 10 <RL 70% R 25% 30% 70% RCarbon Tetrachloride56-23-5Y14/14 14 1311 5035 8260B 1 10 <RL 70% R 25% 30% 70% RChlorobenzene108-90-7Y14/14 14 1311 5035 8260B 1 10 <RL 70% R 25% 30% 70% R 50% RChloroform67-66-3Y14/14 14 1311 5035 8260B 1 10 <RL 70% R 20% 30% 70% R1,4-Dichlorobenzene106-46-7Y14/14 14 1311 5035 8260B 1 10 <RL 70% R 25% 30% 70% R 50% R1,2-Dichloroethane107-06-2Y14/14 14 1311 5035 8260B 1 10 <RL 70% R 25% 30% 70% R1,1-Dichloroethylene75-35-4Y14/14 14 1311 5035 8260B 1 10 <RL 70% R 20% 30% 70% RMethyl Ethyl Ketone78-93-3Y14/14 14 1311 5035 8260B 10 100 <RL 70% R 25% 30% 70% RTetrachloroethene127-18-4Y14/14 14 1311 5035 8260B 1 10 <RL 70% R 25% 30% 70% RTrichloroethene79-01-6Y14/14 14 1311 5035 8260B 1 10 <RL 70% R 25% 30% 70% RVinyl Chloride75-01-4Y14/14 14 1311 5035 8260B 2 20 <RL 70% R 20% 30% 70% RNotes:EM = Identified by the EPA as either a precious or common metal used in electroplating (http://www.epa.gov/guide/electroplating/#guidance)HC = Listed in 40 CFR Part 261 Appendix VII as a Hazardous Constituent that is the Basis for the F006 ListingLDR = Regulated Hazardous Constituent in Land Disposal Restrictions for F006PC = Used in Process Contributing to F006 ClassificationTC = Toxicity Characteristic Metal or CompoundHold time with / = to extraction/to analysis after extraction; with / / = to solid extraction/to liquid extraction/to analysisTwo extraction methods = TCLP and total; one = totalLRB = Laboratory Reagent Blank LFB = Laboratory Fortified Blank CCV = Continuing Calibration Verification Dup = Duplicate LFM = LF Matrix IS = Internal Standards RL = Rep. Limit R = RecoveryLRB criteria for 6010 analysis is greater of <RL or <10% of sample concentration; for 8270/8260 is greater of <RL or <5% of sample concentration%R = percent recovery, with acceptable range both below and above 100% (e.g. 70% means 70% to 130% is acceptable)Surrogate recoveries for 8270 are found in Method QC tables; surrogate recoveries for 8260 are 70%-130%A total of ~ 300 grams of sludge are required for all analyses: 100 for TCLP SVOC, 100 for TCLP metals, 25 for TCLP VOCs, 30 for SVOCs, 20 for VOCs, and ~ 10 for otherATTACHMENT 3Environmental Program ManagersRegulatoryInteractionsReportingReduction andPollution PreventionOperational ControlCapitalProgramsNewChemicalsToolDesignsProcessChangesChemicalChangesSafetyRequirementsChemicalAuthorizations/Chemical InfoEnvironmentalImpactAssessmentsReview and Approvals1. Wastewater Discharge Monitoring2. Hazardous Waste / Chemical WasteDisposal Authorizations3. Air Emissions Control4. Boiler Emissions5. Excavation Permits6. Inspections / Commissioning7. Treatability Studies1. Regulatory Review2. Modify Permits as Required3. Set Requirementts for Waste Generators4. Initiate new Treatment as needed5. Generate Facility Change Notes as Required1. Energy Team for Power Reduction2. Pollution Prevention Team3. Tool Emissions Review Team4. Common Interest Groups1. NPDES2. Air Emissions3. TRI4. RCRA5. SARA6. Act 1007. Regulatory RequiredChemical Management DatabasesFunding ApprovalReview and AuthorizationsChemical Management Inputs and ControlApproval LoopATTACHMENT 4Document Control Copy on Buff colored paper. Any other color is not official version 

# Endyne, Inc.

160 James Brown Dr.

Williston, VT 05495 Phone: (802) 879-4333 Fax: (802) 879-7103



# QUALITY SYSTEMS MANUAL

REVISED: October 6, 2009 Revision #: 11

Technical Director: Date : Harry B. Locker Ph.D.



### QA Officer: Date :
Mark L. FauselEndyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 2 of 42

Document Control Copy on Buff colored paper. Any other color is not official version 

### Table of Contents

1.0 Quality Policy Statement 3 2.0 Organization Structure/Personnel 4 2.1 Personnel Responsibilities 5 2.2 Personnel Qualifications 6 2.3 Personnel Training 7 3.0 Laboratory Environment 7 4.0 Document Control 8 5.0 Sample Management 8 5.1 Review of All New Work 8 5.2 Sampling Protocol 9 5.3 Sample receipt Protocol 10 5.4 Chain-of-Custody 11 5.5 Sample Preservation 11 5.6 Analytical Holding Times 11 5.7 Minimum Required Volumes 12 6.0 Instrumentation and Equipment 12 6.1 De-Ionized Water 11 6.2 Balances, Thermometers and Pipettors 12 6.3 Glassware 12 6.4 Instrumentation 12 7.0 Internal Quality Control of Test Procedures 12 7.1 Method and Analyst Capability Demonstrations 13 7.2 Quality Control Protocols 14 7.3 Analytical Standards 15 7.4 Data Storage and Archival 15 7.5 Internal Audit and Data Review 15 8.0 Testing Discrepancies and Corrective Action 16 9.0 Exceptionally Permitted Departures 16 10.0 Proficiency Testing and Certification 16 11.0 Complaints and corrective Action 17 12.0 Reporting of Results 17 13.0 Revision History 18 14.0 References 18

Figure 1 Chain-of-Custody 19 Table 1 Sampling Preservation and Volumes 20 Table 2 Laboratory Equipment and Instrumentation 35 Appendix A Demonstration of Capability Form 38 Appendix B Client Confidentiality Policy 39 Appendix C Analyst Signature 40 Addendum State of Vermont & Ne w York NELAC Certification Most current documents provided by Certifying AgencyEndyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 3 of 42

Document Control Copy on Buff colored paper. Any other color is not official version 1.0 Quality Policy Statement

Endyne, Inc. is committed to providing cons istent, high quality data in a timely manner. It is our belief that each indi vidual analytical result generated by Endyne is of critical importance to our client. It is thus imperative that Endyne be able to generate and report da ta of known quality. To that end, we have outlined our thorough Quality Systems Protocols with the intent of clarifying for our clients all the procedures and precautions that insure the highest level of quality data. Dem onstration of Endyne’s commitme nt to maintain our quality objective is evidenced in the following.

- An expertly staffed and fully equipped Laboratory facility. - Successful participation in multiple EPA/NELAC approved proficiency testing programs. - Successful implementation of a NELAC compliant quality system. - Annual internal audits with management review. - Timely reporting of analytical results. - Laboratory test results that are supported by quality control data and documented testing procedures.

This quality policy is communicated to all new employees. It is understood, implemented, and maintained by employees at all levels. This is documented by management through the employee evaluation process, the training procedure, the internal audit process, and the document control process.Endyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 4 of 42

Document Control Copy on Buff colored paper. Any other color is not official version 2.0 Organization Structure/Personnel

The laboratory is comprised of 3 major anal ytical divisions; Or ganic, Inorganic and Microbiological. Analysts in each division ar e trained to perform a variety of analyses and each analysis has at least two analys ts trained and qualif ied to perform the procedure. Laboratory mana gement is comprised of four positions; Laboratory Director, Laboratory Manager and QA Officer and Department Managers. There are two auxiliary divisions which a ssist in the overall sample flow within the laboratory; Sample Preparation and Office Staff.



### Board of Directors

Laboratory

Manager

Sample Preparation Office Organic Inorganic Microbiology Laborator y Director

Qualit y Assurance Officer Endyne, Inc. Randolph Vermont Endyne, Inc. Plattsburgh New York

Department Manager Department

ManagerEndyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 5 of 42

Document Control Copy on Buff colored paper. Any other color is not official version 2.1 Position Responsibilities Although Endyne uses a hierarchy structur e in managing employee workload, Endyne has an open-door management policy.. All em ployees have full access to the highest levels of management and ownership and are instructed in how to contact them for any

reason.

2.1.1 Organic and Inorganic and Microbiol ogical analysts are responsible for maintaining their own method workloads. Analysts record data and individual QA/QC results in the appropriate database s. Analysts trained in a method may perform the initial data quality review of a nother analysts’ work. This data review is approved by managerial revi ew before data is accepte d in the LIMS database. Analysts report to their Department Supervisor or Laboratory Manager.

2.1.2 The Chief Microbiologist is respon sible for all microbiology and related abilities. The Chief Microbiologist receives training and education necessary to meet certification requirements. The Chief Micr obiologist reports to the Inorganic-MicroMetals Department Manager.

2.1.3 The Sample Preparation department is responsible for all sample preservation and storage at the laboratory. This includes dispersing sample aliquots to the different divisions of the laboratory and ensuring there is sufficien t sample volume to perform all requested analyses. Sample technician pr epares all sample containers for shipment, including preservation and samp ling instructions. The sample tech is also responsible for assigning every sample its uni que sample identification number.

2.1.4 Office Staff are responsible for the initi al receipt of samples at the laboratory, the proper completion of the C-of-C, and th e entry of analytical requests into the Laboratory Information Management System (L IMS). Office staff is also responsible for the generation of the final report and en suring the proper delivery of all analytical results to the client.

2.1.5 Department Managers are responsible for the immediate supervision of analysts within their department and adhere nce to quality control policies. They coordinate the work load and assist in tec hnical and analytical responsibilities when necessary. Department Supervisors report to the Laboratory Mana ger and QA Officer.

2.1.5 The Laboratory Manager coordinates with clients and analysts to develop work schedules to meet analytical demands. The Laboratory Manage r is available to analysts to assist in analytical troubl eshooting. The Laboratory Manager reports directly to the Laboratory Director.Endyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 6 of 42

Document Control Copy on Buff colored paper. Any other color is not official version 2.1.6 The Quality Assurance Officer revi ews the QA/QC results of individual analyses, compiles the data, and reviews the data with the Laboratory Director. The Q.A. Officer is also responsible for ensu ring that the overall la boratory operations comply with the Laboratory QA/QC Plan. Th e Q.A. Officer reports to the Laboratory Director, but has access to the Board of Directors

2.1.7 The Laboratory Director has overall res ponsibility for the te chnical operation of the laboratory. The Director is res ponsible for arranging and overseeing the maintenance of all equipment and instrumentation, as well as the physical maintenance of the laboratory. The Director provides supervision to all laboratory personnel to ensure adheren ce to all lab-documented proc edures including the Quality Manual.

2.2 Personnel Qualifications

Endyne, Inc. will hire only the most qualifie d and capable applicants for any position to be filled. Each new employee must have a combination of education and experience to adequately demonstrate the specific knowledge necessary to perform their assigned duties as well as a gene ral knowledge of the mathematics and good laboratory techniques, which would be requi red. Endyne sets several conditions to ensure this minimum level of qualificati on. All individuals hi red for analytical positions will have at least two years of course work towards a four-year college degree in a related science discipline or ha ve completed a post-hi gh school laboratory analyst program at a recogni zed technical school. Any i ndividual without a college level education would require two years of on the job training in a laboratory environment prior to performing independent analytical work.

2.3 General Procedural and Ethical Personnel Training

Once hired a new employee will undergo a thorough training regimen to ensure they are capable of performing their tasks to the defined level of acceptance. Proper training consists of an initial training at th e start of employment and continued training through-out their career. This training includes Safe La boratory Practices, Chemical Hygiene, Ethical, Data Integrity and Techni cal education. Endyne tries to use various forms of training tools to inst ill sound learning practices. Most analytical procedures have specific requirements to demonstrate analytical capability. Those requirements are adhered to as well as our general gui delines for training. Documented training activities are stored in employee’s personnel files.Endyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 7 of 42

Document Control Copy on Buff colored paper. Any other color is not official version 2.3.1 Analytical Training

- The trainee reviews litera ture associated with the pub lished methods. This includes all related internal SOPs su ch as the method SOP, equipment SOPs such as balance, glassware or pipettor SOPs and, if pertin ent, the chromatography integration SOP. - The trainee also reviews all MSDSs for chemicals used during the procedure. . Analysts must read and become familiar wi th all elements of each chemical’s MSDS, making special awareness of the symptoms of exposure and potential routes of entry. - If it’s a new procedure and there is no in ternal method SOP, th en the analyst reads the original method, writes a summary and re views the procedure with the Laboratory Manager. - The trainee works several days under the direct supervision of an analyst who is experienced with the method. This trai ning includes any sp ecific laboratory techniques such as pipetti ng, syringe use, titration. Equipment maintenance and use such as probes, scales, meters or chromatograph operation. - The trainee may assist in the generation of data in a trainee mode. However, the trainee may not work independently until certification is fully documented. - The trainee performs a Demonstration of Ca pability (DOC). This is an analysis of four replicate quality control samples. The average of the results must be within 20% of the industry-standard expected mean valu e and the standard deviation must be less than 20%, unless the method specif ically indicates otherwise. - The new analyst completes a DOC Cer tificate (see Appendix A) which documents his training and proficiency in a method. - The Laboratory Manager will authorize an analyst to perform a method only after successful completion of the DOC and upon c onference with the primary trainer. Documentation of this authorization will be kept in the employee’s personnel file in the form of an “Analyst Certification Form”.

2.3.2 Initial Training

- An overall review of sample flow thr ough the laboratory is pr ovided, so that they may better understand their relati onship within th e laboratory. - A review of safety prot ocols and emergency response pr ocedures is performed. A copy of Endyne Safety Handbook is provided and reviewed. - A review of general laboratory proce dures, including balance, pipetting, etc. techniques is performed. - Ethical and legal responsibilities ar e thoroughly reviewe d, including potential punishments and penalties for improper, unethic al or illegal actions. The analyst is given a copy of the “Laboratory Ethics and Data Integrity” SOP, as well as participates in detailed trai ning of Endyne’s ethics policies. New employee signs an attestation agreeing to abide by Endyne’s ethics policies.- A review of Endyne’s client confidentiality policy is performe d, including the privacy of general client information as well as the delivery of analyt ical data via phone or electronic means. Refer to Appendix B.Endyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 8 of 42

Document Control Copy on Buff colored paper. Any other color is not official version 2.3.3 Continued Training

- Regular Inorganic and Orga nic department meetings are held to discuss safety and quality control issues that arise durin g the course of the previous week. - Laboratory wide staff meetings occur as needs dictate. Topics range from employee benefits and staffing changes to analytical issues and ethical/leg al responsibilities. - Employees attend off-site training seminars as well as internet based on-site seminars, which are deemed valuable by management. These have included office skills, hazardous waste handling, safety tr aining, and analytical instrumentation

courses. - Employees on an annual basis demonstrat e continued proficiency in an analytical method by participation in blind proficienc y testing of the me thod or submitting a continuing DOC form summarizing the last f our LFB samples as defined in the initial Demonstration of Capability in Section 2.3.1. - Employees on an annual basis undergo documented refresher training on Laboratory Ethics, Data Integrity and Client Confidentiality.

3.0 Laboratory Environment

Endyne, Inc. consists of three levels cove ring approximately 3,500 square feet of work area. The top floor consists of meeting rooms and organic prep/extraction lab on one side of the building, on the other side of the building is the microbiology lab and Semi-volatile GC laboratory. The middle floor consists of office space and the Volatile Organics instrumentation lab. Th e bottom floor consists of the Metals and Inorganics work areas.

Endyne has no equipment requiring extremely tight environmental conditions. Each floor contains its own heating and cooli ng systems designed to keep temperatures around 70 ° 0 F and humidity around 40%. Electroni c scales are mounted on vibration inhibiting platforms. Exhaust hoods are locat ed on each floor. They are inspected and calibrated on an annual basis

Biological work areas are sterilized betw een uses. Test areas of incompatible activities are separated to eliminate contamination. Work areas are wiped down at the end of each day and good housekeeping practices in general are followed to minimize contamination and health risks.

4.0 Document Control

The Document Control System is designed so that documents, which are generated by the laboratory and deemed critical to proper laboratory operation, are tracked and access is limited to responsible parties. This system ensure s that only the most recent revisions are available to th e appropriate personnel, and al l documents in use have the proper authorization. Documents covered by this system are listed in the Master Document Control List, which lis ts all the records, their location, and revision history. Records covered in the Document C ontrol List include the following;Endyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 9 of 42

Document Control Copy on Buff colored paper. Any other color is not official version -The Master Document Control List -This Quality Assurance Manual -All Analytical SOPs -Equipment Maintenance SOPs, i.e. Analytical Balance and Pipette SOPs -Externally produced literature used in method Development and Troubleshooting. -Sampling Procedures, i.e. Coliform Bacteria -Employee Qualification Summaries

The Quality Assurance Officer is responsib le for maintaining the Document Control System. Master List Controlled Document s are indicated by the paper color indicated in the footer. Uncontrolled copies are determined by being printed on any other colored paper. The Q.A. Officer has cont rol over the supply of the specified colored paper. The Laboratory Direct or approves all newly releas ed control documents. The Q.A. Officer is responsible for archiving the obsolete documents.

5.0 Sample Management

Endyne has policies and pers onnel to manage the sample load generated from its clients. In the event that there is a surplus of work so that Endyne could not process all samples within stated hold times, Endyne would follow the protoc ols as outlined in the Sample Custody SOP for sub-contracting the excess work.

5.1 Review of all New Work

All new work is defined as analytical pr ocedures for which Endyne does not already have an internal documented procedure with established qu ality control objectives. A list of established analyses is provided in Table 1. All new work is accepted by the Laboratory Director or Laboratory Manager, after ensuring the laboratory has the proper facilities and equipment to perform th e analyses. Staff, involved in the new work, meets to discuss any pertinent issues regarding quality assurance considerations. The plan for any new testing must be reviewed and approved by the Laboratory Director. The designated employee(s) shall write a SOP for the procedure, which will be included in the document control. A DOC will be kept in the employees personnel file.

5.2 Sampling Protocol

In general, samples received by Endyne are collected by representatives of firms contracting with the laboratory to perform the analysis. Th ese firms are responsible for insuring that proper sampling pr ocedures are followed. Endyne ’s responsibility is limited to providing written sampling procedures for sample collection, preservation, field filtration and transport for specific analys is when requested. Upon request, Endyne can provide expert sampling services for air, water, and solid media. Endyne makes no guarantee, assumed or otherwise, as to the va lidity of documentation or sample integrity outside the direct control of its personnel.Endyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 10 of 42

Document Control Copy on Buff colored paper. Any other color is not official version 5.3 Sample Receipt Protocol

Upon arrival at the laboratory, samples and associated Chain-of-Custody (C-of-C) are reviewed for accuracy and sample integrity. In summary, the C-of-C should contain the following information: (For a more detailed review, refer to the Sample Custody SOP)

1. Client and contact person. 2. Project Name 3. Client sample identification (station location or number). 4. Name of sample collector, date and time of collection. 5. Analyses requested. 6. Container type and volume. 7. Type of preservation performed in the field. 8. Special requests or instru ctions (e.g. rush analyses). 9. Signature of Endyne personnel who received samples. 10. Date and time of receipt.

Samples are then inspected for general condition, which includes the following:

1. If seals are present on containers, an inspec tion of each seal is made to insure that each seal is intact. Documentation as to the integrity of the seals is made on the Chain-of-Custody. 2. Proper sampling containers have been u tilized for the requested analyses, and adequate sample volume is available. 3. For volatile organic compounds (VOC), any air bubbles will be noted on the C.O.C. 4. Proper temperature and preservation guidelines have been followed. 5. Comparison of notations on sample contai ners with those on the Chain-of-Custody (sample location, date, time) are made to insu re that all samples which were collected have arrived at the laborat ory, and are properly labeled.

If discrepancies or omissions exist in any of these areas, the Laboratory Director and client are notified. If the client cannot be reached, the samples are placed in cold storage (4 ° C) and no further action is taken until the problem is resolved.

In conjunction with the C-of -C, Endyne documents pertinent sample preservation information and sample condition on the Log -In report. The person receiving the sample records the condition of the samples, the temp erature, the accuracy of the C-of-C and the means of delivery to the laboratory. Th e person prepping the sample records any preservation or sample preparation procedures necessary for sample storage until the time of analysis.

Once logged in, the samples are delivered to the appropriate department, preserved, as appropriate, and/or refrigerated at 4 ° C.

For further information refer to the Sample Custody SOP.Endyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 11 of 42

Document Control Copy on Buff colored paper. Any other color is not official version 5.4 Chain-of-Custody

The purpose of the Chain-of-Custody form is to provide a written record, which traces the collection, possession, and handling of samples from the moment of collection to arrival at the laboratory. An example of our Chain-of-Custody Record is provided in Figure 1. The Chain-of-Custody form is signed by the sample collector, by those responsible for the transporta tion of the sample, and finally, by laboratory personnel. Any breach in the Chain-of-Custody is reported to the Laboratory Director, the sampler, and the client. In most instances, the Chai n-of-Custody form will also be used by the client as an order form to specify the request ed analyses, and as a reporting sheet for field results. Upon receipt at the laboratory, a carbon copy of the Chain-of-Custody form is returned to the sampler. All original forms become property of the laboratory.

5.5 Sample Preservation

Sample preservation is divided into two areas. They are the following:

1. Field preservation by sampler. 2. Preservation by Endyne personnel.

Endyne, Inc. takes no responsibility for preserva tion procedures or materials used in the field. As stated in Section 5.2, we will provide methods, bottles and chemicals appropriate for proper field pr eservation. Any observed devi ation of field preservation from these recommended methods will be report ed to the client and noted on the Chain of Custody.

If the sample is received without preservati on, Endyne personnel will preserve the sample following Table 1, as long as handling the samp le will not affect data integrity. Any nonstandard preservation requested by the sampler will be reported to the client and noted on the Chain-of-Custody.

5.6 Analytical Holding Times

Also listed on Table 1 are recommended holding times for all analyses. As discussed in Section 5.3, notification will be ma de to the Laboratory Director of any samples received by Endyne, which have exceeded the specified holding time limit. At Endyne, all samples will be processed within the reco mmended holding time. If, due to equipment malfunction or other circumstances beyond the control of the laboratory, an analysis cannot be performed at Endyne, a subcontrac ting laboratory will be assigned to perform the analysis. The client will be informed in writing of Endyne’s intention to sub-contract the analysis. Once permission from the cl ient has been granted, a Chain-of-Custody record will be forwarded with all sample s sent to the subc ontracting laboratory.Endyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 12 of 42

Document Control Copy on Buff colored paper. Any other color is not official version 5.7 Minimum Required Volumes

Table 1 indicates the minimum required vo lumes to perform all analyses. During laboratory preservation procedures (see S ection 5.5), the sample will be split, if necessary, such that appropriate volumes are preserved for all requested analyses. The notification procedure set fort h in Section 5.3 will be implemented for samples with inadequate volume. In these cases, it will be the client’s responsibility to decide which analyses to perform.

6.0 Instrumentation and Equipment

The proper operation of the analytical instrumentation, all measuring devices, the deionized water supply, as well as the cleanliness of the glassware must be insured to meet the quality control requirement s of the laboratory. Indi vidual Standard Operating Procedures are maintained and adhered to fo r each type of Equipment. The following sections are summaries of those SOPs. A lis ting of all major pieces of equipment is provided in Table 2.

6.1 De-Ionized Water

A continuous resistivity meter is mounted on th e de-ionized water uni t. De-ionized water has an acceptable quality when the resistance value ranges from 14 to 18 μ ohms. If the resistance falls below this value, new filter elements are installed. De-ionized water from the conditioned device is not us ed until it can pass the 14 to 18 μ ohms standard. Grab samples are also analyzed using a separate electronic conductivity meter on at least a monthly basis, to verify the accuracy of the continuous recording device. This conductivity measurement must be < 2.0 μ mhos. Individual methods have their own requirements for reagent water that are de fined in the method specific SOPs. For additional information refer to the De-Ionized water SOP.

6.2 Balances, Thermometers and Pipettors

All weights and calibration thermometers are calibrated against NIST traceable standards at an offsite certified facilit y. In-house use thermometers are calibrated against the offsite calibrated thermometer on an annual ba sis. Balances are inspected by a certified specialist on an annual basis and an internal calibration is performed daily. Balances are checked using NIST traceable weights on a daily basis. A variety of pipettors capable of measuring from 10ul to 10ml are calibrat ed on a monthly basis and spot checked by analysts on a more frequent basis. A record of all calibrations and checks is maintained in instrument logs. A notation of when re- calibration of each instrument is posted on the instrument for easy reference. For additional information refer to the individual equipment SOPs.Endyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 13 of 42

Document Control Copy on Buff colored paper. Any other color is not official version 6.3 Glassware

All glassware used for measurement is Cl ass A certified. Glassware is cleaned thoroughly with soap and water. Tap water is used for the preliminary wash followed by rinses with de-ionized water. For trace metal analysis, the gl assware is also subjected to an acid wash. All glassware used for organic extraction is rinsed with appropriate solvent prior to analysis. . For additional in formation refer to the Glkassware SOP.

6.4 Instrumentation

Each major piece of instrumentation is assigned to an individual analyst, for which they are responsible. A separate bound notebook or excel spreadsheet is maintained at each instrument station. In this notebook, the daily operation status of th e instrument is noted as well as its complete maintenance history. All changes and servicing to the original factory equipment are noted, dated, and si gned by the analyst responsible for the instrument. The Laboratory Director is notif ied of any problems with the equipment. Routine checks of the instrument log note books are made by the La boratory Director to insure proper reporting.

Regular site visits are made to Endyne by manufacturer’s servi ce staff for equipment servicing. Some major instruments are covere d by service contracts, which provide for rapid response by the manufacturer in th e event of an equipment malfunction.

7.0 Internal Quality Contro l of Test Procedures

All method-referenced analyses performed at Endyne adhere to the quality control standards outlined in the published literatu re. Methods, which do not specifically reference quality control parameters, as well as in-house developed meth ods, adhere to, at the minimum, the QA/QC protocols outlined here. In some cases however, some of the following protocols are not possible to pe rform. Individual method SOPs have the appropriate QA/QC protocols referenced within them. Endyne’s internal QA/QC plan consists of me thod and analyst capab ility demonstrations, as well as a suite of quality control protoc ol steps during the analysis of samples.

7.1 Method and Analyst Capability Demonstrations

All records include references to the raw data files or dates analyzed, so that calculations can be regenerated from the original data.

Demonstration of Capability (DOC) - Every new analyst performs a set of four mid-range concentration LFBs. The LFBs should be prep ared as one sample, then split into four aliquots. The percent standard deviation and average pe rcent recovery are determined for each analyte. Each must be less than 20% to ensure proper capability of the analyst for that method. Documentation of the DOC is kept in the analyst’s personnel file.Endyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 14 of 42

Document Control Copy on Buff colored paper. Any other color is not official version Continuing Demonstration of Capability (CDOC) - On an annual basis, every analyst must demonstrate continued proficiency in the analytical method. This may be evidenced by a statistical calculation of the last 4 concurrent LFBs as defined in the initial DOC or by successful completion of blind proficiency test samples. Documentation of the CDOC is kept in the analyst’s personnel file.

Method Detection Limit Study (MDL) - The analyst performs a set of seven LFBs at a concentration of 2 to 5 times the expected MDL value. The standard deviation is multiplied by 3.14 to determine the laborator ies MDL. The MDL should be less than half the laboratory’s repor ting limit. MDLs are performed on an annual basis at the beginning of each year. Copies of the MDL are stored with the QA/QC data for the method.

7.2 Quality Control Protocols

Endyne generates control limits for the qual ity control samples using method-defined limits. Typically, those limits are +/- three st andard deviations of the average recovery. In the event there is no accrued history of QC data an absolute acceptance limit of 70%- 130% is employed. Duplicate precision limits are based on 3.27 multiplied by the mean relative percent differences. In the event, there is no accrued history of duplicate data an absolute acceptance limit of 20% relative percent difference is applied.

Analytical Calibration Line - A minimum of a 3-point calib ration line not including “0”, which must have a linear correlation of 0.995 or better. The lowest point in the line must be less than the reporting limit or regulatory level. Continuing Calibration Check (CCC) - A calibration line standard is analyzed if a calibration line already exists. A CCC is anal yzed at the start of each analytical day. Laboratory Reagent Blank (LRB) - A reagent water sample which is treated as a normal sample and must be shown to be free of all target analytes at re portable levels. An LRB is run with every 20 samples or each anal ytical batch, whichever is more frequent. Laboratory Fortified Blank (LFB) - An independent source st andard containing all the target compounds is analyzed like a normal sa mple. A LFB is run with every 20 samples or each analytical batch, whichever is more frequent. Matrix Duplicate (MD) - Aliquots of the same sample wh ich are analyzed identically. A MD is run with every 20 samples or each anal ytical batch, whichever is more frequent Matrix Spike (MS) - A sample aliquot to which a known amount of analyte(s) is added. A MS is run with every 20 samples or each anal ytical batch, whichever is more frequent. Matrix Spike/Duplicate (MS/D) - This quality control parameter may be employed in place of the Sample Duplicate and Matrix Spik e. Two sample aliquots are spiked with known amounts of analyte and th e percent recovery and percent difference is determined for the samples.Endyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 15 of 42

Document Control Copy on Buff colored paper. Any other color is not official version 7.3 Analytical Standards and Chemicals

Endyne takes special care to ensure the accuracy of all analytical standards. Standards are made in-house from neat materials or purch ased from suppliers with at least an ISO 9001 certification. Whenever possible sta ndards are purchased from independent suppliers. All Certificates of Analysis from suppliers are kept on file. In-house standards are made using Class A glassware and a NIST traceable balance. All working standards are documented in individual method logbooks th at insure traceability to the original manufacturer.

All chemicals and standards have manufactur er defined expirati on dates assigned to them. Chemicals which do not have an expi ration date assigned by the manufacturer are given an expiration date by the laboratory ; liquid chemicals and acids are assigned 10 years and dry chemicals are assigned 20 years. The quality of chemicals and standards is dictated by the analyst and the quality assu rance officer. The purchasing agent has no control over the purchase of less expensive materials.

7.4 Data Storage and Archival

All raw data and calculations, sufficient to co mpletely reconstruct the data packet, are kept on file by the laboratory for a period of at least 7 years. Ne w York drinking water analyses are kept on file for 10 years. Data storage during the course of the year is outlined in individual SOPs. At the start of each calendar year all data and paperwork is archived in banker boxes. Thes e boxes for the two previous y ears are kept on site. Data older than two years is kept off-site in a secured location. In case of transfer of ownership or closure of business, the owners of Endyne will continue storage of required documents for the required time or ensure transfer of documents to new ownership.

7.5 Internal Audit and Data Review

-Raw Data - Each analyst must keep deta iled information of the raw data in a bound notebook or on the computer printout. Entries must include the analys t initials, date and time of analysis, sample identification numb er, parameter tested and analytical method, documentation of all readings, and results of all weightings and dilutions. All calculations documenting the final concentr ation of the constituent as well as determinations of all quality control samples must be recorded with the data.

-Data Checking – Data checking is initially performed by an independent analyst trained in the analytical methodology or Department Manager. After the analyst has processed all the associated data and recorded the results of an analysis, the data reviewer reviews the sample and associated quality control data . The reviewer then signs off on the Data packet and submits to the Department Manage r or other laboratory officer with QC approval authority in the database. The inde pendent analyst is he ld equally accountable for certifying all quality cont rol aspects of the methodology. The completed report is submitted to the Laboratory Director for final review and approval before being released to the client.Endyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 16 of 42

Document Control Copy on Buff colored paper. Any other color is not official version -System Audits – The QA Officer or Depa rtment Manager with oversight by the QA Officer will review in dividual methods on an annual basis with the primary analyst. Procedures will be compared to the SOP, the original referenced method and Quality Systems Manual to confirm adherence. Revi ew of records and logs is performed to ensure proper documentation and traceability. Any corrective actions will be documented. A component of the Audit include s an in-depth review of a random data set focussing on data integrity issues. Where audit findings ca st doubt on the validity of results, clients will be cont acted immediately in writing.

-Managerial Review – On an annual basis, the Laboratory Direct or will review the quality system and its testing and calibrat ion activities. The review will be based on feedback from the QA Officer, the results of proficiency tests, as well as audits from external certification officers. Any necessary changes will be implemented at this time and documented in the Quality Systems Manual.

-Internal Audit – On an annual basis, the Quality Control Officer will present to the management staff a summary of the Internal Au dit. This will incl ude the findings of the systems audits as well as the managerial revi ew, proficiency testing results and customer complaints. For additional information on the topics covered in Sect ion 7.5 refer to the Managerial Review SOP.

8.0 Testing Discrepancies and Corrective Action

Occasionally analytical data fails the quali ty control protocols outlined in each method SOP. Procedures for determining the source of these failures are outlined in the SOP. In general, the primary analyst immediately reviews the work and assesses where the error occurred, corrects the deficiency and reanaly zes the associated samples. No further sample analysis is performed until the source of the error is determined and corrected. The laboratory manager and director are available for immediate consultation if necessary. In some instances, due to the sa mple volume submitted or the expiration of the analytical holding time, it is impossibl e to reanalyze the sample within QA/QC protocols. In that event the client is notified of the viola tion by telephone or in writing. No data, which is outside method specified quality control parame ters, will be reported without the appropriate notation informi ng the client of the transgression.

9.0 Exceptionally Permitted Departures from Documented Policies

The Laboratory Director is responsible fo r ensuring adherence to the documented policies of the laboratory. However, in so me instances departure from documented procedure may be necessary. In this instan ce, digression from the procedure is allowed as long as the changes are fully documente d as well as the reason why the deviation occurred and the Laboratory Direct or approves all the departures.

10.0 Proficiency Testing and CertificationEndyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 17 of 42

Document Control Copy on Buff colored paper. Any other color is not official version Endyne participates in several proficie ncy-testing programs for drinking water, wastewater and solid waste. Endyne participat es in a Potable Water testing program on a semi-annual basis. The testing encompasses all available parameters for which Endyne receives certification for fr om the State of Vermont and New York State Environmental Laboratory Accreditation Pr ogram (ELAP)/NELAC program. Endyne participates in semi-annual wastewater and solid waste/materi al proficiency testing administered by the New York State ELAP. Both sets of prof iciency testing are ap proved by the National Environmental Laboratory A ccreditation Council (NELAC). Endyne also participates annually in the DMR proficiency testi ng program administered by the EPA for wastewater/NPDES testing.

Endyne Inc., maintains accredita tion for a broad suite of para meters in several states. Endyne maintains potable water certification in the State of Vermont as granted by the Vermont Department of Health.. Endyne also maintains accreditation with the National Environmental Laboratory A ccreditation Program in the ar eas of Potable Water, NonPotable Water and Solid Waste/Material for a broad variety of parameters. Our primary NELAC certification is admini stered through the New York ELAP. Endyne maintains secondary NELAC certification in Potable wate r and Non-Potable water for the state of New Hampshire. Currently New Hampsh ire does not offer accreditation in solid waste/material. The State of Vermont does not offer certification in wastewater or solid waste. However Endyne does maintain a leve l of wastewater certi fication in Vermont through our participation in the EPA/NPDES DMR proficiency testing, the results of which are reported to the State of Vermont Wastewater Division which implements the NPDES program in Vermont.

An addendum to this manual is a curren t listing of State of Vermont and NELAC certified methods from our primary accred iting authority. Endyne frequently receives updates to our certification. As copies of our QSM are requested we append the most recent versions of our NELA C certification for distributi on. This is done without revising the QSM manual itself. Therefore, fo r the laboratory’s most current version of NELAC certifications for the multiple states En dyne is certified in refer to our website www.endynelabs.com.

11.0Complaints and Corrective Action Procedures

Endyne continually strives to improve data quality and customer satisfaction. In an effort to track complaints and quality control problems, Endyne maintains a file where complaints, from clients or other parties, and their corrective actio ns are recorded. A five-step plan is implemented to correct the deficiencies. Endyne documents Corrective Actions usi ng a standardized i nvestigative Report Template (Corrective Action Report). Initially the complaint, whether from a client or discovered in any of the internal QA review processes, is documented. Assessment of the route cause of the problem is perfor med. A program to address the cause is implemented. Initial assessment to determin e if the problem/complaint is corrected. Finally the system is reevaluated at a later date to ensure the proposed solution is still effective.Endyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 18 of 42

Document Control Copy on Buff colored paper. Any other color is not official version 12.0Reporting of Results

Endyne policy is to report results solely to the client listed on the Chain-of-Custody. Delivery of results is accomplished in four wa ys. The only authoritative results reported by Endyne are in the form of a hard copy re port with the original signature of the Laboratory Director or appointed signer. The other form s of data deliverables are by fax ,e–mail or verbal. Clients who request a verb al transmission of results must concretely establish themselves as the proper client, This is accomplished by referencing the C-of-C number in the upper right hand corner. Client s who request a fax mu st indicate on the Cof-C whom will receive results or if the request is ma de by phone proof must be made that they are the stated client. This is us ually accomplished by referencing the distinctive C-of-C sequence number. Deliverables in th e form of e-mails are only provided to established customers, whom have made formal arrangements for receipt of results. All electronic transmissions are acco mpanied with a disclaimer st ating that the material is confidential information intended solely for the recipient a nd to notify Endyne immediately upon incorrect receipt. Refer to Appendix C.

13.0 Revision History

Revision 1: July 18, 2000: Complete Draft Revision 2: March 15, 2001: Minor Revision Revision 3: March 15, 2002: Minor Revision Revision 4: January 28, 2003: Minor Revision Revision 5: February 28, 2003: Added Certification Addendum Revision 6: March 2, 2004: 2.2 Personnel Qualifications 2.3.1 Analytical Training 7.5 Internal Audit and Data Review Revision 7: September 20, 2005 2.0 Added refe rence to Scitest, Inc. in corporate Structure. 3.0 Laboratory Environment- Noted reconstruction & location of departments. 4.0 Add instrument ma nuals to Document Control 11.0 Multi-point Corrective Action Report Revision 8 October 12, 2007 2.0 Added Endyne-Plattsburgh and Department Managers to corporate structure. 7.3 Analytical Standards and Chemicals 7.5 Data Checking 10.0 Eliminated reference to AIHA. Clarified proficiency testing partic ipation and defined the Addendum referencing current certifications. Table 1. Update laboratory method container, preservation and holding time information divided into matrix. Table 2. Update laboratory equipment and instrumentation table.Endyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 19 of 42

Document Control Copy on Buff colored paper. Any other color is not official version Revision 9 February 19, 2008 2.3 Re vised Employee Training. Included reference to Data Integrity SOP 5.2 Sampling Protocol 6.0-6.4 Equipment 7.1 Analyst Capability Demonstration 7.5 Internal Audit & Data Review Table 1 - Temperature Requirements Revision 10 October 1, 2009 Figure 1. New Chain-of Custody Form Table 1. Updated Sample Preservation Table Appendix A. Included DOC tracking procedures within LIMS Revision 10 October 6, 2009 Table 2- Laboratory Instrumentationges

14.0 References

Standard Methods for the Examina tion of Water and Wastewater. 17 th Edition. APHA, AWWA, WPCF. Denver Colorado (1989)

Test Methods for Evaluating Solid Watse, Physical/Chemical Methods (SW-846 Version 2) on CD-ROM. NTIS U.S. DOC. Springfield, VA (1997).

EPA Methods and Guidance for Analysis of Water (Version 2) on CD-ROM. Office of Science and Technology, U.S. EPA. Washington DC (1999)

Environmental Laboratory Approval Progr am Certification Manual. New York Department of Health. Albany, NY (1999)

1999 Annual New York and Pennsylvania E nvironmental Laboratory Conference & Exposition. August 8 th -10 th , 1999.

NELAC Quality Systems Checklist Rev. 6. National Environmental Laboratory Accreditation Conference. 1997.Endyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 20 of 42

Document Control Copy on Buff colored paper. Any other color is not official versionEndyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 21 of 42

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### TABLE 1.

POTABLE WATER Parameters Analytical Methods 1 Volume Required

(mls) Container Type 2 Preservative 3,4 Holding Time 5

Escherichia coli enumeration SM18 9223B 100 ml 125 ml

Sterile > 10 ° C 0.008% Na 2 S 2 0 3 6 hrs

Fecal Coliform SM18 9222D 100 ml 125 ml

Sterile > 10 ° C 0.008% Na 2 S 2 0 3 6 hrs

Heterotrophic

Plate Count SM18 9215B 100 ml 125 ml

Sterile > 10 ° C 0.008% Na 2 S 2 0 3 8 hours

Total Coliform

Present/Absent SM18 9223B 100 ml 125 ml

Sterile > 10 ° C 0.008% Na 2 S 2 0 3 30 hrs

Acidity EPA 305.1 200ml P,G 0-6 ° C 14 days
Alkalinity EPA 310.1 200ml P,G 0-6 ° C 14 days
Bromide EPA 300.0 50 ml P.G None Required 28 days Chloride EPA 300.0 50 ml P,G None Required 28 days Chlorine EPA 330.5 200 ml P,G None Analyze Immediat ely
Color EPA 110.2 200 ml P,G 0-6 ° C 48 hrs.

Conductance EPA 120.1 100 ml P,G 0-6 ° C Filter,0- 6 ° C 24 hours 28days Cyanide 9 EPA 335.1 250 ml P,G 0-6 ° C NaOH of pH >12 0.6 g ascorbic acid 7 14 days

Fluoride EPA 300.0 50 ml P,G None Required 28 daysEndyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 22 of 42

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### TABLE 1 continued

POTABLE WATER Parameters Analytical Methods 1 Volume Required

(mls) Container Type 2 Preservative 3,4 Holding Time 5

Hardness EPA 200.7 100 ml P,G HNO 3 to pH 6 mos. Nitrogen,

Nitrate EPA 300.0 50 ml P,G 0-6 ° C 48 hours

Nitrogen,

Nitrite EPA 300.0 50 ml P,G 0-6 ° C 48 hours

Odor EPA 140.1 1000 ml G only 0-6 ° C 48 hrs.

pH EPA 150.1 100 ml P,G None Analyze ASAP

Phenolics 9 EPA 420.1 1000 ml G only 0-6 ° C H 2 SO 4 to pH <2 28 days

Phosphorus,orthoPhosphate, EPA 300.0/365.1 50 ml G 0-6 ° C 48 hours

Solids, Filterable EPA 160.1 500 ml P,G 0-6 ° C 7 days

Solids, Total EPA 160.3 500 ml P,G 0-6 ° C 7 days
Sulfate EPA 300.0 50 ml P,G Cool, 4 ° C 28 days
Sulfide, Hydrogen EPA 376.1 1000 ml P,G 0-6 ° C, 2ml Zinc Acetate NaOH to pH >9 7 days

Sulfite EPA 377.1 50 ml P,G None Analyze Immediat elyEndyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 23 of 42

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### TABLE 1 continued

POTABLE WATER Parameters Analytical Methods 1 Volume Required

(mls) Container Type 2 Preservative 3,4 Holding Time 5

Total Organic Carbon 9 EPA 415.1 2 40ml v mlials Amber G

No Air Bubbles 0-6 ° C

H 2 SO 4 or HCl to pH <2 28 days

Turbidity EPA 180.1 100 ml P,G 0-6 ° C 48 hrs.

UV Transmittance SM20 5910B 100ml ml Glass 0-6 ° C 48 hours

Chromium +6 EPA 7196A 200 ml P,G 0-6 ° C 24 hrs.
Metals, Total SM18 3113B
EPA 200.7, 200.9, 245.1, 500 ml P,G HNO 3 to pH <2 6 mos. Hg 28 days

Carbamates 9 EPA 531 2-40ml

vials G only Na 2 S 2 O 3 Pot. Hydrogen Citrate 28 days

Haloacetic

Acids EPA 552 3-60ml vials Amber G Ammonium Chloridee 14 days/ 14 days

Herbicides EPA 515.4 2-40ml

vials Amber G 0-6 ° C, 3mg Na 2 SO 3 7 14 days/ 21 days
MBAS EPA 425.1 500 ml P,G 0-6 ° C 48 hrsEndyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 24 of 42

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### TABLE 1 continued

POTABLE WATER Parameters Analytical Methods 1 Volume Required

(mls) Container Type 2 Preservative 3,4 Holding Time 5

Microextractables EPA 504 2 40-ml

vials G only

No Air Bubbles 0-6 ° C 10 mg Na 2 S 2 O 3 7 14days/ 1 day

Pesticides/

PCB EPA 505 2 40-ml

vials G only 0-6 ° C 5 mg Na 2 S 2 O 3 7 7 days/ 1day
Synthetic Organic Contaminants EPA 525.2 2 1000-ml Amber G 0-6 ° C 1:1 HCl ,50mg Na 2 SO 3 7 14 days/ 14 days

TriHaloMethanes

VOCs EPA 524.2 2 40ml

vials G only

No Air Bubbles 0-6 ° C 5 mg Na 2 S 2 O 3 14 days

Volatile Organic Contaminants EPA 524.2 2 40ml

vials G only

No Air Bubbles 0-6 ° C

1:1 HCl

Ascorbic Acid 7 14 days

Gross Alpha 9 EPA 900.0 1000 ml P None 24 hours/ 28days

Radium 226,228 9 EPA 903.1 2000 ml P None 28 days

Uranium 9 EPA 200.8 1000 ml P None 28daysEndyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 25 of 42

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### TABLE 1 continued

NON-POTABLE WATER Parameters Analytical Methods 1 Volume Required

(mls) Container Type 2 Preservative 3,4 Holding Time 5

Escherichia coli SM18 9223B 100 ml Sterile 125 ml > 10 ° C 0.008% Na 2 S 2 0 3 6 hrs

Fecal Coliform SM18 9222D 100 ml Sterile 125 ml > 10 ° C 0.008% Na 2 S 2 0 3 6 hrs

Heterotrophic

Plate Count SM18 9215B 100 ml Sterile 125 ml > 10 ° C 0.008% Na 2 S 2 0 3 8 hours

Total Coliform SM18 9223B enumeration 100 ml Sterile 125 ml > 10 ° C 0.008% Na 2 S 2 0 3 6 hrs

Acidity EPA 305.1 200 ml P,G 0-6 ° C 14 days
Alkalinity EPA 310.1 200 ml P,G 0-6 ° C 14 days
BOD EPA 405.1 1000 ml P,G 0-6 ° C 48 hrs.
BOD, Soluble EPA 405.1 1000 ml P,G 0-6 ° C 48 hrs
Bromide EPA 300.0 50 ml P.G None Required 28 days Chloride EPA 300.0 50 ml P,G None Required 28 days
Chlorine EPA 330.5 200 ml P,G Dark, 0-6 ° C 15 min.

COD EPA 410.1 50 ml P,G 0-6 ° C H2SO4 to pH <2 28 days

Color EPA 110.2 200 ml P,G 0-6 ° C 48 hrs.
Conductance EPA 120.1 100 ml P,G 0-6 ° C
Filter, 4 ° C 24 hours 28daysEndyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 26 of 42

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### TABLE 1 continued

NON-POTABLE WATER Parameters Analytical Methods 1 Volume Required

(mls) Container Type 2 Preservative 3,4 Holding Time 5

Cyanide9 EPA 335.1 250 ml P,G 0-6 ° C NaOH pH >10 14 days

Fluoride EPA 300.0 50 ml P,G None Required 28 days Hardness EPA 200.7 100 ml P,G HNO3 to pH 6 mos. Nitrogen, Ammonia EPA 350.3 100 ml P,G 0-6 ° C H2SO4 to pH <2 28 days

Nitrogen,

Nitrate EPA 300.0 50 ml P,G 0-6 ° C 48 hours

Nitrogen,

Nitrite EPA 300.0 50 ml P,G 0-6 ° C 48 hours

Nitrogen, Total Kjeldahl EPA 351.4 100 ml P,G 0-6 ° C H2SO4 to pH <2 28 days

Odor EPA 140.1 1000 ml G only 0-6 ° C 48 hrs.

pH EPA 150.1 100 ml P,G None 15 min.

Phenolics 9 EPA 420.1 1000 ml G only 0-6 ° C H2SO4 to pH <2 28 daysEndyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 27 of 42

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### TABLE 1 continued

NON-POTABLE WATER Parameters Analytical Methods 1 Volume Required

(mls) Container Type 2 Preservative 3,4 Holding Time 5

Phosphorus,orthoPhosphate, EPA 300.0/365.2 50 ml G 0-6 ° C 48 hours

Phosphorus, Total EPA 365.2 200 ml G 0-6 ° C H2SO4 to pH <2 28 days

Phosphorus, Total Dissolved EPA 365.2 200 ml G Filter on-site 0- 6 ° C H2SO4 to pH <2 28 days

Solids, Filterable EPA 160.1 500 ml P,G 0-6 ° C 7 days

Solids, Nonfilterable EPA 160.2 500 ml P,G 0-6 ° C 7 days

Solids, Settleable

Matter EPA 160.5 1000 ml P,G 0-6 ° C 48 hrs.

Solids, Total EPA 160.3 500 ml P,G 0-6 ° C 7 days
Solids, Total Volatile EPA 160.4 500 ml P,G 0-6 ° C 7 days

Sulfate EPA 300.0 50 ml P,G 0-6 ° C 28 days
Sulfide, Hydrogen EPA 376.1 1000 ml P,G 0-6 ° C 2ml Zinc Acetate NaOH to pH >9 7 daysEndyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 28 of 42

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### TABLE 1 continued

NON-POTABLE WATER Parameters Analytical Methods 1 Volume Required

(mls) Container Type 2 Preservative 3,4 Holding Time 5

Sulfite EPA 377.1 50 ml P,G None 15 min. Total Organic Carbon9 EPA 415.1 2 40ml

vials Amber G

No Air Bubbles 0-6 ° C H2SO4 or HCl to pH <2 28 days

Turbidity EPA 180.1 100 P,G 0-6 ° C 48 hrs.

UV Transmittance SM20 5910B 100ml Glass 0-6 ° C 48 hours

Chromium+6 EPA 7196A 200 P,G 0-6 ° C 24 hrs.
Metals, Dissolved SM18 3113B EPA 200.7, 245.1, 6010B, 7471A 25 P,G Filter on-site

Then HNO3 to pH <2 6 mos. Hg 28 days

Metals, Acid Soluble SM18 3113B EPA 200.7, 245.1, 6010B, 7471A 25 P,G HNO3 to pH <2 THEN

Filter on-site 6 mos. Hg 28 days

Metals, Suspended SM-18 3113B EPA 200.7, 245.1, 6010B, 7471A 25 P,G Filter on-site 6 mos. Hg 28 days

Metals, Total SM-18 3113B EPA 200.7, 245.1, 6010B, 7471A 25 P,G HNO3 to pH <2 6 mos. Hg 28 daysEndyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 29 of 42

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### TABLE 1 continued

NON-POTABLE WATER Parameters Analytical Methods 1 Volume Required

(mls) Container Type 2 Preservative 3,4 Holding Time 5

Fats, Oil & Grease EPA 1664 2-1000 G only 0-6 ° C H2SO4 to pH <2 28 days

MBAS EPA 425.1 500 P,G 0-6 ° C 48 hrs

PCBs EPA 608/8082 2 1000ml Amber G 0-6 ° C pH between 5-9 7 days/ 40 days

Pesticides EPA 608/8081A 2 1000-ml Amber G pH between 5- 9 0-6 ° C pH between 5-9 7 days/ 40 days

S.V.O.C.

BN/A EPA 625/8270C 2 1000-ml Amber G 0-6 ° C pH between 5-9 7 days/ 40 days TPH DRO EPA 8015B 2 40-ml G only 0-6 ° C HCl to pH <2 7 days/ 40days
Gross Alpha9 EPA900.0 1000 P None 28days

Radium 226,2289 EPA 903.1 2000 P None 28 days

Uranium9 EPA 200.8 1000 P None 28days

TPH GRO EPA 8015B 2 40-ml VOA G only No bubbles 0-6

° C HCl to pH <2 14 days

Volatiles EPA 624 2 40-ml vials G only No bubbles 0-6

° C 7 days

Volatiles EPA , 8260B, 8021B 2 40-ml vials G only No bubbles 0-6

° C HCl to pH <2 14 daysEndyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 30 of 42

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### TABLE 1 continued

SOIL/SOLID WASTE Parameters Analytical Methods 1 Volume Required

(mls) Container Type 2 Preservative 3,4 Holding Time 5

Fecal Coliform SM18 9222D 20g 125 ml

Sterile 0-10 ° C 24 hrs

Bromide EPA 9056 50g P.G None Required 28 days Chloride EPA 9056 50g P,G None Required 28 days Conductance EPA 120.1 50g P,G 0-6 ° C 28days

Corrosivity as pH EPA 9045D 50g P,G 0-6 ° C 28 days

Reactive Cyanide &

Sulfide 9 EPA Chapter 7.3 50g P,G 0-6 ° C 14 days

Fluoride EPA 9056 50g P,G None Required 28 days

Fraction Organic Matter ASTM D2974-87 25g P.G 4 ° C 28 days

Ignitability/ Flashpoint EPA Ch 7.1

EPA 1010A 100g G 4 ° C 28 days

Nitrogen, Ammonia EPA 350.3 100 P,G 0-6 ° C 28 days

Nitrogen,

Nitrate EPA 9056 10g P,G 0-6 ° C 28 days

Nitrogen,

Nitrite EPA 9056 10g P,G 0-6 ° C 28 daysEndyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 31 of 42

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### TABLE 1 continued

SOIL/SOLID WASTE Parameters Analytical Methods 1 Volume Required

(mls) Container Type 2 Preservative 3,4 Holding Time 5

Nitrogen, Total Kjeldahl EPA 351.4 25g P,G 0-6 ° C 28 days

Paint Filter Test EPA 9095B 100g P,G 0-6 ° C 28 days

pH EPA 9045C 25g P,G 0-6 ° C 14 days
Phosphorus, Total, Reserve, Available EPA 365.2 25g G 0-6 ° 28 days

Solids, Total EPA 160.3 50g P,G 0-6 ° C 7 days
Solids, Total Volatile EPA 160.4 100g P,G 0-6 ° C 7 days

Sulfate EPA 9056 10g P,G 0-6 ° C 28 days
Chromium+6 EPA 7196A 200 P,G 0-6 ° C 24 hrs.
Metals, Total SM18 3113B
EPA 6010B, 7471A 5g P,G None Required 6 mos. Hg 28 days
Metals, TCLP EPA 6010B, 7471A 25g P,G None Required 6 mos. Hg 28 daysEndyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 32 of 42

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### TABLE 1 continued

SOIL/SOLID WASTE Parameters Analytical Methods 1 Volume Required

(mls) Container Type 2 Preservative 3,4 Holding Time 5

Fats, Oil & Grease EPA 1664 50g G only 0-6 ° C 28 days

PCBs EPA 8082 100 g G only 0-6 ° C 14 days/40

days Pesticides EPA 8081A 100 g G only 0-6 ° C 14 days/40

days Herbicides EPA 8151A 100 g G only 0-6 ° C 14 days/40

days

S.V.O.C.

BN/A EPA 8270C 100 g G only 0-6 ° C 14 days/40

daysEndyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 33 of 42

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### TABLE 1 continued

SOIL/SOLID WASTE Parameters Analytical Methods 1 Volume Required

(mls) Container Type 2 Preservative 3,4 Holding Time 5

TCLP SVOC BN/A EPA 1311/

8270C 100 g G only 0-6 ° C 14 days

14 days/40

days

TCLP Pesticides EPA 1311/

8081A 100 g G only 0-6 ° C 14 days

14 days/40

days

TCLP Herbicides EPA 1311/

8151A 100 g G only 0-6 ° C 14 Days

14 days/40

days TPH DRO EPA 8015B 20-g G only 0-6 ° C 14 days/40

days TPH GRO EPA 8015B 20g G-VOA 0-6 ° C , No Head Space 14 days

Volatile Organics EPA 8021B, 8260B 20 g G-VOA 0-6 ° C No Head Space 14 days

TCLP VOC EPA 1311/

8260B 100 g G only 0-6 ° C No Head Space 14 Days 14 daysEndyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 34 of 42

Document Control Copy on Buff colored paper. Any other color is not official version TABLE 1 FOOTNOTES

1. Referenced Methods are from appr oved publications. “EPA” indicates Environmental Protection Agency. “SM” indicates “Standard Methods for the Examination of Water and Wastewater”. ASTM indicates “American Society for Testing and Materials”.
2. A general discussion on sampling water and indu strial wastewater may be found in ASTM, Part 31, pgs. 72-82 (1976) Method D-3370. 3. Plastic (P) or Glass (G). For metals, polyeth ylene with a polypropylene cap with teflon liner is preferred. 4. Sample preservation should be performed immediately upon sample collection. For composite samples each aliquot should be preserve d at the time of collection. When use of an automated sampler makes it impossible to preserve each aliquot, then samples may be preserved by maintaining at 4 ° C until compositing and sample splitting is completed. 5. When any sample is to be shipped by comm on carrier or sent through the United States Mail, it must comply with the Department of Trans portation Hazardous Materials Regulations (49 CFS Part 172). The person offering such ma terial for transportation is responsible for ensuring such compliance. For the preservation requirements of Table 1, the Office of Hazardous Materials, Materials Transportati on Bureau, Department of Transportation has determined that the Hazardous Materials Regula tions do not apply to the following materials: Hydrochloric acid (HCl) in water solutions at c oncentrations of 0.04% by weight or less (pH about 1.96 or greater); Nitric acid (HNO 3 ) in water solutions at concentrations of 0.15% by weight or less (pH about 1.15 or greater); Sulfuric acid (H 2 SO 4 ) in water solutions at concentrations of 0.35% by weight or less (p H about 1.15 or greater); Sodium hydroxide (NaOH) in water solutions at concentrations or 0.080% by weight or less (pH about 12.3 or less). 6. Samples should be analyzed as soon as possibl e after collection. The times listed are the maximum times that samples may be held before analysis and still considered valid. Samples may be held for longer periods only if the perm ittee , or monitoring laboratories, has data on file to show that the specific types of sampl e under study are stable for the longer time, and has received a variance from the Regional Administ rator. Some samples may not be stable for the maximum time period given in the table. A permittee, or monitoring laboratory, is obligated to hold the sample for a shorter time if knowledge exists to show this is necessary to maintain sample stability. 7. Should only be used if residual chlorine is present in the sample.

8. For samples from non-chlorinated drinking water supplies, concentrated H 2 SO 4 should be added to lower sample pH to less than 2. The sample should be analyzed before 14 days.

9. Indicates the analysis is subcontracted to a NELAC certified laboratory.Endyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 35 of 42

Document Control Copy on Buff colored paper. Any other color is not official version Table 2 Laboratory Instrumentation

Item # of Units Manufacturer Model

Air Pump 5 SKC 224-PCXR8 Atomic Absorption, 1 Perkin-Elmer 600 Autoclave 1 N APCO 8000-DSE Autoclave 1 Castle BB Balance, Analytical 0.01g sensitivity 1 Acculab VI-200 Balance, Analytical 0.1mg sensitivity 1 Mettler AE100 Balance, Analytical Class S calibration weights 2 Rick Lake Weighing Systems Centrifuge Centrific 225 Chromatograph, Gas with Mass Selective detector with Purge & Trap sample introduction 1 1 1 Agilent Agilent OI 5890 II w/EPC 5971 DPM-16/4560 Chromatograph, Gas with Mass Selective detector with Purge & Trap sample introduction 1 1 1 Agilent Agilent OI 5890 II w/EPC 5971 DPM-16/4560 Chromatograph, Gas with Mass Selective detector with auto-sample introduction 1 1 1 Agilent Agilent Agilent 5890 Seies II 5970 7673 Chromatograph, Gas with PID/FID detector with Purge & Trap sample introduction 1 1 1 Agilent OI Tekmar 5890 Seies II 4430 ALS 2016/LSC2000 Chromatograph, Gas with Mass Selective detector with Purge & Trap sample introduction 1 1 1 Agilent Agilent OI 5890 SeiesII w/EPC 5971 MPM-16/4560 Chromatograph, Gas with Mass Selective detector with auto-sample introduction 1 1 1 Agilent Agilent Agilent 6890 Plus 5973 7683B Chromatograph, Gas with FID detector with auto-sample introduction 1 1 1 Agilent Agilent Agilent 5890 SeiesII

7673B Chromatograph, Gas with FID detector with auto-sample introduction 1 1 1 Agilent Agilent Agilent 5890 SeiesII

7673B Chromatograph, Gas with ECD detector with auto-sample introduction 1 1 1 Agilent Agilent Agilent 5890 SeiesII w/EPC 19233 7673B Chromatograph, Gas with ECD detector with auto-sample introduction 1 1 1 Agilent Agilent Agilent 5890 SeiesII 19233 7673B Chromatograph, High Performance Liquid With Conductivity Detector 1 Dionex DX-120

Chromatograph, High Performance Liquid with UV and Conductivity Detectors 1 Waters 712/486

Concentrator, Solvent sample 1 TurboVap II Dessicators 4 FisherEndyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 36 of 42

Document Control Copy on Buff colored paper. Any other color is not official version Digestor, 36-Place (metals) 1 Environmental Express ETR-3020

Digestor, 54-Place (metals) 1 Environmental Express SC-154

Digestor, Block Nutrient 1 Lachat BD-46 Digestor, COD 2 HACH 45600 Falsh Tester, Closed Cup 1 Pensky-Martin 74637 Flourimeter 1 Turner Designs 10-005R Glassware, Class A Volumetric Multi-Supplier Hot Plate 10 Multi-Supplier ICP 1 Leeman Prodigy Incubator, BOD 1 Fisher 307C Incubator, BOD 1 Fisher 307 Incubator-Air Jacketed 1 Chicago Surgical & Electrical 200

Incubator-Water bath 1 GCA Precision Incubator-Water Jacketed 1 Forma-Scientific 3187 Incubator-Water Jacketed 1 N APCO 5100 Mercury Analyzer 1 Perkin-Elmer FIMS 100 Meter, Conductivity 1 YSI 35 Meter, Conductivity 1 Fisher 95081372 Meter, Expandable Ion Analyzer 2 Orion EA940 Meter, Oxygen, Dissolved 2 YSI 58 Meter, pH 1 Accumet Meter, pH & Ion specific probes 2 Orion 940 Micro, Quanti-tray Sealer 1 IDEXX 2X Oven, Drying 2 VWR 1305U Oven, Drying 1 Despatch LDB Oven, Drying 1 Agilent 5890 Oven, Muffle Furnace 1 Thermolyne 1500 Pipettors, 10ul up to 10ml Multiple Suppliers Probe, Oxygen, Dissolved 3 YSI 5905 Probe, Redox Combination 1 Orion 9678BN Refrigerator, Sample Double wide 3 United USF Refrigerator, Sample Single Wide 3 Multi-Supplier Refrigerator, Standards Single Wide 4 Multi-Supplie Sonicator 1 Tekmar TM 375 Spectrophotometer 1 Sequoia-Turner 340 Spectrophotometer Thermo Genesys 10UV Scanning Spectrophotometer-Colorimeter 1 HACH DR 890 Sterilizer, UV Light Crosslinker 1 UVP CL-1000 Stirrer, Magnetic Variable Speed 3 Corning PC 351 TCLP Rotator 1 Associated Design 4A TCLP, ZHE Extractor 3 Associated Design Thermal Tube Desorber 1 Dynatherm 890 Thermometer, Digital NIST certified (0.0°C to 105°C) 1 Control Company 4000

Thermometer, Di g ital NIST certified 1 Control Company 4015Endyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 37 of 42

Document Control Copy on Buff colored paper. Any other color is not official version (160°C- 450°C) Thermometer, glass working thermometers ~15 Multi-Supplier

Trap, Refridge-Condensation 1 Savant RT400 Turbidimeter 1 HF Scientific Micro100 Turbo-Vap 2 Caliper Model 500 Vortex 2 Fisher Genie 2 Water Bath 1 Fisher Water Purification System Reverse Osmosis 1 AquaSolutions RO2002

Water Purification, Polisher System 1 Millipore Milli-Q Wet Chemistry, Flow Injection Analyzer, 1 Lachat Quikchem 8000Endyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 38 of 42

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## Appendix A Endyne, Inc.-QSM Manual Rev10
160 James Brown Dr. Williston, VT 05495



## Demonstration of Capability

Certification Statement

Analyst Name:

Parameter: Method #: (Pesticides, BOD, Arsenic, etc.) (EPA #, SM #, etc.)

Matrix: Data Summary Table Attached: (Y / N ) (Solid, Potable and/or Non Potable) Summary of Training:

I, the analyst, agree to use only the most current version of the applicable SOP.

Analyst Signature: Date:

We, the undersigned, certify that:

1. The analyst(s) identified above, using the cited test methods, which is in use at this facility for the analyses of samples under the National Environmental Laboratory Accreditation Program (NELAP), have met the Demonstration of Capability (DOC). 2. The analyst identified on this certification performed the test method 3. A copy of the test method and the laboratory-specific SOPs are available for personnel on-site. 4. The data associated with the DOC are true accurate complete and self-explanatory. 5. All raw data necessary to reconstruct and va lidate these analyses have been retrained at the facility, and that the associated information is well organized and available for review by authorized assessors.

Harry Locker Ph.D. Technical Director Signature Date

Mark Fausel Q.A Officer Signature DateEndyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 39 of 42

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### DOC Submittal Protocol

Introduction: A Demostration of Capability (DOC) is re quired for every Analyst-Parameter-Matrix combination on an annual basis. To track the completion of these DOCs, at the beginning of the year, a WorkOrder is gene rated in LabTask and assigned the project name Demonstration of Capability. Each an alyst is assigned a sample number and all of the tests they perform are logged in under that sample number. When an analyst creates a Workload Management Report, the DOC Sample ID shows up like any other test. This tells the analyst they need to create their DOC and submit it to the QA Officer. Once the DOC has been reviewed and signed off on by th e Technical Director and the QA Officer, the associated DOC sample is “QC Accepted” in LIMS and is removed from the analyst’s Workload Management Report. This provide s an easy way of monitoring an analyst’s suitability to perform a certain test.

The DOC will be either an Initial DOC (IDOC)or a continuing DOC (CDOC). An IDOC is a summary of training and a Statistical calculation of 4 QC samples presented in a Data Summary Table. A CDOC is a summary of on-going training with ei ther a statement of successful participation in blind PT testing or a statistical calculat ion of 4 QC samples presented in a Data Summary Table.

Procedure: 1. Every DOC submitted for authorization shoul d have a Q-list # associated with it. a. The Q-list will only be for one sample: the DOC WO-Analyst Sample Number

b. The Test-code of the anal ysis specific to the DOC.

c. The entered result can be “C omplete” or the default value. d. The Analysis Date is the essential paramete r. Which will be used as the guide to track the annual perf ormance of the DOC. 2. The Data Summary Table is not mandatory for the DOC and form indicates whether a Data Summary Table is attached or not. 3. Whenever possible, there should be no ra w data associated with the DOC Q-List. 4. The raw data should have already gone through full QA review as a component of data sets associated to other Q-lists. 5. If a Data Summary Table is attached, the data must have a refe rence to the Q-lists with which the QCs were originally analyzed. 6. If the DOC QA samples were not analyzed with lab samples and incorporated into a standard Q-list data packet then, the entire data packet must be submitted for review. a. The data packet would consist of a t ypical data packet in cluding all calibration, blanks, etc.Endyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 40 of 42

Document Control Copy on Buff colored paper. Any other color is not official version b. The primary QA Reviewer reviews the entire data packet, signs-off on and forwards to the QA officer WITHOUT QC Accepting in LIMS. c. The Data Summary Table must list the Q-list number for each data point. 7. If there is no raw data packet requiring review, then the LIMS DOC Q-list with DOC form, with or without the Data Summary Ta ble, can be submitted directly to the QA Officer. 8. Once the QA Officer receives the Q-List, it will be signed by the QA Officer and the Laboratory Technical Director. 9. After signing, the Q-list is approved in LabTask and the DOC form with or without the Data Summary Table, is filed in the analyst’s Training Folder. a. The Data Summary Table reference to the Q-list number s is what provides traceability to the raw data. 10. If there is a data packet asso ciated with the Q-list it is fi led with the other Q-lists. If there is no data then the Q-list page is discarded.Endyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 41 of 42

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### Appendix B
Client Confidentiality and Privacy Policy

1. I understand that it is Endyne ’s policy that our clients ha ve a right to the privacy of their information, in all of its manifest ations, and that they are free from the risk of disclosure of this informati on from any current or past employee of Endyne. 2. I understand item 1. includes any discussions in which the name or identity of a client is revealed to any individua l not currently employed by Endyne. The disclosure of this identity includes any refe rence in which the identity of the client is implicit and that the revelation of this information in any way could demean the standing of that clie nt in the community. 3. I understand that this poli cy applies not only to our customers but to any projects or work performed by our customers for wh ich the identity of their clients has been made known to us. 4. I have been apprised of Endyne’s proce dures for the release of all data, be it verbal, electronic or written. I understa nd the only authoritati ve results reported by Endyne are in the form of a hard copy re port with the original signature of the Laboratory Director or appointed signer. a. Clients who request a verbal notifica tion of results must establish proof of identity as the proper client. This is accomplished by referencing the C-of-C number in the upper right hand corner. b. Clients who request a fax must indi cate on the C-of-C whom will receive results or if the request is made by phone, the individual must prove they are the stated client. This is usually acco mplished by referencing the distinctive C-of-C sequence number. c. Deliverables in the form of e-ma ils are only provided to established customers, whom have made formal arrangements for receipt of results. d. All electronic transmissions are accompan ied with a disclaimer stating that the material is confidential information intended solely for the recipient and to notify Endyne immediately upon incorrect receipt

Employee’s Signature: ____________________________ Date: _________________

Trainer’s Signature: ______________________________ Date: _________________Endyne, Inc. Quality Systems Manual 160 James Brown Dr. Revision #: 11 Effective: 10/6/09 Williston, VT 05495 Page 42 of 42

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## Name DateATTACHMENT 5Document Control Copy on Buff colored paper. Any other color is not official version 

# Endyne, Inc.

160 James Brown Dr.

Williston, VT 05495 Phone: (802) 879-4333 Fax: (802) 879-7103



# TOXICITY CHARACTERISTIC LEACHING PROCEDURE (TCLP) Method EPA 1311 Standard Operating Procedure

REVISED: January 21, 2008

Revision #: 9

Technical Director: Date : Harry B. Locker Ph.D.



### QA Officer: Date :
Mark L. FauselEndyne, Inc. TCLP Method EPA 1311 SOP 160 James Brown Drive Revision #9, Effective 1/21/08 Williston, VT 05495 Page 2 of 13

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### TABLE OF CONTENTS

Section Page

I – Overview 3

II – Storage 3

III – Waste Disposal 3

IV – Sample Collection, Preservation & Storage 3-4

V – Equipment & Supplies 4

VI – Reagents 5

VII – Interferences 5

VIII – Quality Control 5

IX – Extraction Procedure 6-8

X – Calibration and Standardization 9

XI – Data Reduction 9

XII – Data Recording 9-10

XIII – Instrument Maintenance 10

XIV – Trouble Shooting 10

XV – References 10

XVI - Definitions and Acronyms 10-11

XVII - Revision History 11

Analyst Review Sign Off Sheet 12Endyne, Inc. TCLP Method EPA 1311 SOP 160 James Brown Drive Revision #9, Effective 1/21/08 Williston, VT 05495 Page 3 of 13

Document Control Copy on Buff colored paper. Any other color is not official version I. Overview:

TCLP is used to evaluate the mobility of analytes in wastes. It is designed to mimic the leaching which occurs in landfills over 20 years. Sample aliquots are spun in a buffered solution for 18 hours. The sample is filtered and the filtrate is analyzed for target compounds that have migrated into the solution.

II. Safety:

A. This method involves the handling of the chemicals outlined below. Each of these chemicals may have specific associated hazards. Analysts must read and become familiar with all elements of each chemical’s MSDS. Make special awareness of the symptoms of exposure and potential routes of entry. Analysts must notify the Safety Officer immediately if any symptoms of exposure are suspected.

B. Personal protective equipment (i.e. gloves, goggles, and lab coats) must be worn at all times in designated work areas. All applicable engineering controls, such as fume hoods or splash shields, must be used when performing analyses. To ensure the safety of all laboratory personnel, work areas must be kept neat and organized. Equipment and bench-tops must be cleaned and sterilized at the completion of each task. All containers must be properly labeled as to contents and hazard ratings. Spills must cleaned promptly and completely.

III. Waste Disposal:

A. Sample extracts should be treated and disposed of in the same manner as the original sample. B. Contact the laboratory’s Hazardous Waste Manager for samples that have high levels of contamination for proper disposal. C. Only personnel that have been trained to properly dispose of hazardous waste may do so in the hazardous waste room in the proper waste drums.

IV. Sample Collection, Preservation & Storage:

A. Samples should be collected and stored in the same manner as if the TCLP procedure were not being performed except there is no chemical preservation until after the samples have been TCLP prepared. 1. Metals should be collected in glass or plastic containers. 2. Organics should be collected in glass containers. 3. Volatiles should be collected in glass containers with minimal headspace. B. Samples must not be preserved until after the TCLP extraction has been performed. Extracts should be preserved in the same manner as typical liquid samples for each method. 1. Metals pH <2.0 with HNO 3
. 2. Semi-volatiles are refrigerated.Endyne, Inc. TCLP Method EPA 1311 SOP 160 James Brown Drive Revision #9, Effective 1/21/08 Williston, VT 05495 Page 4 of 13

Document Control Copy on Buff colored paper. Any other color is not official version 3. Volatiles pH <2.0 with HCl.

Sample Maximum Holding Times

Parameter to TCLP Extraction Preparative Extraction Extraction to Analysis

Volatiles 14 days NA 14 days Semi-Volatiles 14 days 7 days 40 days Mercury 28 days NA 28 days Metals, except Hg 180 days NA 180 days

V. Equipment & Supplies:

• Rotator/Tumbler

• Zero-headspace Extraction Vessel (ZHE)

• Bottle Extraction Vessel

• Filter Pump

• pH Probe (+/- 0.05 accuracy)

• Analytical Balance

• Low metal acid treated filters

• Buchner funnel

• Side arm flask

• Gas tight syringe

• HCl preserved 40 mL VOA vials

• glass jars (for tumbling and final sample storage)- new, borosilicate

• plastic containers

• Nitrogen gas tank for pressuring ZHE

• stirring hot plate and stir bar

• beakers or flasks

• Pressure filtration apparatus

• Magnetic Stirrer and Hot Plate

• Min./Max. ThermometerEndyne, Inc. TCLP Method EPA 1311 SOP 160 James Brown Drive Revision #9, Effective 1/21/08 Williston, VT 05495 Page 5 of 13

Document Control Copy on Buff colored paper. Any other color is not official version VI. Reagents: (ACS Reagent grade or better)

1. Extraction Fluid #1 22.8ml Glacial Acetic Acid and 257.2mls 1N NaOH made up to 4.0 Liters. Target pH : 4.93 +/- 0.05 2. Extraction Fluid #2 22.8ml Glacial Acetic Acid to 4.0 Liters DI Target pH: 2.88+/- 0.05 3. 1N NaOH: 40.0g NaOH in 1L DI Water 4. 1N HCl: 10mls concentrated HCL brought up to 120ml with DI Water

VII. Interferences:

A. Sample carry-over from contaminated extraction vessels. Be sure to clean vessels well after each use. B. Bleed from Filters. Be sure to use proper low metal, TCLP filters. C. Method specific interference’s are outlined in the analytical SOPs.

VIII. Quality Control:

A. Tumbled Reagent Blanks should be performed for all analyses for every 20 samples spun in each extraction vessel used. Reagent Blanks shall be tumbled with new batches of extraction fluid. Volatile blanks should be spun in ZHE vessel. Sufficient volume should be provided for LRB and LFB analyses. B. Matrix spikes shall be performed at the appropriate frequency for each analytical technique. Sample extract volumes should be sufficient to perform these analyses. The analyst shall perform metal and semi-volatile spikes at the time of digestion or extraction. Volatile samples shall be spiked following the TCLP tumble at the time of sample extract preservation. C. Duplicates shall be performed at the appropriate frequency for each analytical technique. Sample extract volumes should be sufficient to perform these analyses. D. MDLs, DOCs and quality control analysis are tracked under the individual analytical method QA protocols.Endyne, Inc. TCLP Method EPA 1311 SOP 160 James Brown Drive Revision #9, Effective 1/21/08 Williston, VT 05495 Page 6 of 13

Document Control Copy on Buff colored paper. Any other color is not official version IX. Extraction Procedure:

A. Sample Evaluation 1. Determination of percent solids (non-filterable). Use only 1 filter per sample. Any sample left behind on the filter (even liquid) is considered non-filterable. Note: aliquots may be allowed to settle or be centrifugedprior to filtering to facilitate more complete filtering prior to filterclogging.

a. If the waste will obviously yield no liquid when subjected to filtration the sample is determined to be 100% solids. Proceed to section IX.A.2 b. If the sample is determined to be liquid or multiphasic, weigh >100g of sample and record the weight.

c. Pre-weigh a filter and the container that will receive the filtrate and filter the sample under gradual pressure increase. i. Apply pressure starting at approximately 10psi and increase incrementally up to a maximum of 50psi. ii. If no filtrate is collected, the percent solid is determined to be 100%. Proceed to section IX.A.2. d. Determine weight of filtrate and that of the solid material.

e. Determine the % solid (% solid = solid mass/total sample mass*100) i. If the % solid is < 0.5%, the coll ected filtrate is the TCLP extract for metal and semi-volatile analysis. Filter additional sample as needed for analytical requirements. ii. If the % solid is < 0.5% and volatile analysis is required, charge a ZHE vessel with a fresh portion of waste sample, the collected filtrate is the volatile TCLP extract. f. If the % solid is determined to be > or equal to 0.5% and it is noticed that a small amount of filtrate is entrained in wetting of the filter, determine the percent dry solids. i. Dry the solid phase and filter at 100 o C (+/-20 o C) until two successive weighing yield the same value within +/- 1%. ii. Calculate the % Dry solids. % Dry = (Dried filter mass – Tare Wt. of filter)/Initial mass*100
g. If the % dry solid is determined to be < 0.5%, follow the procedure outlined in section A.1.e.i for metals and semi-volatile analysis. Follow the procedure outlines in section A.1.e.ii. for volatile analysis. 2. Determination of Extraction Fluid a. All ZHE extractions use Extraction Fluid #1. b. Metal and Semi-Volatile Extraction fluid determination. i. Transfer a 5.0g portion of the solid phase of the sample to a 250ml Beaker. ii. Add 96.5mls of DI water and stir for five minutes. iii. Measure pH, if <5.0 use Extraction fluid #1. iv. If pH >5.0, add 3.5mls of 1N HCl heat to 50 ° C and hold for 10 minutes.Endyne, Inc. TCLP Method EPA 1311 SOP 160 James Brown Drive Revision #9, Effective 1/21/08 Williston, VT 05495 Page 7 of 13

Document Control Copy on Buff colored paper. Any other color is not official version v. Allow solution to cool and measure pH. If pH < 5.0, use extraction fluid #1 otherwise use extraction fluid #2. 3. Determination of Particle Size – Particle size must be sufficiently small so as to provide satisfactory surface area contact with the extraction fluid. (> 3.1cm2/gram or less than 0.95cm at its narrowest dimension). a. Solid phase of sample must be capable of passing through a 9.5mm (0.375 inch) standard sieve, unless material would provide adequate surface area contact. b. If sample is not able to pass through the sieve, the solid portion of sample must be prepared by crushing, cutting or grinding. If the sample is being prepared for volatile analysis, the waste and reduction material should be kept at 4 o C with minimal exposure to the atmosphere.

B. Extraction Procedure - Semi-Volatiles, Metals 1. Liquid samples with <0.5% Solids

a. Filter sample, filtrate is used as extract. Filter is discarded 2. Solid samples with 100% solid determination a. Transfer a minimum of 100g of waste sample to an extraction vessel. b. Add 20x the weight of the sample of proper extraction fluid to the vessel.

c. Spin for 18 hours ± 2 hours. d. Filter sample, filtrate is the TCLP sample to be analyzed. 3. Multi-Phase samples with >0.5% Solids

a. Filter a minimum of 100g sample and collect filtrate. Store filtrate in fridge for later use. b. Determine the weight of the solid phase. Transfer solid phase of sample to Extraction Vessel.

c. Add 20x the weight of the solid phase of proper Extraction fluid to the vessel. d. Spin for 18 hours ± 2 hours.

e. Filter sample and collect tumbled filtrate. Combine the tumbled filtrate with the filtrate from step B. 3. a. Sample aliquots for analysis must maintain the appropriate ratio of pre and post extraction filtrates. f. Combined filtrate is the TCLP extract to be analyzed. 4. Multi-Phase samples with >0.5% Solids where the liquid fraction is not miscible with the TCLP Extraction Fluid.

a. Filter a minimum of 100g sample and collect filtrate. Store filtrate in fridge for later use. b. Transfer solid phase to extraction vessel.

c. Add 20x the weight of the sample of proper Extraction Fluid to the vessel. d. Spin for 18 hours ± 2 hours.

e. Filter sample and collect all of the extract.Endyne, Inc. TCLP Method EPA 1311 SOP 160 James Brown Drive Revision #9, Effective 1/21/08 Williston, VT 05495 Page 8 of 13

Document Control Copy on Buff colored paper. Any other color is not official version f. Separate phases and determine volume of each phase. i. If extracted filtrate contains additional non-aqueous fraction. The non-aqueous fraction should be combined with the pre-extraction, non-aqueous fraction. ii. If the Pre-extraction filtrate contains aqueous fraction. The aqueous fraction should be combined with the TCLP buffer
extract. iii. Once all like-phase extract and filtrates have been combined the volume of each phase should be determined for use in the weighted-average quantitation equation.
g. Analyze sample aliquots separately mathematically combine values to determine final concentration. (V1) (C1) + (V2) (C2) Final Analyte Concentration = V1 + V2

where: V1 = The volume of the first phase (L). C1 = The concentration of the analyte of concern in the first phase (mg/L). V2 = The volume of the second phase (L). C2 = The concentration of the analyte of concern in the second phase (mg/L).

C. Extraction Procedure – Volatiles 1. Liquid samples with < 0.5% solids.

a. Filter samples through a clean ZHS extractor as per Section IXC2 and analyze as a filtrate sample. 2. Solid samples with 100% solid determination.

a. Transfer an aliquot of sample (minimum of 25g) to a Zero Headspace Extraction Vessel (ZHE). b. Add 20x the weight of sample of Extraction Fluid #1.

c. Compress the cylinder piston with 30psi Nitrogen and remove any headspace. d. Spin for 18 hours ± 2 hours.

e. Pull off sample from Extractor using a gas-tight syringe. f. Transfer to 40ml VOA vial with no air bubbles, preserve and analyze as soon as possible. 3. Multi-Phase samples with > 0.5% Solids

a. Based on the % solid, determine how much of the sample combined with 20x the fraction of the solid material is needed to total 500mls. b. Add the unadulterated sample to the ZHE.

c. Gradually charge the ZHE and collect filterable fraction of the sample in a gas tight syringe. Mass of the filtrate is determined and filtrate is stored with zero headspace (in Tedlar bag or VOA vials) at 4 o C until reconstitution with solid extract or analysis. d. Vent the ZHE pressure charge and leave vent valve open.Endyne, Inc. TCLP Method EPA 1311 SOP 160 James Brown Drive Revision #9, Effective 1/21/08 Williston, VT 05495 Page 9 of 13

Document Control Copy on Buff colored paper. Any other color is not official version e. Add 20x the weight of the solid fraction of Extraction Fluid #1 to the ZHE with a gas tight syringe through the sample collection valve. f. Close the ZHE vent valve and the sample collection valve.
g. Charge the ZHE vessel to +/- 30psi and check to ensure there is no headspace h. Spin for 18 hours ± 2 hours. i. Pull off extract from vessel using a gas-tight syringe. j. Combine initial sample filtrate with filtrate from solid phase ZHE extraction. The combined filtrates are the TCLP extract. Sample aliquots for analysis must maintain the appropriate ratio of pre and post extraction filtrates. Preserve to a pH<2 with HCl and store for analysis at 4 o C with zero headspace k. If the two filtrates are not misc ible, each filtrate will be analyzed separately and the final analyte concentration will be determined as outlined in section IX.B.4.f.

X. Calibration & Standardization:

Calibration and standardization is based on individual analytical methods. Refer to individual analytical SOPs.

XI. Data Reduction:

A. Percent Solids Determination

( A - B) x 100 = C A Where: A = Total weight of sample before filtration B = Weight of filtrate C = % Weight of solid portion

B. Analyte Concentration Determination of Biphasic Extracts

FAC = (V 1 x C 1 ) + (V 2 + C 2 ) V 1 + V 2 V 1 = Volume of the 1st phase C 1 = Concentration of Analyte in 1st phase V 2 = Volume of the 2nd phase C 2 = Concentration of Analyte in 2nd phase FAC = Final Analyte ConcentrationEndyne, Inc. TCLP Method EPA 1311 SOP 160 James Brown Drive Revision #9, Effective 1/21/08 Williston, VT 05495 Page 10 of 13

Document Control Copy on Buff colored paper. Any other color is not official version XII. Data Recording:

. A. All TCLP extraction parameters are recorded in the TCLP log book binder. This would include the preparation date, manufacturer, lot #, date of receipt and expiration date of all the chemicals required to make the fluid. Once the fluid is prepared it is given an expiration date of one year from the preparation date. It is discarded if held past longer than the expiration date. B. Before using a batch of extraction fluid the pH must be checked and recorded in the TCLP reagent log located in the log book binder and on the bottle. Calibration of the pH meter is documented in its own maintenance log. C. Descriptions of samples (appearance and form), their preparation (crushing, cutting, grinding) and all details of the extractions (for example: mass of sample. percent solid, extraction fluid used, date and time of start and finish of extraction, etc.) are recorded by sample number in the TCLP log binder. D. Start and stop pressure of the ZHE extraction vessels is documented on the sample extraction sheet in the TCLP log binder. If the ZHE stop pressure is zero upon tumble completion, the extracted sample is invalid. The ZHE vessel must be repaired for leaks and the sample re-extracted. E. The tumble area Min./Max. Thermometer is reset at the start of each extraction tumble. The high and low tumble time temperatures are documented in the sample extraction sheet in the TCLP log binder. If the temperature extremes fall outside 23 o C +/- 2 o C the extracted sample is invalid. The tumble area atmosphere will be corrected to maintain stable temperature, and the sample re-extracted. F. The TCLP tumbler is calibrated monthly and documented in the tumbler log of the TCLP log binder. Acceptance is 30RPM +/- 2RPM. Instrument maintenance is required prior to sample extraction if the tumble rate falls outside method acceptance limits.

XIII. Instrument Maintenance:

A. TCLP Tumbler needs regular cleaning. Contact Associated Designs if RPM fall outside acceptance. Contact information is posted on front of the tumbler. B. Balance Maintenance is performed as the Balance SOP dictates. C. pH Meter maintenance is performed as the pH SOP dictates D. Submerge charged ZHE in sink of water for convenient leak check. Do not submerge pressure gauge above glass PSI display. E. Min./Max. Thermometer is NIST traceable. Refer to thermometer section of TCLP log binder for calibration due date.

XIV. Trouble Shooting:

A. Be sure that all vessels are either brand new or cleaned properly with hot soapy water and rinsed with DI prior to analysis.Endyne, Inc. TCLP Method EPA 1311 SOP 160 James Brown Drive Revision #9, Effective 1/21/08 Williston, VT 05495 Page 11 of 13

Document Control Copy on Buff colored paper. Any other color is not official version B. ZHE gaskets are a likely source of volatiles contamination. If the Volatiles analyst detects high levels of solvents the extractionist should be notified promptly so all gaskets can be replaced with new. C. Be sure that there is no headspace in the ZHS vessels and that it is airtight. If liquid leaks out of the vessel, check and replace gaskets as necessary.

XV. References:

A. EPA Method 1311 Toxicity Characteristic Leaching Procedure. Rev. 0, EPA Methods and Guidance for Analysis of Water CD version 2.0. July, 1992.

XVI. Definitions and Acronyms:

A. TCLP-Toxicity Characteristic Leaching Procedure B. ACS Reagent Grade Chemicals-A Chemical grade of highest purity which meets or exceeds purity standards set by the American Chemical Society. C. Multi-phase sample-a sample with multiple phases which are not miscible with one another. (Solid/Liquid or Liquid/Solvent or multiple combinations) D. ZHE-Zero Headspace Extraction Vessel - For use with the preparation of samples to be analyzed for volatile organic contaminants E. Percent Solid-Method specific definition of percent solid as determined by TCLP sample evaluation procedure. More of an assessment of the portion of sample unable to pass through a TCLP filter than a determination of solid material. (Not to be confused with EPA 160.3 percent solid determination) F. Percent Dry Solid-Method specific definition of percent dry solid as determined by TCLP sample evaluation procedure (Not to be confused with EPA 160.3 percent solid determination) G. DI/DIW-De-ionized filter polished laboratory grade water H. HNO3-Nitric Acid I. HCl-Hydrochloric Acid J. NaOH-Sodium Hydroxide K. MSDS-Material Safety Data Sheet L. 1N-A One Normal Solution

XVII. Revision History:

Revision 5. - April 2004. General review for edits and added References section. Revision 6. - April 2005. General Review for edits and added Revision History Revision 7. - January 2006. General Review for edits. Revision 8 - October, 2007 General review and edits. Revision 9 - January 21, 2008 -Edit typos in section IV. -Added Misc. Equipment and supplies to section V. -Added 1N NaOH and 1N HCl to VI Reagents. -Edit of typos and procedural steps in VIII Quality Control -Modifications to IX Extraction Procedures clarifying method specified extraction requirements and proceduresEndyne, Inc. TCLP Method EPA 1311 SOP 160 James Brown Drive Revision #9, Effective 1/21/08 Williston, VT 05495 Page 12 of 13

Document Control Copy on Buff colored paper. Any other color is not official version -Added tumbler requirements, temperature requirements and ZHE pressure requirements to XII Data recording. -Added thermometer, tumbler and ZHE leak check information to XIII Maintenance. -Added section XVI Definitions and Acronyms section to SOPEndyne, Inc. TCLP Method EPA 1311 SOP 160 James Brown Drive Revision #9, Effective 1/21/08 Williston, VT 05495 Page 13 of 13

Document Control Copy on Buff colored paper. Any other color is not official version I acknowledge that I have read this Standard Operating Procedure and agree to adhere to the Safety and Quality Control policies outlined within.

Name DateDocument Control Copy on Buff colored paper. Do not duplicate 

# Endyne, Inc.

160 James Brown Dr.

Williston, VT 05495 Phone: (802) 879-4333 Fax: (802) 879-7103



# ICP Standard Operating Procedure

EPA Method 6010B

REVISED: October 1, 2009

Revision #: 5

Technical Director: Date: Harry B. Locker Ph.D.



### QA Officer: Date:
Mark L. FauselEndyne, Inc. SW 6010B ICP SOP 160 James Brown Drive Revision #5, Effective: 9/29/09 Williston, VT 05495 Page 2 of 18

Document Control Copy on Buff colored paper. Do not duplicate 

### TABLE OF CONTENTS

Section Page

I – Overview 3

II – Safety 3

III – Waste Disposal 3

IV – Sample Collection, Preservation and Storage 4

V – Equipment & Supplies 4

VI – Reagents & Standards 4

VII – Interferences 5

VIII – Quality Control 5

IX – Analytical Procedure 6

X – Calibration and Standardization 14

XI – Data Reduction 15

XII – Data Recording 15

XIII – Troubleshooting 15

XIV – Revision History 16

XV – References 16

XVI – Method Modifications 16

Appendix 1 – Digestions 17

XVII – SOP Attestation 18Endyne, Inc. SW 6010B ICP SOP 160 James Brown Drive Revision #5, Effective: 9/29/09 Williston, VT 05495 Page 3 of 18

Document Control Copy on Buff colored paper. Do not duplicate I. Overview:

- Inductively coupled plasma-atomic emission spectrometry (ICP-AES) may be used for the determination of dissolved, suspended, or total elements in drinking water, surface water, and domestic and industrial wastewater. This SOP is based upon EPA Method 200.7 and 6010B. The analysis described in this method involves multielemental determinations by ICP-AES using either a sequential or simultaneous instrument. The instruments measure characteristic atomic-line emission spectra by optical spectrometry. Samples are nebulized and the resulting aerosol is transported to the plasma torch. Radio-frequency inductively coupled plasma pr oduces element specific emission spectra. The spectra are dispersed by a grating spectrometer, and the intensities of the line spectra are monitored at specific wavelengths by a photosensitive device. Photocurrents from the photosensitive device are processed and controlled by a computer system. A background correction technique is required to compensate for variable background contribution to the determination of the analytes.

II. Safety:

- Gloves, goggles, and lab coat should be worn when handling all samples, reagents, and standards. Acids and uncovered digesting samples should be handled in the fume hoods. An exhaust fan is installed above the ICP to remove emissions. The toxicity or carcinogenicity of each reagent used in this method has not been fully established. Each chemical should be regarded as a potential health hazard and exposure to these compounds should be as low as reasonably achievable. A reference file of Material Safety Data Sheets (MSDS) is available to all personnel involved in the chemical analysis. Specifically, concentrated nitric and hydrochloric acids present various hazards and are moderately toxic and extremely irritating to skin and mucous membranes. Use these reagents in a fume hood whenever possible and if eye or skin contact occurs flush with large volumes of water. Always wear safety glasses or a shield for eye protection, protective clothing and observe proper mixing when working with these reagents. The acidification of samples containing reactive materials may result in the release of toxic gases, such as cyanides or sulfides. Acidification of samples should be done in a fume hood. The inductively coupled plasma should only be viewed with proper eye protection from the ultraviolet emissions. It is the responsibility of the user of this method to comply with relevant disposal and waste regulations.

III. Waste Disposal: - Liquid waste from the drain lines of the ICP is collected in a plastic container with a cap. When this container fills it is removed and taken to the hazardous waste disposal area and combined with the aqueous acidic metals wastestream.Endyne, Inc. SW 6010B ICP SOP 160 James Brown Drive Revision #5, Effective: 9/29/09 Williston, VT 05495 Page 4 of 18

Document Control Copy on Buff colored paper. Do not duplicate IV Sample Collection Labeling, Preservation, and Storage:

A. Collection: Samples are collected in plastic and glass containers of various sizes.

B. Labeling: All samples are assigned a number, plus a unique identifier to indicate preservative and bottle type. C. Preservation: Upon arrival at the lab, soil samples are refrigerated for preservation.

D. Storage: Soils and sludge samples are stored in the fridge on the first floor.

V. Equipment and Supplies:

- Volumetric flasks for making standards and diluting samples. - Pipettes for digestions - Leeman Labs Inc. ICP Prodigy Dual View System with Auto-sampler. - Water recirculator, exhaust fan, Argon gas - Leeman Labs Salsa computer software - A variable-speed peristaltic pump which is required to deliver both standard and sample solutions to the nebulizer is integral to the instrument. - Analytical balance, with capability to measure to 0.1 mg, for use in weighing solids, for preparing standards, and for determining solids in digests
or extracts. - Block digester capable of maintaining 95 0 C - 50 ml plastic containers for the block digester, plastic watchglasses, caps, and associated plunger-type filters. - Timer for turning block digester on and off - Mixed Cellulose Ester Air Filters - Smear Tabs

VI. Reagents and Standards:

- Concentrated Nitric acid - Concentrated Hydrochloric Acid - 30% Hydrogen Peroxide - Multielement and single element standards - Concentrated Perchloric Acid

NOTE: All incoming standards, reagents, dry chemicals, and acids shall be marked with date of receipt, date of expiration, and date of opening. Dry chemicals and concentrated acids shall be used within 20 years and 10 years respectively of the date of receipt or before the manufacture’s specified expiration date.Endyne, Inc. SW 6010B ICP SOP 160 James Brown Drive Revision #5, Effective: 9/29/09 Williston, VT 05495 Page 5 of 18

Document Control Copy on Buff colored paper. Do not duplicate VII. Interferences:

A. Spectral Interferences are caused by background emission from continuous or recombination phenomena, stray light from the line emission of high concentration elements, overlap of a spectral line from another element, or unresolved overlap of molecular band spectra.

B. High concentrations of Iron may interfere with other elements.

C. Aluminum used in sludges can interfere when analyzing Arsenic by ICP

D. An Interelement Correction Std. is run annually. Relatively high concentrations of the single element standards listed in Table 3 of Method 200.7 are analyzed and the Apparent concentrations of all elements in the method are measured to ascertain which elements each element may interfere with.

E. To perform an Inter-element Correction: 1. The method is calibrated with the IEC function turned off. 2. The single element standards are run at relatively high concentrations. 3. A CSV file is generated. 4. The apparent concentration of each observed element is divided by the measured concentration of the IEC standard. This coefficient may be positive or negative. 5. These coefficients, for any reading greater than the associated MDL, are entered into the IEC tables on the element pages in the method. 6. The instrument is calibrated with the IEC function turned on. 7. An IEC Check Standard as described in the method should be run to confirm an IEC coefficient accuracy of +/- 20%.

F. The ICP is very temperature sensitive. A temperature change of a few degrees an hour will interfere with results, especially for Ba and Al.

VIII. Quality Control:

1. Demonstration of Capability (DOC). Each new analyst performs a set of four mid-range LFBs. The percent standard deviation and average percent recovery are determined for each analyte. Each must be less than 20% to ensure proper capability of the analyst for that method. This process is repeated annually for each metals analyst. 2. Method Detection Limit (MDL). a. An MDL is run annually for each element. The final calculated MDL value must be at least 1⁄2 the reported value and the MCL. MDL’s should be digested and also non-digested. b. A QC is made with a concentration 1-10 times higher than the expected MDL. c. This sample is analyzed 7 times. The calculation should only use sequentially acquired results.Endyne, Inc. SW 6010B ICP SOP 160 James Brown Drive Revision #5, Effective: 9/29/09 Williston, VT 05495 Page 6 of 18

Document Control Copy on Buff colored paper. Do not duplicate 3. The MDL is calculated by taking the standard deviation of the values and multiplying by the appropriate number from the chart from the Code of Federal Regulations Appendix B to part 136 of chapter 1(7 is 3.143 4. Quality Control Standard (QCS) is from an independent source. It shall be run quarterly with acceptance limits of +/- 5%. This is based upon the average of 3 replicates. 5. Laboratory Reagent Blank (LRB) is run every batch, or 20 samples, and be +/- the reporting limit or less than 1/10 of the measured sample concentration.. 6. Laboratory Fortified Blank (LFB ) is from an independent source. It is run every batch, or 20 samples, with acceptance limits determined by a control chart for digested matrix. When digested it will have a prefix of TM and a suffix of S when digested as a soil. 7. Calibration Check/Verification, CCV (or Instrument Performance Check – IPC) is analyzed before samples are analyzed. The percent recovery of the CCV should be + 10%

. The CCV shall be run every 10 samples. There is a CCV for each the axial and radial lines and are labeled CCVA and CCVR respectively 8. A Calibration Blank (BLK) is analyzed before samples are analyzed and after every ten samples. The BLK should have concentration below that of the reporting limit or less than 1/10 th of the measured sample concentration 9. An IEC check standard should be run daily with a percent recovery of +/- 20%. 10. Duplicate samples are run every 10 samples with a percent difference of no more than 20%. 11. LFM (spike) samples are run every 10 samples or when results are questionable. Percent recovery for LFM’s must be +/-30%. 12. LFM’s are not acceptable as Independent QC’s. 13. If data does not meet the criteria outlined above, it may be used, but MUST be noted on the final client report.

IX. Analytical Procedure:

A. Sample Preparation 1. Drinking water sample preparation is dependent on the turbidity. If the turbidity is < 1.0 the samples are preserved, allowed to sit for at least 18 hours, and analyzed “as is”. If the turbidity is > 1.0 the samples are digested and analyzed as “total”. 2. For dissolved metals analysis see Appendix 1 3. For Total metals see Appendix 1 4. For metals analysis in air samples see Appendix 1

B. Data Acquisition 1. Data acquisition is done using Leeman Lab Salsa software. 2. Overview: a. The Leeman Labs Software is "Comma nd Central" of ICP operations. So in order to operate the ICP, the Leeman So ftware must be currently running. There is a shortcut icon on the Desktop to access Salsa (It looks like a chili pepper).Endyne, Inc. SW 6010B ICP SOP 160 James Brown Drive Revision #5, Effective: 9/29/09 Williston, VT 05495 Page 7 of 18

Document Control Copy on Buff colored paper. Do not duplicate b. All data is stored in an Access database file located in the Salsa folder on the C: drive. 3. The Lay of the Land a. The Salsa software is accompanied by a tutorial disk, which takes the operator through all of the major functions of the so ftware. The software also has a very comprehensive manual, which is stored in the cabinet below the instrument. b. The instrument, argon supply, and software must remain on at all times. This will ensure that the camera is purged with argon so that no moisture is allowed to collect on the camera. If moisture were to collect on the camera and the coolers are turned on, then the camera will freeze and the instrument will be inoperable. c. The Instrument Control Page allows the operator to control all parts of the instrument manually: spectrometer, autosampler, torch gas, plasma, and pump. The values for each of these can be entered and saved as part of the method.

C. Igniting the Plasma 1. The plasma should run for 20 minutes pr ior to use in order to reach thermal equilibrium. There are a number of interl ocks as indicated in the interlock drop down box of the Salsa software. These interlocks include Power, Plasma Door, Argon, Water, and ICP Covers. If any one of these interlocks is lit, the plasma will not ignite. Argon supply must be 90 psi. If the Argon pressure falls below 75 psi, the Argon interlocks will begin to flash. If the pressure falls below 60 psi, the plasma will self-extinguish. The Argon pr essure should never go above 120 psi. After installing a new tank allow the instru ment to purge for fifteen minutes to remove any moisture from the camera. If the argon supply is interrupted for any reason (if the tank runs out over night) it is imperative that the camera be purged with the camera cooler off to ensure that there is no moisture on the camera or it will freeze and render the instrument inoperable. a. Automatic Ignition i. Software, instrument and argon should alr eady be on; if not then they need to be. Allow five minutes after turning on the instrument for the camera to stabilize. ii. Make sure all guards and covers are in place. iii. Turn on exhaust fan by flipping the single light switch behind the liquid argon tank and be sure that the baffle is in the open position. iv. Turn on Water recirculator. v. Check pump tubing integrity. vi. Clamp down pump tubing. vii. From the Instrument Control Screen select Autostart.

b. Manual Ignition - only to be used by experienced operators ! Leeman Tech support can guide the opera tor through this process. It is usually only used for diagnostic purposes.Endyne, Inc. SW 6010B ICP SOP 160 James Brown Drive Revision #5, Effective: 9/29/09 Williston, VT 05495 Page 8 of 18

Document Control Copy on Buff colored paper. Do not duplicate D. Open Method 1. A Method is a Leeman data file that cont ains information concerning analytical lines, integration parameters, calibration and check standards, and other related data. A Method must be created and opened before any analysis can begin. Once a Method has been created, it can be saved and opened at a later date. 2. In order to create a Method a. From Method tab in the lower left corn er of the screen, select Method from the tool bar and enter a Method name. Any name can be used, but for month to month general analysis, a Method indica ting the month the Method is used may be a good idea. For example, Method name 02032007 would refer to a Method that was created in Feb. 2003. b. Proceed to Instrument Control panel and modify any necessary settings for spectrometer, autosampler, torch gas, plasma, and pump. c. If you are creating a completely new Method, choose Element Selection. If not, proceed to E. d. Select the atomic symbol for the first element of the list for which you will want to analyze. For example, enter Ba for Barium. i. After you enter the symbol, a list of av ailable lines for the selected element will appear. Each available line will be indicated by the atomic symbol combined with a number. ii. The second major column contains th e wavelength, in nm, of the line. The third column contains either a “I” or “ II”; “I” indicates that emission for that lines originates from an excited atom; “ II” from an excited ion. The fourth column contains the relative intensitie s of each line. The fifth column indicates whether or not that line has b een aligned. This screen also lists those elements known to interfere with each selected line and pressing the add line button. 3. Generally, you will want to choose the preferred line as indicated by the asterisk. If more than one line has an asterisk, choose the line with an asterisk and the highest relative intensity. A line is selected double-clicking on that line. 4. If your chosen line has not been ali gned, you must perform a Peak Wavelength on that line before using it. Peak Wavelength tells the ICP where to find that line in the Optics Box. 5. Continue entering lines until you have entered all the desired elements.

E. Analytical Parameters. Analytical Parameters contains integrati on parameters, sample uptake time, peaking line information, and computation options. 1. Choose 3 Integrations. 2. Uptake time choose a time of 15 seconds and check the ‘fast uptake’ option. The ICP will draw up sample for 15 seconds w ith the pump running faster before the pump slows and it begins analyzing it. 3. Axial integration should be set for 30 seconds and radial should be 15 seconds. 4. If you will be using Weight and Diluti on factors, check the box for each option. More information on these options will appear in the Sample Analysis Section.Endyne, Inc. SW 6010B ICP SOP 160 James Brown Drive Revision #5, Effective: 9/29/09 Williston, VT 05495 Page 9 of 18

Document Control Copy on Buff colored paper. Do not duplicate 5. The Peaking Line is a line that is sca nned to find the optimum viewing position in the plasma. The line Mn 257.610 is a good line to use because it is centrally located within all other lines. Therefore, the line Mn 257.610 should be included in Element Selection regardless of whether you will be testing for Mn. The Position Plasma Routine will be discussed in Section IX. M.

F. Customizing Lines Under element selection when a particular line is selected from the list on the left side of the screen four option tabs appear: general, calibration, alignment, and IEC.

1. General: This is where the torch view can be selected for each line, a line can be activated, and minimum or maximum values can be defined. 2. Calibration: This is where the calibration curve can be viewed, type of calibration can be selected, and the calibration concen trations with their associated emission values are displayed. 3. Alignment: This is where scans can be viewed to manually align peaks and background points can be set. 4. IEC: This is where IEC coefficients are entered to compile the IEC tables.

G. Internal Standards compensates for a group of elements that shift together. However, this option is not used currently.

H. Standards/MSA is where line standards ar e entered. Each standard is assigned a name, checking the box next to their symbol can turn on elements, values are entered and units are assigned. Once a standard is entered the software assigns a location in the autosampler.

I. Quality Control Checks is the screen wh ere the QCS, CCV, BLK, Duplicates, and Spikes are defined. This is accomplished in a very similar manner to the Standards entry.

J. QC Automation is where the operator indi cates which standards should be run with each run. Standards can be run before, duri ng, or after a sequence. Once items have been selected on this screen they can be viewed on the Sequence screen.

K. Summaries Screen is where one can l ook to find the table form of Calibration information, Standards, and QC Checks.

L. General stores the date and times that a method was created and modified and any additional notes that have been entered.Endyne, Inc. SW 6010B ICP SOP 160 James Brown Drive Revision #5, Effective: 9/29/09 Williston, VT 05495 Page 10 of 18

Document Control Copy on Buff colored paper. Do not duplicate M. Position Plasma 1. Prepare a standard that includes Mn at a concentration equal to the mid-point of the line. 2. Put this Mn standard in a cup and send the sampler there by using the instrument control page. Allow 45 seconds for the standard to reach the torch. 3. In the Spectrometer box of the Instrument Control page press the position plasma button. 4. Press the Peak Plasma button in the window that comes up. 5. Watch the peaks that come off. Ther e should be two sets of symmetrical and matching peaks. This may require a second Peak Plasma to achieve. 6. Once the each set of peaks are symmetrical and matching send the tip to rinse.

N. Aligning Peak Wavelengths 1. Once the lines are entered and the plasma is positioned each wavelength will need to be aligned. This can be done using the mid-point of the line. Single-element standards are best but multi-element standards will work for most elements. 2. This can be done Automatically or Manually. a. Automatic Peak Alignment i. Select Tools from the toolbar and Auto Align ii. Select the Hg line and Auto Align. This will align the Hg lamp. iii. Accept the Hg alignment. iv. Send the autosampler to the standard and select those elements to be aligned by checking the box next to their symbol. v. Once the standard has reached the torch hit the Auto align button. vi. Accept the peaked lines. vii. Send auto sampler to rinse. b. Manual Peak Alignment i. From the instrument control page send the autosampler to the standard containing the target analyte. ii. In the tool bar select the Echelle Image Icon(black box with stars) iii. Enter a name for the Echelle Image such as Mn 2ppm iv. Enter a time for exposure such as 10, 1, 0.1, or 0.1 seconds.(When using multi-element standards, running multiple images with different exposure times will help as each element has a specific time that works best) v. Press OK vi. Once the image is acquired (icons w ill return on tool bar) send sampler to rinse. vii. Open the Element list of the Method and select one of the elements that needs to be manually aligned. viii. Select the Align Wavelength tab. ix. Select one of the recently acqui red images by clicking on one of the images listed on the left side of the alignment window. x. The ideal image will have a small ball of bright pixels no larger than the height of the target box.Endyne, Inc. SW 6010B ICP SOP 160 James Brown Drive Revision #5, Effective: 9/29/09 Williston, VT 05495 Page 11 of 18

Document Control Copy on Buff colored paper. Do not duplicate xi. If the image is an appropriate intensity move the box using the arrows on the screen to obtain the greatest intensity number in the lower right corner of the screen. Click accept to save the alignment if it has changed. xii. If the image is too bright try an image with a shorter exposure time. xiii. If the image is too dim to be seen hit the contrast button and see if that helps. If it does not then use an image with a longer exposure time.

O. Selecting Background Points 1. This can be accomplished concurrently with the manual peak alignment. 2. Capture Echelle Images as described above. 3. Open each element and look at the image w ith the most appropriate intensity (should already be aligned). 4. Look at the graph on the lower portion of the window. The background points are in green. The ones that are of import here are the left and right background points. They should be located where the peak meet s the baseline, or before the beginning of the next peak if there is another metal close by. 5. Background points can be moved by clicking and dragging them. 6. The other place that background points can be viewed is in the plot screen of the analysis page.

P. Choose Sequence Tab 1. Sequence screen is where the working seque nce is entered and displayed. The left side of the screen displays graphically the standards and samples that are in the
sequence. 2. The Sample ID column of the table shoul d include all pertinent information for the sample: identification number with suffix, duplicate or spike notation, and dilution ratio if applicable. 3. The Extended ID column is not a working field. Any information entered in this field will not appear on the report. 4. The Weight and Volume columns can be used if these computation options were turned on in the Analytical Parameters screen. 5. The Macro (5 th ) column is for the entry of specifi c codes: D = Duplicate, S1= Spike, and the complete list can be found in the manual on page 158. 6. In order for these changes to take effect the Update button must be pressed. 7. The run sequence button will run the sequence as displayed on the left side of the

screen. 8. The Graphics on the lower part of the right side indicate which cups in the autosampler are active. Q. Calibrating the ICP 1. Select Standards on QC Automation Page (i.e.: S1-S4) 2. Calibration standards should be run before any other samples are run. 3. Go to the Sequence page to be sure that the standards are set to go. 4. UI should be 0 for all lines since an acid blank will be used as the Update Intercept. 5. US should be equivalent to the highest standard. 6. S1 is, again, the acid blank and should be 0 for all lines.Endyne, Inc. SW 6010B ICP SOP 160 James Brown Drive Revision #5, Effective: 9/29/09 Williston, VT 05495 Page 12 of 18

Document Control Copy on Buff colored paper. Do not duplicate 7. S2-S8 are the line standards as defined in the Standards page and in the positions seen on the sequence page. 8. Immediately following the calibration sta ndards should be the following standards CCV, BLK, and an Interference Check. 9. The instrument is ready to be calibrated. 10. Press the test tube rack icon on the t ool bar or the Run Sequence button on the Sequence page to calibrate the ICP. 11. The results of the CCV, and INT CHK sa mples will give a picture of how the instrument is performing. 12. Individual line calibrations can be viewed from the list of elements on the Method
page. 13. The software automatically accepts lines. 14. A calibration summary can be printed from the Summary page.

R. Load Samples into Autosampler 1. Turn off any unnecessary standards in the QC Automation page. 2. Open the Sequence page.4 3. Enter the Sample Identifications and macros in the appropriate columns. 4. Update the Sequence page. 5. Load the samples into the corresponding racks of the autosampler. 6. Run Samples.

S. Printing from the Results Page 1. Open the Results page. 2. Every analysis day should have an associated Analysis folder. 3. To create a new Analysis folder clic k on Analysis, New and a box will pop up for a name. Use the date (i.e.: 01092006). 4. As samples run they can be viewed on th e Analysis Results page. A Detailed view shows each exposure’s value while the Sta tistics view shows a mean value. The detailed values may be helpful for diagnostics, but the statistical value is generally the one that is reported. 5. The Single and All choices allow the operato r to view a single sample or all of the samples in the open Analysis folder. 6. Results can be printed from here by pressi ng the Print button. This will print out the measured value for every element in the method.

T. Viewing Results from the Scan Page. 1. From the Analysis page select the Scan tab. 2. The Scan screen displays the peak a nd background correction points for selected samples. 2 Select samples by checking the box to the left of the sample ID. 3 Select the line by choosing from the list in the Line drop-down-box.Endyne, Inc. SW 6010B ICP SOP 160 James Brown Drive Revision #5, Effective: 9/29/09 Williston, VT 05495 Page 13 of 18

Document Control Copy on Buff colored paper. Do not duplicate U. Viewing Samples from the Profile Page 1. From the Analysis page select the Profile tab 2. The Profile screen displays the peak shape of selected samples. This is a good way to view “scan” samples. 3. Select samples by checking the box to the left of the sample ID.

V. Viewing Samples on the Calculation Validation Page 1. From the Analysis page select the Calc Validation tab. 2. The Calculation Validation page displays the peak shape with background points as well as the raw numbers and IEC corrections. 3. Select a sample by clicking on the Sample ID.

W. Viewing a sample on the Image Page 1. From the Analysis page select the Image tab. 2. Select an Echelle image from the list of samples that have been run. 3. The Image viewer displays the camera’s exposure. Each point of light is a quantifiable wavelength. 4. The Zoom button allows the viewer to look more closely at a particular region. 5. Clicking on any point in the image will re-center the image on that point. 6. Spectral +/- buttons provide for the opti on of compounding images. Icons for these images will appear at the bottom of the analyzed sample list.

X. Viewing sample data on the Control Chart Page 1. From the Analysis page select the Control Chart tab. 2. Select a series of samples or standards that you would like to chart. 3. Control limits and markers can be added to the chart.

Y. Viewing Samples on the Report Page 1. From the Analysis page select the Report tab. 2. Select those standards and samples that should appear on the report. 3. Select Detailed (shows data for all three exposures) or Statistical (shows the mean). 4. Choose the elements that should appear on the report. 5. Choose the Report fields or Load a saved template. 6. Press the Report button to generate a report. 7. For a CSV file press the CSV file button and it will ask where to save it. 8. Print a hard copy by pressing the print button.

Z. Using the Recalculate page. 1. To recalculate a sample with new calibration data. a. After recalibrating select the desired samples b. Press the recalculate button c. The recalculated data will appear at the bottom of the sample list. 2. To Print a Summary of Calibration Data a. Select a sample or standard from the batch of concern. b. Press the Print button. AA. Shutting Down the InstrumentEndyne, Inc. SW 6010B ICP SOP 160 James Brown Drive Revision #5, Effective: 9/29/09 Williston, VT 05495 Page 14 of 18

Document Control Copy on Buff colored paper. Do not duplicate 1. Pour 25% HNO3 into standard cup 14 and send the sampler there. 2. Allow to flush for 2-3 minutes. 3. Send the Sampler to rinse. 4. Pour DI into standard cup 14 and send the sampler there. 5. Allow to rinse for 2-3 minutes. 6. Send the sampler to rinse and immediately to air. 7. Once all of the tubing is dry press either the extinguish button on the tool bar or the Instrument Control page. 8. Unclamp and release the tension from the tubing. 9. Turn off the Exhaust Fan. 10. Turn off the recirculator. 11. Close the baffle on the Fan Duct. 12. Pour any remaining standards into their appropriate containers. 13. Instrument main power should remain on, with argon flowing, and the software
open.

BB. Method of Standard Additions The Method of Standard Additions allows fo r compensation of chemical interference by using the sample as the diluent for samp les. The sample and two spikes of the sample are used as the standards of the calib ration curve. The sample is used as S1. The first spike should contain twice the e xpected concentration while the second will contain four times the expected sample concentration.

Build a new method for this using the sa mple number as the name of the method followed by SA. The line must be calibrated as linear.

To retrieve results go to the calibration sc reen for each element of interest. The negative of the C value is the concentration of the sample in the same units as the line.

X. Calibration and Standardization A. Each method is calibrated on a daily basis before use. 1. Each line must have a correlation of ≥ 0.995. 2. Analyst should verify correlation values and look at the calculated values for each line in the method.

B. A CCV and BLK must be run before samples are run, every ten samples and after the last sample. 1. All CCV must fall within +/-10% of the target concentration. 2. Blank should be less than 1/10 of the MCL or 1/10 of the lowest reported value.

C. An interference check standard must be run daily

D. The interference check standard verifies the effectiveness of the interferal element correction. 1. Recovery for the interference check must be +/-20%.Endyne, Inc. SW 6010B ICP SOP 160 James Brown Drive Revision #5, Effective: 9/29/09 Williston, VT 05495 Page 15 of 18

Document Control Copy on Buff colored paper. Do not duplicate E. Any data that does not meet the above criteria must be appropriately qualified in the database and on the final report.

XI. Data Reduction:

All data is generated as mg/L (ppm) and can be reported in LIMS as such unless the client requests another unit of measure. If another unit of measure was requested the appropriate conversion should be applied before entering the value into LIMS.

-Soil/sludge values are reported as mg/Kg dry weight. These values are calculated using the following equation:

Conc. From Instrument (mg/L) x Digestion Volume (L) = Sample Conc. Mg/Kg dry wt. (Mass Digested (Kg) x Percent Solid (as a decimal )

XII. Data Recording/Archival:

Workload management report is generated from LIMS which indicates any metals analysis that are in house includes information such as Work Order Nos, Client, Due Date, if it’s a RUSH, the type of digestion or the metals requested.

- Data is entered into Queue List and a copy of the data set is attached . - Queue with data is submitted for QC Review. - A metals digestion log is kept in Excel to record when and how samples are digested - A standards log is kept in Excel to record when new stocks are made up. -An instrument maintenance log is kept in Excel to record any maintenance or routine cleaning that may be done, such as when the water in the recirculator is changed or the pump lines are changed. -Data and spreadsheets are backed up and stored on the Inorg Central computer and a copy is burned onto cd. -Hard copy raw data is kept with Queue list in hanging folders in the in the filing cabinets on the second floor. -All raw data is archived annually in banker boxes and kept for a minimum of 5 years.

XIII. Troubleshooting:

• If the torch sputters and goes out immediately after ignition make sure that the lines are clamped down and the lines are dry form the pump to the torch.

• If the torch sputters and goes out while running a sample, and the argon supply is sufficient, then the sample most likely has too many salts in it and should be run at a dilution.

• If the CCV fails twice then try recalibrating, or position plasma.

• If intensities drop off try the position plasma routine. If they are still low try a different nebulizer.Endyne, Inc. SW 6010B ICP SOP 160 James Brown Drive Revision #5, Effective: 9/29/09 Williston, VT 05495 Page 16 of 18

Document Control Copy on Buff colored paper. Do not duplicate • If you have blanks failing for some metals (i.e. Na, Al) look at the scans to confirm a measurable peak on the blank. The sample uptake or torch may be contaminated.

• If the intensities for all the standards of a given line are about the same and the scans confirm, then the instrument is probably peaked on an argon line for that element. Peak the line.

XIV. Revision History

February 2003 April 2004 October 2004 January 2005 April 2006 New ICP Revision 4, September 2009, Changes to QA section, minor revisions

XV. References

Method 6010B Inductively Coupled Plasma-AtomicEmission Spectrometry. EPA Test Methods for Evaluating Solid Waste Physical/ Chemical Methods, Version 2 . EPA SW 846, December 1997 United States Environmental Protection Agency.

Electronic Code of Federal Regulations, 40 CFR – Chapter 1 – Part 136 – Appendix B. Definition and Procedure for the Determination of the Method Detection Limit - Revision 1.11.

XVI. Method Modifications:Endyne, Inc. SW 6010B ICP SOP 160 James Brown Drive Revision #5, Effective: 9/29/09 Williston, VT 05495 Page 17 of 18

Document Control Copy on Buff colored paper. Do not duplicate Appendix 1: Digestions/Sample Preparation

Metals in Soil/Sludge (EPA Method 3050B): Soils: 1-30 grams (depending on how solid the sample is) of the sample is placed in the digestion cups. Teflon chips are added to the QC’s and Blanks. 2.5 mls of 50% Nitric Acid is added. Sample is digested at 95 o C for 15 minutes. An additional 2.5 mls of Conc. Nitric Acid is added to each sample These samples only require 1hr in the block digester at 95 0 C. However, if they are being digested with other Total metals, they can be left in for 4-6hrs. If this is the case, add 30-40mls of DI to the samples so they won’t dry up. 1 ml of DI and 1.5 mls of 30% Hydrogen Peroxide is then added and the samples are returned to the block digester at 95 0 C until they begin to effervesce. They are allowed to cool and an additional 1 ml of 30% Hydrogen Peroxide is added. They are warmed again until they begin to effervesce and removed to cool. Then they are digested for an hour at 95 o C. 5mls of conc. HCl is added and digested for 1 hour. The samples are then brought back up to 50mls with DI. A 2.0 um Teflon fiber filter is then used to be sure no large particulate matter is present that would block the lines of the ICP (Allowing to settle before filtering works well). Sludges: Sludges are digested just like Soils, except that an initial weight of 20-30 grams of sample is used.

Metals in Air (NIOSH 7300): Make ashing acid IN HOOD WITH ALL PPE - In 200ml Volumetric Flask add 40mls Conc. Perchloric Acid (HClO 4 ) bring to the mark with Conc. Nitric Acid (HNO 3 ) Make Dilution Acid - 50mls Ashing Acid to 600mls DI, dilute to 1L Place Cellulose filters (samples, QC’s, Blanks etc.) in 50ml Digestion cups. 1. Add 5mls Ashing acid, cover with watchglass and let sit for 30min at room temperature. 2. Heat in digestion block at 95 o C until 0.5ml remains. 3. Add 2mls Ashing Acid and repeat step 2 until solution is clear. 4. Remove watchglass and rinse residue into digestion cup with DI. Let heat until 0.5mls or less remains. Digest 3-4 hours max. 5. Bring to 50mls with dilution acid. 6. Separate calibration lines are run using the dilution acid matrix.Endyne, Inc. SW 6010B ICP SOP 160 James Brown Drive Revision #5, Effective: 9/29/09 Williston, VT 05495 Page 18 of 18

Document Control Copy on Buff colored paper. Do not duplicate XVI. SOP Attestation

I acknowledge that I have read this Standard Operating Procedure and agree to adhere to the Safety and Quality Control policies outlined within.



## Name DateElement MethodMDL mg/LReportingLimit mg/LIndependentLFBAccuracyLimit %PrecisionLimit %Element MethodMDLmg/KgReportingLimitmg/kgIndependentLFBAccuracyLimit %DuplicatePrecisionLimit %Aluminum EPA 200.70.01995 0.050+/- 10.0 20.0 Aluminum EPA 6010B0.617 2.5+/- 10.0 20.0Antimony SM 3113B 0.00044 0.002 +/- 10.0 20.0 Antimony EPA 6010B 0.296 1.00 +/- 10.0 20.0Arsenic SM 3113B 0.00014 0.002 +/- 10.0 20.0 Arsenic EPA 6010B 0.007 1.00 +/- 10.0 20.0Barium EPA 200.7 0.00036 0.020 +/- 10.0 20.0 Barium EPA 6010B 0.0084 1.00 +/- 10.0 20.0Beryllium EPA 200.7 0.00022 0.001 +/- 10.0 20.0 Beryllium EPA 6010B 0.0059 0.50 +/- 10.0 20.0Boron EPA 200.7 0.01162 0.05 +/- 10.0 20.0 Boron EPA 6010B 1.09 2.50 +/- 10.0 20.0Cadmium EPA 200.7 0.00042 0.002 +/- 10.0 20.0 Cadmium EPA 6010B 0.022 0.50 +/- 10.0 20.0Calcium EPA 200.7 0.00523 0.100 +/- 10.0 20.0 Calcium EPA 6010B 1.620 5.00 +/- 10.0 20.0Chromium EPA 200.7 0.00044 0.005 +/- 10.0 20.0 Chromium EPA 6010B 0.033 0.50 +/- 10.0 20.0Chromium +6 EPA 7196A 0.01100 0.05 +/- 20 20.0 Chromium +6 EPA 7196A 1.083 5.00 +/- 20 20.0Cobalt EPA 200.7 0.00083 0.020 +/- 10.0 20.0 Cobalt EPA 6010B 0.035 1.00 +/- 10.0 20.0Copper EPA 200.7 0.0002 0.020 +/- 10.0 20.0 Copper EPA 6010B 0.484 1.00 +/- 10.0 20.0Iron EPA 200.7 0.00504 0.020 +/- 10.0 20.0 Iron EPA 6010B 1.31 5.00 +/- 10.0 20.0Lead SM 3113B 0.00037 0.001 +/- 10.0 20.0 Lead EPA 6010B 0.151 1.00 +/- 10.0 20.0Magnesium EPA 200.7 0.0341 0.050 +/- 10.0 20.0 Magnesium EPA 6010B 0.162 2.50 +/- 10.0 20.0Manganese EPA 200.7 0.000888 0.020 +/- 10.0 20.0 Manganese EPA 6010B 0.023 1.00 +/- 10.0 20.0Mercury EPA 245.1 0.00003 0.001 +/- 10.0 20.0 Mercury EPA 7471A 0.0004 0.050 +/- 10.0 20.0Nickel EPA 200.7 0.00054 0.005 +/- 10.0 20.0 Nickel EPA 6010B 0.037 1.00 +/- 10.0 20.0Potassium EPA 200.7 0.00256 0.100 +/- 10.0 20.0 Potassium EPA 6010B 4.98 10.0 +/- 10.0 20.0Selenium SM 3113B 0.00033 0.005 +/- 10.0 20.0 Selenium EPA 7740 0.0168 0.250 +/- 10.0 20.0Silver EPA 200.7 0.0028 0.020 +/- 10.0 20.0 Silver EPA 6010B 0.053 1.00 +/- 10.0 20.0Sodium EPA 200.7 0.0427 0.050 +/- 10.0 20.0 Sodium EPA 6010B 1.250 5.00 +/- 10.0 20.0Thallium SM 3113B 0.00023 0.001 +/- 10.0 20.0 Thallium EPA 6010B 0.249 2.50 +/- 10.0 20.0Vanadium EPA 200.7 0.000639 0.020 +/- 10.0 20.0 Vanadium EPA 6010B 0.0216 1.00 +/- 10.0 20.0Zinc EPA 200.7 0.0032 0.005 +/- 10.0 20.0 Zinc EPA 6010B 0.060 1.00 +/- 10.0 20.0Calculated values are based on a standard digestion mass and a 100% dry sample.2010 Quality Control RCRA 8/ PRIORITYPOLLUTANT 13 METALS in Water2010 Quality Control for RCRA 8/ PRIORITYPOLLUTANT 13 METALS in SoilEndyne, Inc.160 James Brown DriveWilliston, VermontPage 1 of 1Document Control Copy on Buff colored paper. Any other color is not official version 

# Endyne, Inc.

160 James Brown Dr.

Williston, VT 05495 Phone: (802) 879-4333 Fax: (802) 879-7103



# VOLATILE ORGANIC COMPOUNDS Method EPA 8260/8260B 

# Standard Operating Procedure

REVISED: September 26, 2007

Revision #: 10

Technical Director: Date : Harry B. Locker Ph.D.


### QA Officer: Date :
Mark L. FauselEndyne, Inc. VOC Method EPA 8260/8260B SOP 160 James Brown Drive Revision #10, Effective 09/26/07 Williston, VT 05495 Page 2 of 21

Document Control Copy on Buff colored paper. Any other color is not official version TABLE OF CONTENTS

Section Page

I – Overview 3

II – Safety 4

III – Waste Disposal 4

IV – Sample Collection, Preservation & Storage 4

V – Equipment & Supplies 5

VI – Reagents 5

VII – Interferences 5-6

VIII – Quality Control 6-9

IX – Procedure 9-11

X – Calibration and Standardization 11-12

XI – Data Reduction 12-13

XII – Data Recording 14-15

XIII – Instrument Maintenance/Trouble Shooting 16

XIV – Method Modifications 16

XV – Bibliography/Reference 17

XVI – Revision History 17

Table 1-BFB Mass Intensity Criteria 18

Appendix A-Soil Sample Preservation with Methanol 19

Table 2 - Reporting limits 20

I. Overview:Endyne, Inc. VOC Method EPA 8260/8260B SOP 160 James Brown Drive Revision #10, Effective 09/26/07 Williston, VT 05495 Page 3 of 21

Document Control Copy on Buff colored paper. Any other color is not official version -Method 8260B is used to determine volatile organic compounds (VOCs) in a variety of waste matrices, including waters, soils, sludg es, waste solvents and petroleum wastes. Samples are purged with an inert gas (N 2 ). Analytes are captured on a packed sorbent trap, then back flushed with a stream of Helium into a capillary GC Column interfaced to a mass spectrometer.

-The following compounds are determined by this method: Dichlorodifluoromethane Chloromethane 2-Hexanone Vinyl Chloride 1,3-Dichloropropane Bromomethane Tetrachloroethene Chloroethane Dibromochloromethane Trichlorofluoromethane 1,2-Dibromoethane Diethyl Ether Chlorobenzene Acetone 1,1,1,2-Tetrachloroethane 1,1-Dichloroethene Ethylbenzene Methylene Chloride m/p-Xylene Carbon Disulfide o-Xylene Methyl-t-butylether (MTBE) Styrene trans-1,2-Dichloroethene Bromoform 1,1-Dichloroethane Isopropylbenzene 2-Butanone 1,1,2,2-Tetrachloroethane 2,2-Dichloropropane 1,2,3-Trichloropropane cis-1,2-Dichloroethene n-Propylbenzene Chloroform Bromobenzene Bromochloromethane 1,3,5-Trimethylbenzene Tetrahydrofuran (THF) 2-Chlorotoluene 1,1,1-Trichloroethane 4-Chlorotoluene 1,1-Dichloropropene tert-Butylbenzene Carbon Tetrachloride 1,2,4-Trimethylbenzene 1,2-Dichloroethane sec-Butylbenzene Benzene p-Isopropyltoluene Trichloroethene 1,3-Dichlorobenzene 1,2-Dichloropropane 1,4-Dichlorobenzene Dichlorobromomethane n-Butylbenzene Dibromomethane 1,2-Dichlorobenzene 4-Methyl-2-pentanone 1,2-Dibromo-3-chloropropane cis-1,3-Dichloropropene 1,2,4-Trichlorobenzene Toluene Hexachlorobutadiene trans-1,3-Dichloropropene Naphthalene 1,1,2-Trichloroethane 1,2,3-Trichlorobenzene Isopropyl Alcohol Methyl isothiocyanate (MITC) ETBE Isopropyl ether TAME t-Butanol Acrylonitrile AcroleinEndyne, Inc. VOC Method EPA 8260/8260B SOP 160 James Brown Drive Revision #10, Effective 09/26/07 Williston, VT 05495 Page 4 of 21

Document Control Copy on Buff colored paper. Any other color is not official version II. Safety:

This method involves the handling of the chemicals outlined below. Each of these chemicals may have specific associated hazards. Analysts must read and become familiar with all elements of each chemical’s MSDS. Make special awareness of the symptoms of exposure and potential routes of entry. Analysts must notify the Safety Officer immediately if any symptoms of exposure are suspected.

PPE must be worn at all times in designated work areas. All applicable engineering controls, such as fume hoods or splash shields, must be used when performing analyses. To ensure the safety of all laboratory personnel; work areas must be kept neat and organized, equipment and bench-tops must be cleaned and sterilized, if necessary, at the completion of each task, all containers must be properly labeled as to contents and hazard ratings and spills cleaned immediately and completely. A. Lab coats, nitrile gloves and protective ey eglasses are to be worn at all times during analysis by this method and when handling any laboratory sample. B. A thorough MSDS review of Hydrochloric Acid, Methanol, Ascorbic Acid, Sodium Thiosulfate and all laboratory calibration standards should be performed prior to analysis by this method. C. All standards should be made in a fume hood away from heat sources. D. Several analytes tested by this method have been classified as human carcinogens. Stock standards of these materials should be handled in fume hoods with appropriate personal protective equipment.

III. Waste Disposal:

A. Expired standards, QCs and misc. solvents are disposed of in the flammable liquids drum in the hazardous waste room. B. Non-contaminated (“non-hot”) samples can be dumped down the drain with a stream of running water. C. Contaminated (“Hot”) samples are disposed of in the corrosive liquids drum in the hazardous waste room. D. Soil samples are disposed of in the soil waste drum in the hazardous waste room.

IV. Sample Collection, Preservation and Storage:

A. Sample holding time is 14 days from the sample time. B. All liquid samples should be sampled in duplicate, pH adjusted to < 2 with HCl and stored at 4 ° C with no headspace. C. All soil samples should be sampled in duplicate and stored at 4 ° C with no headspace. D. Refer to Appendix A for MeOH preservation sample collection (if samples are methanol preserved in the field). E. Air Samples collected in tedlar bags should be analyzed within 8 hours of sampling

V. Equipment and Supplies:Endyne, Inc. VOC Method EPA 8260/8260B SOP 160 James Brown Drive Revision #10, Effective 09/26/07 Williston, VT 05495 Page 5 of 21

Document Control Copy on Buff colored paper. Any other color is not official version -GC: Hewlett Packard 5890 Split/Splitless option with EPC -MS: Hewlett Packard 5971 Series -Miscellaneous Syringes & Vials -Analytical Balance -OI Analytical 4560 sample concentrator with MPM 16 -OI Analytical 4560 sample concentrator with DMP 16 -Injection port liners, 2mm (Supelco P/N 2-0513,01 or equivalent) -Purge Trap (Supelco P/N 2-4938 or equivalent) -Capillary column-60m, 0.32mm ID, 1.8um df (Restek P/N 10972 or equivalent) -Glass vials, 20ml and 40ml with PFTE lined screw cap

VI. Reagents:

-Reagent Grade DI Water (Organic-free) -Methanol (Purge & Trap Grade or Better) -Volatile Mix Standard (NSI Q2479 Custom Volatiles Mix - 200 ppm) -Volatile Mix Standards (AccuStandard #’s M-502A-r, M-8260-ADD-10x, M-502B, S-457S-10X, S-078-10X) -Internal Standard Mix (AccuStandard M-8260-IS 200 ppm) -Surrogate Standard Mix (AccuStandard M-8260-SS 200ppm) -Hydrochloric Acid diluted to 1:1 v/v with DI water. -Ultra high purity Helium -Ultra High purity Nitrogen -2-Chloroethylvinylether Standard (AccuStandard M-601C-10X 2000ppm) -Oxygenated Gas Additive Standard (AccuStandard OGAD-001 2000ppm) -Priority Pollutant Standards (Acrylonitrile APP-9-008; Acrolein APP-9-007 100ppm) -Misc. neat standards (Isopropanol – Fisher Sci; MITC – Sigma Aldrich)

Note: Standards in Italic font are refere nced as a convenience for analysts reordering analytical standards. The use of these sta ndards is subject to change based on several variables including manufacture pricing and various analytical needs. All standards used by this method shall be referenced in th e Volatile Standards Log, including manufacture information, lot numbers, expiration dates a nd date of use. These standards shall be traceable back to the manufacture certificate of analysis. Calibration and independent source standards should be from different lot numbers and when possible different manufactures.

VII. Interferences:

A. Special precaution must by taken to isolate samples from all atmosphere Methylene Chloride contamination. MeCl 2 will permeate through PTFE tubing. It is readily carried on clothing exposed to fumes during common liquid/liquid extractions creating random background levels. B. Interfering contamination may occur when a sample containing low concentration of VOCs is analyzed immediately after samples containing high concentrations of VOCs. Late eluting analytes tend to “carry over” in greater abundance than early eluting analytes.Endyne, Inc. VOC Method EPA 8260/8260B SOP 160 James Brown Drive Revision #10, Effective 09/26/07 Williston, VT 05495 Page 6 of 21

Document Control Copy on Buff colored paper. Any other color is not official version C. Trace levels of Ketones, Methylene Chlori de, Chloroform and other organic solvents can be present in high purity methanol. Analysis of each new lot of methanol should be performed prior to use. D. Impurities from purge and carrier gas can be minimized with gas traps. E. Trihalomethanes may occur in blanks as traps from the DI water system age. Replace traps as needed.

VIII. Quality Control:

A. Initial demonstration of capability (DOC) is performed by analysts training under the supervision of individuals familiar with interpreting GC/MS data. DOCs will be updated annually thereafter and at any time th ere is a change in instrument type, personnel or test method. Continuing DOC studies are stored in analyst personnel files and filed with the VOC QA/QC data. Electronic copies of current DOCs are located at the VOC workstation. 1. Four replicate aliquots of mid-calibration reference standards are analyzed by the procedure outlines in section IX 2. Calculate the average recovery, the standard deviation and the % standard deviation of the recoveries for each analyte of interest. 3. Results of DOC are compared to laboratory control charts to see if acceptance criteria are met. In the absence of laboratory acceptance criteria recoveries of 70- 130% can be used as guidance in evaluating the results. 4. If any % standard deviation fails precision limits of 20% or any mean fails accuracy limits (+/-30% or control limit va lue, whichever is lower), the source of the problem must be found and corrected. Analytes that failed must be reanalyzed and acceptance criteria must be met.

B. Method detection limits (MDL) study is performed annually on each operating system to determine acceptable detection limits. Current MDL studies are stored with the VOC QA/QC data. Electronic copies of current MDLs are located at the VOC workstation. 1. Seven reference standards at 2.5 times the minimum reporting limit are analyzed according to the procedure outlines in section IX 2. Determine the standard deviation of each compound. Multiply the standard deviation by 3.14 to determine the MDL value. 3. The calculated MDL value must be 2.5 – 5 times less than the target of the reference standards or the MDL is reanalyzed. 4. The calculated MDL value must be lower than reporting limits outlined in Tbl.2

C. Method Reporting Limit (quan titation limit) determination 1. Laboratory quantitation limit is established by the concentration of the lowest standard analyzed during the initial ca libration, which exceeds the calculated MDL value for that analyte. 2. Reporting limits can be increased for analytes with poor purge efficiencies, analytes frequently present in the laboratory atmosphere, or analytes which tend to carry over from one run to the next. The increased reporting limits must be in compliance with regulatory limits, acti on limits, client permit requirements, NELAC and the State of Vermont.Endyne, Inc. VOC Method EPA 8260/8260B SOP 160 James Brown Drive Revision #10, Effective 09/26/07 Williston, VT 05495 Page 7 of 21

Document Control Copy on Buff colored paper. Any other color is not official version D. 4-Bromofluorobenzene analysis (BFB)- 50ng of BFB is introduced to the MSD at the beginning of each data set by direct injec tion or standard purge and every 12 hours of sample analytical time. The mass intensities are then compared to the tune criteria listed in Table 1. 1. If all tune criteria is not met, system maintenance and reanalysis of the BFB are required until system performance is acceptable. 2. A maximum of 50ng of BFB is analyzed at the start of each data set. 3. Continuous monitoring of BFB tune criteria may be observed with each sample analyzed as BFB is use as a method surrogate.

E. A Line check (calibration) standard is analyzed, following the BFB analysis, and with every 12-hour analytical batch. 1. Analyte recovery from the line check sta ndard must be within +/- 25% of the target. System maintenance and reanalys is of standards is required prior to sample analysis if recovery criteria are not met. All data is qualified if recoveries are outside acceptance range. 2. System performance check compounds (SP CC) are calculated daily from the line check standard. Minimum acceptable average RFs should be > 0.100 for chloromethane, 1,1-dichloroethane and Bromoform. Minimum acceptable average RF should be > 0.300 for Chlorobenzene and 1,1,1,2-Tetrachloroethane. See calibration and standardization section for RF calculation 3. Calibration check compounds (CCC) are calculated daily from the line check standard. The RF % difference for 1,1 Dichloroethene, Chloroform, 1,2- Dichloropropane, Toluene, Ethylbenzene and Vinylchloride should be < 20% of the initial calibration. % Difference = (RF of Initial Cal-RF of Current Check std) x 100 RF of Initial Cal F. An Independent fortified blank is anal yzed, following the continuing calibration analysis, and with every 12-hour analytical batch. 1. Independent fortified standards are tabulated prior to sample analysis. Percent recoveries should fall within acceptable limits tabulated in the method control charts. System maintenance and reanalysis of standards is required prior to sample analysis if recovery criteria are not met. All data is qualified if recoveries are outside-tabulated acceptance ranges. 2. Control charts are tabulated annually from the percent recoveries of the independent fortified standards. Upper and lower warning limits are ± 2 standard deviations of the mean. Upper and lower control limits are ± 3 standard deviations of the mean. Control limits are posted and stored electronically at the VOC workstation. 3. Analysts should periodically review rec overy trends with graphic printouts of compound recoveries to avoid instrument bias.

G. A method blank is analyzed, following the Independent fortified blank, and with every 12-hour analytical batch. 1. Additionally, a blank should be used to check for contamination by carryover from a high-concentration sample into subsequent samples when practical. 2. Blank results should be less than 5% of the regulatory limit associated with an analyte or less than 5% of the sample result for the same analyte, whichever is greater.Endyne, Inc. VOC Method EPA 8260/8260B SOP 160 James Brown Drive Revision #10, Effective 09/26/07 Williston, VT 05495 Page 8 of 21

Document Control Copy on Buff colored paper. Any other color is not official version 3. If blank criteria are not met, corrective action to locate and reduce the source of contamination is taken and reanalysis of samples associated with the contaminated blank is required. Data is qualified if blank criteria are not met.

H. Calibration line quality control 1. The relative standard deviation (RSD) of the initial calibration should be less than 15% for each analyte. Reanalysis of calibration standards and acceptable RSD levels must attained prior to sample analysis. 2. As an alternative to calculating mean r esponse and applying the RSD test to the initial calibration, a linear or second order regression calibration curve is acceptable. Correlation coefficient (r) acceptance of > 0.990 is required. All changes to the calibration are documente d and control standard requirements must be met. It should not be the intention of the analyst to use alternate line calculation equations to supercede good instrument performance and maintenance practices.

I. Instrument and software performance 1. Good column and GC performance should produce symmetrical peaks. 2. Software should recognize and integrate 99% of compounds analyzed or instrument maintenance is required. 3. Entire symmetrical peak for each analyte must elute in the retention time window established in the initial calibration. Instrument maintenance is require if analytes fall outside retention time windows

J. Matrix spike and matrix spike dupli cate (MS/MSD) samples are analyzed every 20 samples. 1. Percent recoveries should fall within accep table limits tabulated annually in the method control charts. Data is qualifie d if recoveries are outside tabulated acceptance ranges. 2. MS/MSD Precision is measured from the relative percent difference (RPD) of the concentrations measured for MS/MSD pairs. Acceptance limits are tabulated annually in the method control charts. The RPD upper control limit, recommended by NELAC, is defined as 3.27 times the average RPD of minimum 30 data points.

K. Internal Standards (IS) are Chlor obenzene-d5, 1,4-Dichlorobenzene-d4, Pentafluorobenzene, and 1,4-Difluoroben zene. 10uL of a 25 ppm (target=50ppb) IS solution is added to each 5ml sample and standard analyzed. 1. IS area counts of the continuing calibration standard, analyzed with each analytical batch, are compared to th e initial calibration IS area counts with an acceptance range of a factor of 2 (-50 to +100% recovery). 2. IS area counts of the samples and standards analyzed in each analytical batch are compared to the IS area counts of the continuing calibration of that batch with an acceptance range of a factor of 2(-50 to +100%).

L. Surrogates are 4-Bromofluorobenzene, Dibromofluoromethane, and Toluene-d8. 10uL of a 25 ppm (target=50ppb) surrogate solution is added to each 5ml sample and standard analyzed.Endyne, Inc. VOC Method EPA 8260/8260B SOP 160 James Brown Drive Revision #10, Effective 09/26/07 Williston, VT 05495 Page 9 of 21

Document Control Copy on Buff colored paper. Any other color is not official version 1. Surrogate percent recoveries should fall within acceptable limits tabulated annually in the method control charts. Da ta is qualified if recoveries are outside tabulated acceptance range.

M. If the above mentioned quality control el ements are outside laboratory acceptance limits, corrective action must be taken. Refer to the SOP troubleshooting section, instrument maintenance logs and manuf acturer operating manuals. If corrective action is not possible due to hold times or limited sample volume, the data must be qualified in the final report as not acceptable.

IX Procedure

A. Instrument Operating Conditions 1. 5971 GC/MS suggested operating paramete rs could be modified as instrument conditions change over time. Purge time of 11 min. and desorb time of 4 ins. are defined by the method and must remain c onstant. MS tune parameters used to acquire the BFB tune at time of initial calibration must be carried forward on all subsequent standards and sample analysis. a. Trap: VOCARB 3000 or 4000 Supelco b. Column: 60m; 0.32mm ID; 1.8um dF Restek (RTX-624)

c. Constant flow inlet B ON 9.0 PSI (He) d. Purge Flow (N2); 20-25mls/min e. Source vacuum; 5.3 x 10-5 Torr. (Approximate) f. Purge time 11 min; desorb time 4 min; bake time 12 min g. Acquisition parameters save in method aq-8260.m are as follows: -Sample Inlet: B 200C – Detector B: 280C -Pressure 7.00 – Velocity 29.0ml/min -Tune file “BFB.U”- -Mass Scan 42-260AMU -Split Ratio 10:1 -Initial Set points – valves 3and 4 are on, all others valves and relays off -Initial Temp: 45C; ms on at 1.5 min -Gradient is 8.0 c/min to final temp of 210 – hold final time 1.0min

B. 50ng BFB direct injection: performed at the beginning of each analytical set and every 12 hours of analysis. BFB introduction to the MS detector by purge and trap is acceptable following the sequence procedure outlined in section C of the procedure section. 1. Activate the MS Top Software 2. Select “Sequent-Edit sample log table” 3. Enter data file: date/year/cycle # 4. Enter current acquisition method 5. Enter sample information (example: “50ng BFB” )and press “ok” 6. Select “sequence-run”, enter “full method” 7. Data file directory (example“c:\hpchem\1\data\feb03”), press “ok” 8. When temperatures on GC oven equilibrate a “start” message will appear on the acquisition computer. Inject 2 μ L of 25ppm 8260 IS/SURR mix. 9. Press start on GC ovenEndyne, Inc. VOC Method EPA 8260/8260B SOP 160 James Brown Drive Revision #10, Effective 09/26/07 Williston, VT 05495 Page 10 of 21

Document Control Copy on Buff colored paper. Any other color is not official version 10. Confirm BFB spectral scan and ion abundance criteria are calculated, plotted and printed. Reanalysis of BFB and instrument maintenance must be performed if any abundance criteria are not met.

C. Sequence Set Up 1. Enter and save sample information in GC/MS daily run log stored at the VOS workstation. Include date, tube number, file name, reference number, reference number suffix, sample preservation, client, project, site dilutions and miscellaneous notes. For soil analysis includes injection volume, sample mass and extraction volume. 2. Load samples at appropriate dilutions on MPM 16 and DPM 16 3. Press “SPL” on sample concentrator and enter range of tubes to be analyzed. Press “start”. 4. When sample concentrator indicates “DSB-RDY” activate ms top software 5. Program sequence-enter data file nam es to be analyzed, acquisition method is “AQ-8260” on the 5971 workstation. 6. At sample info section enter laboratory reference number, dilution and miscellaneous sample information then press “ok” 7. Select “sequence-run”, enter “full method” 8. Data is saved to the server at “s:\ appropriate subdirectory ”, press “ok”, sequence will start automatically when temperatures equilibrate.

D. Aqueous sample preparation/introduction. 1. Samples and standard solutions are allowe d to warm to room temperature before analysis. Insure sample containers have no headspace. 2. Calibration verification and instrument performance criteria are met prior to sample analysis. 3. Pour sample to the top of the barrel of a 5ml-gas tight lure-lock syringe. Attach the plunger and adjust the sample volume to 5mls. Add 10uL of 25ppm IS/Surr mix to each 5mls of sample, QC, Line Check Blank and spike prior to loading purge and trap. 4. If there is only one VOA vial for the sample, transfer the remaining sample to a 20ml VOA vial, sealed with zero headspace and stored until the analyst has determined the first sample has been analyzed properly. 5. Attach the 5ml lure-lock syringe to the syringe valve on the purge device. Open the valves and inject the sample to the purging chamber. Close the valve and follow the procedure outlined in section IX.C. to purge the sample for 11mins. 6. Sample desorption to the GC is for 4min. at 180 degree C, followed by the trap bake, which should not exceed 210 degrees C. 7. Dilutions are performed when compound concentration exceeds analytical calibration range using volumetric flasks or syringes (class A). 8. Process the sample file through the current calibration method in the MS ChemStation software after all quality control criteria have been met. Check the integration of each peak to be quantitated upon.

E. Soil and Solid waste sample preparation/introduction. 1. Appendix A outlines the collection of soil samples in the field using methanol as the sample preservation and extraction solvent. 2. Soil/Sludge in house extractionEndyne, Inc. VOC Method EPA 8260/8260B SOP 160 James Brown Drive Revision #10, Effective 09/26/07 Williston, VT 05495 Page 11 of 21

Document Control Copy on Buff colored paper. Any other color is not official version a. Weigh approximately 10g of soil on an analytical balance into a 40ml vial. Steps to insure a homogeneous sample from the container should be taken. Whenever practical, mix the contents of the sample container by shaking without opening the vial. When shaking is not practical, quickly mix the sample container contents with a narrow metal spatula prior to removing sample fraction to be analyzed. b. Add 5ml purge and trap grade methanol.

c. Shake samples gently for 2min and a llow samples to settle in the dark, refrigerated for 24 hours. d. Analyze a fraction of the methanol extract in 5mls DI water following the procedure outlined in section IX. D.

F. Tedlar bag air sample preparation/introduction. 1. Tedlar bags are analyzed at first available opportunity.

a. With gas tight syringe, extract no more than 100cc sample b. When auto-sampler cycles to purge on a clean tube, open sample valve and introduce sample at approximately 20mls /min.

c. Process results and associated QA/QC via external standard method of most recent calibration

X. Calibration and Standardization (make/use/storage):

A. Prepare a 10 ppm Working Standard in methanol containing all 8260 analytes: -50 μ L 200 ppm NSIQ2479 Custom VOC mix (or equivalent standard) -5 μ L 2000 ppm Accustandard M-601C-10x (or equivalent standard) -945 μ L Purge and Trap Methanol -Store at < 0C in organic standard freezer

B. Prepare a 25 ppm Internal Standard/Surrogate Solution: -500 μ L 200 ppm M-8260-IS IS Mix (or equivalent standard) -500 μ L 200 ppm M-8260-SS Surr Mix (or equivalent standard) -3000 μ L Purge and Trap MeOH. -Store at < 0C in organic standard freezer

C. Analyze a series of calibration standards. The following concentrations historically bracket a wide range of contamination observed in environmental samples with good instrument performance. However, the an alyst has the discretion to change initial calibration point concentrations based on current instrument performance, reporting limit requirements or other analytical needs. Analyze a 1.0ppb, 2.0ppb, 5.0ppb, 10ppb, 20ppb, 50ppb, 100ppb, 150ppb and 200ppb standard following the steps outlined in section IX.C. The initial calibration must have a minimum of 5 points with an RSD of < 15%, the low calibration standard should be at or below the laboratory reporting limit and the range of standards should bracket all reported analytes. Sample dilution is required when reported analytes exceed the analytical calibration range.

1. Good GC and column performance will produce symmetrical peaks with minimal tailing. 2. The GC/MS software should recognize a GC peak in the appropriate retention time window. If fewer than 99% of the compounds are recognized, system maintenance is required.Endyne, Inc. VOC Method EPA 8260/8260B SOP 160 James Brown Drive Revision #10, Effective 09/26/07 Williston, VT 05495 Page 12 of 21

Document Control Copy on Buff colored paper. Any other color is not official version 3. The Chemstation software will calculate the response factor for each analyte, surrogate and isomer pair as follows. RF = A x Q is A is Q x

A x = Quantitation Ion Abundance of the Analyte A is = Quantitation Ion Abundance of the Internal Standard Q x = Quantity of Analyte Purged Q is = Quantity of Internal Standard RF = Response factor 4. The mean RF from the analysis is calculated. 5. The standard deviation and relativ e standard deviation (RSD) from each mean are calculated: RSD = 100*(SD/M). If the RSD exceeds 15% reanalyze additional aliquots of calibration solution to obtain an acceptable RSD. Perform instrument maintenance as needed if reanalysis of standards does not provide an acceptable RSD.

D. Evaluation of Retention Times 1. The relative retention time of each target analyte should agree within 0.06 RRT units

E. Peak Integration 1. Peak integration should be consistent for all analytes. Refer to laboratory integration SOP for detailed protocol. 2. Single peaks, the integration should begin at the start of the upward slope of the peak and end at the bottom of the downward slope. 3. If there is a raised baseline, the analyst should be careful to not integrate the raised baseline as part of the area of the target peak. 4. In the instance of co-elution isomer pairs, the baseline should start at the beginning of the upward slope of the peak and remain level until the slope of the valley of the two peaks is at its lowest level. If the target peak is the second of a co-eluting pair, the baseline should be drawn backwards to the same level. The valley of the co-eluting pair should be less than 25% of the sum of the two peak heights or the pair is reported as a total.

XI. Data Reduction and Interpretation:

A. Chemstation software calculates analyte and surrogate concentrations in water samples as follows:

Cx = [(Ax) (Qis) 1000 ÷ (Ais) (RF) (V)] V = Volume water in mls RF = Response factor from initial calibration C x = Concentration in μ g/L A x = Integrated Abundance of the quantitation ion of the Analyte A is = Integrated Abundance of the quantitation ion of the Internal Standard Q is = Quantity of Internal Standard added to the sampleEndyne, Inc. VOC Method EPA 8260/8260B SOP 160 James Brown Drive Revision #10, Effective 09/26/07 Williston, VT 05495 Page 13 of 21

Document Control Copy on Buff colored paper. Any other color is not official version B. Analyte concentration in soil samples:

Cs = C x x 5 x V E +((M*(1-P))*1000) M x P V I

Where: C s = analyte concentration as μ g/kg, dry C x = analyte concentration from instrument expressed as ng/ml M = sample mass in grams P = percent solid expressed as a decimal extraction V E = extraction volume in μ L V I = Injection volume in μ L

C. Qualitative Analysis-Compound identification is determined by satisfying two criteria. 1. Elution of sample compound at the same GC relative retention time as the standard analyte ± 0.06 RRT units. 2. Comparison of sample and standard mass spectrum.

a. All ions greater than 10% of the primary ion in the standard must be present in the sample spectrum. b. Relative intensities of secondary ions must agree within + or - 30%.

c. Identification of compounds not in the calibrated standard is determined by comparing to library mass spectra

D. Percent Recovery of compounds in the continuing calibration standard, matrix spike, matrix spike duplicate and independent laboratory fortified blank are calculated as follows: % Recovery = Measured Value * 100 Target Value

E. The relative percent deviation (RPD) between the recovery (REC) from the matrix spike (MS) and matrix spike duplicate (MSD) is calculated as follows:

RPD = ABS(MSREC-MSDREC) *100 ((MSREC+MSDREC)/2)Endyne, Inc. VOC Method EPA 8260/8260B SOP 160 James Brown Drive Revision #10, Effective 09/26/07 Williston, VT 05495 Page 14 of 21

Document Control Copy on Buff colored paper. Any other color is not official version XII. Data Recording: A. Sample data is electronically imported to the LIMS from the VOC/GCMS computer after it has been reduced to a usable format. Current data reduction MACRO is LIMSMAC.XLM stored at c:\EXCELFILES\REPORTS. on the VOC/GCMS computer. B. Record any Instrument Maintenance in the maintenance log for the PT/GC/MS C. All standards opened and made are reported in the VOC standards log D. Individual calibration standard and associated QC dilutions are recorded in the daily run log. E. Sample pH is measured using pH stri ps and recorded in the daily run log. F. Analysts initial and date each sample chromatogram. The analyst will initial each data sheet associated with that chromatogram. Sample chromatograms and data sheets are filed sequentially with other organic chromatograms and stored for a minimum of 3 years. G. All QC, line check, blank data, MS, MSD and BFB Tune Criteria is printed and stored sequentially by date with the VOC/GCMS QC Data and is stored for a minimum of 5 years. H. Individual QC data is entered to 8260 QC Spread Sheets to determine if acceptable QA/QC Criteria has been attained prior to reporting each analytical batch. Data is stored on VOC/GCMS computer (c:\EXCELQC\QC\CONTROL) and is tabulated and printed annually. I. Sample data is entered to LIMS w ith Analyst ID, Date, Units and analyte concentration. J. A hard copy of all quality control da ta is stored with the PT/GCMS data K. Computer hard drive is backed up quarterly to a CD. This includes run log, QC charts, and sample data, line standards, me thods and QC standards. Sample data acquired to the server is backed up daily. L. Method hard copies are printed and stored with the PT/GCMS QC hard copies. N. QC summary data packages are prep ared for each analytical batch daily and incorporate the following criteria. 1. Instrument run log-Includes date, time, analyst initials, auto-sampler tube #, sample data file names, Reference #, container ID, Client, project, site ID, dilutions, sample preservation verification, standard ID, Standard date reference to standards log, standard dilution/prep., and Misc. notes 2. BFB tune spectra results. 3. GC/MS QA-QC Check Report – Documents Sample/Standard IS area compared to the continuing calibration standard. Documents sample/standard analysis within 12 hour BFB window. Performed as follows:

a. Load continuing calibration standard in software. Select pull down window “ConCal” select “Save continuing ISDT response” b. Select pulldown “ConCal”, Select “QA check report”

c. Name Data file unique to data set d. Enter BFB Tune File for data set

e. Highlight samples/standards analyzed with data set and select for processing. Press “process” key and print the tabulated summary f. IS areas outside acceptance range (-50% to +100%) are flagged with “*”. Files analyzed outside the 12 hour BFB are flagged “t”. 4. Continuing calibration (CC) raw data results with “Evaluate Continuing Calibration Report” are printed. This re port shows the comparison of the average of the RRF from the initial calibration versus the RRF from the continuingEndyne, Inc. VOC Method EPA 8260/8260B SOP 160 James Brown Drive Revision #10, Effective 09/26/07 Williston, VT 05495 Page 15 of 21

Document Control Copy on Buff colored paper. Any other color is not official version calibration level. To print this report, lo ad the CC file in the software, select pull down “ConCal”, select “Evaluate data file as continuing cal to printer”. Information is summarized as follows:

a. AvgRRF displays the average RF of all calibration levels of the initial calibration. b. CCRRF is the calculated RF for the CC data file. SPCC compounds are verified here. (see section VIII. E. 2. For acceptance limits.

c. %Dev. is the absolute value of th e percentage difference between the AvgRRF and the CCRRF - %DEV=(AvgRRF-CCRRF)/AvgRRF*100 CCC compounds are verified here. Target compound recoveries are verified here (+/- 25%). d. Area % - The integrated area of the quantitation ion of the CC file is compared with the same ion in the initial calibration at the same concentration. CC IS area vs. the initia l calibration is verified here (-50 to +200%) - %AREA = (Ccarea/INITarea)*100 5. Laboratory fortified Ind. Standard, Blank ra w data is printed. Percent recoveries are compared to laboratory control charts for acceptance limits. 6. Method blank raw data is printed and system contamination is evaluated as outlined in section VIII.G. 7. Matrix Spike and Matrix Spike Duplicat e (MS/D) raw data is printed with a MS/D report which summarizes analysis reproducibility and aids in the determination of matrix interference. Generate report from software “tools” pull down, select “MS/D recovery report” and follow software prompts. Report summary is as follows:

a. Sample Conc – Indicates the concentration of analyte in the unknown sample. b. Spike Added – Concentration of compound added to unknown sample

c. Spike Res - The concentration of the MS compound in the MS sample d. Dup Res - The concentration of the MS compound in the MS/D sample

e. Spike %Rec - % recovery of the MS compound in the MS Sample Percent Recovery = (MS Conc .-Unknown Conc)*100/Spike Added f. Dup %Rec - % recovery of the MS compound in the MS/D Sample
g. RPD – Relative % Deviation between MS/MSD recoveries RPD=ABS(MSREC-MSDREC)*100/((MSREC+MSDREC)/2) h. RPD QC Limits – 30% until laboratory control limits are established i. % Rec QC Limits – entered from established laboratory control chartsEndyne, Inc. VOC Method EPA 8260/8260B SOP 160 James Brown Drive Revision #10, Effective 09/26/07 Williston, VT 05495 Page 16 of 21

Document Control Copy on Buff colored paper. Any other color is not official version XIII. Instrument Maintenance/Trouble Shooting: In strument maintenance is documented in the maintenance section of the current instrument run log.

A. Injection port septa is replaced every 20 injections or as needed. B. Poor response or failed tune criteria may be indicative of a dirty MS source. Follow procedures in the HP MSD 5971 operator manual to clean the source. C. No sample response or emission current indicates a worn of broken filament. Follow procedures in the HP MSD 5971 operators manual to replace filaments or manually switch to alternate filament on back of MSD. D. A high baseline or poor instrument response may indicate a leak in the system. Leaks will oxidize the column and shorten column life. Perform an air and water check following any instrumental maintenance. E. Varying surrogate and analyte response and excessive analyte carry over are common with deteriorating traps. Replace the Vocarb 4000 in the Tekmar LCS-2 according to the operating manual. F. Varying response may indicate a contaminated injection port. Replace the injector liner or salanize an old injection liner in accordance to HP GC oven 5890 operators manual.

XIV. Method Modifications:

Purge flows most effective for O/I auto-sampler and trap are 20-25mls/min. Method 8260 recommends 25 to 40mls/min.

MS/MSD RPD upper control limit, recommended by NELAC, is defined as 3.27 times the average RPD of minimum 30 data points. This reference was not found in literature review as of 3/20/07.

The GC/MS operating systems are programmed to scan mass ranges between 42- 260AMU as opposed to 35-260AMU recommend by method 8260. The reduced range effectively reduces baseline noise allowing for easier chromatogram interpretation. All primary characteristic ions and qualifying ions for each compound are present at this mass range. In instance where a broader mass range is required the laboratory will adjust its scan range accordingly.Endyne, Inc. VOC Method EPA 8260/8260B SOP 160 James Brown Drive Revision #10, Effective 09/26/07 Williston, VT 05495 Page 17 of 21

Document Control Copy on Buff colored paper. Any other color is not official version XV. Bibliography/References:

EnviroQuant Chemstation, G1701BA Version b.01-00 © Hewlett-Packard 1989-1998

HP 5971A Mass Selective Detector Hardware Manual, edition 1 © Hewlett-Packard Feb. 1990, Publication # 05971-90011

HP 5890A Series II Programmable Cool on Column Inlet, eighth edition © HewlettPackard, Sept. 1995 Publication # 05890-90300

HP 5890A Series II Reference Manual, fifth edition © Hewlett-Packard, Sept. 1991Publication # 05890-90270

Method 8000b Determinative Chromatographic Separations, EPA SW-846 NTIS ,CD ROM Version 2, Dec. 1997

Method 8260b– Volatile Organic Compounds by Gad Chromatography/Mass Spectrometry (GC/MS), Revision 2, US EPA December 1996

Method 5035-Closed System Purge and Trap and Extraction for Volatile Organics in Soil and Waste Samples, CD-ROM Revision 0, US EPA December 1996

Method 5030B-Purge and Trap for Aqueous Samples, CD-ROM Revision 2, US EPA December 1996

XVI. Revision history

Revision #7 January 26, 2004 -Added Bibliography/Reference section; Added Revision History section; Added sign off sheet. -Edited typos; formatted tab sets a nd spacing; updated table of contents -Added laboratory safety requirements -Added NH gas additive compounds; Added priority pollutant compounds; Added OMYA compounds. -Added Tedlar bag requirements. Revision #8 – April 7, 2005 -Edit for content and grammar Revision #9 Began September 2006 -Edited quality control to reflect discovered software capabilities and Documentation Revision #9 Finished March 20,2007 -Reviewed content, clarifie d software calculations, edits for grammar -Updated method modifi cation section after literature review. -Adjusted table of contents for new page fit. Revision #10 September 26, 2007 -Section VIII.H.2 Defined acceptance criteria for calibration models.

TABLE 1Endyne, Inc. VOC Method EPA 8260/8260B SOP 160 James Brown Drive Revision #10, Effective 09/26/07 Williston, VT 05495 Page 18 of 21

Document Control Copy on Buff colored paper. Any other color is not official version BFB (4-BROMOFLUOROBENZENE) MASS INTENSITY CRITERIA

m/z Required Intensity (relative abundance)

50 15 to 40 % of m/z 95 75 30 to 60% of m/z 95 95 Base peak, 100% relative abundance 96 5 to 9% of m/z 95 173 Less than 2% of m/z 174 174 Greater than 50% of m/z 95 175 5 to 9% of m/z 174 176 Greater than 95% but less than 101% of m/z 174 177 5 to 9% of m/z 176Endyne, Inc. VOC Method EPA 8260/8260B SOP 160 James Brown Drive Revision #10, Effective 09/26/07 Williston, VT 05495 Page 19 of 21

Document Control Copy on Buff colored paper. Any other color is not official version Appendix A VOLATILE ORGANIC COMPOUND SAMPLING WITH METHANOL PRESERVATION

Endyne is recommending to its clients that they modify their sampling procedure for Volatile Organic Compounds (VOCs) in soil/solid matrices; SW-846 Method 5035.

The recommended protocol calls for the sampler to notify the laboratory approximately 1 week before sampling date. Once notified the laboratory will prepare 40-ml vials for each site.

Preparation will involve adding exactly 10.0 ml of a high purity grade methanol (MeOH) to a 40-ml vial and determining the exact weight, which will be recorded on the vial along with the date prepared. A pen mark is made on the label to note the meniscus of the solvent at the time of preparation.

The sampler will then add approximately 20.0 g of soil in the field to each vial. This is roughly equivalent to 2 rounded ta blespoons or 1.5 inches in the vial of a loosely packed soil or one heaping tablespoon of a denser/damper soil. Once the soil has settled, there should be approximately one centimeter of MeOH as a supernatant. The sampler should mark on the bottle the level of the meniscus after sample addition, this will allow the laboratory to confirm that there was no sample loss at the time of analysis.

The sampler will also include a 40.0-ml vial of soil sampled the standard way. This vial will be used to determine percent solids as well as a b ack up in case of sample loss with the MeOH vial.

Once returned to the lab, the soil is ready for analysis. The weight of the sample will be determined by the difference of the before and after weights.

Advantages:

-More accurate and generally higher analyte recoveries

Disadvantages:

-Poor sampling/handling procedure can result in greater erroneous results.

Hints:

- It is very important to not splash any of the MeOH out of the vial when collecting the sample. - Do not add any additional labels to the vial, as it will affect the sample weight. - Keep vials refrigerated/even before sampling. - Do not leave caps open for very long since MeOH evaporates quite quickly. - After sampling, be sure to wipe the threads of the vial & cap with a clean tissue. Even the slightest amount of dirt can prevent a good seal. - Unused sample vials are stable for several weeks when refrigerated. Always confirm that no methanol has evaporated from the vial by checking the meniscus line.Endyne, Inc. VOC Method EPA 8260/8260B SOP 160 James Brown Drive Revision #10, Effective 09/26/07 Williston, VT 05495 Page 20 of 21

Document Control Copy on Buff colored paper. Any other color is not official version Table 2 TABLE 2-SW 8260B Water Reporting Limits

Limit Limit Parameter ug/L Parameter ug/L Acetone 10.0 1,1-Dichloropropene 1.0 Benzene 1.0 cis-1,3-Dichloropropene 1.0 Bromobenzene 1.0 trans-1,3-Dichloropropene 1.0 Bromochloromethane 2.0 Diethyl Ether 10.0 Bromodichloromethane 1.0 Ethylbenzene 1.0 Bromoform 1.0 Hexachlorobutadiene 5.0 Bromomethane 5.0 2-Hexanone 10.0 2-Butanone 10.0 Isopropylbenzene 1.0 n-Butylbenzene 1.0 p-Isopropyltoluene 1.0 sec-Butylbenzene 1.0 Methylene Chloride 10.0 tert-Butylbenzene 1.0 4-Methyl-2-Pentanone 10.0 Carbon Disulfide 10.0 MTBE 2.0 Carbon Tetrachloride 1.0 Naphthalene 2.0 Chlorobenzene 1.0 n-Propylbenzene 1.0 Chloroethane 5.0 Styrene 1.0 2-Chloroethyl Vinyl Ether 20.0 1,1,1,2-Tetrachloroethane 2.0 Chloroform 1.0 1,1,2,2-Tetrachloroethane 2.0 Chloromethane 3.0 Tetrachloroethene 1.0 2-Chlorotoluene 1.0 Tetrahydrofuran 10.0 4-Chlorotoluene 1.0 Toluene 1.0 Dibromochloromethane 1.0 1,2,3-Trichlorobenzene 2.0 1,2-Dibromo-3-Chloropropane 2.0 1,2,4-Trichlorobenzene 2.0 1,2-Dibromoethane 2.0 1,1,1-Trichloroethane 1.0 Dibromomethane 2.0 1,1,2-Trichloroethane 1.0 1,2-Dichlorobenzene 1.0 Trichloroethene 1.0 1,3-Dichlorobenzene 1.0 Trichlorofluoromethane 2.0 1,4-Dichlorobenzene 1.0 1,2,3-Trichloropropane 2.0 Dichlorodifluoromethane 5.0 1,2,4-Trimethylbenzene 1.0 1,1-Dichloroethane 1.0 1,3,5-Trimethylbenzene 1.0 1,2-Dichloroethane 1.0 Vinyl Chloride 2.0 1,1-Dichloroethene 1.0 Xylenes, Total 2.0 cis-1,2-Dichloroethene 1.0 Isopropanol 50.0 trans-1,2-Dichloroethene 1.0 MITC 5.0 1,2-Dichloropropane 1.0 ETBE 2.0 1,3-Dichloropropane 1.0 TAME 2.0 2,2-Dichloropropane 1.0 t-Butanol 10.0 Isopropyl ether 2.0 Acrylonitrile 20.0 Acrolein 20.0

Note: Soil reporting limits are base on the sample percent solid, extraction mass, and extraction solvent volume and therefore vary with each individual sample. See section XI for soil calculation conversion to ug/kg, dry.

Note: Current MDL study can be referenced at “Wayne” C :/EXCELQC/QC/MDL. Hard copied and raw data are filed with VOC QC data.Endyne, Inc. VOC Method EPA 8260/8260B SOP 160 James Brown Drive Revision #10, Effective 09/26/07 Williston, VT 05495 Page 21 of 21

Document Control Copy on Buff colored paper. Any other color is not official version I acknowledge that I have read this Standard Operating Procedure and agree to adhere to the Safety and Quality Control policies outlined within.



## Name DateAqueousSolidMethod Method Calibration Lab. FortifiedDetection Reporting Detection Reporting Verifivation Blank (QC) Matrix Spike MS Dup.Compound Limit ug/L Limit ug/L Limit ug/Kg Limit ug/Kg % Recovery % Recovery % Recovery RPD %Dichlorodifluoromethane 0.37 5.0 2.2 50.0 75 - 125 70 - 130 70 - 130 < 30 %Chloromethane 0.70 3.0 9.5 30.0 75 - 125 70 - 130 70 - 130 < 30 %Vinyl chloride 0.75 2.0 6.4 20.0 80 - 120 70 - 130 70 - 130 < 30 %Bromomethane 0.85 5.0 10.2 50.0 75 - 125 70 - 130 70 - 130 < 30 %Chloroethane 0.74 5.0 21.2 50.0 75 - 125 70 - 130 70 - 130 < 30 %Trichlorofluoromethane 0.36 2.0 11.6 20.0 75 - 125 70 - 130 70 - 130 < 30 %Diethyl ether 1.18 5.0 17.4 50.0 75 - 125 70 - 130 70 - 130 < 30 %1,1-Dichloroethene 0.65 1.0 6.2 10.0 80 - 120 70 - 130 70 - 130 < 30 %Acetone 2.50 10.0 52.0 100.0 75 - 125 70 - 130 70 - 130 < 30 %Carbon disulfide 0.69 5.0 9.2 50.0 75 - 125 70 - 130 70 - 130 < 30 %Methylene chloride 0.53 5.0 10.0 50.0 75 - 125 70 - 130 70 - 130 < 30 %t-Butanol 6.20 20.0 125 200 75 - 125 70 - 130 70 - 130 < 30 %MTBE 1.52 2.0 14.5 20.0 75 - 125 70 - 130 70 - 130 < 30 %trans-1,2-Dichloroethene 0.50 1.0 9.2 10.0 75 - 125 70 - 130 70 - 130 < 30 %Diisopropyl ether 0.68 2.0 6.1 20.0 75 - 125 70 - 130 70 - 130 < 30 %1,1-Dichloroethane 0.50 1.0 6.8 10.0 75 - 125 70 - 130 70 - 130 < 30 %ETBE 0.63 2.0 7.2 20.0 75 - 125 70 - 130 70 - 130 < 30 %2-Butanone 1.07 10.0 43.6 100.0 75 - 125 70 - 130 70 - 130 < 30 %2,2-Dichloropropane 0.59 2.0 5.8 20.0 75 - 125 70 - 130 70 - 130 < 30 %cis-1,2-Dichloroethene 0.49 1.0 6.5 10.0 75 - 125 70 - 130 70 - 130 < 30 %Bromochloromethane 0.69 2.0 3.2 20.0 75 - 125 70 - 130 70 - 130 < 30 %Control Limits 2010 EPA 8260B/624 - Aqueous & Soil SamplesEndyne, Inc.160 James Brown DriveWilliston, VermontPage 1 of 4AqueousSolidMethod Method Calibration Lab. FortifiedDetection Reporting Detection Reporting Verifivation Blank (QC) Matrix Spike MS Dup.Compound Limit ug/L Limit ug/L Limit ug/Kg Limit ug/Kg % Recovery % Recovery % Recovery RPD %Control Limits 2010 EPA 8260B/624 - Aqueous & Soil SamplesEndyne, Inc.160 James Brown DriveWilliston, VermontChloroform 0.40 1.0 4.8 10.0 80 - 120 70 - 130 70 - 130 < 30 %Tetrahydrofuran 1.63 10.0 69.1 100.0 75 - 125 70 - 130 70 - 130 < 30 %1,1,1-Trichloroethane 0.34 1.0 5.7 10.0 75 - 125 70 - 130 70 - 130 < 30 %Carbon tetrachloride 0.36 1.0 7.1 10.0 75 - 125 70 - 130 70 - 130 < 30 %1,1-Dichloropropene 0.56 1.0 6.8 10.0 75 - 125 70 - 130 70 - 130 < 30 %Benzene 0.53 1.0 7.4 10.0 75 - 125 70 - 130 70 - 130 < 30 %TAME 0.66 2.0 4.9 20.0 75 - 125 70 - 130 70 - 130 < 30 %1,2-Dichloroethane 0.64 1.0 5.9 10.0 75 - 125 70 - 130 70 - 130 < 30 %Trichloroethene 0.41 1.0 4.9 10.0 75 - 125 70 - 130 70 - 130 < 30 %1,2-Dichloropropane 0.37 2.0 7.0 20.0 80 - 120 70 - 130 70 - 130 < 30 %Dibromomethane 0.50 2.0 10.0 20.0 75 - 125 70 - 130 70 - 130 < 30 %Bromodichloromethane 0.17 0.50 3.5 5.0 75 - 125 70 - 130 70 - 130 < 30 %cis-1,3-Dichloropropene 0.33 1.0 5.8 10.0 75 - 125 70 - 130 70 - 130 < 30 %MIBK 0.98 10.0 9.5 100.0 75 - 125 70 - 130 70 - 130 < 30 %Toluene 0.35 1.0 5.7 10.0 80 - 120 70 - 130 70 - 130 < 30 %trans-1,3-Dichloropropene 0.50 2.0 4.9 20.0 75 - 125 70 - 130 70 - 130 < 30 %1,1,2-Trichloroethane 0.32 1.0 6.2 10.0 75 - 125 70 - 130 70 - 130 < 30 %Tetrachloroethene 0.37 1.0 2.8 10.0 75 - 125 70 - 130 70 - 130 < 30 %1.3-Dichloropropane 0.42 1.0 5.5 10.0 75 - 125 70 - 130 70 - 130 < 30 %2-Hexanone 0.84 10.0 13.1 100.0 75 - 125 70 - 130 70 - 130 < 30 %Dibromochloromethane 0.49 2.0 5.6 20.0 75 - 125 70 - 130 70 - 130 < 30 %Page 2 of 4AqueousSolidMethod Method Calibration Lab. FortifiedDetection Reporting Detection Reporting Verifivation Blank (QC) Matrix Spike MS Dup.Compound Limit ug/L Limit ug/L Limit ug/Kg Limit ug/Kg % Recovery % Recovery % Recovery RPD %Control Limits 2010 EPA 8260B/624 - Aqueous & Soil SamplesEndyne, Inc.160 James Brown DriveWilliston, Vermont1,2-Dibromoethane 0.48 1.0 4.6 10.0 75 - 125 70 - 130 70 - 130 < 30 %Chlorobenzene 0.29 1.0 6.4 10.0 75 - 125 70 - 130 70 - 130 < 30 %Ethylbenzene 0.36 1.0 4.5 10.0 80 - 120 70 - 130 70 - 130 < 30 %1,1,1,2-Tetrachloroethane 0.24 2.0 7.9 20.0 75 - 125 70 - 130 70 - 130 < 30 %m & p - Xylene 0.76 2.0 11.6 20.0 75 - 125 70 - 130 70 - 130 < 30 %o-Xylene 0.35 2.0 4.6 20.0 75 - 125 70 - 130 70 - 130 < 30 %Styrene 0.33 1.0 6.0 10.0 75 - 125 70 - 130 70 - 130 < 30 %Bromoform 0.56 2.0 7.1 20.0 75 - 125 70 - 130 70 - 130 < 30 %Isopropylbenzene 0.45 1.0 7.0 10.0 75 - 125 70 - 130 70 - 130 < 30 %1,1,2,2-Tetrachloroethane 0.88 2.0 9.1 20.0 75 - 125 70 - 130 70 - 130 < 30 %Bromobenzene 0.32 1.0 5.1 10.0 75 - 125 70 - 130 70 - 130 < 30 %n-Propylbenzene 0.37 1.0 4.8 10.0 75 - 125 70 - 130 70 - 130 < 30 %1,2,3-Trichloropropane 0.54 2.0 6.2 20.0 75 - 125 70 - 130 70 - 130 < 30 %2-Chlorotoluene 0.28 1.0 5.7 10.0 75 - 125 70 - 130 70 - 130 < 30 %1,3,5-Trimethylbenzene 0.40 1.0 6.6 10.0 75 - 125 70 - 130 70 - 130 < 30 %4-Chlorotoluene 0.21 1.0 3.9 10.0 75 - 125 70 - 130 70 - 130 < 30 %tert-Butylbenzene 0.43 1.0 4.9 10.0 75 - 125 70 - 130 70 - 130 < 30 %1,2,4-Trimethylbenzene 0.46 1.0 6.1 10.0 75 - 125 70 - 130 70 - 130 < 30 %sec-Butylbenzene 0.45 1.0 5.0 10.0 75 - 125 70 - 130 70 - 130 < 30 %4-Isopropyltoluene 0.46 1.0 5.7 10.0 75 - 125 70 - 130 70 - 130 < 30 %1,3-Dichlorobenzene 0.49 1.0 5.8 10.0 75 - 125 70 - 130 70 - 130 < 30 %Page 3 of 4AqueousSolidMethod Method Calibration Lab. FortifiedDetection Reporting Detection Reporting Verifivation Blank (QC) Matrix Spike MS Dup.Compound Limit ug/L Limit ug/L Limit ug/Kg Limit ug/Kg % Recovery % Recovery % Recovery RPD %Control Limits 2010 EPA 8260B/624 - Aqueous & Soil SamplesEndyne, Inc.160 James Brown DriveWilliston, Vermont1,4-Dichlorobenzene 0.38 1.0 4.7 10.0 75 - 125 70 - 130 70 - 130 < 30 %n-Butylbenzene 0.29 1.0 4.7 10.0 75 - 125 70 - 130 70 - 130 < 30 %1,2-Dichlorobenzene 0.28 1.0 5.1 10.0 75 - 125 70 - 130 70 - 130 < 30 %1,2-Dibromo-3-chloropropa0.98 2.0 7.7 20.0 75 - 125 70 - 130 70 - 130 < 30 %1,2,4-Trichlorobenzene 0.28 2.0 5.5 20.0 75 - 125 70 - 130 70 - 130 < 30 %Hexachlorobutadiene 0.42 0.50 5.3 5.0 75 - 125 70 - 130 70 - 130 < 30 %Naphthalene 2.14 2.0 9.0 20.0 75 - 125 70 - 130 70 - 130 < 30 %1,2,3-Trichlorobenzene 0.32 2.0 7.4 20.0 75 - 125 70 - 130 70 - 130 < 30 %1/22/09 2/17/09SurrogateDibromofluoromethane S1 70 - 130 70 - 130 70 - 130Toluene-d8 S2 70 - 130 70 - 130 70 - 1304-Bromofluorobenzene S3 70 - 130 70 - 130 70 - 130Specific instrument control charts may supersede value only when control range is less than default method limit.Page 4 of 4Document Control Copy on Buff colored paper. Any other color is not official version 

# Endyne, Inc.

160 James Brown Dr.

Williston, VT 05495 Phone: (802) 879-4333 Fax: (802) 879-7103



# SEMIVOLATILE ORGANIC COMPOUNDS 

# METHOD EPA 8270C 

# Standard Operating Procedure

REVISED: September 26, 2007

Revision: 9

Technical Director: Date : Harry B. Locker Ph.D.



### QA Officer: Date :
Mark L. FauselEndyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 2 of 40

Document Control Copy on Buff colored paper. Any other color not official version TABLE OF CONTENTS

Section Pages

1. Overview 3-4

2. Summary of Method 4-5

3. Safety 5

4. Waste Disposal 5-6

5. Sample Collection, Preservation and Storage 6

6. Equipment and Supplies 6-7

7. Reagents and Standards 7-8

8. Interferences 8-9

9. Quality Control 9-14

10. Procedure 14-30

11. Data Reduction 30-31

12. Data Recording 31

13. Data Archiving 31-32

14. Instrument Maintenance 32-33

15. Trouble Shooting 34

16. Method Modifications 34

17. Bibliography/Reference 35

18. Revision History 35 Table 1 – DFTPP Key Ions/Ion Abundance Criteria 36 Table 2 – Calibration Check Compounds 36 Table 3 – Reporting Limits 37

Table 4 – Characteristic Ions 38-39 Sign Off Sheet 40Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 3 of 40

Document Control Copy on Buff colored paper. Any other color not official version 1. Overview

1.1. M ethod 8270 is used to determine the concentration of semivolatile organic compounds in extracts prepared from soil, water and solid waste matrices. The following compounds are determined by this method:

Base/Neutral Extractable:

Anthracene Azobenzene Benzidine Benzo(a)anthracene Benzo(b&k )fluoranthene Benzo(a)pyrene Benzo(g,h,i)perylene Bis(2-chloroethyl)ether Bis(2-chloroethoxy)methane Bis(2-ethylhexyl)phthalate Bis(2-chloroisopropyl)ether 4-Bromophenyl phenyl ether Butyl benzyl phthalate Carbazole 4-Chloroaniline 1-Chloronaphthalene 2-Chloronaphthalene 4-Chlorophenyl phenyl ether Chrysene Dibenzofuran Dibenzo(a,h)anthracene Di-n-butylphthalate 1,3-Dichlorobenzene 1,2-Dichlorobenzene 1,4-Dichlorobenzene 3,3’-Dichlorobenzidine Diethyl phthalate Dimethyl phthalate 2,4-Dinitrotoluene 2,6-Dinitrotoluene Di-n-octylphthalate Fluoranthene Fluorene Hexachlorobenzene Hexachlorobutadiene Hexachlorocyclopentadiene Hexachloroethane Indeno(1,2,3-cd)pyrene Isophorone 1-Methylnapththalene 2-Methylnaphthalene Naphthalene 1-Naphthylamine 2-Naphthylamine 2-Nitroaniline 3-Nitroaniline 4-Nitroaniline Nitrobenzene N-Nitrosodipheylamine N-Nitrosodimethylamine N-Nitrosodi-n-propylamine N-Nitrosopiperidine Phenanthrene Pyrene Pyridine 1,2,4-Trichlorobenzene

Acid Extractables:

Benzyl Alcohol 4-Chloro-3-methylphenol 2-Chlorophenol 2,4-Dichlorophenol 2,6-Dichlorophenol 2,4-Dimethylphenol 4,6-Dinitro-2-methylphenol 2,4-Dinitrophenol 2-Methylphenol 3&4-Methylphenol 2-Nitrophenol 4-Nitrophenol Pentachlorophenol Phenol 2,4,5-Trichlorophenol 2,4,6-Trichlorophenol

1.2. Sample preparation techniques: 1.2.1. Method 3510 is a separatory funnel technique used to extract aqueous samples. 1.2.2. Method 3550 is an ultrasonic technique used for soil samples.

1.3. Method 8270 can be used to quantify most neutral, acidic, and basic organic compounds that are soluble in methylene chloride and capable of being eluted without derivatization as sharp peaks from a gas chromatographic fused-silica capillary column coated with a slightly polar silicone. Such compounds include polynuclear aromatic hydrocarbons, chlorinated hydrocarbons and pesticides, phthalate ester, organophosphate ester, nitrosamines, aromatic nitro compounds, and phenols, including nitrophenols.Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 4 of 40

Document Control Copy on Buff colored paper. Any other color not official version 1.4. The following compounds may require special treatment when being determined by this method:

1.4.1. Benzidine can be subject to oxidative losses during solvent concentration. Also, chromatography is poor. 1.4.2. Under the alkaline conditions of the extraction step, alpha-BHC, gammaBHC, Endosulfan I and II, and Endrin are subject to decomposition in the inlet of the gas chromatograph, chemical reaction in acetone solution, and photochemical decomposition. 1.4.3. Hexachlorocyclopentadiene is subject to thermal decomposition in the inlet of the chromatograph, chemical reaction in acetone solution and photochemical decomposition. 1.4.4. N-Nitrosodimethylamine is difficult to separate from the solvent under the chromatographic conditions described. N-nitrosodiphenylamine decomposes in the gas chromatographic inlet and cannot be separated from diphenylamine. 1.4.5. Pentachlorophenol, 2,4-Dinitrophenol , 4-Nitrophenol, 4,6-Dinitro-2- methylphenol, 4-Chloro-3-methylphenol, Benzoic acid, 2-Nitroaniline, 4- Chloroaniline, and Benzyl alcohol are subject to erratic chromatographic behavior, especially if the GC system is contaminated with high boiling material. 1.4.6. Pyridine may perform poorly at higher injection port temperatures. Consideration of the performance of other analytes is necessary when lowering the injection port temperature.

1.5. The method detection limit (MDL) of Method 8270 ranges from 1.0 to 10ug/L. Practical quantitation limit (PQLs) will be proportionately higher for sample extracts that require dilution to avoid saturation of the detector.

1.6. This method is restricted to use by or under the supervision of analysts experienced in the use of gas chromatograph/mass spectrometers and skilled in the interpretation of mass spectra. Each analyst must demonstrate the ability to generate acceptable results with this method.

2. Summary of Method

2.1. The samples are prepared for analysis by gas chromatography/mass spectrometry (GC/MS) using the appropriate sample preparation technique and, if necessary, sample cleanup procedures. 2.2. The semivolatile compounds are introduced into the GC/MS by injecting the sample extract into a GC with a narrow-bore fused silica capillary column. The GC column is temperature programmed to separate the analytes, which are then detected with a MS. 2.3. Analytes eluted from the capillary column are introduced into the MS via direct connection. Identification of target analytes is accomplished by comparing their mass spectra with the electron impact spectra of authentic standards.Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 5 of 40

Document Control Copy on Buff colored paper. Any other color not official version Quantitation is accomplished by comparing the response of a major (quantitation) ion relative to an internal standard using a minimum five-point calibration curve.

3. Safety

3.1. This method involves the handling of chemicals outlined below. Each of these chemicals may have specific associated hazards. Analysts must read and become familiar with all elements of each chemical’s MSDS. Make special awareness of the symptoms of exposure and potential routes of entry. Analysts must notify the Safety Officer immediately if any symptoms of exposure are suspected. 3.2. PPE must be worn at all times in designated work areas. All applicable engineering controls, such as fume hoods and splash shields, must be used when performing analyses. 3.3. To ensure the safety of all laboratory personnel: work areas must be kept neat and organized; equipment and bench-tops must be cleaned and sterilized, if necessary, at the completion of each task; all containers must be properly labeled as to the contents and hazard ratings; and spills need to be cleaned immediately and completely. 3.4. Lab coats, nitrile gloves and protective eyeglasses are to be worn at all times during analysis by this method and while handling any laboratory sample. 3.5. A thorough MSDS review of methylene chloride, sodium sulfate and all laboratory calibration standards should be performed prior to analysis by this method. 3.6. All standards are to be made in a fume hood away from heat sources. 3.7. This method uses reagents that may cause anemia, eye/liver/kidney/central nervous disorders, reproductive disorders and cancer upon exposure. Stock standards of these materials should be handled in fume hoods. Toxic gas respirators should be worn when handling concentrated standards and samples.

4. Waste Disposal

4.1. Solvent Waste : All solvent waste must be disposed of in the solvent waste satellite container, then placed in the larger container located in the hazardous waste room. Note: a technician certified to do so can only dump solvent waste in the hazardous waste room.

4.2. Water/Soil Waste : Solid and aqueous material must sit in a vented area until all the solvent has been evaporated. Alternatively, wastewater may be collected in a carboy and bubbled with the exhaust of the pump in the extraction lab hood. The water can be flushed down the drain with copious amounts of tap water. Soil waste is stored in a satellite container and disposed of in the solid waste container in the hazardous waste room.Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 6 of 40

Document Control Copy on Buff colored paper. Any other color not official version 4.3. Acid Waste should be contained separate from all other waste streams and disposed of in the proper waste container in the hazardous waste room by a technician who is trained to do so.

5. Sample Collection, Preservation and Storage

5.1. Sample Collection and Preservation

5.1.1. Collect water samples in 1L amber glass bottles with PTFE-lined screw
caps. 5.1.2. Adjust the pH to 5.0 - 9.0, using 6N HCl or 6N NaOH as needed. Store the sample at 4 o C in a refrigerator and away from light. 5.1.3. Collect solids in 250mL amber glass bottle with PTFE-lined screw caps, and refrigerate at 4 o C.

5.2. Storage

5.2.1. All samples are stored in the Extraction Lab refrigerator at 4 o C. 5.2.2. All extracts are stored in the Sample Extract refrigerator in the extraction lab at 4 o C. 5.2.3. Standards are stored in the Extraction Lab and Organics Lab Standard refrigerators at 4 o C.

5.3. Holding Times

5.3.1. Extraction Waters: 7 days from sampling Soils: 14 days from sampling 5.3.2. Analysis 40 days from extraction

6. Equipment and Supplies

6.1. Gas Chromatograph/Mass Spectrometer (GC/MS) 6.1.1. Hewlett Packard 6890 Series GC 6.1.2. Agilent 5973 Network Mass Selective Detector 6.1.3. Agilent 7683B Series Injector 6.1.4. Dell desktop computer running Agilent MSD Chemstation D.02.00.275 6.1.5. Capillary Column - Rxi-5ms, 30m, 0.25 mmID, 0.25umdf (or equivalent) 6.1.6. 10ul, 23guage injector syringe 6.1.7. Merlin microseal – septa 6.1.8. Restek drilled uniliner with hole on bottom injection port liner (or equivalent) 6.1.9. Vent Carbon Trap 6.1.10. Ultra-High Purity He gas supply 6.2. 1L and 250mL Amber glass bottles with PTFE-lined screw caps.Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 7 of 40

Document Control Copy on Buff colored paper. Any other color not official version 6.3. 375 watt Ultrasonic Disrupter ( Tekmar ) 6.3.1. 3⁄4” horn (low concentration) 6.3.2. 1/8” tapered microtip attached to a 1⁄2” horn (high concentration) 6.4. 250mL Beakers 6.5. 500mL Erlenmeyer Flasks 6.6. Glass funnels 6.7. Various sized syringes 6.8. 2 Liter Teflon separatory funnels 6.9. 1 Liter graduated cylinder 6.10. 9” Glass Pasteur pipettes 6.11. 2mL and 4mL vials, Teflon septa caps, and micro inserts 6.12. Metal spatulas 6.13. Zymark TurboVap II concentrator 6.14. Zymark TurboVap II concentration vials

7. Reagents and Standards

7.1. Reagents Log

• All reagents are recorded in the Reagents Log when opened. The date reagents are entered into the Reagents Log is then used to trace reagents on the Extraction Log.

7.2. Reagents

• Reagent grade chemicals that conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society shall be used in all tests. Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high purity to permit its use without lessening the accuracy of the determination. Reagents should be stored in glass to prevent the leaching of contaminants from plastic containers.

7.2.1. Acetone – Fisher Optima 7.2.2. Methylene chloride – GC Resolv 7.2.3. Methanol 7.2.4. Anhydrous granular sodium sulfate – Certified ACS

• Purify by heating to 400 o C for 4 hours in a shallow tray.

• The sodium sulfate log is kept by the analyst who is responsible for baking the sodium sulfate in the muffle furnace. Reagent information as well as baking information (time, temperature...) is recorded here. 7.2.5. De-ionized water – produced by Endyne, Inc 7.2.6. Pool sand – Methylene chloride rinsed 7.2.7. Glass wool – Silanated 7.2.8. Concentrated sulfuric acid 7.2.9. 10 N NaOHEndyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 8 of 40

Document Control Copy on Buff colored paper. Any other color not official version 7.3. Standards

• Store standards at 4 o C in PTFE-sealed containers in the standards refrigerator in the extraction lab.

• Ensure that all purchased standards are in solvents compatible with methylene chloride.

• Standards purchased for QCS samples should come from a separate supplier than calibration standards – when possible.

• Equivalent standards may be ordered from alternate sources.

7.3.1. Internal Standard Mix – AccuStandard, Z-014J, 4000ppm Internal Standard Mix in methylene chloride. 7.3.2. Surrogate Standard Mix – AccuStandard, M-8270-SS, 4000ppm Method 8270 – Surrogate Standard in methylene chloride 7.3.3. Calibration Stock Standards – Restek, 31815, 8270/Appendix IX Kit

• Restek, 31850, 500-1000ppm 8270 MegaMix in methylene chloride

• Restek, 31625, 2000ppm Appendix IX Mix #1 in methylene chloride

• Restek, 31806, 1000ppm Appendix IX Mix #2 in methylene chloride

• Restek, 31030, 2000ppm 605 Benzidines Calibration Mix in MeOH 7.3.4. QCS/Independent Calibration Stock Standard– NSI Solutions, Inc., Q1261, 100ppm Custom BNA Spiking Mix in MeOH 7.3.5. QC/MS Spiking Stock Standards – AccuStandard, CLP-007 includes: 7.3.5.1. CLP-007A, 1.0mg/mL Base/Neutral in MeOH 7.3.5.2. CLP-007B, 2.0mg/mL Acids in MeOH

• These two standards are diluted together in MeOH to make a 200ppm spiking standard. 7.3.6. Instrument Performance Check/DFTPP Tuning Standard – AccuStandard, M625-TS-20X, 1,000ppm GC/MS Tuning Std for EPA Method 624/625 in methylene chloride

8. Interferences

8.1. Raw GC/MS data from all blanks samples and spikes must be evaluated for interferences. Determine if the source of interference is in the preparation and/or cleanup of the samples and take corrective action to eliminate the problem.

8.2. Contamination by carryover can occur whenever high-concentration and co concentration samples are sequentially analyzed. To reduce carryover, the sample syringe must be rinsed with solvent between sample injections. Whenever an unusually concentrated sample is encountered, it should be followed by the analysis of a solvent to check for cross-contamination.

8.3. Sources

8.3.1. Contaminated solvents, reagents, or sample processing hardware. 8.3.2. Contaminated GC carrier gas, parts, column surfaces, or detector surfaces.Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 9 of 40

Document Control Copy on Buff colored paper. Any other color not official version 8.3.3. Compounds extracted from the sample matrix to which the detector will respond.

8.4. Prevention and Solutions

8.4.1. Common flexible plastics contain varying amounts of phthalate esters which are easily extracted or leached from such materials during laboratory operations. Interference from phthalate esters can best be minimized by avoiding contact with any plastic materials and checking all solvents and reagents for phthalate contamination 8.4.2. Glassware must be scrupulously cleaned. Clean all glassware as soon as possible after use by rinsing with the last solvent used. This should be followed by detergent washing with hot water, and rinses with tap water and DI water. Drain the glassware and dry it in an oven at 130 o C for several hours or rinse with MeOH and drain. Volumetric glassware should not be subjected to heating. Store dry glassware in a clean environment.

9. Quality Control

9.1. Extraction

9.1.1. The following should be extracted at least 1 per set or 1 per 20 samples, whichever is more frequent: 9.1.2. Laboratory Reagent Blank (LRB)

• 1.0L DI H 2 O or 30.0g pool sand spiked with 10uL of 4,000ppm Surrogate Standard and 10uL of 4,000ppm Internal Standard 9.1.3. Laboratory Fortified Blank (LFB)/ Laboratory Control Sample (LCS)

• 1.0L DI H 2 O or 30.0g pool sand spiked with 10uL of 4,000ppm Surrogate Standard, 200uL of 200 ppm QC/MS spiking std in MeOH, and 10uL of 4,000ppm Internal Standard

• 400uL of 100ppm NSI Custom BNA Spiking Mix should be used when a project requires that all reported analytes are evaluated in the LCS.

• The stock QC/MS spiking mix should come from a source independent from the calibration stock standard. 9.1.4. Laboratory Duplicate (LD)

• A sample aliquot taken in addition to the first, spiked 10uL of 4,000ppm Surrogate Standard and 10uL of 4,000ppm Internal Standard, extracted, and analyzed with an identical procedure to the first in order to measure the precision associated with this laboratory procedure. 9.1.5. Laboratory Fortified Sample Matrix (LFM)

• A sample aliquot taken in addition to the first, and spiked the same as an LFB to determine whether the sample matrix contributes bias to the analytical results.

9.2. Method Blanks/LRBEndyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 10 of 40

Document Control Copy on Buff colored paper. Any other color not official version 9.2.1. When samples that are extracted together are analyzed on separate instruments or on separate analytical shifts, the method blank must be analyzed on at least one of those instruments. 9.2.2. The method blank may be analyzed immediately after the calibration verification standard, to ensure that there is no carryover from the standard, or at another point in the analytical shift. 9.2.3. When sample extracts are subjected to cleanup procedures, the associated method blank must also be subjected to the same cleanup procedures. 9.2.4. LRBs should have target compounds:

• Less than the reporting limit for the analyte;

• Less than 5% of the regulatory limit associated with an analyte;

• Less than 5% of the sample result for the same analyte, whichever is greater. 9.2.5. If the method blank results do not meet the acceptance criteria above, then the laboratory should take corrective action to locate and reduce the source of the contamination and to re-extract and reanalyze any samples associated with the contaminated method blank. 9.2.6. If method blank does not meet acceptance criteria and samples are past holding times, reported data will be qualified “B” indicating that blank contamination was observed at levels affecting analytical results. 9.2.7. Blank subtraction is not permitted. 9.2.8. Method blanks and/or solvent blanks may be used to check for contamination by carryover from a high-concentration sample into subsequent samples. 9.2.9. When analysis of such blanks is not possible the analyst should review the result for at least the next two samples after the high-concentration sample. 9.2.9.1. If the analytes in the high-concentration sample are not present in subsequent samples, the lack of carryover has been demonstrated. 9.2.9.2. If there is evidence that carryover may have occurred, then the affected samples should be reanalyzed.

9.3. LFB/LCS sample

9.3.1. The LFB consists of an aliquot of a clean (control) matrix similar to the sample matrix and of the same weight or volume. It is fortified at the same concentration as the matrix spike. 9.3.2. Recovery calculations are as follows:

%Recovery = ((Cs – Cu)/ Cn)*100 where:

• Cs = Measured concentration of the spiked sample aliquot

• Cu = Measured concentration of the unspiked sample aliquot (use 0 for the LFB)

• Cn = Nominal (theoretical) concentration increase that results from spiking the sample or the nominal concentration of the spiked aliquotEndyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 11 of 40

Document Control Copy on Buff colored paper. Any other color not official version 9.3.3. The LFB should fall within established laboratory control limits. In the absence of control limits, 70-130% may be used. 9.3.4. If the LFB falls outside of acceptance limits, the laboratory should take the following corrective action: 9.3.4.1. Check to be sure that there are no errors in the calculations or standard solutions. If errors are found, recalculate the data accordingly. Examine chromatograms for interfering peaks and integrated peak

areas. 9.3.4.2. Check instrument performance. If an instrument performance problem is found, correct the problem and re-analyze the extracts as well as all associated sample extracts. 9.3.4.3. If no instrument problem is found, the analytical batch should be re-extracted and re-analyzed if still within holding time. 9.3.4.4. If upon re-analysis (of initial extract or re-extracted extract), the recovery is again not within limits, affected analytes should be qualified “QA” indicating that associated QA/QC did not meet laboratory guidelines.

9.4. Matrix Spike (MS)/LFM sample

9.4.1. A duplicate field sample is fortified with a known amount of analyte in order to document the effect of the matrix on method performance. 9.4.2. Matrix spikes are fortified with the same amount of analyte as the LFB/LCS. 9.4.3. Matrix Spike recoveries are not calculated if the fortified concentration is <20% of the background concentration of the sample. 9.4.4. Recoveries for Matrix Spike samples are calculated in the same manner as the LFB/LCS and must meet established control limits.

• In the absence of control limits, 70-130% may be used. 9.4.5. When the results of a matrix spike analysis indicates a potential problem due to the sample matrix itself (a positive of negative bias) the LFB/QCS results are used to verify that the laboratory can perform the analysis in a clean matrix. 9.4.6. If it is determined that the matrix is biasing quantitation, affected analytes are to be qualified “M+” or “M-“ indicating a positive or negative bias due to the sample matrix. 9.4.7. If both the LFB and MS fall outside of acceptance limits, follow the corrective action outlined for the LFB/QLCS (sec. VII.C.4).

9.5. Duplicate/LD

9.5.1. A duplicate sample is analyzed along side the sample in order to measure the precision associated with this method. 9.5.2. Precision is an estimate of the relative percent difference (RPD) of the concentrations for the analysis of the unspiked samples.Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 12 of 40

Document Control Copy on Buff colored paper. Any other color not official version RPD = ((C1-C2)/((C1+C2)/2))*100 where:

• C1 = measured concentration of the first sample aliquot

• C2 = measured concentration of the second sample aliquot 9.5.3. Acceptance limits for precision are +/- 30% RPD 9.5.4. Duplicates that fall outside acceptance criteria should be qualified as “DS,” indicating that there were disparate results between laboratory duplicate analyses.

9.6. Surrogates

9.6.1. In addition to the fortification of all QA/QC samples with 10uL of 4,000ppm surrogate standard, all field samples must also be fortified and evaluated versus in-house acceptance criteria. 9.6.2. Surrogate recoveries is calculated as: (Recovered Surrogate Concentration / Surrogate Target Concentration) * 100 9.6.3. Surrogate recoveries must fall within established acceptance limits. If surrogate recoveries are outside of acceptance limits the following steps should be taken. 9.6.3.1. Check to be sure that there are no errors in the calculations or surrogate standard solutions. If errors are found, recalculate the data accordingly. Examine chromatograms for interfering peaks and integrated peak areas. 9.6.3.2. Check instrument performance. If an instrument performance problem is found, correct the problem and re-analyze the extract. 9.6.3.3. Some samples may require dilution in order to bring one or more target analytes within the calibration range or to overcome significant interferences with some analytes. This may result in the dilution of the surrogate responses to the point that the recoveries cannot be measured. If the surrogate recoveries are available from a less-diluted or undiluted aliquot of the sample or sample extract, those recoveries may be used to demonstrate that the surrogates were within the QC limits, and no further action is required. However, the results of both the diluted and undiluted (or less-diluted) analysis should be provided to the data user. 9.6.3.4. If no instrument problem is found, the sample should be reextracted and re-analyzed if still within holding time. 9.6.3.5. If upon re-analysis (of initial extract or re-extracted extract), the recovery is again not within limits, Surrogate value reported to the client must be qualified as “NR” indicating that the surrogate falls outside laboratory QA/QC parameters.

9.7. Internal Standard Response – If the area for any of the internal standards in a QA/QC or field sample changes by a factor of two (-50% to +100%) from that in the midpoint standard level of the most recent valid initial calibration sequence, the sample must be reanalyzed. If, upon reanalysis, the IS response is stillEndyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 13 of 40

Document Control Copy on Buff colored paper. Any other color not official version unacceptable, the sample may be re-extracted if within holding time or reported with a qualifier on affected analytes stating that the associated internal standard recovery did not meet laboratory acceptance criteria.

9.8. Quality Control Sample/Independent Calibration Verification

9.8.1. A 40ug standard is diluted from the 100ppm Custom BNA Spiking Mix from NSI in methylene chloride. 9.8.2. This standard is analyzed immediately after the last initial calibration standard and evaluated as if it were a Calibration Verification Standard (sec. 10.3). 9.8.3. If the QCS does not meet the calibration verification criteria, a newly prepared QCS standard must be acquired and evaluated. If the new QCS does not meet calibration verification criteria all calibration standards must be evaluated for proper preparation, possible concentration and degradation. New calibration standards should be prepared and a new initial calibration should be run and evaluated with a QCS.

9.9. Demonstration of Capability (DOC)

9.9.1. Prior to extracting samples for clientele, a new extractionist must extract 4 LFB samples at the standard QC concentration. These LFB must be analyzed as other laboratory samples and then processed according to the following acceptance criteria: 9.9.1.1. Calculate the average concentration and the standard deviation for each parameter using the four results 9.9.1.2. The average % Recovery must fall within established control limits for LFBs, and the percent standard deviation must be less than 20%.

9.10. Method Detection Limits (MDL)/Reporting Limits

9.10.1. An MDL study should be performed once a year. 9.10.1.1. Seven low-level LFBs are extracted. To determine the MDL for each analyte and surrogate, the standard deviation of the seven values is multiplied by 3.14. 9.10.1.2. The target concentration of the low-level QCs should be 2.5-5 times the calculated MDL value. 9.10.1.3. Method Detection Limit should be no greater than one-fifth the Reporting Limit. 9.10.2. The reporting limit is based on achieving the requested detection limits of our clients as well as being below known environmental action limits. The laboratory takes into account known interferences, such as contamination peaks. It should be no less than 5 times the MDL. 9.10.3. For established reporting limits refer to Table 3.

9.11. Limits, Tables, and ChartsEndyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 14 of 40

Document Control Copy on Buff colored paper. Any other color not official version 9.11.1. Tables of surrogate and analyte recoveries from LFBs and LFMs are maintained, and updated annually. Surrogate data is established from field samples and LFB and LFM data come from LFBs and Matrix Spike samples. 9.11.2. Limits are based on the previous chronological year’s data, unless significant modification has been made to the methodology in which case limits are established after the first twenty samples have been analyzed. 9.11.2.1. Control Limits: parameter average +/- 3(Standard Deviation) 9.11.2.2. Warning Limits: parameter average +/- 2(Standard Deviation) 9.11.2.3. Control Charts must be separated by matrix and extraction procedure (Ex: Soil by Sonication, Soil by Soxhlet, Soil by Continuous) 9.11.2.4. Up to date Control Charts are kept in the 8270 analyst’s workspace.

9.12. Qualifying Data

• Any deviations from the above outlined quality control as well as any sample container, preservation or holding time discrepancies, outlined in Section 5, are noted on the final report.

10. Procedure

10.1. Extraction Log – An 8270/625 Extraction Log is to be filled out for every extraction batch and kept in the extraction log binder in the extraction lab. Copies of the extraction log are to be stapled to the Login Reports and given to the analyst when extractions have been completed.

10.2. Separatory Funnel Liquid-Liquid Extraction (SW-846 Method 3510C) for full 8270 and TCLP analysis. Method 3510C allows the following pH adjustment steps to be reversed to better separate acid and neutral waste components. This will be performed at the analyst discretion.

10.2.1. *Pre-rinse all extraction apparatus with MeCl 2 before use. 10.2.2. Using a 1-L graduated cylinder, measure 1-L of sample. Alternatively, if the entire contents of the sample bottle are to be extracted, mark the level of the sample on the outside of the bottle. If high analyte concentrations are anticipated, a smaller sample volume may be taken and diluted to 1-L with DI. 10.2.3. 1-L of DI H 2 O is to be used for the blank and QC sample. 10.2.4. Spike 10ul of the 4,000ppm 8270 surrogate spiking solution into each sample (including blanks, QC samples and matrix spike samples) in the graduated cylinder (or sample bottle) and mix well. 10.2.5. For the sample in each batch selected for use as a matrix spike sample and the QC sample, spike 200ul of the 200ppm 8270 QC/MS spiking standard.Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 15 of 40

Document Control Copy on Buff colored paper. Any other color not official version 10.2.6. Check the pH of the sample with wide-range pH paper to ensure a neutral pH between 5 and 9. 10.2.7. Quantitatively transfer the sample from the graduated cylinder (or sample bottle) to the 2-L separatory funnel and adjust the pH to > 11 using 10N NaOH. Shake sample in separatory funnel to ensure mixing and check the pH using narrow-range pH paper. Add more 10N NaOH, if necessary, to achieve a pH > 11. 10.2.8. Use 60mL of methylene chloride to rinse the cylinder (or bottle) and transfer this rinse solvent to the separatory funnel. 10.2.9. If the sample was transferred directly from the sample bottle, refill to the mark made in Sec. 10.2.2. with water and then measure the volume of sample that was in the bottle. 10.2.10. Seal and shake the separatory funnel vigorously for 2 minutes with periodic venting to release excess pressure. The automatic shaker may be employed on the high setting for 2 minutes after the separatory funnel has been shaken by hand and vented periodically for 30 seconds.

• Methylene chloride creates excessive pressure very rapidly; therefore, initial venting should be done immediately after the separatory funnel has been sealed and shaken once. The separatory funnel should be vented into a hood to avoid exposure of the analyst to solvent vapors. 10.2.11. Allow the organic layer to separate from the water phase for a minimum of 10 minutes. If the emulsion interface between layers is more than one-third the size of the solvent layer, the analyst must employ mechanical techniques to complete the phase separation.

• The optimum technique depends on the sample and may include stirring, filtration of the emulsion through glass wool, centrifugation, or other physical methods. 10.2.12. Decant the solvent extract through a glass funnel containing sodium sulfate and into a 500mL Erlenmeyer flask.

• Plug a glass funnel with glass wool and add sodium sulfate until it is 2-3cm above the glass wool plug. 10.2.13. Repeat the extraction (Sec. 10.2.10 to 101.2.12) two more times adding fresh 60mL portions of methylene chloride directly to the separatory funnel. 10.2.14. Adjust the pH to < 2 using concentrated sulfuric acid. Shake sample in separatory funnel to ensure mixing and check the pH using narrow-range pH paper. Add more concentrated sulfuric acid, if necessary, to achieve a pH <2. 10.2.15. Add 60mL methylene chloride to the separatory funnel, seal and shake vigorously for 2 minutes with periodic venting to release excess pressure. The automatic shaker may be employed on the high setting for 2 minutes after the separatory funnel has been shaken by hand and vented periodically for 30 seconds.

• Methylene chloride creates excessive pressure very rapidly; therefore, initial venting should be done immediately after theEndyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 16 of 40

Document Control Copy on Buff colored paper. Any other color not official version separatory funnel has been sealed and shaken once. The separatory funnel should be vented into a hood to avoid exposure of the analyst to solvent vapors. 10.2.16. Allow the organic layer to separate from the water phase for a minimum of 10 minutes. If the emulsion interface between layers is more than one-third the size of the solvent layer, the analyst must employ mechanical techniques to complete the phase separation.

• The optimum technique depends on the sample and may include stirring, filtration of the emulsion through glass wool, centrifugation, or other physical methods. 10.2.17. Decant the solvent extract through a glass funnel containing sodium sulfate and into a 500mL Erlenmeyer flask.

• Plug a glass funnel with glass wool and add sodium sulfate until it is 2-3cm above the glass wool plug. 10.2.18. Repeat the extraction (Sec. 10.2.15 to 101.2.17) two more times adding fresh 60mL portions of methylene chloride directly to the separatory funnel. 10.2.19. On the final extraction, rinse the sodium sulfate with two 30ml portions of methylene chloride and collect with the rest of the extract in the 500mL Erlenmeyer flask. 10.2.20. Perform the concentration using the TurboVap Concentration Method (Sec. 10.6)

10.3. Separatory Funnel Liquid-Liquid Extraction (SW-846 Method 3510C) for PAH analysis.

10.3.1. *Pre-rinse all extraction apparatus with MeCl 2 before use. 10.3.2. Using a 1-L graduated cylinder, measure 1-L of sample. Alternatively, if the entire contents of the sample bottle are to be extracted, mark the level of the sample on the outside of the bottle. If high analyte concentrations are anticipated, a smaller sample volume may be taken and diluted to 1-L with DI. 10.3.3. 1-L of DI H 2 O is to be used for the blank and QC sample. 10.3.4. Spike 10ul of the 4,000ppm 8270 surrogate spiking solution into each sample (including blanks, QC samples and matrix spike samples) in the graduated cylinder (or sample bottle) and mix well. 10.3.5. For the sample in each batch selected for use as a matrix spike sample and the QC sample, spike 200ul of the 200ppm 8270 QC/MS spiking standard. 10.3.6. Check the pH of the sample with wide-range pH paper to ensure a neutral pH between 5 and 9. 10.3.7. Quantitatively transfer the sample from the graduated cylinder (or sample bottle) to the 2-L separatory funnel. 10.3.8. Use 60mL of methylene chloride to rinse the cylinder (or bottle) and transfer this rinse solvent to the Separatory funnel. 10.3.9. If the sample was transferred directly from the sample bottle, refill to the mark made in Sec. 10.3.2. with water and then measure the volume ofEndyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 17 of 40

Document Control Copy on Buff colored paper. Any other color not official version sample that was in the bottle. 10.3.10. Seal and shake the Separatory funnel vigorously for 2 minutes with periodic venting to release excess pressure. The automatic shaker may be employed on the high setting for 2 minutes after the Separatory funnel has been shaken by hand and vented periodically for 30 seconds.

• Methylene chloride creates excessive pressure very rapidly; therefore, initial venting should be done immediately after the separatory funnel has been sealed and shaken once. The separatory funnel should be vented into a hood to avoid exposure of the analyst to solvent vapors. 10.3.11. Allow the organic layer to separate from the water phase for a minimum of 10 minutes. If the emulsion interface between layers is more than one-third the size of the solvent layer, the analyst must employ mechanical techniques to complete the phase separation.

• The optimum technique depends on the sample and may include stirring, filtration of the emulsion through glass wool, centrifugation, or other physical methods. 10.3.12. Decant the solvent extract through a glass funnel containing sodium sulfate and into a 500mL Erlenmeyer flask.

• Plug a glass funnel with glass wool and add sodium sulfate until it is 2-3cm above the glass wool plug. 10.3.13. Repeat the extraction (Sec. 10.3.10 to 101.3.12) two more times adding fresh 60mL portions of methylene chloride directly to the separatory funnel. 10.3.14. On the final extraction, rinse the sodium sulfate with two 30ml portions of methylene chloride and collect with the rest of the extract in the 500mL Erlenmeyer flask. 10.3.15. Perform the concentration using the TurboVap Concentration Method (Sec. 10.6)

10.4. Ultrasonic Extraction (SW-846 Method 3550B)-Low Concentration, < 20mg/kg.

10.4.1. The following steps should be performed rapidly to avoid the loss of the more volatile extractable compounds. 10.4.2. *Pre-rinse all extraction apparatus with methylene chloride before use. 10.4.3. Weigh approximately 30g of sample into a 500ml beaker. Record the weight to the nearest 0.01g. 30g of methylene chloride rinsed pool sand are to be used for the blank and QC sample. 10.4.3.1. Samples must be well mixed prior to weighing. Dump entire contents of sample into a tared beaker, remove any foreign objects (sticks, leaves and rocks) and thoroughly mix the sample with a spatula. Replace sample into original sample container leaving 30g in the beaker to be extracted. 10.4.3.2. Nonporous or wet samples (gummy or clay type) that do not have a free flowing sandy texture must be mixed with 60g of anhydrousEndyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 18 of 40

Document Control Copy on Buff colored paper. Any other color not official version sodium sulfate, using a spatula. If required, more sodium sulfate may be added. 10.4.3.3. After addition of sodium sulfate, the sample should be free flowing. 10.4.4. Spike 10ul of the 4,000ppm surrogate standard solution onto all samples, matrix spike samples QC samples and blanks. 10.4.5. For the sample in each batch selected for use as a matrix spike sample and the QC sample, spike 200ul of the 200ppm 8270 QC/MS spiking standard. 10.4.6. Immediately add 100mL of 1:1 acetone/methylene chloride. Method 3550B allows for the use of other extraction solvents, provided the analyst can demonstrate adequate performance for the compounds of interest in the sample matrix. This will include MDL and DOC studies. Associated QA/QC with the extraction set must meet laboratory acceptance limits. 10.4.7. Tune sonicator daily or after changing the horn (use 3⁄4 inch horn). 10.4.7.1. Ensure that the probe is not immersed in liquid and that it does not come in contact with anything. 10.4.7.2. Set PULSER to OFF. 10.4.7.3. Set OUTPUT CONTROL to “10” 10.4.7.4. Set POWER SWITCH to ON. The switch will illuminate. 10.4.7.5. Momentarily depress TUNE SWITCH and rotate the tuner clockwise or counterclockwise until a minimum (not maximum) reading (usually <20) is obtained on power monitor. 10.4.7.6. Set OUTPUT CONTROL to “10” 10.4.7.7. Set % DUTY CYCLE to “50” 10.4.7.8. Set TIMER to “180S” 10.4.7.9. Set PULSER to ON position 10.4.8. Before each sample, place the probe tip in fresh 1:1 acetone/methylene chloride and energize the power supply for a few seconds to remove any residue. 10.4.9. Place the bottom surface of the tip of the 3⁄4 inch disrupter horn about 1⁄2 inch below the surface of the solvent, but above the sediment layer. If the horn comes in contact with the sediment output is reduced. 10.4.10. Press START on sonicator and extract ultrasonically for 3 minutes, with output control knob set to 10 (full power) at 50% duty cycle. Do not use microtip probe.

• It is highly advisable to wear earplugs during the sonication process to prevent possible damage to one’s hearing. 10.4.11. Decant the solvent extract through a glass funnel containing sodium sulfate and into a 500mL Erlenmeyer flask.

• Plug a glass funnel with glass wool and add sodium sulfate until it is 2-3cm above the glass wool plug. 10.4.12. Repeat the extraction two or more times with two additional 100mL portions of 1:1 acetone/methylene chloride. Decant off the solvent after each ultrasonic extraction. On the final ultrasonic extraction, pour the entire sample onto the sodium sulfate and rinse with two 50ml portions of 1:1 acetone/methylene chloride.Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 19 of 40

Document Control Copy on Buff colored paper. Any other color not official version 10.4.13. Perform the concentration using the TurboVap Concentration Method (Sec. 10.6)

10.5. Ultrasonic Extraction (SW-846 Method 3550B)-High Concentration, >20mg/kg

10.5.1. The following steps should be performed rapidly to avoid the loss of the more volatile extractable compounds. 10.5.2. Transfer approximately 2g (record weight to the nearest 0.01g) of wellmixed sample to a 40mL VOA vial. Wipe the mouth of the vial with a Kimwipe to remove any sample material. Record the exact weight of the sample taken. 10.5.3. Add 2g anhydrous sodium sulfate to the sample in the 40mL vial and mix well. 10.5.4. Spike 25ul of the 4,000ppm surrogate standard solution onto all samples, matrix spike samples QC samples and blanks. 10.5.5. For the sample in each batch selected for use as a matrix spike sample and the QC sample, spike 100ul of the 1,000ppm CLP-007A, Base/Neutral QC/MS stock standard and 50ul of the 2,000ppm CLP-007B, Acid QC/MS stock standard. 10.5.6. Immediately add 10.0ml methylene chloride to the vial. 10.5.7. Tune sonicator daily or after changing the horn (use 1/8 inch-tapered microtip). 10.5.7.1. Ensure that the probe is not immersed in liquid and that it does not come in contact with anything. 10.5.7.2. Set PULSER to OFF. 10.5.7.3. Set OUTPUT CONTROL to “5” **Never exceed this level with the microtip.** 10.5.7.4. Set POWER SWITCH to ON. The switch will illuminate. 10.5.7.5. Momentarily depress TUNE SWITCH and rotate the tuner clockwise or counterclockwise until a minimum (not maximum) reading (usually <20) is obtained on power monitor. 10.5.7.6. Set OUTPUT CONTROL to “5” 10.5.7.7. Set % DUTY CYCLE to “50” 10.5.7.8. Set TIMER to “120S” 10.5.7.9. Set PULSER to ON position 10.5.8. Before each sample, place the probe tip in fresh methylene chloride and energize the power supply for a few seconds to remove any residue. 10.5.9. Disrupt the sample with the 1/8 inch tapered microtip ultrasonic probe for 2 minutes at output control setting 5 and with a 50% duty cycle. 10.5.10. Loosely pack a disposable Pasteur pipette with 2-3cm glass wool. Filter approximately 4ml of extract through the glass wool into a 4ml vial.

• Note final volume in Extraction Log as 10.0ml. 10.5.11. Spike 10ul of 4,000ppm 8270 Internal Standard mix into the 4mL extract and proceed to Vial Labeling and Extract Archival (Sec. 10.7). If performing Silica Gel Cleanup do not spike IS and proceed to Section 10.8.Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 20 of 40

Document Control Copy on Buff colored paper. Any other color not official version 10.6. Turbo Vap Concentration Method (nitrogen blowdown technique)

10.6.1. *Pre-rinse all extraction apparatus with MeCl 2 before use. 10.6.2. Transfer a maximum 200-mL of the extract to a 200-mL TurboVap concentrator vial. As the volume in the concentrator vial decreases, additional extract can be added. 10.6.3. Place the concentrator vial into the TurboVap II workstation at a water bath temperature of 42 o C. If the concentrator vials are initially full, start with a low gas pressure and increase the pressure as the volume in the vial decreases. Operate at a maximum gas pressure of 15psi (1.0 bars). 10.6.4. Caution : when the volume of solvent is reduced below 1-mL, analytes may be lost. 10.6.5. When the solvent volume reaches ~1.5-mL (at the bottom of the tapered part of the vial) remove the vial from the water bath. 10.6.6. With a 9.0” Pasteur pipette, use the entire sample volume to rinse the lower, tapered portion of the concentrator vial a couple of times. Transfer the extract to a 4-mL vial. 10.6.7. Repeat Step 5, two times with fresh 1-mL portions of methylene chloride. 10.6.8. Bring extract up to a final volume of 4-mL with methylene chloride. 10.6.9. Spike 10ul of 4,000ppm 8270 Internal Standard mix into the 4mL extract and proceed to Vial Labeling and Extract Archival (Sec. 10.7). If performing Silica Gel Cleanup do not spike IS and proceed to Section 10.8.

10.7. Vial Labeling and Extract Archival

10.7.1. All sample extracts are to be archived in 4.0-mL vials in the sample extract refrigerator for a minimum of 40 days. 10.7.2. For each sample, a portion of the extract to be analyzed is to be transferred to a 2.0-mL vial lined with a 500uL micro-insert if necessary. If matrix is a solid, the extraction analyst should prepare a 2-mL vial and cap it without transferring the extract. This will allow suspended particles to settle to the bottom. The 8270 analyst will transfer the extract before analysis on the GC/MS. 10.7.3. All vials are to be labeled with the following: 10.7.3.1. Method ID (8270) & Matrix 10.7.3.2. Sample Reference Number 10.7.3.3. Extraction Date 10.7.3.4. Extraction Analyst Initials

10.8. Silica Gel Cleanup Method for PAH compounds (SW-846, Modified Method 3630C).

10.8.1. Place a large drying column in a clamp on a ring stand. 10.8.2. Pack a wad of glass wool down into the tip of a large drying column. 10.8.3. Fill the column with 3-4” of silica gel.Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 21 of 40

Document Control Copy on Buff colored paper. Any other color not official version 10.8.4. Rinse the column with 20mls of Methylene Chloride but do not let the column go dry. 10.8.5. Once almost all of the Methylene Chloride is through the column place the column in a clean TurboVap Tube and transfer the extract onto the column via pipet. 10.8.6. Rinse the old TurboVap tube with 3, 2ml aliquots of Methylene Chloride and transfer these onto the column. 10.8.7. Let the solvent flow through the column without applying pressure. This may take awhile. 10.8.8. Rinse the column with at least 20mls of Methylene Chloride. 10.8.9. Finally, gently blow the last bit of solvent through the column with a large pipet bulb. 10.8.10. Repeat the concentration using the TurboVap Concentration Method (Sec. 10.6)

10.9. Analysis

10.9.1. A single-column analysis is performed using a 0.25mm ID Restek Rxi5ms capillary column (or equivalent). 10.9.2. MSD Chemstation D.02.00 software is employed to operate the GC/MS and acquire/store raw data on the Chemist (8270) computer. 10.9.3. GC operating conditions are determined by the analyst and recorded in the following places:

• Temperature, pressure and injection programs are all saved as acquisition method AQ-8270x. These conditions are printed and filed with the calibration method and chromatograms after a new calibration method is created. 10.9.4. Established operating conditions are used for both calibration and sample analyses. 10.9.5. All analyses of calibration standards, LRBs, LFBs, LFMs, LDs, and field samples must be recorded in the “5973 Run Log” file located on the Chemist computer.Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 22 of 40

Document Control Copy on Buff colored paper. Any other color not official version 10.10. Dilutions

10.10.1. Some samples may require dilution in order to bring one or more target analytes within the calibration range or to overcome significant interferences with some analytes. 10.10.2. Dilutions are made using methylene chloride and adjusting the amount of IS to 40ug. 10.10.3. Dilutions must be re-analyzed with all necessary calibration verification requirements being met.

10.11. Percent Solids

10.11.1. Dry weight, used for soil calculations, is determined by measuring the percent solids of the sample. 10.11.2. The BOD/Solids analyst determines percent solids using EPA Method 160.3.

10.12. Initial Calibration:

10.12.1. Instrument Performance Check – Decafluorotriphenylphosphine (DFTPP) analysis performed every 12 hours to confirm that the mass spectrometer is tuned properly for 8270 analysis. The mass intensities are then compared to the tune criteria listed in Table 1. 10.12.1.1. Three scans (the peak apex scan and the scans immediately preceding and following the apex) are acquired and averaged. Background subtraction is required and must be accomplished using a scan no more than 20 scans prior to the elution of DFTPP. The background subtraction should be designed to eliminate column bleed or instrument background ions. Do not subtract part of the DFTPP peak.

• MSD Chemstation software is used to automatically evaluate the DFTPP.

• All subsequent standards, field samples and QA/QC samples associated with a DFTPP analysis must use the identical MS instrument conditions.

• If all tune criteria is not met, system maintenance (possibly including re-tuning the MS) and reanalysis of the DFTPP are required until performance is acceptable. 10.12.1.2. A 25ng of DFTPP is analyzed at the start of each data set and every 12 hours of analysis by injecting 1uL of a 25ppm DFTPP tuning standard. 10.12.1.3. Also included in the mix are Benzidine and Pentachlorophenol to monitor peak shape and total recovery. These compounds are very susceptible to active site degradation and peak tailing. They should be present at their normal responses and no peak tailing should be visible.Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 23 of 40

Document Control Copy on Buff colored paper. Any other color not official version

10.12.1.4. Also included is 4,4’-DDT which degrades to DDE and DDD. Degradation byproducts must be less than 20% of DDT peak area in the total ion chromatogram (TIC). Evaluation can be performed by integrating all three peaks and using the area counts to calculate percent breakdown using the following formula:

((area DDD + area DDE) / (area DDD + area DDE + area DDT)) x 100

10.12.1.5. If degradation is excessive and/or chromatography is poor, the injection port may require cleaning. It may also be necessary to clip off 20-40 cm from the head of the column.

10.12.2. Calibration Standards

10.12.2.1. All calibration standards are recorded in the GC/MS SVOC Standards log at the 8270 workstation. Standards opened and used in the extraction lab are recorded in the Extraction Lab Standards log. 10.12.2.2. A minimum of five calibration standards is required for calibration curves using average of response factor and linear regression models; a minimum of six calibration standards are needed for a quadratic regression curve fit model. 10.12.2.3. Because of the number of compounds analyzed by Method 8270, it may be necessary to use multiple curve fit models for calibration. Also, the response of all the compounds in the calibration standards are not equal and it is therefore necessary to include additional calibration standards in the initial calibration so that there are sufficient calibration points within the calibration range for all compounds. 10.12.2.4. Typically, a minimum of 10 calibration standards ranging in concentration from 0.5ug to 100ug are prepared by diluting a primary dilution standard (PDS) containing 200ppm target compounds and surrogate compounds to 4ml with methylene chloride. 40ug of all internal standards is added to each calibration standard. Typical calibration standard concentrations are 0.5, 1.0, 2.0, 5.0, 10, 20, 40, 50, 60, 80 and 100ug. 10.12.3. 1uL of each calibration standard (containing internal standards) is analyzed. 10.12.4. An internal standard calibration procedure is used for initial calibration.

10.12.5. System Performance Check Compounds (SPCCs)

10.12.5.1. A system performance check must be performed to ensure that minimum average response factors (RFs) are met before the calibration curve is used. SPCCs are: N-nitroso-di-n-propylamine; hexachlorocyclopentadiene; 2,4-dinitrophenol; and 4-nitrophenol.Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 24 of 40

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10.12.5.2. The minimum acceptable average RF is 0.050. These SPCCs typically have very low RFs (0.1-0.2) and tend to decrease in response as the chromatographic system or the standard material begins to deteriorate. 10.12.5.3. If the minimum response factors are not met, the system must be evaluated and corrective action must be taken before sample analysis begins. Possible problems include standard mixture degradation, injection port inlet contamination, contamination at the head of the column and active sites in the column or chromatographic system.

10.12.6. Calibration Check Compounds (CCCs)

10.12.6.1. The purpose of the CCCs is to evaluate the calibration from the standpoint of the integrity of the system. High variability for these compounds may be indicative of system leaks or reactive sites on the column. 10.12.6.2. Calculate the mean response factor and the relative standard deviation (RSD) of the response factors for each target analyte. The RSD should be less than or equal to 15% for each target analyte. However, the RSD for each individual CCC (see table 2) must be less than or equal to 30% 10.12.6.3. If the RSD for any CCC is greater than 30%, then the chromatographic system is too reactive to begin sample analysis. Clean or replace the injection port liner and/or capillary column, then repeat the calibration procedure.

10.12.7. Evaluation of retention times – The relative retention time (RRT) of each target analyte in each calibration standard should agree within 0.06RRT units.

10.12.8. Calibration Range and the Linearity of Target Analytes

10.12.8.1. Due to the quantity of target analytes analyzed by Method 8270, it may be necessary to narrow the calibration range for individual analytes by removing data points from either extreme ends of the calibration range to achieve linearity. 10.12.8.2. The method quantitation limit (MQL) is established by the concentration of the lowest standard analyzed during the initial calibration. Hence narrowing the calibration range by changing the concentration of the lowest standard will, by definition, change the MQL. The analyst must ensure that the MCL is at least as low as the reporting limit and preferably one calibration point below that level. 10.12.8.3. It is prohibited to remove data points from within a calibration range while retaining the extreme ends of the calibration range. There must also be a minimum of 5 standards (6 standards if using the quadratic regression model) remaining for the calculation of the RSD.Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 25 of 40

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10.12.8.4. When employing a linear or quadratic curve fit model for a target analyte, in addition to meeting the acceptance criteria for that model, it must also have an RSD less than or equal to 30% when fit with an average of response factor model. If this is unachievable the system must be evaluated. Corrective action must be taken before a new initial calibration is analyzed.

10.12.9. Quality Control Sample/Independent Calibration Verification

10.12.9.1. A 40ug standard is diluted from the 100ppm Custom BNA Spiking Mix from NSI in methylene chloride. 10.12.9.2. This standard is analyzed immediately after the last initial calibration standard and evaluated as if it were a Calibration Verification Standard (sec. 10.3). 10.12.9.3. If the QCS does not meet the calibration verification criteria, a newly prepared QCS standard must be acquired and evaluated. If the new QCS does not meet calibration verification criteria all calibration standards must be evaluated for proper preparation, possible concentration and degradation. New calibration standards should be prepared and a new initial calibration should be run and evaluated with a QCS.

10.12.10. Calibration Models

10.12.10.1. Linear Calibration Using the Response Factor

10.12.10.1.1. The MSD Chemstation Environmental Data Analysis software is used to determine the RF and relative standard deviation (RSD) for each analyte from a minimum of five calibration standards. 10.12.10.1.2. If the RSD is less than or equal to 15% over the calibration range the response factor may be used to determine sample concentrations. 10.12.10.1.3. If the RSD exceeds 15% or at the discretion of the analyst, another calibration method listed below may be used.

10.12.10.2. Linear Calibration Using a Least Squares Regression

10.12.10.2.1. The MSD Chemstation Environmental Data Analysis software is used to perform a linear regression of the instrument response versus the concentration of a minimum of five calibration standards. 10.12.10.2.2. A weighted least squares regression may be used if replicate multi-point calibrations have been performed. For all other instances an unweighted least squares method should be used.Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 26 of 40

Document Control Copy on Buff colored paper. Any other color not official version 10.12.10.2.3. The analyst should not force the line through the origin nor include the origin as an additional calibration point. The intercept is to be calculated from the data points. 10.12.10.2.4. The regression calculation will generate a correlation coefficient (r) that is a measure of good fit. When r is greater or equal to 0.990 this calibration method may be used to determine sample concentration.

10.12.10.3. Non-linear Calibration Using a Quadratic Model

10.12.10.3.1. The MSD Chemstation Environmental Data Analysis software is used to perform a quadratic calibration of the instrument response versus the concentration of a minimum of six calibration standards. 10.12.10.3.2. The curve may not be forced through the origin nor may the origin be included as a calibration point. 10.12.10.3.3. Weighting using a quadratic calibration model may significantly improve its accuracy. 10.12.10.3.4. A coefficient of the determination greater than or equal to 0.990 indicates that the curve may be used to determine sample concentration. 10.12.10.3.5. The quadratic model is not to be used to compensate for detector saturation at higher concentrations or to avoid proper instrument maintenance.

10.12.10.4. Whichever calibration option is employed, analyte and surrogate concentrations must fall within the calibration range in order for calculations to be valid. Dilutions may be necessary in order to bring analyte concentrations within this range. 10.12.10.5. Individual analytes and surrogates within the method may be calibrated using any of the three methods described above. 10.12.10.6. If initial calibration does not meet acceptance criteria the following steps need to be taken: 10.12.10.6.1. Check to be sure that there are no errors in the calculations or preparation of calibration standard solutions. If a standard is found to be prepared wrong a new standard should be made and injected. 10.12.10.6.2. Examine chromatograms for interfering peaks and integrated peak areas. If coelution with contaminant peaks is an issue, instrument conditions may need to be changed to achieve better separation or new calibration standards may need to be made with new reagents. 10.12.10.6.3. Check instrument performance. If an instrument performance problem is found, correct the problem and re-analyze the initial calibration standards. 10.12.10.6.4. If no instrument problem is found and reanalysis of initialEndyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 27 of 40

Document Control Copy on Buff colored paper. Any other color not official version calibration standards is unsuccessful, new calibration standards must be made.

10.13. Calibration Verification – consists of three steps that are performed at the beginning of each 12-hour analytical shift.

10.13.1. Prior to the analysis of samples or calibration standards, inject 25ng of the DFTPP standard into the GC/MS system. The resultant Mass Spectrum for DFTPP must meet the criteria given in Table 1 before sample analysis begins. These criteria as well as other IPC criteria (Sec. 10.12.1) must be demonstrated each 12-hour shift during which samples are analyzed.

10.13.2. The initial calibration for each compound of interest should be verified once every 12 hours prior to sample analysis, using the sample introduction technique and conditions used for samples. This is accomplished by analyzing a calibration standard at a concentration near the midpoint concentration (40ug) for the calibration range of the GC/MS. The results from the calibration standard analysis should meet the verification acceptance criteria provided in sections 10.2.4 through 10.2.7.

10.13.3. A method blank should be analyzed after the calibration standard, or at any other time during the analytical shift, to ensure that the total system is free of contaminants. If the method blank indicates contamination, then it may be appropriate to analyze a solvent blank to demonstrate that the contamination is not a result of carryover from standards or samples. See section 9.2 for method blank performance criteria.

10.13.4. SPCCs – A system performance check must be made during every 12- hour analytical shift. Each SPCC in the calibration verification standard must meet a minimum response factor of at least 0.050. This is the same check applied during the initial calibration in section 10.1.5.

10.13.5. CCCs

10.13.5.1. After the system performance check is met, the CCCs listed in Table 2 are used to check the validity of the initial calibration. Use percent difference when performing the average of response factor model calibration. Use percent drift when calibrating using a regression fit model.

10.13.5.2. If the percent difference for each CCC is less than or equal to 20%, then the initial calibration is assumed to be valid. If the criterion is not met for any one CCC, then corrective action must be taken prior to the analysis of samples. If the CCCs are not included in the list of analytesEndyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 28 of 40

Document Control Copy on Buff colored paper. Any other color not official version for a project, and therefore not included in the calibration standards, then all analytes must meet the 20% difference or drift criterion.

10.13.6. Internal Standard retention time – the retention times of the internal standards in the calibration verification standard must be evaluated immediately after or during data acquisition. If the retention time for anyinternal standard changes by more than 30 seconds from that in the midpoint standard level of the most recent initial calibration sequence, then the chromatographic system must be inspected for malfunctions and corrections must be made as required. When corrections are made, reanalysis of samples analyzed while the system was malfunctioning is required.

10.13.7. Internal standard response – if the EICP area for any of the internal standards in the calibration verification standard changes by a factor of two (-50% to +100%) from that in the mid-point standard level of the most recent initial calibration sequence, the mass spectrometer must be inspected for malfunctions and corrections must be made, as appropriate. When corrections are made, reanalysis of samples analyzed while the system was malfunctioning is required.

10.14. GC/MS Analysis of Samples

10.14.1. Inject a 1-2ul aliquot of the sample extract into the GC/MS system, using the same operating conditions that were used for the initial calibration. The sample to be injected must contain 40ug of base/neutral and acid surrogates (assuming 100% recovery). The injection volume must be the same volume used for the calibration standards. 10.14.2. If the response for any quantitation ion exceeds the initial calibrationrange of the GC/MS system, the sample extract must be diluted and reanalyzed. Additional internal standard must be added to the diluted extract to maintain the same concentration as in the calibration standards (40ug).

10.14.3. Internal standard response in all field and QA samples must meet the same criteria as the calibration verification standard (Sec. 10.2.7) to effectively check drifting method performance, poor injection execution, and anticipate the need for system inspection and/or maintenance. If the criteria is not met, affected samples must be reanalyzed.

10.15. Qualitative Analysis – the qualitative analysis identification of compounds determined by this method is based on retention time and on comparison of the sample mass spectrum, after background correction, with characteristic ions in a reference mass spectrum. The reference mass spectrum must be generated by the laboratory using the conditions of this method. The characteristic ions from the reference mass spectrum are defined as the three ions of greatest relative intensity, or any ions over 30% relative intensity, if less than three such ionsEndyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 29 of 40

Document Control Copy on Buff colored paper. Any other color not official version occur in the reference spectrum. Compounds are identified when the following criteria are met.

10.15.1. The intensities of the characteristic ions of a compound must maximize in the same scan or within one scan of each other. Selection of a peak by a data system target compound search routine where the search is based on the presence of a target chromatographic peak containing ions specific for the target compound at a compound-specific retention time will be accepted as meeting this criterion.

10.15.2. The RRT of the sample component is within +/- 0.06 RRT units of the RRT of the standard component.

10.15.3. The relative intensities of the characteristic ions agree within 20% of the relative intensities of these ions in the reference spectrum. (Example: for an ion with an abundance of 50% in the reference spectrum, the corresponding abundance in a sample spectrum can range between 30% and 70%.)

10.15.4. Structural isomers that produce very similar mass spectra should be identified as individual isomers if they have sufficiently different retention times. Sufficient GC resolution is achieved if the height of the valley between two isomer peaks is less than 25% of the sum of the two peaks. Otherwise, structural isomers are identified as isometric pairs. Diastereomeric pairs that may be separable by the GC should be identified, quantitated and reported as the sum of both compounds by the GC.

10.15.5. Identification is hampered when sample components are not resolved chromatographically and produce mass spectra containing ions contributed by more than one analyte. When gas chromatographic peaks obviously represent more than one sample component, appropriate selection of analyte spectra and background spectra is important.

10.15.6. Examination of extracted ion current profiles of appropriate ions can aid in the selection of spectra and in qualitative identification of compounds. When analytes coelute, the identification criteria may be met, but each analyte spectrum will contain extraneous ions contributed by the coeluting compound.

10.16. Unidentified Peak (UIP) Reporting

10.16.1. For samples containing components not associated with the calibration standards, a library search may be made for the purpose of tentative identification.Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 30 of 40

Document Control Copy on Buff colored paper. Any other color not official version 10.16.2. The concentration of any non target analytes identified in the sample should be estimated by rearranging the formula:

RF = (As x Cis) / (Ais x Cs) Where: RF = 1 (assumed) As = peak area of the unknown compound from the TIC Ais = peak area of the nearest IS from the TIC Cs = Concentration of the unknown compound in ug. Cis = Concentration of the internal standard in ug.

10.16.3. The resulting concentration should be reported in a UIP report indicating: the qualitative identification; that the value is an estimate; and the % quality match with the data system library.

10.17. Quantitative Analysis

10.17.1. Once a compound has been identified, the quantitation of that compound will be based on the integrated abundance of the primary characteristic ion from the EICP.

10.17.2. The data analysis software using the initial calibration data may be used to determine the concentration in the extract.

10.17.3. Structural isomers that produce very similar mass spectra should be quantitated as individual isomers if they have sufficiently different retention times. Sufficient GC resolution is achieved if the height of the valley between two isomer peaks is less than 25% of the sum of the two peaks. Otherwise, structural isomers are quantitated as isometric pairs. Diastereomeric pairs that may be separable by the GC should be summed and reported as the sum of both compounds.

11. Data Reduction

11.1. Aqueous calculations

11.1.1. Calculated analyte masses in micrograms (ug) are divided by the volume of sample in liters (L) resulting in calculated sample concentrations in ug/L. 11.1.2. Concentrations may also need to be adjusted for dilutions by multiplying the final concentration by the dilution factor.

11.2. Soil calculations

11.2.1. Soils are reported out as a dry weight concentration using the equation:

Cs = Cex/(Ms*(PS/100)Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 31 of 40

Document Control Copy on Buff colored paper. Any other color not official version where; Cs = Concentration in the sample (ug/Kg, dry) Cex = Calculated mass in ug of analyte in the final extract Ms = Mass of the sample in Kg PS = Percent solid

11.2.2. Concentrations may also need to be adjusted for dilutions by multiplying the final concentration by the dilution factor.

12. Data Recording

12.1. Locating the 8270 Chain-of-Custody and extracted samples

12.1.1. The Chain-of-Custody for extracted 8270 samples will be found in the bins dedicated to methods of the Organic Department labeled “8270”. 12.1.2. Extracted samples are located in the Organics Department refrigerator found in the extraction lab. 12.1.3. Enter the individual sample information found on the Extraction Log sheet into the Excel Run-log (“5973”).

12.2. Data from MSD Chemstation is directly imported into the LIMS system using a Microsoft Excel macro. The macro calculates the reported values taking into consideration: volume/mass extracted; percent solid (soils only); and post extraction dilutions.

12.3. Target Compounds

12.3.1. If analyte concentration is below the reporting limit, report “< (Reporting Limit)” 12.3.2. As long as it is within the calibration curve, report that value. Otherwise, dilute the sample and rerun OR add additional standards to the calibration tables.

13. Data Archiving

13.1. Hard Copies

13.1.1. All QC packets from method analyses are to be kept for 5 years. 13.1.2. QC packets are separated by method and kept in the filing cabinet near the 8270 workstation or in banker boxes (the most recent QC packets are kept in the filing cabinet, space permitting, while all others are kept in folders in labeled banker boxes beneath the workstation). 13.1.3. Only the previous and present year QC data are kept on the premises. All other QC data is kept in the Endyne storage facilities. 13.1.4. Hard copies of all chromatograms are saved as data packets by order ID with all other Organic data packets.Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 32 of 40

Document Control Copy on Buff colored paper. Any other color not official version 13.2. Electronic Backup

13.2.1. An electronic backup of all new data files should occur at least once a month. 13.2.2. Data is archived in 8270-525 Backup in the Shared folder on the Server. 13.2.3. Annually, data is backed up on CD-R.

14. Instrument Maintenance

14.1. Recalibration

14.1.1. In addition to recalibration being necessary when calibration verification does not meet acceptance criteria, significant maintenance activities or hardware changes may also require recalibration. 14.1.2. Maintenance that should not automatically require recalibration: 14.1.2.1. Changing septa; compressed gas cylinders; syringes; moisture, hydrocarbon, or oxygen traps; split seals; column fittings; inlet liners. 14.1.2.2. Other procedures include breaking off or changing a guard column or cleaning the inlet. 14.1.2.3. Whenever such procedures are performed, the analyst must demonstrate that the results for a calibration verification standard meet the acceptance criteria. 14.1.3. Maintenance that automatically requires recalibration: 14.1.3.1. Changing, replacing, or reversing the column; and replacing the injection port. 14.1.3.2. Changing or replacing the column will also require that the retention time windows be redetermined.
14.1.3.3. Cleaning the MS source; changing the electron multiplier, ion source chamber or injection port all require recalibration.

14.2. Maintenance Log

14.2.1. In the Instrument Maintenance Log found on a separate sheet in the 5973 Run Log, enter any problems that have arisen with any methods and how the problem was solved. Also log in any changes made to the instrument (i.e. gas flow changes, column changes, injection port changes, etc.). 14.2.2. Each entry must be accompanied by the Date and Analyst’s Initials

14.3. Standards Log

14.3.1. Whenever any standard is opened or made up, enter the date, analyst’s initials, source of standard, type and concentration, and detailed steps as to how the standards were prepared.

14.4. MaintenanceEndyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 33 of 40

Document Control Copy on Buff colored paper. Any other color not official version 14.4.1. General 14.4.1.1. The Merlin Micro Seal is good for more than 2000 injections. However, if the traditional septa are used, they must be changed every 30 or so runs.

• Occasional inspection of the microseal for coring or cracking is recommended. 14.4.1.2. Replace injection port liner every 100-150 injections; whenever standard degradation is evident 14.4.1.3. Replace injection port orange O-Rings if dried and cracking 14.4.1.4. Replace column ferrules when cutting the column

14.4.2. Injection Port Liner Cleaning

• Rinse with MeCl 2

• Rinse with HNO 3

• Rinse with HCl

• Rinse with DI

• Rinse with MeOH

• Dry with N 2

• Rinse for 30 seconds with silanating agent

• Rinse with Toluene

• Rinse with MeOH

• Dry with Nitrogen

14.4.3. Changing a Column

14.4.3.1. Vent the MS 14.4.3.2. Lower all GC temperatures (oven and injector) to < 70 o C 14.4.3.3. Remove the detector end of the column first 14.4.3.4. Plug the detector end of the column with and injection port septa 14.4.3.5. Remove the injector end of the column and plug it into the septa. 14.4.3.6. Remove the old column from the oven and install the new column in the injection port. Ensure there is carrier gas flow by dipping the tail end of the column into solvent and condition the column for a couple of hours outside the MS. 14.4.3.7. After conditioning, position the column in the MS so that 2-3mm of column is sticking beyond the end of the transfer line. 14.4.3.8. Close and pump down the MS. Additional conditioning of the column may be necessary.

15. Trouble Shooting

15.1. No Signal

15.1.1. Switch to alternate filament. 15.1.2. Check for MS malfunctions.Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 34 of 40

Document Control Copy on Buff colored paper. Any other color not official version 15.2. Noisy / High Baseline

15.2.1. Using an air duster, check for leaks into the MS by spraying at system seals and the MS transfer line. Monitor ion scans in manual tuning window for primary ions of fluorinated compound in air duster. 15.2.2. Use a leak detector to check for helium leaks in connections in the supply line and the injection port. 15.2.3. Double check column insertion distances.

15.3. High or Low Column Flows / Head Pressure Not Adjustable

15.3.1. Split vent lines may be contaminated with sample waste. To resolve this problem, rinse the purge lines with MeOH and blow dry. 15.3.2. The column may be plugged. Check the detector and injector ends of the column for blockage

15.4. No Head Pressure

15.4.1. Make sure the injector column fittings are tight. 15.4.2. Make sure the septum is not leaking.

15.5. Reduction in Response / Coelution of Certain Analytes

15.5.1. There may be active sites in the injector / column. Try changing the injection port liner, gold plated seal, septa, or removing 1-2 loops of column. 15.5.2. Check column flow. If flow is too high or too low, coelution and/or tailing may occur. 15.5.3. Check column insertion distance into the MS.

16. Method Modifications

16.1. Sec. 10.4, Method 3550B calls for the solvent to be decanted through filter paper after sonication. Endyne filters through muffled sodium sulfate and glass wool to remove particulate and further dry the extract.

17. Bibliography/Reference

Method 8270C Semivolatile Organic Compounds by GC/MS. Revision 3. USEPA, SW-846, December 1996.

Method 8000B Determinative Chromatographic Separations, Revision 2. USEPA, SW-846, December 2006.Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 35 of 40

Document Control Copy on Buff colored paper. Any other color not official version Method 3500B, Organic Extraction and Samp le Preparation, Revision 2. USEPA, SW-846, December 2006.

Method 3510C, Separatory Funnel Liquid- Liquid Extraction, Revision 3. USEPA, SW-846, December 2006.

Method 3550B, Ultrasonic Extraction, Revision 2. USEPA, SW-846, December 2006.

Method 3630C, Silica Gel Cleanup, Revision 3. USEPA, SW-846, December 2006.

18. Revision History

Revision #7, April 6, 2005 -Revised safety section -Updated QC section -Added Table #3 – Detection Limits -Added Bibliography -Added Revision History -Added sign off sheet Reviewed Method: March 2006 Revision #8, April 4, 2007, Matthew White Complete revision of the SOP, which includes: -Clarification of calibration models -Updated QA/QC criteria including corrective action and qualifying data -Revised extractions, which now include method numbers and high and low level soil extractions -Detailed sections on initial calibration and calibration verification Revision #9, September 20, 2007 -Section 10.2.10 & 10.2.15 & 10.3.10 Defined 2 minute extraction shake. -Section 10.2 Defined option of reversing extraction pH sequence. -Section 10.4.6 Defined the acceptability of using alternate extraction solvents in the sonication method.Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 36 of 40

Document Control Copy on Buff colored paper. Any other color not official version TABLE 1. DFTPP KEY IONS AND ION ABUNDANCE CRITERIA

Mass Ion Abundance Criteria

51 30-60% of mass 198 68 < 2% of mass 69 70 < 2% of mass 69 127 40-60% of mass 198 197 < 1% of mass 198 198 Base peak, 100% relative abundance 199 5-9% of mass 198 275 10-30% of mass 198 365 > 1% of mass 198 441 Present but less than mass 443 442 > 40% of mass 198 443 17-23% of mass 442

a J.W. Eichelberger, L.E. Harris, and W.L. Budde. “Reference Compound to Calibrate Ion Abundance Measurement in Gas Chromatography-Mass Spectrometry”, Analytical Chemistry, 47, 995 (1975).

TABLE 2. CALIBRATION CHECK COMPOUNDS (CCC)

Base/Neutral Fraction Acid Fraction

Acenaphthene 4-Chloro-3-methylphenol 1,4-Dichlorobenzene 2,4-Dichlorophenol Hexachlorobutadiene 2-Nitrophenol Diphenylamine Phenol Di-n-octyl phthalate Pentachlorophenol Fluoranthene 2,4,6-Trichlorophenol Benzo(a)pyreneEndyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 37 of 40

Document Control Copy on Buff colored paper. Any other color not official version TABLE 3.

Reporting Limit Reporting Limit Compound Waterug/L Soilug/Kg Compound Waterug/L Soilug/K g Acenaphthene-d (IS) NA NA 2,4-Dinitrophenol 20.0 400. Acenaphthene 2.0 40.0 2,6-Dinitrophenol 20.0 400. Acenaphthylene 2.0 40.0 2,4-Dinitrotoluene 5.0 100. Aniline 5.0 100. 2,6-Dinitrotoluene 5.0 100. Anthracene 2.0 40.0 Fluoranthene 2.0 40.0 Benz(a)anthracene 2.0 40.0 Fluorene 2.0 40.0 Benzidine 15.0 300. Hexachlorobenzene 5.0 100. Benzo(a)pyrene 2.0 40.0 Hexachlorobutadiene 5.0 100. Benzo(b)fluoranthene 2.0 40.0 Hexachlorocyclopentadiene 20.0 400. Benzo(k)fluoranthene 2.0 40.0 Hexachloroethane 5.0 100. Benzo(g,h,i)perylene 2.0 40.0 I ndeno(1,2,3-cd)pyrene 2.0 40.0 Benzyl alcohol 10.0 200. Isophorone 2.0 40.0 Bis(2-chloroethoxy)methane 5.0 100. 1-Methylnaphthalene 2.0 100. Bis(2-chloroethyl) ether 5.0 100. 2-Methylnaphthalene 2.0 100. Bis(2-chloroisopropyl) ether 10.0 200. 2-Methylphenol 5.0 100. Bis(2-ethylhexyl) phthalate 5.0 100. 3-Methylphenol 5.0 100. 4-Bromophenyl phenyl ether 2.0 40.0 4-Methylphenol 5.0 100. Butyl benzyl phthalate 5.0 100. Naphthalene-d (IS) NA NA Carbazole 10.0 200. Naphthalene 2.0 40.0 4-Chloroaniline 5.0 100. 1-Naphthylamine 10.0 200. 4-Chloro-3-methylphenol 10. 0 200. 2-Naphthylamine 10.0 200. 1-Chloronaphthalene 2.0 40.0 2-Nitroaniline 20.0 400. 2-Chloronaphthalene 2.0 40.0 3-Nitroaniline 10.0 200. 2-Chlorophenol 5.0 100. 4-Nitroaniline 20.0 400. 4-Chlorophenyl phenyl ether 2.0 40.0 Nitrobenzene 2.0 40.0 Chrysene 2.0 40.0 2-Nitrophenol 10.0 200. Chrysene-d (IS) NA NA 4-Nitrophenol 10.0 200. Dibenz(a,h)anthracene 2.0 40.0 N-Nitrosodi-n-butylamine 5.0 100. Dibenzofuran 2.0 40.0 N-Nitrosodi-n-propylamine 10.0 200. 1,2-Dichlorobenzene 2.0 40.0 N-Nitrosodiphenylamine 5.0 100. 1,3-Dichlorobenzene 2.0 40.0 N-Nitrosopiperidine 10.0 200. 1,4-Dichlorobenzene-d (IS) NA NA N-Nitrosodimethylamine 5.0 100. 1,4-Dichlorobenzene 2.0 40.0 Pentachlorophenol 15.0 300. 3,3'-Dichlorobenzidine 5.0 100. Perylene-d (IS) NA NA 2,4-Dichlorophenol 5.0 100. Phenanthrene 2.0 40.0 Di-n-butyl phthalate 5.0 100. Phenanthrene-d (IS) NA NA Di-n-octyl phthalate 5.0 100. Phenol 5.0 100. Diethyl phthalate 5.0 100. Pyrene 2.0 40.0 2,4-Dimethylphenol 5.0 100. 1,2, 4-Trichlorobenzene 2.0 40.0 Dimethyl phthalate 5.0 100. 2,4,5-Trichlorophenol 10.0 200. 4,6-Dinitro-2-methylphenol 50.0 2 ,000. 2,4,6-Trichlorophenol 10.0 200.Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 38 of 40

Document Control Copy on Buff colored paper. Any other color not official version TABLE 4.

Compound Primary Ion Confirmation Ion(s) Acenaphthene-d (IS) 164 162,160 Acenaphthene 154 153,152 Acenaphthylene 152 151,153 4-Aminobiphenyl 169 168,170,115 Aniline 93 66,65 Anthracene 178 176,179 Benz(a)anthracene 228 229,226 Benzidine 184 92,185 Benzoic acid 122 105,77 Benzo(a)pyrene 252 253,125 Benzo(b)fluoranthene 252 253,125 Benzo(k)fluoranthene 252 253,125 Benzo(g,h,i)perylene 276 138,277 Benzyl alcohol 108 79,77 Bis(2-chloroethoxy)methane 93 95,123 Bis(2-chloroethyl) ether 93 63,95 Bis(2-chloroisopropyl) ether 45 77,121 Bis(2-ethylhexyl) phthalate 149 167,279 4-Bromophenyl phenyl ether 248 250,141 Butyl benzyl phthalate 149 91,206 Carbofuran 164 149,131,122 4-Chloroaniline 127 129,65,92 4-Chloro-3-methylphenol 107 144,142 1-Chloronaphthalene 162 127,164 2-Chloronaphthalene 162 127,164 2-Chlorophenol 128 64,130 4-Chlorophenyl phenyl ether 204 206,141 Chrysene 228 226,229 Chrysene-d (IS) 240 120,236 12 Dibenz(a,h)anthracene 278 139,279 Dibenzofuran 168 139 1,2-Dichlorobenzene 146 148,111 1,3-Dichlorobenzene 146 148,111 1,4-Dichlorobenzene-d (IS) 152 150,115 1,4-Dichlorobenzene 146 148,111 3,3'-Dichlorobenzidine 252 254,126 2,4-Dichlorophenol 162 164,98 Di-n-butyl phthalate 149 150,104 Di-n-octyl phthalate 149 167,43 Diethyl phthalate 149 177,150 2,4-Dimethylphenol 122 107,121 Dimethyl phthalate 163 194,164 1,4-Dinitrobenzene 168 75,50,76,92,122 1,3-Dinitrobenzene 168 76,50,75,92,122 1,2-Dinitrobenzene 168 50,63,74 4,6-Dinitro-2-methylphenol 198 51,105 2,4-Dinitrophenol 184 63,154Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 39 of 40

Document Control Copy on Buff colored paper. Any other color not official version TABLE 4. cont.

Compound Primary Ion Confirmation Ion(s) 2,6-Dinitrophenol 162 164,126,98,63 2,4-Dinitrotoluene 165 63,89 2,6-Dinitrotoluene 165 63,89 Diphenylamine 169 168,167 Fluoranthene 202 101,203 Fluorene 166 165,167 Hexachlorobenzene 284 142,249 Hexachlorobutadiene 225 223,227 Hexachlorocyclopentadiene 237 235,272 Hexachloroethane 117 201,199 Indeno(1,2,3-cd)pyrene 276 138,227 Isophorone 82 95,138 1-Methylnaphthalene 142 141 2-Methylnaphthalene 142 141 2-Methylphenol 107 108,77,79,90 3-Methylphenol 107 108,77,79,90 4-Methylphenol 107 108,77,79,90 Naphthalene-d (IS) 136 68 Naphthalene 128 129,127 1-Naphthylamine 143 115,89,63 2-Naphthylamine 143 115,116 2-Nitroaniline 65 92,138 3-Nitroaniline 138 108,92 4-Nitroaniline 138 65,108,92,80,39 Nitrobenzene 77 123,65 2-Nitrophenol 139 109,65 4-Nitrophenol 139 109,65 N-Nitrosodiethylamine 102 42,57,44,56 N-Nitrosodi-n-butylamine 84 57,41,116,158 N-Nitrosodi-n-propylamine 70 42,101,130 N-Nitrosodiphenylamine 169 168,167 N-Nitrosopiperidine 114 42,55,56,41 N-Nitrosopyrrolidine 100 41,42,68,69 Pentachlorophenol 266 264,268 Perylene-d (IS) 264 260,265 12 Phenanthrene 178 179,176 Phenanthrene-d (IS) 188 94,80 10 Phenol 94 65,66 Pyrene 202 200,203 1,2,4-Trichlorobenzene 180 182,145 2,4,5-Trichlorophenol 196 198,97,132,99 2,4,6-Trichlorophenol 196 198,200Endyne, Inc. SVOC Method SW 8270C SOP 160 James Brown Drive Revision #9, Effective 9/26/07 Williston, VT 05495 Page 40 of 40

Document Control Copy on Buff colored paper. Any other color not official version I acknowledge that I have read this Standard Operating Procedure and agree to adhere to the Safety and Quality Control policies outlined within.



## Name DateParameter Method Detection Limit ug/L Reporting Limit ug/L Calibration Verification % Recovery Ext. Lab Fortified

Blank % Recovery Matrix Spike % Recovery Duplicate % Difference N-Nitrosodimethylamine 0.590 10.0 80 - 120 < 30 % Pyridine 0.844 10.0 80 - 120 < 30 % Aniline 0.894 10.0 80 - 120 < 30 % Phenol 0.327 5.0 80 - 120 14 - 36 12 - 36 < 30 % 2-Chorophenol 0.755 5.0 80 - 120 39 - 87 28 - 85 < 30 % bis(2-chloroethyl) Ether 0.907 5.0 80 - 120 < 30 % 1,3-Dichlorobenzene 0.885 2.0 80 - 120 < 30 % 1,4-Dichlorobenzene 0.983 2.0 80 - 120 23 - 73 18 - 78 < 30 % 1,2-Dichlorobenzene 0.979 2.0 80 - 120 < 30 % Benzyl Alcohol 0.880 20.0 80 - 120 < 30 % 2-Methylphenol 0.674 5.0 80 - 120 < 30 % b is(2-chloroisopropyl)Et h 0.837 5.0 80 - 120 < 30 % N-Nitrosodi-n-propylami n 0.893 5.0 80 - 120 45 - 87 32 - 88 < 30 % 3&4-Methylphenol 0.695 10.0 80 - 120 < 30 % Hexachloroethane 1.11 5.0 80 - 120 < 30 % Nitrobenzene 0.956 5.0 80 - 120 < 30 % N-Nitrosopiperidine 0.860 10.0 80 - 120 < 30 % Isophorone 0.952 2.0 80 - 120 < 30 % 2-Nitrophenol 0.809 10.0 80 - 120 < 30 % 2,4-Dimethylphenol 0.201 5.0 80 - 120 < 30 % b is(2-chloroethoxy)Meth a 0.870 5.0 80 - 120 < 30 % 2,4-Dichlorophenol 0.837 5.0 80 - 120 < 30 % 1,2,4-Trichlorobenzene 1.10 2.0 80 - 120 30 - 82 22 - 87 < 30 % Naphthalene 0.135 2.0 80 - 120 < 30 % 4-Chloroaniline 0.983 5.0 80 - 120 < 30 % 2,6-Dichlorophenol 0.882 5.0 80 - 120 < 30 % Hexachlorobutadiene 1.30 5.0 80 - 120 < 30 % N-Nitrosodi-n-butylamin e 0.735 5.0 80 - 120 < 30 % 4-Chloro-3-methylphenol 0.754 10.0 80 - 120 45 - 115 44 - 107 < 30 % 2-Methylnaphthalene 0.087 2.0 80 - 120 < 30 % 1-Methylnaphthalene 0.059 2.0 80 - 120 < 30 % 

### Control Limits 2010 EPA 8270C Aqueous 

## Endyne, Inc. 160 James Brown Drive Williston, Vermont

Page 1 of 6Parameter Method Detection Limit ug/L Reporting Limit ug/L Calibration Verification % Recovery Ext. Lab Fortified

Blank % Recovery Matrix Spike % Recovery Duplicate % Difference 

### Control Limits 2010 EPA 8270C Aqueous 

## Endyne, Inc. 160 James Brown Drive Williston, Vermont

Hexachlorocyclopentadie n 0.818 20.0 80 - 120 < 30 % 2,4,6-Trichlorophenol 0.890 10.0 80 - 120 < 30 % 2,4,5-Trichlorophenol 0.939 10.0 80 - 120 < 30 % 2-Chloronaphthalene 0.935 2.0 80 - 120 < 30 % 1-Chloronaphthalene 0.994 2.0 80 - 120 < 30 % 2-Nitroaniline 0.845 20.0 80 - 120 < 30 % Dimethylphthalate 0.988 5.0 80 - 120 < 30 % 2,6-Dinitrotoluene 0.992 10.0 80 - 120 < 30 % Acenaphthylene 0.135 2.0 80 - 120 < 30 % 3-Nitroaniline 0.778 20.0 80 - 120 < 30 % Acenaphthene 0.129 2.0 80 - 120 45 - 98 33 - 103 < 30 % 2,4-Dinitrophenol 0.577 20.0 80 - 120 < 30 % Dibenzofuran 0.951 2.0 80 - 120 < 30 % 4-Nitrophenol 0.325 20.0 80 - 120 14 - 59 12 - 61 < 30 % 2,4-Dinitrotoluene 0.939 10.0 80 - 120 50 - 97 31 - 98 < 30 % 1-Naphthylamine 1.57 10.0 80 - 120 < 30 % 2-Naphthylamine 0.810 10.0 80 - 120 < 30 % Fluorene 0.123 2.0 80 - 120 < 30 % Diethylphthalate 1.04 5.0 80 - 120 < 30 % 4-Chlorophenylphenyleth 1.17 2.0 80 - 120 < 30 % 4-Nitroaniline 1.15 20.0 80 - 120 < 30 % 2-Methyl-4,6-dinitrophen o 0.598 50.0 80 - 120 < 30 % N-Nitrosodiphenylamine 0.990 5.0 80 - 120 < 30 % Azobenzene 1.03 5.0 80 - 120 < 30 % 4-Bromophenylphenyleth 1.01 2.0 80 - 120 < 30 % Hexachlorobenzene 1.07 5.0 80 - 120 < 30 % Pentachlorophenol 1.15 20.0 80 - 120 42 - 135 27 - 128 < 30 % Phenanthrene 0.120 2.0 80 - 120 < 30 % Anthracene 0.079 2.0 80 - 120 < 30 % Carbazole 1.05 5.0 80 - 120 < 30 % Di-n-butylphthalate 1.07 5.0 80 - 120 < 30 %

Page 2 of 6Parameter Method Detection Limit ug/L Reporting Limit ug/L Calibration Verification % Recovery Ext. Lab Fortified

Blank % Recovery Matrix Spike % Recovery Duplicate % Difference 

### Control Limits 2010 EPA 8270C Aqueous 

## Endyne, Inc. 160 James Brown Drive Williston, Vermont

Fluoranthene 0.094 2.0 80 - 120 < 30 % Benzidine 0.534 20.0 80 - 120 < 30 % Pyrene 0.078 2.0 80 - 120 62 - 122 45 - 128 < 30 % Benzylbutylphthalate 0.933 5.0 80 - 120 < 30 % B enzo ( a ) ant h racen e 0

. 071 2

. 0 80 - 120 < 30 % Chrysene 0.081 2.0 80 - 120 < 30 % 3,3'-Dichlorobenzidine 0.819 5.0 80 - 120 < 30 % b is(2-ethylhexyl)phthalat e 1.70 5.0 80 - 120 < 30 % Di-n-octylphthalate 0.906 5.0 80 - 120 < 30 % Benzo(b)fluoranthene 0.097 2.0 80 - 120 < 30 % Benzo(k)fluoranthene 0.120 2.0 80 - 120 < 30 % Benzo(a)pyrene 0.068 2.0 80 - 120 < 30 % Indeno[1,2,3-cd]pyrene 0.099 2.0 80 - 120 < 30 % Dibenz(a,h)anthracene 0.114 2.0 80 - 120 < 30 % Benzo(g,h,i)perylene 0.097 2.0 80 - 120 < 30 %

12/31/09 12/31/09 Acid Surrogates 2-Fluorophenol (E.S.) 80 - 120 16 - 50 16 - 50 Phenol-d5 (E.S.) 80 - 120 11 - 42 11 - 42 2,4,6-Tribromophenol (E.S.) 80 - 120 45 - 124 45 - 124

BN Surrogates Nitrobenzene-d5 (E.S.) 80 - 120 34 - 107 34 - 107 2-Fluorobiphenyl (E.S.) 80 - 120 31 - 102 31 - 102 Terphenyl-d14 (E.S.) 80 - 120 55 - 133 55 - 133

Page 3 of 6Parameter Method Detection Limit ug/Kg Reporting Limit ug/Kg Calibration Verification % Recovery Ext. Lab Fortified Blank %

Recovery Matrix Spike % Recovery Duplicate % Difference N-Nitrosodimethylamin e 56.7 400 80 - 120 < 30 % Pyridine 312 800 80 - 120 < 30 % Aniline 10.6 800 80 - 120 < 30 % Phenol 46.7 200 80 - 120 26 - 97 31 - 92 < 30 % 2-Chorophenol 48.1 200 80 - 120 30 - 96 30 - 94 < 30 % bis(2-chloroethyl) Ether 44.4 200 80 - 120 < 30 % 1,3-Dichlorobenzene 44.0 80 80 - 120 < 30 % 1,4-Dichlorobenzene 46.9 80 80 - 120 31 - 78 26 - 80 < 30 % 1,2-Dichlorobenzene 46.3 80 80 - 120 < 30 % Benzyl Alcohol 36.4 800 80 - 120 < 30 % 2-Methylphenol 45.6 200 80 - 120 < 30 % b is(2-chloroisopropyl)E t 42.6 200 80 - 120 < 30 % N-Nitrosodi-n-propylam i 44.1 200 80 - 120 46 - 85 31 - 87 < 30 % 3&4-Methylphenol 38.8 400 80 - 120 < 30 % Hexachloroethane 39.5 200 80 - 120 < 30 % Nitrobenzene 53.8 200 80 - 120 < 30 % N-Nitrosopiperidine 38.5 400 80 - 120 < 30 % Isophorone 41.0 80 80 - 120 < 30 % 2-Nitrophenol 51.5 400 80 - 120 < 30 % 2,4-Dimethylphenol 42.5 200 80 - 120 < 30 % b is(2-chloroethoxy)Met h 42.0 200 80 - 120 < 30 % 2,4-Dichlorophenol 41.0 200 80 - 120 < 30 % 1,2,4-Trichlorobenzene 47.1 80 80 - 120 37 - 86 32 - 90 < 30 % Naphthalene 6.07 80 80 - 120 < 30 % 4-Chloroaniline 12.4 200 80 - 120 < 30 % 2,6-Dichlorophenol 42.5 200 80 - 120 < 30 % Hexachlorobutadiene 49.1 200 80 - 120 < 30 % N-Nitrosodi-n-butylami n 42.0 200 80 - 120 < 30 % 4-Chloro-3-methylphen o 55.6 400 80 - 120 48 - 108 41 - 111 < 30 % 2-Methylnaphthalene 2.90 80 80 - 120 < 30 % 1-Methylnaphthalene 1.95 80 80 - 120 < 30 % 

## Endyne, Inc. 160 James Brown Drive Williston, Vermont

Control Limits 2010 EPA 8270C Solid

Page 4 of 6Parameter Method Detection Limit ug/Kg Reporting Limit ug/Kg Calibration Verification % Recovery Ext. Lab Fortified Blank %

Recovery Matrix Spike % Recovery Duplicate % Difference 

## Endyne, Inc. 160 James Brown Drive Williston, Vermont

Control Limits 2010 EPA 8270C Solid

Hexachlorocyclopentadi e 18.0 800 80 - 120 < 30 % 2,4,6-Trichlorophenol 49.6 400 80 - 120 < 30 % 2,4,5-Trichlorophenol 41.7 400 80 - 120 < 30 % 2-Chloronaphthalene 42.9 80 80 - 120 < 30 % 1-Chloronaphthalene 46.7 80 80 - 120 < 30 % 2-Nitroaniline 65.9 800 80 - 120 < 30 % Dimethylphthalate 38.8 200 80 - 120 < 30 % 2,6-Dinitrotoluene 61.7 400 80 - 120 < 30 % Acenaphthylene 6.38 80 80 - 120 < 30 % 3-Nitroaniline 34.5 800 80 - 120 < 30 % Acenaphthene 6.57 80 80 - 120 49 - 95 50 - 91 < 30 % 2,4-Dinitrophenol 264 800 80 - 120 < 30 % Dibenzofuran 41.2 80 80 - 120 < 30 % 4-Nitrophenol 44.9 800 80 - 120 30 - 98 25 - 101 < 30 % 2,4-Dinitrotoluene 67.5 400 80 - 120 48 - 106 36 - 101 < 30 % 1-Naphthylamine 18.6 800 80 - 120 < 30 % 2-Naphthylamine 13.0 800 80 - 120 < 30 % Fluorene 6.61 80 80 - 120 < 30 % Diethylphthalate 37.8 200 80 - 120 < 30 % 4-Chlorophenylphenylet h 38.2 80 80 - 120 < 30 % 4-Nitroaniline 51.5 800 80 - 120 < 30 % 2-Methyl-4,6-dinitrophe n 56.3 2000 80 - 120 < 30 % N-Nitrosodiphenylamin e 40.7 200 80 - 120 < 30 % Azobenzene 38.3 200 80 - 120 < 30 % 4-Bromophenylphenylet h 40.7 80 80 - 120 < 30 % Hexachlorobenzene 39.3 200 80 - 120 < 30 % Pentachlorophenol 87.6 800 80 - 120 32 - 120 41 - 118 < 30 % Phenanthrene 6.15 80 80 - 120 < 30 % Anthracene 4.35 80 80 - 120 < 30 % Carbazole 44.0 200 80 - 120 < 30 % Di-n-butylphthalate 51.1 200 80 - 120 < 30 %

Page 5 of 6Parameter Method Detection Limit ug/Kg Reporting Limit ug/Kg Calibration Verification % Recovery Ext. Lab Fortified Blank %

Recovery Matrix Spike % Recovery Duplicate % Difference 

## Endyne, Inc. 160 James Brown Drive Williston, Vermont

Control Limits 2010 EPA 8270C Solid

Fluoranthene 5.73 80 80 - 120 < 30 % Benzidine 120 800 80 - 120 < 30 % Pyrene 5.43 80 80 - 120 58 - 109 49 - 113 < 30 % Benzylbutylphthalate 65.1 200 80 - 120 < 30 % B enzo ( a ) ant h racen e 4

. 95 80 80 - 120 < 30 % Chrysene 4.89 80 80 - 120 < 30 % 3,3'-Dichlorobenzidine 24.2 200 80 - 120 < 30 % b is(2-ethylhexyl)phthala t 78.3 200 80 - 120 < 30 % Di-n-octylphthalate 124 200 80 - 120 < 30 % Benzo(b)fluoranthene 4.01 80 80 - 120 < 30 % Benzo(k)fluoranthene 6.15 80 80 - 120 < 30 % Benzo(a)pyrene 9.48 80 80 - 120 < 30 % Indeno[1,2,3-cd]pyrene 5.37 80 80 - 120 < 30 % Dibenz(a,h)anthracene 5.12 80 80 - 120 < 30 % Benzo(g,h,i)perylene 5.34 80 80 - 120 < 30 %

12/31/09 12/31/09 Acid Surrogates 2-Fluorophenol (E.S.) 80 - 120 25 - 111 25 - 111 Phenol-d5 (E.S.) 80 - 120 45 - 108 45 - 108 2,4,6-Tribromophenol (E.S.) 80 - 120 36 - 146 36 - 146

BN Surrogates Nitrobenzene-d5 (E.S.) 80 - 120 28 - 110 28 - 110 2-Fluorobiphenyl (E.S.) 80 - 120 41 - 109 41 - 109 Terphenyl-d14 (E.S.) 80 - 120 58 - 117 58 - 117

Page 6 of 6Document Control Copy on Buff colored paper. Any other color is not official version 

# Endyne, Inc.

160 James Brown Dr.

Williston, VT 05495 Phone: (802) 879-4333 Fax: (802) 879-7103



# Alkaline Digestion for Chromium VI in Solid Samples

Method SW 3060A 

# Standard Operating Procedure

Written: March 8, 2006

Technical Director: Date : Harry B. Locker Ph.D.



### QA Officer: Date :
Mark L. FauselEndyne, Inc. Chromium VI Method SW 3060A SOP 160 James Brown Drive Effective 03/31/06 Williston, VT 05495 Page 2 of 8

Document Control Copy on Buff colored paper. Do not duplicate 

### TABLE OF CONTENTS

Section Page

I – Overview 3

II – Safety 3

III – Waste Disposal 3

IV – Sample Collection, Preservation & Storage 3

V – Equipment & Supplies 3-4

VI – Reagents & Standards 4

VII – Interferences 4

VIII – Quality Control 4-5

IX – Analytical Procedure 5

X – Calibration & Standardization 6

XI – Data Reduction 6

XII – Data Recording 6

XIII – Trouble Shooting 6

XIV – Method Modifications 6

XV – Revision History 6

XVI – References 7

Analyst Attestation 8Endyne, Inc. Chromium VI Method SW 3060A SOP 160 James Brown Drive Effective 03/31/06 Williston, VT 05495 Page 3 of 8

Document Control Copy on Buff colored paper. Do not duplicate Overview :

This method is an alkaline digestion and is used to solubilize water soluble/insoluble Cr(VI) compounds in solid/soil samples. The digested samples are then analyzed for Cr(VI) by method SW 7196A, a spectrophotometric method employing the reaction of a coloring agent diphenylcarbazide with Cr(VI). Please refer to SOP SW 7196A for further details.

I. Safety :

A. This method involves the handling of the chemicals outlined below. Each of these chemicals may have specific associated hazar ds. Analysts must read and become familiar with all elements of each chemical ’s MSDS. Make special awareness of the symptoms of exposure and potential routes of entry. Analysts must notify the Safety Officer immediately if any symptoms of exposure are suspected. B. Personal protective equipment i.e. gloves goggles and lab coat must be worn at all times in designated work areas. All applicable engineering controls, such as fume hoods or splash shields, must be used when perform ing analyses. To ensure the safety of all laboratory personnel; work areas must be ke pt neat and organized, equipment and bench-tops must be cleaned and sterilized, if necessary, at the completion of each task, all containers must be properly labeled as to contents and hazard ratings and spills cleaned immediately and completely.

II. Waste Disposal :

A. Cr(VI) solutions or waste materials that are generated are dumped in the metals waste satellite container found underneath the fume hood on the inorganic floor. B. When the satellite container is full contact one of the hazardous waste personnel who is fitted with a respirator and properly trained in hazardous waste disposal, to dispose of metals waste in the proper corrosive liquid drain. C. Cr(VI) spills are to be treated with ascorb ic acid or another reducing agent to reduce Cr(VI) as well as Cr(III).

III. Sample Collection, Preservation and Storage :

A. Samples should be collected in clean plastic or glass containers that do not contain stainless steel. B. Samples are to be stored at 4 ° C until the time of digestion. C. Cr(VI) is stable in properly stored samples for 30 days from the date of sample. D. The digestate is stable for 7 days from the date of digestion.

IV. Equipment & Supplies :

1. Digestion vessels: 250mL/500mL Erlenmeyer flasks 2. 50mL/100mL graduated cylinder 3. Volumetric flasks, varying sizes 4. Vacuum filtration apparatus 5. Filter membranes (0.90um glass filter) & (0.45um cellulose filter) 6. Stirring hot plates 7. Volumetric pipettesEndyne, Inc. Chromium VI Method SW 3060A SOP 160 James Brown Drive Effective 03/31/06 Williston, VT 05495 Page 4 of 8

Document Control Copy on Buff colored paper. Do not duplicate 8. Calibrated pH meter (refer to pH SOP) with stirring device 9. Calibrated balance (refer to balance SOP) 10. Thermometer capable of measuring 100  ̊ C and with NIST traceable calibration 11. Magnetic stir bars 12. 250mL beakers

V. Reagents & Standards :

1. Nitric Acid (HNO 3 ): 5.0M analytical reagent grad e. Do not use concentrated HNO 3 to make 5.0M solution if it has a yellow tinge as this is an indication of photoreduction of NO 3 to NO 2 , a reducing agent for Cr(VI). 2. Laboratory reagent grade water 3. Digestion Solution: 1) 20g Sodium Hydroxide 2) 30g Sodium Carbonate brought up1000mL volumetrically with reagent water; pH must be 11.5 or greater 4. Magnesium Chloride anhydrous (MgCl 2 ) 5. Phosphate Buffer: 1) 8.71g K 2 HPO 4 2) 6.80g KH 2 PO 4 brought up 100mL volumetrically with reagent water; pH must around 7 6. Potassium Dichromate, 1000ppm soluble spiking solution 1) Dissolve 0.2829g H 2 Cr 2 O 7 in a 100mL volumetric flask with reagent water 2) Prepare 10ppm working stock solution by adding 1mL of 1000ppm stock to 100mL reagent water volumetrically. 3) Prepare all laboratory QC’s and soluble matrix spikes from 10ppm working stock. 7. Lead Chromate (PbCrO 4 ), insoluble matrix spike. 8. ERA Hexavalent Chromium Soil QC – Independent QC 9. ERA blank soil for metals digestion.

VI. Interference :

This method is usually free from interfere nces. However, certain reducing/oxidizing substances may interfere with the results of the analytical method if the chromium concentration is relatively low and the reducing/oxidizing substances are high. The addition of Mg with phosphate buffer is desi gned to suppress oxidation in the digestion.

VII. Quality Control :

A. All samples and QA are analyzed via method SW 7196A and quality control is pertinent to that method. (refer to SOP SW 7196A) B. A laboratory reagent blank must be prepared with the ERA blank soil and analyzed with each digestion batch. The recovery must be 1/10 less than the MDL as defined in method SW 7196A. C. A laboratory QC prepared at varying concentrations from the10ppm Potassium Dichromate stock must be spiked to the ERA blank sand and digested and analyzed with each digestion batch. Recovery must be 100 ± 20%.Endyne, Inc. Chromium VI Method SW 3060A SOP 160 James Brown Drive Effective 03/31/06 Williston, VT 05495 Page 5 of 8

Document Control Copy on Buff colored paper. Do not duplicate D. An independent soil QC from ERA must be digested and analyzed with each digestion batch. Recovery must be with in the certified accepted range as defined by the ERA certificate of analysis. E. A separately prepared duplicate sample mu st be analyzed each digestion batch. Duplicates samples must have a relative percent difference of ≤ 20%. F. Both a soluble and insoluble digestion sp ike must be prepared and analyzed during each digestion batch. The soluble digestion spike is analyzed at 0.2ppm (2mL, 10ppm working stock added predigestion). The insoluble digestion spike is prepared by adding 20mg of Lead Chromate to the sample prior to digestion. The acceptance range for both matrix spike recoveries is 75-125%. G. Any data that falls outside of the above stated criteria are either redigested/analyzed or qualified with the appropriate qualifier. H. All in-house prepared reagents and sta ndards must be properly labeled and have preparation and expiration dates noted on them. I. All reagents and standards must be properly documented with manufacture, lot numbers and expiration dates as well as a brief description of preparation in the miscellaneous logbook.

VIII. Analytical Procedure :

1. Weigh and record in logbook a known amount of homogeneous sample into a clean labeled 250mL Erlenmeyer flask. Samples ma y need to be ground prior to weighing. For blanks and QC’s weigh 2.5g ±0.1g. 2. Add appropriate volume of spiking solu tion from 10ppm working stock to QC’s and matrix spikes. 3. Add 50mL ± 1mL digestion solution to each sample, QC and blank using a graduated cylinder. 4. Add approximately 400mg MgCl 2 and 0.5mL phosphate buffer to each sample and cover with watch glasses. 5. Stir samples continuously with out heat for five minutes on the stirring hot plate with magnetic stir bars. 6. Adjust the temperature setting of each stirring hot plate to 185oC. 7. Monitor temperatures with thermometer until they reach 90-95oC. Maintain temperature for at least 60 minutes with continuous stirring. 8. Turn off heat on all hot plates and maintain stirring while the samples gradually cool. 9. Filter each sample individually through a glass filter, rinsing the digestion vessel with three successive portions of reagent water. Rinse the filter and apparatus with reagent water. 10. Collect filtrate and transfer to a 250mL beaker. Discard solid portion of the sample in proper waste recepticle. 11. Adjust pH with constant stirring of filtered sample drop by drop with 5M HNO3 until the pH is 7.5 ± 0.5. 12. Filter pH adjusted sample through a 0.45um cellulose filter and collect filtrate in a 250mL beaker. 13. Transfer sample to a 100mL or 200mL volumetric flask and bring up to the mark with reagent water. Record final volume in logbook. 14. Analyze samples for Cr(VI) via method SW 7196A.Endyne, Inc. Chromium VI Method SW 3060A SOP 160 James Brown Drive Effective 03/31/06 Williston, VT 05495 Page 6 of 8

Document Control Copy on Buff colored paper. Do not duplicate IX. Calibration & Standardization :

A. Calibrate pH meter prior to each use (refer to pH SOP). B. Calibrate balance once a week (refer to balance SOP). C. Calibrate thermometer yearly against NIST traceable thermometer (refer to thermometer SOP).

X. Data Reduction :

Refer to SOP for method SW 7196A for all calculations.

XI. Data Recording :

A. All data pertaining to the digestion, data and calculations are to be recorded in the miscellaneous logbook. B. All results are recorded as mg/kg C. Refer to SOP for method SW 7196A for further information on data recording.

XII. Troubleshooting :

1. Some samples upon pH adjusting form a gel. Filter samples through another glass filter rather than 0.45um cellulose filter.

XIII. Method Modifications :

1. Method SW 3060A describes procedures for indicating the reductive nature of the samples in the event the matrix spike falls out side accepted limits. This is so that that data may be accepted without qualifying it. Not all sample matrixes are compatible with the digestive procedures and for the sak e of time and resources, data that falls outside of the strict matrix spike criteria is flagged as such and reported to the client. 2. Method SW 3060A states that 2.50g of sample is to be analyzed, for the sake of minimizing the reductive potential of the samples it may be necessary to digest a smaller known amount such as 1g. 3. Method SW 3060A states that the final volume is to be 100mL. The final volume of the sample may be brought up to any volume as long as the final volume is noted in the logbook.

XIV. Revision History:

N/A

XV. References:

1. Alkaline Digestion for Hexavalent Chromium. Method SW 3060A. CD-ROM, Revision 1, December I acknowledge that I have read this Standard Operating Procedure and agree to adhere to the Safety and Quality Control policies outlined within.Endyne, Inc. Chromium VI Method SW 3060A SOP 160 James Brown Drive Effective 03/31/06 Williston, VT 05495 Page 7 of 8

Document Control Copy on Buff colored paper. Do not duplicate Name DateDocument Control Copy on Buff colored paper. Any other color is not official version 

# Endyne, Inc.

160 James Brown Dr.

Williston, VT 05495 Phone: (802) 879-4333 Fax: (802) 879-7103



# CHROMIUM VI

Method SW 7196A 

# Standard Operating Procedure

REVISED: March 25, 2010

Revision #: 6

Technical Director: Date : Harry B. Locker Ph.D.



### QA Officer: Date :
Mark L. FauselEndyne, Inc. Chromium VI Method SW 7196A SOP 160 James Brown Drive Revision #5, Effective 3/25/10 Williston, VT 05495 Page 2 of 8

Document Control Copy on Buff colored paper. Do not duplicate 

### TABLE OF CONTENTS

Section Page

I – Overview 3

II – Safety 3

III – Waste Disposal 3

IV – Sample Collection, Preservation & Storage 3

V – Equipment & Supplies 3-4

VI – Reagents & Standards 4

VII – Interferences 4

VIII – Quality Control 4-5

IX – Analytical Procedure 5

X – Calibration & Standardization 6

XI – Data Reduction 6

XII – Data Recording 6-7

XIII – Trouble Shooting 7

XIV – Method Modifications 7

XV – Revision History 7

XVI – References 7

Analyst Attestation 8Endyne, Inc. Chromium VI Method SW 7196A SOP 160 James Brown Drive Revision #5, Effective 3/25/10 Williston, VT 05495 Page 3 of 8

Document Control Copy on Buff colored paper. Do not duplicate I. Overview :

This method is used to determine the c oncentration of dissolved Chromium VI (hexavalent chromium) in the absence of in terfering amounts of substances such as Mo, V, and Hg. This is done by colorimetric r eaction with diphenylcarbazide in acid solution. This is suitable for water samples, EP/TCLP characteristic extracts as well as soil samples that have been digested via method SW3060A. This method may also be applicable to certain domestic and industrial wastes provide d that no interfering substances are present.

II. Safety : Health=3 Fire=0 Reactivity=0

A. This method involves the handling of the chemicals outlined below. Each of these chemicals may have specific associated hazar ds. Analysts must read and become familiar with all elements of each chemical ’s MSDS. Make special awareness of the symptoms of exposure and potential routes of entry. Analysts must notify the Safety Officer immediately if any symptoms of exposure are suspected. B. Personal protective equipment i.e. gloves goggles and lab coat must be worn at all times in designated work areas. All appli cable engineering controls, such as fume hoods or splash shields, must be used wh en performing analyses. To ensure the safety of all laboratory personnel; work areas must be kept neat and organized, equipment and bench-tops must be cleaned and sterilized, if necessary, at the completion of each task, all containers must be properly labeled as to contents and hazard ratings and spills cleaned immediately and completely.

III. Waste Disposal :

A. Cr(VI) solutions or waste materials that are generated are dumped in the metals waste satellite container found underneath the fume hood on the inorganic floor. B. When the satellite container is full cont act one of the hazardous waste personnel to dispose of metals waste in the proper corrosive liquid drain. C. Cr(VI) spills are to be treated with ascorbic acid or another reducing agent to reduce Cr(VI) as well as Cr(III).

IV. Sample Collection, Preservation and Storage :

1. Samples should be collected in clean plastic or glass containers that do not contain stainless steel. 2. Samples are to be stored at 4 ° C until the time of digestion. 3. Water samples must be analyzed 24 hours from the time of collection. 4. Cr(VI) is stable in properly stored soil samples for 30 days from the date of sample. 5. The digestate is stable for 24 hours from the date of digestion.

V. Equipment & Supplies :

1) Spectrophotometer set at 540nm 2) Appropriate absorption cell 3) Pipettes, graduated/volumetric for sample dilutions 4) 25mL sample cups 5) 100mL volumetric flasksEndyne, Inc. Chromium VI Method SW 7196A SOP 160 James Brown Drive Revision #5, Effective 3/25/10 Williston, VT 05495 Page 4 of 8

Document Control Copy on Buff colored paper. Do not duplicate VI. Reagents & Standards : 1. Potassium Dichromate, 1000ppm soluble spiking solution 1) Dissolve 0.2829g K 2 Cr 2 O 7 in a 100mL volumetric flask with reagent
water 2) Prepare 10ppm working stock solution by adding 1mL of 1000ppm stock to 100mL reagent water volumetrically. 3) Prepare all laboratory QC’s and soluble matrix spikes from 10ppm working stock. 2. Diphenyl Carbizide Solution in acetone 0.125gm DC in 25 mls Acetone kept in the dark 3. Concentrated H 2 S0 4 4. Reagent grade water

VII. Interferences :

This method is usually free from interferen ces. However, certain substances such as hexavalent Mo/Hg may form color, however th e color intensity tends to be much lower than that of chromium. Concentrations of up to 200ppm Mo and Hg can be tolerated, V up to 10X the concentration of Cr will not cau se trouble. Iron at levels greater than 1ppm may produce a yellow color but is usually not very strong.

VIII. Quality Control :

A. Demonstration of Capability (DOC) Prior to extracting samples for clientele, a new analyst must prepare 4 LFB samples at the standard QC concentration. These LFB must be analyzed as other laboratory samples and then processed according to the following acceptance criteria: 1. Calculate the average in mg/L and the standard deviation for each parameter using the four results. 2. The average % recovery must fall within 80-120% of the target result, and the percent standard deviation must be less than 20%. Analysts must perform annual DOC (demonstration of capability) by analyzing 4 mid-range QC’s. Values must have an average percent recovery and a percent standard deviation <20. DOC results are turned into the lab manager. B. An MDL must be run yearly. Run 7 standards that are roughly 2-5X estimated detection limit based on the calibration line and are calculated according to the Code of Federal Regulations chapter 1 part 136 appendix b. The MDL benchsheet is stapled to the miscellaneous logbook. C. A line calibration must be performed each analytical day and the correlation must be 0.995 or greater. A line calibration is made from the 10ppm stock Potassium Dichromate solution into a 100ml volumetric flask as follows: 0.02ppm = 0.2mL 0.05ppm = 0.5mL 0.10ppm = 1.0mL 0.25ppm = 2.5mL 0.50ppm = 5.0mL 1.00ppm = 10.0mL D. A lab reagent blank is run 1 every 10 samples.Endyne, Inc. Chromium VI Method SW 7196A SOP 160 James Brown Drive Revision #5, Effective 3/25/10 Williston, VT 05495 Page 5 of 8

Document Control Copy on Buff colored paper. Do not duplicate E. An undigested Line Check at varying concentrations is run 1 every 10 samples. Results should be + 20%. F. Laboratory fortified matrix samples are run 1 every sample matrix or 10 samples, which ever comes first. For example, 100ul of 10ppm stock Potassium Dichromate can be added to 10mls of water sample to form a 0.1ppm spike. Results must be + 30%. G. Duplicate water samples are run 1 per set or 1 every 10 samples. The relative difference must be ≤ 20%. H. One of the two following QC protocols must be performed for each batch of digested soil samples: (a) An independent soil QC prepared at varying concentrations from the10ppm Potassium Dichromate stock must be spiked to the blank Teflon chips and digested and analyzed with each digestion batch. Recovery must be 100 ± 20%. (refer to SOP SW 3060A).

I. A separately prepared duplicate sample mu st be analyzed each digestion batch. Duplicate samples must have a relative percent difference of ≤ 20%. (refer to SW 3060A) J. A soluble digestion spike must be prepared and analyzed during each digestion batch. The soluble digestion spike is analyzed at 0.2ppm (2mL, 10ppm working stock added predigestion). K. Any data that falls outside of the above st ated criteria are either redigested/analyzed or qualified with the appropriate qualifier. L. All in-house prepared reagents and sta ndards must be properly labeled and have preparation and expiration dates noted on them. M. All reagents and standards must be properly documented with manufacture, lot numbers and expiration dates as well as a brief description of preparation in the Cr+6 log.

IX. Analytical Procedure :

1. Turn on the spectrophotometer and set the wavelength to 540nm. 2. Add 10mL of each line point to a labeled sample cup and add 0.2mls Diphenylcarbazide solution. 3. Add two drops of concentrated H 2 S0 4 and allow reacting for 5 minutes. 4. Zero the spectrophotometer by following the instrument instructions. 5. Once the reaction has occurred in the line points, from lowest concentration to the highest, pour of an aliquot into a clean sample cell, place it in the spectrophotometer and record the absorbance in the logbook. 6. Repeat steps 2-5 for all samples, line checks and blanks. All results are given in absorbance. 7. If a sample is turbid or has a discolora tion to it, it may be necessary to zero that specific sample against itself without color reagent. If this is performed for a particular sample be sure to rezero the sp ectrophotometer with reagent water prior to analyzing other samples.Endyne, Inc. Chromium VI Method SW 7196A SOP 160 James Brown Drive Revision #5, Effective 3/25/10 Williston, VT 05495 Page 6 of 8

Document Control Copy on Buff colored paper. Do not duplicate X. Calibration & Standardization :

The spectrometer software performs the linear regression and provides an output of line and the correlation coefficient.

XI. Data Reduction :

1. The spectrometer software convert s the absorbance to a mg/L value 2. For samples with no observable Cr6+ the reporting limit is the lowest point on the line. 3. Water samples are reported out as ppm or mg/L. 4. Soil digested samples must be converted from mg/L to mg/kg. The calculation is as follows: A x D x E/ B x C = mg/kg Whereas: A= Concentration observed in the digestate (ppm) B= Initial moist sample weight (g) C= % Solids/100 D= Dilution Factor E= Final digest volume (mL)

5. Duplicate relative percent difference calculation is as follows: (S-D)/[(S+D)/2] Whereas: S= Initial sample result D= Duplicate sample result

6. Spike recovery calculation is as follows: [(SSR –SR)/SA] x 100 Whereas: SSR= Spike sample result SR= Unspiked sample result SA= Spike added

XII. Data Recording :

1. All digestion information, data and final r esults are recorded in a computer file saved in the Metals Subdirectory 2. Water results are recorded in LIMS as mg/L. 3. Soil results are recorded in LIMS as mg/kg. 4. Results are to be recorded with 2 significant figures

XIII. Troubleshooting :

1. If samples are turbid or have a color, r ezero the sample against itself without reagent to obtain a proper absorbance value or try filtering the sample. See section IX. 2. If the correlation is not at 0.995 or above, drop points on the line and plug in the numbers again to get the best fit. If there are only five points to begin with, it will be necessary to make a new calibration from the 10ppm stock and try again.Endyne, Inc. Chromium VI Method SW 7196A SOP 160 James Brown Drive Revision #5, Effective 3/25/10 Williston, VT 05495 Page 7 of 8

Document Control Copy on Buff colored paper. Do not duplicate XIV. Method Modifications :

1. It is stated in the original SOP that it ma y be appropriate to treat all standards and line points as the samples, indicating the possib ility to digest the line calibration. However, when spoken to ERA, although digesting the line may help to compensate for possible loss of Cr6+ during digestion, as long as the QA values fall within mandated limits, line digestion is not necessary. 2. The method states that every sample must be spike to ensure that a reducing agent is not affecting the color reaction and thereby th e results. This protocol is impractical and the random matrix spike requirements s hould be enough to fulfill this criterion. If reducing reagent is suspected, obtain a fully prepared sample and add 0.1ppm matrix spike from the 10ppm stock as would be done with a water sample and analyze if according to section IX.

XV. Revision History:

Rev. # 3- Wrote SOP according to new SOP format Rev. #4- Rewrote SOP according to using a new spectrophotometer as well as the implementation of the digestion method SW 3060A. Amended Health and Safety and QA QC sections. Added Method Modificati ons, Revision History, References and Analyst Attestation. Rev. #5 – analysis time for soils is 24hours a nd made modifications in reference to new digestion procedure. Opened spiking crite ria to allow analyst to choose level. Rev. #6 – Changed LFM target and calculator use.

XVI. References:

1. Alkaline Digestion for Hexavalent Chromium. Method SW 3060A. CD-ROM, Revision 1, December 2. Chromium, Hexavalent (Colorimetric). Method 7196A. CD-ROM, Revision 1, July 1992.Endyne, Inc. Chromium VI Method SW 7196A SOP 160 James Brown Drive Revision #5, Effective 3/25/10 Williston, VT 05495 Page 8 of 8

Document Control Copy on Buff colored paper. Do not duplicate I acknowledge that I have read this Standard Operating Procedure and agree to adhere to the Safety and Quality Control policies outlined within.



# Name DateDocument Control Copy on Buff colored paper. Any other color is not official version 

# Endyne, Inc.

160 James Brown Dr.

Williston, VT 05495 Phone: (802) 879-4333 Fax: (802) 879-7103



# MERCURY IN SOLID OR SEMISOLID WASTE 

# Method SW 7471A 

# Standard Operating Procedure

REVISED: October 3, 2007

Revision #: 5

Technical Director: Date : Harry B. Locker Ph.D.



### QA Officer: Date : Mark L. FauselEndyne, Inc. Mercury Method SW 7471A SOP 160 James Brown Drive Revision #5, Effective 10/3/07 Williston, VT 05495 Page 2 of 11

Document Control Copy on Buff colored paper. Any other color is not official version TABLE OF CONTENTS

Section Page

I – Overview 3

II – Safety 3

III – Waste Disposal 3

IV – Sample Collection, Preservation and Storage 3

V – Equipment and Supplies 4

VI – Reagents and Standards 4

VII – Interferences 4

VIII – Quality Control 5

IX – Analytical Procedure 5

X – Calibration 7

XI – Data Reductions 9

XII – Data Recording 9

XIII – Instrument Maintenance 9

XIV – Troubleshooting 9

XV – References 10

XVI -- Revision History 10

XVII – Method Modifications 10

XVIII SOP Attestation 11Endyne, Inc. Mercury Method SW 7471A SOP 160 James Brown Drive Revision #5, Effective 10/3/07 Williston, VT 05495 Page 3 of 11

Document Control Copy on Buff colored paper. Any other color is not official version I. Overview:

This method employs the Perkin Elmer FIMS 100 ( Flow Injection Mercury System) a dedicated Atomic Absorption Spectrometer, for determination of mercury in soils, sediments, bottom deposits and sludges. Prior to analysis, the solid or semi-solid samples must be prepared according to the procedures discussed in this method. This cold-vapor atomic absorption method is based on the absorption of radiation at the 253.7 nm wavelength by mercury vapor. The mercury is reduced to the elemental state and aerated from solution in a closed system. The mercury vapor passes through a cell positioned in the light path of the atomic absorption spectrophotometer. Absorbance (peak height) is measured as a function of mercury concentration.

II. Safety:

This method involves the handling of the chemicals outlined below. Each of these chemicals may have specific associated hazards. Analysts must read and become familiar with all elements of each chemical ’s MSDS. Make special awareness of the symptoms of exposure and potential routes of entry. Analysts must notify the Safety Officer immediately if any symptoms of exposure are suspected.

PPE must be worn at all times in designated work areas. All applicable engineering controls, such as fume hoods or splash shields, must be used when performing analyses. To ensure the safety of all laboratory personnel; work areas must be kept neat and organized, equipment and bench-tops must be cleaned and sterilized, if necessary, at the completion of each task, all containers must be properly labeled as to contents and hazard ratings and spills cleaned immediately and completely.

III. Waste Disposal:

Samples that do not contain mercury may be flushed down the drain with copious amounts of water. Samples containing mercury, as well as all standards and QC samples, must be disposed of in the Hazardous Waste drum. Expired hollow cathode lamps may not be placed in the trash; they are considered hazardous waste since they contain the target element(s). Lamps should be disposed of in an appropriate waste stream or returned to the vendor for recycling.

IV. Sample Collection, Preservation, and Storage:

A. Collection: Samples are collected in plastic and glass bottles of various sizes. B. Labeling: All samples are assigned a sample number, plus a unique identifier suffix to indicate preservative and bottle type.Endyne, Inc. Mercury Method SW 7471A SOP 160 James Brown Drive Revision #5, Effective 10/3/07 Williston, VT 05495 Page 4 of 11

Document Control Copy on Buff colored paper. Any other color is not official version C. Preservation: Non-aqueous samples, or those known to react violently with acid preservation, are stored in the inorganics refrigerator below 4 o C and analyzed as soon as possible. D. Storage: Samples are stored in the inorganic fridge.

V. Equipment and Supplies:

Digestion Tubes with screw caps Block digester capable of maintaining 95 ο C +/- 5 ο C Volumetric Flasks, Various Sizes Class A Perkin Elmer FIMS 100 Absorption Cell Argon, Compressed Gas

VI. Reagents and Standards:

Reductant #1 - 12% W/V Sodium Chloride and 12% W/V Hydroxylamine hydrochloride in DI. Ex. Dilute to 30g of each compound to 250 mL Reductant #2 – 1.1% Stannous Chloride in 3% HCl. Ex. 6g Æ 200mls Nitric Acid, concentrated, Trace Metal Grade 5% Nitric Acid Hydrochloric, concentrated, Trace Metal Grade 3% Hydrochloric Acid Potassium Permanganate, 5% W/V ex. 50g Æ 1L Mercury Stock Standard Aqua Regia – 40 mLs DI, 30 mLs Conc HCL, 10 mLs conc HNO3 Anti Foam from Sigma

NOTE: All incoming reagents, standards, dry chemicals and acids shall be marked with the date of receipt, date of opening, and date of expiration. Dry chemicals shall be used within 20 years, and concentrated acids shall be used within 10 years of the date of receipt or before the manufacturer’s expiration date, which ever is sooner.

VII. Interferences:

The vapor generation technique demands a high standard of care: scrupulous cleanliness is essential in all laboratory procedures; standards and samples must be meticulously prepared and carefully handled; and strict precautions must be taken to avoid contamination of the apparatus.

VIII. Quality Control

A. ( See Table A in the “SOP” SOP for more detailed definitions of the following) 1. Demonstration of Capability (DOC). Each new analyst performs a set of four midrange LFBs. The LFBs should be prepared as one sample, then split into fourEndyne, Inc. Mercury Method SW 7471A SOP 160 James Brown Drive Revision #5, Effective 10/3/07 Williston, VT 05495 Page 5 of 11

Document Control Copy on Buff colored paper. Any other color is not official version aliquots. The percent standard deviation and average percent recovery are determined for each analyte. Each must be less than 20% to ensure proper capability of the analyst for that method. This process is repeated annually for each metals analyst. 2. Method Detection Limit (MDL).

a. An MDL is run annually for each element. The final calculated MDL value must be at least 1⁄2 the reporting limit and the MCL. MDLs should be prepared in a manner identical to that of sample analysis. b. Seven to ten QCs are made at at concentration 2-5 times highger than the expected MDL.

c. The MDL is calculated by taking the standard deviation of the values and multiplying by the appropriate number from the chart from the Code of Federal Fregulations Appendix B to part 136 of Chapter 1 (7 is 3.143, 8 is 2.998, 9 is 2.896and 10 is 2.821).

3. Calibration Check/Verification (or Instrument Performance Check – IPC). The concentrations of the calibration verification shall be varied within the established calibration range. 4. Laboratory Reagent Blank (LRB). 5. Laboratory Fortified Blank (LFB or Independent QCS) 6. For all determinations the laboratory must analyze a calibration blank and line check (IPC) at the start of the sample run, after every tenth sample (or more frequently, if required) and at the end of the sample run. 7. The percent recovery for IPC’s must be +/-10%. 8. The calibration blanks can not be greater than 1/10 of the measured concentration of any sample in the associated sample batch; or exceed the concentration present in the samples or be greater than 1/10 of the regulatory limit. 9. Percent Recovery for the LFB must be +/-10%. 10. Duplicate samples are run every batch or every 20 samples 11. LFM samples are run every 20 samples or when results are questionable. Percent recovery for LFM’s must be +/-30%. 12. LFM’s are acceptable as Independent QC’s. 13. If data does not meet the criteria outlined above, it may be used, but MUST be noted on the final client report.Endyne, Inc. Mercury Method SW 7471A SOP 160 James Brown Drive Revision #5, Effective 10/3/07 Williston, VT 05495 Page 6 of 11

Document Control Copy on Buff colored paper. Any other color is not official version IX. Analytical Procedure:

Digestion: 1) Turn on block digester and set at 95 o C. 2) Prepare a rack of digestion tubes by labeling with the sample identification nos. Record sample reference number on the Mercury page of the metals digestion log. Record all pertinent information concerning reagents and standards. 3) Prepare a blank and 0.5, 1, 2, and 4 ppb standards from a 1 ppm Mercury solution - each at a volume of 25 mLs with 5 % Nitric acid . Prepare QC's at 2 ppb in digestion tubes. Samples may also be run against the water line since the absorbances have proven to be the same for both lines. 4) A duplicate (LD) and spike (LFM) should be run with each project or C.O.C. with a minimum of one dup and spike per digestion. The spike target may be between 3-5 ppb. 5) Using the soils spreadsheet calculate the amount of sample needed to yield a desirable detection limit. Weigh out that amount of sample (in three separate weights to assure a representative sample) into a digestion tube. Use 1 gram for dry solids, 5 grams for dewatered sludges and 25 grams for watery sludges. Record the mass of each sample used on the mercury page of the digestion log. 6) After samples and standards are prepared, add1 mL of DI to each tube. Add 1.5 ml of Aqua regia and mix thoroughly. Heat 10 min in 95 0 C block digestor then allow to cool. 7) Add 4.0 mL Potassium Permanganate to each tube. Mix thoroughly. Allow to sit for 15 minutes. If purple color does not persist then add an additional 3.0 mLs Potassium Permanganate to each tube. If it fades again repeat process with less sample. 8) Place in block digestor for 30 minutes at 95 0 C covered loosely with green caps. 9) Remove bottles from block and cool for 20 min. Add 2 .0 mls Reductant #1 to each tube, and swirl until all purple particles are gone. Bring all samples back to 40mls volume with 5% nitric acid. 10) Allow samples to cool to room temperature, filter, and dilute (using digested blank) before analysis.

Analysis: 1) Turn on the Argon carrier gas should be set for 52 Psig. 2) Switch on the FIMS 3) Allow Hg lamp to warm-up at least one-half hour before use. 4) Switch on the computer, start windows then Winlab 32 5) Verify that tubing configuration is correct. 6) Set the argon gas flow to 70-100 mls per minute. 7) Remove the reductant and carrier tubes from DI 8) Fill SnCl2 (reductant) and 3%HCl ( carrier) solutions and empty waste containers 9) Place the carrier tube ( yellow/blue) into the carrier solution 3% HCL 10) Place the reductant tube ( red/red) into the SnCl2 reductant solution. 11) Check for cleanliness. If tubes are dirty, replace before analysis. 12) Swing the pump pressure levers over the and press the pump tube magazines against the rollers. 13) Under Toolbar : Open Method and select mercury method 14) Under Toolbar : select HGEndyne, Inc. Mercury Method SW 7471A SOP 160 James Brown Drive Revision #5, Effective 10/3/07 Williston, VT 05495 Page 7 of 11

Document Control Copy on Buff colored paper. Any other color is not official version 15) Enter Sample Info.: Name the file. 16) Enter sample information for each autosample location starting at location 8 17) Save sample information file 18) Under Tools : Open Automated Analysis Control: Under Select Sample Info . select Location: enter location of sample tubes to be analyzed.(i.e. 8-20) 19) Open: Results Data Set update the file name where you plan to save the data. 20) Open Peak display, Calibrationdisplay, and Results display to ensure run quality. 21) Under Analysis open Rebuild List then select Analyze All 22) Autorun sequence begins. 23) Insure that there is not an excessive amount of foam in the gas/liquid separator during analysis. 24) When analysis is complete, place all three tubes back in DI for five minutes and then air dry for 5 minutes. 25) Shut off power to FIMS and release tubes from pump rollers. 26) Place the carrier and reductant tubes in DI water.

X. Calibration:

A. Calibration is performed by analyzing a series of digested standards from zero to 4ppb. The Perkin Elmer Windlab 32 software will then prepare a calibration curve by plotting instrument response versus standard concentration. The calibration line may be digested or undigested. For an undige sted line, follow the digestion procedure listed in IX and omit step #9. B. A digested calibration line is often stable for several weeks. C. For instrument operating conditions refer to the following from Method Editor :

Method Hg 7471 Spectrometer Element : Hg Wavelength (nm) : 253.7 Signal Type : AA Measurement : Peak height Smoothing : 9pts

Read Parameters Time 20 sec Delay Time 0.0sec BOC Time 2sec Replicates ...Same for all Samples : 2

Operation Sample volume 500ul Use Amalgam? No

Step Time Pump1 Pump2 Valve Remotes (sec) speed speed position 2 3 4 5 6 7 8 9 10 Prefill 15 120 0 Fill 1 10 120 0 Fill 2 15 120 0 InjectEndyne, Inc. Mercury Method SW 7471A SOP 160 James Brown Drive Revision #5, Effective 10/3/07 Williston, VT 05495 Page 8 of 11

Document Control Copy on Buff colored paper. Any other color is not official version Read Step 2 Steps to repeat 1 to 1 Number of repeats 0

Wash Frequency : After all solutions Wash Location : 0 Normal Cycles : 1 Use FIAS steps : 1 to 1

Equation : Linear, calculated intercept Max Decimal places : 3 Max Sig. Figs. ; 4 Cal. Units ; ug/L Sample Units ; ug/L

ID Concentration A/S Loc Calib Blank Calib. Blank 1 Standard 1 Calib Standard 1 0.5 2 Standard 2 Calib Standard 2 1 3 Standard3 Calib Standard 3 2 4 Standard4 Calib Standard 4 4 5

When opening this method manually: clear cal. Curves and construct new cal. Curves When using this method in a multimethod sequence: start by constructing new cal. Curves

Check: Samples, QC samples Limits: Precision check signal : Conc. (cal. units) Signal Limits : 1.00ug/L If signal > limit and RSD 20% then action Out of Limit actions : Reanalyze 1 time

Check Range on : Samples, QC Samples Overcal. Limit : 110% of cal. Range Take action after 1 replicate Alternate Method : Hg

A/S Count as Subtract QC Sample ID Loc Sample Reagent Blk QC1 ICV 2ppb 4 No No QC2 ICB 6 No No QC3 LFB 2ppb 7 No No QC4 CCV 2ppb 4 No No QC5 CCB 6 No No

QC1 ICV 2ppb Conc. 2 Lower limit 1.8 Upper limit 2.2 QC2 ICB Conc. 0 Lower limit –2 Upper limit 1 QC3 LFB 2ppb Conc. 2 Lower limit 1.8 Upper limit 2.2 QC4 CCV 2ppb Conc. 2 Lower limit 1.8 Upper limit 2.2 QC5 CCB Conc. 0 Lower limit –2 Upper limit 1

After After QC Sample ID Init. Cal Recal Periodic Freq At End QC1 ICV 2ppb Yes Yes No 10 NoEndyne, Inc. Mercury Method SW 7471A SOP 160 James Brown Drive Revision #5, Effective 10/3/07 Williston, VT 05495 Page 9 of 11

Document Control Copy on Buff colored paper. Any other color is not official version QC2 ICB Yes Yes No 10 No QC3 LFB 2ppb Yes Yes Yes 20 No QC4 CCV 2ppb No No Yes 10 Yes QC5 CCB No No Yes 10 Yes Frequency : Variable Count : Samples

When QCs fail : Times to retry – 1 When all Tries Fail – Recal and repeat after trouble shooting.

XI. Data Reduction:

Insure that any dilutions are factored into the final result. Solid samples are reported as mg/kg, dry wt. The calculations may be performed using an Excel spreadsheet. The calculation is as follows:

(Conc. in PPM)(Vol. In L)(1000) = Mg/Kg, dry wt. (% Solid)(Mass in G)

XII. Data Recording:

1. All analyses are recorded on the Mercury page of the Metals Digestion Log Each log sheet should include the sample reference number, analyst’s name, and concentrations for standards, LFB’s, and LFM’s 2. Record final data in the LIMS databank. 3. Raw data is stored in the binder labeled “AA Metals” located in the Inorganics laboratory. 4. For long-term storage, data is stored in a banker’s box labeled “AA Raw Data”. 5. Data from the hard drive C is backed up onto the partitioned D drive

XIII. Instrument Maintenance:

A. Refer to instruction manual for preventative maintenance procedures for the Perkin Elmer FIMS. B. Replace sample and reagent tubes on when they appear discolored or worn. C. Quarterly check gas supply for leaks. D. Record any maintenance performed in the maintenance log.

XIV. Troubleshooting:

A. If condensation is present in the flow cell, install and turn on a heat lamp over spec. to facilitate approximately a 10 ο C rise in the ambient temperature in the cell. B. Filter soil samples to prevent a clog in the sample line, using a 2.0 um Teflon fiber filter. C. Rinse sample line thoroughly with DI between high samplesEndyne, Inc. Mercury Method SW 7471A SOP 160 James Brown Drive Revision #5, Effective 10/3/07 Williston, VT 05495 Page 10 of 11

Document Control Copy on Buff colored paper. Any other color is not official version D. There should be gentle bubbling in the gas-liquid separator. If not, disconnect the inlet line to the absorption cell, allow the separator chamber to fill up with DI, then re-attach inlet line. Still no bubbling, remove inlet line and clean out with compressed air. E. If contamination is suspected compare the EHT voltage on the optimization page with the original value from the beginning of the run. An elevated voltage indicates that there is Hg in the system.

XV. References

Method 7471A: Mercury in Solid or Semisolid Waste (Manual Cold-Vapor Technique) Revision 1,September 1994, EPA Test Methods for Evaluating Solid Waste Physical/ Chemical Methods, Version 2. EPA SW 846, December 1997 United States Environmental Protection Agency.

Electronic Code of Federal Regulations, 40 CFR – Chapter 1 – Part 136 – Appendix B. : Definition and Procedure for the Determination of the Method Detection Limit – Revision 1.11.

XVI. Revision History

May 14, 2003 March 26, 2004 April 17, 2006 XVII. Method Modifications/Analyst Notes:Endyne, Inc. Mercury Method SW 7471A SOP 160 James Brown Drive Revision #5, Effective 10/3/07 Williston, VT 05495 Page 11 of 11

Document Control Copy on Buff colored paper. Any other color is not official version XVIII. SOP Attestation

I acknowledge that I have read this Standard Operating Procedure and agree to adhere to the Safety and Quality Control policies outlined within.



## Name DateCyanide EPA 335.4 / 9012A Revised 04-May-10 Rev#6 Created: 21-Sep-04 Page 1 of 16 16

Controlled Document - DO NOT PHOTOCOPY 

# Standard Operating Procedure

Cyanide

Distillation Method EPA 335.4 Potable & Non-Potable Water Method EPA 335.4 Total Cyanide in Solids EPA 9012A Solid Samples Prep Method 9010B

Revision: 6

Endyne, Inc. 315 New York Road, Suite 85 Plattsburgh, NY 12903

Approved for Distributi on:_______________________________

Approval Date:_______________________________

Out of Service Date:________________________Cyanide EPA 335.4 / 9012A Revised 04-May-10 Rev#6 Created: 21-Sep-04 Page 2 of 16 16

Controlled Document - DO NOT PHOTOCOPY 1. Identification of Test Method METHOD #: EPA 335.4, 9012A TITLE: Cyanide ANALYTE: Free and Total Cyanide INSTRUMENTATION: Seal AQ 2 Discrete Analyzer, Midi-Dist Distillation Apparatus

2. Applicable Matrix: 2.1. This method is applicable to the concentration of Free and Total Cyanide in drinking and surface waters, domestic and industrial wastes, and solids.

3. Method Detection Limit: 3.1. See Methods Manual Appendix A for current MDL and PQL numbers.

4. Scope and Application, Components: 4.1. This method covers the determinat ion of cyanide in drinking, surface and saline waters, domestic and industrial wastes, and solids. 4.2. The method is based upon reactions that are intended to be specific for cyanide.
5. Summary of Test Method: 5.1. This method is the Endyne-Pla ttsburgh adaptation of methods EPA 335.4 and EPA 9012A. 5.2. The midi-distillation system is us ed to process Total Cyanide samples prior to their analysis in the AQ 2 discreet analyzer. 5.3. In the distillation process, cyanide as hydrocyanic acid (HCN) is released from cyanide complexes by means of a reflux-distill ation operation and adsorbed in a scrubber containing sodium hydroxide solution. The cyanide ion in the absorbing solution is then determined colorimetrically on the AQ 2
. 5.4. In the colorimetric determinati on, cyanides are converted to cyanogen chloride by reaction with chloramine- T (N-Chloro-p-toluenesulfonamide sodium salt). The cyanogen chlori de then reacts with pyridine and barbituric acid to form a reddish-vio let colored complex. The absorbance of this complex is measured spectrophotometrically at 578 nm.

6. Definitions: 6.1. CYANIDE – Cyanide (CN) ion and complex cyanides converted to hydrocyanic acid (HCN) by reaction in a reflux system of a mineral acid in the presence of magnesium ion.
6.2. FREE CYANIDE – The fraction of cyanide that is reactive prior to the distillation step. Samples analyzed for SDWA compliance monitoring are reported as free cyanide.Cyanide EPA 335.4 / 9012A Revised 04-May-10 Rev#6 Created: 21-Sep-04 Page 3 of 16 16

Controlled Document - DO NOT PHOTOCOPY 6.3. BATCH – Environmental sa mples that are prepared and/or analyzed together with the same proc ess and personnel, using the same lot(s) of reagents.
6.4. PREPARATION BATCH – A set of samples composed of one to 20 environmental samples of the same NELAC-defined matrix, meeting the above-mentioned criteria and with a ma ximum time between the start of processing of the first and last sample in the batch to be 24 hours. The preparation batch determines the frequen cy of the quality control sample to be processed.
6.5. ANALYTICAL BATCH – A set of samples composed of prepared environmental samples (extracts, diges tates, or concentrates) which are analyzed together as a group. An analyt ical batch can include prepared samples originating from various environmental matrices and can exceed 20 samples.
6.6. CALIBRATION BLANK (CB) – A volume of reagent water in the same matrix as the calibrati on standards, but without the analyte. 6.7. CALIBRATION STANDARD (CAL ) – A solution prepared from the primary dilution standard solution or stock standard solutions. The CAL solutions are used to calibrate the instrument response with respect to analyte concentration. 6.8. METHOD BLANK (MB) – An aliq uot of reagent water or blank matrices that are treated exactly as a sample including exposure to all glassware, equipment, solvents, r eagents, internal standards, and surrogates that are used wit h all other samples in the batch. The MB is used to determine if method analytes or other interferences are present in the laboratory environment, th e reagents, or the apparatus.
6.9. LABORATORY CONTROL ST ANDARD (LCS) (however named, such as laboratory fortified blank, sp iked blank, or QC check sample) – A sample matrix, free from the analytes of interest, spiked with verified known amounts of analytes or a mate rial containing known and verified amounts of analytes. It is generally us ed to establish in tra-laboratory or analyst specific precision and bias or to assess the performance of all or a portion of the measurement system. 6.10. LABORATORY DUPLICATES (LD) – Aliquots of a sample taken from the same container under labor atory conditions an d processed and analyzed independently. Analysis of laboratory duplicates indicates precision associated with laborator y procedures but not with sample collection, preservation, or storage procedures. 6.11. QUALITY CONTROL CHECK SAMPLE (QCS) – A sample containing analytes of interest at k nown concentrations (true values). The QCS is obtained for a source ex ternal to the laboratory or isCyanide EPA 335.4 / 9012A Revised 04-May-10 Rev#6 Created: 21-Sep-04 Page 4 of 16 16

Controlled Document - DO NOT PHOTOCOPY prepared from standards obt ained from a different performance using test materials that have been pr epared independently from the normal preparation process. 6.12. METHOD DETECTION LIMIT (MDL ) – A statistical calculation of the lowest concentration at whic h an analyte can be detected with 99 percent confidence that the analyte concentration is greater than zero. 6.13. MINIMUM LEVEL (ML) – The lowest standard used in the calibration. 6.14. MAXIMUM CONTAMINANT LEVEL (MCL) - The highest level of a contaminant that is allowed in drinki ng water. MCLs are set as close to level at which there are no known or expected health risks as feasible using the best available treatment technology and taking cost into consideration. MCLs are enforceable standards.

7.0. Interferences: 7.1. Thiocyanates are a positive interference. 7.2. Oxidizing agents, such as chlorine, decompose most of the cyanides. Test the sample with pota ssium iodide – starch paper. A blue color indicates the need for tr eatment with ascorbic acid. If needed, add ascorbic acid one crystal at a time until the sample yields no color change. Add an additional 0.06g of ascorbic acid for each liter of sample. This step should be done in the field during sample collection. 7.3. Sulfides adversely affect the colo rimetric procedure. If a drop of the sample on lead acetate test paper i ndicates the presence of sulfide, treat 25 mL more of the stabilized sa mples (pH>/=12) than that required for the cyanide determination with powdered cadmium carbonate. Yellow cadmium sulfide precipitates if the sample contains sulfide. Repeat this operation until a drop of the treated sample solution does not darken the lead acetate test paper. Filter the solution through a dry filter paper into a dry b eaker and, from the filtra te, measure the sample to be used for analysis. Avoid a large excess of cadmium and a long contact time in order to minimize a loss by complexation or occlusion of cyanide. Record the treatment in the cyanide logbook. ( NOTE: The sample may alternatively be subc ontracted to another ELAP accredited lab to be treated for the interference and analyzed).
8.0. Safety: 8.1. Safety glasses, gloves and labc oat are required. The toxicity or carcinogenicity of each reagent used in this method has not been fully established. Each chemical s hould be regarded as a potential health hazard and exposure should be as lo w as reasonably achievable. Cautions are included for known extremely hazardous materials.Cyanide EPA 335.4 / 9012A Revised 04-May-10 Rev#6 Created: 21-Sep-04 Page 5 of 16 16

Controlled Document - DO NOT PHOTOCOPY 8.2. A reference file of Material Sa fety Data sheets (MSDS) is available to all personnel involved in the chem ical analysis. A formal safety plan is also available. 8.3. The following chemicals have t he potential to be highly toxic or hazardous, for detailed explanations consult the MSDS. Chloramine-T: causes burns, sensit ization by inhalation, contact with acids liberates very toxic gas Pyridine: highly flammable, toxi c by ingestion, inhalation, and skin contact Cyanide standards: toxic, contact with acids liberates toxic gas Barbituric Acid: irritating to eyes, skin, and respiratory tract Hydrochloric Acid: causes severe burns Sodium Hydroxide: causes severe burns

9.0. Equipment and Supplies: 9.1. Analytical balance capable of accuracy to the nearest 0.0001 g. 9.2. Glassware - Class A volumetric flasks and pipettes. Glass or plastic containers as required. 9.3. SEAL AQ 2 discrete analyzer with Test and Reagent Parameters programmed for this cyanide application. 9.4. Reflux distillation apparatus c onsistent with samp le pre-treatment procedure described in USEPA method 335.4.
10.0. Reagents and Standards:

10.1. PREPARATION OF REAGENTS : Use of ASTM Type II water for all solutions. All standards and reagents must be prepared using ammonia-free water. 10.1.1. Collection Reagents: 10.1.1.1. Ascorbic Acid : Crystal (CASRN-50-81-7) 10.1.1.2. 10N Sodium Hydroxide : Place a 500mL volumetric flask in a cold water bath in a fume hood. Turn on the hood. Add 250mL of deionized water to t he flask. Add 200g of solid NaOH to the deionized water in the flask. Swirl to mix. After the solution has cooled and the NaOH has dissolved, fill the flask to volume with deion ized water. Invert to mix. 10.1.1.3. Cadmium Carbonate : Powdered (CASRN- 513-78-0)

10.1.2. Distillation Reagents: 10.1.2.1. 0.25 N Sodium Hydroxide (see section 10.1.3.1.) 10.1.2.2. Sulfamic Acid (NH 2 SO 3 H): (CASRN-212-57-3) 10.1.2.3. 18N Sulfuric Acid (1:1): Place a 500mL volumetric flask in a cold water bath in a fume hood. Turn on the hood. WithCyanide EPA 335.4 / 9012A Revised 04-May-10 Rev#6 Created: 21-Sep-04 Page 6 of 16 16

Controlled Document - DO NOT PHOTOCOPY a graduated cylinder, add 250mL of deionized water to the flask. With a graduated cylinder, slowly add 250mL of concentrated sulfuric acid to the flask, swirling occasionally. The flask will get very hot and water will evaporate. After the flask has cooled to room temperature, add deionized water to bring the volume up to 500mL. Invert to mix. Store at room temperature in a glass stoppered glass container. 10.1.2.4. Magnesium Chloride Solution : Weigh 51g of Magnesium Chloride crystals into a beaker. Rinse the crystals into a 100mL volumetric flask using a funnel and deionized water. Bring to 100mL volume. Invert to mix. Store at 4C in a plastic container.

10.1.3. AQ 2 Reagents: 10.1.3.1. Sodium Hydroxide, 0.25 N : From a stock solid NaOH : Dissolve 20g of NaOH in 2L of DI water. Invert to mix. Caution: This solution will get hot during mixing. From a traceable 10N NaOH solution : Pipette 25mL of 10N Sodium Hydroxide into a 1L volumetric flask. Bring to volume with deionized water, cooling in an ice bath as the water is added. Invert to mix. 10.1.3.2. Phosphate Buffer : Dissolve 138 g of sodium dihydrogen phosphate in 900 mL deionized water and dilute to 1 Liter. Refrigerate this reagent. NOTE: This reagent may be purchased ready to use from EST Analytical. 10.1.3.3. Chloramine-T : Dissolve 1.0 g of chloramine-T (N-Chlorop-toluenesulfonamide sodium salt) in 100 mL deionized water. Prepare fresh daily. NOTE: This reagent may be purchased ready to use from EST Analytical. 10.1.3.4. Pyridine Barbituric Acid : Place 3.75 g of barbituric acid in a 250 mL volumetric flask and add just enough deionized water to wash the sides of the flask and wet the barbituric acid. Add 18.75 mL of pyridine and mix. Add 3.75 mL concentrated hydrochloric acid, mix and cool to room temperature. Dilute to 250 mL with deionized water and mix well to ensure complete so lution of the barbituric acid. Stored in a dark bottle at a cool temperature, this solution should be stable for up to 6 months. THIS REAGENT MUST BE PREPARED IN A FUME CUPBOARD – TAKE EXTREME CARE! NOTE: This reagent may be pur chased already prepared.Cyanide EPA 335.4 / 9012A Revised 04-May-10 Rev#6 Created: 21-Sep-04 Page 7 of 16 16

Controlled Document - DO NOT PHOTOCOPY NOTE: For lowest detection limits, chill the pyridine barbituric acid reagent and perform gravity filtration at the time of use.

10.2. PREPARATION OF STANDARDS :

10.2.1. Stock standard so lution (1000 mg CN/L): Dissolve 2.51 g of potassium cyanide and 2.0 g of potassium hydroxide in 900 mL of deionized water and mix. Dilute to 1 Liter in a volumetric flask. If necessary, standardize with 0.0192N silver nitrate to appropriate concentration (1 mL = 1 mg CN). NOTE: A traceable stock 1000mg /L cyanide standard may be purchased ready to use. 10.2.2. Intermediate stock standard solution (1 mg CN/L): Dilute 1 mL stock standard (1000 mg CN/L) to 1 Liter with 0.25N NaOH reagent. 10.2.3. Preparation of Wo rking standard solutions:

Concentration μg CN/L 0 1 4 10 25 50 75 150 200 250 Volume (mL) Intermediate stock standard diluted as indicated with deionized water 0 1 1 1 25 25 15 150 20 25

Final Volume, mL 100 1000 250 100 1000 500 200 1000 100 100 Note: Working standards are to be br ought to volume using 0.25N NaOH.

11.0. Sample collection, preservation and storage: 11.1. Samples should be collected in plastic bottles. All bottles must be thoroughly cleaned and t horoughly rinsed to remove soluble material from containers. Sample volume must be large enough to treat the samples for interferences as needed and analyze the sample with all applicable quality control parameters. The recommended sample size is 1L. 11.2. Oxidizing agents such as chlorine decompose most of the cyanides. In the field, test a dr op of the sample with potassium iodide-starch test paper (KI starch paper); a blue color indicates the need for treatment. Add ascorbic acid, a few crystals at a time, until a drop of sample produces no colo r on the indicator paper. Then add an additional 0.6 g of ascorbic acid for each liter of sample volume. The sample may then be preserved with sodium hydroxide. 11.3. Samples must be preserv ed with 2 ml of 10N sodium hydroxide per liter of sample (pH ≥ 12) at time of collection. 11.4. Samples should be analyzed as rapidly as possible after collection. If storage is required the samples must be stored in aCyanide EPA 335.4 / 9012A Revised 04-May-10 Rev#6 Created: 21-Sep-04 Page 8 of 16 16

Controlled Document - DO NOT PHOTOCOPY refrigerator or in an ice chest fi lled with water and ice to maintain temperature at <= 6C. Samples mu st be analyzed within 14 days. 11.5. Solid samples are collected in plastic or glass containers and must be chilled to 4C until analysis.

12.0. Quality Control: 12.1. Analyze one sample duplicate and one matrix spike per preparation batch or 10% of samp les, whichever is more frequent. Duplicate determinations must agr ee within 20% of each other. Matrix spike recoveries must be 80- 120%. Note: Matrix spikes that fall outside the accept ance criteria require that only the spiked sample be qualified as th is problem is matrix or solution related, not system related. 12.2. One CCV (Continuing Calibrati on Verification) must be run with each batch. The CCV concen tration must agree within 10% of its acceptable value. In addition, a distilled standard (or lab-fortified blank) must be analyzed with each batch. The distilled standard must be within 10% of its non-distilled value. 12.3. One QC (Quality Control) sample must be run with each batch. The QC is distilled with the preparation batch. The value must fall within its acceptable range. 12.4. A lab blank must be distilled with the preparation batch and the value must be belo w the PQL. Blank re sults greater than the PQL indicate a possible s ource of contamination.

13.0. Calibration and Standardization:
13.1. The standard curve is a 2 nd order polynomial equation. A minimum correlation coefficient of 0.995 must be achieved to accept the calibration. If this va lue is not achieved, the analytical system is judged to be out of cont rol, and the problem must be immediately identified and corrected. 13.2. The initial calibration must be verified using a second source or certified standard that has a c oncentration within the calibrated range. Compute the per cent recovery using the following equation:

100 x % K D recovery =
13.3. Where, D = Determined concentration of analyte in the calibration standard, K = actual concentration of the analyte in the calibration standard 13.4. Verify the calibration usi ng a calibration standard every ten samples or every analytical batch.Cyanide EPA 335.4 / 9012A Revised 04-May-10 Rev#6 Created: 21-Sep-04 Page 9 of 16 16

Controlled Document - DO NOT PHOTOCOPY 13.5. If % recovery of calibration verification falls outside the + 10% acceptance limit, the analytical system is judged to be out of control, and the problem must be immediately identified and corrected and the analytic al batch reanalyzed.
13.6. At least one st andard should be taken through the distillation process with each batch. The distilled and undistilled standard must be within 10% of each other.

14.0. Procedure:
14.1. Midi-Distillation : NOTE: Drinking water samples to be reported for SDWA compliance monitoring, skip to section 14.2. 14.1.01. Pour 50mL of sample into the reflux flask (the back row of tubes). Samples may be diluted by pipetting the sample volume then bringing the tube up to a total of 50mL with deionized water. For solid samples use 1 g of sample and fill the tube up to 50mL with deionized water. Record the weight.
14.1.02. Pour 50mL of 0. 25N NaOH into the absorber flask (the front row of tubes). 14.1.03. Add 3 glass boiling beads and 2 drops of antifoam to the reflux flask. Repeat steps 14.2. 01 to 14.2.03 for each sample.
14.1.04. Assemble the reflux im pinger, absorber impinger, and tubing. 14.1.05. Turn on the cold water tap to the cold fingers, keep the water at a higher flow than will be required for the distillation. Starting at the left-most side of the Midi-Dist apparatus, hold each cold finger paralle l with the block and jiggle it lightly to remove air bubbles. After air bubbles are removed, assemble the cold finger and repeat the pr ocess, moving to the right, for the rest of the tubes. After all air bubbles are removed adjust the flow down to the level requir ed for the distillation. Set the flow at 6 GPH per sample (per bl ock). The tubing is split such that each block will read the flow for the samples in that block only. 14.1.06. Turn on the vacuum pumps. Adjust the vacuum valves to obtain approximately 3 bubbles/second in the reflux flask. Allow vacuum draw for at least 5 minutes. Note: the vacuum may need to be slightly higher for solid samples so that the solids are suspended in the reflux flask.
14.1.07. To reduce interferences from nitrate and nitrit e, add 0.2 g of sulfamic acid through the air inle t above the reflux flask. RinseCyanide EPA 335.4 / 9012A Revised 04-May-10 Rev#6 Created: 21-Sep-04 Page 10 of 16 16

Controlled Document - DO NOT PHOTOCOPY down with a small amount of water. Let the flask bubble for 3 minutes. 14.1.08. Inject 5 mL of 18N Sulfur ic Acid through the air inlet above the reflux flask. Rinse down wit h a small amount of water. Let the flask bubble for 5 minutes. 14.1.09. Inject 2 mL of magnesium chloride solution through the air inlet. Rinse down with a small amount of water. Repeat if foaming occurs. 14.1.10. For the LabCrest Midi-Dist, turn on the red rocker switch and turn the dial to 105. For t he Glastron Midi-Dist, turn on the heating mantle. The timer has been programmed to ramp the temperature to 150C in 10 minutes, hold that temperature for 1 1⁄2 hour and then turn off the heat. At the end of the run the unit will shut off. Leave the samples in the block for another 15 minutes with the vacuum and cooling fingers on. 14.1.11. Close each valve, disconnec t the absorber, then starting at the right open the valve to draw a ll solution from th e frit. Close valve and remove frit. 14.1.12. After the Midi-Dist apparat us have cooled to below 100C disconnect the reflux flask from the absorber flask. Place the impingers in a tote of tap water to be washed. Turn off the vacuum valves for each position. Turn off the vacuum pumps. Turn of the cold water tap to the cold fingers. 14.1.13. Collect the samples from t he absorber flasks. This solution is now ready for analysis. If the samples will not be analyzed immediately they must be stored at <=6C until analysis. 14.1.14. For solid samples being reported on a dr y-weight basis, weigh approximately 5g of samp le into a pre-dried, preweighed crucible. Place in a drying oven at 103C until a constant weight is reached. Calculate the percent solids of the sample. Note: The sample used mu st be a different aliquot than that used for the CN determination.
14.2. AQ 2 Analysis : 14.2.01. All parameters necessary to run calibration standards,QC's and unknown samples for this method are preprogrammed in the AQ 2 software.
14.2.02. The AQ 2 analyzer's computer and software serve to control and monitor all mechanical functions, mathematical computations, sample data storage and report generation.Cyanide EPA 335.4 / 9012A Revised 04-May-10 Rev#6 Created: 21-Sep-04 Page 11 of 16 16

Controlled Document - DO NOT PHOTOCOPY SCHEDULING: 14.2.03. Open a new schedule and se lect the WW reagent set. In the column labeled “type” skip rows 1, 2 and 3 (these are pre-programmed into th e method to be the curve standard and undistilled CCB and CCV). In row 4 enter your method blank as “MB”. This is the start of the distilled preparat ion batch.
14.2.04. In the column labeled “Sample ID” in rows 5 and 6 enter the distilled CCV (a s “CCV xx mg/L”) and the second source QC (as “QC#xxxxxx”). The “type” column will show “u1” and “u2” indica ting that the CCV and QC will be treated as AQ2 unknown s. This guarantees that the standards will be treated t he same as the samples. 14.2.05. Starting in row 7 enter each sample, including duplicates and matrix spikes, as unknowns. After all samples are entered, highlig ht the column “Requested tests” to the right of each scheduled sample and standard. Select the test cyani de by clicking on “CN” in the test box above the schedule.
14.2.06. Save the schedule: Cli ck “file” at the top left-hand side of the screen. Click “sav e”. If any piece of the schedule is missing (ie. Forgot to select a test) then a prompt will show up asking if you really want to save. Cancel the save and fix the problem. Note: If you click save with pieces missing all or part of your schedule will disappear and you will have to start over.
14.2.07. Place the standards and samples into a sample wheel according to the location in the schedule. Each 2mL sample cup must be completely filled. Place the sample wheel on the AQ 2 and tighten the lock in the center of the wheel.
SETUP : 14.2.08. Replace any used reac tion segments. Fill the deionized water reservoir. Empty waste containers. Place the waste tubing into the empty glass waste container. (CN AQ 2 waste must be entered into the cyanide waste container after each run). 14.2.09. The reagents are to be placed into their reagent wedges and placed on the AQ2 as follows: Pyridine-Barbitu ric Acid: Reagent Wedge 11 Phosphate Buffer: Reagent Wedge 9Cyanide EPA 335.4 / 9012A Revised 04-May-10 Rev#6 Created: 21-Sep-04 Page 12 of 16 16

Controlled Document - DO NOT PHOTOCOPY Chloramine-T: Reagent Wedge 10 0.25N NaOH: Reagent Wedge 1

RUN : 14.2.10. Double click on the “ RUN” icon at the top left-hand side of the screen. Select t he cyanide schedule from the list of trays and click “OK”.
14.2.11. Check the box for “set tube counter to zero”. Click “OK”. The run will start.
14.2.12. The AQ2 will analyze the samples in the order that they are on the screen. Sa mples that are over the calibration range will be resc heduled at a dilution (dilutes with 0.25N NaOH from reagent wedge 1) then ran again at the end of the run. If samp les are auto-diluted in this manner they will show up blue on the screen. If any samples are auto-diluted t hen the last CCV and CCB on the run must be manually re scheduled after the run has been completed in order to brac ket the diluted samples. Samples that remain over range must be rescheduled with a manual dilution with 0. 25N NaOH. The run must always end with a CCV and CCB set. 14.2.13. After the run is comple te, the prompt at the top lefthand side of the screen will s how “Finished” in red. Assess the quality controls. To accept the run, click the “acceptance” icon al ong the left-hand side of the screen. Select the cyanide run. Click “Accept All”. A prompt will show up asking if you want to permanently accept the run. Accept the run and a screen will open with the printable results fo r the bench notebook. For information regarding analyzer maintenance and troubleshooting refer to the relev ant sections of the Operator Manual. 14.3. Cleanup : 14.3.01. Distillation flasks are cleaned in the Mi ele glassware washer. Glass beads are washed by hand in the sink then dried and re-used. 14.3.02. The reflux impinger s and absorber impingers are soaked in hot tap water. C hange the water each time it cools for at least 3 cycles, being careful to remove the water from the tubes between ea ch step. After 3 washes with hot tap water, rinse t he impingers well with flowing hot tap water then place them into a tub of deionizedCyanide EPA 335.4 / 9012A Revised 04-May-10 Rev#6 Created: 21-Sep-04 Page 13 of 16 16

Controlled Document - DO NOT PHOTOCOPY water over night. In the morn ing, drain the water from the impingers and allow them to dry completely before putting the apparatus back together. NOTE: The tubes and impingers must be periodically acid washed to remove staining and other residue. Acid washing is completed with HCl or H 2 SO 4 and tap water. The acid wash sign MUST be posted above the sink during acid washing. NOTE: The tubes and impingers do not have to be dried completely if they are going to be used again immediately after the cleaning process.
14.3.03. The distillation blo cks may be cleaned with damp paper towels. Check the system for leaks and damage after each run.
14.3.04. The AQ 2 has an automatic cleaning process at the shutdown of each run. The AQ 2 waste must be emptied into the cyanide waste contai ner. Rinse the container into the waste with a small am ount of water. Follow the end-of-day prompts to shutdo wn the equipment for the night.

15.0. Calculations:
15.1. AQ 2 Results are reported in ug CN/L. 15.2. Sample results that fall be low the practical quantitation limit (PQL), must be reported as <.

15.3. Results entered into LabTa sk must be converted from ug/L to mg/L and reported as mg/L CN.
15.4. The EPA Maximum Contaminant Level (MCL) is 0.2 mg/L (posted on the EPA website http://www.epa.gov/safewater/contaminants/index.html ). 15.5. For solid samples, calculate the result in mg/Kg (dry weight basis) based on the weight used in the distillation. The EXCEL spreadsheet for the calculati on is saved on the server at:
\\Server1\public\1 Plattsburgh Lab Task\Cyanide Solids.XLS. The calculations page must be printed and filed with the q-list. Calculation: mg/kg dry = (mg/L x final vol (L) x 1000) (mass (g) x %s as a decimal)Cyanide EPA 335.4 / 9012A Revised 04-May-10 Rev#6 Created: 21-Sep-04 Page 14 of 16 16

Controlled Document - DO NOT PHOTOCOPY 16.0. Method Performance: 16.1. Studies to determine the Method Detection Limit (MDL) and Practical Quantitation Limit (PQL ) are completed at least annually per SAP EL00029. 16.2. Proficiency testing is comp leted at least twice annually per SAP EL0047 and passing the best two out of three is required. 16.3. Tracking of the quality contro l results is completed with each

run.

17.0. Pollution Prevention: 17.1. Completed samples that c ontain no cyanide are disposed of via the sanitary sewer. 17.2. Leftover sample volume is stored in the sample archive fridge for 1 month. Samples that contain no cyanide can be disposed of via the sanitary sewe r. Samples that contain cyanide are labeled “Contains Cyanide Do Not Dump” (go to 17.5.01). 17.3. Expired hydrochloric ac id and sodium hydroxide are neutralized and disposed of via the sanitary sewer. 17.4. AQ2 waste is stored in the waste chemical disposal area until in can be disposed of as haz ardous waste by a certified waste disposal company. 17.5. Expired cyanide standards , quality control standards, and samples containing cyanide are stor ed in the “waste storage” area until they can be reacted with hou sehold bleach then disposed of via the sanitary sewer. 17.5.01. To treat cyanide samples or standards, place the sample in a beaker in the fume hood. While stirring, add sufficient chlorine to maintain a chlorine residual. Check for the presence of chlorine with KI-starch indicator strips. Allow standards to remain in the hood for at least 1 hour. Check again for chlorine. If chlorine has dissipated, add more chlorine and repeat the process. Once a chlorine residual has been maintained fo r 1 hour, flush the sample down the fume hood drain with copious amounts of water. 17.6. Samples treated with cadm ium carbonate must be stored and disposed of as hazardous waste.

18.0. Data Assessment and acceptance criteria: 18.1. Quality control parameters must be met. See section 12.

19.0. Corrective action fo r out-of-control data: 19.1. Check reagents. 19.2. Check for proper heating of the Midi-Dist sample tubes.Cyanide EPA 335.4 / 9012A Revised 04-May-10 Rev#6 Created: 21-Sep-04 Page 15 of 16 16

Controlled Document - DO NOT PHOTOCOPY 19.3. Complete the AQ 2 troubleshooting and maintenance.
20.0. Contingencies for handling out-of-control data: 20.1. Repeat the analysis.

21.0. Waste Management: 21.1. Refer to SAP# EL0005

22.0. References:

22.1. Methods for Chemical Analysis of Waters and Wastes, U.S. Environmental Protection Agency : Method 335.4, Rev.1, 1993. 22.2. Total Cyanide in Drinking, Saline an d Surface Waters, and Domestic and Industrial Wastes , SEAL Method NO:EPA-130-A Rev 3, USEPA Method 335. 4, Range 3-250 ug CN/ L, Revision Date: 01- Jun-05. 22.3. Total Cyanide in Drinki ng, Surface and Groundwater and Wastewater, Endyne Inc - Randolph Lab (formerly SciTest), SOP No. IC-024, Revision 5.0, Date: 3/8/2006. 22.4. Andrews Glass Company LabCrest ® Midi-Dist TM Cyanide Distillation System Model 110- 10 Operation Manual, Andrews Glass Company, EP Document #3100.
22.5. Glastron TM Instruction Manual Enviro Midi-Dist Distillation System, Glastron Inc. 22.6. EPA Method 9010B, Total and Amenable Cyanide: Distillation, Revision 2, December 1996. 22.7. EPA Method 9012A, Total and Amenable Cyanide (Automated Colorimetric, with off line distillation), Revision 1, December 1996.

23.0. Tables, diagrams, flowcharts and validation data:

23.1. TEST PARAMETERS for the up to 2.5 mg CN/L RANGE PARAMETER AQ2 SETTING Test Name CYANIDE 335.4 Chemistry type End point Decimals 3 Units ug/L Number of mixes 1 Reaction time (seconds) 480 Sample volume ( μ L) 250 Water volume ( μ L) 0Cyanide EPA 335.4 / 9012A Revised 04-May-10 Rev#6 Created: 21-Sep-04 Page 16 of 16 16

Controlled Document - DO NOT PHOTOCOPY Number of reagents 3 1. Phosphate Buffer ( μ L) 100 2. Chloramine-T ( μ L) 25 3. Pyridine Barbituric acid ( μ L) 240 Reagent 3 Delay (sec) 85 Filter (nm) 578 Flowcell wash 2 Flowcell prime 1 Polynomial order 1

Date Tech Revision # Revisions

14-Jan-08 CAL 2 Changed to method EPA 335.4, Rev.1, ELAP#9119. Updated reagents, distillation procedure, and QC requirements. Added to section 7.3 that samples containing sulfide interference may be subcontracted. Added section 17.6.

10-Jun-09 CAL 3 Added references to Free Cyanide – drinking water analyzed for SDWA compliance monitoring ar e reported as free cyanide.
22-Sep-09 CAL 4 Updated the acceptance criteria fo r duplicate and matrix spike acceptance. Added the use of antif oam to prevent bumping in the distillation step.

10-Mar-10 CAL 5 Added info from methods 9010B and 9012A to include solid samples. Added to 14.1.10 and 14.1.11 the process to properly disconnect the samples from the unit.
04-May-10 CAL 6 Added sections 14.1.14 (percent solids determination) and 15.5 (solids calculation).ATTACHMENT 6Elemental Analysis of Water and Sludge Samples as Submitted by Endyne, Inc of Williston,Vt.

1. Samples are logged into our accounting system and assigned a unique identification job number. Date received is recorded and a contract review is completed. 2. Sample preparation: a. Water samples : The entire Water sample submitted is weighed to three significant figures and then digested in the appropriate stabilizing acid for the elements of interest (see list below). The digested solution is then brought back to the original weight w ith deionized water. b. Sludge samples : A 0.5 gram aliquot of a Sludge sample is weighed to three significant figures, in duplicate, and digest ed in the appropriate stabilizing acid(see list below). The digested solution is then diluted to weight to 100 fold with deionized water. c. Reagent blanks are prepared in the same manner as the samples. 3. Standards and QC controls : Standards of 0 and 10ppm are prepared for the elements of interest in the same acid matrix as the samples. QC Controls are also acid matrix matched to the samples and are prepared at 1ppm and 0.1 ppm. All standards and controls are prepared weight/weight and are Nist traceable. 4. Analysis : The samples are then analyzed by ICP-OES on a PE 3300RL instrument according to the manufacturer’s specifications. The instrument is calibrated with each use for the elements of interest onl y. Appropriate dilution factors are entered into the analysis program so the resulting concentration reported is that of the ‘as is’ delivered sample.

Elements of Interest Stabilizing Acid Elements of Interest Stabilizin g Acid

Gold Aqua regia(HCL+HNO3) Strontium HNO3

Iridium Aqua regia(HCL+HNO3) Tantalum HNO3 + HF

Lanthanum HNO3 Tin HCL

Palladium Aqua regia(HCL+HNO3) Titanium HNO3 + HF

Platinum Aqua regia(HCL+HNO3) Zirconium HCL

Rhodium Aqua regia(HCL+HNO3)

Note: When analyzing for Pt, the same p rep and standards procedure is used as for all other elements in this SOP ensuring aqua regia is used as the stabilizing acid. The analysis is performed as in step 4, utilizing Pt wavelengths 214.423nm and 265.945nm