DRAFT 

# Generic Sampling and Analysis Plan for Steam Electric Power Plants

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

February 24, 2010

EPA Contract No. 68-C-02-095 Work Assignment 7-29DRAFT i TABLE OF CONTENTS

Page

1.0 I NTRODUCTION ................................................................................................................ 1-1 1.1 Background ........................................................................................................... 1-1 1.2 Objectives and Scope ............................................................................................ 1-2 1.3 Plant Selection ...................................................................................................... 1-3

2.0 S AMPLING P ROCEDURES .................................................................................................. 2-1 2.1 Sampling Point Selection ...................................................................................... 2-1 2.1.1 FGD Scrubber Purge .............................................................................. 2-1 2.1.2 Mid-Point of FGD Wastewater Treatment ............................................. 2-3 2.1.3 Effluent from FGD Wast ewater Treatment ............................................ 2-3 2.2 Analyte Selection .................................................................................................. 2-4 2.3 Sample Fractions, Bottle Sets, and Sample Collection ......................................... 2-5 2.4 Sample Collection Methodology .......................................................................... 2-5 2.4.1 Composite Sample Collection ................................................................ 2-7 2.4.2 Grab Sample Collection ....................................................................... 2-13 2.4.2.1 Grab Sample Collection from Tap ....................................................... 2-13 2.4.2.2 Grab Sample Collection from Basin (or Tank) .................................... 2-18 2.5 Preservation, Shipping, and Analysis ................................................................. 2-21 2.6 Field Measurements and Engineering Data Collection ...................................... 2-22 2.7 Sample Labeling ................................................................................................. 2-23 2.8 Traffic Reports .................................................................................................... 2-24 2.9 Quality Assurance/Quality Control .................................................................... 2-24 2.10 Sample Splitting .................................................................................................. 2-26

3.0 S AMPLING A CTIVITIES ..................................................................................................... 3-1 3.1 Sampling Team Organization ............................................................................... 3-1 3.2 Pre-Sampling Preparation ..................................................................................... 3-1 3.3 Field Sampling Activities ..................................................................................... 3-2 3.4 Standard Logistics ................................................................................................. 3-3 3.4.1 Plant Contacts ......................................................................................... 3-3 3.4.2 EPA Contacts .......................................................................................... 3-3 3.4.3 Analytical Laboratories .......................................................................... 3-4 3.4.4 ERG Contacts ......................................................................................... 3-4 3.4.5 Freight Forwarders ................................................................................. 3-4

4.0 S AMPLE S HIPMENT .......................................................................................................... 4-1 4.1 Sample Set Preparation ......................................................................................... 4-1 4.2 Sample Packing ..................................................................................................... 4-2

5.0 R EFERENCES .................................................................................................................... 5-1DRAFT ii LIST OF TABLES

Page

2-1 Sample Collection at St eam Electric Plants ....................................................................... 2-27

2-3 Summary of Sample Container and Planned Preservation ................................................ 2-29

2-4 Sampling Point Field Measurements ................................................................................. 2-30DRAFT iii LIST OF FIGURES

Page

2-1 Sample Preservation Log Sheet ......................................................................................... 2-3 1

2-2 Field Sampling Log Sheet .................................................................................................. 2-32

2-3 Engineering Data Collection Sheet (Page 1 of 3) .............................................................. 2-33

2-4 Engineering Data Collection Sheet (Page 2 of 2) .............................................................. 2-34

2-5 Engineering Data Collection Sheet (Page 3 of 3) .............................................................. 2-35

2-6 Example SCC Traffic Report ............................................................................................. 2- 36DRAFT 1-1 

### 1.0 I NTRODUCTION

The Engineering and Analysis Divisi on (EAD) of the U.S. Environmental Protection Agency (EPA) is planning to conduc t a sampling program of up to seven steam electric power plants to 1) obt ain wastewater characterization data and 2) obt ain wastewater treatment technology performance data. EPA will use these data in combination with other industry-supplied data to evaluate wastewater di scharges resulting from steam electric generating plants and to evaluate technology options for the handling and trea tment of these wastewaters. This “generic” sampling plan provides general sampling procedures and methods to be followed when conducting sampling activities. Sampling will be performed eith er by EPA’s technical
contractor, Eastern Research Gr oup, Inc. (ERG) or by industry re presentatives. This document, in combination with plant-specific sampling plans, is intended to serve as a guide to the field sampling crew. The plan also provides a review mechanism for EPA personnel, and a source of procedural information for plant personnel.

1.1 Background

During EPA’s recently completed detailed study of the steam electric industry,

EPA identified metals and certain other constituen ts present in the wastewater discharges from steam electric power plants are c ontributing the majority of the t oxic loadings for the industry. Additionally, EPA determined that one of the wa ste streams contributing the majority of these toxic loadings are associated with wet flue ga s desulfurization (FGD) systems present at coalfired power plants.

This sampling and analysis plan (SAP) will focus on characterizing treatment system discharges from coal-fired steam electric power plants. For a description of the steam electric process and the wastewat ers generated during the operation of a coal-fired steam electric power plant, see Chapters 3 and 4 of the Steam Electric Power Generating Point Source
Category: Final Detailed Study Report [1].DRAFT 1-2 1.2 Objectives and Scope

EPA is preparing to collect and analy ze samples to characterize wastewater streams generated at coal-fired steam electric power plants. This SAP describes the approach EPA will use to collect and analyze samples to characterize untreated FGD scrubber purge and treated FGD wastewater from the following t ypes of FGD wastewater treatment systems:

 Chemical precipitation: Physical/che mical precipitation for heavy metals removal using hydroxide or a combination of hydroxide and sulfide precipitation; and

 Biological: Biological treatment specifi cally designed for metals removal.

Generally, the analytical results colle cted during this sampling program will support EPA in answering the following key questions:

 What are the characteristics (i.e ., pollutants present, pollutant concentrations, flow rate/volume) of untreated FGD scrubber purge wastewater?

 What is the performance (e.g., efflue nt pollutant concentrations) of technologies for the treatment of FGD scrubber purge wastewater?

 What are the average effluent concen trations for pollutants present in treated FGD wastewater?

 What are the pollutant loadings a ssociated with discharges of FGD wastewater following treatment?

EPA will conduct one-day pre-sampling site visits at the plants selected for the sampling program; however, if EPA previously visi ted the plant as part of the detailed study, a site visit may not be necessary. The objectiv es of the pre-sampling site visits are to:

 Gather general information about the plant’s operations, including exisiting sampling data and results;

 Gather process-specific information;

 Gather information on polluti on prevention and wastewater treatment/operations;

 Gather plant-specific information to tailor sampling plans; and

 Select and evaluate pot ential sampling points.DRAFT 1-3 The sampling program will consist of four-day sampling episodes at up to seven selected plants. The sampling will characterize the wastewaters generated by wet FGD scrubbers and the treatment performance of the systems used to treat the FGD scrubber purge wastewaters. EPA will also collect field quality control (QC) samples consisting of bottle blanks, field blanks, equipment blanks, and duplicate samples, a nd laboratory QC samples used for matrix spike/matrix spike duplicate analyses.

EPA’s sampling program will provide data to perform an engineering assessment of the design, operation, and perf ormance of treatment systems at steam electric power plants. Specifically, EPA will collect information regardi ng system design and day-to-day operation.

1.3 Plant Selection

EPA expects to select up to seven coal-f ired steam electric plants for wastewater sampling. EPA will base the plant selection on the process configur ations and characteristics of the plants. The following primary criteria will be used to select the plants for the sampling

program:

 Coal-fired power plant : EPA expects that all of the plants selected for the sampling program will be coal-fired pl ants because the waste streams of interest for the sampling program data objectives are associated with coalfired power plants.

 Wet FGD system : EPA will evaluate wastewaters generated from wet FGD systems and the treatment of thes e wastewaters. EPA will consider the following selection criteria regarding FGD systems:

o Type of FGD wastewater treatment system : The primary factor for selection is the type of wastewat er treatment system being operated for the treatment of FGD wastewater . EPA plans to select plants operating the following types of wa stewater treatment systems:

 Chemical precipitation – EPA will sample up to five plants operating chemical precipitation systems.

 Biological – EPA will sample up to two plants operating biological systems that use an anaerobic/anoxic biological system specifically designed for the treatment of nitrates and selenium.DRAFT 1-4 o Age of FGD wastewater treatment system : EPA does not intend to collect samples from a wastewater treatment system that has not reached steady state operation be cause the performance of the system may not be optimized. Generally, EPA plans to sample FGD wastewater treatment systems that have been operating for at least six months, or where data ha ve shown the system to be at steady state.

o Type of FGD system : EPA will consider the type of FGD system operated by the plant (e.g., lim estone forced oxidation, lime inhibited oxidation) when selecting plants for sampling. Although EPA may sample different types of FGD systems, the plants operating the types of FGD wast ewater treatment system of interest for the rulemaking are like ly to operate limestone forced oxidation systems. The limestone forced oxidation system has the capability of producing wallboard-grade gypsum, but it typically requires a purge stream that needs to be treated prior to discharge. Plants operating most other types of FGD systems either reuse the FGD water stream or treat it in a settling pond (often commingled with other plant wastewaters, such as ash sluice water).

 NO x controls : EPA will consider whether the plants operate a selective catalytic reduction (SCR) system or a selective non- catalytic reduction (SNCR) system when selecting pl ants for sampling. Although these NO x control systems do not generate a specific wastewater stream, their operation can impact the FGD wastew ater characteristics.

 Power load cycling : EPA will consider a plant’s load cycling (i.e., baseload, cycling, peaking). EPA expect s that most of the plants selected for sampling will be baseload plants; however, EPA will consider sampling a cycling plant. EPA does not believe that there are any coalfired peaking plants.

 Type of Coal: EPA will consider the type of coal that the plant burns. EPA plans to select plants that burn different types of coal. EPA expects to sample at least two different types of coal.

EPA will consider the following charact eristics as secondary factors to be considered in the selection of plants. Although th ese are not primary criter ia for plant selection, these characteristics may be used as a determining factor where warranted.

 Continuous versus batch operation of FGD wastewater treatment system (e.g., five days per week vers us seven days per week);DRAFT 1-5  Use of advanced mercury control system and configuration;

 Type of boiler;

 Age of boiler and FGD unit (i.e., time of last upgrade);

 Source of lime/limestone used in wet FGD system;

 Plant location; and

 Other plant conditions that may aff ect wastewater characteristics or sample collection, such as whether targ et waste streams are segregated or commingled.DRAFT 2-1 

### 2.0 S AMPLING 

### P ROCEDURES

This section discusses th e general sampling procedures to be followed during all sampling activities. This section also provides th e necessary information to plan for the logistics of potential sampling activities.

2.1 Sampling Point Selection

In general, EPA plans to collect representa tive samples at the influent and effluent

of the FGD wastewater treatment system that is operating und er steady-state conditions. In addition, EPA may collect samples at a mid-point of the FGD treatment system (e.g., effluent from chemical precipitation system prior to biol ogical treatment). EPA plans to collect 24-hour composite samples at the mid-point and effluent sampling points and grab samples at the influent sampling points of the wastewater treatment syst em. The proposed sampling points were selected by EPA to answer the questions that are th e objective of the sampling program, which are presented in Section 1.2. The specific sampli ng points and locations, samples, and list of parameters selected for each plant will be desc ribed in the plant-specific sampling plans.

2.1.1 FGD Scrubber Purge

EPA plans to collect samples of untreat ed FGD scrubber purge wastewater. The scrubber blowdown generated directly from the FGD system is expected to contain large amounts of solids (i.e., calcium sulfite or calcium sulfate (gypsum)); therefore, EPA will collect
the FGD wastewater after initial solids removal, which represents the FGD scrubber purge waste

stream.

Many of the FGD wastewater treatment systems that EPA has observed thus far contain a surge tank (or equalizati on tank) prior to the wastewater entering the treatment system.

For some of these treatm ent systems, FGD scrubber purge is the only waste stream that enters the surge tank; however, for other systems, th e FGD scrubber purge may be combined with recycle streams from the treatment system (e .g., filter backwash) within the surge tank. EPA will collect the FGD scrubber purge from the following locations depending on the set up of the influent to the FGD wastewater treatment system:DRAFT 2-2  No surge tank prior to treatment system: EPA will collect a sample of the FGD scrubber purge stream prior to it entering the fi rst-stage of the treatment system;

 Surge tank with only FGD scrubber purge prior to treatment system: EPA will collect a sample of the FGD scr ubber purge either directly from the surge tank or from the effluent stream leaving the surge tank; and

 Surge tank with other recycle streams prior to treatment system: EPA will collect a sample of the FGD scrubber purge prior to it entering the surge tank.

EPA will collect grab samples of th e FGD scrubber purge. Because of the intermittent nature of the FGD scrubber purge waste stream, EPA anticipates working closely with the plants to determine the expected dura tion and frequency of purging the FGD wastewater to the treatment system. Based on this informa tion, EPA will determine when to collect the grab samples.

EPA expects that the wastewater enteri ng the FGD treatment system will contain high concentrations of certain pa rameters, including suspended a nd dissolved solids, chlorides, sulfates, and various cations. The high solids co ntent of the samples may make it difficult to filter the samples for the dissolved metals analyses ; therefore, EPA plans to allow the sample to settle for one hour prior to running the sample through the filter.

Due to the high suspended solids content (on the order of 1-5 percent) of the samples collected at the influent to the FGD wa stewater treatment syst em, EPA may analyze the samples as bi-phasic samples. If the suspended solids content of the sample is greater than one percent, then the laboratory will separate the aqueous portion of the sample from the solid portion of the sample and analyze both for the an alyte of interest. In this instance, Group I (chloride and sulfate only), Group II (ammonia as n itrogen, nitrate/nitrite as nitrogen, and total phosphorus only), and total metals (including merc ury, but not hexavalent chromium because it is filtered in the field during sample collection) samples will be analyzed as bi-phasic samples. Group I (TSS and TDS only), Group II (COD only), BOD 5 , hexavalent chromium, and dissolved metals (including mercury) samples will not be analyzed as bi-phasic samples. Scrubber purgeDRAFT 2-3 samples with less than one percent suspended so lids will not require bi -phasic separation and analysis.

2.1.2 Intermediate Point of FGD Wastewater Treatment

EPA may collect samples at an interm ediate point of the FGD wastewater treatment system. EPA expects to collect this samp le after some initial treatment steps that could represent a wastewater treatment system of intere st for the program. For example, some plants operate a chemical precipitation sy stem followed by a biological trea tment system. For this type of treatment system, EPA may consider collec ting a sample after the chemical precipitation system to represent the effec tiveness of the chemical precip itation portion of the system.

EPA expects that these samples will be coll ected either after a clarification step or after a filtration system, and will be collected from the effluent stream leaving the particular system before it enters the next stage of the treatment process. EPA will collect 24-hour composite samples of the intermediate point of the FGD wastewater treatment system, preferably using an automatic compositor.

EPA expects that the wastewater at an intermediate point in the FGD treatment system will contain high concentrations of certain parameters, such as chlorides, sulfates, and various cations. The suspended solids content of th e sample is expected to be lower than at the influent; however, it may still be difficult to filter the samples for the dissolved metals analyses.

2.1.3 Effluent from FGD Wastewater Treatment

EPA plans to collect samples of the effl uent from the FGD wa stewater treatment system. EPA expects to collect this sample fr om the waste stream that exits the wastewater treatment system; however, if EPA is unable to co llect the sample from this location, then EPA will select a point within the syst em to represent the effluent. For example, if the wastewater is collected in an effluent tank pr ior to being transferred to addi tional treatment (e.g., an ash pond) and a sample cannot be collected from the wastew ater piping leading to the additional treatment system, then it may be necessary to collect an e ffluent sample directly from the effluent tank.DRAFT 2-4 EPA does not expect to collect the infl uent and effluent samples from the FGD treatment system as “paired” samples because th e primary objective of the sampling program is

to collect effluent data to esta blish effluent limitations for the waste stream. Additionally, these treatment systems can have long residence times and therefore, could ex tend the amount of time required for EPA to be on site, which is a burde n for the plant and unnecessary to achieve the sampling objectives.

EPA expects that the wastewater at the effluent from the FGD treatment system will still contain high concentrations of certain parameters, such as chlorides, sulfates, and various cations. The suspended solids content of the sample should be minimal (less than 0.01 percent) and should not present any issues for filtering the sample fo r dissolved metals analyses.

2.2 Analyte Selection

Analytes that will be included in this EPA/EAD sampling program include those in the following classes of pollutants:

 Classicals:

— Biochemical oxygen demand, 5-day (BOD 5 ),

— Chemical oxygen demand (COD)

— Total suspended solids (TSS),

— Total dissolved solids (TDS),

— Sulfate,

— Chloride,

— Total Kjeldahl nitrogen (TKN),

— Ammonia as nitrogen,

— Nitrate/nitrite as nitrogen,

— Total phosphorus,

— Total cyanide;

 Total metals:

— Aluminum, antimony, arsenic, barium, beryllium, boron, cadmium, calcium, chromium, cobalt, copper, iron, lead, magnesium, manganese, mercury, molybdenum, nickel, selenium, silver, sodium, thallium, tin, titanium, vanadium, and zinc.

 Dissolved metals

— Same parameters as listed for total metals, plus hexavalent chromium.DRAFT 2-5 The analytes selected for analysis refl ect the current understanding of coal-fired power plant FGD wastewaters, in cluding contributions from coal , scrubber sorb ents, treatment chemicals, and other sources. Table 2-1 lists th e potential analytes for each sampling point and Table 2-2 lists the analytical methods that will be used. In addition to these analytes, the sampling crew will conduct field measurements at all sampling points (see Section 2.6). The plant-specific sampling plans will specify the list of parameters and collection frequency for each sampling point.

2.3 Sample Fractions, Bottle Sets, and Sample Collection

Samples are collected as a se ries of “fractions” or bottles designated for particular analyses requiring the same preservation. A t ypical, comprehensive sample set consists of sample fractions for all pollutant classes listed in Section 2.2. Note that some sample fractions

will be collected in the same sa mple bottle, such as Group I (TSS, TDS, sulfate, and chloride) and Group II (ammonia as nitrogen, COD, nitrate/nitrite, TKN, a nd total phosphorus). Table 2-3 presents a summary of the parameters, bottle types, sample volume, and planned on-site preservation requirements.

Sample containers and bottles will be purchased pre-cleaned and certified and will not require rinsing with sample. The sample bo ttles for the metals analyses will be cleaned according to EPA Method 1669.

2.4 Sample Collection Methodology

To characterize the various waste streams expected to be sampled during the sampling program, the samplers may employ varying methods of sample collection depending on the sampling point, pollutant parameters, and th e nature of the sample flow and composition at each sampling point. This se ction provides a general descrip tion of the anticipated sample collection techniques. Plant-specific sampling pl ans will contain detailed information regarding specific sampling points and locations, sa mpling methodologies, and analytes.DRAFT 2-6 In general, samplers will work in team s of at least two to ensure that proper sampling techniques are followed and adequate notes are taken at each sampling location. Samplers will wear disposable gloves, Tyve k® suits, masks (when sampling for mercury by EPA Method 1631E), steel-toed boots, and safety eyewear, and will observe precautions while collecting samples, remaining awar e of his/her surroundings. Note that the use of masks is to prevent contamination of the mercury samples and not for respiratory protection. The plantspecific sampling plans will identify any sampli ng points that require additional precautions.

Samplers will take care not to touch the insides of bottles or lids/caps during
sampling. Samples that require cooling to ≤ 6  C for preservation will be cooled immediately in

an ice-water bath to ≤ 6  C and then placed into coolers containing bagged ice to maintain a
sample temperature of ≤ 6  C throughout sample storage, shipment , and receipt at the analytical

laboratories.

Discharge practices vary from plant to pl ant and process to process. For example,

some processes may generate wastewater co ntinuously, while others may only generate wastewater when parameters reach a certain predetermined threshold and require blowdown from the process. Thus, the plant-specific sa mpling plan will outline the sample collection methodology that EPA plans to implement at ea ch sampling point at a particular plant.

EPA will collect 24-hour composite samples at the intermediate point and effluent

of the FGD wastewater treatment system sampling points and grab samples at the influent sampling point during the sampling episodes. Additionally, EPA will collect samples over four consecutive 24-hour periods. Each sampling point will be collected each day; therefore, EPA will collect four samples for each sampling point . ERG will follow protocols described in EPA Method 1669 to collect metal sample fractions . All sampling equipment (e.g., tubing) and sample bottles will be cleaned according to the procedures described in EPA Method 1669. Samplers will use “clean hands / dirty hands” sa mple collection techniques when collecting metal sample fractions, as described in EP A Method 1669. In addition to the differences between collecting grab or composite samples, ERG will also use two different techniques to collect samples from steam electric plants based on the location of the sampling point: collectionDRAFT 2-7 from a tank or basin and collection from a sample tap. Specific instructions for the potential sampling techniques are described below.

2.4.1 Composite Sample Collection

The preferred approach for collecting the composite samples will use two automatic compositors which will be programmed to collect individual sample volumes into two large containers (e.g., two 20-liter HPDE containers). To collect sufficient sample volume, ERG will calculate the total volume required for ERG sample collection as well as plant split sample collection and also add additional volume for pu rging tubing and contingencies. The volume will then be programmed to be collected in one-hour intervals during the 24-hour composite period. Following the composite period, ERG will pour and/or pump-off the specific sample volumes into the individual sample containers.

ERG will use one automatic compositor to collect sample volume for the metals analyses and another automatic compositor to co llect sample volume for all classical analytes (i.e., BOD 5 , Group I, and Group II).

ERG’s preferred approach is to collect sample volume from a basin (or tank), where the composite samplers will be located outsi de, positioned near the edge of the basin. If the collection point is a sample tap, the compos ite samplers may be outside, depending on the location of the tap, and will be near wastewat er piping and equipment. ERG may have to engineer a basin that draws a slip stream from a sample tap if the collection point is located at pressurized piping. This basin would be level controlled and would draw volume continuously into the basin, with the overflow entering the plan ts sumps. In this case, ERG would set up the composite samplers to draw volume from the engineered basin. The field sampling personnel will use care when setting up the sample poi nt to avoid any contamination from the surroundings. The sampling equipment will consist of the following:

 Colorless, electronic-gr ade, non-nitrile gloves;

 Peristaltic pump (automatic compositor – battery powered);

 Large composite containers (e.g., 20-liter containers);

 Funnel;DRAFT 2-8  “Y” splitter;

 Teflon® tubing;

 Silicone tubing;

 0.45 um filter;

 Cleanbox;

 Tyvek® suits (for metals samples);

 Masks (for mercury samples); and

 Sample containers.

All metals sampling equipment will be specially-cleaned according to the procedures described in EPA Method 1669. ER G will follow protocols described in EPA Method 1669 to collect metal sample fractions. Two or more ERG samplers (“clean hands” and “dirty hands”) will follow the pr otocols described in the steps be low to set up the sampling point, collect the field blank samples, a nd collect wastewater samples. Th is section describes the set up of the sample point and collection of the EPA samples 1

.

1. Samplers remove the bags containing th e gloves and HDPE plastic wrap from the coolers or storage containers in which th ey are packed. Samplers identify which coolers or boxes contain the double-bagge d composite contai ners, pre-cleaned tubing, blank water, and cleanbox.

2. Both samplers put on Tyvek® suits, mask s, and gloves. “Dirty hands” covers work surfaces (ground or table) with HDPE plastic wrap and places the doublebagged composite containers within easy access on the covered surface.

3. “Dirty hands” opens the outer bag of the cleanbox and “clean hands” opens the clear inner bag. “Clean hands” places the cleanbox at the point of sample collection. “Clean hands” opens the cl eanbox and secures it ope n with the clips located inside the box.

4. “Dirty hands” opens up the peristaltic pump portion of the automatic compositor so the tubing can be added. “Dirty hands ” opens the outer bag containing a length of pre-cleaned Teflon® tubing attached to a 4-foot length of pre-cleaned silicone tubing, if sampling from a ba sin (or a length of pre-cl eaned silicone tubing if sampling from a sample tap). “Clean ha nds” takes the inner bag containing the tubing and moves it into th e cleanbox. “Clean hands” opens the inner bag and removes the tubing. “Clean hands” places a clean plastic bag over the end of the Teflon® and silicone tubing.

1 For the sample collection, EPA assumes that samples will be split with the plant (or the plant’s representative) and therefore, the sample set-up describes equipment needed fo r split samples. However, EPA is not responsible for the collection of the split samples collected by the plant and therefore, the collection of their samples is not described.DRAFT 2-9 5. “Dirty hands” threads the silicone tubing through the peristaltic pump portion of the automatic compositor.

6. Both samplers change gloves.

7. “Dirty hands” opens the outer bag of th e mercury and metals field blank water and the field blank composite container. “Clean hands ” opens the inner bag for the field blank water, unscrews the lid and places it in the inner bag. “Clean hands” then places the Teflon® end of the tubing into the blank water. “Clean hands” also opens the inner bag for th e field blank composite container and loosens the lid. “Clean hands” holds th e silicone tubing with the plastic bag covering the end out of the cleanbox and ove r a bucket and “dirty hands” operates the pump to pump blank water through th e tubing. After the tubing has been purged with sufficient volume, “clean ha nds” holds the silicone tubing at the mouth of the field blank composite container and fills the composite container with enough field blank water for the colle ction of the total and dissolved mercury and metals field blank samples collected for the specific sampling point. “Dirty hands” stops the pump. “Clean hands” plac es the plastic bag over the end of the silicone tubing, replaces the lid on the fiel d blank composite container, places the silicone tubing back in the cleanbox, and closes the inner ba g on the field blank composite container. “Dirty hands” cl oses the outer bag of the field blank composite container.

8. Both samplers work together to move the sampling tubing, automatic compositor, and composite containers into position for the sample collection. Samplers will ensure that the tubing will stay in pl ace during the 24-hour sample collection period.

9. “Dirty hands” changes gloves.

10. “Clean hands” holds the e nd of the silicone tubing outside the cleanbox over a bucket, with the plastic bag still covering the end of the tubing . “Dirty hands” operates the pump to purge the tu bing for a minimu m of 2 minutes.

11. Samplers fill a 1-L jar for the field measur ements. The samplers will give the jar to another sampling team member to measure the temperature and pH.

12. “Dirty hands” programs the automatic co mpositor to collect the 20 liters of sample over a 24-hour time period in one- hour intervals (i.e., collect 800 mL of sample every hour). “Dirty hands” calib rates the compositor to ensure that 800 mL is being collected for each individual grab.

13. “Dirty hands” opens the outer bag of th e large composite container. “Clean hands” opens the inner bag and connects the silicone tubing to the port on the composite container, securing the connec tion with a cable tie. “Clean hands” closes the inner bag around the composite bottle, and “dirty hands” closes the outer bag.DRAFT 2-10 14. Samplers repeat steps 1-13 to set up the automatic compositor for the conventional analyses (skipping step 7). Samplers will use another composite container. The samplers will put the classi cals composite container in ice to keep the samples cold during compositing time period.

15. Samplers collect a total cyanide grab sa mple using a bottle dipper. NOTE: if sample collection is from a tap, the samplers will need a third tap to allow for the collection of total cyanide and field meas urements. The samplers will attach the bottle to the bottle dipper a nd dip the bottle directly into the tank or basin.

16. The samplers will collect field measurements and total cyanide samples every six hours during the compositing time period, which will result in a total of four total cyanide samples for each day of sampling. The four grab samples will be composited by the laboratory.

17. At the end of the sampling period, “dirty hands” stops each of the automatic compositors and opens the outer bag of each composite container. For each container, “clean hands” detaches the us ed tubing from the composite container and covers the port with a lid or small pl astic bag. Then samplers transport each of the composite containers, including the field blank composite container, to the pump–off area to pump off the sample s into the specified containers.

18. The samplers then repeat steps 1 through 17 to set up th e composite containers for the next day of sample collection.

After the composite samples have been collected, the sampling team then needs to transfer the sample into the individual samp le containers. EPA will use a sample pump-off approach to transfer the sample volume to indi vidual sample containers at the pump-off area. For this sample pump-off procedure, the dissolved metals samples will be collected before the total metals and classical samples to prevent cr oss-contamination within the tubing which could lead to greater concentrations in the dissolved metals fractions.

Sample Pump–Off Procedure

19. Samplers remove the bags containing th e gloves and HDPE plastic wrap from the coolers or storage containers in which th ey are packed. Samplers identify which coolers or boxes contain the double-bagge d sample bottles, pre-cleaned tubing, and cleanbox.

20. Both samplers put on Tyvek® suits and gloves. “Dirty hands” covers work surfaces with HDPE plastic wrap and pl aces the double-bagged sample bottles and pre-cleaned tubing within ea sy access on the covered surface.DRAFT 2-11 21. “Dirty hands” opens the outer bag of the cleanbox and “clean hands” opens the clear inner bag. “Clean hands” places the cleanbox at the point of sample collection. “Clean hands” opens the cl eanbox and secures it ope n with the clips located inside the box.

22. “Dirty hands” opens the opening on the peri staltic pump head so the tubing can be placed in the pump head. “Dirty hands” opens the outer bag containing a length of pre-cleaned Teflon® tubing connected to a length of pre-cleaned silicone tubing, a “Y” splitter, and two additional pi eces of silicone t ubing. “Clean hands” moves the tubing into the cleanbox and opens the inner bag and removes the tubing. “Clean hands” places a clean plas tic bag over the end of the Teflon® and silicone tubing.

23. “Dirty hands” threads the silicone tu bing into the peristaltic pump head.

24. Both samplers change gloves.

25. “Dirty hands” opens the outer bag of the field blank composite container and total metals field blank sample bottle. “Clean hands” removes the total metals field blank sample bottle and places it in the cl eanbox. “Clean hands” opens the inner bag of the field blank composite containe r. “Clean hands” removes the lid from the field blank composite container and places the end of the Teflon® tubing in the blank water. “Clean hands” holds th e end of the silicone tubing outside the cleanbox over a bucket, with the plastic bag still cove ring the end of the tubing and “dirty hands” operates the pump to pump about 750 mL of blank water from the field blank composite container. “Clean hands” places the end of the silicone tubing in the cleanbox, opens the inner bag of the total metals field blank sample bottle, and removes the lid. “Dirty hands ” operates the pump to collect the total metals field blank sample. “Dirty hands ” stops the pump. “Clean hands” closes the lid on the sample bottle and closes the inner bag. “Clean hands” places the inner bag and bottle in the outer bag and “dirty hands” closes the outer bag. The samplers repeat this procedure for the remaining total metals field blank samples (i.e., total metals and total mercury field blank samples).

26. “Dirty hands” opens the outer bag of a capsule filter. “Clean hands” opens the inner bag and removes the capsule filter. “Clean hands” attaches the capsule filter to the silicone tubing just before the “Y” splitter.

27. “Dirty hands” opens the outer bag of th e dissolved metals field blank sample bottle. “Clean hands” rem oves the dissolved metals field blank sample bottle and places it in the cleanbox. “Clean hands” holds the end of the silicone tubing outside the cleanbox over a bucket, with th e plastic bag still covering the end of the tubing and “dirty hands” operates th e pump to pump about 750 mL of blank water from the field blank composite cont ainer. “Clean hands” places the end of the silicone tubing in the cleanbox, opens the inner bag of the dissolved metals field blank sample bottle, and removes the lid. “Dirty hands” operates the pumpDRAFT 2-12 to collect the dissolved metals field bl ank sample. “Dirty hands” stops the pump. “Clean hands” closes the lid on the sample bottle and closes the inner bag. “Clean hands” places the inner bag and bottle in the outer bag and “dirty hands” closes the outer bag. The samplers repeat this procedure for the remaining dissolved metals field blank samples (i.e., dissolve d metals and hexavalent chromium field blank samples) 2 . “Clean hands” closes the inner bag of the field blank composite container and “dirty hands” closes the outer bag. Note: 750 mL of blank water does not need to be purged for each sample, just at the beginning of each new filter. If a new filter is needed, “clean hands” removes the used filter and samplers follow step 25 to replace the filter.

28. “Dirty hands” opens the outer bag of the large composite container for the metals samples and “clean hands” opens the inne r bag. “Clean hands” transfers the Teflon® tubing from the field blank com posite container to the metals sample composite container. “Clean hands” holds the end of the silicone tubing outside the cleanbox over a bucket, with the plas tic bag still coveri ng the end of the tubing and “dirty hands” operates the pump to pump about one liter of sample through the tubing and filter. “Dirty hands” stops the pump.

29. “Dirty hands” opens the outer bag of the dissolved metals sample bottle. “Clean hands” removes the inner bag and bottle and places it in the cleanbox. “Clean hands” opens the inner bag and removes th e lid. “Dirty hand s” operates the pump to collect the dissolved metals sample. “Dirty hands” stops the pump. “Clean hands” closes the lid on the sample bottle and closes the inner bag. “Clean hands” places the inner bag and bottle in the outer bag and “dirty hands” closes the outer bag. The samplers repeat this procedure for the dissolved metals and hexavalent chromium samples. During one day of the sampling episode, the samplers will collect additional sample volume for th e duplicate samples and laboratory QC analyses.

30. “Clean hands” removes the capsule filter from the sample tubing configuration and reconnects the two pieces of tubing together.

31. “Clean hands” holds the silicone tubi ng outside the cleanbox over a bucket, with the plastic bag covering the end of th e tubing. “Dirty hands” pumps about one liter of sample through the tubing. “Dirty hands” stops the pump. “Clean hands” places the end of the silicone tubing back in the cleanbox.

32. “Dirty hands” opens the outer bag of th e total mercury sample bottle. “Clean hands” removes the inner bag and bottle and places it in the cleanbox. “Clean hands” opens the inner bag and removes th e lid. “Dirty hand s” operates the pump to collect the total mercury sample. “D irty hands” stops the pump. “Clean

2 ERG only plans to collect field blan k samples at each sampling point for one day of sampling ep isode. ERG will collect the dissolved mercury sample using the same technique as the total mercury sample, but the dissolved sample will be filtered at the laboratory. A dissolved mercury field blank will be performed by the laboratory to assess any mercury contamination from the filtering performed at the laboratory. Therefore, ERG does not need to collect a dissolved mercury field blank sample in the field.DRAFT 2-13 hands” closes the lid on the sample bottle and closes the inner bag. “Clean hands” places the inner bag and bottle in the outer bag and “dirty hands” closes the outer bag. The samplers repeat this procedur e for the dissolved mercury and total metals samples. During one day of the sa mpling episode, the samplers will collect additional sample volume for the duplicate samples and laboratory QC analyses.

33. “Dirty hands” places an ERG label on the outer bags of the sample bottles.

34. “Dirty hands” shakes the large composite containers for the classical analytes to mix the sample. “Dirty hands” opens the outer bag for the composite container. “Clean hands” opens the inner bag and transfers the Teflon® tubing from the metals composite container to the compos ite container for the classical analytes.

35. “Clean hands” holds the silicone tubi ng outside the cleanbox over a bucket, with the plastic bag covering the end of th e tubing. “Dirty hands” pumps about one liter of sample through the tubing. “Dirty hands” stops the pump.

36. Both samplers collect the BOD 5 , Group I, and Group II samples. During one day of the sampling episode, the samplers will collect additional sample volume for the duplicate samples and laboratory QC analyses.

2.4.2 Grab Sample Collection

ERG will collect the grab samples from the FGD scrubber purge, which is expected to contain a significan t amount of suspended solids. ER G will collect samples directly into individual sample containers for all samples that are not required to be filtered in the field. For the samples that will to be filtered in the field, ERG will collect a large volume of sample into a large container (e.g., 10- L HDPE container) and then pump off the specific sample volumes into the individual sample containers.

The grab sample collection technique can vary significantly depending on the specific sampling point location (e .g., collection from a basin (or tank) compared to collection from a sample tap. The following two subsectio ns describe the specifi c collection techniques that will be used to collect grab sample s from the differing sampling point locations.

2.4.2.1 Grab Sample Collection from Tap

For grab samples that are collected from a sample tap, ERG will set up the sampling equipment near the sample tap that re presents the FGD scrubber purge sample. TheDRAFT 2-14 field sampling personnel will use care when setting up the sample point to avoid any contamination from the surroundings. The sampling equipment will consist of the following:

 Colorless, electronic-gr ade, non-nitrile gloves;

 Silicone tubing with “Y” splitter;

 10-L containers;

 Teflon® tubing;

 Silicone tubing;

 0.45 um filter;

 Funnel;

 Peristaltic pump;

 Small table;

 Cleanbox;

 Tyvek® suits (for metals samples);

 Masks (for mercury samples); and

 Sample containers.

All metals sampling equipment will be specially-cleaned according to the procedures described in EPA Method 1669. ER G will follow protocols described in EPA Method 1669 to collect metal sample fractions. Two or more ERG samplers (“clean hands” and “dirty hands”) will follow the pr otocols described in the steps be low to set up the sampling point, collect the field blank samples, a nd collect wastewater samples. Th is section describes the set up of the sample point and collection of the EPA samples 3

.

1. Samplers remove the bags containing th e gloves and HDPE plastic wrap from the coolers or storage containers in which th ey are packed. Samplers identify which coolers or boxes contain the double-bagge d sample bottles, pre-cleaned tubing, blank water, and cleanbox. Depending on the condition of the sample tap, it may be necessary to wipe the tap with a cl ean paper towel to remove any build up on the tap that could potentially fall in the sample bottles during sample collection.

2. Both samplers put on Tyvek® suits, ma sks, and gloves. “Dirty hands” covers work surfaces (ground or table) with HDPE plastic wrap and places the doublebagged sample bottles within easy access on the covered surface.

3. “Dirty hands” opens the outer bag of the cleanbox and “clean hands” opens the inner bag. “Clean hands” places the clea nbox at the point of sample collection. “Clean hands” opens the cleanbox and s ecures it open with the clips located inside the box.

3 For the sample collection, EPA assumes that samples will be split with the plant (or the plant’s representative) and therefore, the sample set-up describes equipment needed fo r split samples. However, EPA is not responsible for the collection of the split samples collected by the plant and therefore, the collection of their samples is not described.DRAFT 2-15 4. “Dirty hands” opens the outer bag cont aining a length of pre-cleaned silicone tubing. “Clean hands” opens the inner bag inside of the cleanbox and removes the tubing. “Clean hands” places clean plastic bags over the ends of the silicone tubing.

5. “Dirty hands” opens the outer bag of the funnel and “clean hands” opens the inner bag inside of the cleanbox. “Clean hands ” attaches the funne l to the tubing.

6. “Dirty hands” opens the outer bags of the mercury field blank water and total mercury field blank sample bottles. “Cl ean hands” opens the inner bag for the field blank water, unscrews the lid and places it in the inner bag. “Clean hands” passes the funnel end of the tubing with a plastic bag shrouding the funnel to another “clean hands” person to hold outside the cleanbox. “Clean hands” removes the inner bag for the total mercur y field blank sample bottle and places it in the cleanbox. “Clean hands” holds the end of the silicone tubing outside the cleanbox over a bucket, with the plastic bag still cove ring the end of the tubing. “Dirty hands” pours field blank water through the funnel and tubing. After the tubing has been purged with sufficient vol ume, “clean hands” places the silicone tubing back in the cleanbox. Worki ng inside the cleanbox, “clean hands” unscrews the lid of the field blank samp le bottle, removes the tubing from the plastic bag, and prepares to fill the field blank sample bottle. “Dirty hands” pours field blank water into the funnel and t ubing, and “clean hands” fills the total mercury field blank sample bottle. “Clean hands” places the e nd of the silicone tubing into the plastic bag, replaces the lid on the sample bottle, and closes the inner bag. “Clean hands” removes the bottle from the cleanbox and places it in the outer bag. “Dirty hands” clos es the outer bag. The sample rs repeat this procedure for the total metals field blank samples 4

.

7. “Dirty hands” opens the outer bag for a pre-cleaned 10-L container. “Clean hands” opens the inner bag and loosens the lid. “Clean hands” holds the end of the silicone tubing at the m outh of the 10-L container a nd removes the lid. “Dirty hands” pours field blank water through th e funnel and tubing, and “clean hands” fills the 10-L container with enough fiel d blank water to collect the dissolved metals field blank samples. “Clean hands” places the lid back on the 10-L container, places the plastic bag over the end of the silicone tubing, and places the tubing in the cleanbox. “Clean hands” scre ws the lid on the 10-L container and closes the inner bag. “Dirty hands” clos es the outer bag of the 10-L container.

8. After collecting the field blank samples, “clean hands” removes the funnel from the tubing. “Clean hands” and “dirty hands” wo rk to attach the e nd of the silicone tubing to the sample tap.

4 ERG only plans to collect field blan k samples at each sampling point for one day of sampling ep isode. ERG will collect the dissolved mercury sample using the same technique as the total mercury sample, but the dissolved sample will be filtered at the laboratory. A dissolved mercury field blank will be performed by the laboratory to assess any mercury contamination from the filtering performed at the laboratory. Therefore, ERG does not need to collect a dissolved mercury field blank sample in the field.DRAFT 2-16 9. “Clean hands” holds the opposite end of the silicone tubing outside the cleanbox over a bucket, with the plas tic bag covering the end of the tubing. “Dirty hands” opens the valve to the sample tap to pur ge the piping for a minimum of 2 minutes. “Clean hands” places the end of the silicone tubing back in the cleanbox.

10. “Dirty hands” opens the outer bag for a pre-cleaned 10-L container. “Clean hands” opens the inner bag and loosens the lid. “Clean hands” holds the end of the silicone tubing at the mouth of the 10-L container and removes the lid. “Dirty hands” opens the sample valve to allow sample to flow into the 10-L container. Samplers fill the 10-L container for the collection of dissolved metals and hexavalent chromium, which are all required to be filtered. The samplers will allow the solids to settle for one hour while collecting the remaining samples. “Clean hands” places the lid back on th e 10-L container, places the plastic bag over the end of the silicone tubing, a nd places the tubing into the cleanbox. ”Clean hands” screws the lid on the 10-L container a nd closes the inner bag. “Dirty hands” closes the outer bag of the 10-Liter container. Both samplers change their gloves.

11. “Dirty hands” opens the outer bag for the total mercury sample bottle. “Clean hands” removes the inner bag and bottle and places it in the cleanbox. “Clean hands” opens the inner bag and bottle lid. “Clean hands” removes the plastic bag from the tubing and fills the sample bottl e. “Clean hands” places the tubing back in the plastic bag, replaces the lid on the sample bottle and closes the inner bag. “Clean hands” removes the sample bottl e from the cleanbox and places it in the outer bag. “Dirty hands” clos es the outer bag. The sample rs repeat this procedure for the dissolved mercury and total metals samples.

12. “Dirty hands” places an ERG label on the outer bags of the sample bottles.

13. Samplers fill a 1-L jar for the field meas urements. The samplers will give the jar to another sampling team member to measure the temperature and pH.

14. Both samplers collect the BOD 5 , Group I, Group II, and total cyanide samples from the sample location.

Dissolved Metals Sample Collection

15. Samplers allow the 10-L sample container to continue to settle if one hour has not elapsed since the collection of the sample.

16. “Dirty hands” covers the work surfaces (ground or table) with HDPE plastic wrap and places the double-bagged sample bottl es within easy access on the covered surface.

17. “Dirty hands” opens the outer bag of th e clean box and “Clean hands” opens the inner bag. “Clean hands” places the clea nbox at the point of sample collection.DRAFT 2-17 “Clean hands” opens the cleanbox and s ecures it open with the clips located inside the box.

18. “Dirty hands” opens the opening on the peri staltic pump head so the tubing can be placed in the pump head. “Dirty hands” opens the outer bag containing a length of pre-cleaned Teflon® tubing attached to a 5-foot length of pre-cleaned silicone tubing, a “Y” splitter, and two additional pieces of pre-clea ned silicone tubing. “Clean hands” moves the tubing into the cleanbox, opens the inner bag, and removes the tubing. “Clean hands” places a clean plastic bag over the end of the Teflon® and silicone tubing.

19. “Dirty hands” threads the silicone tu bing into the peristaltic pump head.

20. Both samplers change gloves.

21. “Dirty hands” opens the outer bag of a capsule filter. “Clean hands” opens the inner bag and removes the capsule filter. “C lean hands” attaches the capsule filter to the silicone tubing just before the “Y” splitter.

22. “Dirty hands” opens the outer bag of the 10-L container that wa s used to collect the field blank water for the dissolved me tals fractions. “Clean hands” opens the inner bag of the 10-L container. “Clean hands” removes the Teflon® tubing from the cleanbox, opens the lid of the 10-L plastic container, removes the plastic bag from the Teflon® tubing, and places the Te flon® into the 10-L container. “Dirty hands” opens the dissolved metals fiel d blank sample bottle. “Clean hands” removes the dissolved metals field bla nk sample bottle and places it in the cleanbox. “Clean hands” holds the end of the silicone tubing outside the cleanbox over a bucket, with the plas tic bag still covering the e nd of the tubing and “dirty hands” operates the pump to pump about 750 mL of blank water from the field blank water bottle. “Clean hands” places the end of the silicone tubing in the cleanbox, opens the inner bag of the dissolv ed metals field blank sample bottle, and removes the lid. “Dirty hands” operat es the pump to collect the dissolved metals field blank sample. “Dirty hands” stops the pump. The samplers repeat the procedure for the dissolved metals and hexa valent chromium field blank samples. If a new filter is needed, “clean hands” removes the used filter and samplers following step 22 to replace the filter.

23. Both samplers change gloves.

24. “Dirty hands” opens the outer bag of one of the 10-L containers. “Clean hands” opens the inner bag, removes the lid, a nd places the end of the Teflon® tubing into the container. “Clean hands” holds th e end of the silicone tubing outside the cleanbox, with the plastic bag still coveri ng the end of the tubing. “Dirty hands” starts the pump and passes approximately 750 mL through the tubing and filter. “Dirty hands” stops the pump.DRAFT 2-18 25. “Dirty hands” opens the outer bag of the dissolved metals sample bottle. “Clean hands” removes the inner bag and bottle and places it in the cleanbox. “Clean hands” opens the inner bag and removes the lid. “Dirty hands ” operates the pump to collect the dissolved metals sample . “Dirty hands” stops the pump. “Clean hands” closes the lid on the sample bottle and closes the inner bag. “Clean hands” places the inner bag and bottle in the outer bag and “dirty hands” closes the outer bag. The samplers repeat this procedure for the dissolved metals and hexavalent chromium samples.

26. “Dirty hands” places an ERG label on the outer bags of the sample bottles.

2.4.2.2 Grab Sample Collection from Basin (or Tank)

For grab samples that are collected fr om a basin (or tank), ERG will set up the sampling equipment near the basin that represen ts the FGD scrubber purge sample. The field sampling personnel will use care when setting up the sample point to avoid any contamination from the surroundings. The sampling equipm ent will consist of the following:

 Peristalic pump;

 Colorless, electronic-gr ade, non-nitrile gloves;

 PVC piping;

 0.45 um filter;

 Teflon® tubing;

 Silicone tubing;

 “Y” splitter;

 Small table;

 Cleanbox;

 Tyvek® suits (for metals samples);

 Masks (for mercury samples); and

 Sample containers.

All metals sampling equipment will be specially-cleaned according to the procedures described in EPA Method 1669. ER G will follow protocols described in EPA Method 1669 to collect metal sample fractions. Two or more ERG samplers (“clean hands” and “dirty hands”) will follow the pr otocols described in the steps be low to set up the sampling point, collect the field blank samples, a nd collect wastewater samples. Th is section describes the set up of the sample point and collection of the EPA samples 5

.

5 For the sample collection, EPA assumes that samples will be split with the plant (or the plant’s representative) and therefore, the sample set-up describes equipment needed fo r split samples. However, EPA is not responsible for the collection of the split samples collected by the plant and therefore, the collection of their samples is not described.DRAFT 2-19 1. Samplers remove the bags containing th e gloves and HDPE plastic wrap from the coolers or storage containers in which th ey are packed. Samplers identify which coolers or boxes contain the double-bagge d sample bottles, pre-cleaned tubing, and cleanbox.

2. Both samplers put on Tyvek® suits, glove s, and masks. “Dirty hands” covers work surfaces (tables and platform) w ith HDPE plastic wrap and places the double-bagged sample bottles and Teflon® tubing within easy access on the covered surface.

3. “Dirty hands” opens the outer bag of the cleanbox and “clean hands” opens the inner bag. “Clean hands” places the clea nbox at the point of sample collection. “Clean hands” opens the cleanbox and s ecures it open with the clips located inside the box.

4. “Dirty hands” opens the opening on the peri staltic pump head so the tubing can be placed in the pump head. “Dirty hands” opens the outer bag containing a length of pre-cleaned Teflon® tubing attached to a 5-foot length of pre-cleaned silicone tubing with a “Y” splitter and two separate pieces of silicone tubing attached to the “Y” splitter. “Clean hands” moves the tubing into the cleanbox, opens the inner bag, and removes the tubing. “Clean hands” places a clean plastic bag over the end of the Teflon® and silicone tubing and places the end of the tubing in the cleanbox.

5. “Dirty hands” threads the silicone tubing into the pe ristaltic pump head.

6. Both samplers change gloves.

7. “Dirty hands” opens the outer bags of the mercury field blank water and total mercury field blank sample bottles. “Cl ean hands” opens the inner bag for the field blank water, unscrews the lid and pl aces it in the inner bag. “Clean hands” then places the Teflon® end of the tubi ng into the blank water. “Clean hands” moves the total mercury sample bottle in to the cleanbox and opens the inner bag. Working inside the cleanbox, “clean hands” unscrews the lid. “Clean hands” holds the end of the silicone tubing ou tside the cleanbox over a bucket, with the plastic bag still covering th e end of the tubing. “Dir ty hands” operates the pump to pump blank water through the tubing. After the tubing has been purged with sufficient volume, “clean hands” places th e silicone tubing back in the cleanbox, removes the plastic bag, and fills the total mercury field blank sample bottle. “Dirty hands” stops the pump. “Clean hands” places the plastic bag over the end of the silicone tubing, replaces the lid on the sample bottle, and closes the inner bag. “Clean hands” removes the bottle from the cleanbox and places it in the outer bag. “Dirty hands” clos es the outer bag. The sample rs repeat this procedure for the total metals field blank samples 6

.

6 ERG only plans to collect field blan k samples at each sampling point for one day of sampling ep isode. ERG will collect the dissolved mercury sample using the same technique as the total mercury sample, but the dissolved sample will be filtered at the laboratory. A dissolved mercury field blank will be performed by the laboratory to assess anyDRAFT 2-20 8. “Dirty hands” opens the outer bag of a capsule filter. “Clean hands” opens the inner bag and removes the capsule filter. “Clean hands” attaches the capsule filter to the end of the silicone tubi ng, prior to the “Y” splitter.

9. “Dirty hands” opens the outer bag of th e dissolved metals field blank water and dissolved metals by field blank sample bottle. “Clean hands” moves the dissolved metals field blank sample bottle to the cleanbox. “Clean hands” opens the inner bag of the field blank water. “Clean hands” removes the lid from the dissolved metals field blank water, places it in th e inner bag, and places the end of the Teflon® tubing in the blank water. “Cl ean hands” holds the end of the silicone tubing outside the cleanbox over a bucket, w ith the plastic bag still covering the end of the tubing and “dirty hands” operat es the pump to purge about 750 mL of blank water from the field blank water bot tle through the tubing and filter. “Clean hands” places the end of the silicone t ubing in the cleanbox, opens the inner bag of the dissolved metals field blank samp le bottle, and removes the lid. “Clean hands” holds the silicone tubing over th e bottle and “dirty hands” operates the pump to collect the dissolved metals fiel d blank sample. “Dirty hands” stops the pump. “Clean hands” closes the lid on the sample bottle and closes the inner bag. “Clean hands” places the inner bag and bottle in the outer bag and “dirty hands” closes the outer bag. The samplers repeat this procedure for the dissolved metals and hexavalent chromium field blank sa mples. Note: 750 mL of blank water does not need to be purged into the wa ste bottle for each sample, just at the beginning of each new filter. If a new filter is needed, “clean hands” removes the used filter and samplers follow step 8 to replace the filter.

10. Both samplers change gloves.

11. After collecting all of the total and dissolved metals field blank samples, “clean hands” and “dirty hands” work together to place the Teflon® end of the tubing into the sample water, taking care that the end of the tubing does not touch anything other than the sample water. The samplers will secure the Teflon® tubing to a piece of PVC piping so the samp lers can easily control the position of the tubing in the basin/tank.

12. “Clean hands” holds the e nd of the silicone tubing outside the cleanbox over a bucket, with the plastic bag still covering the end of the tubing and “dirty hands” operates the pump to purge the tubing for a minimum of 2 minutes. After the tubing is purged, “Dirty hands” turns off th e pump. “Clean hands” places the end of the silicone tubing back in the cleanbox. .

13. “Dirty hands” opens the outer bag of the dissolved metals sample bottle. “Clean hands” removes the inner bag and bottle and places it in the cleanbox. “Clean hands” opens the inner bag and removes the lid. “Clean hands” holds the silicone

mercury contamination from the filtering performed at the laboratory. Therefore, ERG does not need to collect a dissolved mercury field blank sample in the field.DRAFT 2-21 tubing over the bottle and “dirty hands” ope rates the pump to collect the dissolved metals sample. “Clean hands” closes the lid on the sample bottle and closes the inner bag. “Clean hands” places the inne r bag and bottle in the outer bag and “dirty hands” closes the outer bag. The samplers repeat this procedure for the dissolved metals and hexavalent chromium samples.

14. Both samplers change gloves.

15. “Clean hands” removes the capsule filter from the silicone tubing and reattaches the tubing to the “Y” splitter.

16. “Clean hands” holds the e nd of the silicone tubing outside the cleanbox over a bucket, with the plastic bag still covering the end of the tubing . “Dirty hands” operates the pump to purge the tu bing for at least 2 minutes.

17. “Dirty hands” opens the outer bag for th e total mercury sample bottle. “Clean hands” removes the inner bag and bottle and places it in the cleanbox. “Clean hands” opens the inner bag and bottle lid. “Clean hands” removes the plastic bag from the tubing and fills the sample bottle. “Clean hands” places the tubing back in the plastic bag, replaces the lid on the sample bottle and closes the inner bag. “Clean hands” removes the sample bottl e from the cleanbox and places it in the outer bag. “Dirty hands” clos es the outer bag. The samplers repeat this for the dissolved mercury and total metals samples.

18. “Dirty hands” places an ERG label on the outer bags of the sample bottles.

19. Samplers fill a 1-L jar for the field measur ements. The samplers will give the jar to another sampling team member to measure the temperature and pH.

20. Both samplers collect the BOD 5 , Group I, Group II, and total cyanide samples from the sample location. Samples will be pumped directly into sample bottles.

2.5 Preservation, Shipping, and Analysis

All samples will be maintained on ic e immediately upon collection (except the

total and dissolved metals and the total and di ssolved mercury samples, which do not require cooling). In addition, all samples will follow the on-site preservation requirements specified in 40 CFR 136 method-specified protoc ols, including hexavalent chromium. The dissolved metals (not including mercury) and hexavalent chromium samples will be filtered in the field. The dissolved mercury samples will be filtered upon r eceipt at the laboratory. Samplers will filter samples within 15 minutes of the completion of the compositing period (or as soon thereafter as possible). For the FGD influent, filtration of dissolved samples will occur approximately one hour after the compositing period (o r after the large sample volume is collected during the grabDRAFT 2-22 sample collection) to allow for solids settling be cause it has a high suspen ded solids content that would clog the filter.

The total cyanide samples will be pres erved according to the method-specific protocols. The samplers will first adjust the pH of the sample to >10 S.U. using sodium hydroxide. The samplers will then test the sample for the presence of sulf ide using lead acetate test strips. If sulfide is present, the samplers will dilute the sample by pouring some of the sample into another sample bottle containing a measured amount of bl ank reagent water (e.g., add 50 mL of sample to 200 mL of blank reagent wa ter). The samplers will then test the diluted sample for the presence of sulfide. If sulfide is still present, the samplers will create a more diluted sample and retest for sulfide until sulfide is not present in the sample. The samplers will then test the sample for the presence of total ch lorine using potassium-iodide starch paper. If total chlorine is present, the samplers will add sodium arsenite in small increments until total chlorine is no longer present in the sample. The samplers will then readjust the pH to >10 S.U. using sodium hydroxide, if necessa ry, and place the sample on ice.

Table 2-3 lists the parameters, required sample and QC volume, bottle types, and on-site preservation requirements for each type of analysis. The type and amount of preservation used will be recorded on sample preservation log sheets (Figure 2-1). Preservation will be

discontinued and noted on the tra ffic report if 10 percent of the sample volume is added and the required pH is not achieved. The wastewater samples, except certain metals samples, will be
packed in ice chests with a sufficient quant ity of ice to maintain a temperature of ≤ 6  C. All
samples will be prepared for overnight ship ment via Federal Expr ess to laboratories.

2.6 Field Measurements and Engineering Data Collection

Temperature and pH will be measured and recorded by the sampling crew at each sampling point when the automatic composite samp lers are set up (and ever y six hours after the composite set up) or during the grab sample collec tion. A 1-liter glass jar will be filled prior to connecting the sample tubing to the composite co ntainers for field measurements. Temperature and pH will be measured immediately after the collection of the field measurement aliquot.
Table 2-4 summarizes the field measurements, the method to be used for the measurement, andDRAFT 2-23 the detection range of each field test instrument. In addition, EPA will collect flow rate data for

all waste streams.

Field sampling log sheets (Figure 2-2) w ill be completed at each sampling point. This sheet will record the sampling methodology, na mes of the samplers, sample collection time, field measurements, and any notes and observations.

During each sampling episode, engineeri ng information will be collected with regard to design and operation of the plant bei ng sampled. For example, information such as coal usage, plant capacity, wast ewater flow rates, sludge genera tion rates (if applicable), and retention times in wastewater treatment proce ss stages. Engineering data collection sheets (Figures 2-3, 2-4, and 2-5) will be completed for each plant. This information will be used to determine if the specific design or operational criteria of the st eam electric operations affect the

wastewater characteristics.

2.7 Sample Labeling

Each sample will be coded with a unique sample number and labeled at the time of collection. Typically, labels are printed prior to arrival in the field, though they may also be completed by hand. Each self-adhesive label is completed in indelible ink and contains the following information:

 Sample number;

 Sampling episode number;

 Sampling point/description;

 Date of sample collection;

 Analysis to be performed;

 Sample bottle type; and

 Required preservation.

If any of the pre-printed inform ation is incorrect, it will be re vised using indelible ink. In particular, if a required preservation is not used, it will be marked out (additional preservation

details will be noted on the tra ffic report). Once applied to the sample container, labels are covered with clear tape to pr event tampering, abrasion, smeari ng, or loss during transit.DRAFT 2-24 2.8 Traffic Reports

To maintain a record of sample collec tion, transfer between personnel, shipment, and receipt by the laboratory, a traffic report is completed for each sample set at each sampling

location. These forms are used to document sa mple custody transfer from the field to the laboratory. Traffic report forms are completed for all samples sent to all laboratories. Figure 2-6 includes an example traffic report. At the time of sample shipment , a copy of the traffic report is sent to ERG, another copy is kept by sampling personnel, and two copies are transmitted with the samples to the analytical laboratory.

In addition to the transfer of custody, th e traffic report provides information to the analytical laboratory on the sample number, type of water sample (in- line process, untreated wastewater, treated effluent), sa mple description, whether the sa mple is preserved, pH of the sample after preservation, type of sample (grab, composite), sample collection date and time, and the analyses requested. The comment section is used to provide special notes or instructions to the laboratory, such as how to composite separate samples prior to analysis. The sampling team will also comment if sample bottles are not comple tely filled (i.e., less than 75 percent full). In
addition, the comments section will be used to note deviations from sta ndard sampling protocols (for example, if a sample could not be acid- preserved because of excessive buffering).

2.9 Quality Assurance/Quality Control

Quality assurance/quality control (QA/QC) procedures applicable to this project

are outlined in the Quality Assurance Project Plan for th e Steam Electric Effluent Guidelines
Rulemaking [2]. The QA/QC program for sample collec tion at steam electric plants will include the following:

 Documentation for samples thr ough laboratory traffic reports;

 Collection of duplicate samples;

 Collection of field blank(s) for total metals, dissolved metals, total mercury, dissolved mercury, and hexavalent chromium samples.

 Analysis of bottle blank(s) for me tals by the clean-equipment supplier;DRAFT 2-25  Analysis of equipment blank(s) for metals by the clean-equipment supplier;

 Collection of laboratory QC sample s for matrix spike/matrix spike duplicate analyses.

Duplicate sample sets will be collected as part of the quality assurance program for sampling. Duplicate samples ar e collected as separate aliquots in the field. EPA will collect one duplicate sample for every ten samples collec ted at a sampling event, excluding field blank samples. For example, EPA will collect four samples from each sampling point selected at a plant; therefore, if the EPA collects samples fr om two sample points at a plant (total of 8 samples), only one duplicate sample will be collected, but if EPA collects samples from three sample points at a plant (total of 12 samples), then two duplicate samples will be collected. The field blank samples associated with the sampling poi nts will not be included in the count of the total samples collected. Results of the duplicate analyses will be used to evaluate precision, including variability in sample collec tion, handling, prepara tion, and analysis.

Bottle blanks are used to evaluate possible contamination from the sample bottles. The bottle blank will consist of an analyte- free matrix (Ultra Pure Blank Water DI+ TM ) poured into the appropriate sample bottle s (250-mL plastic bottle for meta ls by) and stored for several days prior to shipment to the la boratory. The supplier of the cl eaned metals bottles will prepare and analyze the bottle blanks prior to shipping the equipm ent to the sampling episode.

Field blanks will be used to evaluate possible contamination caused by sampling equipment or by sampling equipment decontamina tion procedures. Fi eld blanks will be prepared in the field prior to sample collecti on and analyzed for all sampling equipment, other than sample bottles, that come into direct contact with samples. Examples of sampling equipment are:

 On-site sampling devices or piping in stalled for sample collection; and

 Pumps, tubing, bottle dippers, buckets, and other equipment used to collect samples from less accessible sampling locations.DRAFT 2-26 For all metals samples (i.e., total mercury, total and dissolved metals, and hexavalent chromium), EPA will prepare a field blank at each sampling point for one day of the sample episode 7

.

Equipment blanks will be used to ev aluate possible contamination of metals caused by the sampling equipment. The supplier of the equipment used for metals sample collection will prepare and analyze the equipment blanks for metals.

As part of standard laboratory quality control, matrix effects on analytical performance are assessed through the analysis of matrix spikes and laboratory duplicates. Consequently, additional sample volume must be collected for these QC analyses. The ERG sampling team will be responsible for collect ing, labeling, and shipping the laboratory QC volumes. Laboratory QC volumes will be collect ed as duplicate samples collected immediately after the original sample aliquot. For metals and classical analyses, EPA will collect one QC sample volume (i.e., MS/MSD sample) for every ten samples collected at a sampling event, excluding field blank samples. For example, EP A will collect four samples from each sampling point selected at a plant; theref ore, if EPA collects samples from two sample points at a plant (total of 8 samples), only one QC sample volum e will be collected, but if EPA collects samples from three sample points at a plant (total of 12 samples), then two QC sample volumes will be collected. The field blank samples associated with the sampling points will not be included in the count of the total samp les collected.

2.10 Sample Splitting

The plant being sampled has the option to collect split or duplicate samples at each of the sampling points. If this option is exer cised, the plant will supply all of the personnel, equipment, glassware, and reagents required to collect the samples and to coordinate the analysis of samples.

7 ERG will collect the dissolved mercury sample using the same technique as the total mercury sample, but the dissolved sample will be filtered at the laboratory. A dissolved mercury field blank will be performed by the laboratory to assess any mercury contamination from the f iltering performed at the laboratory. Therefore, ERG does not need to collect a dissolved mercury field blank sample in the field.DRAFT 2-27 Table 2-1. Sample Collection at Steam Electric Plants

Analytical Parameter Influent to FGD Wastewater Treatment Intermediate Point in FGD Wastewater Treatment Effluent from FGD Wastewater Treatment

BOD 5 X X X

Total Cyanide X X X

Group I (a) X X X

Group II (b) X X X

Total Metals X X X

Dissolved Metals X X X

Total Mercury X X X

Dissolved Mercury X X X

Hexavalent Chromium X X X
(a) Group I includes TSS, TDS, sulfate, and chloride. (b) Group II includes ammonia as nitrogen, COD, nitr ate/nitrite as nitrogen, TKN, and total phosphorus. (c) Actual sample location and specific pollutants will be defined in the plant-specific sampling plan.DRAFT 2-28 Table 2-2. Analytical Methods

Parameter Method Number Classicals Biochemical Oxygen Demand (BOD5) SM 5210 B (or other 40 CFR Part 136-approved method Chemical Oxygen Demand (COD) EPA 410.3 (or other 40 CFR Part 136-approved method) Total Suspended Solids (TSS) SM 2540 D (or other 40 CFR Part 136-approved method) Total Dissolved Solids (TDS) SM 2540 C (or other 40 CFR Part 136-approved method) Sulfate ASTM D516-90 (or other 40 CFR Part 136-approved method) Chloride SM 4500–Cl–C (or other 40 CFR Part 136-approved method) Ammonia as Nitrogen SM 4500—NH 3 B, F (or other 40 CFR Part 136-approved method) Nitrate/Nitrate as Nitrogen SM 4500—NO 3 -H (or other 40 CFR Part 136-approved method) Total Kjeldahl Nitrogen (TKN) SM 4500—NH 3 B or C, F (or other 40 CFR Part 136- approved method) Total Phosphorus EPA 365.3 (or other 40 CFR Part 136-approved method) Total Cyanide EPA 335.4 (or other 40 CFR Part 136-approved method) Total and Dissolved Metals Mercury EPA 1631E Hexavalent Chromium (dissolved only) EPA 218.6 (or other 40 CFR Part 136-approved method)

Aluminum, antimony, arsenic, barium, beryllium, boron, cadmium, calcium, chromium, cobalt, copper, iron, lead, magnesium, manganese, molybdenum, nickel, selenium, silver, sodium, thallium, tin, titanium, vanadium, and zinc EPA 200.7, EPA 200.8 (Note: EPA 200.8 may include the use of collision cell or dynamic reaction cell instrumentation for se lected analytes.)DRAFT 2-29 Table 2-3. Summary of Sample Co ntainer and Planned Preservation

Parameter Sample Container and Volume QC Sample Container and Volume On-Site Preservation

Classicals

BOD 5 One 1-L plastic bottle One 1-L plastic bottle ≤ 6  C

Group I a Two 1-L plastic bottle Two 1-L plastic bottle ≤ 6  C

Group II b Two 1-L plastic bottle Three 1-L plastic bottle H 2 SO 4 to pH <2, ≤ 6  C

Total cyanide One 1-L plastic bottle Two 1-L plastic bottle NaOH to pH >10, dilution until sulfide is not present, NaAsO 2 until total chlorine is not present, ≤ 6  C

Metals Total metals (except mercury) One 250-mL plastic bottle One 250-mL plastic bottle None (acid preserve at laboratory)

Dissolved metals (except mercury and hexavalent chromium) One 250-mL plastic bottle One 250-mL plastic bottle 0.45 μm filter (performed in field) (acid preserve at laboratory)

Total mercury One 250-mL glass (ultraclean), fluoropolymer lined caps One 250-mL glass (ultraclean), fluoropolymer lined caps None (acid preserve at laboratory)

Dissolved mercury Two 250-mL glass (ultraclean), fluoropolymer lined caps Two 250-mL glass (ultraclean), fluoropolymer lined caps None (filter and acid preserve at laboratory)

Hexavalent chromium One 250-mL plastic bottle One 250-mL plastic bottle 0.45 μm filter (performed in field) Ammonium sulfate buffer to pH 9.3 – 9.7, ≤ 6 o C (a) Group I includes TSS, TDS, sulfate, and chloride. (b) Group II includes ammonia as nitrogen, COD, nitr ate/nitrite as nitrogen, TKN, and total phosphorus.DRAFT 2-30 Table 2-4. Sampling Point Field Measurements

Field Measurements Method Detection Range (or Gradation of Scale)
Temperature Thermometer -20 to 150 ± 1 o C
pH (Standard Units) Four color indicator strip pH meter 0 to 12 ± 1 pH S.U. -1.0 to 15.0 ± 0.1 pH S.U.DRAFT 2-31 Sampling Episode

________

Preservation Chemicals - List St rength of Solution from Bottle

H 2 SO 4 ______________________ NH 4 SO 4 ____________________ NaOH ______________________

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

Figure 2-1. Sample Preservation Log SheetDRAFT 2-32 Sampling Episode: _________________________________

Sampling Point: ___________________________________

Sample Numbers: __________________________________

Date: ____________________________________________

Manual Composite 

# □ Grab 

# □

Automatic Composite 

# □

Time of Sample Collection:

Start Time 

# □ AM 

# □ PM

End Time 

# □ AM 

# □ PM

Equipment Used: _________________________________________________

Samplers’ Names: ________________________________________________

Sample

Point Time Temp

°C

Thermometer / Meter pH

(S.U.)
Meter / Strips Waste Stream Flow Rate

(GPM)

1

2

3

4

5

6

7

Notes: (include observations of odor and color of each aliquot, take pi ctures if necessary)

______________________________________________________________________________

______________________________________________________________________________

______________________________________________________________________________

______________________________________________________________________________

______________________________________________________________________________ Figure 2-2. Field Sampling Log Sheet2-33DRAFTPlant Name: ____________________________________________________________________________Plant Contact: ____________________________________________________________________________Dates of Sample Collection: ___________________________________________________________________Data Collectedby: __________________________________________________________________________Instructions: In the tables below, fill out information on the generating units and FGD systems operating at the plant based onall four days of the samplingepisode. Note any changes in operation that occur during the four-day period. Provide actual data if possible. If actual data are not available, provide estimatesfor the specific information. Some of the data requested may not be susceptible to estimation. Enter “URE” for “unable to reasonably estimate.” Otherwise,specify whether data provided are actual or estimated by writing in “ACT” or EST” wherever appropriate.Generating Unit Operating Characteristics During Sample CollectionUnitIDBoiler TypeCapacity(MW)ElectricityProduction(or PercentCapacity)SCR(No, On,Off)ParticulateControl System(HS/CS ESP, orBH)FGD System Operating Characteristics During Sample CollectionUnitIDWet FGDSystem(Yes/No)Type ofScrubberForcedOxidation(Yes/No)SorbentAdditives(DBA, formicacid, etc.)FGD Makeup WaterSourceSO2RemovalPercentageType ofSolidsSeparationNote changes in operation over the past month (e.g., turned off SCRs on October 1 or burned 5% petroleum coke previous week):Figure 2-3. Engineering Data Collection Sheet (Page 1 of 3)DRAFT 2-34 Plant Name: ____________________________________________________________________________ Plant Contact: ____________________________________________________________________________ Dates of Sample Collection: ___________________________________________________________________ Data Collected by: __________________________________________________________________________

Instructions: In the tables below, provide information on the coal burned and FGD scrubber slurry at the plant for each day of the sampling episode. Provide actual data if po ssible. If actual data are not available, provide estimates for the specific information. Some of the data requested may not be susceptible to estimation. Enter “URE” for “unable to reasonably estimate.” Otherw ise, specify whether data provided are actual or estimated by writing in “ACT” or EST” wherever appropriate.

Coal Information

Day of Sampling Unit ID Coal Type Amount of Coal Used

During Day of Sampling Source of Coal (Coal

Region and/or State) Percent Sulfur in

Coal Chlorine Content of Coal

1

2

3

4

Note changes in operation over the past month (e.g., turned off SCRs on October 1 or burned 5% petroleum coke previous week) as well as conditions and changes during the sampling episode:

Scrubber Slurry Information

Day of Sampling FGD System ID Associated Unit IDs Scrubber Slurry Blowdown Flow Rate Scrubber Slurry Percent Solids Time of Dewatering

During Sampling Day Percent Filtrate Recycled Back to Scrubber Flow Rate

(gpm) Duration

1

2

3

4

Figure 2-4. Engineering Data Co llection Sheet (Page 2 of 2)DRAFT2-35Plant Name: ____________________________________________________________________________Plant Contact: ____________________________________________________________________________Dates of SampleCollection: ___________________________________________________________________Data Collectedby: __________________________________________________________________________Instructions: In the table below, provideinformation on the FGD wastewater treatment system for each day of the sampling episode and the volumes of the FGDwastewater treatment system tanks and reactors. If possible, provide the name of the acid and polymer used during the samplingepisode. Provide actual data ifpossible. If actual data are not available, provide estimates for the specific information. Some of the data requested may notbe susceptible to estimation. Enter“URE” for “unable to reasonably estimate.”Otherwise, specify whether data providedare actual or estimated by writing in “ACT” or EST” whereverappropriate.FGD Wastewater Treatment System Operation InformationDay ofSamplingScrubber PurgeChemical Usage(specify units)Flow Rate(gpm)DurationLimeFerricChlorideOrgano-sulfide_________(specify type)Polymer:_________(specify type)Acid:_________(specify type)1234Volume of equalization tank ________________Volume of reaction tanks: 1) ________________ 2) ________________ 3) ________________Volume of clarifiers 1) ________________ 2) ________________Volume of first-stage bioreactors ________________Volume of second-stage bioreactors ________________Figure 2-5. Engineering Data Collection Sheet (Page 3 of 3)DRAFT 2-36 Figure 2-6. Example Traffic Report EPISODE NO:

RANGE OF SAMPLE NOS:

Return completed form to:

FOR LAB USE ONLY

NAME: SHIP TO: DATE REC'D:

CITY: ATTN: REC'D BY:

STATE: CARRIER: SAMPLE CONDITION ON RECEIPT:

INDUSTRIAL CATEGORY: AIRBILL:

DATE SHIPPED:

CONFIDENTIAL (Y/N): SAMPLING OFFICE/SAMPLER:

SAMPLE NUMBER S O U R C E W A T E R

( c i t y , r i v e r , w e l l )

I N L I N E P R O C E S S

U N R E A T E D E F F L U E N T

( r a w w a s t e w a t e r )

T R E A T E D E F F L U E N T

O T H E R

( s p e c i f y ) ADDITIONAL SAMPLE DESCRIPTION P H L E V E L

P R E S E R V E D ( Y / N )

G = G R A B / C = C O M P O S I T E

S A M P L E C O L L E C T I O N

T I M E / D A T E

Comments:

EPA Form 7500-50 (Rev 6-94) Previous editions are obselete. Page 1: SCC Copy Page 2: Lab Copy Copy of Page 1: Sampler Copy Copy of Page 2: Lab Copy for return to SCC United States 

# EPA Environmental Protection Agency Washington, DC 20460

TRAFFIC REPORT P.O. BOX 1407

USEPA ENGINEERING AND ANALYSIS DIVISION ALEXANDRIA, VA 22313

SAMPLE CONTROL CENTER (703) 519-1140

INDUSTRIAL FIRM SAMPLED SHIPPING & INFORMATION

SAMPLE POINT DESCRIPTION SAMPLE ANALYSESDRAFT 3-1 

### 3.0 S AMPLING 

### A CTIVITIES

This section discusses the sampling team organization, site visit preparation, and sampling activities.

3.1 Sampling Team Organization

The sampling crew will consist of a cr ew chief from ERG, crew members from ERG, and EPA representative(s). The actual number of ERG crew members will be determined based on the number of sampling poi nts at the plant. The crew ch ief will be responsible for all health and safety, sample collection, preser vation, and shipping activities on site. After completion of the visit, the analytical results from each laboratory will be collated. This

information will be summarized and transmitted in a trip report to EPA. After EPA review, the report will be forwarded to the plant for their review.

3.2 Pre-Sampling Preparation

EPA will conduct a pre-sampling site vi sit at each selected plant prior to sampling, unless EPA has already visited the plant pr eviously. The site vi sits will provide EPA with site-specific process information such as:

 Types of wastewater streams genera ted by the steam electric operations;

 Feasibility of sampling FGD wastewat er streams prior to commingling with other wastewater;

 Locations of potential sampling points;

 Conditions at potential sampling point s (e.g. temperature and pH); and

 Type of discharge at each sampling poi nt (e.g. continuous or intermittent); and

 Health and safety concerns at each potential sampling point.DRAFT 3-2 EPA will use this information to sele ct sampling points and plan the sampling episode. Prior to the sampling episode, the ERG crew chief will prepare a plant-specific sampling plan outlining the descriptions of sa mpling points (including any information on flow rate, temperature, solids content, and pollutant concentrations pr ovided by the facility contact), equipment needed (e.g., bottle clamp, dipper, and pole), anticipated health and safety requirements and procedures, the sample team organization, plant names and contacts, location of the local Federal Express office, and the names and addresses of analytical laboratories. The ERG Health and Safety Coordinato r (HSC), Kevin Sikora, will iden tify the plant-specific health and safety requirements.

The ERG crew chief will distribute the pl ant-specific sampling plan to each team member and make sure they are completely fam iliar with the plant-specific health and safety requirements. Plant personnel will be given copi es of the generic sampling plan, generic health and safety plan, and plant-specific samp ling plan prior to the start of sampling.

The ERG crew chief will also coordina te the procurement and shipment of all necessary sampling and health and safety equipment.

3.3 Field Sampling Activities

At each site, the ERG crew chief, in conjunction with the EPA Work Assignment Manager (WAM), will meet with plant personnel to determine whether samples can be collected at each of the planned sampling points. Upon ma king the decision to collect samples, the ERG crew chief will update the descriptions of th e proposed sampling points, if necessary, in consultation with EPA and plant personnel. If necessary, additional equipment and glassware will be obtained. The revised description shall include:

 A sample point description and co llection procedure for each sample point;

 A list of the sample fractions to be collected at each point;

 A list of potential physical hazards (such as pH, temperature, and potentially hazardous equipment);DRAFT 3-3  A list of potential chemical hazards associated with each sample point; and

 A list of proposed health and safety procedures.

Prior to sampling, the ERG crew chie f will also notify the ERG HSC of any revised sampling activity descrip tions along with recommended revisions to the proposed health and safety procedures. Together, the crew ch ief and HSC will review the proposed health and safety procedures. The crew chief will incorpor ate any plant-specific changes indicated by the HSC, and gain approval for sampling from the HSC before proceeding with sampling activities.

All sample bottles will be labeled, co llected, and preserved, according to method
protocols. Sample fractions requiring ≤ 6  C preservation will be placed on ice until desired
temperature is reached. Sample fractions will then be sealed, and placed in coolers for shipment to the laboratory. The Traffic Report forms will be completed and placed in plastic sleeves

inside the coolers. The cooler s will then be taken to the nearest Federal Express office and shipped to the analytical laboratories. At th e conclusion of the sampling episode, the sampling equipment will be prepared for return shipping.

3.4 Standard Logistics

This section of the sampling plan summari zes plant contacts, analytical laboratory contacts and addresses, and sampling team personnel and support functions.

3.4.1 Plant Contacts

To be determined prior to sampling.

3.4.2 EPA Contacts

Ron Jordan Engineering and Analysis Division U.S. Environmental Protection AgencyDRAFT 3-4 1200 Pennsylvania Avenue, NW (4303T) Washington, D.C. 20460 (202) 566-1003

Jezebele Alicea Engineering and Analysis Division U.S. Environmental Protection Agency 1200 Pennsylvania Avenue, NW (4303T) Washington, D.C. 20460 (202) 566-1755

3.4.3 Analytical Laboratories

To be determined prior to sampling.

3.4.4 ERG Contacts

Deb Bartram (ERG Work Assignment Manager) Eastern Research Group, Inc. 14555 Avion Parkway, Suite 200 Chantilly, VA 20151 (703) 633-1669

TJ Finseth (Sampling Program Lead) Eastern Research Group, Inc. 14555 Avion Parkway, Suite 200 Chantilly, VA 20151 (703) 633-1698

3.4.5 Freight Forwarders

Federal Express General Information (800) 463-3339

Specific location to be determined for each sampling trip.DRAFT 4-1 

### 4.0 S AMPLE 

### S HIPMENT

All sample containers will be labeled with ERG's standard address labels. All samples will be tracked using Traffic Report fo rms. Custody will be maintained by the sampling crew chief from sample collection until samples are delivered to Federal Express.

All samples will be packaged and sh ipped in accordance with DOT or IATA regulations. The general IATA packaging requirements for air shipment are as follows:

 “Inner packaging must be so packed, secu red or cushioned as to prevent their breakage or leakage and so as to cont rol their movement within the outer packaging during normal conditions of tran sport. Cushioning material must not react dangerously with the contents of the inner pack aging. Any leakage of the contents must not substantially impair th e protective propertie s of the cushioning material. Unless otherwise provided in this paragraph or in the Packing Instructions, liquids in Classe s, 3, 4, 5, 6, or 8 of Packing Gr oups I or II in glass or earthenware inner packaging, must be packaged using material capable of absorbing the liquid. Absorbent material must not react dangerously with the liquid. Absorbent material is not required...” (IATA Dangerous Goods Regulations, 5.0.16).

 “When filling receptacles for liquids, sufficient ullage (outage) must be left to ensure that neither leakage nor permanent distortion of the receptacle will occur as a result of an expansion of the liquid caused by temperatures likely to prevail during transport. Liquids must not complete ly fill a receptacle at a temperature of 55°C (130°F).” (IATA Danger ous Goods Regulations, 5.0.12).

The packing and labeling procedures in the following subsections may be used for nonhazardous samples. Hazardous samples will be identified based on consultation with the hazardous shipments contact, and appropriate ha zardous shipping procedures will be followed. Based on process considerations, sa mples collected are not expected to be classified as IATA dangerous goods.

4.1 Sample Set Preparation

Samples are collected as a series of “fractions,” or bottles designated for particular analyses requiring the same preser vation. The comprehensive water sample set consists of sample fractions for all polluta nts listed in Section 2.2, collected as 24-hour composite samples and transferred in to the individual sample bottles.DRAFT 4-2 4.2 Sample Packing

All dilute samples from the plant will be packed according to the following guidelines (there is no limit on the amount of liquid each sample container may contain):

1. Label each sample bottle. If a required preservation is not used, cross it off with indelible ink. Cover the label with clear tape to protect this information. Metals sample bottles will not be labeled; inst ead, the outer plastic bag for each bottle will be labeled.

2. Tighten the lid on each filled sample bottle, being careful not to overtighten the lid. If bottle threads are dirty to where th e lid is impeded from closing, clean the threads on the bottle being careful to not introduce contamination into the sample. Clean the sample bottle with a cloth rag or paper towel. The bottle threads will not be cleaned for the mercury sample bottles.

3. Place each sample bottle requiring ≤ 6  C preservation into an ice chest with wet ice prior to packaging to cool.

4. When each sample requiring ≤ 6  C preservation has reached the desired temperature, wrap each glass sample bottle with two la yers of “bubble wrap” (or place bottle in two “bubble bags”). The bubble wrap must fit snugly and completely cover the sample bottle. Each “bubble-wrapped” c ontainer and plastic container must then be enclosed in an individual sealable plastic freezer bag.

5. Place two garbage bags inside each other in the cooler.

6. Place sample bottles in garbage bags in the cooler with proper end up, close the interior garbage bag by tying, or with a twist-tie.

7. Add ice to cooler to keep samples cold during shipment. Arrange blue ice or sealed plastic freezer bags filled with we t ice on top of the sample bottles (if samples require ≤ 6  C preservation). If using wet i ce, place the ice inside two onegallon sealable freezer bags. Put at least 4 × 1⁄2 gallons of ice (4 × 2.5 lbs of ice) in each large cooler and 2 × 1⁄2 ga llons of ice (2 × 2.5 lbs of ice) in each small cooler. More ice should be used when ambient te mperatures are very high. The ice should be placed inside the second garbage bag. Close the second garbage bag with a twist-tie.

8. Fill in around the bottles and any free sp ace with additional cushioning material. Sufficient packing material should be used so that the sample containers will not shift during shipment.

9. Seal the Traffic Report form in a plastic zip-lock bag and tape securely to the inside of the cooler lid.DRAFT 4-3 10. Place a "Return to ..." label on th e inside of the cooler lid.

11. Close cooler.

12. Make several wraps with ta pe around the cooler perpendicular to the seal to ensure that the lid will remain closed if the latch is accidentally released or damaged.

13. Tape the cooler drain plug so it will not open.

14. Place a completed address label on the lid of the cooler including name, address, and telephone number of the receiving laboratory and the return address and telephone number of the shipper.DRAFT 5-1 

### 5.0 R EFERENCES

U.S. EPA. 2009. Steam Electric Power Generating Point So urce Category: Final Detailed Study Report . EPA 821-R-09-008. Washington, DC. (October). Available online at: http://www.epa.gov/guide/steam/finalreport.pdf . DCN SE00003.

Eastern Research Group, Inc. 2009. Quality Assurance Project Plan for the Steam Electric Effluent Guidelines Rulemaking . (September). DCN SE00058.