SECTION 17 PROFESSIONAL PROFILES

SECTION 17

PROFESSIONAL PROFILESOF LABORATORY PERSONNEL

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BCMROCCO T. ALESSANDRO, PH.

Assistant Vice Preside1Technical Director, BCM Lab

PROFESSIONAL SUMMARY

Mr. Alessandro serves in a dual capacity as Technical Director for thelaboratory and Operations Director for the Organics Department. Inaddition to his administrative duties, Mr. Alessandro is responsible forimproving the quality of the analytical product by implementing newanalytical technology and methods. At other laboratories, he has refinedtechniques for Appendix 8 and 9 Organic analysis; implemented CLPprotocols; managed the development and implementation of USATHAMA methods;directed client-specific non-routine environmental analyses; performedoperation, maintenance, and modification of HP and Finnigan MS; anddeveloped identification methods for crude petroleum, essential and fattyoils. Mr. Alessandro serves as a technical resource for BCM's engineers.

KEY PROJECT EXPERIENCE

At ETC Corp., planned and supervised conversion of laboratory intovertically organized product-line work groups; eliminated severalpersistent sources of extract contamination; reorganized the separ-ations department by developing new training programs and a careerladder which successfully cut the attrition rate; planned andimplemented construction of specialized racks for liquid/liquidextractors which drastically reduced the labor required to extractaqueous samples; and managed a development group which certifiedUSATHAMA methods and performed unusual analyses for industrial clients,where official methods did not exist

- At the U.S. Customs Service Laboratory, directed routine analysis andmethod development projects for tariff classification on a number ofproducts; appointed technical advisor to the Saudi Arabian customs andtraveled to Saudi Arabia, Great Britian, Prance, and throughout the •U.S. evaluating linear accelerator based cargo X-ray systems and MSbased "sniffers" for the Saudis

- At NY Testing Laboratories, directed the MS laboratory and consulted onGC and GC/MS analysis. Major accomplishments involved implementationof CLP protocols for determination of pollutants in soils and water

- At Stauffer Chemical Co., determined pollutants in sediment and groundwater samples from around company plants. Major accomplishment wascreating a method for determination of incidentally produced (non-Arachlor) PCBs in aryl phosphinic and phosphonic acids

- At Kentile Floors, developed structural and pigmentation formulae forasphalt and vinyl asbestos tiles and mottles, enabling greater reusescrapped tile

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EDUCATION

B.S. ChemistrySt. John's University 1965

Ph. D. ChemistrySt. John's University 1977

PROFESSIONAL AFFILIATIONS

American Chemical SocietyAmerican Society for Mass SpectrometryAir Pollution Control Association

PUBLICATIONS AND PRESENTATIONS

Alessandro, R.T. and Adams, J.M. 1985. "Gas Chromatographic-MassSpectrometric Detection of the Adulteration of Natural Lime Oils."Assoc. Off. Anal. Chem. 68; 1154-1159

Alessandro, R.T. 1980. "Determination of the Animal Origin of Cheese."NY Chromatographic Society, First Annual Minisymposium

Alessandro, R.T. 1980 "Identification of Spermaceti in Cosmetics."First Annual Symposium on Federal Government Mass Spectrometry

Alessandro, R.T. 1980 "Distinguishing Characteristics of Mentha SpeciesOils." First Annual Symposium on Federal Government Mass Spectrometry

Lengyel, I. and Alessandro, R.T. 1979. "Reactions of Some Hetero-cumulenes under Electron Impact: A Comparison of Carbodiimides and SulfurDiimides." American Chemical Society, National Meeting

Governo, T.F., Alessandro, R.T., and Prager, M.J. 1977. "A GasChromatographic-Mass Spectrometric Detection and Identification ofAmbergris." J. Assoc. Off. Anal. Chem. 60: 160-163

Alessandro, R.T. 1977. "Mass Spectroscopy of Some Alkyl and ArylCarbodiimides." Ph. D. Thesis, St. John's University, Jamaica, NY

Publications in the Technical Bulletin of the U.S. Customs Service:

Alessandro, R.T. and Adams, J.M. 1986. "Determination of the Country ofOrigin of Some Western Hemisphere Natural Lime Oils." Technical Bulletin19: 104-113

Alessandro, R.T. and Barnwell, J.L. 1986 "Computer Assisted Processingand Calculation of Cheese Analysis Data." Technical Bulletin 19: 57-62

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PUBLICATIONS (Continued)

Alessandro, R.T. and Adams, J.M. 1985. "Computer Analysis ofChromatographic Peak Area Percent Data, II: The Identification of SomeLauric Acid Oils." Technical Bulletin 18: 141-161

Alessandro, R.T. and Adams, J.M. 1985. "Computer Assisted Evaluation ofManually Acquired Mass Spectral Data." Technical Bulletin 18: 109-116

Alessandro, R.T. and Adams, J.M. 1985. "Computer Analysis ofChromatographic Peak Area Percent Data, I" Technical Bulletin 18: 68-72

Alessandro, R.T. 1980. "Determination of the Animal Origin of Cheese."Technical Bulletin 14: 12-13

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DEBORAH J. CONTE-TOTHScientist


Ms. Toth is responsible for managing all aspects of client services. Sheprovides liaison between the BCM Laboratory and municipal, commercial,industrial, and governmental clients. 'Ms. Toth expedites projects,manages project tasks to ensure compliance with deadlines, and informsclients of progress.


Maintained a quality control program for production of Class 1 and 2medical devices under U.S. FDA jurisdiction. Supervised 13 inspectors,coordinated and initiated all product development, developed andmaintained client relations with technical and sales personnel of otherfirms, and provided sales support through development and participationin presentations

- Conducted laboratory and mill research into pulp processcontrol/improvement for a major paper manufacturer. Prepared technicalreports, maintained and operated an environmental laboratory (includedwet chemistry analytical equipment), and assisted in bleach pilot plantoperations

- Coordinated, prepared, and planned laboratory programs while alaboratory technician at Drexel University. Purchased supplies andequipment, and instructed faculty and teaching assistants inexperimental procedures and techniques

EDUCATION

B.S. ChemistryCabrini College 1978

M.B.A. Business AdministrationOklahoma City University 1986

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gwrD. LINDA

u Section Manaj* Asbestos/Microbiology


As a section manager at the BCM Laboratory, Ms. Cox supervises theMicrobiology and Asbestos Industrial Hygiene Departments and has assumedrepsonsibility for the Transmission Electron Microscopy area. One of herprimary duties is maintaining AIHA accreditation for airborne asbestos andNVLAP accreditation for bulk asbestos. Ms. Cox's experience in biologicalanalyses includes treating effluents from wastewater treatment plants andtesting municipal and industrial potable drinking water. She hasinstructed plant personnel in analytical procedures and has providedassistance in preparing designs and specifications for new laboratoriesand refurbishing existing facilities.


- Participated in the design of BCM's new Electron Microscopy laboratoryand the procurement of its equipment

- Identified bulk asbestos and quantified airborne asbestos for a publicschool system in Alabama, a major department store chain, and a numbôf food processing companies

Conducted accurate and reproducible analyses of bulk asbestos con-census standards from Research Triangle Institute and airborne as-bestos AIHA PAT performance samples

- Conducted biological treatment studies for manufacturers of extractsand fragrances. Data were subsequently used in design and engineeringof a two-stage activated sludge wastewater treatment facility

- Prepared microtesting, bacteriological adaptation studies, and bac- •teriological air and water pollution studies for a pharmaceuticalquality control study

Supervised the monitoring of bench-scale biotreatability studies ofwastewaters

Tested water samples for pathogenic microorganisms. Also conductedsterility tests on ethical drugs, purity tests on raw materials, andair quality sampling

•-. - Conducted air and water sampling to maintain standards in an environ-mentally controlled production area. Identified bacteria andinstructed personnel in proper sterility techniques

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EDUCATION

B.S. BiologyThe Pennsylvania State University

Additional Education and Training

Asbestos Identification by Polarized Light Microscopy, ESI, Inc.Quality Control in Asbestos Analysis Lab, University of North CarolinaSampling and Evaluation of Airborne Asbestos Dust (NIOSH 582), TempleUniversity

PROFESSIONAL REGISTRATIONS

Asbestos Analyst Registry for airborne asbestos, No. 1592NIOSH-Certified in Airborne Asbestos Analysis by PCM (NIOSH 582)


American Industrial Hygiene AssociationAmerican Society of Quality ControlNational Asbestos CouncilPhiladelphia Geological Society

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PRESTON L.Metals Supervisor


Mr. Golstein is the supervisor of the Metals Section of the BCM Labor-atory. The Metals Section performs analyses on water, wastewater, soils,sludges, and filter samples by atomic absorption spectrophotometry,utilizing flame and graphite furnace techniques, inductively coupled argonplasma emission spectrophotometry, and cold vapor analysis. Mr. Goldsteinimplements Quality Assurance/Quality Control programs in his section andis on the Laboratory Safety Committee.

Mr. Goldstein has more than 21 years of technical experience inenvironmental testing and industrial hygiene programs and has heldsupervisory positions with a wide range of responsibilities for the last 9years.


Coordinated a Quality Assurance/Quality Control program for BCM'slaboratory

Initiated an in-house safety program by writing a safety manualformatting a contingency safety plan

Constructed an automatic computerized calibration system for determi-nation of instrument drift and need for recalibration

Coordinated aerometric data collection programs between clients andstate agencies for environmental impact statements

Supervised all testing and sampling procedures for an environmentalfirm in New Jersey, including chemistry analyses of water, wastewater,effluent, and sludge samples; atomic absorption spectrophotometryanalyses of metals in water, wastewater, soil, and sludge samples;coliform bacteria testing of water samples; and gas chromatographyanalyses for pesticides, herbicides, and trihalomethanes, Alsoensured that in-house QA/QC programs were in accordance with U.S. EPAguidelines, and managed all proficiency samples in order to maintainlaboratory certification

Supervised three laboratory sections (wet chemistry analyses ofvarious substances, heavy metals analysis by atomic absorption

:. spectrophotometry, and microbiological analyses of water samples).Also tested air samples for asbestos fibers

Acted as quality control coordinator and established an in-houseprogram in accordance with U.S. EPA guidelines. Also acted asofficer to establish an in-house safety program and prepare a safelmanual

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KEY PROJECT EXPERIENCE (Continued)

Maintained 12 air quality monitoring stations to assess ambient levelsof pollution. Calibrated instruments to measure various pollutants.Assessed instrument performance by interpreting computer printouts

Determined appropriate chemical doses for treatment of municipal water,based on quantitative analyses of samples

EDUCATION

B.S. ChemistryPhiladelphia College of Textiles and Science 1970

Additional training:

Seminar on "Electronics for Chemists"Sadtler Research Center, Philadelphia, PA

Seminar on "Fundamentals of Industrial Hygiene"Canisius College, Buffalo, NY

Training course on "ICP Analysis"Perk in Elmer, Norwalk, CT

PROFESSIONAL AFFILIATION

Air Pollution Control Association

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AMBER V. REYNOTechnical Client Laborato

Services Representative


Ms. Reynolds is responsible for various liaison duties between the BCMLaboratory and our clients. She informs clients of progress, directsquestions to the appropriate laboratory personnel, delivers specifi-cations and reports, and schedules and expedites laboratory tasks.


Calibrated, maintained, and operated stack air sampling equipment andconducted all analyses of resultant data at U.S. Steel's Fairless Worksin Bucks County, PA. Analyzed and consolidated data for en-vironmental monitoring reports, maintained statistical records, andreconciled all corporate, U.S. EPA, OSHA, and PADER audit inquires.Conducted visual emissions testing of stationary pollution sources.Conducted analyses of samples for the testing of H2S. Also col-lected and prepared effluent samples for analysis and determinedeffluent flow rates

Conducted various chemical analyses while employed by a commercialanalytical laboratory. In adition, maintained a distilled waterproduction system to provide water for laboratory procedures

EDUCATION

B.S.. ChemistryRider College 1984

Source Sampling for Particulate PollutantsU.S. EPA Air Pollution Training Institute

Visual Emissions CertificationRutgers University

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ALAN M. ROBINSONVice President

Laboratory Director


Mr. Robinson has more than 14 years of experience in the performance ofhazardous waste site investigations and environmental planning projects.He has accomplished a variety of technical project management and admin-istrative management assignments, leading to his present position asLaboratory Director and Vice President at BCM Engineers Inc. As the Lab'sDirector, Mr. Robinson has overall responsibility for laboratoryscheduling and performance, analyses, quality control, customer service,and final report review and approval. Prior to becoming director of theBCM Laboratory Division, Mr. Robinson was BCM's Senior Geologist andDirector of BCM's Groundwater and Hazardous Waste Site Investigation,Assessment, and Environmental Planning Department. His work has included:

Stormwater and floodplain managementSolid waste planning and managementEnvironmental impact statementsRisk assessments

- Water supplyGroundwater contamination investigation, assessment, and remediation

- Site audits- Hazardous waste site investigation, assessment, and remediation- Laboratory programs


- Detailed potential impacts of land development on flood flow rates in arapidly urbanizing watershed. Developed a scope of work and directedseveral projects in the watershed to design, implement, and managerecommendations. Structural and nonstructural flood control managementalternatives and various development schemes were evaluated, and astormwater management handbook for use by developers and a revisedcomprehensive stormwater and floodplain management ordinance wereprepared

Assessed county-wide stormwater management needs and prepared acomprehensive stormwater drainage and management program, taking intoaccount growth, land use, natural resources, and hydrogeologic charac-teristics. Developed specific control requirements., application cri-teria, and enforcement procedures. Prepared a handbook to assistdevelopers and engineers in complying with ordinance requirements

- Developed a program to retrofit site-specific drainage improvements inan 80-acre residential development. Project construction was staged tosystematically improve drainage conditions while remaining within thefinancial constraints of the municipal improvements program

- Served as stormwater management consultant to the Municipal Training}Division of the Pennsylvania Department of Community Affairs.Developed a statewide program to educate municipal officials on theproblems of urban runoff and the mitigative approaches available

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Directed and served as Project Manager, senior geologist, regulatoryliaison, and client contact for the Henderson Road Site RemedialInvestigation/Feasibility Study and Remedial Design work plan for thisNational Priorities List site underlain by a highly complex geologicand hydrogeologic system. Hydrogeologic and risk assessment componentswere extremely important due to the presence of a large water supplyreservoir 2,000 feet downgradient from the site.

- Principal-in-Charge of Environmental Impact Statement, Siting Study,and Site Assessment, U.S. Navy Northern Division Engineering Commandfor the Earle Ammunitions Base Homeporting Expansion. Work involved inthis comprehensive project included sampling and analysis of estuarinesediments proposed for dredging, ship fuel storage facility siteevaluation, soil and groundvater quality assessment of one potentialsite, and environmental impact statement review. BCM staff workedclosely with Navy personnel throughout the course of this project.

- Project Manager for the investigation of groundwater contaminationassociated with landfilling and other methods of hazardous wastedisposal at a 200-acre chemical manufacturing facility along theDelaware River. Investigation work included aerial photograph review,site history evaluation, computer modelling, surface geophysicalsurveys, soil borings, test pits, groundwater monitoring well instalation, sampling and analysis, and site evaluation and reporting.Remedial design is now proceeding as part of a Resource ConservationRecovery Act corrective action.

Principal-in-Charge providing technical and administrative leadershipfor site audits and investigations at over 500 sites from 1-day auditsto multi-year projects.

EDUCATION

B.A. GeologyUniversity of Pennsylvania 1972

M.S. Secondary EducationUniversity of Pennsylvania 1972

M.A. Geography (Water Resources)The Johns Hopkins University 1976


National Water Well AssociationPhiladelphia Geological SocietyAmerican Water Resources Association

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TEACHING EXPERIENCE

Mr. Robinson has taught Hydrology in the Department of LandscapeArchitecture arid Regional Planning at the University of Pennsylvania.

PAPERS AND PUBLICATIONS

Robinson, Alan M., "The Effects of Urbanization on Stream ChannelMorphology." Proceedings of the National Symposium on Urban Hydrology,Hydraulics, and Sediment Control, Lexington, KY, July 1976, p. 115-127

Robinson, Alan M., and Collier, Carol R., "Planning for RiparianEnvironmental Quality Options in a Small Watershed in New Jersey."Proceedings of the National Conference on Stormwater ManagementAlternatives, Wilmington, DE, October 1979

Robinson, Alan M., "The Problems of a Stormwater ManagementPractitioner." Keynote address at the Pennsylvania Conference onStormwater Management, The Pennsylvania State University, March 1980

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JOHN T. RLaboratory Supervis

Wet Chemistry


Mr. Ruane manages BCM Laboratory's Wet Chemistry Laboratory. His dutiesinclude supervising and training personnel, scheduling analyses, perform-ing analytical testing, reviewing analytical data, and developing andimplementing both Standard Operating Procedures (SOPs) and a QualityControl (QC) program. Before becoming a supervisor at the Lab, Mr. Ruaneperformed analytical testing, sample custody, client services, and QualityAssurance duties


- Performed analytical testing for various clients including Rohm andHaas, Shell Chemical, Sterling Drug, Encoat, and others

EDUCATION

B.S. MicrobiologyThe Pennsylvania State University 1983

Additional Education and Training

Bran & Lubbe Technicon Autoanalyzer GTPC Training Seminar, February 1989

Management Seminar, Take Charge Consultants, 1989

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JOHN J. TOBIN, JR.Laboratory Operations Manager


Operations Manager of BCM's Analytical Laboratory, Mr. Tobin has a broadbackground in industrial hygiene, analytical chemistry, and biology. Heis thoroughly familiar with state and federal environmental regulationsand has more than 15 years of experience in the performance and super-vision of all laboratory operations and environmental testing associatedwith municipal, institutional, and industrial water and wastewater,groundwater and soil contamination, and hazardous waste. He is respons-ible for laboratory quality control, proper production procedures, andcompliance with all relevant government regulations. Under his super-vision, the laboratory staff perform wet chemistry procedures, asbestosanalysis, analyses of water, wastewater, and soil samples, and analyses ofvolatile and semivolatile organic compounds by gas chromatograph and gaschromatograph/mass spectrometer, HPLC, atomic adsorption, and ultra-violet spectrophotometry.


- Directs the activities of the BCM Laboratory staff in successfullycompleting quick turnaround analysis of soil and water samples requiredfor audits of industrial, institutional, and commercial facilities andreal estate

- Worked with BCM's computer specialists to develop BCH's LaboratoryInformation Management System (LIMS) and historical database. Thesesystems are constantly in use for tracking samples within the labor-atory, producing reports, and drawing upon information from past workto provide additional services to clients.

- Directed laboratory activities for the analysis of over 100 samples forPriority Pollutant analysis at a major hazardous waste site. Inaddition to Priority Pollutant analysis, analyses were conducted forseveral manufacturing-specific compounds. The analyses performeddetected a wide range of inorganic and organic contaminants. Con-siderable effort was made in proper extraction techniques due to thedifficult matrices encountered.

- Qualified the BCM Laboratory for certification by the U.S. EPA andother federal and state agencies, and for the AIHA accrediation program

- Conducted field sampling, sample preparation, and analytical pro-cedures for Priority Pollutant, Hazardous Substance List, and TargetCompound List compounds

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Performed all types and phases of analyses by atomic absorption, gaschromatography, infared, and ultraviolet spectrophotometry method-ologies for various projects

On numerous projects, has conducted compliance monitoring inaccordance with OSHA, FDA, RCRA, and EPA regulations

EDUCATION

B.S. BiologyStockton State College 1976

Additional courses in environmental education, environmental and physicalscience, atomic absorption, spectrophotometry, gas chromatography, andmass spectral interpretation

TEACHING EXPERIENCE

Instructor of Environmental ChemistryGloucester County Community College, Sewell, NJ

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WAYNE WANScienti


Mr. Wang supervises the organics department which includes samplepreparation, and the GC and GC/MS groups. His specific duties includesupervising and scheduling of a staff of chemists and technicians;reviewing and interpreting GC/MS data and evaluating GC results;implementing new analytical methodologies and modification through groupleaders; assisting the laboratory manager in the preparation and review ofthe analytical reports; and evaluating and reviewing quality controltesting program results and maintaining quality control records.


Provided confirmation and quantification of organochlorine pesticidesand PCBs in industrial wastes under contract with the State of Ohio'sEPA

Assisted in the submission of a proposal and receipt of funding by theU.S. EPA, for 150 ground wells, 200 multiphases waste sample of CLPorganics for remediation

Ground monitoring well organic analysis for DuPont, Union Carbide,Borg-Warner, American Cyanamide, PPG, Shell, and Mobay

Performed PCB analysis for Ohio Colombus Gas Company

Performed PCB and VOC analysis for Consolidate Aluminum waste disposal

EDUCATION

B.S. ChemistryTarn Kang University, Taiwan 1975

M.S. ChemistryMarshall University, Huntington, WV 1980


American Chemical Society

PAPERS AND PUBLICATIONS

"The Michael Addition Products of the Reaction of 2-Quinolyl-Acetone withDiMethyl Acetylene Dicarboxylate," Thesis, Marshall University, 1980

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BCM Laboratory Effective Date: 6/25/90Standard Operating Procedure (SOP) Superceded Date: NEW

Method #: 350-SVCLP

Method:EXTRACTION FOR CLPSEMIVOLATILE ANALYSIS

Authored By:Edited By:Dept. Supervi

Approved By:

6/ixTfry cdjujriality eoQrialityeontrol Dept. Date'

u JLwiL u k tfafoSectiony Manager Q Date' TSJSjmcal Director Date

Lab Director Date

This monograph is based on Exhibit D, Section II, Sample Preparationand Storage for Analysis of Semivolatiles, USEPA Contract LaboratoryProgram Statement of Work for Organic Analysis, 2/88.

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BCM Laboratory SOP Page 1 of 38Method: Extraction for CLP Effective Date: 6/25/90

Semivolatile Analysis Superceded Date: NEW

I. ApplicationThis method is applicable to water and soil samples that areextracted for the organic compounds listed in thecorresponding instrumental method.

II. Sample Handling and PreservationLiquid samples are collected in glass, amber, small-mouthcontainers. Soil samples are collected in glass, amber,wide-mouth containers. The containers are fitted with screwcaps lined with Teflon. Samples are to be refrigerated at4 deg. C (+2 deg. C) from the time of receipt untilextraction. The extract must also be refrigerated untilanalysis. Water samples must be extracted within 5 days ofsample receipt and soils within 10 days.

The following are the steps an analyst follows for loggingsamples in/out to uphold an internal chain of custody:1. Remove samples from cold room.2. Bar code samples out of Log-in.3. Take samples to Extractions.4. Return samples to Log-in after extraction.5. Bar code samples back into Log-in.

III. InterferencesMethod interferences may be caused by contaminants insolvents, reagents, glassware, and other sample processinghardware. All of these materials must be routinelydemonstrated to be free from interferences by runninglaboratory reagent blanks (i.e., method blanks). Matrixinterferences may be caused by contaminants that arecoextracted from the sample. The extent of matrixinterferences will vary considerably from source to source.

IV. Method Summaries

Water Sample ExtractionsA measured volume of sample, approximately one liter, isserially extracted with methylene chloride at a pH >11 andagain at pH <2, using a separatory funnel or a continuousextractor. The extracts are dried and concentrated separatelyto a volume of 1 mL.

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IV. Method Summaries (cont.)

Soil Sample ExtractionsLow Level Sample Preparation: A 30 g sample is mixed withanhydrous powdered sodium sulfate and extracted with 1:1methylene chloride/acetone using a sonicator.Medium Level Sample Preparation: A 1 g portion ofsediment/soil is transferred to a vial and extracted withmethylene chloride.

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V. Apparatus

- Separately funnel, 2000 mL, with Teflon stopcock, AtmarGlass Co., Stock NO. 1639607

- Concentrator tube, Kuderna-Danish, 10 mL or 15 mL graduatedwith ground glass stopper, Kontes K-570050-1025 orequivalent

- Evaporative flask, Kuderna-Danish, 250 mL or 500 mL, KontesK-57001-0500 or equivalent (This is attached to concentratorwith springs)

- Snyder column, Kuderna-Danish, three ball macro, KontesK-503000-0121 or equivalent

- Snyder column, Kuderna-Danish, two ball macro, KontesK-569001-0219 or equivalent

- Sonicator: Model 375 from Ultrasonics, Inc. with a 375 Wattoutput capability or equivalent. NOTE: The horn (i.e., tip)must be replaced if the tip begins to erode which is evidentby a rough surface.

- Sonabox acoustic enclosure- Vials, 2.0 mL, amber glass with Tefon-lined screw cap

- Vials, 20 mL, with Teflon-lined screw cap

- Amber jars, 100 mL, 250 mL, 500 mL with Teflon-lined caps- Pipet, automatic, repeating, 60 mL, Atmar Glass Co.

- Disposable Pasteur pipets

- Continuous liquid-liquid extractors: equipped with Teflon orglass connecting joints and stopcocks requiring nolubrication, Hershberg-Wolf Extractor-Ace Glass Company,Vineland, NJ P/N 6841-10 or equivalent

- Automated gel permeation chromatography (GPC) cleanup devicefrom Analytical Biochemical Labs, Inc., GPC Autoprep 1002 orequivalent which includes the following:- 25 mm ID x 600-700 mm glass column packed with 70 g of

Bio-Beads SX-3

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V. Apparatus (cont.)

- Syringe, 10 mL with Luer-Lock fitting- Syringe filter holder and filters, stainless steel and

TFE, Gelman 4310 or equivalent

- Silicon carbide boiling chips, approximately 10/40 meshPreparation; Heat to 400 deg. C for 30 minutes or Soxhlet

extract with methylene chloride.

- Steam bath in hood and capable of temperature control to ±2deg. C.

- Top loading balance or equivalent capable of weighing to0.01 g

- Analytical balance or equivalent capable of weighing to0.0001 g

- Microliter syringes, 500 uL, 1000 uL, Hamilton brand (1750LTN) which is gas tight or equivalent

- Volumetric flasks, class "A", 50 mL, 100 mL, 400 mL

- Volumetric pipets, class "A", 0.5 mL, 2.0 raL, 10.0 mL- Graduated cylinder, 100 mL, 1 L- Erlenmeyer flasks, 250 mL

- Beaker, 400 mL- Spatula, stainless steel or Teflon

- Glass woo'l

- Glass weighing boat- Nitrogen tank of zero grade equipped with regulator

- Drying oven set at 105 deg. C- Desiccator- Crucibles, porcelain

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- pH meter

- Buchner funnel- Filter paper, Whatman No. 41 or equivalent- Vacuum filtration flask

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VI. Reagents

A. Stock Reagents- Sodium hydroxide, NaOH, Stock No. 3728-01, J.T. Baker- Sodium thiosulfate, Na2S2O3, Stock No. 78926, J.T. Baker- Sulfuric acid, H2SO4, stock No. 9681-33, J.T. Baker- Bis(2-ethylhexylphthalate) and pentachlorophenol in

methylene chloride, 4.0 mg/L

- Methylene chloride, CH2C12, pesticide quality orequivalent, Stock No. 9264-03, J.T. BakerSodium sulfate, Na2SO4, anhydrous granular crystals,Stock No. 3375-07, J.T. Baker

- Sodium sulfate, Na2SO4, anhydrous powdered. Stock No.3898-07, J.T. BakerSodium sulfite, Na2SO3, Stock No. 78890, J.T. Baker

- Corn oil in methylene chloride, 200 mg/L- Acetone, CH3-CO-CH3, pesticide quality or equivalent,

Stock No. 9254-03, J.T. Baker

Hexane, pesticide quality or equivalent, Stock No.9262-03, J.T. Baker

- Methanol, CH2OH, pesticide quality or equivalent, StockNo. 9263-03, J.T. Baker

* ACS grade or equivalent

B. Reagent Preparation1) Reagent Water: Reagent water is defined as deionized

water in which an interferent is notobserved at the MDL of the parameters ofinterest. Use reagent water forpreparing solutions, dilutions, andrunning blanks.

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VI. Reagents (cont.)

2) Sodium Hydroxide, 10 N

Preparation: Weigh 40 g of NaOH and record weight innotebook. Quantitatively transfer to a 100mL volumetric flask and dilute to volumewith reagent water.

3) Sulfuric Acid, fl:l v/v)Preparation: Slowly, add 50 mL of cone. H2S04 to 50 mL

of reagent water in a suitable glasscontainer which is immersed in a coolingwater bath or equivalent. CAUTION: Alwaysadd acid to water slowly.

4) Sodium Sulfate

NOTE: The preparation below is applicable to bothgranular and powdered forms.

Preparation: Line the bottom of a shallow tray withsodium sulfate and completely rinse withmethylene chloride. Place" tray in a 400deg. C oven for 4 hours. Transfer to130-150 deg. C oven until needed.

5) Methylene Chloride-Acetone Solution (1:1 v/v)

Preparation: Add 2000 mL of methylene chloride to a fourliter suitable container which contains2000 mL of acetone. Mix well.

C. Surrogate Spiking Solution StocksNitrobenzene-dS (20,000 ppm): Weigh 1.0 g +0.1 g ofnitrobenzene-d5 into a 50.0 mL volumetric flask and diluteto volume with methylene chloride. Record weight and lotnumber of neat material in standard notebook.

2-Fluorobiphenyl (20,000 ppm); Weigh 1.0 g +0.1 g of2-fluorobiphenyl into a 50.0 mL volumetric flask and diluteto volume with methylene chloride. Record weight and lotnumber of neat material in standard notebook.

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C. Surrogate Spiking Solution Stocks (cont.)Terphenyl-dl4 f40,OOP ppm); Weigh 2.0 g +0.1 g ofterphenyl-dl4 into a 50.0 mL volumetric flask and dilute tovolume with methylene chloride. Record weight and lotnumber of neat material in standard notebook.Phenol-d6 (40,000 ppm); Weigh 2.0 g +0.1 g of phenol-d6into a 50.0 mL volumetric flask and dTlute to volume withmethylene chloride. Record weight and lot number of neatmaterial in standard notebook.

2-Fluorophenol (40,000 ppm); Weigh 2.0 g +0.1 g of2-fluorophenol into a 50.0 mL volumetric fTask and diluteto volume with methylene chloride. Record weight and lotnumber of neat material in standard notebook.2,4,6-Tribromophenol (40,000 ppm); Weigh 2.0 g +0.1 g of2,4,6-tribromophenpl into a 50.0 mL volumetric fTask anddilute to volume with methylene chloride. Record weightand lot number of neat material in standard notebook.

D. Matrix Spiking Solution Stocks

1,2,4-Trichlorobenzene (20,000 ppm); Weigh 1.0 g +0.1 g of1,2,4-trichlorobenzene into a 50.0 mL volumetric fTask anddilute to volume with methylene chloride. Record weightand lot number of neat material in standard notebook.

Acenaphthene (20,000 ppm); Weigh 1.0 g +0.1 g ofacenaphthene into a 50.0 mL volumetric flask and dilute tovolume with methylene chloride. Record weight and lotnumber of neat material in standard notebook.

2,4-Dinitrotoluene f20,000 ppm); Weigh 1.0 g +0.1 g of2,4-dinitrotoluene into a 50.0 mL volumetric fTask anddilute to volume with methylene chloride. Record weightand lot number of neat material in standard notebook.

Pyrene (20,000 ppm); Weigh 1.0 g +0.1 g of pyrene into a50.0 mL volumetric flask and dilute to volume withmethylene chloride. Record weight and lot number of neatmaterial in standard notebook.

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D. Matrix Spiking Solution Stocks (cont.)N-nitroso-di-n-propylamine (20.000 ppm); Weigh 1.0 g +0.1 gof n-nitroso-di-n-propylamine into a 50.0 mL volumetricflask and dilute to volume with methylene chloride. Recordweight and lot number of neat material in standardnotebook.P-dichlorophenol f20,000 ppm); Weigh 1.0 g +0.1 g ofp-dichlorophenol into a 50.0 mL volumetric flask and diluteto volume with methylene chloride. Record weight and lotnumber of neat material in standard notebook.Pentachlorophenol [40,000 ppm); Weigh 2.0 g +0.1 g ofpentachlorophenol into a 50.0 mL volumetric flask anddilute to volume with methylene chloride. Record weightand lot number of neat material in standard notebook.Phenol (40,000 ppm): Weigh 2.0 g +0.1 g of phenol into a50.0 mL volumetric flask and dilute to volume withmethylene chloride. Record weight and lot number of neatmaterial in standard notebook.2-Chlorophenol (40,000 ppm); Weigh 2.0 g +0.1 g of2-chlorophenol into a 50.0 mL volumetric fTask and diluteto volume with methylene chloride. Record weight and lotnumber of neat material in standard notebook.

4-chlorp-3-methylphenol (40fOOP ppm); Weigh 2.0 g +0.1 gof 4-chloro-3-methylphenol into a 50.0 mL volumetric flaskand dilute to volume with methylene chloride. Recordweight and lot number of neat material in standardnotebook.4-nitrophenbl f40,OOP ppm); Weigh 2.0 g +0.1 g of4-nitrophenol into a 50.0 mL volumetric flask and dilute tovolume with methylene chloride. Record weight and lotnumber of neat material in standard notebook.

NOTE: The shelf life of the above solutions is twelve monthsand all solutions are stored in 100 mL amber jars at 4deg. C.

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E. GPC Calibration Solutions1) Corn Oil (200 mq/L)

Preparation: Weigh 10.0 g of corn oil into a glassweighing boat and record weight innotebook. Quantitatively transfer to a50.0 mL volumetric flask and dilute tovolume with methylene chloride.

2) Bis(2-ethylhexylphthalate) + Pentachlorophenol(4.0 mq/L)

Preparation: "Weigh 0.20 g each ofbis(2-ethylhexylphthalate andpentachlorophenol into a 50.0 mL volumetricflask and dilute to volume with methylenechloride. Record weights of each compoundin notebook.

NOTES:

1. Each standard bottle must be labelled with thefollowing: name of standard, concentration, analyst'sinitials, and date prepared. The preparation is recordedin the standard notebook.

2. The lot numbers are created by using the standard booknumber, followed by the page number, and finally theentry number (e.g., 1-26-1).

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u} BCM'BCM Laboratory SOP Page 11 of 38Method: Extraction for CLP Effective Date: 6/25/90


VII. Standard Preparation

A. CLP Surrogate Standard SolutionPreparation: Pipet 2.5 mL of each surrogate stock solution

prepared in Section VI, C, into a 500 mLvolumetric flask. Dilute to volume withmethanol and record preparation in notebook.Transfer the solution to a 500 mL amber jar.Seal jar with a Teflon-lined lid and store at4 deg. C. Below is a chart indicating theconcentration of the compounds in thesolution.

Compound____________ Concentration (ppm)Nitrobenzene-d5 1002-fluorobiphenyl 100Terphenyl-dl4 100Phenyl-d6 1002-fluorophenol 2002,4,6-tribromophenol 200

B. CLP Matrix Spike SolutionPreparation: Pipet 2.5 mL of each matrix spike stock

solution prepared in Section VI, C, into a500 mL volumetric flask. Dilute to volume withmethanol and record preparation in notebook.Transfer the solution to a 500 mL amber jar.Seal jar with a Teflon-lined lid and store at4 deg. C. Below is a chart indicating theconcentration of the compounds in thesolution.

Compound_____________ Concentration (ppm)

1,2,4-trichlorobenzene 100Acenaphthene 1002,4-dinitrotoluene 100Pyrene 100N-nitroso-di-n-propylamine 100p-dichlorobenzene 100Pentachlorophenol 200Phenol 2002-chlorophenol 2004-chloro-3-methylphenol 2004-nitrophenol 200



VII. Standard Preparation (cont.)

C. Blank Spike Spiking Solution1) Stock Solutions: The following is a list of mixes with

their respective compounds and concentrations, whichmake up the Working Blank Spike Spiking Solution:

fese - Neutrals Solution n Ba" ~ N»utral1 Solutlon «

Iliswssi ssssssa-ssssssr -N-Nitrosodimeihylaminesassssasr

Benzidines SolutionPolynuclw Aromatic 2000«g/ml each in 5ml metnanol inHydrocarbons Solution an amt)9r via,2000ug7ml each in 2ml methylene Benztamechionde:benzene (50:50) in an S^Dichiorooanziameamber vial.AcenaofttheneAcentpnthyten*AnthraceneBenz(i)anthracene Phenols SolutionBenzo<a)pyfene 2WQnglm\ each in 5ml methyleneBSSSSSST chioride in an amber vial.Benzo(k)fluorantnene 4-Chioro-a-metnyiphenolChrysane 2-ChloroonenoiDibenz(a.h)anthracene 2.4-OichiorophenolRuoranthane 2.4-OimetnylpnenolFiuorene 2.4-Oinitroonencnlnd«no<l.25<d)pyr«n« 2-M«ihyM,6 initrophtnolNaphtnalane 2-NitrophanoiPhenantnrene 4 gitropnenol

PentacntofpphtnolPhenol2.4,6-Trichloropnenoi

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C. Blank Spike Spiking Solution (cont.)

2) Working Blank Spike Spiking Solution (cont.)Preparation: Pipet 2.5 mL of each solution into a 50.0

mL volumetric flask. Dilute to volume withmethanol and record preparation innotebook. Store at 4 deg. C. Below is achart indicating the concentration of themixes in the solution.

Mix_____________ Concentration (ppm)Base Neutral Solution #1 100Base Neutral Solution #2 100Polynuclear AromaticHydrocarbons Solution 100Benzidines Solution 100Phenols Solution 200

NOTE: All freshly prepared standards are separatelyextracted (i.e., not extracted as part of a batch)and analyzed on the GC/MS to ensure consistency withthe "old" standard.

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VIII. Quality ControlA. The following quality control samples are run at a

frequency of one every batch of samples per extractionanalyst: matrix spike, matrix spike duplicate, methodblank, and spiked method blank.

B. An analytical batch is defined as containing <20 samplesand the 4 quality control samples mentioned aBove.

C. Matrix Spike and Matrix Spike Duplicate Analysis: Using amicroliter syringe, add 1.0 mL of spiking solution to eachof two samples chosen for spiking either in the separatoryfunnel (liquid extraction) or beaker (soil extraction).Run as usual samples.

D. Method Blank; Using deionized water in place of sample,follow the appropriate matrix extraction procedure.

E. Spiked Method Blank; Using a microliter syringe, add250 uL of matrix spiking solution to 1000 mL of deionizedwater in the separatory funnel or beaker (i.e., step 2 ofthe Liquid Sample Extraction procedure, step 4 of the SolidSample Extraction (low level) procedure, and step 5 of theSolid Sample Extraction (medium level). Run as a usualsample.

F. GPC Cleanup Blank: Using 10.0 mL of methylene chloridespiked with 1.0 mL of the CLP surrogate standard solution,go through the GPC cleanup procedure. NOTE: The GPC CleanupBlank is to be run before the method blank.

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IX. Procedure

A. Liquid Sample Extraction1. Mark the sample bottle at the sample meniscus for later

determination of sample volume and pour the sample intoa 2000 mL separatory funnel.

2. Pipet 1.0 mL of the CLP surrogate standard solutioninto the funnel.

3. Mix sample well with a stirring rod. Basify the sampleto a pH >11 using 10 N sodium hydroxide solution.

4. Using the Atmar repeating pipet, transfer 60 mL ofmethylene chloride to the separatory funnel.

5. Extract by shaking vigorously for 2 minutes. Vent thefunnel often to prevent a pressure buildup. Allow theorganic layer to separate from the water phase for atleast 10 minutes.

NOTE: If the emulsion interface between layers is morethan one-third the volume of the solvent layer,the analyst must employ mechanical techniques tocomplete the phase separation. The optimumtechnique depends upon the sample, and mayinclude: stirring, filtration of the emulsionthrough glass wool, centrifugation, or otherphysical methods. If the techniques stated abovefail, transfer the sample, solvent, and emulsioninto the extraction chamber of a continuousextractor. Proceed to the ContinuousLiquid-Liquid Extraction procedure, step 4.

6. Collect the methylene chloride extract in a 250 mLErlenmeyer flask.

7. Add a second 60 mL volume of methylene chloride to thesample bottle and repeat the extraction procedure asecond time (i.e., steps 5-7), combining the extractsin the Erlenmeyer flask.

8. Perform a third extraction in the same manner.

aBCM



IX. Procedure (cont.)

A. Liquid Sample Extraction (cont.)9. Label the combined extract as the base neutral

fraction.10. Acidify the aqueous phase to a pH <2 using (1:1)

sulfuric acid.11. Serially extract three times with 60 mL aliquots of

methylene chloride following steps 5-7 above.12. Collect the methylene chloride extracts in a 250 mL

Erlenmeyer flask.13. Label the combined extract as the acid fraction.

14. Assemble a Kuderna-Danish (K-D) concentrator byattaching a 10 mL concentrator tube to a 500 mLevaporative flask.

15. Individually transfer the base neutral and acidfractions through funnels containing anhydrousgranular sodium sulfate and collect the extracts inseparate K-D concentrators.

16. Rinse the Erlenmeyer flasks and funnels with three10 mL portions of methylene chloride to complete thequantitative transfer.

17. Add 1-2 clean boiling chips and attach a three-ballSnyder column to the evaporative flask.

18. Pre-wet the Snyder column by adding about 1 mL ofmethylene chloride to the top.

19. Place the K-D apparatus on a hot water bath (80-90deg. C) so that the concentrator tube is partiallyimmersed in the hot water, and the entire lowerrounded surface of the flask is surrounded by hotvapor.

20. Adjust the vertical position of the apparatus and thewater temperature as needed to complete theconcentration in 10-15 minutes.NOTE: At the proper rate of distillation, the balls

will actively chatter but the chambers will notflood with condensed solvent.

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IX. Procedure (cont.)A. Liquid Sample Extraction (cont.)

21. When the apparent volume of liquid reaches 1 mL,remove the K-D apparatus from the water bath andallow it to drain and cool for at least 10 minutes.

22. Remove the Snyder column and rinse the flask and itslower joint into the concentrator tube with 1-2 mL ofmethylene chloride using a disposable Pasteur pipet.

23. Add another 1-2 clean boiling chips to theconcentrator tube and attach a two-ball micro-Snydercolumn.

24. Pre-wet the Snyder column by adding a few drops ofmethylene chloride to the top.

25. Place the K-D apparatus on a hot water bath (80-90deg. C) so that the concentrator tube is partiallyimmersed in hot water.


of the column will actively chatter but thechambers will not flood with condensedsolvent.

27. When the apparent volume of liquid reaches about2.0 mL, remove the K-D apparatus from the water bathand allow it to drain and cool for at least 10minutes.

28. Place the adaptor, which is connected by plastictubing to the nitrogen tank, along the inside wall ofthe flask.

29. Open the valve of the tank and be sure the regulatoris displaying a pressure reading between 0-10 psi.

30. Evaporate the solvent volume to just below 1 mL.NOTE; The extract must never be brought to dryness.

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A. Liquid Sample Extraction (cont.)

31. Using a volumetric pipet, adjust the final volume to1.0 mL with methylene chloride. Record volume innotebook.

32. Transfer to a 2 mL glass vial with a Teflon-linedscrew cap.

33. Label vial with the following information: samplenumber, test, batch number, date, analyst's initials,and initial and final volumes. Store vial at 4 deg.C.

34. Determine the original sample volume by filling thesample bottle with water up to the mark designated asthe sample meniscus.




B. Continuous Liquid-Liquid Extraction1. Basify the sample to a pH >11 using 10 N sodium

hydroxide solution.

2. Transfer a one liter sample aliquot to the continuousextractor.

3. Pipet 1.0 mL of the CLP surrogate standard solutioninto the extractor and mix well.

4. Add 500 mL of methylene chloride to a clean distillingflask and attach it to the continuous extractor.

5. Add sufficient reagent water to the continuous'extractor to ensure proper operation.

6. Extract the sample for 18-24 hours.7. Allow the sample to cool and detach the distilling

flask.8. Concentrate the extract by following steps 14 to 33 of

this procedure.


10. Acidify the aqueous phase to a pH <2 using (1:1)sulfuric acid.

11. Add sufficient reagent water to the continuousextractor to ensure proper operation.

12. Extract the sample for 18-24 hours.

13. Allow sample to cool.14. Assemble a Kuderna-Danish (K-D) concentrator by.

attaching a 10 mL concentrator tube to a 500 mLevaporative flask.

15. Individually transfer the base neutral and acidfractions through funnels containing anhydrous granularsodium sulfate and collect the extracts in separate K-Dconcentrators.




B. Continuous Liquid-Liquid Extraction (cont.)16. Rinse the Erlenmeyer flasks and funnels with three

10 mL portions of methylene chloride to complete thequantitative transfer.





will actively chatter but the chambers willnot flood with condensed solvent.


22. Remove the Snyder column and rinse the flask and itslower joint into the concentrator tube with 1-2 mL ofmethylene chloride using a disposable Pasteur pipet.

23. Add another 1-2 clean boiling chips to theconcentrator tube and attach a two-ball micro-Snydercolumn.

24. Pre-wet the Snyder column by adding a few drops ofmethylene chloride to the top.

25. Place the K-D apparatus on a hot water bath (80-90deg. C) so that the concentrator tube is partiallyimmersed in hot water.

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B. Continuous Liquid-Liquid Extraction (cont.)26. Adjust the vertical position of the apparatus and the

water temperature as needed to complete theconcentration in 5-10 minutes.

NOTE: At the proper rate of distillation, the ballsof the column will actively chatter but thechambers will not flood with condensedsolvent.

27. When the apparent volume of liquid reaches about2.0 mL, remove the K-D apparatus from the water bathand allow it to drain and cool for at least 10minutes.






33. Label vial with the following information: samplenumber, test, batch number, date, analyst's initials,and initial and final volumes. Store vial at 4 deg.C.

34. Determine the original sample volume by filling thesample bottle with water up to the mark designated asthe sample meniscus.

BCM




C. pH Determination for Solid Sample ExtractionsNOTE: This analysis is usually performed by the Wet

Chemistry department following SOP 600-150.1, pHElectrometric.

1. Weigh 50 g of soil/sediment in a 100 mL beaker andrecord weight in notebook.

2. Add 50 mL of deionized water and a stir bar.3. Place beaker on a magnetic stirrer and mix for one

hour.

4. Determine pH with a glass electrode and pH meter whilestirring.

5. Record pH in notebook.NOTE: If the pH of the soil is >11 or <5, contact the

Deputy Project Officer cited in the contract forinstructions on how to handle the sample.

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u ___fBovrBCM Laboratory SOP Page 23 of 38Method: Extraction for CLP Effective Date: 6/25/90



D. Total Solids Determination (% Moisture) for Solid SampleExtractionsNOTE: This analysis is usually performed by the Wet

Chemistry department using SOP 600-160.41, TotalSolids %.

1.' Weigh 5-10 g of sediment into a tared porcelaincrucible and record weight in notebook.

2. Dry sample overnight in a 105 deg. C oven.3. Allow sample to cool in a desiccator prior to weighing.

4. Calculation:

% Moisture = (grams of sample) - (grams of dry sample) x 100grams of sample

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E. Solid Sample Extraction (Low Level Sample Preparation)NOTE: A low level sample preparation is done on all soil

samples; however, if samples are found to be highlyconcentrated after GC/MS analysis, the sample isre-extracted using the medium level preparationprocedure.

1. Decant and discard any water layer on sample. Mixsamples thoroughly especially composited samples.Discard any foriegn objects such as sticks, leaves, androcks.

2. Weigh 30 g +0.1 g of sample into an amber jar. Recordweight in notebook.

3. Add about 60 g of pre-conditioned powdered sodiumsulfate (i.e., enough to dry the soil)to the beaker.

4. Mix the sample until it has a sand-like texture.5. Add 100 mL of (1:1) methylene chloride-acetone and

1.0 mL of CLP surrogate standard solution to thebeaker.

6. Place the beaker in sonicator.7. Place the bottom surface of the tip of the 3/4 inch

disrupter horn about 1/2 inch below the surface of thesolvent but above the sediment layer.

8. Sonicate for 3 minutes with output control knob set at10 and mode switch on "1 sec. pulse" and % duty cycleknob set at 50%.

9. Decant and filter extract through Whatman #41 filterpaper using vacuum filtration.

10. Repeat the extraction twice more (i.e., steps 5-8) withadditional 100 mL portions of (1:1) methylenechloride-acetone.

NOTES:1. Before each extraction, make certain that the sodium

sulfate is free flowing and not a consolidatedmass. Break up large lumps with a clean spatula.

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E. Solid Sample Extraction (Low Level Sample Preparation)(cont.)

2. On the final sonication, pour the entire sampleinto a Buchner funnel and rinse the beaker and thefunnel with (1:1) methylene chloride-acetone.

11. Transfer the extract to a K-D concentrator consistingof a 10 mL concentrator tube and a 500 mL evaporativeflask.

12. Add 1-2 clean boiling chips to the evaporative flaskand attach a three-ball Snyder column.


14. Place the K-D apparatus on a hot water bath (80-90deg. C) so that the concentrator tube is partiallyimmersed in hot water and the entire lower roundedsurface of the flask is bathed with hot vapor.

. 15. Adjust the vertical position of the apparatus and thewater temperature as needed to complete theconcentration in 10-15 minutes.NOTE: At the proper rate of distillation, the balls

will actively chatter but the chambers will notflood with condensed solvent.

NOTE; If GPC cleanup is used, concentrate liquid toapproximately 10 mL and proceed to the GPC Cleanupprocedure.

16. When the apparent volume of liquid reaches 2 mL,remove the K-D apparatus from the water bath and allowit to drain and cool for at least 10 minutes.




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E. Solid Sample Extraction (Low Level Sample Preparation)(cont .T ——————————.



22. Label vial with the following information: Samplenumber, test, batch number, date, analyst's initials,and initial and final volumes. Store vial at 4 deg.C.

X

"X

£8301629

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IX. Procedure (cont.)F. Solid Sample Extraction (Medium Level Sample Preparation)

1. Open sample container in a hood.

2. Decant and discard any water level and then mix samplewell.

3. Weigh 1.0 g of sample into a 20 mL vial. Record weightin notebook to the nearest 0.1 g.

4. Add 2.0 g of anhydrous powdered sodium sulfate to thesample and mix well. NOTE: Be sure sodium sulfate isfree flowing. Break up large lumps with a spatula.

5. Pipet 1.0 mL of the CLP surrogate standard solutioninto the vial.

6. Immediately add 9.0 mL of methylene chloride to thesample. NOTE; Add only 8.0 mL of methylene chloride tomatrix spike samples to achieve a final volume of 10mL.

7. Place vial in sonicator.8. Disrupt the sample with the 1/8 inch tapered microtip

ultrasonic probe for 2 minutes. The output controlsetting is to be set at 5, in continuous mode.

9. Loosely pack a disposable Pasteur pipet with 2-3 cmglass wool plugs.

10. Filter the extract through the glass wool and collect5.0 mL in a concentrator tube.

11. Place the adaptor, which is connected by plastic tubingto the nitrogen tank, along the inside wall of theflask.

12. Open the valve of the tank and be sure the regulator isdisplaying a pressure reading between 0-10 psi.

13. Evaporate the solvent volume to just below 1 mL. NOTE:The extract must never be brought to dryness.

14. Using a volumetric pipet, adjust the final volume to1.0 mL with methylene chloride. (NOTE; Final volume formatrix spike is 10.0 mL.) Record volume in notebook.

u




F. Solid Sample Extraction (Medium Level Sample Preparation)(cont.)

15. Transfer to a 2 mL glass vial (20 mL for matrix spike)with a Teflon-lined screw cap.

16. Label vial with the following information: samplenumber, test, batch number, date, analyst's initials,and initial and final volumes. Store vial at 4 deg. C.

LI



IX. Procedure (cont.)G. Extract Cleanup Procedure

1) Gel Permeation Chromatoqraphy (GPC) Setup1. Weigh out 70 g of Bio Beads SX-3 and place in a 400

mL beaker.

2. Cover the beads with methylene chloride and allowthem to swell overnight.

3. Transfer the swelled beads to the glass column.

4. Begin pumping methylene chloride through thecolumn, from bottom to top, at 5.0 mL/min.

5. After approximately one hour, adjust the pressureon the column to 7-10 psi. Pump an additional 4hours to remove air from the column.

NOTE: Adjust the column pressure periodically asrequired to maintain this pressure range.

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G. Extract Cleanup Procedure (cont.)

2) Calibration of Column1. Wash the column at least 15 minutes between

samples.2. Typical parameters selected are:

o Dump time = 30 minutes (150 mL)o Collect time =36 minutes (180 mL)o Wash time = 15 minutes (75 mL)

3. The column is calibrated by the use of a 254 mm UVdetector.

4. Measure the peak areas at various elution times todetermine appropriate fractions.

5. The SX-3 Bio Beads column may be reused for severalmonths, even if discoloration occurs. Systemcalibration usually remains constant over thisperiod of time if column flowrate remains constant.

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IX. Procedure (cont.)G. Extract Cleanup Procedure (cont.)

3) GPC CleanupNOTE: Pre-filter or load all extracts via the filter

holder to avoid particulates that might stop theflow.

1. Load one 5.0 mL BNA aliquot of the extract onto theGPC column. CAUTION; Do not apply excessivepressure when loading the GPC.NOTE: The other 5.0 mL of the BNA aliquot is wasted

when the sample loop is first loaded.2. Process the extracts using the dump.3. Collect and wash parameters determined from the

calibration.4. Collect the clean extracts in 500 mL amber jars

tightly covered with aluminum foil.5. Transfer the extract to a K-D concentrator

consisting of a 10 mL concentrator tube and a500 mL evaporative flask.

6. Add 1-2 clean boiling chips to the evaporativeflask and attach a three-ball Snyder column.



9. Adjust the vertical position of the apparatus andthe water temperature as needed to complete theconcentration in 5-10 minutes.NOTE: At the proper rate of distillation, the balls

will actively chatter but the chambers willnot flood with condensed solvent.




3) GPC Cleanup (cont.)


11. Dilute to 10.0 mL volume with methylene chloride.

NOTES:

1. Purge the sample loading tubing thoroughly with solventbetween extracts.

2. After especially dirty samples, run a GPC blank(methylene chloride) to check for carry-over.

3. Run the phthalate-phenol calibration solution throughthe cleanup cycle after every 23 extracts.

4. The recovery for each compound must be 85%.5. The recovery is determined using a UV recording

spectrophotometer.6. A copy of the printouts of standard and check solution

are required as deliverables with each case. Also, show% recovery on the copy.

7. The analysis of a batch (i.e., 20 samples) takes morethan 24 hours to complete.

D




4) Optional Extract SplittingNOTES:1. If the extract is to be used only for Semivolatile

analysis, go to page 34 to concentrate extract to1.0 mL.

2. If the extract is to be used for both Semivolatile andpesticide/PCB analyses, go to page 35 to split theextract into two portions.

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5) Concentration of Non-Split Semivolatile Extract ,

1. Reattach the micro-Snyder column to theconcentrator tube used in the GPC cleanup procedurewhich contains the 10 mL extract.

2. Add a fresh silicon carbide boiling chip to theconcentrator tube.

3. Pre-wet the Snyder column with 0.5 mL of methylenechloride.

4. Place the K-D apparatus on the hot water bath (80 -90 deg. C) so that the concentrator tube ispartially immersed in the hot water.

5. Adjust the vertical position of the apparatus andthe water temperature as required to complete theconcentration in 5 - 10 minutes.

6. When the apparent volume of the liquid reaches2.0 mL, allow it to drain for at least 10 minuteswhile cooling.

7. Remove the Snyder column and rinse the lower jointinto the concentrator tube with methylene chloride.

8. Place the adaptor, which is connected by plastictubing to the nitrogen tank, along the inside wallof the flask.

9. Open the valve of the tank and be sure theregulator is displaying a pressure reading between0-10 psi.

10. Evaporate the solvent volume to just below 1 mL.NOTE; The extract must never be brought to .dryness.

11. Adjust the final volume to 1.0 mL with methylenechloride. NOTE: This 1.0 mL represents a two-folddilution to account for only half of the extractgoing through the GPC.

&R30I637

BCM Laboratory SOP Page 35 of 38Method: Extraction for CLP . Effective Date: 6/25/90



6) Splitting Out Pesticide Extract

1. Transfer 0.5 mL of the 10 mL methylene chlorideextract from the GPC Cleanup procedure to aseparate concentrator tube.

2. Add 5 mL of hexane and a silicon carbide boilingchip.

3. Mix using a vortex mixer.

4. Attach a two-ball micro-Snyder column.

5. Pre-wet the Snyder column by adding 0.5 mL ofhexane to the top of the column.

6. Place the K-D apparatus on a hot water bath (80 -90 deg. C) so that the concentrator tube ispartially immersed in the hot water.

7. Adjust the vertical position of the apparatus andthe water temperature required to complete theconcentration in 5-10 minutes.

8. Concentrate the extract to an apparent volume ofless than 1 mL.



11. Evaporate the solvent volume to 0.5 mL.12. Add 0.5 mL of acetone.NOTE: Refer to the extraction SOP for pesticides/PCB's.

250-PEST/PCB CLP, for specific instructionsregarding the treatment of the extract forpesticides analysis.

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uIBCMBCM Laboratory SOP Page 36 of 38Method: Extraction for CLP Effective Date: 6/25/90



7) Concentration of Split Semivolatile Extract .

1. Reattach the micro-Snyder column to theconcentrator tube used in the GPC Cleanup procedurewhich contains 9.5 mL of extract.

2. Add a fresh silicon carbide boiling chip to theconcentrator tube.

3. Pre-wet the Snyder column with 0.5 mL of methylenechloride.

4. Place the K-D apparatus on the hot water bath(80-90 deg. C) so that the concentrator tube ispartially immersed in the hot water.

5. Adjust the vertical position of the apparatus andthe water temperature as required to complete theconcentration in 5-10 minutes.

6. When the apparent volume of the liquid reaches2.0 mL, remove the K-D apparatus from the waterbath and allow it to drain for at least 10 minuteswhile cooling.

7. Remove the Snyder column and rinse the lower jointinto the concentrator tube with 0.2 mL of methylenechloride.



10. Evaporate the solvent volume to 0.5 mL.

11. Using a microliter syringe, adjust the final volumeto 0.95 mL with methylene chloride. NOTE; This 0.95mL represents a twofold dilution to account foronly half of the extract going through the GPC.Therefore, the sample detection limit would be 2times the CRQL.

BCMBCM Laboratory SOP Page 37 of 38Method: Extraction for CLP Effective Date: 6/25/90


X. Calculations - not applicable

XI. Data Documentation

All pertinent data for the extraction of samples forSemivolatile analyses are recorded in a bound volume-numberednotebook. This information includes:1. Place data in tabular form including sample number, client

name, initial and final volumes, test, batch number, andsurrogate amount.

2. Note anything different or unusual with any samples in acolumn on each page of the notebook under the heading,"Comments".

See Figure 1 for an example of a formatted notebook page.

Notebook Entry Notes

1. The laboratory notebook must be signed and dated by theanalyst at the bottom of the page. In addition, thedepartment supervisor or a witness must cosign thenotebook.

2. Each batch starts a new page. Consequently, if an entirepage is not used, the analyst signs and dates below thelast entry. A diagonal line is drawn through the unusedportion of the last page. Any extractions continuing tothe next consecutive page are to be noted as "continued onpage x" or "continued from page y".

3. If an error is made in recording data, one line is drawnthrough the error. The analyst initials, dates the error,and a reason for the correction is noted (if necessary) atthe bottom of the page.

u



XI. Data Documentation (cont.)

55 !

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BCM ' ' —— N9 14354

-71AS " :-0 ' \'1-737C !: -co --- ~ "• ' V-73*72 II ' :/C., ' ! )|137^^•^ . t

A i / OCC : : : • !'/>!/- . • 1 / r«x».ta su~>i

1

0,.

FIGURE 1. EXAMPLE OF FORMATTED NOTEBOOK PAGE

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CO

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BCMBCM Laboratory Effective Date:Standard Operating Procedure (SOP) Superceded Date: NEW

Method #: 500-SVCLP

Method:

CLP SEMIVOLATILE ANALYSIS

Authored By: [A-WuVv\-g IA;></.vEdited By: /• -rU.Dept. Supervisor:

Approved By:ê. ,.. •<

Ojuality Assurance Dept. Date

'•.' V- ''C\*f i \ \ > - - (• +'1* ^Vl-l" //\<££* " IJP<&*MM 3> ft'ISection! Manager Q Date CXTecMrlcal pire,ctor Date

Lair'Director Dgfte

This monograph is based on Section I-IV, Analytical Methods forSemivolatiles, USEPA Contract Laboratory Program Statement of Workfor Organic Analysis, 2/88.

J ___IBCMBCM Laboratory SOP Page 1 of 45Method: Semivolatiles Analysis Effective Date: a!'f°

Superceded Date: NEW

I. ApplicationThe analytical methods that follow are designed to analyze water,soil, and sediment for the organic compounds on the TargetCompound List (TCL) Table 1 by "USEPA Contract Laboratory ProgramStatement of Work February 1988 revision".The Contract Required Quantitation Limits (CRQL) for eachcompound are listed in Table 1. The actual MDL for any specificsamples depends upon interference in the sample matrix.

II. Sample Handling and PreservationA. Log-In

1. Sample custody transfer from the carrier to the Labwill be documented by hard copy chain-of-custodydocuments.

2. Sample inventory and analytical request data will beentered into the LIMS for all sample aliquots accordingto the sample control SOP.

3. At sample reception a unique BCM Lab number will beassigned to each sample.a. Each aliquot receives the same sample number.

b. Each aliquot will be labelled with a bar-code labelcontaining sample number.c. The Lab no. is a 6-digit number of the form xyyyyy,where x = last digit of the current year, and yyyyy =serial number from 00001 each year.

B. Sample Storage

1. After log-in, samples will be stored in a refrigeratorat 4 deg. C until analyzed.

2. Refrigerator temperature will be noted by analysts *every day on the temperature log book.

3. If temperature is <2 deg. C or >6 deg. C, custodianwill be notified for corrective action.

4. After analysis, unused sample volume must be protectedfrom light and refrigerated at 4 deg. C (+/- 2 deg. C)for 30 days of the sample receipt and extracts for 1year.

IR3GISW

BCM!BCM Laboratory SOP Page 2 of 45 >Method: Semivolatiles Analysis Effective Date:y 1°

Superceded Date:' NEW

Target Compound List (TCL; andContract Required Ouantitation Liaics (CROP**

QuantisationWater Low SoiL/Sediment

SemivoLatilea GAS Number ___ ug/L uig:/Kg

35. Phenol 108-95-2 10 33036. bis(2-Chloroethyl) ether 111-44-4 10 33037. 2-Chlorophenol 95-57-8 10 33038. 1,3-Dichlorobenzene 541-73-1 10 33039. L,4-Dichlorobenzene 106-46-7 LO 330

40. Benzyl alcohol LOO-51-6 LO 33041. L,2-Dichlorobenzene 95-50-1 10 33042. 2-Methylphenol 95-48-7 10 33043. bis(2-ChloroisopropyL)

.ether L08-60-L LO 33044. 4-Methylphenol 106-44-5 LO 330

45. N-Nitroso-di-n-dipropylamine 621-64-7 LO 330

46. Hexachloroethane 67-72-1 10 33047. Nitrobenzene 98-95-3 LO 33048. Isophorone 78-59-L LO 33049. 2-Nitrophenol 88-75-5 LO 330

50. 2,4-Dimethylphenol 105-67-9 LO 33051. Benzoic acid 65-85-0 50 160052. bis(2-Chloroethoxy)

methane 111-91-1 LO 33053 2,4-DichlorophenoL L20-83-2 LO 33054. L,2,4-Trichlorobenzene L20-82-L LO 330

55. Naphthalene • 91-20-3 LO 33056. 4-Chloroaniline 106-47-8 LO 33057. Hexachlorobutadiene 87-68-3 LO 33058. 4-Chloro-3-methylphenol

(para-chloro-meta-cresol) 59-50-7 LO 33059. 2-Methylnaphthalene . 91-57-6 LO 330

60. Hexachlorocyclopentadiene 77-47-4 LO 3306L. 2,4,6-TrichlorophenoL 88-06-2 LO 33062. 2,4,5-TrichlorophenoL 95-95-4 50 L60063. 2-Chloronaphthalene 91-58-7 10 33064. 2-Nitroaniline 88-74-4 50 L600

65. Dimethylphthalate 131-11-3 LO ' 33066. Acenaphthylene 208-96-8 LO 33067. 2,6-Dinicroeoluene 606-20-2 LO 33068. 3-Nitroaniline 99-09-2 50 AB&8 161*569. Acenaphthene 83-32-9 LO 330

;BCM:BCM Laboratory SOP Page 3 of 45 /-Method: Semivolatiles Analysis Effective Date: '/ '"


Ouanritacion Limits**Water Low SolI/Sedimenc0

CAS dumber _________ ug/L ___________ ug/Kg _____

70. 2,4.DinitrophenoL 51-28-5 50 L60071. ^-Nicrophenol 100-02-7 50 L60072. Dibenzofuran 132-64-9 LO 33073. 2.4.Dinitrocoluene L2L-L4-2 LO 33074. Diechyiphthalace 84-66-2 LO 330

75. 4-Chlorophenyl-phenyl echer 7005-72-3 LO 33076. Fluorene 86-73-7 10 33077. 4-Nitroaniline 100-01-6 50 L60078. 4,6-Dinitro-2-methyLphenol 534-52-L 50 L60079. N-nicrosodiphenylaaine 86-30-6 LO 330

80. 4.Broraophenyl-phenylecher L01-55-3 10 3308L. HexachLorobenzene ' 118- 74- L LO 33082. PentashLorophenol 87-86-5 50 L60083. Phenanthrene 85-OL-8 LO 33084. Anthracene L20-L2-7 10 330

85. Di-n-butylphthalate 84-74-2 LO 33086. Fluoranthene 206-44-0 LO 33087. Pyrene L29-00-0 LO 33088. ButyLbenzylphthaLate 85-68-7 10 33089. 3,3' -Dichlorobenzidine 91-94.1 20 660

90. Benzo( a) anthracene 56-55-3 LO 33091. Chrysene 218-01-9 LO 33 092. bis(2-Ethylhexyl)phthaLate 117-81-7 LO 33"093. Di-n-octylphthalate L17-84-0 LO 3309^* Benzo(b)fluoranthene 205-99-2 LO 330

95. Benzo(k)fluoranthene 207-08-9 LO 33096. Benzo( a) pyrene 50-32-8 LO 33097 Indeno(L,2,3-cd)pyrene 193-39-5 LO 33098. Dibenz(a,h)anthracene 53-70-3 10 33099. Benzo(g,h,i)perylene 191-24-2 10 330

° Medium SoiL/Sediment Contract Required Quantitation Limits (CRQL) forSemiVoLatile TCL Compounds are 60 times the individual Low SoiL/SedimentCRQL.

•• Specific quantitation limits are highly matrix dependent. .The 1quantitation limits listed herein are provided for guidance and raiy nocalways be achievable.

** Quantitation Limits Listed for soil/sediment are based 9PDwl?J £§|}%i Thequaneitacion limits calculated by the Laboratory for so&piw«nf»Pc7 ®

- calculated on dry weight basis as required by the contract, will be

u

BCM Laboratory SOP Page 4 of 45Method: Semivolatiles Analysis Effective Date: Z/Y<>


II. Sample Handling and Preservation (cont.)C. Internal Sample Control

1. Analysts will remove samples for analysis based ontheir analytical queue list.

2. Transfer from the custodian to the analyst will bedocumented by the analyst using the bar-code readerwhich will record removal of the sample in the LIMS.

3. Return of sample to the custodian will be documented bythe custodian in the same way at the end of theanalytical day or upon completion of analysis,whichever comes first.

D. Contract Required Holding TimesIf separatory funnel or sonication procedures are employedfor extractions for semivolatile analyses, extraction ofwater samples shall be completed within 5 days of VTSR(Validated Time of Sample Receipt), and extraction ofsoil/sediment samples shall be completed within 10 days ofVTSR. If continuous liquid-liquid extraction procedures areemployed, extraction of water samples shall be startedwithin 5 days of VTSR.

Extracts of either water or soil/sediment samples must beanalyzed within 40 days following extraction.

III. Interferences

A. Sources

1. Sample bottle2. Field sample equipment

3. Glassware

4. Reagent impurities5. Carry-over from heavily contaminated samples

B. Identifying Sources1. Field Blank - A field blank prepared from reagent water

that carried through the sampling and handling canserve as a check on contamination caused by field rinsewater, field equipment, and from the shipment.

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iBCMBCM Laboratory SOP Page 5 of 45Method: Semivolatiles Analysis Effective Date:


III. Inteferences (cont.)2. Lab Blanks - A lab reagent water is carried through the

sample preparation and analysis to determine ifcontamination is caused by lab reagents, glassware, orother lab sources.

C. Minimizing Interferences

1. Glassware must be scrupulously cleaned, clean all theglassware as soon as possible as follows:a. Detergent washing with hot waterb. Rinse 3 times with tap water

c. Rinse 3 times with DI waterd. Rinse with acetone and hexane or heat in a mufflefurnace at 400 deg. C for 15 to 30 mins.

e. After draining,,drying, and cooling, the glasswareshould be sealed and stored in a clean environment

2. Only high purity pesticide grade solvents should beused for glassware rinsing.

IV. Method SummaryA. Water sample - A measured volume of sample (1 liter for low

level) is serially extracted with methylene chloride at a pH>11 3 times and pH <2 3 times by separatory funnel or bycontinuous extractor for 18 hours.Methylene chloride extract is dried through anhydrous sodiumsulfate concentrated to a volume of 1.0 ml and analyzed byGC/MS direct injection.

B. Soil sample - A measured volume of sample (30 grams for lowlevel), mixed with sodium sulfate anhydrous is seriallysonicated with an ultrasonic cell disrupter with 1:1methylene chloride-acetone solvent. The extract is driedover sodium sulfate anhydrous then concentrated to a volumeof 1.0 mL and analyzed by GC/MS direct injection.

•BCMBCM Laboratory SOP Page 6 of 45 /Method: Semivolatiles Analysis Effective Date:


V. Apparatus

A. Syringes - 10 uL, 25 uL, 50 uL, 100 uL, and 500 uL gas tightsyringe

B. Balance - analytical balance, top loading balanceC. Glassware

1. Class A volumetric flasks with ground-glass stoppers

2. Bottle - 15 mL, 50 mL, or larger screw cap with Tefloncap liner

3. Vial - clear and amber 2 mL vial for GjC autosamplerD. GC/MS/DS

1. GC/MS MSD 5970 equipped with HP 7673A automaticinj ectora. Column - 30 m x 0.25 mm ID (or 0.32 mm) bonded-phasesilicone coated fused silica capillary column (J&WScientific DB-5, Supelco PTE5 or equivalent). A filmthickness of i.o micron or 0.25 micron may be used.b. Data system - HP RTE-A system equipped with Aquariussoftware, two 130 Mbyte HP 7958A disc drive and HP2563B and HP1934A printers.

2. GC/MS 5985B equipped with precision GC-411V autosamplerand same column as GC/MS 5970a. Data system - HP RTE-6 system equipped with Aquariussoftware, two 130 Mbyte HP 7559B disc drive and HP-2563B and HP 1934A printers.

3. Report Production SystemAll required CLP forms are produced on an HP Vectracomputer equipped with 32 Mbyte hard drive, 1.2 Mbytefloppy drive using MS-DOS 3.2 operating system and EPAPublic Domain (Terwilliger) software.

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(BCMBCM Laboratory SOP Page 7 of 45 /Method: Semivolatiles Analysis Effective Date: £//'c


V. Apparatus (cont.)4. GC/MS Operating Conditions

a. The following instrumental parameters are requiredfor all performance tests (DFTPP) and for all sampleand standard analyses:Electron energy - 70 volts (nominal)Mass range - 35 to 500 amuScan time - not to exceed 1 second per scan

b. The GC operating conditions to be used are asfollows:

Initial column temperature - 40 deg. C for 4 mins.Column temperature program - 40 to 270 deg. C at 10deg./min.Final column temperature hold - 270 deg. C for 10 mins.Injector temperature - 250-300 deg. CTransfer line temperature - 250-300 deg. CSource Temperature - according to manufacturer's specs.Injector - Grob-type, splitlessSample volume - 1-2 uL 3Carrier gas - helium at 30 cm /sec.Instrument conditions must be identical to those usedin sample analysis, except that a different temperatureprogram may be used for DFTPP injection.

uIBCMBCM Laboratory SOP Page 8 of 45Method: Semivolatiles Analysis Effective Date:


VI. Reagents

A. Reagent water - deionized water.

B. Acetone, methylene chloride - pesticide quality orequivalent

C. Sodium sulfate anhydrous - Baker anhydrous powder, catalog#73898 or equivalent

BCM,BCM Laboratory SOP Page 9 of 45 njMethod: Semivolatiles Analysis Effective Date: £•?£



A. Internal standards - l,4-dichlorobenzene-d4, naphthalene-dS,acenaphthene-dlO, phenanthrene-dlO, chrysene-d!2, perylene-d!2(all @ 2000 ug/mL).

1. Internal standard stock solution purchased from Supelco:Supelpreme-HC internal standards mix, catalog no. 4-8902.

2. A 20 uL portion of this solution should be added to each 1 mLof sample extract. This will give a concentration of 40ug/ml of each constituent.

B. Calibration standards

1. Prepare calibration standards at a minimum of fiveconcentration levels.

2. The stock standard solution purchased from Supelco eachcontain:

a. Supelpreme-HC Base-Neutrals Mix 1, catalog no. 4-8900M.b. Supelpreme-HC Polynuclear Aromatic Hydrocarbons Mix, catalog

no. 4-8905Mc. Supelpreme-HC Benzidines Mix, catalog no. 4-8906M

d. Supelpreme-HC Base-Neutrals Mix 2, catalog no. 4-8901M

e. Supelpreme-HC Phenols Mix, catalog no. 4-8904Mf. Supelpreme-HC Hazardous Substances Mix 1, catalog no.

4-8907M

g. Supelpreme-HC Hazardous Substances Mix 2, catalog no.4-8908M

u'BCMBCM Laboratory SOP Page 10 of 45Method: Semivolatiles Analysis Effective Date: £/'/<?



3. An example of a calibration standard solution that contains allthe TCL compounds and 4-chlorophenyl phenyl ether:

stock 160 uq/mL 120 uq/mL 80 uq/roL 50 uq/mL 20 uq/mLBN Mix 1 2000 ug/mL 240 uL 180 uL 120 uL 250 uL 30 uLBN Mix 2 " " " " " "Haz. 1 " " " " " "Haz. 2 " " " " " "Benzidines " " " " " "PAH M ii u u u iiPhenols " » " » " "Acid Surr. " " " " " "BN Surr. * lOOOug/ml 480 Ul 360 Ul 240 ul 500 ul 60 ulMecl2 (Solvent) —— 504 ul 1128 Ul 1752 ul 7400 ul 2688 ul4-chlorophenyl-ether 5000 ug/mL 96 uL 72 uL 48 uL 100 uL 12 uL

Final Volume 3.0 mL 3.0 mL .3.0 mL 10.0 mL 3.0 mL

4. Each calibration standard should contain each compound ofinterest and each surrogate standard. Store all standardsolutions at -10 deg. C to -20 deg. C in screw-cap amber bottleswith Teflon liners. Fresh standards should be prepared everytwelve months at a minimum. The continuing calibration standardshould be prepared weekly and stored at 4 deg. C (+/- 2 deg. c).

5. 20 uL of the internal standard solution (Supelco catalog no.4-8902) is added to each 1 mL of calibration standards. Thiswill give a concentration of 40 ug/mL of internal standard.

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IBCMBCM Laboratory SOP Page 11 of 45 ^,Method: Semivolatiles Analysis Effective Date: ?/v?(?


VIII. ProcedureA. Tuning and GC/MS Mass Calibration1. SummaryEach GC/MS system must meet the standard mass spectralabundance criteria prior to initiating any on-going datacollection. This is accomplished through the analysis ofdecafluorotriphenylphosphine (DFTPP) each 12-hour period.Definition: The twelve (12) hour time period for GC/MS systemtuning and standards calibration (initial or continuingcalibration criteria) begins at the moment of injection of theDFTPP analysis. The time period ends after twelve (12) hourshas elapsed according to the system clock.2. Decafluorotriphenylphosphine (DFTPP)

Each GC/MS system used for the analysis of semivolatile orpesticide TCL compounds must be hardware tuned to meet theabundance criteria listed in Table 1.2 for a 50 ng injection ofdecafluorotriphenylphosphine (DFTPP). DFTPP may be analyzedseparately or as part of the calibration standard. Thecriteria must be demonstrated daily or for each twelve (12)hour period, whichever is more frequent, before samples can beanalyzed. DFTPP must be injected to meet this criterion. Ifrequired, background subtraction must be straight forward anddesigned only to eliminate column bleed or instrumentbackground ions. Background subtraction actions resulting inspectral distortions for the sole purpose of meeting thespecifications are unacceptable.

3. Tune CriteriaWhenever the Lab takes corrective action which may change oraffect the tuning criteria for DFTPP (i.e., ion source cleaningor repair, etc.), the tune must be verified irrespective of the12-hour tuning requirements.

'BCM!BCM Laboratory SOP Page 12 of 45 ,Method: Semivolatiles Analysis Effective Date: ?''fC>


VIII. Procedure (cont.)Table 2. DFTPP Key Ions and Ion Abundance CriteriaMass Ion Abundance Criteria

51 30.0-60.0 percent of mass 19868 less than 2.0 percent of mass 6970 less than 2.0 percent of mass 69127 40.0 - 60.0 percent of mass 198197 less than 1.0 percent of mass 198198 base peak, 100 percent relative abundance199 5.0 - 9.0 percent of mass 198275 10.0 - 30.0 percent of mass 1983 65 greater than 1.00 percent of mass 198441 present but less than mass 443442 greater than 40.0 percent of mass 198443 17.0 - 23.0 percent of mass 442

4. DocumentationThe Lab shall provide documentation of the calibration in theform of a bar graph spectrum and as a mass listing.The Lab shall complete a Form V (GC/MS Tuning and MassCalibration) each time an analytical system is tuned. Inaddition, all samples, standards, blanks, matrix spikes, andmatrix spike duplicates analyzed during a particular tune mustbe summarized in chronological order on the bottom of theappropriate Form V.

B. Calibration of the GC/MS System

1. SummaryPrior to the analysis of samples and required blanks and aftertuning criteria have been met, the GC/MS system must beinitially calibrated at a minimum of five concentrations todetermine the linearity of response utilizing TCL compoundstandards. Once the system has been calibrated, thecalibration must be verified each twelve (12) hour time periodfor each GC/MS system by continuous standard.

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I BCM.BCM Laboratory SOP Page 13 of 45 /Method: Semivolatiles Analysis Effective Date: o/yo


VIII. Procedure (cont.)

2. Semivolatile TCL Compounds

Initial calibration of semivolatile TCL compounds is requiredat 20, 50, 80, 120, and 160 total nanograms. If an analytesaturates at the 160 total nanogram concentration level, andthe GC/MS system is calibrated to achieve a detectionsensitivity of no less than the CRQL, the laboratory mustdocument it on Form VI and in the Case Narrative, and attach aquantitation report and RIG. In this instance, the laboratoryshould calculate the results based on a four-point initialcalibration for the specific analyte. The use of a secondaryion for quantitation is only allowed when there are sampleinterferences with the primary ion. If secondary ionquantitation is performed, document the reasons in the caseNarrative. If interferences are noted, use the next mostintense ion as the secondary ion, i.e., forl,4-dichlorobenzene-d4 use m/z 152 for quantification.

3. The internal standards are added to all calibration standardsand all sample extracts just prior to analysis by GC/MS. A20 uL aliquot of the internal standard solution, Supelcocatalog no. 4-8902, should be added to a 1 ml aliquot ofcalibration standards.

4. Analyze 1 uL of each calibration standard and tabulate thearea of the primary characteristic ion against concentrationfor each compound including the surrogate compounds.Calculate relative response factors (RRF) for each compound.(See Table 3).

5. After analysis of each initial calibration level, the datafiles are quantitated with program "QT". The calibrationinformation from the quantitation reports is entered into thecalibration file using the program "CBUPD". This programprompts for the quant output filenames for each of the fivelevels, clears the previous calibration, and enters the newcurves. The program "CBRPT" generates a hard copy of theinitial calibration report with average RRT's, average RRF's,and percent relative standard deviations in tabular format.The analyst reviews this report for compliance to CLPcriteria.

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(BCMBCM Laboratory SOP Page 14 of 45 /Method: Semivolatiles Analysis Effective Date: i/ic


VIII. Procedure (cont.)

Table 3 Calibration Check CompoundsBase Neutral Fraction Acid Fraction

Acenaphthene 4-Chloro-3-MethyIphenol1,4-Dichlorobenzene 2,4-DichlorophenolHexachlorobutadiene 2-NitrophenolN-Nitroso-di-n-phenylamine PhenolDi-n-octylphthalate PentachlorophenolFluoranthene 2,4,6-TrichlorophenolBenzo(a)pyrene6. A system performance check must be performed to ensure that

minimum average relative response factors are met before thecalibration curve is used.

a. For semivolatiles, the System Performance Check Compounds(SPCCs) are: N-Nitroso-Di-n-Propylamine,Hexachlorocyclopentadiene, 2,4-Dinitrophenol and4-Nitrophenol. The minimum acceptable average relativeresponse factor (RRF) for these compounds is 0.050. SPCCstypically have very low RRFs (0.1-0.2) and tend to decreasein response as the Chromatographic system begins todeteriorate or the standard material begins to deteriorate.Therefore, they must meet the minimum requirement when thesystem is calibrated.

b. The initial calibration is valid only after both the %RSDfor CCC compounds and the minimum RRF for SPCC have beenmet. Only after both these criteria are met can sampleanalysis begin.

7. DocumentationOnce the initial calibration is validated, calculate and reportthe average relative response factor and percent relativestandard deviation for all TCL compounds. The Lab shallcomplete and submit Form V (the GC/MS tune for the initialcalibration) and Form VI (Initial Calibration Data) for eachinstrument used for analysis.

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VIII. Procedure (cont.)C. Continuing Calibration

1. A calibration standard(s) containing all semivolatile TCLcompounds, including all required surrogates, must beanalyzed each twelve hours during analylsis. Compare therelative respone factor data from the standards each twelvehours with the average relative response factor from theinitial calibration for a specific instrument. A systemperformance check must be made each twelve hours.

2. If the SPCC criteria are met, a comparison of relativeresponse factors is made for all compounds. -This is the samecheck that is applied during the initial calibration (FormVI). If the minimum relative response factors are not met,the system must be evaluated and corrective action must betaken before sample analysis begins.

3. Some possible problems are standard mixture degradation,injection port inlet contamination, contamination at thefront end of the analytical column, and active sites in thecolumn or chromatography system. This check must be metbefore analysis begins. The minimum relative response factorfor semivolatile system performance check compounds is 0.050.

4. Calibration Check Compounds (CCC)After the system performance check is met, calibration checkcompounds listed in Table 3 are used to check the validity ofthe initial calibration. Calculate the percent difference atthe beginning of each twelve hour period, after the tune ischecked; a 50 ppm standard is analyzed, quantitated, andchecked against the initial curve. The program "CBCHK" promptsfor the quant output filename of this standard, and a hard copycontinuing calibration report is produced with tabular formatdisplay of percent difference of RRF for each target compoundin the calibration file.5. Documentation

The Lab shall complete and submit a Form VII for each GC/MSsystem utilized for each twelve hour time period. Calculate andreport the relative response factor and percent difference (%D)for all compounds. Ensure that the minimum RRF forsemivolatile SPCCs is 0.050. The percent difference (%D) foreach CCC compound must be less than or equal to 25.0 percent.

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BCM Laboratory SOP Page 16 of 45 „Method: Semivolatiles Analysis Effective Date: t


VIII. Procedure (cont.)D. Method Blank Analysis1. SummaryA method blank is a volume of deionized, distilled laboratorywater for water samples, or a purified solid matrix forsoil/sediment samples, carried through the entire analyticalscheme (extraction, concentration, and analysis). The methodblank volume or weight must be approximately equal to thesample volumes or sample weights being processed.

2. Method blank analysis must be performed at the followingfrequency.

For the analysis of semivolatile TCL compounds, a method blankanalysis must be performed once:a. each order, orb. each 14 calendar day period during which samples in an order

are received (said period beginning with the receipt of thefirst sample in that Sample Delivery Group), or

c. each 20 samples in a Case, including matrix spikes andreanalyses, that are of similar matrix (water or soil) orsimilar concentration (soil only), or

d. whenever samples are extracted by the same procedure(separatory funnel, continuous liquid-liquid extraction, orsonication),

whichever is most frequent, on each GC/MS or GC system used toanalyze samples.

3. An acceptable laboratory method blank should meet thecriteria as follows:

a. A method blank for semivolatile analysis must contain lessthan or equal to five times (5x) the Contract RequiredQuantitation Limit (CRQL from Exhibit C) of the phthalateesters in the TCL.

b. For all other TCL compounds not listed above, the methodblank must contain less than or equal to the CRQL of anysingle TCL analyte.

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VIII. Procedure (cont.)4. If a laboratory method blank exceeds these criteria, the Lab

must consider the analytical system to be out of control.The source of the contamination must be investigated andappropriate corrective measures must be taken and documentedbefore further sample analysis proceeds. All samplesprocessed with a method blank that is out of control, i.e.,contaminated, must be reextracted and reanalyzed. Thelaboratory manager, or his designee, must address problemsand solutions in the Case Narrative.

5. Documentation

The Lab shall report results of method blank analysis using theOrganic Analysis Data Sheet (Form I) and the form fortentatively identified compounds (Form I, TIC). In addition,the samples associated with each method blank must besummarized on Form IV (Method Blank Summary). The Lab shallreport all sample concentration data as uncorrected for blanks.Using Terwilliger software after analysis to create CLP Forms.

E. Sample Analysis1. Combine 0.5 mL of the base/neutral extract and 0.5 mL of acid

extract for water sample prior to analysis.2. Internal standard solution is added to each sample extract.

For water and/or medium soil extracts, add 20 uL of internalstandard solution to each accurately measured 1.0 mL ofsample extract (for water sample, after combined 2fractions). If the low soil extracts required a pesticidesplit, add 19 uL of internal standard solution to eachaccurately measured 0.95 mL of sample extract. Analyze 1.0ul of the extract by GC/MS.

3. Make any extract dilution indicated by characterization priorto the addition of internal standards. If any furtherdilutions of water or soil/sediment extracts are made,additional internal standards must be added to maintain therequired 40 ng/uL of each constituent in the extract volume.If the concentration on the column of any compound exceedsthe initial calibration range, the extract must be dilutedand reanalyzed. Secondary ion quantitation is only allowedwhen there are sample interferences with the primary ion. Ifsecondary ion quantitation is performed, document the reasonsin the Case Narrative.

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;BCM,BCM Laboratory SOP Page 18 of 45 r. /„Method: Semivolatiles Analysis Effective Date: V/c


IX. Analytical Results

A. Target Compound Identification1. Relative retention time (RRT) verifiction - The sample

component RRT must compare with +/- 0.06 RRT units of the RRTof the standard component. For reference, the standard mustbe run on the same 12 hour shift as the sample. If coelutionof interfering components prohibits accurate assignment ofsample component RRT from the total ion chromatogram, the RRTshould be assigned by using extracted ion current profilesfor ions unique to the component of interest.

2. Mass spectral comparison of standard and sample - Thestandard spectra used for identification purposes may beobtained from the run used to obtain reference RRTs.The requirements for qualitative verification by comparisonof mass spectra are as follows:

a. All ions present in the standard mass spectra at a relativeintensity greater than 10% (most abundant ion in thespectrum equals 100%) must be present in the samplespectra.

b. The relative intensities of ions must agree within plus orminus 20% between the standard and sample spectra.(Example: For an ion with an abundance of 50% in thestandard spectra, the corresponding sample ion abundancemust be between 30 and 70 percent.)

c. Ions greater than 10% in the sample spectrum but notpresent in the standard spectrum must be considered andaccounted for by the analyst making the comparison. Allcompounds meeting the identification criteria must bereported with their spectra. For all compounds below theCRQL report the actual value followed by "J", i.e., "3J."

3. If a compound cannot be verified by all of the criteria butin the technical judgement of the mass spectralinterpretation specialist, the identification is correct,then the Lab shall report that identification and proceedwith quantification.

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Superceded Date:'NEW

IX. Analytical Results (cont.)B. Tentatively Identified Compounds Identifications

1. A library search shall be executed for non-TCL samplecomponents for the purpose of tentative identification. The1985 release of the National Bureau of Standards MassSpectral Library (or more recent release), containing 42,261spectra, shall be used. Use the library search program fromAquarius.

2. Up to 20 nonsurrogate organic compounds of greatest apparentconcentration not listed in TCL for the combinedbase/neutral/acid fraction shall be tentatively identifiedvia a forward search of the NBS mass spectral library.(Substances with responses less than 10% of the nearestinternal standard are not required to be searched in thisfashion). Only after visual comparison of sample spectrawith the nearest library searches will the mass spectralinterpretation specialist assign a tentative identification.

3. Guidelines for making tentative identification:a. Relative intensities of major ions in the reference

spectrum (ions greater than 10% of the most abundant ion)should be present in the sample spectrum.

b. The relative intensities of the major ions should agreewithin +/~20%. (Example: For an ion with an abundance of50% in the standard spectrum, the corresponding sample ionabundance must be between 30 and 70 percent.)

c. Molecular ions present in reference spectrum should bepresent in sample spectrum.

d. Ions present in the sample spectrum but not in thereference spectrum should be reviewed for possiblebackground contamination or presence of coelutingcompounds.

e. Ions present in the reference spectrum but not in thesample spectrum should be reviewed for possible subtractionfrom the sample spectrum because of backgroundcontamination or coeluting compounds.

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1BCMBCM Laboratory SOP Page 20 of 45Method: Semivolatiles Analysis Effective Date:


IX. Analytical Results (cont.)

4. If in the technical judgement of the mass spectralinterpretation specialist, no valid tentative identificationcan be made, the compound should be reported as unknown.The mass spectral specialist should give additionalclassification of the unknown compound, if possible, i.e.,unknown phthalate, unknown hydrocarbon, unknown acid type,unknown chlorinated compound). If probable molecularweights can be distinguished, include them.

C. Target Compound Quantitative Analysis

1. TCL components identified shall be quantified by the internalstandard method. The internal standard used shall be the onenearest the retention time to that of a given analyte (SeeTable 4). The EICP area of characteristic ions of analytesare used (See Table 5).

2. Internal standard responses and retention times in allsamples must be evaluated during or immediately after dataacquisition. If the retention time for any internal standardchanges by more than 30 seconds from the latest daily (12hour) calibration standard, the Chromatographic system mustbe inspected for malfunctions, and corrections made asrequired. The extracted ion current profile (EICP) of theinternal standards must be monitored and evaluated for eachsample, blank, matrix spike, and matrix spike duplicate. Ifthe EICP area for any internal standard changes by more thana factor of two (-50% to +100%), the mass Spectrometricsystem must be inspected for malfunction and corrections madeas appropriate. If the analysis of a subsequent sample orstandard indicates that the system is functioning properly,then corrections may not be required. The samples orstandards with EICP areas outside the limits must bereanalyzed. If corrections are made, then the laboratorymust demonstrate that the mass Spectrometric system isfunctioning properly. This must be accomplished by theanalysis of a standard or sample that does meet the EICPcriteria. After corrections are made, the reanalysis ofsamples analyzed while the sytem was malfunctioning isrequired. Document in the instrument log.

HR30I6S3

:BCM!BCM Laboratory SOP Page 21 of 45 /Method: Semivolatiles Analysis Effective Date: */1°


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BCM:BCM Laboratory SOP Page 22 of 45 ,Method: Semivolatiles Analysis Effective Date: ?fve>


T«bl«

Charaecarixtie Ion* for S«aivol*eil« TCL Covpeuad*

??!««*» Ta* __________ S«eMd«rv To* CO

Ph«nol 94 65 f 66bi«<-2-Oiloro«chyl)Eth«r 93 63, 952-Chloroph«nol 128 64, 130l,3-Diehlorob«nzan« 146 148, 113l,4-Dichlorob«nz«iM 146 142 1 jjBenzyl Alcohol .108 79 ( 77l,2-Dichlorob«nz«n« 146 148, 1132-M«cfaylph«nol 108 107bi«<2-chloroi«opropyl)Eth«r 45 77, 794«ltech}rlph«tiol 108 107N-NlOfo«o-Di-Propyl«ain« 70 42, 101, 130Hmrhloro«cfaan« 117 201, 199HItrob«nz«n« 77 123, '55I*ophoron« 82 95, 1382-Nirroph«nol . 139 . 65, 1092,4*DiaMCbylph«nol 107 121, 122B«azoic Acid 122 105, 77bi*<-2-Chloro«chox7)M«eh*na 93 95, 1232,4-Diehloroph«nol 162 164, 98l,2,4-Tzichlorob«nz«n« ' 180 182, 145NAphch*l«n« 128 129; 127

127 129H«x*chlorobuc*di«na 225 223, 2274«Chloro-3-M«ttaylph«aol 107 144, 1422-M«chyln»phciiAl«n« 142 141H«x*chloroeyelop«nc*di«n« 237 235, 2722,4,6-Triehloroph«nol 196 198, 2002,4,5-Trichloroph«nol 196 198, 2002-Chloron*phrhAl«n« 162 164, 127(eoncinuad)

u ___!BCMBCM Laboratory SOP Page 23 of 45Method: Semivolatiles Analysis Effective Date:


Table (continued)Character is tie Ions for Semivolatile TCL Compounds

2-Nitroanillne 65 92, 128Dimethyl Phthalate 163 194, 164Acenaphthylene 152 1S1, 1533-Nitroaniline 138 108, 92Acenaphthene 153 152, 1542,4.Dinitrophanol 184 63, 1544-Nitrophanol 109 139, 65Dibenrofuran 168 1392,4-Dinitrotoluana 165 63, 1822,6-Dinitrotoluane ' 165 89. 121Dlathylphttnalata 149 177, 1504-Chlorophenyl-phenylether 204 206, 141Fluortna 166 165, 1674.Kitroaailiaa '138 92, 1084,6-Dinitro.2-Mechylphenol 198 182, 77N-Nitrosodiphanylaaine 169 168, 1674-Broaophenyl-phanylathar 248 25 0-, 141Kaxachlorobanzana 284 142, 249Fantachlorophanol 266 264, 268Fhanaathrana 178 179, 176Anthraccna 178 179, 176Di>N-Butylphthalate 149 150, 104Fluoranthana 202 101, 100Pyr«na 202 101, 100Butylbanzylphthalata 149 91, 2063f3'-Dichlorobenzidine 252 254, 126B«nzo (a) Anthracene 228 229, 226bis(2-Ethylhexyl)Fhthalate 149 167, 279Chrysena 228 226, 229Di-N-Octyl Fhthalata 149Benzo(b)Fluo ran thane 252 253, -125Banzo(k)Fluoranchana 252 253, 125Banzo(a)Fyrene 252 253, 125Indeno(l,2.3*cd)Pyrene 276 138, 227Dibenz<a, h)Aathraeene 278 139, 279Benzo(g, h, DFerylene 276 138, 277

[BCM!BCM Laboratory SOP Page 24 of 45 ^/Method: Semivolatiles Analysis Effective Date: t,'rtc



a. If after reanalysis, the EICP areas for all internalstandards are inside the contract limits (-50% to +100%),then the problem with the first analysis is considered tohave been within the control of the laboratory. Therefore,only submit data from the analysis with EICPs within thecontract limits. This is considered the initial analysisand must be reported as such on all data deliverables.

b. If the reanalysis of the sample does not solve the problem,i.e., the EICP areas are outside the contract limits forboth analyses, then submit the EICP data and sample datafrom both analyses. Distinguish between the initialanalysis and the reanalysis on all data deliverables, usingthe sample suffixes. Document in the Case Narrative allinspection and corrective actions taken.

3. The RRF from the daily standard analysis is used to calculatethe concentration in the sample. Secondary ions may be usedif interferences are present. The area of a secondary ioncannot be substituted for the area of a primary ion unless arelative response factor is calculated using the secondaryion.

4. Aquarius software automatically calculates concentration ofeach compound detected by internal standard method accordingto equations:

a. WaterU9/! = (Ax )(Is )(Vi )

Concentration (Ais)(RRF)(Vo)(Vt)

Ax - Area of the characteristic ion for the compound to bemeasuredAis - Area of the characteristic ion for the internal standardIs - Amount of internal standard injected in nanograms (ng)Vo - Volume of water extracted in milliliters (mL)Vi - Volume of extract injected (uL)Vt - Volume of total extractFor Vt: (Use 2000 uL or a factor of this when dilutions aremade. The 2000 uL is derived from combining half of the 1 mLBN extract and half of the 1 mL A extract).

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b. Soil/Sediment

ug/kg = (Ax)(Is )(Vt )Concentration (Ais)(RRF)(Vi)(Ws)(D)(dry weight basis)

Where:

Ax,Is,Ais - Same as given for water, aboveVt - Volume of low level total extract (Use 1000 ulor a factor of this when dilutions are made. If GPC cleanup isused, the volume is 2000 ul.

- or -

Vt - Volume of medium level extract (use 2000 ul ora factor of this when dilutions are made)Vi - Volume of extract injected (ul)D - 100 - % moisture

100Ws - Weight of sample extracted (grams)5. Aquarius will print out a quant report containing all alleged

hits and their spectra. If they do not conform toidentification criteria, line out the results on the Aquariusquant report, and initial and date the report.

6. When TCL compounds are below contract required quantitationlimits (CRQL) but the spectra meet the identificationcriteria, report the concentration with a "J." For example,if CRQL is 10 ug/L and concentration of 3 ug/L is calculated,report as "3J."

7. Before transferring results to "EPA Public domain reportingsoftware," insure that any % solids data is available foreach soil/sediment sample.

8. Each analytical run must also be checked for saturation. Thelevel at which an individual compound will saturate thedetection system is a function of the overall systemsensitivity and the mass spectral characteristics of thatcompound. The initial method calibration requires that thesystem should not be saturated for high response compounds at160 nanograms for semivolatile TCL compounds.

CJ

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a. If the on-column concentration of any compound in any sampleexceeds the initial calibration range, that sample must bediluted, the internal standard concentration readjusted, andthe sample reinjected. Secondary ion quantitation is onlyallowed when there are sample matrix interferences with theprimary ion.

b. If the dilution of the sample causes any compound detectedin the first analysis to be undetectable in the secondanalysis, then the results of both analyses shall bereported on separate Forms I, according to the instructionsin Exhibit B.

D. Tentatively Identified Compounds Quantitation

1. An estimated concentration for non-TCL components tentativelyidentified shall be quantified by the internal standardmethod. For quantification, the nearest internal standardfree of interferences shall be used.

2. The formula for calculating concentrations is the same as inSection IX4a. Total area counts (or peak heights) from thetotal ion chromatograms are to be used for both the compoundto be measured and the internal standard. A relativeresponse factor of one (1) is to be assumed. The value fromthis quantitation shall be qualified as estimated. Thisestimated concentration should be calculated for alltentatively identified compounds as well as those identifiedas unknowns.

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X. Semivolatiles QA/QC RequirementsThis section outlines the minimum quality control operationsnecessary to satisfy the analytical requirements associated withthe determination of semivolatile organic TCL compounds in waterand soil/sediment samples. These QC operations are as follows:- Documentation of GC/MS Mass Calibration and Abundance Pattern- Documentation of GC/MS Response Factor Stability- Internal Standard Response and Retention Time Monitoring- Method Blank Analysis- Surrogate Spike Response Monitoring- Matrix Spike and Matrix Spike Duplicate AnalysisA. Tuning and GC/MS Mass Calibration

1. DFTPP Tuning

a. It is necessary to establish that a given GC/MS meets thestandard mass spectral abundance criteria prior toinitiating any on-going data collection. This isaccomplished through the analysis ofDecafluorotriphenylphosphine (DFTPP).

b. Definition: The twelve (12) hour time period for GC/MSsystem tuning and standards calibration (initial orcontinuing calibration criteria) begins at the moment ofinjection of the DFTPP analysis that the laboratory submitsas documentation of a compliant tune. The time period endsafter twelve (12) hours has elapsed according to the systemclock.

2. Each GC/MS system used for the analysis of semivolatile orpesticide TCL compounds must be hardware tuned to meet theabundance criteria for a 50 ng injection ofdecafluorotriphenylphosphine (DFTPP). DFTPP may be analyzedseparately or as part of the calibration standard. Thecriteria must be demonstrated daily or for each 12 hourperiod, whichever is more frequent, before samples can beanalyzed. DFTPP must be injected to meet this criterion. Ifrequired, background subtraction must be straightforward anddesigned only to eliminate column bleed or instrumentbackground ions. Background subtraction actions resulting inspectral distortions for the sole purpose of meeting thecontract specifications are unacceptable. Note: Allinstrument conditions must be identical to those used insample analysis, except that a different temperature programmay be used.

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[BCM!BCM Laboratory SOP Page 28 of 45 iMethod: Semivolatiles Analysis Effective Date: yvo


X. Semivolatiles QA/QC Requirements (cont.)

3. Whenever the laboratory takes corrective action which maychange or affect the tuning criteria for DFTPP, (i.e., ionsource cleaning or repair, etc.), the tune must be verifiedirrespective of the 12 hour tuning requirements.

Table 1.2 DFTPP Key Ions and Ion Abundance Criteria

Mass Ion Abundance Criteria51 30.0-60.0 percent of mass 19868 less than 2.0 percent of mass 6970 less than 2.0 percent of mass 69127 40.0 - 60.0 percent of mass 198197 less than 1.0 percent of mass 198198 base peak, 100 percent relative abundance199 5.0 - 9.0 percent of mass 198275 10.0 - 30.0 percent of mass 198365 greater than 1.00 percent of mass 198441 present but less than mass 443442 greater than 40.0 percent of mass 198443 17.0 - 23.0 percent of mass 4424. DocumentationThe laboratory shall provide documentation of the calibrationin the form of a bar graph spectrum and as a mass listing.The laboratory shall complete a Form V (GC/MS Tuning and MassCalibration) each time an analytical system is tuned. Inaddition, all samples, standards, blanks, matrix spikes, andmatrix spike duplicates analyzed during a particular tune mustbe summarized in chronological order on the bottom of theappropriate Form v.

B. Calibration of the GC/MS System1. Initial Calibrationa. Prior to the analysis of samples and required blanks and

after tuning criteria have been met, the GC/MS system mustbe initially calibrated at a minimum of five concentrationsto determine the linearity of response utilizing TCLcompound standards. Once the system has been calibrated,the calibration must be verified each 12 hour time periodfor each GC/MS system.

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X. Semivolatiles QA/QC Requirements (cont.)b. Prepare calibration standards to yield the following

specific concentrations.

c. Initial calibration of semivolatile TCL compounds isrequired at 20, 50, 80, 120, and 160 total nanograms. If ananalyte saturates at the 160 total nanogram concentrationlevel, and the GC/MS system is calibrated to achieve adetection sensitivity of no less than the CRQL, thelaboratory must document it on Form VI and in the caseNarrative, and attach a quantitation report and Ric. Inthis instance, the laboratory should calculate the resultsbased on four-point initial calibration for the specificanalyte. The use of a secondary ion for quantitation isonly allowed when there are sample interferences with theprimary ion. If secondary ion quantitation is performed,document the reasons in the Case Narrative. Ninecompounds: Benzoic acid, 2,4-Dinitrophenol,2,4,5-Trichlorophenol, 2-Nitroaniline, 3-Nitroaniline,4-Nitroaniline, 4-Nitrophenol, 4,6-Dinitro-2-Methylphenol,and pentachlorophenol will only require a four-point initialcalibration at 50, 80, 120, and 160 total nanograms sincedetection at less than 50 nanograms per injection isdifficult.

d. Analyze each calibration standard and tabulate the area ofthe primary characteristic ion (Exhibit D SV, Table 4)against concentration for each compound including allcontract required surrogate compounds. The relativeretention times of each compound in each calibration runshould agree within 0.06 relative retention time units.Late eluting compounds usually will have much betteragreement.

e. The %RSD for each individual calibration check compound mustbe.less than or equal to 30.0 percent. This criteria mustbe met for the initial calibration to be valid.

f. A system performance check must be performed to ensure thatminimum average relative response factors are met before thecalibration curve is used.

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For semivolatiles, the System Performance Check Compounds(SPCCs) are : N-Nitroso-Di-n-Propylamine,Hexachlorocyclopentadiene, 2,4-Dinitrophenol, and4-Nitrophenol. The minimum acceptable average relativeresponse factor for these compounds is 0.050. SPCCs typicallyhave very low RRFs (0.1-0.2) and tend to decrease in responseas the Chromatographic system begins to deteriorate or thestandard material begins to deteriorate. These compounds areusually the first to show poor performance. Therefore, theymust meet the minimum requirement when the system iscalibrated.

g. The initial calibration is valid only after both the %RSDfor CCC compounds and the minimum RRF for SPCC hve beenmet. Only after both these criteria are met can sampleanalysis begin.

h. Documentation - Once the initial calilbration is validated,calculate and report the average RRF and %RSD for all TCLcompounds. The laboratory shall complete and submit Form V(the GC/MS tune for the initial calibration) and Form VI(Initial Calibration Data) for each instrument used toanalyze samples under this protocol.

2. Continuing Calibrationa. A calibration standard(s) containing all semivolatile TCL

compounds, including all required surrogates, must beanalyzed each twelve hours during analysis. Compare therelative response factor data from the standards each 12hours with the average relative response factor from theinitial calibration for a specific instrument. A systemperformance check must be made each 12 hours.

b. If the SPCC criteria are met, a comparison of relativeresponse factors is made for all compounds. This is thesame check that is applied during the initial calibration(Form VI). If the minimum relative response factors are notmet, the system must be evaluated and corrective action mustbe taken before sample analysis begins.

c. Some possible problems are standard mixture degradation,injection port inlet contamination, contamination at thefront end of the analytical column, and active sites in thecolumn or chromatography system. This check must be metbefore analysis begins. The minimum RRF for SPCC is 0.050.

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d. After the system performance check is met, Calibration CheckCompounds listed in Table 2.3 are used to check the validityof the initial calibration. Calcualte the percentdifference.

e. If the percent difference for any compound is greater than20%, the laboratory should consider this a warning limit.If the percent difference for each CCC is less than or equalto 25% , the initial calibration is assumed to be valid. Ifthe criteria are not met (>25.0% difference), for any onecalibration check compound, corrective action must betaken. Problems similar to those listed under SPCC couldaffect this criteria. If no source of the problem can bedetermined after corrective action has been taken, a newinitial five point calibration must be generated. Thesecriteria must be met .before sample analysis begins.

f. Calibration Check Compounds:Base/Neutral Fraction Acid FractionAcenaphthene 4-Chloro-3-Methylphenol1,4-Dichlorobenzene 2,4-DichlorophenolHexachlorobutadiene 2-NitrophenolN-Nitroso-di-n-phenylamine PhenolDi-n-octylphthalate PentachlorophenolFluoranthene 2,4,6-TrichlorophenolBenzo(a)pyreneg. Documentation - The laboratory shall complete and submit a

Form VII for each GC/MS system utilized for each 12 hourtime period. Calculate and report the relative responsefactor and percent difference (%D) for all compounds.Ensure that the minimum RRF for semivolatile SPCCs is0.050. The percent difference (%D) for each CCC compoundmust be less than or equal to 25.0 percent.

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X. Semivolatiles QA/QC Requirements (cont.)C. Method Blank Analysis

1. Summary

a. A method blank is a volume of deionized, distilledlaboratory water for water samples, or a purified solidmatrix for soil/sediment samples, carried through the entireanalytical scheme (extraction, concentration, andanalysis). For soil/sediment samples, a solid matrixsuitable for semivolatile analyses is available fromEMSL/LV. The method blank volume or weight must beapproximately equal to the sample volumes or sample weightsbeing processed.

b. Method blank analysis must be performed at the followingfrequency.

For the analysis of semivolatile TCL compounds, a method blankanalysis must be performed once:

- each Case, or- each 14 calendar day period during which samples in an orderare received (said period beginning with the receipt of thefirst sample in that sample delivery group), or

- each 20 samples in an order, including matrix spikes andreanalyses, that are of similar matrix (water or soil) orsimilar concentration (soil only), or

- whenever samples are extracted by the same procedure(separatory funnel, continuous liquid-liquid extraction, orsonication),

whichever is most frequent, on each GC/MS or GC system used toanalyze samples.

2. It is the Lab's responsibility to ensure that method• interferences caused by contaminants in solvents, reagents,glassware, and other sample processing hardware that lead todiscrete artifacts and/or elevated baselines in gaschromatograms be minimized.

a. For the purposes of this protocol, an acceptable laboratorymethod blank should meet the criteria as follows:

- A method blank for semivolatile analysis must contain lessthan or equal to five times (5x) the contract requiredquantitation limit (CRQL from Exhibit C) of the phthalateesters in the TCL.

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X. Semivolatiles QA/QC Recpiirements (cont.)- For all other TCL compounds not listed above, the methodblank must contain less than or equal to the contract requiredquantitation limit of any single TCL analyte.b. If a lab method blank exceeds these criteria, the lab must

consider the analytical system to be out of control. Thesource of the contamination must be investigated andappropriate corrective measures must be taken and documentedbefore further sample analysis proceeds. All samplesprocessed with a method blank that is out of control, i.e.,contaminated, must be reextracted and reanalyzed at noadditional cost to the Agency. The laboratory manager, orhis designee, must address problems and solutions in theCase Narrative.

3. Documentation

The Lab shall report results of method blank analysis using theOrganic Analysis Data Sheet (Form I) and the form fortentatively identified compounds (Form I, TIC). In addition,the samples associated with each method blank must besummarized on Form IV (Method Blank Summary).

D. Surrogate Spike (SS) Analysis1. SummarySurrogate standard determinations are performed on all samplesand blanks. All samples and blanks are fortified withsurrogate spiking compounds before extraction in order tomonitor preparation and analysis of samples.2. Each sample, matrix spike, matrix spike duplicate, and blank

are spiked with surrogate compounds prior to extraction. Thesurrogate spiking compounds shown in Table 6 are used tofortify each sample, matrix spike, matrix spike duplicate,and blank with the proper concentrations.

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:BCM!BCM Laboratory SOP Page 34 of 45Method: Semivolatiles Analysis Effective Date:



Table 6 Surrogate Spiking CompoundsAmount in Sample Extract*

(before any optional dilutions)Compounds Fraction Water Low/Medium Soil

Nitrobenzene-d5 BNA 50 ug 50 ug2-Fluorobiphenyl BNA 50 ug 50 ugp-Terphenyl-d!4 BNA 50 ug 50 ugPhenol-d5 BNA 100 ug 100 ug2-Fluorophenyl BNA 100 ug 100 ug2,4,6-Tribromophenol BNA 100 ug 100 ug*at time of injectiona. Surrogate spike recovery must be evaluated by determining

whether the concentration (measured as percent recovery)falls inside the lab required recovery limits listed inTable 7.

Table 7 Lab Required Surrogate Spike Recovery Limits

Fraction Surrogate Compound Water Low/Medium SoilBNA Nitrobenzene-d5 35-114 23-120BNA 2-Fluorobiphenyl 43-116 30-115BNA p-Terphenyl-d!4 33-141 18-137BNA Phenol-d5 10-94 24-113BNA 2-Fluorophenol 21-100 25-121BNA 2,4,6-Tribromophenol 10-123 19-122

3. Method Blank Surrogate Spike Recoverya. The laboratory must take the actions listed below if

recovery of any one surrogate compound in either thebase/neutral or acid fraction is outside of contractsurrogate spike recovery limits.

b. Check calculations to ensure that there are no errors; checkinternal standard and surrogate spiking solutions fordegradation, contamination, etc.; also check instrumentperformance.

c. Reanalyze the blank extract if step (b) fails to reveal thecause of the noncompliant surrogate recoveries.

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X. Semivolatiles QA/QC Requirements (cont.)d. Reextract and reanalyze the blank.

e. If the measures fail to correct the problem, the analyticalsystem must be considered to be out of control. The problemmust be corrected before continuing. This may meanrecalibrating the instrumentation but it may also mean moreextensive action. The specific corrective action is left upto the GC/MS operator. When surrogate recovery(ies) in theblank is outside of the Lab required windows, all samplesassociated with that blank must be reanalyzed.

4. Sample Surrogate Spike RecoveryThe laboratory must take the actions listed below if either ofthe following conditions exists:a. Recovery of any one surrogate compound in either base

neutral or acid fraciton is below 10%.

b. Recoveries of two surrogate compounds in either base neutralor acid fractions are outside surrogate spike recoverylimits.

5. The Lab shall document deviations outside of acceptablequality control limits in the Case Narrative and take thefollowing actions:

a. Check calculations to ensure that there are no errors; checkinternal standard and surrogate spiking solutions fordegradation, contamination, etc.; also check instrumentperformance.

b. Reanalyze the extract. If reanalysis of the extract solvesthe problem, then the problem was within the laboratory'scontrol. Therefore, only submit data from the analysis withsurrogate spike recoveries within the contract windows.This shall be considered the initial analysis and shall bereported as such on all data deliverables.

c. If steps (a) and (b) fail to solve the problem, thenreextract and reanalyze the sample. If the reextraction andreanalysis solves the problem, then the problem was in thelaboratory^ control. Therefore, only submit data from theextraction and analysis with surrogate spike recoverieswithin the contract windows. This shall be considered theinitial analysis and shall be reported as such on all datadeliverables.

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JBCMBCM Laboratory SOP Page 36 of 45 /Method: Semivolatiles Analysis Effective Date: $/r<'O



d. If the reextraction and reanalysis of the sample does notsolve the problem, i.e., surrogate recoveries are outsidethe contract windows for both analyses, then submit thesurrogate spike recovery data and the sample data from bothanalyses. Distinguish between the initial analysis and thereanalysis on all data deliverables, using the samplesuffixes "RE".

6; DocumentationThe Lab shall report surrogate recovery data for the following:

a. Method blank analysisb. Sample analysis

c. Matrix spike/matrix spike duplicate analysisd. All sample reanalyses that substantiate a matrix effect

The surrogate spike recovery data is summarized on theSurrogate Spike Percent Recovery Summary (Form II).

E. Matrix Spike/Matrix Spike Duplicate Analysis (MS/MSP)

1. Summary

In order to evaluate the matrix effect of the sample upon theanalytical methodology, the USEPA has developed the standardmixes listed in Table 5.1 to be used for matrix spike andmatrix spike duplicate analyses.

2. MS/MSD Frequency of Analysisa. A matrix spike and matrix spike duplicate must be performed

for each group of samples of a similar matrix, once:

- each order of field samples received, or- each 20 field samples in an order, or- each group of field samples of a similar concentration level(soils only), or- each calendar day period during which field samples in anorder were received (said period beginning with the receipt ofthe first sample in that sample delivery group), whichever ismost frequent.

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jBCMI__..BCM Laboratory SOP Page 37 of 45Method: Semivolatiles Analysis Effective Date: ?/"c

Superceded Date:' NEW


b. Use the compounds listed in Table 8 to prepare matrixspiking solutions. Each method allows for optional dilutionsteps which must be accounted for when calculating percentrecovery of the matrix spike and matrix spike duplicatesamples

Table 8 Matrix Spiking Solutions

Base/Neutrals Acids1,2,4-Trichlorobenzene PentachlorophenolAcenaphthene Phenol2,4-Dinitrotoluene 2-ChlorophenolPyrene 4-Chloro-3-MethylphenolN-Nitroso-Di-n-Propylamine 4-Nitrophenol1,4-Dichlorobenzenec. Samples requiring optional dilutions and chosen as the

matrix spike/matrix spike duplicate samples, must beanalyzed at the same dilution as the original unspikedsample.

d. Individual component recoveries of the matrix spike arecalculted using Equation:

Matrix Spike Percent Recovery = SSR - SRSA x 100

where "*SSR - spike sample resultsSR - sample resultSA - spike added from spiking mix3. Relative Percent DifferenceThe Lab is required to calculate the relative percentdifference between the matrix spike and matrix spikeduplicate. The relative percent differences (RPD) for eachcomponent are calculated using Equation:

Dl - D2RPD - (Dl + D2)/2 X 100

AR30I680

[BCMiBCM Laboratory SOP Page 38 of 45Method: Semivolatiles Analysis Effective Date



whereRPD - relative percent differenceDl - first sample valueD2 - second sample value (duplicate)4. DocumentationThe matrix spike (MS) results (concentrations) for nonspikedsemivolatile TCL compounds shall be reported on Form I (OrganicAnalysis Data Sheet) and the matrix spike percent recoveriesshall be summarized on Form II (MS/MSD Recovery).The results for nonspiked semivolatile TCL compounds in thematrix spike duplicate (MSD) analysis shall be reported on FormI (Organic Analysis Data Sheet) and the percent recovery andthe relative percent difference shall be summarized on Form III(MS/MSD Recovery).

Hi30i68i

u'BCMBCM Laboratory SOP Page 39 of 45Method: Semivolatiles Analysis Effective Date:



Table 9 Matrix Spike Recovery Limits*Fraction Matrix Spike Compound Water Soil/Sediment

BN 1,2,4-Trichlorobenzene 39-98 38-107BN Acenaphthene 46-118 31-137BN 2,4-Dinitrotoluene 24-96 28-89BN Pyrene 26-127 35-142BN N-Nitroso-Di-n-Propylamine 41-116 41-126BN 1,4-Dichlorobenzene 36-97 28-104AE Pentachlorophenol 9-103 17-109AE Phenol 12-89 26-90AE 2-Chlorophenol 27-123 25-102AE 4-Chloro-3-Methylphenol 23-97 26-103AE 4-Nitrophenol 10-80 11-114

1682



XI. Forms

A. Form Instruction GuideEach of the forms is specific to a given fraction (volatile,semivolatile, pesticide/PCB), and in some instances specificto a given matrix (water or soil) within each fraction. TheLab shall submit only those forms pertaining to the fractionsanalyzed for a given sample or samples. For instance, if asample is scheduled for semivolatile analysis only, provideonly semivolatile forms.

Form I - Organic Analysis Data SheetsForm II - Surrogate RecoveryForm III - Matrix Spike/Matrix Spike Duplicate RecoveryForm IV - Method Blank SummaryForm V - GC/MS Tuning and Mass CalibrationForm VI - Initial Calibration DataForm VII - Continuing Calibration DataForm VIII - Internal Standard Area Summary

B. General Information

1. Values must be reported on the hardcopy forms according tothe individual form instructions in this Section. Forexample, results for concentrations of semivolatile TCLcompounds must be reported to two significant figures if thevalue is greater than or equal to 10.

2. All samples, matrix spikes, matrix spike duplicates, blanks,and standards shall be identified with an EPA sample numberor BCM sample number. For samples, matrix spikes, and matrixspike duplicates, the EPA sample number is the uniqueidentifying number given in the Traffic Report thataccompanied that sample.

3. In order to facilitate data assessment, the following samplesuffixes must be used:

XXXXX - EPA sample number or BCM Number*XXXXXMS - matrix spike sampleXXXXXMSD - matrix spike duplicate sampleXXXXXRE - reanalyzed sampleXXXXXDL - sample analyzed at a secondary dilution* If BCM numbers are used, drop off the first digit, only usethe last five digits.

A830I683

BCM Laboratory SOP Page 41 of 45 /Method: Semivolatiles Analysis Effective Date: 0/70


XI. Forms (cont.)

4. Use "ZZZZZ" as the EPA sample number for any sample analysesnot associated with the SDG being reported.

5. For blanks and standards, the following identification schememust be used as the "EPA sample number."

a. Volatile blanks shall be identified as VBLK##.b. Semivolatile blanks shall be identified as SBLK##.c. Pesticide/PCB blanks shall be identified as PBLK##.

6. The "EPA sample number" must be unique for each blank withinan SDG. Within a fraction, a laboratory must achieve this byreplacing the two-character "##" terminator of the identifierwith one or two characters or numbers, or a combination ofboth. For example, possible identifiers for volatile blankswould be VBLK1, VBLK2, VBLKA1, VBLKB2, VBLK10, VBLKAB, etc.

7. Volatile and semivolatile standards shall be identified asFSTD###, where:

F - fraction (V for volatiles; S for semivolatiles).STD - indicates a standard### - the concentration in ug/1 of volatile standards, (i.e.,20, 50, 100, 150, and 200) or the amount injected in ng forsemivolatile standards, (i.e., 20, 50, 80, 120, and 160).8. As for the blank identifiers, these designations will have to

be concatenated with other information to uniquely identifyeach standard.

9. Several other pieces of information are common to many of theData Reporting Forms. These include: Matrix, Sample wt/vol,Level, Lab Sample ID, and Lab File ID.10. For "Matrix" enter"SOIL" for soil/sediment samples, and enter "WATER" for watersamples. NOTE: The matrix must be spelled out.Abbreviations such as "S" or "W" shall not be used.

11. For "Sample wt/vol" enter the number of grams (for soil) ormilliliters (for water) of sample used in the first blankline, and the units, either "G" or "ML" in the second blank.



XI. Forms (cont.)12. For "Level" enter the determination of concentration level

made from the mandatory screening of soils. Enter as "LOW"or "MED", not "L" or "M". All water samples are "LOW" leveland shall be entered as such.

13. "Lab Sample ID" is an optional laboratory-generated internalidentifier. Up to 12 alpha-numeric characters may bereported here.

14. "Lab File ID" is the laboratory-generated name of the GC/MSdata system file containing information pertaining to aparticular analysis. Up to 14 alpha-numeric characters maybe used here.

15. Forms II, IV, y, VIII, IX, and X contain a field labelled"page _ of _" in the bottom lefthand corner. If the numberof entries required on any of these forms exceeds theavailable space, continue entries on another copy of thesame fraction-specific form, duplicating all headerinformation. If a second page is required, number themconsecutively, as "page 1 of 2" AND "page 2 of 2". If asecond page is not required, number the page "page 1 of 1."NOTE: These forms are fraction-specific, and oftenmatrix-specific within fraction. For example, Form II VOA-1and Form II VOA-2 are for different data. Therefore, do notnumber the pages of all six versions of Form II as "1 of 6,2 of 6, etc." Only number pages within a fraction-specificand matrix-specific form.

16. For rounding off numbers to the appropriate level ofprecision, observe the following common rules. If thefigure following those to be retained is less than 5, dropit (round down). If the figure is greater than 5, drop itand increase the last digit to be retained by 1 (round up).If the figure following the last digit to b retained equals5, round up if the digit to be retained is odd, and rounddown if that digit is even.

1685

BCMBCM Laboratory SOP Page 43 of 45 /,Method: Semivolatiles Analysis Effective Date: tpa

Superceded Date;-' NEW

XI. Forms (cont.)C. For reporting results to the USEPA, the following contract

specific qualifiers are to be used. The seven qualifiersdefined below are not subject to modification by thelaboratory. Up to five qualifiers may be reported on Form Ifor each compound.

1. The seven EPA-defined qualifiers to be used are asfollows:

U - Indicates compound was analyzed for but notdetected. The sample quantitation limit must becorrected for dilution and for percent moisture. Forexample, 10 U for phenol in water if the sample finalvolume is the protocol-specified final volume. If a 1to 10 dilution of extract is necessary, the reportedlimit is 100 U. For a soil sample, the value must alsobe adjusted for percent moisture. For example, if thesample had 24% moisture and a 1 to 10 dilution factor,the sample quantitation limit for phenol (330 U) wouldbe corrected to:

(330 U) x df where D= 100 - % moistureD 100

and df - dilution factorat 24% moisture, D= 100-24 = 0.76

100

(330 U) x 10 = 4300 U rounded to the appropriate.76 significant figures

For soil samples subjected to GPC clean-up procedures,the CRQL is also multiplied by 2, to account for thefact that only half of the extract is recovered.

ftR30i68S

CJ _____

'BCMBCM Laboratory SOP Page 44 of 45Method: Semivolatiles Analysis Effective Date:


XI. Forms (cont.)J - Indicates an estimated value. This flag is usedeither when estimating a concentraiton for tentatively.identified compounds where a 1:1 response is assumed,or when the mass spectral data indicate the presence ofa compound that meets the identification criteria butthe result is less than the sample quantitation limitbut greater than zero. For example, if the samplequantitation limit is 10 ug/1, but a concentration of 3ug/1 is calculated, report it as 3J. The samplequantitation limit must be adjusted for both dilutionand percent moisture as discussed for the U flag, sothat if a sample with 24% moisture and a 1 to 10dilution factor has a calculated concentration of 300ug/1 and a sample quantitation limit of 430 ug/kg,report the concentration as 300J on Form I.

B - This flag is used when the analyte is found in theassociated blank as well as in the sample. Itindicates possible/probable blank contamination andwarns the data user to take appropriate action. Thisflag msut be used for a TIC as well as for a positivelyidentified TCL compound.E - This flag identifies compounds whose concentrationsexceed the calibration range of the GC/MS instrumentfor that specific analysis. If one or more compoundshave a response greater than full scale, the sample orextract must be diluted and reanalyzed according to thespecifications in Exhibit D. All such compounds with aresponse greater than full scale should have theconcentration flagged with an "E" on the Form I for theoriginal analysis. If the dilution of the extractcauses any compounds identified in the first analysisto be below the calibration range in the secondanalysis, then the results of both analyses shall bereported on separate Forms I. The Form I for thediluted sample shall have the "DL" suffix appended tothe sample number. NOTE: For total xylenes, wherethree isomers are quantified as two peaks, thecalibration range of each peak should be consideredseparately, i.e., a diluted analysis is not requiredfor total xylenes unless the concentration of eitherpeak separately exceeds 200 ug/1.

AR30I687



XI. Forms (cont.)

D - This flag identifies all compounds identified in ananalysis at a secondary dilution factor. If a sampleor extract is reanalyzed at a higher dilution factor,as in the "E" flag above, the "DL" suffix is appendedto the sample number on the Form I for the dilutedsample, and all concentration values reported on thatForm I are flagged with the "D" flag.A - This flag indicates that a TIC is a suspectedaldol-condensation product.

X - Other specific flags may be required to properlydefine the results. If used, they must be fullydescribed and such description attached to the SampleData Summary Package and the Case Narrative. Begin byusing "X". If more than one flag is required, use "Y" Iand "Z", as needed. If more than five qualifiers are Irequired for a sample result, use the "X" flag tocombine several flags, as needed. For instance, the"X" flag might combine the "A", "B", and "D" flags forsome sample.

2. The combination of flags "BU" or "UB" is expresslyprohibited. Blank contaminants are flagged "B" onlywhen they are also detected in the sample.

3. If analyses at two different dilution factors arerequired, follow the data with the "D" and "E" flagsabove.

AR30I688

CO

ftR3Ql689

BCM Laboratory Effective Date:Standard Operating Procedure (SOP) Superceded Date': NEW

Method ft: 250-PEST/PCB CLP

Method:

EXTRACTION FOR CLPPESTICIDES/PCB'S ANALYSIS

Authored By: flfojj. i iTjJLt'f''~^-' -"

Edited By: ! I '

Dept. Supervisor

Approved By: ,~

isor: J/V ;'/t 'L • P.lAi*L

/sQuality Cofttrol'Depc. D£te

Sectiojy Manager l\ Date

Lab Director Dace

This monograph is based on Exhibit D, Section II, Sample PreparatiStorage for Pesticides/PCB's Analysis, USEPA Contract Laboratory PStatement of Work for Organic Analysis, 2/88.

AR30I690

oBCM Laboratory SOP Page 1 of 34 ;Method: Extraction for Pesticides/ Effective Date: y/a

PCB's Analysis Superceded Date: NEW

I. Application

This method is applicable to water and soil samples that areextracted for the organic compounds listed in thecorresponding instrument method.

II. Sample Handling and Preservation

Liquid samples are collected in glass/ amber/ small-mouthcontainers. Soil samples are collected in glass/ amber/wide-mouth containers. The containers are fitted with screwcaps lined with Teflon. Samples are to be refrigerated at 4deg. C (±.2 deg. C) from the time of receipt until extraction.The extract must also be refrigerated until analysis. Watersamples must be extracted within 5 days of sample receipt andsoils within 10 days.

The following are the steps an analyst follows for loggingsamples in/out to uphold an internal chain of custody:

1. Remove samples from cold room.2. Bar code samples out of Log-in.3. Take samples to Extractions.4. Return samples to Log-in after extraction.5. Bar code samples back into Log-in.

Ill. Interferences

Method interferences may be caused by contaminants insolvents, reagents, glassware, and other sample processinghardware. All of these materials must be routinelydemonstrated to be free from interferences by runninglaboratory reagent blanks (i.e./ method blanks).Interferences can also occur from phthalates which can best beminimized by avoiding the use of plastics in the laboratory.Matrix interferences may be caused by contaminants that arecoextracted from the sample. The extent of matrixinterferences will vary considerably from source to source.

IV. Method Summaries

Water Sample Extractions

A measured volume of sample, approximately one liter, issolvent extracted with methylene chloride using a separatoryfunnel or a continuous extractor. The methylene chlorideextract is dried, exchanged to hexane and adjusted to a finalvolume of 10 mL.

uBCM Laboratory SOP Page 2 of 34 .Method: Extraction for Pesticides/ Effective Date:<f/7<>


IV. Method Summaries (cont.)

Soil Sample Extractions

Low Level Sample Preparation; A 30 g sample is mixed withanhydrous powdered sodium sulfate and extracted with 1:1methylene chloride/acetone using a sonicator.

Medium Level Sample Preparation; A 1 g portion ofsediment/soil is transferred to a vial and extracted withhexane.

SR301692

BCM Laboratory SOP Page 3 of 34 /Method: Extraction for Pesticides/ Effective Date: t/9°


V. Apparatus

- Separatory funnel/ 2000 mL, with Teflon stopcock/ AtmarGlass Co./ Stock No. 1639607

- Concentrator tube/ Kuderna-Danish/ 10 mL or 15 mL graduatedwith ground glass stopper, Kontes K-570050-1025 orequivalent

- Evaporative flask, Kuderna-Danish, 250 mL or 500 mL, KontesK-57001-0500 or equivalent (This is attached to concentratorwith springs)

- Snyder column, Kuderna-Danish, three ball macro, KontesK-503000-0121 or equivalent

- Snyder column, Kuderna-Danish, two ball macro, KontesK-569001-0219 or equivalent

- Sonicator: Model 375 from Ultrasonics, Inc. with a 375 Wattoutput capability or equivalent. NOTE: The horn (i.e./ tip)must be replaced if the tip begins to erode which is evidentby a rough surface.

- Sonabox acoustic enclosure

- Vials, 2.0 mL, amber glass with Tefon-lined screw cap

- Vials, 20 mL, with Teflon-lined screw cap

- Amber jars, 500 mL with Teflon-lined caps

- Pipet, automatic, repeating, 60 mL, Atmar Glass Co.

- Disposable Pasteur pipets

- Continuous liquid-liquid extractors: equipped with Teflon orglass connecting joints and stopcocks requiring nolubrication, Hershberg-Wolf Extractor-Ace Glass Company,Vineland, NJ P/N 6841-10 or equivalent

- Automated gel permeation chromatography (GPC) cleanup devicefrom Analytical Biochemical Labs/ Inc./ GPC Autoprep 1002 orequivalent which includes the following:

- 25 mm ID x 600-700 mm glass column packed with 70 g ofBio-Beads SX-3

AR301693

BCM Laboratory SOP Page 4 of 34 iMethod: Extraction for Pesticides/ Effective Date:y7°

PCB's Analysis Superceded Dater NEW


- Syringe/ 10 mL with Luer-Lock fitting

- Syringe filter holder and filters, stainless steel andTFE, Gelman 4310 or equivalent

- Silicon carbide boiling chips, approximately 10/40 meshPreparation; Heat to 400 deg. C for 30 minutes or Soxhletextract with methylene chloride.

- Steam bath in hood capable of temperature control to +.2 deg,C

- Chroraatographic column for alumina: 10 mL graduated pipetsplugged with Pyrex glass wool in the tip

- Glass wool, Pyrex, pre-rinsed with appropriate solvents

- Analytical balance or equivalent capable of weighing to0.0001 g

- Top loading balance or equivalent capable of weighing to0.01 g

- Nitrogen tank equipped with a regulator having zero gradenitrogen

- Spatula, stainless steel or Teflon

- Drying oven set at 105 deg. C

- Desiccator

- Crucibles, porcelain

- pH meter

- Buchner funnel

- Vacuum filtration flask

- Filter paper, Whatman No. 41 or equivalent

- Erlenmeyer flasks, 250 mL

- Beaker, 400 mL

BCM Laboratory SOP Page 5 of 34 ,Method: Extraction for Pesticides/ Effective Date:y?°



-Guth bottle

-pH paper

-Glass stirr rod

- Glass weighing boat

- Volumetric flasks, class "A", 50 mL, 100 mL, 500 mL

- Volumetric pipets, class "A", 0.5 mL. 2.0 mL

- Microliter syringes, 500 uL, 1000 uL, Hamilton brand (1750LTN) which is gas tight or equivalent

1895

u

BCM Laboratory SOP Page 6 of 34Method: Extraction for Pesticides/ Effective


VI. Reagents

A. Stock Reagents

- Sodium hydroxide, NaOH, Stock No. 3728-01, J.T. Baker*

- Sodium thiosulfate, Na2S203, Stock No. 78926, J.T. Baker*

- Sulfuric acid/ H2S04, Stock No. 9681-33, J.T. Baker*

- Bis(2-ethylhexylphthalate) and pentachlorophenol inmethylene chloride, 4.0 mg/L

- Methylene chloride, CH2C12, pesticide quality orequivalent, Stock No. 9264-03, J.T. Baker

- Sodium sulfate, Na2S04, anhydrous granular crystals,Stock No. 3375-07, J.T. Baker

- Sodium sulfate/ Na2S04/ anhydrous powdered. Stock No.3898-07, J.T. Baker

- .Sodium sulfite, Na2S03, Stock No. 78890, J.T. Baker

- Corn oil in methylene chloride, 200 mg/L

- Acetone, CH3-CO-CH3, pesticide quality or equivalent,Stock No. 9254-03, J.T. Baker

- Hexane, pesticide quality or equivalent, Stock No.9262-03, J.T. Baker

- Methanol, CH20H, pesticide quality or equivalent,Stock No. 9263-03, J.T. Baker

Tetrabutylammonium (TEA) hydrogen sulfate, *

- Alumina-Neutral, Super I Woelm (Univeral Scientific,Incorporated, Atlanta, Georgia) or equivalent

Isooctane

* ACS grade or equivalent

B. Reagent Preparation

1) Reagent Water; Reagent water is defined as deionizedwater in which an interferent is not observed at the MDLof the parameters of interest. Use reagent water forpreparing solutions, dilutions, and running blanks.

AR30I696

BCM Laboratory SOP Page 7 of 34 .Method: Extraction for Pesticides/ Effective Date: 3n<?

PCB's Analysis Superceded Date:7 NEW


2) Sodium Hydroxide, 10 N

Preparation: Weigh 40 g of NaOH and record weight innotebook. Quantitatively transfer to a 100mL volumetric flask and dilute to volumewith reagent water.

3) Sulfuric Acid. (1:1 v/v)

Preparation: Slowly, add 50 mL of cone. H2S04 to 50 mLof reagent water in a suitable glasscontainer which is immersed in a coolingwater bath or equivalent. CAUTION: Alwaysacid acid to water slowly.

4) Sodium Sulfate

NOTE: The preparation below is applicable to bothgranular and powdered forms.

Preparation: Line the bottom of a shallow tray withsodium sulfate and completely rinse withmethylene chloride. Place tray in a 400deg. C oven for 4 hours. Transfer to130-150 deg. C oven until needed.

5) Alumina-Neutral, Super I

Preparation: Prepare activity III by adding 7% (v/w)reagent to the Super I neutral alumina.Tumble or shake in a wrist action shakerfor a minimum of 2 hours or preferablyovernight. There should be no lumpspresent. Store in a tightly sealed glasscontainer. NOTE; A 25 cycle soxhletextraction of the alumina with methylenechloride is required if a solvent blankanalyzed by the pesticide techniqueindicates any interferences for thecompounds of interest.

A-83QI697

BCM Laboratory SOP Page 8 of 34 .Method: Extraction for Pesticides/ Effective Date: Z/cfO



6) Tetrabutylammonium (TEA) Sulfite Reagent

Preparation: Weigh 3.39 g of tetrabutylammonium hydrogensulfate and record weight in notebook.Dissolve in 100 mL of distilled water.Remove impurities by extracting thissolution 3 times with 20 mL portions ofhexane. Discard the hexane extracts, andadd 25 g sodium sulfite to the watersolution. Store the solution in an amberbottle with a Teflon-lined screw cap. Thesolution can be stored at room temperaturefor at least one month.

7) Isooctane - Hexane (20:1 v/v)

Preparation: Add 475 mL of isooctane to a 500 mLvolumetric which contains 25 mL of hexane.Mix well. Store in a 500 mL amber jar at 4deg. C.

C. Surrogate Spiking Solution Stock

Preparation: Using the chart below, weigh the stated amountto the nearest 0.1 g of each compound into a500 mL volumetric flask and dilute to volumewith (20:1) isooctane/hexane. Record weightsand lot number in standard notebook. Theconcentration of'each compound in thissolution is also stated.

Compound Weight (q) Concentration (ng/uL)

Aldrin 0.01 20Lindane 0.01 20Heptachlor 0.01 20Endrin 0.025 50Dieldrin 0.025 50DOT 0.025 50

D. Matrix Spiking Stock Solution

This solution is purchased from Supelco. The concentrationof dibutylchlorendate (DEC), which is the only compound inthis solution is 200 ng/uL.

HR3QI698

ECM Laboratory SOP Page 9 of 34Method: Extraction for Pesticides/ Effective Date:



E. GPC Calibration Solutions

1) Corn Oil (200 mq/L)

Preparation: Weigh 10.0 g of corn oil into a glassweighing boat and record weight innotebook. Quantitatively transfer to a50.0 mL volumetric flask and dilute tovolume with methylene chloride.

2) Bis(2-ethylhexylphthalate) + Pentachlorophenol(4.0 mq/L)

Preparation: Weigh 0.20 g each ofbis(2-ethylhexylphthalate andpentachlorophenol into a 50.0 mL volumetricflask and dilute to volume with methylenechloride. Record weights of each compoundin notebook.

NOTES:

1. Each standard bottle must be labelled with the following:name of standard, standard lot numbers, analyst's initials,and date prepared. The preparation is recorded in thestandard notebook.

2. The lot numbers are created by using the standard booknumber, followed by the page number, and finally the entrynumber (e.g., 1-26-1).

A.R30I699

BCM Laboratory SOP Page 10 of 34Method: Extraction for Pesticides/ Effective Date:



A. CLP Surrogate Standard Solution

Preparation: Pipet 5.0 mL of the Surrogate Spiking SolutionStock into a 500 mL volumetric flask anddilute to volume with methanol. Recordpreparation in standard notebook. Transfer thesolution to a 500 mL amber jar and seal with aTeflon-lined lid. Store at 4 deg. C. Theconcentration of DEC in this solution is 1.0ng/uL.

B. CLP Matrix Spike Solution

Preparation: Pipet 2.5 mL of Matrix Spike Stock Solutioninto a 500 mL volumetric flask and dilute tovolume with methanol. Record preparation instandard notebook. Transfer the solution to a500 mL amber jar and seal with a Teflon-linedlid. Store at 4 deg. C. Below is a chartindicating the concentration of the compoundsin the solution.

Compound Concentration (nq/uL)

Aldrin 0.2Lindane 0.2Heptachlor 0.2Endrin 0.5Dieldrin 0.5

(700

BCM Laboratory SOP Page 11 of 34 >Method: Extraction for Pesticides/ Effective Date: Z/9&

PCB's Analysis Superceded Date:'NEW

VIII. Quality Control

A. The following quality control samples are run at afrequency of one every batch of samples per extractionanalyst: matrix spike, matrix spike duplicate, methodblank, and spiked method blank.

B. An analytical batch is defined as containing <.20 samplesand the 4 quality control samples mentioned above.

C. Matrix Spike and Matrix Spike Duplicate Analysis; Using a1000 microliter syringe, add 1.0 mL of spiking solution toeach of two samples chosen for spiking either in theseparatory funnel (liquid extraction) or beaker (soilextraction). Run as usual samples.

D. Method Blank: Using deionized water in place of sample,follow the appropriate matrix extraction procedure.

E. Spiked Method Blank; Using a 1000 microliter syringe, add500 uL of matrix spiking solution to 1000 mL of deionizedwater in the separatory funnel or beaker (i.e., step 3 ofthe Liquid Sample Extraction procedure, step 5 of the SolidSample Extraction (low level) procedure, and step 5 of theSolid Sample Extraction (medium level). Run as a usualsample.

F. GPC Cleanup Blank; Using 10.0 mL of methylene chloridespiked with 1.0 mL of the pesticide surrogate standardsolution, go through the GPC cleanup procedure.

18301701

IBCM Laboratory SOP Page 12 of 34Method: Extraction for Pesticides/ Effective Date:


IX. Procedure

A. Liquid Sample Extraction

1. Mark the sample bottle at the sample meniscus for laterdetermination of sample volume and pour the sample intoa 2000 mL separatory funnel.

2. Check the pH of the sample with wide range pH paper andadjust to between 5-9 pH with 10 N sodium hydroxideand/or 1:1 sulfuric acid solution.

3. Pipet 1.0 mL of the pesticide surrogate standardsolution into the funnel. Mix sample well.

4. Using the Atmar repeating pipet, transfer 60 mL ofmethylene chloride to the separatory funnel.

5. Extract by shaking vigorously for 2 minutes. Vent thefunnel often to -prevent a pressure buildup. Allow theorganic layer to separate from the water phase for atleast 10 minutes.

NOTE: If the emulsion interface between layers is morethan one-third the volume of the solvent layer,the analyst must employ mechanical techniques tocomplete the phase separation. The optimumtechnique depends upon the sample, and mayinclude: stirring, filtration of the emulsionthrough glass wool, centrifugation, or otherphysical methods. If the techniques stated abovefail, transfer the sample, solvent, and emulsioninto the extraction chamber of a continuousextractor. Proceed to the ContinuousLiquid-Liquid Extraction procedure, step 4.

6. Collect the methylene chloride extract in a 250 mLErlenmeyer flask.

7. Add a second 60 mL volume of methylene chloride to thesample bottle and repeat the extraction procedure asecond time (i.e./ steps 5-7), combining the extracts inthe Erlenmeyer flask.

8. Perform a third extraction in the same manner.

6R301702

LJ

(ft BCM Laboratory SOP Page 13 of 34 /Method: Extraction for Pesticides/ Effective Date: y9°





10. Transfer the extract through a funnel containinganhydrous granular sodium sulfate and collect in aK-D concentrator.

11. Rinse the Erlenmeyer flask and funnel with three 10 mLportions of methyiene chloride to complete thequantitative transfer.




15. Adjust the vertical position of the apparatus and thewater temperature as needed to complete theconcentration in 10-15 minutes to less than 10 ml.

NOTE: At the proper rate of distillation, the ballswill actively chatter but the chambers will notflood with condensed solvent.

16. Momentarily remove the Snyder column, add 50 mL ofhexane and a new boiling chip.

17. Reattach the Snyder column and pre-wet by adding about1 mL of hexane to the top.


1703


PCB's Analysis Superceded Date:' NEW



* Rinse all the glassware and Funnel with anhydrousgranular sodium sulfate before using.

Rinse all glassware with methylene chloride.

19. Adjust the vertical position of the apparatus and thewater temperature as needed to complete theconcentration in 5-10 minutes.


20. When the apparent volume of liquid reaches 1 mL,remove the K-D apparatus and allow it to drain andcool at least 10 minutes.

21. Remove the Snyder column, rinse the flask and itslower joint into the concentrator tube with 1 to 2 raLof hexane.



24. Evaporate the solvent volume to 0.5 mL. NOTE; Theextract must never be brought to dryness.

25. Dilute the extract to 1.0 mL with acetone and proceedto Alumina Column Cleanup procedure.

*

BCM Laboratory SOP Page 15 of 34 iMethod: Extraction for Pesticides/ Effective Date: Z/fo



B. Continuous Liquid-Liquid Extraction

1. Check the pH of the sample with wide range pH paper andadjust to between 5-9 pH with 10 N sodium hydroxideand/or 1:1 sulfuric acid solution.

2. Transfer a one liter sample aliquot to the continuousextractor.

3. Pipet 1.0 mL of the pestcide surrogate standardsolution into the extractor and mix well.


5. Add sufficient reagent water to the continuousextractor to ensure proper operation.

6. Extract the sample for 18-24 hours.

7. Allow the sample to cool and detach the distillingflask.


9. Transfer the extract through a funnel containinganhydrous granular sodium sulfate and collect theextract in a K-D concentrator.

10. Rinse the concentrator tube and funnel with three 10 mLportions of methylene chloride to complete thequantitative transfer.



13. Place the K-D apparatus on a hot water bath (80-90 deg.C) so that the concentrator tube is partially immersedin the hot water, and the entire lower rounded surfaceof the flask is surrounded by hot vapor.

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BCM Laboratory SOP Page 16 of 34 /Method: Extraction for Pesticides/ Effective Date: 8/?°



B. Continuous Liquid-Liquid Extraction (cont.)

14. Adjust the vertical position of the apparatus and thewater temperature as needed to complete theconcentration in 10-15 minutes to less than 10 ml.


15. Momentarily remove the Snyder column, add 50 mL ofhexane and a new boiling chip.

16. Reattach the Snyder column and pre-wet by adding about1 mL of hexane to the top.

17. Place the K-D apparatus on a hot water bath (80-90• deg. C) so that the concentrator tube is partiallyimmersed in the hot water, and the entire lowerrounded surface of the flask is surrounded by hotvapor.



19. When the apparent volume of liquid reaches 1 mL,remove Jche K-D apparatus and allow it to drain andcool at least 10 minutes.

20. Remove the Snyder column, rinse the flask and itslower joint into the concentrator tube with 1 to 2 mLof hexane.

21. Place the adaptor/ which is connected by plastictubing to the nitrogen tank/ along the inside wall ofthe flask.

NOTE: Rinse all the glassware and funnel containinganhydrous sodium sulfate before using withmethylene chloride.



IX. Procedure (cont.j

B. Continuous Liquid-Liquid Extraction (cont.)


23. Evaporate the solvent volume to 0.5 mL. NOTE; Theextract must never be brought to dryness.

24. Dilute the extract to 1.0 mL with acetone and proceedto Alumina Column Cleanup procedure.

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uBCM Laboratory SOP Page 18 of 34Method: Extraction for Pesticides/ Effective Date:

PCB's Analysis Superceded Date:7NEW


C. Alumina Column Clean-Up

1. Add 3 g of activity III neutral alumina to the 10 mLChromatographic column. Tap the column to settle thealumina. NOTE; Do not pre-wet the alumina.

2. Transfer the 1 mL hexane/acetone extract to the top ofthe alumina using a disposable Pasteur pipet. Collectthe eluate in a clean 10 mL concentrator tube.

3. Add 1 mL of hexane to the original extract concentratortube to rinse it. Transfer these rinsings to thealumina column.

4. Elute the column with an additional 9 raL of hexane.NOTE; Do not allow the column to go dry during theaddition and elution of the sample.

5. Adjust the extract to a final volume of 10 mL usinghexane.



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uBCM Laboratory SOP Page 19 of 34 ,Method: Extraction for Pesticides/ Effective Date: ?/9e



D. pH Determination for Solid Sample Extractions

NOTE: This analysis is usually performed by the WetChemistry department following SOP 600-150.I/ pHElectrometric.

1. Weigh 50 g of soil/sediment in a 100 mL beaker andrecord weight in notebook.

2. Add 50 mL of deionized water and a stir bar.

3. Place beaker on a magnetic stirrer and mix for onehour.

4. Determine pH with a glass electrode and pH meter whilestirring.

5. Record pH in notebook.

NOTE: If the pH of the soil is >11 or <5/ contact theDeputy Project Officer cited in the contract forinstructions on how to handle the sample.

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E. Total Solids Determination (% Moisture) for Solid SampleExtractions

NOTE: This analysis is usually performed by the WetChemistry department using SOP 600-160.41, TotalSolids %.

1. Weigh 5-10 g of sediment into a tared porcelaincrucible and record weight in notebook.

2. Dry sample overnight in a 105 deg. C oven.

3. Allow sample to cool in a desiccator prior to weighing

4. Calculation:

% Moisture = (grams of sample) - (grams of dry sample) x 100grams of sample

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E. Solid Sample Extraction (Low Level Sample Preparation)

NOTE: A low level sample preparation is done on all soilsamples; however, if samples are found to be highlyconcentrated after analysis, the sample isre-extracted using the medium level preparationprocedure.

1. Decant and discard any water layer on sample. Mixsamples thoroughly especially composited samples.Discard any foriegn objects such as sticks, leaves/ androcks .

2. Weigh 30 g +.0.1 g of sample into a 400 mL beaker.Record weight in notebook.

3. Add about 60 g of pre-conditioned powdered sodiumsulfate (i.e./ enough to dry the soil) to the beaker.

4. Mix the sample until it has a sand-like texture.

5. Add 100 mL of (1:1) methylene chloride-acetone and200 uL of pesticide surrogate if using GPC cleanup(1000 uL of DCB surrogate if not using GPC) to thebeaker.

6. Place the beaker in sonicator.

7. Place the bottom surface of the tip of the 3/4 inchdisruptor horn about 1/2 inch below the surface of thesolvent but above the sediment layer.

8. Sonicate for 3 minutes with output control knob set at10 and mode switch on "1 sec. pulse" and % duty cycleknob set at 50%.

9. Decant and filter extract through Whatman £41 filterpaper using vacuum filtration.

10. Repeat the extraction twice more (i.e., steps 5-8) withadditional 100 mL portions of (1:1) methylenechloride-acetone.

NOTES:

1. Before each extraction, make certain that thesodium sulfate is free flowing and not aconsolidated mass. Break up large lumps with aclean spatula.

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uBCM Laboratory SOP Page 22 of 34 ,Method: Extraction for Pesticides/ Effective Date: 3nc


" *X. Procedure (cont.)

E. Solid Sample Extraction (Low Level Sample Preparation)(cont. )

2. On the final sonication, pour the entire sampleinto a Buchner funnel and rinse the beaker and thefunnel with (1:1) methylene chloride-acetone.

11. Transfer the extract to a K-D concentrator consistingof a 10 mL concentrator tube and a 500 mL evaporativeflask.

12. Add 1-2 clean boiling chips to the evaporative flaskand attach a three-ball Snyder column.





NOTE; If GPC cleanup is used, concentrate liquid toapproximately 10 mL and proceed to the GPC Cleanupprocedure.

16. When the apparent volume of liquid reaches 2 mL,remove the K-D apparatus from the water bath and allowit to drain and cool for at least 10 minutes.


18. Open the valve of the tank and ±>e sure the regulatoris displaying a pressure reading between 0-10 psi.

19. Evaporate the solvent volume to just below 1 mL.NOTE: The extract must never be brought to dryness. 4

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BCM Laboratory SOP Page 23 of 34 /Method: Extraction for Pesticides/ Effective Date: g/'°



E. Solid Sample Extraction (Low Level Sample Preparation)(cont. )

20. Adjust the final volume to 1 mL with methylenechloride. Record volume in notebook.


22. Label vial with the following information: Samplenumber, test, batch number/ date, analyst's initials,and initial and final volumes. Store vial at 4 deg.C.

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uBCM Laboratory SOP Page 24 of 34 /rMethod: Extraction for Pesticides/ Effective Date: '/f°

PCB's Analysis Superceded Dater NEW


F. Solid Sample Extraction (Medium Level Sample Preparation)

1. Open sample container in a hood.

2. Decant and discard any water level and then mix samplewell.

3. Weigh 1.0 g of sample into a 20 mL vial. Record weightin notebook to the nearest 0.1 g.

4. Add 2.0 g of anhydrous powdered sodium sulfate to thesample and mix well. NOTE; Be sure sodium sulfate isfree flowing. Break up large lumps with a spatula.

5. Pipet 1.0 mL of the CLP surrogate standard solutioninto the vial.

6. Immediately add 9.0 mL of methylene chloride to thesample. NOTE; Add only 8.0 mL of methylene chloride tomatrix spike samples to achieve a final volume of 10mL.

7. Place vial in sonicator.

8. Disrupt the sample with the 1/8 inch tapered microtipultrasonic probe for 2 minutes. The output controlsetting is to be set at 5, in continuous mode.

9. Loosely pack a disposable Pasteur pipet with 2-3 cmglass wool plugs.

10. Filter the extract through the glass wool and collect5.0 mL in a concentrator tube.

11. Place the adaptor, which is connected by plastic tubingto the nitrogen tank/ along the inside wall of theflask.

12. Open the valve of the tank and be sure the regulator isdisplaying a pressure reading between 0-10 psi.

13. Evaporate the solvent volume to just below 1 mL. NOTE:The extract must never be brought to dryness.

14. Adjust the final volume to 1 mL with methylenechloride. (NOTE; Final volume for matrix spike is 10mL.) Record volume in notebook.

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JBCM Laboratory SOP Page 25 of 34 ,Method: Extraction for Pesticides/ Effective Date:^/7<?



F. Solid Sample Extraction (Medium Level Sample Preparation)(cont. )

15. Transfer to a 2 mL glass vial (20 mL for matrix spike)with a Teflon-lined screw cap.


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BCM Laboratory SOP Page 26 of 34 _•Method: Extraction for Pesticides/ Effective Date: yf°

PCB's Analysis Superceded Date:' NEW


G. Extract Cleanup Procedure

1) Gel Permeation Chromatoqraphv (GPC) Setup

1. Weigh out 70 g of Bio Beads SX-3 and place in a 400mL beaker.

2. Cover the beads with methylene chloride and allowthem to swell overnight.

3. Transfer the swelled beads to the glass column.

4. Begin pumping methylene chloride through thecolumn, from bottom to top, at 5.0 mL/min.

5. After approximately one hour, adjust the pressureon the column to 7-10 psi. Pump an additional 4hour& to remove air from the column.

NOTE: Adjust the column pressure periodically asrequired to maintain this pressure range.

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uBCM Laboratory SOP Page 27 of 34Method: Extraction for Pesticides/ Effective Date:

PCE's Analysis Superceded Date: NEW



2) Calibration of Column

1. Wash the column at least 15 minutes betweensamples .

2. Typical parameters selected are:

o Dump time = 30 minutes (150 mL)o Collect time = 36 minutes (180 mL)o Wash time = 15 minutes (75 mL)

3. The column can also be calibrated by the use of a254 mm UV detector in place of gravimetric and GCanalyses of fractions.

4. Measure the peak areas at various elution times todetermine appropriate fractions.

5. The SX-3 Bio Beads column may be reused for severalmonths, even if discoloration occurs. Systemcalibration usually remains constant over thisperiod of time if column flowrate remains constant.

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JBCM Laboratory SOP Page 28 of 34 »Method: Extraction for Pesticides/ Effective Date: offo




3) GPC Cleanup

NOTE: Pre-filter or load all extracts via the filterholder to avoid particulates that might stop theflow.

1. Load one 5.0 mL pesticide/PCB aliquot of theextract onto the GPC column. CAUTION; Do not applyexcessive pressure when loading the GPC.

2. Process the extracts using the dump.

3. Collect and wash parameters determined from thecalibration.

4. Collect the clean extracts in 400 mL beakerstightly covered with aluminum foil.

5. Transfer the extract to a K-D concentratorconsisting of a 10 mL concentrator tube and a500 mL evaporative flask.

6. Add 1-2 clean boiling chips to the evaporativeflask and attach a three-ball Snyder column.



9. Adjust the vertical position of the apparatus andthe water temperature as needed to complete theconcentration in 5-10 minutes.

NOTE: At the proper rate of distillation, the ballswill actively chatter but the chambers willnot flood with condensed solvent.


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uBCM Laboratory SOP Page 29 of 34 /Method: Extraction for Pesticides/ Effective Date: $[?<?




3) GPC Cleanup (cont.)

11. Dilute to 10.0 mL volume with methylene chloride.

NOTES:

1. Purge the sample loading tubing thoroughly with solventbetween extracts.

2. After especially dirty samples, run a GPC blank(methylene chloride) to check for carry-over.

3. Run the phthalate-phenol calibration solution throughthe cleanup cycle after every 23 extracts.

4. The recovery for each compound must be >.85%.

5. The recovery is determined using a UV recordingspectrophotometer.

6. A copy of the printouts of standard and check solutionare required as deliverables with each case. Also, show% recovery on the copy.

7. The analysis of a batch (i.e., 20 samples) takes morethan 24 hours to complete.

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uBCM Laboratory SOP Page 30 of 34 iMethod: Extraction for Pesticides/ Effective Date: */7C


IX. Procedure~~ (cont.)


4) Optional Extract Splitting

NOTES:

1. If the extract is to be used only for pesticide/PCBanalysis, go to page 31 to concentrate extract to1.0 mL.

2. If the extract is to be used for both pesticide/PCBand semivolatile analyses, go to page 32 to splitthe extract into two portions.

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BCM Laboratory SOP Page 31 of 34 ,Method: Extraction for Pesticide/ Effective Date: ?no




5) Concentration of Non-Split Pesticide/PCB Extract

1. Using a microliter syringe, transfer 0.5 mL of the10 mL methylene chloride extract to a separateconcentrator tube.

2. Add 5 mL of hexane and a silicon carbide boilingchip.

3. Mix using a vortex mixer.

4. Attach a two-ball micro-Snyder column.

5. Pre-wet the Snyder column by adding 0.5 ml ofhexane to the top of the column.

6. Place the K-D apparatus on a hot water bath (80-90deg.C) so that the concentrator tube is partiallyimmersed in the hot water.

7. Adjust the vertical position of the apparatus andthe water temperature as required to complete theconcentration in 5-10 minutes.

8. When the apparent volume of the liquid reaches1.0 mL, allow it to drain for at least 10 minuteswhile cooling.

9. Remove the Snyder column and rinse the lower jointinto the concentrator with 1-2 mL of hexane.

10. Place the adaptor, which is connected by plastictubing to the nitrogen tank, along the inside wallof the concentrator.


12. Evaporate the solvent volume to 0.5 mL.

13. Using a microliter syringe, add 0.5 mL of acetone.

14. The pesticide extract must now be passed throughthe Alumina Column Cleanup procedure.

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uBCM Laboratory SOP Page 32 of 34 ,Method: Extraction for Pesticide/ Effective Date: ?/?o

PCB's Analysis Superceded Date." NEW



6) Splitting Out Semivolatile Extract

NOTE: Follow G./ (5) to obtain the pesticide portionand refer to SOP £ 350-SVCLP, Extraction for CLPSemivolatile Analysis for the treatment of thesemivolatile portion.

X. Calculations - not applicable

BCM Laboratory SOP Page 33 of 34Method: Extraction for Pesticide/ Effective Date:


XI. Data Documentation

All pertinent data for the extraction of samples forpesticide/PCB's analyses are recorded in a boundvolume-numbered notebook. This information includes:

1. Place data in tabular form including sample number, ordernumber, initial and final volumes, test/ batch number/ andsurrogate amount.

2. Note anything different or unusual with any samples in acolumn on each page of the notebook under the heading,"Comments".

See Figure 1 for an example of a formatted notebook page.

Notebook Entry Notes

1. The laboratory notebook must be signed and dated by theanalyst at the bottom of the page. In addition, thedepartment supervisor or a witness must co-sign thenotebook.

2. Each batch starts a new page. Consequently, if an entirepage is not used, the analyst signs and dates below thelast entry. A diagonal line is drawn through the unusedportion of the last page. Any extractions continuing tothe next consecutive page are to be noted as "continued onpage x" or "continued from page y".

3. If an error is made in recording data, one line is drawnthrough the error. The analyst initials, dates the error,and a reason for the correction is noted (if necessary) atthe bottom of the page.

At301723

uBCM Laboratory SOP Page 34 of 34 ,Method: Extraction for Pesticides/ Effective Date: ?'?0


XI. Data Documentation (cont.)

BCM

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FIGURE 1. EXAMPLE OF FORMATTED NOTEBOOK PAGE

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