# Final Generic Sampling Plan for Determining Baseline Loads for Proposed VCM Voluntary Program

Prepared for:


## U.S. Environmental Protection Agency Engineering and Analysis Division Office of Water 1200 Pennsylvania Avenue, NW Washington, D.C. 20460

Prepared by:


### Eastern Research Group, Inc

. 14555 Avion Parkway Suite 200 Chantilly, VA 20151

October 19, 2007

EPA Contract No. 68-C-02-095 Work Assignment 5-18i TABLE OF CONTENTS

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1.0 I NTRODUCTION .....................................................................................................1-1 1.1 Background..............................................................................................1-1 1.2 Objectives and Scope...............................................................................1-4 1.3 Facilities Included in Sampling Program.................................................1-5

2.0 O VERVIEW OF CCH M ANUFACTURING P ROCESSES AND W ASTEWATER T REATMENT ..............................................................................................................................2 -1

3.0 S AMPLING A PPROACH ...........................................................................................3-1 3.1 Sampling Point Selection.........................................................................3-1 3.2 Analytical Method Requirements ............................................................3-2 3.3 Sample Collection Methodology .............................................................3-3 3.4 Quality Assurance/Quality Control..........................................................3-4 3.5 Field Measurements...............................................................................3-10 3.6 Engineering Data Collection..................................................................3-10 3.7 Sample Shipment ...................................................................................3-11

4.0 S AMPLING A CTIVITIES ..........................................................................................4-1 4.1 Sampling Preparation...............................................................................4-1 4.2 Field Sampling Activities ........................................................................4-1 4.3 Analysis of Results ..................................................................................4-2 4.4 Final Data Package ..................................................................................4-2 4.5 Site-Specific Logistics .............................................................................4-3

5.0 R EFERENCES .........................................................................................................5-1

Appendix A L IST OF D IOXIN AND F URAN A NALYTESii LIST OF TABLES

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Table 1-1. U.S. Industry Coverage of Participating Sites........................................................... 1-3

Table 3-1. Guidelines for Se lecting Sampling Points............................................................... 3-12

Table 3-1A. Analytes to be Collected by Sampling Point for Stand-Alone CCH Facility (Example)........................................................................................................... 3-12

Table 3-1B. Analytes to be Co llected by Sampling Point for Integrated Facility (Example) .. 3-13

Table 3-2. CCH Sampling Screen Anal ytes and Method Requirements.................................. 3-13

Table 3-3. Sampling Point Field Measurements....................................................................... 3-13iii LIST OF FIGURES

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Figure 2-1. Process Flow Diagram for Stand-Alone CCH Facility............................................ 2-2

Figure 2-2. Process Flow Diagram for Integrated CCH Facility................................................ 2-3

Figure 3-1. Sample Pres ervation Log Sheet ............................................................................. 3-14

Figure 3-2. Example Fiel d Sampling Log Sheet....................................................................... 3-15

Figure 3-3. Example Engin eering Data Sheet........................................................................... 3-161-1 1.0 I NTRODUCTION

Under the direction of th e Engineering and Analysis Division (EAD) of the U.S. Environmental Protection Agency (EPA), 12 U.S. manufacturing facilities of vinyl chloride monomer (VCM) are conducting a sampling progr am to characterize process wastewaters generated by chlorine and chlorinated hydrocar bon (CCH) manufacturing operations, including

the characterization of total site outfall discha rges. The primary use for the data from this sampling effort is for EPA to estimate baseline loads for 17 dioxin and furan congeners (hereinafter “dioxin”) and tota l suspended solids from CCH process wastewater at these 12 facilities. The data from this sampling effort will also be used to calculate separate loading

contributions from the different CCH process types (e.g. PVC, chlo r-alkali), when possible, and to further assess the need for regulation of each CCH process type. Finally, the data will also be

used to estimate total manufactur ing site dioxin discharges.

EPA is interested in characterizing process wastewater streams prior to commingling with non-CCH wastewater. For st and-alone CCH facilities that do not operate non-CCH manufacturing processes, facilities will collect samples from the effluent from wastewater treatment. For integrated facilities, fa cilities will collect wa stewater samples for each CCH process type prior to entering the combined wastewater treatment system. With these goals in mind, EPA will select the sampling points for each facility with input from facility personnel. This generic version of the sampling plan prov ides project background, scope and objectives, as well as general sampling procedures and methods to be followed during all sampling episodes. Once EPA develops site-specific sampling plans fo r each of the 12 facilities, the site-specific plan will serve as a detailed guide to facility personnel (including facility cont ractors, if utilized) conducting the sampling and an alysis activities.

1.1 Background

The 1972 Clean Water Act directs EPA to develop national technology-based regulations placing limits on the pollutants that are discharged by categories of industry to surface waters (termed “effluent guidelin es”) or to sewage treatment plants 1 (termed1-2 “pretreatment standards”). The Act also di rects EPA to develop na tional technology-based regulations (termed “new source performance standa rds”) for new industrial facilities that are discharging nontrivial am ounts of toxic or non-conventional pollutants.

EPA’s Office of Water has begun an effort to determine if revised regulations are required for facilities manufacturing chlorine and chlorinated hydrocar bons (including polyvinyl chloride (PVC)), under the authority of Secti on 308 of the Clean Water Act (Federal Water Pollution Control Act, 33 U.S.C. Section 1318). EP A refers to the manufacturers of chlorine and chlorinated hydrocarbons as the Chlorine and Chlorinated Hydrocarbon (CCH) manufacturing segments. Wastewater from chlorine manufactur ing via the chlor-alkali process is regulated by the Inorganic Chemicals Manufacturing Point Sour ce Category (40 CFR Pa rt 415). Wastewater from chlorinated hydrocarbon manufacturing is regul ated under the Organic Chemicals, Plastics, and Synthetic Fibers (OCPSF) Poin t Source Category (40 CFR Part 414).

In February 2007, several member companie s of the Vinyl Institute (VI) and the American Chemistry Council (ACC) (referred to as the Vinyl Chloride Producers, or “VCP”) proposed a voluntary dioxin control program fo r vinyl chloride facili ties (1). The proposed voluntary program included all 13 (consisting of 12 existing and 1 future) U.S. VCM manufacturing sites. Accordi ng to the VCP, the 12 existing sites account for 97 percent of ethylene dichloride (EDC) manufactured in the U.S and represented 97 percent of the dioxin loadings into wastewater iden tified in Table 6-43 of EPA’s Technical Support Document for the 2004 Effluent Guidelines Program Plan (see Table 1-1). 2 The proposed program focused on vinyl chloride manufacturing sites because of industry knowledge, based primarily on the Vinyl Institute Dioxin Characterization study, that the oxyhydrochlorination (OHC) process and the thermal oxidation of chlorinated hydrocarbons are potential dioxin sources in the CCH manufacturing segments. 3

The VCP initially investigated voluntary programs that would focus only on the wastewater streams from the OHC process at these facilities. However, the VCP determined that

2 U.S. EPA. 2004. Technical Support Document for the 2004 Effluent Guidelines Program Plan. (August). EPA821-R-04-014.
3 Vinyl Institute. 2002. The Vinyl Institute Dioxin Characterization Program Final Report. (July 1).1-3 it was not practical to isolate OHC wastewater streams at all faciliti es, and, thus, decided that the program should include wast ewater streams from all site operat ions so that dioxin sources other than CCH manufacturing ( e.g ., combustion) would be include d. The VCP therefore proposed a program that would include discharges from chlo r-alkali operations at thes e sites (60 percent of U.S. chlor-alkali production according to industry), as well as discharges from other on-site CCH and non-CCH manufacturing processes. Chemical Market Associates, Inc. provided the U.S. industry capacity information for VCM and PVC. 4

Table 1-1. U.S. Industry Coverage of Participating Sites

Metric Percent Coverage Source U.S. VCM manufacturing capacity 100 CMAI, 2006 U.S. EDC OHC manufacturing capacity 97 CMAI, 2006 D/F wastewater loading (TRI, TM17, CY2000) for sites listed in Table 6-43 of EPA’s 2004 Section 304(m) plan Technical Support Document 97 Vinyl Institute, EPA 304(m) plan Technical Support Document U.S. chlor-alkali manufacturing capacity (2005) ~60 Chlorine Institute, Vinyl Institute U.S. PVC manufacturing capacity (which the VCP believes is a negligible contributor to overall CCH D/F loadings) ~25 Vinyl Institute

U.S. high-volume chlorinated hydrocarbon solvent manufacturing capacity known by the participating companies to exist ~60 Halogenated Solvents Industry Alliance; Vinyl Institute

Because it directly addressed dioxin in wastewater from EDC/VCM facilities, the VCP selected the European Commission Integr ated Pollution Prevention and Control (IPPC)
Reference Document on Best Available Tec hniques (BAT) in the Large Volume Organic Chemical Industry (2) as the basis for the voluntary pr ogram. The IPPC document identifies a BAT maximum concentration of 0.1 nanogram per l iter, international toxic equivalent basis (ng/L I-TEQ) for dioxin congeners in treated EDC/VCM wastew ater. Under the voluntary program, the VCP proposed to first analytically calculate a quantitati ve baseline of dioxin surface wastewater discharges from particip ating VCP sites through monitoring/reporting of

dioxin on both an international t oxic equivalent (I-TEQ) and “TM-17” basis. The VCP sites then proposed to achieve, as an initial target, maximu m dioxin mass discharges equivalent to process wastewater flow multiplied by 0.1 ng/L TEQ, on a coll ective, 12-facility basi s. For the sum of

4 http://www.cmaiglobal.com/1-4 discharges from the 12 EDC/VCM facilities, the maximum daily di scharge was thus proposed to be no more than 42 milligrams of dioxin per day (I-TEQ).

1.2 Objectives and Scope

This sampling program is intended to provide EPA with information to allow

determination of the current es timated dioxin discharges from treatment of CCH wastewater. When CCH wastewater is sampled prior to exis ting wastewater treatment, the estimated dioxin discharges will be modeled using percent removal information from similar wastewater treatment systems. The modeling accuracy wi ll be limited by the amount and type of dioxin removal data EPA has or obtains during the time period of the sampling program. This

information will allow EPA to further evaluate the appropriateness of the industry proposed maximum target of 42 mg/day I-TEQ and could l ead EPA to conclude that other dioxin control targets/options may be more appr opriate, including revision of one or more Effluent Limitations Guidelines (ELGs) for the CCH manufacturing segment.

Under this industry monitoring progra m, 12 VCM-manufacturing facilities will collect and analyze samples to characterize av erage and maximum dioxin discharges from CCH manufacturing sites. For stan d-alone CCH facilities that do not operate non-CCH manufacturing processes, facilities will colle ct samples from the effluent fr om wastewater treatment and, as agreed by EPA and the site, and consistent with the purposes of this program, other site outfalls

that contain treated or untreate d wastewaters. For integrated facilities at which CCH process wastewater is significantly diluted with other non-CCH wastewaters before treatment, facilities will sample streams representing all CCH processe s prior to entering the combined wastewater treatment system and may composite wastewater streams from each CCH process type in a flowweighted manner for analysis. EPA will use th e above sampling data, along with information collected under its own sampling effort for tr eatment performance, as well as relevant performance data from other sources, to estima te baseline annual a nd daily maximum dioxin discharge loads related to CCH process wastewaterat the 12 facilities. When possible, flowweighted composite samples from all relevant site outfalls will also be collected to estimate total site annual and maximum discharges of dioxin. When more than one outfall exists at a facility, a facility may decide to flow-weight composite multip le facility outfalls into a single sample. EPA1-5 will use the industry dioxin monitoring data to further evaluate industr y’s proposed voluntary program for VCM facilities, as well as other options for proceeding with dioxin discharge

controls.

Sampling episodes will consist of at l east four 24-hour composite samples, each collected at least one month apart. Secti on 3.0 contains additional information about the sampling procedures.

1.3 Facilities Included in Sampling Program

Industry’s proposed voluntary program includes the following 13 facilities:

• Dow, Freeport, TX;

• Dow, Plaquemine, LA;

• Formosa, Baton Rouge, LA

• Formosa, Point Comfort, TX;

• Georgia Gulf, Lake Charles, LA;

• Georgia Gulf, Plaquemine, LA;

• OxyVinyls, Deer Park, TX;

• OxyChem/OxyVinyls, Ingleside, TX;

• OxyVinyls, La Porte, TX;

• Shintech, Plaquemine, LA 5 ;

• PPG, Lake Charles, LA;

• Westlake, Calvert City, KY; and

• Westlake, Geismar, LA.

5 The Shintech Plaquemine, LA facility is scheduled to begin manufacturing operations in 2007, and is the only known U.S. VCM manufacturing facility not in cluded in this program at this time.2-1 2.0 O VERVIEW OF CCH M ANUFACTURING P ROCESSES AND W ASTEWATER T REATMENT

For the site-specific sampling plans, this section will include an overview of the CCH manufacturing processes at each facility and the configur ation of site outfalls. Sections will include descriptions of the manufactur ing process and wastewater streams for:

• Chlor-alkali manufacturing;

• EDC/VCM manufacturing;

• Other chlorinated hydrocarbon manufact uring using direct chlorination, oxychlorination, dehydrochlorinat ion, or hydrochlorination;

• PVC manufacturing; and

• Wastewater outfalls for all si te manufacturing activities.

This section will also describe the wastewater treatment operations for CCH process wastewater at each facility. EPA will note any non-CCH process wastewater streams that enter combined wastewater treatment syst ems. Block diagrams will be provided for the CCH manufacturing processes and wastewater treatment system, including locations of sampling points and those for all relevant site outfalls. Figure 2-1 shows an example diagram for the wastewater treatment system at a stand-alone CCH facility. Figure 2-2 shows an example diagram for a wastewater treatment system at an integrated facility. The recommended sampling points are noted on each example diagram. The s ite-specific plans will show the sampling points proposed by EPA for each facility and the sample s that can be composited for dioxin analysis. EPA will discuss and agree upon the proposed samp ling points with each facility prior to finalizing the site-specific plans.2-2Figure 2-1. Process Flow Diagramfor Stand-Alone CCH FacilityEDC/VCM plantWastewaterStripperPVC plantWastewaterStripperPrimaryClarifierBiological TreatmentFinal Equalization/NeutralizationEqualizationTankIncineratorScrubberVCM RecoveryWastewaterCentrifuge WastewaterNonprocess stormwaterQuenchAndwash tankwastewaterCausticScrubberBlowdownOutfall 001Sampling PointEDC/VCM plantWastewaterStripperPVC plantWastewaterStripperPrimaryClarifierBiological TreatmentFinal Equalization/NeutralizationEqualizationTankIncineratorScrubberVCM RecoveryWastewaterCentrifuge WastewaterNonprocess stormwaterQuenchAndwash tankwastewaterCausticScrubberBlowdownOutfall 001Sampling Point2-3Figure 2-2. Process Flow Diagramfor Integrated CCH FacilityEDC/VCM plantWastewaterStripperPVC plantWastewaterStripperPrimaryClarifierBiological TreatmentFinal Equalization/NeutralizationEqualizationTankIncineratorScrubberVCM RecoveryWastewaterCentrifuge WastewaterNonprocess stormwaterQuenchAndwash tankwastewaterCausticScrubberBlowdownOutfall 001Sampling PointMethanol PlantEDC/VCM plantWastewaterStripperPVC plantWastewaterStripperPrimaryClarifierBiological TreatmentFinal Equalization/NeutralizationEqualizationTankIncineratorScrubberVCM RecoveryWastewaterCentrifuge WastewaterNonprocess stormwaterQuenchAndwash tankwastewaterCausticScrubberBlowdownOutfall 001Sampling PointMethanol Plant3-1 3.0 S AMPLING A PPROACH

This section will provide sampling pro cedures, methods, and logistics to be followed during each of the multi-day sampling events at the 12 VCM facilities included in the proposed voluntary program. Specifically, this section will contain information regarding selection of sampling points, sampling methodol ogies, analytes, and sampling frequency and duration for each facility. All tables and fi gures appear at the end of this section.

3.1 Sampling Point Selection

Twelve VCM-manufacturing facilities plan to collect samples to assist EPA in characterizing the discharges of total suspe nded solids (TSS) and dioxin from CCH processes and from the sampled site. At least four sampling episodes will be conducted at each facility, consisting of 24-hour sample compos ite collection periods spaced at least one month apart, or as needed to capture all relevant site operating modes. Facilities should consider various operating modes in selecting the number a nd frequency of sampling episodes to ensure that a typical (or representative) annual average di oxin discharge can be estimated. For this sampling effort, sampling points for CCH process wastewater str eams prior to commingling with wastewater from non-CCH processes will be included where n ecessary. For facilitie s with CCH-dedicated wastewater treatment systems, the effluent fr om wastewater treatment will suffice. For integrated facilities that operate combined wa stewater treatment systems, sampling points to

characterize the influent to wastewater treatmen t from each CCH process at the facility will be necessary. In addition, samples of all relevant ou tfalls from the entire site will be identified. Facilities will collect at least four samples for all sampling points specified by EPA and agreed to by each facility in the site-specific sampling plans. Note that some facilities may not sample for TSS in some samples taken prior to wastewater treatment. Facilities are also encouraged to measure turbidity in outfall and final treatment system samples for potential correlation with dioxin levels. Details on how turbidity is meas ured should be provided to EPA by each facility.

Table 3-1 presents the guidelines for selection of sampling points for various

wastewater treatment and flow s cenarios at CCH facilities. Tabl es 3-1A and 3-1B are examples of the sample collection tables that EPA will pr ovide in the site-specific sampling plans. The3-2 tables describe the number of 24-hour composite samples to be collected, including quality assessment samples. Table 3-1A shows an exam ple sample collection table for a wastewater treatment system at a stand-alone CCH facility (see Figure 2-1). Table 3-1B shows an example sample collection table for a wastewater treatment system at an integrated facility (see Figure 2-2).

3.2 Analytical Method Requirements

Analytes that are included in this sampling effort include TSS and dioxin. Appendix A lists the individual c ongeners for the dioxin and furan analysis. Table 3-2 lists the sample container, sample volume, and preser vation requirements for Total Suspended Solids (TSS) and EPA Method 1613B (dioxin). TSS will be measured using Standard Method 2540D, which is the approved method referenced in 40 CFR 136.

Facility or contractor personnel will add chemical preservatives to samples according to method-specified protocol s, either upon sample collection ( i.e ., grab samples) or following preparation of sample fractions from the composite sample. In addition, facilities will

communicate with their laboratories to ensure th at proper preservation pr otocols are followed in the field. The type and amount of preservation us ed will be recorded on sample preservation log sheets (Figure 3-1). Preservation will be disc ontinued if the preserva tive added reaches 10 percent of the sample volume and the required pH is not achieved. Facilities will send copies of the completed preservation log sheets to EPA as pa rt of the final data package (see Section 4.4).

TSS and 1613B methods require that sample s be maintained at a temperature of

≤ 6 o C. To ensure adequate cooling of samples, f acility personnel will either place all samples on ice or store in a refrigerator promptly upon collec tion. In addition, the samples will be packed in
a manner to ensure that samples maintain a temperature of ≤ 6 ° C until they arrive at the designated analytical laboratories . Facilities will communicate with their laboratories to ensure that proper packing and shipping proce dures are followed in the field.

The analysis should follow method 1613B. The laboratory must ensure a proper separation of all target analytes from co -eluting and interferin g non-2378-PCDD/F-congeners3-3 which could cause significantly biased data. A second GC column (confirmation column) will be used to confirm target analytes. Since the particip ating facilities will use various laboratories, the

VCP will review initial results a nd verify comparability of results across all laboratories in the

program.

3.3 Sample Collection Methodology

To characterize the CCH wast ewater streams at the 12 f acilities, facility personnel may use varying methods of sample collection depending on the location of the sampling point and the nature of the sample flow and compositi on at each sampling point. Sampling points will fall under one of three categories:

• Automatic composites: Facilities may collect flow-weighted composites using automatic compositors for cont inuous streams that are located in plant areas that the facility has deem ed safe for operating an automatic compositor. If facility is unable to set up an automatic compositor for collecting flow-weighted composite, then time-weighted composites may be collected.

• Manual composites: Facilities may collect manual composites for continuous streams for sampling point s where it is not possible or recommended to sample using an auto matic compositor. The absence of a flow signal from an appropriate fl ow meter may necessitate using the manual composite method.

• Intermittent streams: Prior to sampling, the facility will provide information on the frequency and dura tion of flow, and coordinate with EPA to determine the appropriate collection frequency.

The remainder of this subsection descri bes sample collection techniques.

For all sampling locations, facility personnel will conduct the sampling episode using the site-specific sampling plan provided by EPA. Facility personnel will evaluate the specific hazards at each sampling point and de termine the appropriate personal protective equipment required.3-4 • Automatic Composites : Facility personnel will collect one automatic composite sample for each sampling point. Wherever possible, facilities will set up automatic compositors to co llect flow-weighted composites. If flow-weighted composites are not possible, then facilities may collect time-weighted automatic compos ites. The compositor will be programmed to collect enough wastew ater over the 24-hour period to provide adequate sample volume for analysis of TSS and dioxin (approximately three to four liters). At the end of the 24-hour period, facility personnel will divide the composite volume in to one 100mL or 1- L plastic jar for TSS testing and tw o 1-L amber glass jars for dioxin analysis. Samplers will then preserve these fractions following the guidelines in Table 3-2. The mixing of the composite sample before division into the sub-samples is a cr ucial step to achieve representative samples for the analysis.

• Manual Composites : Facility personnel wi ll collect one manual composite sample for each sampling point. Each composite will comprise six 500mL sample aliquots that will be collected approximately four hours apart. The composite container wi ll contain enough sample volume for analysis of TSS and dioxin (approximately three to four liters). At the end of the 24-hour period, facility personne l will divide the composite volume into one 100 mL or 1-L plastic jar for TSS and two 1-L amber glass jars for dioxin analysis. Samplers will th en preserve these fractions following the guidelines in Table 3-2. The mixi ng of the composite sample before division into the sub-samples is a cr ucial step to achieve representative samples for the analysis.

Facilities may opt to collect samples for dioxin as lab-composited grabs. For lab-composited grabs, facility personnel will fill six 500mL amber glass jars over the 24-hour collectio n period (i.e. one 500mL jar every four hours). Facility personnel will preser ve the contents of each 500mL jar immediately following sample collection. The six sample jars will remain unopened until receipt at the analyti cal laboratory. The laboratory will then composite the six 500mL samples for one analysis for the 24-hour compositing period. Facilities should communicate with th eir analytical laboratories to determine the pref erred method of compositing. The mixing of the composite sample before division into the sub-samples is a crucial step to achieve represen tative samples for the analysis.

3.4 Quality Assurance/Quality Control

Facilities will provide information to EPA regarding any company-specific quality assurance/quality control (QA/QC) procedures that will be followed during the sampling episode. The following is a discussion of the qual ity elements to be included in the sampling:3-5 • Sampling Process Design. Facilities will follow the sampling procedures described in the site-specific samp ling plan. Based on site-specific conditions, facilities may modify the sampling methodology of the sitespecific sampling plan. For exampl e, hazardous conditions created by volatile chemicals at CCH facilitie s may complicate sampling. All deviations from the site-specific sampli ng plan will be discussed with the EPA contact in a timely manner. Facil ities will document all deviations in the samplers’ field notes, which will be provided to EPA in the final data package (see Section 4.4).

• Sampling Methods. The site-specific sampling plan will describe the specific field sampling methodology for each sampling point in detail. Facilities will ensure that samplers have received adequate training to conduct the sampling activities descri bed in the site-specific plan. Training may include health and safe ty training, as well as training for proper handling, collection, mixing, and division of samples.

This sampling program is intended to characterize wastewater generationand treatment during normal, representative facility operations. If a nonroutine process event occurs during sampling, facility personnel will record the times and dates that the ev ents occur for futu re reference during the data analysis phase. Facility personnel will record information regarding the non-routine process event in the field notes (see Section 3.5). In the event of an non-routin e process event (i.e., outside the facility’s normal range of operations), facility personnel should discard the sample volume collected during the n on-routine process event. Sample collection should not recommence until normal operations resume.

Facility personnel will conduct all sampling activities in a manner to minimize potential contamination and cross-contamination of samples. If samples are collected with an automa tic compositor or with a peristaltic pump, facility personnel will install ne w tubing for each sampling point at the beginning of the collection peri od. Facility personnel will use noncontaminating pH indicator paper or a pH probe during field tests and preservation. A 1-liter glass jar will be filled during collection of each grab sample set for field measurements to ensure that thermometers and test kits do not contaminate the samples (see Section 3.5).

Facility personnel who collect samp les will wear proper new gloves at each sampling point to avoid exposure to pollutants and other chemical, physical, and biological hazards, and to prevent cross-contamination of samples. Samplers should use a new pa ir of gloves at each sampling point each time they collect a grab or composite sample. Samplers should use care not to touch the insides of bottles or lids/caps during sampling.

• Typical field sampling equipment that may be used for the sampling program includes: precleaned sample bottles and composite jars for chemical analyses, pH indicator paper, pH probes, thermometers, chlorine3-6 test kits, and sampling collection devices such as an automatic sampler. Table 3-2 provides information for the proper size and type of bottle to use for each sample. An automatic sample r is a pumping device that collects sample through FEP, Teflon, or othe r tubing at preset frequencies and durations and discharges collected sample into a sample container. EPA and facility personnel will together determine the specific field sampling devices to use for each sampling loca tion based on the specific sampling location logistics and EPA will describe these devices in the site-specific sampling plans.

• Sampling Frequency. Facilities will collect a minimum of four samples with at least one month between sample s to provide EPA with variation in process conditions. Facilities may c hoose to collect more than four samples, or may need to collect additional samples to cover all significant operating modes. The goal is for th e average sample results to be representative of normal operations over a typical 12-month period and is the best engineering estimate that can be reasonably obtained of an annual average dioxin loading from CCH ma nufacturing to surface waters. For a facility with CCH manufacturing units that are operated in only two modes ( e.g ., operating at normal production ra tes, or not operating), the best engineering estimate may be as simp le as a statistical average of four samples spaced out over time. For a more complex facility, sampling may have to be planned to capture di oxin loadings under each significant operating mode. For example, if th e EDC/VCM plant is normally down or running at reduced rates, while anothe r CCH process runs at full rates, then it may be best engineering j udgment to schedule a sample during each mode of operation and then we ight the resulting annual dioxin loading for the approximate time the f acility was operating in each mode. The technical staff at each facility w ill assess typical operations for each facility prior to initiating sample collection to determine the most representative set of samples needed to fully characterize discharges from CCH operations on site. For complex operating modes, as many as 9 samples (or more) may need to be collected to provide enough data to establish a typical annual dioxin loading using best engineering judgment.

Facilities may chose to stagger samp ling between locati ons to account for hydraulic residence time through treatment systems. To assist EPA in evaluating variability, the facility should provide:

— Its rationale for collecting numb er and frequency of samples.

— All of the data collected duri ng the study, because subsets are unlikely to represent the full range of measured values and associated variability. If a facility is concerned that some data are not representative, the facility s hould still provid e the data, and note its concerns, and iden tify any unusual condition.3-7 • Sampling Handling and Custody. Facilities will be responsible for developing a method to track samples from sample collection through creation of sub-samples, shipping, analys is at the laboratory, and receipt of analytical results. This includes id entification of samp les through sample ID numbers, labeling of sample bo ttles, organization of samples, and tracking of sample shipments.

• Analytical Methods . Table 3-2 at the end of this section lists the analytical methods that will be used to characterize CCH waste stream samples. All analytical methods are pub licly available. Table 3-2 lists the typical volume of sample to be co llected, typical container type, and typical preservation. EPA will use this information in combination with the site-specific sample conditions to specify the proper bottle type and preservation methods in each site-s pecific sampling plan. Facility personnel will use the sampling equipment and preservation methods described in the site-specific plan. In addition, faciliti es will provide information to EPA on the procedures for laboratory and data quality review in the final data package (see Section 4.4). As proposed by the VCP, both level 2 and level 4 data packages will be provided for each sample analyzed for dioxin (Industry pl ans to better define what is meant by Level 2 and 4 packages).

• Quality Control. EPA will require facilitie s to collect field quality control samples for this sampling effort . Facility personnel will follow all required QC measures for Standa rd Method 2540D (TSS) and EPA Method 1613B (dioxin). At least on e field duplicate and one equipment field blank (as described below) will be collected for analysis at each sampled site. Tables 3-1A and 3-1B show the number of QC volumes to be collected and specify the sampli ng points for which the QC volumes will be collected. EPA will coordinate with facilities to determine the appropriate sampling locations for QC fo r each site-specific plan. Facility personnel should coordinate with their analytical laboratory to determine whether additional QC volumes are needed.

— Equipment Field Blanks. The facility will collect equipment field blanks for any special equipment used during the sample collection, such as cooling coils, ISCO composite samplers, tubing, funnels, etc. The equipmen t field blank evaluates any contamination of the sample from either the equipment used or ambient conditions. To collect equi pment field blanks if no special equipment is used, the facility wi ll pour HPLC grade water directly into sample bottles or composite containers at the sample point location. If special equipment is used, the facility will pass HPLC grade water through all equipment us ed and into sample bottles at the sample point location. Multiple equipment field blanks may be required if different sampling techniques are used or if ambient conditions are expected to vary from sample point to sample point.3-8 The site-specific sampling plans will list the equipment field blanks to be collected at each site.

Purpose: To monitor any contamination from sampling techniques (equipment used or ambient conditions).

— Field Duplicates. Each site-specific sampling plan will specify a sampling point for duplicate sampling. EPA will assist the facility in selecting the duplicate point. At the duplicate sampling point, the facility will fill up twice the number of sampling containers per analysis type (using one composite for the original sample and a separate composite for the duplicate).

Purpose: To evaluate total m easurement precision and cover all the sources of data va riability, including sample collection, handling, preparation, and analysis.

• Instrument/Equipment Testing, Inspection, and Maintenance. Facility personnel will inspect the sampling devices prior to use to ensure that they are working properly. Facility pers onnel will conduct any required maintenance for the sampling equipment including equipment cleaning.

• Instrument/Equipment Calibration and Frequency. Whenever appropriate, facility personnel will us e disposable equipment to reduce the potential for contamination. If the f acility uses non-disposable sampling equipment, it will be cleaned and decontaminated prior to subsequent sampling. Field sampling equipment a nd decontamination procedures will be consistent with cleaning proce dures described in the analytical methods. Facility personnel will be responsible for ensuring that all equipment is maintained in good working condition and that decontamination procedures are proper ly followed. Any variations from the guidelines will be fully documented in field logs.

Facility personnel will cl ean the automatic sampling machines prior to use for the sampling episode and install new tubing on the sampling pump. Each automatic sampling machine will be dedicated to a specific sampling point for the entire sampling episode.

Facility personnel will be responsible for maintaining and repairing the test meters used for field measur ements to ensure proper operation. Samplers will follow applicable test kit calibration procedures specified by the manufacturer for any meters used.

• Inspection/Acceptance of Supplies and Consumables. Critical supplies and consumables for this sampling e ffort include those that come in contact with samples. These include sample bottles, preservation chemicals, blank water, and sampling equipment. Facility personnel will3-9 be responsible for purchasing required materials and in specting materials upon receipt to ensure they are usab le for this project (e.g., looking for breakage, evidence of tamper ing, or contamination).

Where practical, facility personnel will use new sampling equipment materials, such as gloves or tubing for automatic samplers that will be dedicated to a single sampling point for the each 24-hour collection period. If decontamination of non- disposable equipment is needed, facility personnel will describe the d econtamination procedures in the field notes (see Section 3.5).

• Non-direct Measurements. This sampling program will be augmented and complemented by the following t ypes of data generated and provided by the CCH facility:

— Process flow diagrams,

— Daily chemical production, and

— Daily flow rate through the treatment plant.

Loading values consist of both a diox in concentration and a wastewater flow, thus, flow meters should be checked for calibration during this project. Best engineering estimates of flow are needed in many cases, especially when sampling locations where no flow meters exist, e.g., at upstream raw wastewater locations. Pr ocedures to obtain best engineering estimates for flows should be part of the planning process early in the project, and be detailed in th e site-specific sampling plan.

In addition, facilities will provide relevant information on treatment techniques specific to the particular CCH stream being sampled. EPA and the facility will develop a checklist of limited engineering data to be collected during each sampling episode, which will be included in the sitespecific sampling plan (see Section 3.6).

• Project Data Management. Field documentation tools for this project will include preservation log sheets, fi eld log sheets, and engineering data sheets completed by facility personnel. The facility will review all field documentation and ensure that all re cords are legible and complete, and retain copies of the documents until the sampling episode is complete. At the end of the sampling episode, facil ities will provide all documentation to EPA as part of the final data package (see Section 4.4). EPA will retain as CBI all sample collection data for this sampling program, including site-specific sampling plans, field sa mpling log sheets, engineering data sheets, and preservation l og sheets, as requested.3-10 3.5 Field Measurements

During each 24-hour collection period, facili ty personnel will fill a 1-liter glass jar for field measurements. For manual composite sampling points that require sample collection every four hours, facility personne l will collect the field measurement sample at the same time as collecting one of the manual composite samples. Field measurements include temperature, pH,

and total residual chlorine. Faci lities may also provide turbid ity measurements on outfall and final treated effluent samples. Temperature a nd pH will be measured in the 1-liter glass jar immediately upon collection; total residual chlorine may be taken shortly thereafter, upon return to the sample staging area. Facility personnel will note the type of equipment used for field measurements on field sampling log sheets (Fi gure 3-2). Table 3-3 summarizes the field measurements, measurement procedure, and the measurement frequency.

The field sampling log sheets (Figure 3- 2) will be completed at each sampling point for each 24-hour sampling period. This sheet will record the sampling methodology, names of the samplers, sample collection times, wastewater flow rate at the time of sample collection, field measurements, and any notes and obs ervations. Facilities will send copies of the completed field sampling log sheets to EPA as pa rt of the final data package (see Section 4.4).

3.6 Engineering Data Collection

The goal of Engineering Data Collection is to support the determination that the CCH manufacturing units are operating in a norma l mode during the 24-hour compositing period for each sampling event and to document the operational criteria of the CCH operations that may

affect the wastewater characterist ics of each facility. This typi cally consists of the following type of information:

1. Daily production rate for the CCH pr ocess(es) as percent of nameplate capacity.

2. Operating mode, including units that are down which may impact D/F loading results.

3. Status of, and feed rates for, combustion units generating scrubber
wastewater.3-11 4. WWTP units operating and not opera ting (stand-alone facilities).

5. Any non-routine process event or maintenance events/conditions that may impact D/F loading results.

6. Composition of each sample point (i.e. % of each process water type making up the sample point).

7. Any of the above factors which have changed significantly in the 3-day period prior to sampling.

Engineering data collection at each facility will be site-specific and will be developed by EPA with facility staff to ensure capture of all major vari ables that could impact dioxin results. Figure 3-3 shows example engineer ing data sheets for chlor-alkali, EDC, PVC,
incinerators, and wastewater treatment. EPA w ill tailor the data sheets in Figure 3-3 for each site-specific plan. Dependi ng on the CCH manufacturing operati ons and the locations of the site-specific sampling points, EPA may not requ est all information shown in Figure 3-3. EPA may request detailed wastewater treatment sy stem operating information for an integrated facility that operates a combined wastewater treatment system in or der to be able to have enough information to model subsequent pollutant removals. Facilities will send copies of the completed engineering data sheets to EPA as part of the final da ta package (see Section 4.4).

3.7 Sample Shipment

Facilities should coordinate with their analytical labor atories and Department of Transportation (DOT) personnel to ensure that proper packing and sh ipping procedures are followed in the field. Facility personnel will identify samples that are hazardous and require shipment as dangerous goods. Facility pers onnel will follow all DOT and IATA guidelines when shipping these samples.3-12 Table 3-1. Guidelines for Selecting Sampling Points

Scenario Monitoring Location 1. Wastewater treatment pl ant treats wastewater for CCH processes only. (see Table 3-1A) Effluent from wast ewater treatment.

2. Wastewater treatment plant treats wastewater for CCH processes and non-CCH processes. (see Table 3-1B) Influent to wastewater treatment from all CCH processwastewater streams prior to commingling with nonCCH process wastewater. Individual sampling locations could include:

− Process wastewater stripper effluent;

− Absorber discharge (other than WAPC);

− WAPC streams;

− Dryer effluent;

− Product wash; or

− Process wastewater collection sump.

Samples can be flow-proportionally composited for dioxin analysis if they enter treatment at the same location and from same CCH process type. 3. Site has separate outfalls for different CCH processes. All relevant site outfalls to be monitored for total site discharge estimation. Monitor each outfall separately.

4. Site transfers discharg es of CCH wastewater to another facility for treatment. Monitor stream prior to discharge to neighboring facility and after any pret reatment, if applicable.

Table 3-1A. Analytes to be Collected by Sampling Point for Stand-Alone CCH Facility (Example)

Sampling Point Number (Type) Sampling Point Name TSS Dioxins and Furans SP-1 (AC) Effluent from wastewater treatment 4 +1 QC 4 SP-2 (AC) Final Outfall(s) 4 (minimum) 4 (minimum) SP-3 (AC) Field Duplicate 1 1 SP-4 (G) Equipment field blank 1 1 Total Number of Samples 10 +1 QC 10 Type: AC-Automatic composite (24 hours); G- One time grab; MC- Manual composite (6x per day) QC – Includes extra sample volume re quired to analyze matrix spikes and laboratory duplicates (see Table 3-2).3-13 Table 3-1B. Analytes to be Collected by Sa mpling Point for Integrat ed Facility (Example)

Sampling Point Number (Type) Sampling Point Name TSS Dioxins and Furans
SP-1 (MC) Centrifuge wastewater 4 4 SP-2 (MC) PVC plant wastewater stripper 4+1QC 4 SP-3 (MC) EDC/VCM plant wastewater stripper 4+1QC 4 SP-4 (AC) Caustic scrubber blowdown 4 4 SP-5 (AC) Final Outfall 4 4 SP-6 (AC) Field Duplicate 1 1 SP-7 (G) Equipment field blank 1 1 Total Number of Samples (can be flow-proportionally composited for dioxin analysis if they enter trea tment at same location and from same CCH process type) 22 +2QC 22

Type: AC-Automatic composite (24 hours); G- One time grab; MC- Manual composite (6x per day) QC – Includes extra sample volume re quired to analyze matrix spikes and laboratory duplicates (see Table 3-2).

Table 3-2. CCH Sampling Screen An alytes and Method Requirements

Method Number Parameter Procedure Sample Container Additional QC Containers On-Site Preservation (a) SM 2540D TSS Gravimetric 1 100 mL plastic jar None Cool to ≤ 6oC

EPA 1613B Dioxins and Furans HRGC/MS 2 1-L amber glassbottles with PTFElined cap None Store in the dark, Cool to ≤ 6 o C, If pH>9 H 2 SO 4 to pH 7-9, If total Cl 2 ≥ 0.1mg/L, add 80mg Na 2 S 2 O 3 per 1L H 2 O HRGC/MS: High resolution gas chromatography with mass spectrometry.

Table 3-3. Sampling Point Field Measurements

Field Measurements Tool Used Frequency Temperature Thermometer Once every day pH pH Probe or pH paper Once every day Total Chlorine Colorimetric test kit Once every day3-14 Sampling Episode

Preservation Chemicals – List St rength of Solution from Bottle

H 2 SO 4 ____________________ Na 2 S 2 O 3

____________________

Sample Number Analysis Date Chemical Initial pH Final pH Number of Drops

Figure 3-1. Sample Preservation Log Sheet3-15 Sampling Episode: Sampling Point:______________ Sample ID Numbers:___________

Automatic Composite 

##  Manual Composite 

##  Grab 

## 

Time of Compositing period, if applicable:
Start Time 

##  AM 

##  PM Start Date______________
End Time 

##  AM 

##  PM End Date ______________

Equipment Used for Sample Collection: Samplers’ Names: Equipment Used for Field Measurements:

Aliquot Time Wastewater Stream Flow rate (gpm)

Flow Meter (M) or Best Estimate (E) Temp C pH Total Residual Chlorine (mg/L) Amount (L)

1

2

3

4

5

6

Composite

Notes: (include any other observations for each aliquot)

Grab 1:

Grab 2:

Grab 3:

Grab 4:

Grab 5:

Grab 6:

Figure 3-2. Example Field Sampling Log Sheet3-16 Engineering Sheet Sampling Episode ______

Chlor-Alkali Plant

Date:

Average daily chlorine production (note units): _________

Flow Information for pH Tank (treatmen t system for chlor-alkali wastewater)

Wastewater Stream Average Daily Flowrate (note units) Range of Flowrates for Sampling Day

(note units) Basis for Flow Value (Flow meter or Best Estimate) Sulfate Purge Cooling Tower Blowdown
Other: Effluent from pH tank

List chemical additions to pH tank:

Additional Information: (Include any observations, n on-routine process events, or deviations from the sampling plan)

Figure 3-3. Example Engineering Data Sheet3-17 Engineering Sheet Sampling Episode ______

EDC Plant Wastewater Stripper

Date:

EDC Production Information Oxychlorination Reactor Direct Chlorination Reactor Reactor 1 Reactor 2 EDC Production (average daily, note units) Daily Reactor Temperature Range (note units)

Flow Information for EDC Wastewater Stripper

Process Unit/Wastewater Stream Average Daily Flowrate (note units) Range of Flowrates for Sampling Day (note units) Basis for Flow Value (Flow meter or Best Estimate)
Direct chlorination Oxychlorination Reactor 1 Oxychlorination Reactor 2
Process Area Stormwater
Other: Effluent from wastewater stripper

Additional Information: (Include any observations, n on-routine process events, or deviations from the sampling plan)

Figure 3-3. (Continued)3-18 Engineering Sheet Sampling Episode ______

Incinerator Caustic Scrubber

Date:

Incinerator Feed Streams (including percentages of each): (example: vent gases from EDC plant)

Incinerator/Scrubber Information

Parameter Flow Rate Basis for Flow or Feed Rate (Flow meter or Best Estimate) Incinerator Feed Rate Flowrate of caustic scrubber blowdown

Additional Information: (Include any observations, n on-routine process events, or deviations from the sampling plan)

Figure 3-3. (Continued)3-19 Engineering Sheet Sampling Episode ______

PVC Plant

Date:

Production Information for PVC Reactors
Reactor 1 Reactor 2 Reactor 3 Reactor 4 Reactor 5 Reactor 6 Production (average daily, note units) Average daily reactor temperature, note units

Flow Information for PVC Process

Process Unit/Wastewater Stream Average Daily Flowrate (note units) Range of Flowrates for Sampling Day (note units) Basis for Flow Value (Flow meter or Best Estimate) Centrifuge Water Wastewater Stripper
Reactor Wash Water
Total WW flow
Other:

Additional Information: (Include any observations, n on-routine process events, or deviations from the sampling plan)

Figure 3-3. (Continued)3-20 Engineering Sheet Sampling Episode ______

Combined Wastewater Treatment System

Date:

Flow Information for Combined Wastewater Treatment System

Process Unit/Wastewater Stream Average Daily Flowrate (note units) Range of Flowrates for Sampling Day

(note units) Basis for Flow Value (Flow meter or Best Estimate)
Influents to Wastewater Treatment EDC Wastewater Stripper
Incinerator Caustic Scrubber
Non CCH Process 1
Non CCH Process 2 Other: ______________

Effluent from Wastewater Treatment

Figure 3-3. (Continued)3-21 Engineering Sheet Sampling Episode ______

General Wastewater Treatment System Inform ation (Specify units for all parameters)

Biological Treatment Units Design capacity flowrate: Unit liquid depth: Volume of aeration zone: Air/oxygen flow to unit: Sludge retention time: MLSS concentration range: Design loading to treatment system (BOD or COD lbs/day): F/M ratio: Operating temperature: Return activated sludge concentration: Return activated sludge flow: MLSS removal rate: MLSS percent solids:

Clarifiers Design capacity flowrate: Residence time: Overflow rate (gpm): Target pH: Sludge removal rate: Percent solids of sludge:

Equalization Tanks Design capacity flowrate: Residence time: Overflow rate (gpm): Target pH: Sludge removal rate: Percent solids of sludge:

Filters Design capacity flowrate: Operating pressure: Cross-sectional flow rate: Method of regeneration (if applicable): Frequency of regeneration/backwash:

Figure 3-3. (Continued)4-1 4.0 S AMPLING A CTIVITIES

This section discusses the sampling pr eparation activities, sampling activities, analysis of results, and information to be in cluded in the final data package to EPA.

4.1 Sampling Preparation

For sample collection at the 12 VCM f acilities, the sampling team will consist entirely of facility personnel. EPA and ERG will not be present for the collection of the samples, unless they wish to be observers. Facility personnel will be res ponsible for all health and safety (H&S), sample collection, preservati on, and shipping activities on site.

Prior to the sampling episode, EPA will pr ovide a Site-Specific Sampling Plan to facility personnel. Facility personnel will revi ew the sampling plan and conduct a pre-sampling teleconference with EPA to review the sampling activities outlined in the plan.

4.2 Field Sampling Activities

During sampling, facility personnel will:

• Collect and preserve all sampling bo ttles according to Section 3.0 of the site-specific sampling plan;

• Cool samples to a temperature ≤ 6C prior to packing;

• Seal sample fractions and place them in shipping containers with ice for shipment; and

• Complete preservation log sheets, fiel d log sheets, and engineering data sheets and send to EPA with the fina l data package (see Section 4.4).4-2 4.3 Analysis of Results

Facility personnel will be responsible fo r coordinating with an alytical laboratories and overseeing the analysis of the results of the sampling episode. Facilities will compile the analytical results for each sampling day and pr ovide a summary electronic spreadsheet to EPA containing the following information:

• Dates of sample collection;

• Sampling point identifier;

• Analytical method used;

• Concentrations for TSS (mg/L) and for individual congeners of dioxins and furans in aqueous concentration units ( e.g ., pg/L);

• Concentrations units;

• Dilution factors for analysis; and

• Detection limits.

All dioxin analyses will be reporte d down to the laboratory and samp le specific detection limits. Values between the detection limit and the ML (min imum level) will be fl agged as being outside the validated range of the method.

The electronic spreadsheet will be sent to EPA as part of the final data package (see Section 4.4). In addition, fac ilities will keep copies of the Level 2 and Level 4 (dioxin only) data packages from the an alytical laboratories.

4.4 Final Data Package

No later than three months after the completion of the last sampling episode, facilities will send a final data package to EPA. EPA expects that facili ties will complete the sampling episodes within twelve months of receiv ing the final site-specific sampling plan. The package will contain:4-3 • An electronic spreadsheet showing the analytical results for all samples;

• Completed field log sheets;

• Completed preservation log sheets; and

• Completed engineering data sheets.

4.5 Site-Specific Logistics

Below is a list of industry, company, EPA, and ERG contacts.

Industry Contacts

Frank Borrelli Vinyl Institute (703) 741-5668 Frank_Borrelli@americanchemistry.com

Company Contacts

[To be determined in Site-Specific Sampling Plans]

EPA Contacts

Samantha Lewis Engineering and Analysis Division U.S. Environmental Protection Agency Ariel Rios Building 1200 Pennsylvania Avenue, NW (4303T) Room 6233F Washington, D.C. 20460 (202) 566-1058

Paul Shriner Engineering and Analysis Division U.S. Environmental Protection Agency Ariel Rios Building 1200 Pennsylvania Avenue, NW (4303T) Room 6233L Washington, D.C. 20460 (202) 566-10764-4 ERG Contacts

Lori Weiss 14555 Avion Parkway, Suite 200 Chantilly, VA 20151 (703) 633-1658

Meghan Camp 14555 Avion Parkway, Suite 200 Chantilly, VA 20151 (703) 633-16845-1 5.0 R EFERENCES

1. Vinyl Institute, U.S. “Vinyl Chloride Producers” (“VCP”) Proposed Voluntary Alternative to Dioxin/Fu ran (D/F) ELG for CCH Manufacturing Sites; EPA-HQOW-2005-0012, February 9, 2007

2. European Commission, Integrated Pollu tion Prevention and Control (IPCC), Reference Document on Best Available T echniques in the Large Volume Organic Chemical Industry , February 2003, http://eippcb.jrc.es/pages/FActivities.htm

.Appendix A

LIST OF DIOXIN AND FURAN ANALYTESA-1 Table A-1

List of Constituents for Analysis - Dioxin and Furan Analytes

CAS Number Common Name Technique Method

1746016 2,3,7,8-TETRACHLORODIBENZO- P-DIOXIN HRGCMS 1613B 40321764 1,2,3,7,8-PENTACHLORODIBENZO- P-DIOXIN HRGCMS 1613B 39227286 1,2,3,4,7,8-HEXACHLORODIBENZO- P-DIOXIN HRGCMS 1613B 57653857 1,2,3,6,7,8-HEXACHLORODIBENZO- P-DIOXIN HRGCMS 1613B 19408743 1,2,3,7,8,9-HEXACHLORODIBENZO- P-DIOXIN HRGCMS 1613B 35822469 1,2,3,4,6,7,8-HEPTACHLORODIBENZO -P-DIOXIN HRGCMS 1613B 3268879 OCTACHLORODIBENZO-P- DIOXIN HRGCMS 1613B

51207319 2,3,7,8-TETRACHLORODIBENZOFURAN HRGCMS 1613B 57117416 1,2,3,7,8-PENTACHLORODIBENZ OFURAN HRGCMS 1613B 57117314 2,3,4,7,8-PENTACHLORODIBENZ OFURAN HRGCMS 1613B 70648269 1,2,3,4,7,8-HEXACHLORODIBENZ OFURAN HRGCMS 1613B 57117449 1,2,3,6,7,8-HEXACHLORODIBENZ OFURAN HRGCMS 1613B 60851345 2,3,4,6,7,8-HEXACHLORODIBENZ OFURAN HRGCMS 1613B 72918219 1,2,3,7,8,9-HEXACHLORODIBENZ OFURAN HRGCMS 1613B 67562394 1,2,3,4,6,7,8-HEPTACHLORODIBENZOFURAN HRGCMS 1613B 55673897 1,2,3,4,7,8,9-HEPTACHLORODIBENZOFURAN HRGCMS 1613B 39001020 OCTACHLORODIBENZOF URAN HRGCMS 1613B

17 DIOXIN ANALYTES