# Draft Sampling Plan Duke Energy Carolinas’
Allen Steam Station Belmont, NC
Sampling Episode XXXX

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

April 9, 2010

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

Page

1. I NTRODUCTION ................................................................................................................. 1-1 1.1 Background .......................................................................................................... 1-1 1.2 Objectives and Scope ........................................................................................... 1-1

1.3 Plant Selection ..................................................................................................... 1-2

2. F ACILITY O VERVIEW ........................................................................................................ 2-1 2.1 FGD Scrubber Systems ........................................................................................ 2-1

2.2 FGD Wastewater Trea tment System ................................................................... 2-2

3. S AMPLING P ROCEDURES ................................................................................................... 3-1 3.1 Sampling Point Selection ..................................................................................... 3-1 3.2 Analyte Selection ................................................................................................. 3-1 3.3 Sample Collection Procedures ............................................................................. 3-2

3.3.1 Influent to FGD Wastewater Treatment System (SP-1) .......................... 3-3 3.3.2 Influent to Bioreactor System (SP-2) ....................................................... 3-8

3.3.3 Effluent from Bioreactor System (SP-3) ................................................ 3-16 3.4 Sample Preservation, Shi pping, and Analysis ................................................... 3-25 3.5 Field Measurements and Engineering Data Collection ..................................... 3-26 3.6 Sample Labeling ................................................................................................ 3-27 3.7 Traffic Reports ................................................................................................... 3-27 3.8 Quality Assurance/Quality Control .................................................................... 3-28 3.9 Sample Splitting ................................................................................................. 3-30

4. S AMPLING A CTIVITIES ...................................................................................................... 4-1 4.1 Sampling Team Organization .............................................................................. 4-1 4.2 Presampling Preparation ...................................................................................... 4-1 4.3 Field Sampling Activities .................................................................................... 4-1 4.4 Logistics ............................................................................................................... 4 -2

4.4.1 Allen Steam Station Contacts .................................................................. 4-2

4.4.2 EPA Contacts ........................................................................................... 4-2 4.4.3 Analytical Laboratories ............................................................................ 4-3

4.4.4 ERG Contacts ........................................................................................... 4-3 4.4.5 Freight Forwarders ................................................................................... 4-3

5. S AMPLE S HIPMENT ........................................................................................................... 5-1 5.1 Sample Set Preparation ........................................................................................ 5-1 5.2 Sample Packing .................................................................................................... 5-1

6. S ITE -S PECIFIC H EALTH AND S AFETY P ROCEDURES .......................................................... 6-1 6.1 Emergency/Medical Procedures .......................................................................... 6-1

6.1.1 First Aid 6-1 6.1.2 Site Evacuation/Emergency Response Plan ............................................. 6-1 6.1.3 Emergency Showers and Eye Washes ..................................................... 6-1 6.1.4 Local Hospital .......................................................................................... 6-1 6.2 ERG Health and Safety Responsibilities and Authority ...................................... 6-1TABLE OF CONTENTS (Continued)

Page

ii 6.2.1 Work Assignment Manager ..................................................................... 6-2

6.2.2 Crew Chief ............................................................................................... 6-2 6.2.3 Sampling Team Members ........................................................................ 6-2 6.3 Briefings ............................................................................................................... 6 -2 6.3.1 Off-Site Briefings..................................................................................... 6-2 6.3.2 On-Site Briefings ..................................................................................... 6-3 6.4 Safety Procedures ................................................................................................. 6-3 6.4.1 Personal Protective Equipment (PPE) ..................................................... 6-3 6.4.2 Safety Practices ........................................................................................ 6-3

6.4.3 Safe Work Practices ................................................................................. 6-4 6.5 Sampling-Point-Specific Safety Procedures ........................................................ 6-4 6.5.1 Physical Hazards ...................................................................................... 6-4

6.5.2 Thermal Hazards ...................................................................................... 6-5

6.5.3 Chemical Hazards .................................................................................... 6-5 6.6 Temperature Extremes ......................................................................................... 6-5

6.6.1 Heat Stress ............................................................................................... 6-5 6.6.2 Heat Stress Monitoring ............................................................................ 6-6

6.7 First Aid ............................................................................................................... 6 -7 6.8 Sample Preservation and Safety Considerations .................................................. 6-7 6.9 Training and Medical Mon itoring Requirements ................................................ 6-8

6.10 Shift Work Protocol ............................................................................................. 6-9

7. R EFERENCES ..................................................................................................................... 7-1iii LIST OF TABLES

Page

3-1 Sample Collection at Allen Steam Station ..................................................................... 3-31

3-2 Analytical Methods ....................................................................................................... 3-32

3-3 Summary of Sample Container and Planned Preservation ............................................ 3-33

3-4 Sampling Point Field Measurements ............................................................................. 3-33

6-1 Sample-Point-Specific PPE and Potential Hazards ....................................................... 6-10

LIST OF FIGURES

Page

2-1 Simplified Diagram of the FGD Wast ewater Treatment System, Allen Steam

Station ....................................................................................................................... ....... 2-6

2-2 Physical/Chemical Separation and Biologi cal Reactor Portion of FGD Wastewater Treatment System, Alle n Steam Station .......................................................................... 2-7

3-1 Sample Preservation Log Sheet ..................................................................................... 3-34

3-2 Field Sampling Log Sheet .............................................................................................. 3-3 5

3-3 Engineering Data Collection Sheet (Page 1 of 4) .......................................................... 3-36

3-4 Engineering Data Collection Sheet (Page 2 of 4) .......................................................... 3-37

3-5 Engineering Data Collection Sheet (Page 3 of 4) .......................................................... 3-38

3-6 Engineering Data Collection Sheet (Page 4 of 4) .......................................................... 3-39

3-7 Example Traffic Report ................................................................................................. 3- 401-1 1. I NTRODUCTION

The Engineering and Analysis Division (E AD) of the U.S. Environmental Protection Agency (EPA) is currently conducting a sampli ng program at steam electric power plants. The sampling program will characterize raw wastewaters generated by coal-fired steam electric power plants, as well as evaluate treatment tec hnologies and best management practices used to reduce pollutant discharges. This sampling pl an, developed for the Duke Energy Carolinas’ Allen Steam Station (Allen), located in Belm ont, North Carolina, provides plant-specific sampling procedures and methods EPA and its contractors will follow when conducting sampling activities. Sampling will be performed by EPA’s technical contractor, Eastern Research Group, Inc. (ERG), under Contract No. 68-C-02-095. This document, in combination with the Generic Sampling and Analysis Plan for Coal-Fired Steam Electric Power Plants [1], is intended to serve as a guide to the ER G field sampling crew, a review mechanism for EPA personnel, and a source of procedural inform ation for plant personnel.

1.1 Background

During EPA’s recently completed detailed study of the steam electric industry, EPA identified metals and certain other constituents pr esent in the wastewater discharges from steam electric power plants that are contributing the majority of the toxic loadings for the industry. Additionally, EPA determined that one of the wa ste streams contributing most of these toxic loadings are associated with wet flue gas desu lfurization (FGD) systems present at coal-fired power plants.

This sampling plan will focus on charact erizing wastewaters and treatment system discharges at Allen. For a genera l description of the steam electr ic process and the wastewaters 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 Detail ed Study Report [2].

1.2 Objectives and Scope

EPA is preparing to collect and analyze samples to characterize wastewater streams generated at coal-fired steam el ectric power plants. This sampli ng plan 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/chemical treatment for heavy metals removal using hydroxide or a combination of hydr oxide and sulfide precipitation; and

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

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

 What are the characteristics (i.e., pollutant s present, pollutant concentrations, flow rate/volume) of untreated F GD scrubber purge wastewater?1-2  What are the effluent concentrations for pollutants present in treated FGD

wastewater?

 What are the pollutant loadings associat ed with discharges of FGD wastewater following treatment?

EPA conducted a one-day presampling s ite visit at Allen on October 22, 2009 and collected the following information:

 Information about the plant’s operations , including existing sampling data and results;

 Process-specific information;

 Information on pollution prevention a nd wastewater treatment/operations;

 Plant-specific information to tailor sampling plans; and

 Information on potential sampling points.

The sampling program will consist of four-day sampling episodes at selected plants. The sampling will characterize the wastewaters gene rated 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 cons isting 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 performance of treatment systems at steam electric power plants. In addition to sampling the wastewater, EPA will co llect information regarding system design and day-to-day operation.

1.3 Plant Selection

EPA expects to select up to seven coal-fir ed steam electric plants for FGD wastewater sampling, basing the plant selection on the proces s configurations and characteristics of the plants.

Allen was selected by EPA for sampling ba sed on the following site characteristics:

 The plant is a coal-fired power plant that burns bituminous coal in each of its five generating units;

 The plant operates two limestone forced oxidation wet FGD systems that service all five generating units;

 The plant operates a segregated FGD wastewater treatment system, which includes the following steps:

— Equalization,

— pH adjustment (lime addition),

— Ferric chloride addition,1-3 — Polymer addition,

— Clarification,

— Filtration, and

— Biological treatment (nitrogen and metals);

 The plant operates a SNCR on a ll five generating units; and

 The plant produces a commerc ial-grade gypsum by-product.2-1 2. F ACILITY O VERVIEW

Allen operates five steam electric units a nd each has a coal-fired boiler. Units 1 and 2 came on line in 1957, and each has a capacity of 165 megawatts (MW). Units 3, 4, and 5 came on line in 1959, 1960, and 1961, respectively, and each has a capacity of 275 MW. All five generating units burn bituminous coal. The electr ic generating units at Allen are operated on a cycling basis and are not baseload units. The pl ant is located on 1,000 acres adjacent to the

Catawba River.

Allen recently retrofitted all five units with two FGD scr ubber systems (Absorbers 1 and 3) to control the sulfur dioxide (SO 2 ) releases from the plant. Units 1, 2, and 5 exhaust to FGD Absorber 1 (which began operation in Februa ry 2009), and Units 3 and 4 exhaust to FGD Absorber 3 (which began operation in May 2009). The wet FGD scrubbe rs are designed to remove more than 95 percent of SO 2 from the flue gas. With the recent addition of the FGD scrubber systems, Allen also installed an FGD wastewater treatment system to control the discharges of the wastewater generated during the operation of the FGD scrubbers. Sections 2.1 and 2.2 further discuss the FGD scrubber system s and the FGD wastewater treatment system, respectively.

Allen operates electrostatic precipitators (ESPs) to control fly ash and particulate emissions from the plant. Allen also opera tes SNCR systems year-round to control nitrogen oxide (NO

x ) emissions from the plant. Additionall y, the boilers are operated with low-NO

x burners and a separated overfire air system.

The ESPs at Allen are particulate contro l devices that are de signed to remove 99.9 percent of the fly ash and other particulates from the flue gas. Allen utili zes ESPs to remove the fly ash from all five generating units. The fly as h and other particulates are collected in hoppers and usually pneumatically transferred to fly ash s ilos. However, Allen also has the capability of handling the fly ash wet by sluicing the fly as h in the hoppers and tr ansferring the fly ash transport water to the ash basin.[QUESTION FOR ALLEN: When does the plant use the wet fly ash handling system?]

All five generating units have the following configuration:

 Boiler (SNCR system contained in boiler);

 Air preheater;

 ESP; and

 FGD scrubber system.

2.1 FGD Scrubber Systems

Allen operates two wet FGD scrubber systems that treat the flue gas fr om all five electric generating units. The plant uses limestone slurry as the sorbent for su lfur dioxide absorption.

Limestone and service water are fed to on-site ba ll mills, which pulverize the limestone to create the slurry. From the ball mills, the slurry is transferred to hydroclones to collect limestone particles that are too la rge for use in the FGD system. The underflow from the hydrocyclones is transferred to the reject tank and then sent back to the ball mill for additional processing. The2-2 overflow from the hydroclones, which is approxim ately 50 percent solids, is transferred to the reagent tank for storage and then used as fresh limestone slurry in the absorber.

The fresh limestone slurry is fed to the r eaction tank of the FGD system and the recycle pumps pump the slurry to the va rious levels of the FGD scrubbe r. Both absorbers have four spray levels; however, the plant typically operates only three levels at one time. The slurry is pressurized and sprayed downward into the scru bber vessel through spray nozzles. As the slurry falls downward and the flue gas flows countercurr ent to the slurry, the spray droplets of the limestone slurry contact the flue gas and absorb the SO 2 , which reacts with the limestone particles and produces calcium sulfite. The spra y droplets continue to flow downward in the scrubber until they reach the reaction tank. Alle n bubbles air through the reaction tank to oxidize

the calcium sulfite to calci um sulfate (i.e., gypsum).

Allen intermittently blows down the gypsum sl urry from the reaction tank to control the

solids and/or chlorides concentration in the sc rubbers. The chlorides concentration in the scrubbers is maintained between 3,000 and 10,000 ppm (parts per million), with a design maximum chlorides concentration of 12,000 ppm. Th e typical percentage of solids within the

scrubber is 14 to 16.

The gypsum slurry is pumped to the prim ary hydrocyclones where the solid gypsum is separated from the water by centrifugal force. The solid gypsum is forced outward to the walls of the hydrocyclones and falls downward, while the wa ter exits the top of the hydrocyclones. The gypsum from the primary hydrocyclones is transf erred to the filter feed tank, which is then

transferred to the vacuum filter belts. Th e overflow from the primary hydrocyclones is transferred to a holding tank and then pumped to the secondary hydrocyclones. The underflow from the secondary hydrocyclones is returned to the scrubber. The overflow from the secondary hydrocyclones is sent to the FGD wastewater treatment system. Th is FGD purge stream contains 0.5 to 0.8 percent solids.

Allen washes the gypsum sent to the vacuum fi lter belts with service water as it is applied to the belts to reduce the chlorides in the gyps um to typically less th an 20 ppm. The vacuum filter belts dry the gypsum to a moisture conten t of approximately four percent. The gypsum produced at the plant must have a chloride cont ent of less than 120 ppm and a moisture content of less than 10 percent to be so ld to a wallboard manufacturer. Allen transfers the dry gypsum to a storage area and then trucks the gypsum to a wallboard manuf acturer in Mount Holly, North

Carolina.

2.2 FGD Wastewater Treatment System

The FGD wastewater treatment system is de signed to receive intermittent transfers of FGD wastewater from the FGD sy stem, which consists of seconda ry hydrocyclone overflow, at a flow rate of approximately 400 gallons per minut e (gpm). The FGD wastew ater treatment system consists of chemical precipitation and biologi cal treatment technologies. Allen installed the

wastewater treatment system to treat the FGD scrubber purge wa stewater to meet its permit limits, which include limits for total suspe nded solids (TSS) and selenium. The Allen FGD wastewater treatment system contains the following treatment operations:2-3  Physical/Chemical Separation:

— Equalization,

— pH adjustment (lime addition),

— Ferric chloride addition,

— Polymer addition,

— Clarification, and

— Filtration; and

 Biological Reactors:

— Cooling (heat extraction),

— Nutrient addition,

— First-stage biol ogical reaction,

— Nutrient addition, and

— Second-stage biolog ical reaction.

Figures 2-1 and 2-2, located at the end of th is section, present pro cess flow diagrams of the FGD wastewater treatment system, as well as the planned sampling locations for EPA’s sampling episode. Figure 2-1 is a simplified diag ram of the FGD wastewat er treatment system, showing different portions of the system. Figure 2-2 is a diagram of the chemical precipitation and biological reactor portions of the treatment system.

The secondary hydrocyclone overflow from the scrubbers is transferred to the equalization tank at the beginning of the wast ewater treatment system. Allen also has a maintenance tank that is used as either a spar e equalization tank or a spare sludge holding tank. The equalization tank also receives water from the filtrate sump (which includes filter press filtrate), gravity filter backwash reject, backflush waste from the biological treatment system, and off-specification biological tr eatment effluent. The wastewater entering the equalization tank has a pH of 6.7-6.9 S.U. and a temperature of 105-115o F.

From the equalization tank, the wastewater en ters three reaction tanks in series: reaction tank 1, in which lime is added to increase th e pH to between 8.6 and 9.2 S.U.; reaction tank 2, formerly used for organosulfide addition, but wh ich is now used to pr ovide additional mixing; and reaction tank 3, in which ferric chloride is added.

The overflow from reaction tank 3 flows thr ough a flow splitter, which distributes the flow evenly to two clarifiers. Allen operates the two clarifiers in pa rallel, each capable of handling 100 percent of the waste stream flow. A polymer is added to the wastewater just before it enters the clarifiers. Hydrochl oric acid is added to the wast ewater at a point between the

clarifiers and the sand filters to ensure that the pH is adjusted closer to neutral prior to the biological treatment system. Af ter the hydrochloric acid addition, the overflow from the two clarifiers is split and sent th rough three sand filters in parallel, each of which can handle 75 percent of the waste stream capac ity. The sand filters are continuous backwash gravity filters and produce an effluent with a TSS concentration of approximately 1 to 2 ppm. The filter backwash is sent to a sump and then tran sferred to the equalization tank.

The sludge collected in the clarifier is tr ansferred to a sludge hol ding tank. A portion of the clarifier sludge is recycled from the sludge ho lding tank to reaction tank 1, while the majority is pumped to a filter press for dewatering. The filter press uses hydraulic power from2-4 compressors to remove water. The solids are transferred to an off-site landfill and the filtrate is recycled to the equalization tank.

Prior to entering the biol ogical portion of the wastew ater treatment system, the wastewater is cooled by heat exchangers to 95 o F, the optimal temperature for the biological treatment system. The heat exchangers were constr ucted with a titanium alloy that can withstand the high levels of chlorides and suspended solids in the FGD wastewater entering the biological treatment system. The heat exchanger requires 300 to 350 gpm of cooling water. Allen adds nutrients (in the form of molasses) to the wastewater as it flows from the heat exchanger to the biological treatment system. The nutrients prov ide a source of carbon to feed the bacteria.

In the bioreactor portion of th e treatment, Allen treats the wa stewater in two stages. Each stage contains eight bioreactor cells, which are oper ated in parallel. Each cell contains 20 feet of

activated carbon media. Within the activated carbon bed, specialized microbes fill the voided areas and reduce selenium to its elemental form, while other metals are precipitated as sulfide complexes. The microbes also reduce the concentr ation of nitrogen present in the wastewater. The wastewater is divided evenly among the first stage of eight cells. The flow to each cell is sent to 16 distribution pipes to create an even di stribution of flow into the top of the cell. The water level in the cell is designe d to be approximately six inches above the activated carbon bed; however, at the time of the site visit, the wa ter level was below the top of the carbon bed.

Allen operates the bioreactors to achieve a negative oxidation reduc tion potential within the system, which provides the optimum environmen t to reduce selenium to its elemental form. This reduction potential is contro lled by the amount of nutrient that is fed to the system. The plant also controls the pH in the bioreactor cells to between 6.0 and 9.0 S.U. because extreme high or low pH levels could a ffect the performance of the microbes and potentially allow

nondesirable microbe s to propagate.

The effluent from the first-stage bioreactor cel ls is transferred to the first-stage effluent storage area, where it is commingl ed with the other wastewater in the area. The wastewater is then transferred to the eight second-stage bi oreactor cells, which are operated in parallel.

Nutrients are added to the wastewater as feed fo r the microbes as the wa stewater is transferred. As in the first stage, the wastewater is divi ded evenly among the eigh t second-stage cells and each cell has 16 distributor pipes to evenly distribute the flow into the cell.

Occasionally the bioreactor cells must be b ackflushed to remove accumulated solids. The plant pumps the effluent from the first-stage bi oreactor cells backward s through each cell and it overflows into a spillover chamber. The plan t then returns the backwash overflow to the equalization tank at the start of th e FGD wastewater treatment system.

Because the first-stage bioreac tor cells denitrify the waste stream, they produce nitrogen and carbon dioxide gas. To remove the gas from the cells, the plant oc casionally performs a degassing operation where water is sent backward s through the cells, like a backflush, but the flush is only long enough for the gas to “burp” out of the system. The second-stage bioreactor cells are primarily anoxic and do not produce as much gas as the first-stage cells, requiring less frequent degassing than the first-stage cells. The TSS concentration within the first- and secondstage bioreactor cells is approximately 40 ppm. The solids in the cells are mostly biological

materials.2-5 From the second stage of the bioreactor trea tment system, the wastew ater is commingled with the heat exchanger cooling water and transfe rred to the ash basin. The effluent from the ash basin is discharged to the Catawba River via Outfall 002.

Because the steam electric generating units at Allen are operated on a cycling basis and are not baseload units, there are times when the units are shut down for a few days. During these shut-down periods, the wastewat er treatment system does not receive any scrubber purge wastewater and, therefore, the plan t has to find a way to feed the microbes to keep them alive. If

Allen knows ahead of time that all units will be shut down for a couple of days, they can build up additional scrubber purge in the equalization a nd maintenance tanks and then operate the FGD wastewater treatment system at a reduced flow rate until they begin opera ting again. If the plant is down for several days without advanced know ledge, the plant can run service water through the system and feed nutrients to the bi oreactors to sustain biological growth.

Figure 2-2 shows the planned sampling point s for the sampling episode at Allen. The influent sampling point at Allen’ s FGD wastewater treatment system is located upstream of the equalization tank. Thus, the influe nt sampling point is upstream of any chemical addition. The in-process sampling point within Allen’s FGD wastewater treatment system is located downstream of the sand filters and the holding tank. The biological reactor effluent sampling point at Allen’s FGD wastewater treatment syst em is located downstream of the second-stage effluent storage area and upstream of where the FGD wastewater treatment effluent is commingled with the heat exchanger cooling water.2-6Phys/ChemSeparationBioreactorSystemAsh BasinFGD Scrubber PurgeInternalOutfall 005Outfall 002Bottom ash sluice, runoff(stormwater, coal pile, limestonehandling), and plant sumpsCatawbaRiverFigure 2-1. Simplified Diagramof the FGD Wastewater Treatment System, Allen Steam Station2-7Figure 2-2. Physical/Chemical Separation and Biological Reactor Portion of FGD Wastewater Treatment System, Allen SteamStation3-1 3. S AMPLING P ROCEDURES

This section discusses th e planned sampling procedures to be followed during the sampling episode at Allen. This section also prov ides the necessary information to plan for the logistics of this sampling episode. All tables and fi gures in this section are presented at the end of

the section.

3.1 Sampling Point Selection

EPA selected the following eight sampling points for this plant (the three proposed sampling locations for Allen’s FGD wastewater treatment system as well as the related Quality Assurance/Quality Control (QA/QC) samples):

 SP-1 Influent to FGD Wastewater Treatment System;

 SP-2 Influent to Bioreactor System;

 SP-3 Effluent from Bioreactor System;

 SP-4 Duplicate of Influent to Bioreactor System (SP-2);

 SP-5 Duplicate of Effluent fr om Bioreactor System (SP-3);

 SP-6 Influent to FGD Wastewater Treat ment System (SP-1) Field Blank;

 SP-7 Influent to Bioreactor Sy stem (SP-2) Field Blank; and

 SP-8 Effluent from Bioreactor System (SP-3) Field Blank.

3.2 Analyte Selection

Analytes that will be included in EPA’s Allen sampling episode 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;3-2  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.

The analytes selected for analysis reflect the current understanding of coal-fired power plant FGD wastewaters, including contributi ons from coal, scrubbe r sorbents, treatment chemicals, and other sources. Table 3-1 lists the potential analytes for each sampling point, Table 3-2 lists the analytical methods that will be us ed, and Table 3-3 lists the sample container and volume and planned on-site preservation for each parameter or parameter group.

3.3 Sample Collection Procedures

To characterize the influent to FGD wastewat er treatment system (SP-1), the influent to bioreactor system (SP-2), and th e effluent from bioreactor syst em (SP-3) at Allen, the sampling team will use varying methods to collect th e samples depending on the sampling point and pollutant parameters. This section describes in detail the sample co llection techniques.

Samples are collected as a se ries of “fractions,” or bottl es designated for particular analyses requiring the same preservation. The co mprehensive sample set consists of sample fractions for all pollutant classes listed in Sect ion 3.2. Note that some sample fractions will be collected in the same sample bottl e, such as Group I analytes (T SS, TDS, sulfate, and chloride) and Group II analytes (ammonia as nitrogen, COD, nitrate/nitrit e as nitrogen, TKN, and total phosphorus).

In general, samplers will work in teams of two to ensure that proper sampling techniques are followed and adequate notes are taken at each sampling location. Samplers will wear disposable gloves, Tyvek® suits, masks (when sampling for mercury by EPA Method 1631E), steel-toed boots, hard hats, and safety eyew ear, and will observe precautions while collecting samples, remaining aware of their surroundings. Note that the use of masks is to prevent contamination of the mercury samples and not for respiratory protection.

Sample containers and bottles will be pur chased precleaned and certified and will not require rinsing with sample. The sample bottles for the metals analyses will be cleaned according to EPA Method 1669. For this sampling episode, ERG will collect 24-hour composite samples at

the influent to and the effluent from the bior eactor sampling points for most analytes; however, cyanide will be collected as a single grab samp le and mercury will be collected as four grab samples. ERG will collect individual grab samp les at the influent to the FGD wastewater treatment system sampling point for all analytes . ERG will collect one sample at each sampling point each day over four consecutive 24-hour peri ods (mercury will be collected as four grab samples each day for the influent to and efflue nt from the bioreactor sampling points). 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 procedures3-3 described in EPA Method 1669. Samplers will use “clean hands / dirty hands” sample collection techniques when collecting metal sample fr actions, as described in EPA Method 1669.

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 and then placed into coolers containing ba gged ice throughout sample storage, shipment, and receipt at the analytical laboratories.

3.3.1 Influent to FGD Wastewater Treatment System (SP-1)

The influent to FGD wastewater treatment sy stem (SP-1) has a sample tap located on the wastewater piping downstream of the purge tank and upstream of the equalization tank. ERG will collect the sample prior to the wastewater entering the equalization tank because the FGD scrubber purge is commingled with other waste streams in the equalization tank and, therefore, the sampling point upstream of the tank provides the best representation of the FGD scrubber purge from the Allen FGD system. Because the fl ow from the purge tank to the equalization tank is not continuous, ERG will need to coordinate closely with A llen personnel during the sampling episode to determine when grab samples can be collected (i.e., when wastewater is being transferred to the FGD wastewater treatment sy stem). ERG will follow protocols described in EPA Method 1669 to collect metal sample fractions from SP-1.

ERG plans to collect split samples with A llen (or its representative), where possible; therefore, ERG plans to attach a piece of silicon e tubing to the sample ta p with a “Y” splitter at the other end of the tubing to allow ERG and Al len (or its representative) to collect samples simultaneously. If problems occur during the co llection of split samples (e.g., the splitters become clogged and the flow is split unevenly between the sampling crews), then EPA may stop the split sample collection and offer instead to collect duplicate samples with Allen or its representative. For all analyses (except dissolved metals and hexa valent chromium), the samplers will collect samples through the tubing directly in to the specified containers. For the dissolved metals (excluding mercury) and hexavalent chro mium samples, the samplers will fill one 10-L container, allow the solids to settle for one hour, and then pump the aqueous portion of the sample through a 0.45- μ m filter and then through a “Y” splitt er into the specified containers; therefore, the dissolved metals and hexavalent chromium samples will be collected as split samples.

Due to the high suspended solids content (t ypically 0.5 to 0.8 per cent at Allen, but has been observed on the order of 1 to 5 percent at other plants) of the samples collected at the influent to the FGD wastewater treatment syst em, EPA may analyze the samples as bi-phasic samples. If the TSS content of the sample is gr eater than one percent, then the laboratory will separate the aqueous and solid portio ns of the sample and analyze bo th for the analyte of interest. In this instance, Group I (chloride and su lfate only), Group II (ammonia as nitrogen, nitrate/nitrite as nitrogen, and total phosphorus only), and total metals (including mercury, 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 asbi-phasic samples. Scrubber purge samples with less than one percent TSS will not require biphasic separation and analysis.3-4 The samples for the influent to the FGD wastewater treatment system (SP-1) will be collected from a sample tap. 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 speci ally-cleaned according to the procedures

described in EPA Method 1669. ERG will follow protocols described in EPA Method 1669 to collect metal sample fractions. Two or more ER G samplers (“clean hands” and “dirty hands”) will follow the protocols described in the steps below to set up the sampling point, collect the field blank samples, and collect wastewater samp les. This 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-ba gged sample bottles, precleaned tubing, blank water, and cleanbox. Depending on the condition of the sample tap, samplers may need to wipe the tap with a clean paper towel to remove any buildup on the tap that could potentially fa ll 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 cleanbox at the point of sample collection and secures it open with the c lips located inside the box.

1 For the sample collection, the samples will be split with th e plant (or the plant’s representative) and, therefore, the sample set-up describes equipment needed for 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 in this plan.3-5 4. “Dirty hands” opens the outer bag cont aining a length of pr ecleaned silicone tubing. “Clean hands” opens the inner ba g inside of the cleanbox, removes the tubing, and places clean plastic bags ove r 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 and attaches the funnel 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 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 total metals field blank samples 2

.

7. “Dirty hands” opens the outer bag for a precleaned 10-L contai ner. “Clean hands” opens the inner bag and loosens the li d. “Clean hands” holds the end of the silicone tubing at the mouth of the 10-L container and 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” closes 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.

2 ERG will collect field blank samples at the influent to the FGD wastewater treatment system only during one day of the sampling episode. Additionally, 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 sample will be analyzed 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 bl ank sample in the field.3-6 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 precleaned 10-L contai ner. “Clean hands” opens the inner bag and loosens the li d. “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 with samp le to be analyzed for dissolved metals and hexavalent chromium, which is required to be filtered for these analyses. The samplers will allow the solids to settle for one hour while collecting the remaining samples. “Clean hands” places the lid back on the 10-L container, places the plastic bag over the end of the silico ne tubing, and places the tubing into the

cleanbox. ”Clean hands” screws the lid on th e 10-L container and 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. The samplers need to test the total cyanide samples for sulfides and oxidants and preserve th e samples immediately after sample collection, according to the preservati on protocols outlined in Section 3.4.

Dissolved Metals Sample Collection

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

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.3-7 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. “Clean hands” secures the cleanbox 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 precleaned Teflon® tubing attached to a 5-foot length of pr ecleaned silicone tubing, a “Y” splitter, and two additional pieces of precleaned silicone tubing. “Clean hands” moves the tubing into the cleanbox, opens the inner bag, and removes the tubing. “Clean hands” places a cl ean plastic bag over the ends 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 and then stops the pump. The samplers repeat the procedure for the dissolved metals and he xavalent chromium field blank samples. If a new filter is needed, “clean hands” removes the used filter and samplers following step 21 to replace the filter 3

.

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”

3 ERG will collect field blank samples only at the influent to the FGD wastewater treatment system during one day of the sampling episode.3-8 starts the pump and passes approximately 750 mL through the tubing and filter and then stops the pump.

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 and then stops the pump. “Clean hands” closes the lid on the sample bottle and cl oses the inner bag. “Clean hands” places the inner bag and bottle in the outer bag and “dirty ha nds” closes the outer bag. The samplers repeat this procedure fo r the dissolved metals and hexavalent chromium samples.

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

EPA plans to collect samples at the influe nt to the FGD wastewater treatment system (SP-1) on four consecutive days. The sample collection setup and sampling technique for each day of sampling will be the same.

3.3.2 Influent to Bioreact or System (SP-2)

The influent to the bioreactor system (SP- 2) will be collected downstream of the sand

filters after the wastewater from the three filter s is commingled. Allen has a sample tap located on the wastewater piping after the three sand fi lter effluent streams are commingled, downstream of the holding tank and upstream of the heat exchanger. ERG will follow protocols described in

EPA Method 1669 to collect metal sample fractions at SP-2.

ERG will collect the influent from the bior eactor system composite samples using two automatic compositors, which will be programmed to collect individual sample volumes into two large containers (e.g., two 20-liter containers). To collect suff icient sample volume, ERG will calculate the total volume required for ERG samp le collection as well as plant split sample collection and also add additional volume for purging 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 pump off the specific sample volumes into the individual sample containers.

ERG will use one automatic compositor to coll ect sample volume for the metals analyses (excluding mercury) and another automatic compos itor to collect sample volume for all classical analytes (i.e., BOD 5 , Group I, and Group II). In addition to collecting automatic composite samples for the analytes listed above, ERG will co llect total and dissolved mercury grab samples every six hours during each compositing period. ERG will also collect one grab sample for cyanide during each compositing period.

ERG plans to collect split samples with A llen (or its representative), where possible; therefore, when pumping off the composite sample s, a “Y” splitter will be used with two pieces of silicone tubing attached to th e “Y” splitter to allow ERG and A llen (or its representative) to collect samples simultaneously. If problems occu r during the collection of split samples (e.g., the splitters become clogged and the flow is split unevenly between the sampling crews), then EPA3-9 may stop the split sample collection and offer inst ead to collect duplicate samples with Allen (or its representative).

ERG has two approaches for collecting the total and dissolved me rcury grab samples; however, the approach used will depend on how Alle n is able to configure the sample taps. The preferred approach for the mercur y collection is to have a thir d tap available at the sampling point (i.e., one tap for the metals compositor, on e tap for the classicals compositor, and one tap for mercury grab samples). If Allen can accommod ate this configuration, then ERG will collect the total and dissolved mercury grab samples by shrouding the third sample tap and collecting the samples directly from the tap. If this config uration is not possible, then ERG will collect the samples from the composite tubing line that disc harges to the sump/drain, described in more detail in the steps below. For bot h of these collection approaches, ERG will not be able to collect split samples with Allen (or its representative); therefore, duplicate samples will be collected.

[QUESTION FOR ALLEN: Would the plant be able to set up the sample tap to have a three-way splitter with each splitter having its own valve to control flow?]

For all analytes, ERG will collect QC samples at the influent to the bioreactor system (SP-2) during one day of the sampling episode. In addition, for all analytes, ERG will collect a duplicate sample of the influent from bioreactor system (SP-4) during one day of the sampling episode.

The samples for the influent to the bioreactor system (SP-2) will be collected from a sample tap. 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;

 “Y” splitter;

 “T” 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 speci ally cleaned according to the procedures described in EPA Method 1669. The supplier of the cleaned bottles, tubing, and composite containers will prepare and analyze bottle blanks and equipment blanks to evaluate possible contamination. ERG will follow protocols desc ribed in EPA Method 1669 to collect metal sample fractions. Two or more ERG samplers (“ clean hands” and “dirty hands”) will follow the protocols described in the step s below to set up the sampling point, collect the field blank3-10 samples, and collect wastewater samples. This section describes the set- up of the sample point and collection of the EPA samples 4

.

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 containers, precleaned tubing, blank water, and cleanbox.

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 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 clea nbox 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 precleaned silicone tubing, a “T” splitter, and two additional pieces of silicone tubing. “Clean hands” takes the inner bag containing the tubing and moves it into the cleanbox. “Clean hands” opens the i nner bag and removes the tubing. “Clean hands” places a clean plastic bag over each end of the silicone tubing. The tubing configuration will be set up such that one end will be connected to the sample tap,

one end will be threaded through the automatic compositor and connected to the large composite container, and one end w ill be placed next to a sump/drain near the sampling point. To collect the samples, the sample tap will be left open during the entire sample collection time period a nd will flow directly to the sump/drain; however, the automatic compositor will pull sample from the flowing stream as dictated by the sampling program. Additionally, the automatic compositor will be capable of purging the line back to th e flowing stream between each individual sample aliquot.

5. “Dirty hands” threads one portion of th e silicone tubing through the peristaltic pump portion of the au tomatic compositor.

6. Both samplers change gloves.

7. “Dirty hands” and “Clean hands” then wo rk to collect the total mercury field blank sample. The total mercury field blank sample collection will depend on the sampling configuration for mercury, so both configurations are described in this plan.

4 For the sample collection, the samples will be split with th e plant (or the plant’s representative) and, therefore, the sample set-up describes equipment needed for 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 in this plan.3-11 Collection from third sample tap : “Dirty hands” shrouds the sample tap with a clear plastic bag that covers the end of the sample tap and provides enough room for samplers to work in with their hands . “Dirty hands” then opens the outer bag of the mercury field blank water and the total mercury field blank sample bottle. “Clean hands” opens the inner bag for th e field blank water and the total mercury field blank sample bottle, unscrews the lid s and places each in their inner bags. “Clean hands” pours the field blank wate r into the field blank sample bottle, closes the lids, and closes the inner ba gs. “Clean hands” places the total mercury sample bottle in the outer bag and “D irty hands” closes the outer bag.

Collection from compositor tubi ng discharging to sump/drain : “Dirty hands” places the end of the silicone tubing in a plastic ring stand clamp to keep the tubing off the floor and shrouds the end of the silicone tubing with a clear plastic bag that covers the end of the tubing and provides enough room for samplers to work in with their hands. “Dirty hands” threads tubing after the “T” splitter into through a peristaltic pump and then opens th e outer bag of the mercury field blank water and the total mercury field blank sample bottle. “Clean hands” opens the inner bag for the field blank water, unscre ws the lid, places it in the inner bag and places the end of the silicone tubing into blank water. “Dirty hands” operates the pump to pump blank water through the tu bing. After the tubing has been purged, with sufficient volume, “Clean hands” holds the total mercury field blank sample bottle under the shrouded tubing and opens the inner bag. “Dirty hands” operates the pump to collect the total mercury fiel d blank sample. “Clean hands” closes the lid on the sample bottle, closes the inne r bag, and places the bottle in the outer bag. “Dirty hands” closes the outer bag. “Dirty hands” removes the tubing from the peristaltic pump.

8. “Dirty hands” opens the outer bag of th e 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 one end of the silicone tubing into the bl ank water. “Clean hands” also opens the inner bag for the field blank composite container and loosen s the lid. “Clean hands” holds the silicone tubing with the plastic bag covering the end out of the cleanbox and over a bucket and “dirty hands ” operates the pump to pump blank water through the tubing. After the tu bing has been purged with sufficient volume, “clean hands” holds the silicone tubing at the mouth of the field blank composite container and fills the composite container with sufficient volume to

collect the total and dissolved metals fi eld blank samples at the pump-off location. “Dirty hands” stops the pump. During the purging of the tubing and collection of the field blank sample volume, “dirty ha nds” holds the end of the silicone tubing placed by the sump/drain above the composite container to prevent this portion of the tubing configuration from filling with blank water during the pumping process. “Clean hands” places the plastic bag over the end of the silicone tubing, replaces the lid on the field blank composite container, places the silicone tubing back in the cleanbox, and closes the i nner bag of the field blank composite3-12 container. “Dirty hands” closes the out er bag of the field blank composite

container 5

.

9. 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.

10. “Dirty hands” changes gloves.

11. “Clean hands” holds the e nd of the silicone tubing outside the cleanbox over a bucket, with the plastic bag still coveri ng the end of the tubi ng. “Dirty hands” places the end of the silicone tubing near the sump/drain and opens the sample tap

valve to allow the wastewater to flow through the tubing. “Dirty hands” operates the pump to purge the pump portion of th e tubing for a mini mum of 2 minutes.

12. 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.

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

14. “Dirty hands” opens the outer bag of the 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. The samplers put ice around the composite container to keep the samples cold during the compositing time period.

15. Samplers repeat steps 1-14 to set up th e automatic compositor for the classical analytes (skipping steps 7 and 8). Samplers will use another com posite container.

16. “Clean hands” and “Dirty hands” work to collect a total mercury grab sample. The total mercury sample collection technique will depend on the sampling configuration at the sample tap, so both potential collec tion techniques are described in this plan.

Collection from third sample tap : “Dirty hands” positions a bucket under the sample tap, opens the valve and purges the valve for at least one minute and then closes the tap. Dirty hands” then opens th e outer bag of the total mercury sample

bottle. “Clean hands” takes the bottles a nd positions himself/herself at the tap

with the bottle under the shrouding and opens the inner bag. “Dirty hands” opens

5 ERG will only collect field blank samp les at the influent to the bioreactor system during one day of the sampling episode.3-13 the sample tap and adjusts the flow. “C lean hands” open the lid of the total mercury sample bottle and places the bottle under the flowing stream to fill the

bottle. “Clean hands” then closes the lid on the bottle and cl oses the inner bag. “Dirty hands” closes the sample tap. “Cl ean hands” places the bottle in the outer bag and “dirty hands” closes the outer bag. The samplers repeat this procedure for the collection of the dissolved mercury sample.

Collection from compositor tubi ng discharging to sump/drain : “Dirty hands” opens the outer bag of the total mercury sample bottle. “Clean hands” positions himself/herself at the end of the sample tubing and holds the total mercury sample bottle under the shrouded tubing and opens the inner bag. “Clean hands” opens the lid of the sample bottle and places th e bottle under the flowing stream to fill

the bottle. “Clean hands” then closes the lid on the bottle, closes the inner bag, and places the bottle in the outer bag. “D irty hands” closes the outer bag. The samplers repeat this procedure for the co llection of the dissolved mercury sample.

The samplers will fill the bottle directly from the sample tap (or tubing); therefore, the total and dissolved mercur y samples will not be collected as split samples with Allen (or it s representative), but will be collected as duplicate samples.

17. The samplers will collect total and disso lved mercury grab samples every six hours during the compositing time period.

18. Samplers collect a total cyanide grab sample out of the tubing that is discharging into the sump/drain at the sample loca tion. The samplers will fill the bottle directly from the tubing used for the clas sicals composite contai ner; therefore, the cyanide sample will not be collected as a split sample with Allen (or its representative). Immediatel y after collection, the sample rs test for sulfides and oxidants and preserve the sample according to the preservation protocols outlined

in Section 3.4.

19. The samplers will collect field measur ement samples every six hours during the compositing time period. The field measurem ent samples will be collected from the tubing that is discharging into th e sump/drain at the sample location.

20. At the end of the composite sampling period, “dirty hands” stops each of the automatic compositors and opens the outer bag of each composite container. For each container, “clean hands” opens the inner bag and detaches the used tubing from the composite container and covers the port with a closed lid or small plastic bag. The samplers transport each of the composite containers, including the field blank composite container, to the pump–of f area to pump off the samples into the specified containers.

21. The samplers then repeat steps 1 through 20 to collect the composite samples for the next day of sample collection.3-14 After the composite samples have been collect ed, the sampling team will then transfer the sample into the individual sample containers at the pump-off area. For this sampling point, ERG will use a sample pump-off approach to transfer the composite samples to the individual sample bottles, because the samples are expected to have a low solids content. For this sample pump-off procedure, the dissolved metals samples will be collected before the total metals and classical samples to prevent cross-contamination with in the tubing, which could lead to greater

concentrations in the dissolved metals fractions.

Sample Pump-Off Procedures

22. 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, precleaned tubing, and

cleanbox.

23. 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 precleaned tubing within easy access on the covered surface.

24. “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 clea nbox and secures it ope n with the clips

located inside the box.

25. “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 precleaned Teflon® tubing connected to a length of precleaned silicone tubing, a “Y” splitter, and two additio nal pieces of silicone tubing. “Clean hands” moves the tubing into the cleanbox and opens the inner bag and removes the tubing. “Clean hands” places a clean plastic bag over the end of the Teflon® and silicone tubing.

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

27. Both samplers change gloves.

28. “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 cleanbox. “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 the 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 sample3-15 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.

29. “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.

30. “Dirty hands” opens the outer bag of th e dissolved metals field blank sample

bottle. “Clean hands” removes 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 field blank co mposite container. “Clean hands” places

the end of the silicone tu bing in the cleanbox, opens the inner bag of the dissolved metals field blank sample bottle, and re moves the lid. “Dirty hands” operates the pump to collect the dissolved metals fi eld 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 samples 6 . “Clean hands” closes the inner bag of the field blank composite containe r 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 ne w filter is needed, “clean hands” removes the used filter and samplers follow step 29 to replace the filter.

31. “Dirty hands” opens the outer bag of the large composite container for the metals samples and “clean hands” opens the i nner 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. “D irty hands” stops the pump.

32. “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

6 ERG will collect field blank samples onl y at the influent to the bioreactor system during one day of the sampling episode. 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 analyzed 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.3-16 chromium samples. During one day of th e sampling episode, the samplers will collect additional sample volume for th e duplicate samples. The samplers will also collect additional sample volume for the laboratory QC analyses during one day of the sampling episode.

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

34. “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.

35. “Dirty hands” opens the outer bag of the total metals sample bottle. “Clean hands” removes the inner bag and bottle and pl aces it in the cleanbox. “Clean hands” opens the inner bag and removes the lid. “Dirty hands” operates the pump to collect the total metals sample and then stops the pump. “Clean hands” closes the lid on the sample bottle and cl oses the inner bag. “Clean hands” places the inner bag and bottle in the outer bag and “dirty hands” closes the outer bag. During one day of the sampling episode, the samplers will collect additional sample volume for the duplicate samples and during anot her day of the sampling episode, the samplers will collect additional sample volume for the laboratory QC analyses.

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

37. “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.

38. “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.

39. 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. The samplers will also collect additional sample volume for the laboratory QC analyses during one day of the sampling episode.

EPA plans to collect samples at the influent to the bioreactor sy stem (SP-2) on four consecutive days. The sample collection setup and sampling technique for each day of sampling

will be the same.

3.3.3 Effluent from Biorea ctor System (SP-3)

The effluent from bioreactor system (SP-3) will be collected dow nstream of the secondstage effluent storage tank from the second-stage bioreactor cells. Allen ha s a sample tap located3-17 on the wastewater piping downstream of the s econd-stage effluent storage tank. ERG will follow protocols described in EPA Method 1669 to co llect metal sample fractions from SP-3.

ERG will collect the effluent from the bior eactor system composite samples using two automatic compositors that will be programmed to collect indi vidual 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 purging 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 pump off the specific sample volumes into the individual sample containers.

ERG will use one automatic compositor to coll ect sample volume for the metals analyses (excluding mercury) and another automatic compos itor to collect sample volume for all classical analytes (i.e., BOD 5 , Group I, and Group II). In addition to collecting automatic composite samples for the analytes listed above, ERG will co llect total and dissolved mercury grab samples every six hours during each compositing period. ERG will also collect one grab sample for cyanide during each compositing period.

ERG plans to collect split samples with A llen (or its representative), where possible; therefore, when pumping off of the composite samples, a “Y” splitter will be used with two pieces of silicone tubing atta ched to the “Y” splitter to allow ERG and Allen (or its representative) to collect sample s simultaneously. If problems occu r during the collection of split samples (e.g., the splitters become clogged and th e flow is split unevenly between the sampling crews), then EPA may stop the split sample co llection and offer instead to collect duplicate samples with Allen (or its representative).

ERG has two approaches for collecting the total and dissolved me rcury grab samples; however, the approach used will depend on how Alle n is able to configure the sample taps. The preferred approach for the mercur y collection is to have a thir d tap available at the sampling point (i.e., one tap for the metals compositor, on e tap for the classicals compositor, and one tap for mercury grab samples). If Allen can accommod ate this configuration, then ERG will collect the total and dissolved mercury grab samples by shrouding the third sample tap and collecting the samples directly from the tap. If this config uration is not possible, then ERG will collect the samples from the composite tubing line that disc harges to the sump/drain, described in more detail in the steps below. For bot h of these collection approaches, ERG will not be able to collect split samples with Allen (or its representative); therefore, duplicate samples will be collected.

[QUESTION FOR ALLEN: Would the plant be able to set up the sample tap to have a three-way splitter with each splitter having its own valve to control flow?]

For all analytes, ERG will collect QC samples at the effluent from the bioreactor system (SP-3) during one day of the sampling episode. In addition, for all analytes, ERG will collect a duplicate sample of the effluent from bioreactor system (SP-5) during one day of the sampling episode.3-18 The sample of the effluent from the biorea ctor system (SP-3) will be collected from a sample tap. 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;

 “Y” splitter;

 “T” 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 speci ally cleaned according to the procedures described in EPA Method 1669. The supplier of the cleaned bottles, tubing, and composite containers will prepare and analyze bottle blanks and equipment blanks to evaluate possible contamination. ERG will follow protocols desc ribed in EPA Method 1669 to collect metal sample fractions. Two or more ERG samplers (“ clean hands” and “dirty hands”) will follow the protocols described in the step s below to set up the sampling point, collect the field blank samples, and collect wastewater samples. This section describes the set up of the sample point and collection of the EPA samples 7

.

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 containers, precleaned tubing, blank water, and cleanbox.

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 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 clea nbox 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 precleaned silicone tubing, a “T” splitter, and two additional pieces of silicone

7 For the sample collection, the samples will be split with th e plant (or the plant’s repres entative) and therefore, the sample set-up describes equipment needed for 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.3-19 tubing. “Clean hands” takes the inner bag containing the tubing and moves it into the cleanbox. “Clean hands” opens the i nner bag and removes the tubing. “Clean hands” places a clean plastic bag over each end of the silicone tubing. The tubing configuration will be set up such that one end will be connected to the sample tap,

one end will be threaded through the automatic compositor and connected to the large composite container, and one end w ill be placed next to a sump/drain near the sampling point. To collect the samples, the sample tap will be left open during the entire sample collection time period a nd will flow directly to the sump/drain; however, the automatic compositor will pull sample from the flowing stream as dictated by the sampling program. Additionally, the automatic compositor will be capable of purging the line back to th e flowing stream between each individual sample aliquot.

5. “Dirty hands” threads one portion of th e silicone tubing through the peristaltic pump portion of the au tomatic compositor.

6. Both samplers change gloves.

7. “Dirty hands” and “Clean hands” then wo rk to collect the total mercury field blank sample. The total mercury field blank sample collection will depend on the sampling configuration for mercury, so both configurations are described in this plan.

Collection from third sample tap : “Dirty hands” shrouds the sample tap with a clear plastic bag that covers the end of the sample tap and provides enough room for samplers to work in with their hands . “Dirty hands” then opens the outer bag of the mercury field blank water and the total mercury field blank sample bottle. “Clean hands” opens the inner bag for th e field blank water and the total mercury field blank sample bottle, unscrews the lid s and places each in their inner bags. “Clean hands” pours the field blank wate r into the field blank sample bottle, closes the lids, and closes the inner ba gs. “Clean hands” places the total mercury sample bottle in the outer bag and “D irty hands” closes the outer bag.

Collection from compositor tubi ng discharging to sump/drain : “Dirty hands” places the end of the silicone tubing in a plastic ring stand clamp to keep the tubing off the floor and shrouds the end of the silicone tubing with a clear plastic bag that covers the end of the tubing and provides enough room for samplers to work in with their hands. “Dirty hands” threads tubing after the “T” splitter into through a peristaltic pump and then opens th e outer bag of the mercury field blank water and the total mercury field blank sample bottle. “Clean hands” opens the inner bag for the field blank water, unscre ws the lid, places it in the inner bag and places the end of the silicone tubing into blank water. “Dirty hands” operates the pump to pump blank water through the tu bing. After the tubing has been purged, with sufficient volume, “Clean hands” holds the total mercury field blank sample bottle under the shrouded tubing and opens the inner bag. “Dirty hands” operates the pump to collect the total mercury fiel d blank sample. “Clean hands” closes the lid on the sample bottle, closes the inne r bag, and places the bottle in the outer3-20 bag. “Dirty hands” closes the outer bag. “Dirty hands” removes the tubing from the peristaltic pump.

8. “Dirty hands” opens the outer bag of th e 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 one end of the silicone tubing into th e blank water. “Clean hands” also opens the inner bag for the field blank composite container and loosens the lid. “Clean hands” holds the silicone tubing with the plastic bag covering the end out of the cleanbox and over a bucket and “dirty hands ” operates the pump to pump blank water through the tubing. After the tu bing has been purged with sufficient volume, “clean hands” holds the silicone tubing at the mouth of the field blank composite container and fills the composite container with sufficient volume to the collect the total and dissolved metals field blank samples at the pump-off location. “Dirty hands” stops the pump. During the purging of the tubing and collection of the field blank sample volume, “dirty hands” holds the end of the silicone tubing that will be placed by the sump/drain above the composite container to prevent this portion of th e tubing configuration from filling with blank water during the pump ing process. “Clean hands ” places the plastic bag over the end of the silicone tubing, repl aces the lid on the field blank composite container, places the silicone tubing back in the cleanbox, and closes the inner bag of the field blank composite container. “D irty hands” closes the outer bag of the field blank composite container 8

.

9. 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.

10. “Dirty hands” changes gloves.

11. “Clean hands” holds the e nd of the silicone tubing outside the cleanbox over a bucket, with the plastic bag still coveri ng the end of the tubi ng. “Dirty hands” places the end of the silicone tubing near the sump/drain and opens the sample tap

valve to allow the wastewater to flow through the tubing. “Dirty hands” operates the pump to purge the pump portion of th e tubing for a mini mum of 2 minutes.

12. 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.

13. “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” calibra tes the compositor to ensure that 800 mL is being collected for each individual grab.

8 ERG will only collect field blank sa mples at the effluent from the bior eactor system during one day of the sampling episode.3-21 14. “Dirty hands” opens the outer bag of the 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. The samplers put ice around the composite container to keep the samples cold during the compositing time period.

15. Samplers repeat steps 1-14 to set up th e automatic compositor for the classical analytes (skipping steps 7 and 8). Samplers will use another composite container. The samplers will put the classicals co mposite container in ice to keep the samples cold during the compositing time period.

16. “Clean hands” and “Dirty hands” work to collect a total mercury grab sample. The total mercury sample collection technique will depend on the sampling configuration at the sample tap, so both potential collec tion techniques are described in this plan.

Collection from third sample tap : “Dirty hands” positions a bucket under the sample tap, opens the valve and purges the valve for at least one minute and then closes the tap. Dirty hands” then opens th e outer bag of the total mercury sample

bottle. “Clean hands” takes the bottles a nd positions himself/herself at the tap

with the bottle under the shrouding and opens the inner bag. “Dirty hands” opens the sample tap and adjusts the flow. “C lean hands” open the lid of the total mercury sample bottle and places the bottle under the flowing stream to fill the

bottle. “Clean hands” then closes the lid on the bottle and cl oses the inner bag. “Dirty hands” closes the sample tap. “Cl ean hands” places the bottle in the outer bag and “dirty hands” closes the outer bag. The samplers repeat this procedure for the collection of the dissolved mercury sample.

Collection from compositor tubi ng discharging to sump/drain : “Dirty hands” opens the outer bag of the total mercury sample bottle. “Clean hands” positions himself/herself at the end of the sample tubing and holds the total mercury sample bottle under the shrouded tubing and opens the inner bag. “Clean hands” opens the lid of the sample bottle and places th e bottle under the flowing stream to fill

the bottle. “Clean hands” then closes the lid on the bottle, closes the inner bag, and places the bottle in the outer bag. “D irty hands” closes the outer bag. The samplers repeat this procedure for the co llection of the dissolved mercury sample.

The samplers will fill the bottle directly from the sample tap (or tubing); therefore, the total and dissolved mercur y samples will not be collected as split samples with Allen (or it s representative), but will be collected as duplicate samples.

17. The samplers will collect total and disso lved mercury grab samples every six hours during the compositing time period.3-22 18. Samplers collect a total cyanide grab sample out of the tubing that is discharging into the sump/drain at the sample loca tion. The samplers will fill the bottle directly from the tubing use for the classi cals composite contai ner; therefore, the cyanide sample will not be collected as a split sample with Allen (or its representative). Immediately after collection, the samplers need to test for sulfides and oxidants and preserve the sample according to the preservation protocols

outlined in Section 3.4.

19. The samplers will collect field measurements samples every six hours during the compositing time period. The field measurem ent samples will be collected from the tubing that is discharging into th e sump/drain at the sample location.

20. At the end of the composite sampling period, “dirty hands” stops each of the automatic compositors and opens the outer bag of each composite container. For each container, “clean hands” opens the inner bag and detaches the used tubing from the composite container and covers the port with a closed lid or small plastic bag. The samplers transport each of the composite containers, including the field blank composite container, to the pump-o ff area to pump off the samples into the specified containers.

21. The samplers then repeat steps 1 through 20 to collect the composite samples for the next day of sample collection.

After the composite samples have been collect ed, the sampling team will then transfer the sample into the individual sample containers at the pump-off area. For this sampling point, ERG will use a sample pump-off approach to transfer the composite samples to the individual sample bottles, because the samples are expected to have a low solids content. For this sample pump-off procedure, the dissolved metals samples will be collected before the total metals and classical samples to prevent cross-contamination with in the tubing, which could lead to greater

concentrations in the dissolved metals fractions.

Sample Pump-Off Procedures

22. 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, precleaned tubing, and

cleanbox.

23. 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 precleaned tubing within easy access on the covered surface.

24. “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 clea nbox and secures it ope n with the clips

located inside the box.3-23 25. “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 precleaned Teflon® tubing connected to a length of precleaned silicone tubing, a “Y” splitter, and two additio nal pieces of silicone tubing. “Clean hands” moves the tubing into the cleanbox and opens the inner bag and removes the tubing. “Clean hands” places a clean plastic bag over the end of the Teflon® and silicone tubing.

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

27. Both samplers change gloves.

28. “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 cleanbox. “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 the 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 th e outer bag and “dirty ha nds” closes the outer bag.

29. “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.

30. “Dirty hands” opens the outer bag of th e dissolved metals field blank sample

bottle. “Clean hands” removes 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 field blank co mposite container. “Clean hands” places

the end of the silicone tu bing in the cleanbox, opens the inner bag of the dissolved metals field blank sample bottle, and re moves the lid. “Dirty hands” operates the pump to collect the dissolved metals fi eld 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 samples 9 . “Clean hands” closes the inner

9 ERG will collect field blank samples at the effluent from the bioreactor system only during one day of the sampling episode. ERG will collect the dissolved mercury sample using the same technique as the total mercury3-24 bag of the field blank composite containe r 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 ne w filter is needed, “clean hands” removes the used filter and samplers follow step 29 to replace the filter.

31. “Dirty hands” opens the outer bag of the large composite container for the metals samples and “clean hands” opens the i nner 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. “D irty hands” stops the pump.

32. “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. During one day of th e sampling episode, the samplers will collect additional sample volume for th e duplicate samples. The samplers will also collect additional sample volume for the laboratory QC analyses during one day of the sampling episode.

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

34. “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.

35. “Dirty hands” opens the outer bag of the total metals sample bottle. “Clean hands” removes the inner bag and bottle and pl aces it in the cleanbox. “Clean hands” opens the inner bag and removes the lid. “Dirty hands” operates the pump to collect the total metals sample. “Dirty hands” stops the pump. “Clean hands” closes the lid on the sample bottle and cl oses the inner bag. “Clean hands” places the inner bag and bottle in the outer bag and “dirty ha nds” closes the outer bag. During one day of the sampling episode, the samplers will collect additional sample volume for the duplicate samples. The samplers will also collect additional sample volume for the laborato ry QC analyses during one day of the sampling episode.

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 contam ination from the filtering performed at the laboratory. Therefore, ERG does not need to collect a dissolv ed mercury field blank sample in the field.3-25 36. “Dirty hands” places an ERG label on the outer bags of the sample bottles.

37. “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 composite container for the classical analytes.

38. “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 tubi ng. “Dirty hands” stops the pump.

39. 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. The samplers will also collect additional sample volume for the laboratory QC analyses during one day of the sampling episode.

EPA plans to collect samples at the effluent from the bioreactor system (SP-3) on four consecutive days. The sample collection setup and sampling technique for each day of sampling

will be the same.

3.4 Sample Preservation, Shipping, and Analysis

All samples will be maintained on ice immediately upon collection (except metals samples that do not require cooling). Because the classical and hexavalent chromium samples are required to be cooled, all composite containers will be maintained on ice. After pumping off the composite samples into the individual sample c ontainers, the classical an d hexavalent chromium samples will be put in an ice-water bath; how ever, the other metals samples, which do not require cooling, will not be placed on ice. The classical and hexavalent chromium grab samples collected at the FGD influent sampling point will also be placed on ice immediately after

collection.

The dissolved metals (excluding mercury) and hexavalent chromium samples will be filtered in the field. The dissolved mercury samples will be filtered upon receipt at the laboratory. All metals samples, except hexavalent chromium, will be acid-preserved prior to extraction at the laboratory. Hexavalent chromi um samples will be preserved on site, according to the method-specified protocols. Samplers w ill filter samples within 15 minutes after the compositing period ends (or as soon thereafter as possible). The dissolved samples of the FGD influent will be filtered approximately one hour after they are collected to allow for solids settling because the samples’ high solid s content that would clog the filter.

The total cyanide grab samples will be preserved according to the method-specific protocols immediately following collection. Prior to sample collection, the samplers will test the wastewater at each sampling point fo r sulfide using lead acetate test strips. If sulfide is present, the samplers will use the proce dure identified in Section 3.5 to determine the minimal amount of dilution necessary to reduce sulfide to a nondete ctable concentration. Af ter determining this minimal dilution factor for the sampling point, the samplers will dilute all samples collected at3-26 this sampling point using blank water. After dilution, the sample rs will retest the sample for sulfides. If sulfides are still detected, the sample will be diluted further using the same technique

as identified in Section 3.5 to ensure that the sa mple is not over-diluted. The samplers will then test the diluted sample for the presence of oxida nts (i.e., chlorine) using potassium-iodide starch paper. If total chlorine is present, the samplers will add sodium arsenite in small increments until

the oxidants are at nondetectable concentrations in the sample. The samplers will then carefully adjust the pH to >10 S.U. using sodium hydroxide and place the sample on ice. The preservation, including the amount of dilution, will be reported to the labor atory on the traffic reports.

Table 3-3 lists the parameters, bottle type s, sample volume, and on-site preservation requirements for each type of analysis. The t ype and amount of pres ervation used will be recorded on sample preservation log sheets (Fig ure 3-1).With the exception of total cyanide samples, if 10 percent of the sample volume is added and the required pH is not achieved, ERG will stop diluting the samples by discontinuing pres ervation and noting it on the traffic report. The wastewater samples, except metals samples th at do not require cooling, will be packed in ice chests with a sufficient quantity of ice to maintain a temperature of ≤ 6  C. All samples will be prepared for overnight shipment vi a Federal Express to laboratories.

3.5 Field Measurements and Engineering Data Collection

Temperature, pH, sulfide, and oxidants w ill be measured and recorded by the sampling crew at each sampling point ( SP-1, SP-2, and SP-3). The samplers will measure temperature and pH when the automatic composite samplers are initially set up and ev ery six hours during the compositing period. The samplers will test the wast ewater for sulfide and oxidants at the time the total cyanide grab sample is collected. For temperature and pH, the samplers will fill a 1-liter glass jar with sample and test the wastewater i mmediately after co llecting the ali quot. For sulfide and oxidants, the samplers will fill the cyanide sa mple bottle directly and test for sulfide and oxidants using test strips immedi ately after sample collection.

During a presampling set-up day (i.e., the da y before the sampling episode begins), the samplers will test the wastewater at each sampli ng point for sulfide using le ad acetate test strips to determine if preservation is needed for cyanid e. If sulfide is presen t, the samplers should

determine the minimal amount of dilution necessar y to reduce the sulfide concentration to below detection by the lead ace tate test strips. To identify the mi nimal amount of dilution, the samplers will dilute the sample by a factor of two (1:1) and re test for sulfide. If sulfide is still detected, the samplers will dilute the original sample by a factor of 3 (2:1). This process will be continued until sulfide is not detected in the sample. After th is minimal dilution factor is determined for the sampling point, the samplers will use this minimal dilution factor to dilute all samples collected at the sampling point. The samplers will also test both the original (i.e., nondiluted) and diluted sample for the presence of oxidants (e.g., chlo rine) during the presam pling set-up day using potassium-iodide starch paper.

Samplers will follow applicable test k it calibration procedur es specified by the

manufacturer. Table 3-4 summari zes the field measurements, the method to be used for the measurement, and the detection range of each fiel d test instrument. In addition, EPA will collect flow rate data for each sampled waste stream. The flow rates for all the sampling points will be collected from the plant’s existing flow recorders.3-27 Field sampling log sheets (Figure 3-2) will be completed at each sampling point. This sheet will record the sampling methodology, names of the samplers, sample collection time, field measurements, and any notes and observations.

Samplers will also collect engineering inform ation with regard to design and operation of the plant. For example, they will collect info rmation such as coal usage, plant capacity, wastewater flow rates, sludge ge neration rates (if applic able), and retention times in wastewater treatment process stages. Engineering data collec tion sheets (Figures 3-3, 3-4, and 3-5) will be completed for the plant. This information will be used to determine if the specific design or operational criteria of the steam electric operations affect th e wastewater characteristics.

3.6 Sample Labeling

Each sample will be coded with a unique sample number and labeled at the time of collection. Typically, labels are pr inted prior to arrival in the fi eld, although 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 preprinted information is incorr ect, it will be revised 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, smearing, or loss during transit. For metal samples, the samplers will not label the sa mple bottles, but will label the outer plastic bag of the sample bottle.

3.7 Traffic Reports

To maintain a record of sample collection, transfer between personnel, shipment, and receipt by the laboratory, samplers will complete a traffic report for each sample set at each sampling location. These forms are used to documen t sample custody transfer from the field to the laboratory. Traffic report forms will be completed for all samples sent to all laboratories. Figure 3-6 includes an example of a traffic report. At the time of sample shipment, a copy of the traffic report will be sent to ERG, another copy will be kept by sampling personnel, and two copies will be 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 the3-28 sample after preservation, type of sample (grab, composite), sample collection date and time, and the analyses requested. Samplers will use the comment section to provi de special notes or instructions to the laboratory, such as whether samples have been filtered on site or how to composite separate samples prior to analysis. The sampling team will also comment if sample bottles are not completely filled (i.e., less than 75 percent full). In addition, the comments section

will be used to note deviations from standard sa mpling protocols (for example, if a sample could not be acid-preserved because of excessive buffering).

3.8 Quality Assurance/Quality Control

The QA/QC program for sample collecti on at Allen will include the following:

 Documentation for samples thr ough laboratory traffic reports;

 Collection of duplicate samples for all analytes;

 Collection of bottle blank(s) for metals;

 Collection of field blank(s) for metals;

 Collection of equipment blank(s) for metals; and

 Collection of laboratory QC samples fo r matrix spike/matrix spike duplicate analyses.

Duplicate sample sets will be collected as part of the quality assurance program for sampling. During one day of the sampling episode, ERG will collect one duplicate sample (SP-4) of the influent to the bioreactor system (SP-2) and one duplicate sample (SP-5) of the effluent from the bioreactor system (SP-3). The duplicate samp les will be collected as separate aliquots in the field. Results of the duplicate analyses wi ll be used to evaluate precision, including variability in sample collection, ha ndling, preparation, and analysis.

Bottle blanks will be used to evaluate po ssible 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 bot tles (e.g., 250-mL plastic bottle for metals) and stored for several days prior to shipment to the laboratory. The supplier of the cleaned 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 decontaminati on procedures. Field bla nks will be prepared in the field prior to sample collection and analy zed for all sampling equipment, other than sample bottles, that come into direct contact with samples (e.g., tubing or filters).3-29 ERG will prepare field blanks for each of the total and dissolved metals analyses at each of the three sampling points during one day of the sampling episode 10 . ERG samplers will use “clean hands / dirty hands” sampling techniques to prepare the metals field blanks, as discussed

in more detail in Section 3.3. The total metals fiel d blanks (including mercur y) at the influent to the FGD wastewater treatment system will be prepared by gravity-feeding ASTM Type 1 water through the silicone tubing into the sample bottle s. The total metals field blanks (excluding mercury) at the influent to and effluent from the bioreactor system sampling points will be prepared by pumping ASTM Type 1 water thr ough the composite tubing set into a large composite container where it will be held fo r the 24-hour compositing period, then pumping the ASTM Type 1 water from the large composite c ontainer through the Teflon® and silicone tubing and into the sample bottles. The total mercury field blanks at the influent to and effluent from the bioreactor sampling points will be prepared by e ither pouring ASTM Type 1 water directly into the sample bottles, or pumping ASTM Type 1 wa ter through the tubing that discharges to the sump/drain and into the sample bottles. The dissol ved metals field blanks at the influent to the FGD wastewater treatment system will be prep ared by gravity-feeding the ASTM Type 1 water through the silicone tubing into a 10-L composite container and then pumping the ASTM Type 1 water from the 10-L container through the Tefl on® and silicone tubing, through a 0.45-um filter, and into the sample bottles. The di ssolved metals field blanks at th e influent to and effluent from the bioreactor system sampling points will be prepared by pumping ASTM Type 1 water through the composite tubing set into a large composite c ontainer where it will be held for the 24-hour compositing period, then pumping the ASTM Type 1 water from the large composite container through the Teflon® and silicone tubing, through a 0.45-um filter, and into the sample bottles. The field blanks will determine if there is any contamination from the sampling equipment, atmospheric contamination, or other contamination from the surroundings.

EPA Method 1669 requires that equipment blanks also be prepared and analyzed for metals to evaluate possible contamination of metals caused by the sampling equipment. The supplier of the tubing and composite containers will prepare and analyze these equipment blanks and provide a report certifyi ng the equipment as clean.

As part of standard laborator y quality control, matrix eff ects 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 sampling team will collect, label, and ship the necessary laborat ory QC volumes. Laboratory QC volumes (i.e., MS/MSD sample) will be collected for every 10 samples collected at a sampling event, excluding field blank samples. For classical anal yses, EPA will collect one QC sample volume at the effluent from the bioreactor system (SP-3) sample point at each episode. For all analytes requiring laboratory QC volumes, the sampling t eam will collect QC sample volume from the influent to the bioreactor syst em (SP-2) during one day of the sampling episode and from the effluent from the bioreactor system (SP- 3) during one day of the sampling episode.

10 ERG is not planning to collect the field blanks for all sampling points on the same day during the sampling episode. Additionally, ERG will not collect a field blank for dissolved mercury because a filter blank will be prepared and analyzed for by the laboratory.3-30 3.9 Sample Splitting

Allen or its representative has elected to collect split samples at each of the sampling points. Allen or its representative will supply a ll of the personnel, equipment, glassware, and reagents required to collect the split samples and to coordinate the analysis of samples. For each of the sampling points, the sampling crew will atte mpt to collect split samp les with Allen or its representative as described in this plan; however, if problems oc cur (e.g., the splitters become clogged and the flow is split unevenly between th e sampling crews), then EPA may stop the split sample collection and offer instead to collect duplicate sa mples with Allen or its representative.3-31Table 3-1. Sample Collection at Allen Steam StationSamplingPoint NumberSampling Point Name Total Metals (EPA Method 200.7, 200.8, and 200.8 with collision cell,) Dissolved Metals (EPA Method 200.7, 200.8, and 200.8 with collision cell,) Total Mercury Dissolved Mercury Hexavalent Chromium BOD5 Group I

a Group II b Total CyanideSP-1 Influent to FGD Wastewater TreatmentSystem4 4 4 4 4 4 4 4 4SP-2 Influent to Bioreactor System 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC4+1QCSP-3 Effluent from Bioreactor System 4+1QC4+1QC 41+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC4+1QCSP-4 Duplicate of Influent to Bioreactor System 1 1 1 1 1 1 1 1 1SP-5 Duplicate of Effluent from BioreactorSystem1 1 1 1 1 1 1 11SP-6 Influent to FGD Wastewater TreatmentSystem Field Blank1 1 1 1SP-7 Influent to Bioreactor System Field Blank 1 1 1 1SP-8 Effluent from Bioreactor System FieldBlank1 1 1 1Total Number of Samples 17+2QC 17+2QC 17+2QC 14+2QC 17+2QC 14+2QC 14+2QC 14+2QC 14+2QCa – Group I includes total suspended solids (TSS), total dissolved solids (TDS), sulfate, and chloride.b – Group II includes ammonia as nitrogen, nitrate/nitrite as nitrogen, total Kjeldahl nitrogen (TKN), chemical oxygen demand (COD), and total phosphorus.3-32 Table 3-2. Analytical Methods

Parameter Method Number

Classicals

Biochemical oxygen demand (BOD 5 ) 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 selected analytes.)3-33 Table 3-3. 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

bottles Two 1-L plastic

bottles ≤ 6  C

Group II b Two 1-L plastic

bottles Three 1-L plastic bottles H 2 SO 4 to pH <2, ≤ 6  C

Total cyanide One 1-L plastic

bottle Two 1-L plastic

bottles Dilution until sulfide is not present,

NaAsO 2 until total chlorine is not present, NaOH to pH >10, ≤ 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 bottle (ultraclean),fluoropolymerlined caps One 250-mL glass bottle (ultraclean),fluoropolymerlined caps None (acid preserve at laboratory)

Dissolved mercury Two 250-mL glass bottles (ultraclean),fluoropolymerlined caps Two 250-mL glass bottles (ultraclean),fluoropolymerlined 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  C

a – Group I includes TSS, TD S, sulfate, and chloride. b – Group II includes ammonia as nitrogen, COD, nitr ate/nitrite as nitrogen, TKN, and total phosphorus.

Table 3-4. Sampling Point Field Measurements

Field Measurements Method Detection Range (or Gradation of Scale)

Temperature Thermometer -20 to 150 ± 1oC

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.

Sulfide Lead acetate test strip >50 mg/L sulfide (S 2- )

Oxidants (i.e., chlorine) Potassium-iodide starch paper >1 mg/L free chlorine (Cl 2 )3-34 Sampling Episode ____________

Preservation Chemicals – List Strength of Solution from Bottle and Lot Number

H 2 SO 4 _____________________ NH 4 SO 4 ________________________

NaOH _____________________

Sample

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

Figure 3-1. Sample Preservation Log Sheet3-35 Sampling Episode: __________________________________

Sampling Point: ____________________________________

Sample Numbers: __________________________________

Date:

Manual Composite 

## □ Grab 

## □

Automatic Composite 

## □

Time of Grab Sample Collection:

Start Time 

## □ AM 

## □ PM

End Time 

## □ AM 

## □ PM

Equipment Used: _________________________________________________

Samplers’ Names: ________________________________________________

Sample Day Time Temp

°C pH (S.U.) meter / strips Waste Stream Flow Rate (MGD)

1

2

3

4

5

6

7

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

______________________________________________________________________________

______________________________________________________________________________

______________________________________________________________________________

______________________________________________________________________________

______________________________________________________________________________

______________________________________________________________________________

Figure 3-2. Field Sampling Log Sheet3-36Plant 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(MW)(or PercentCapacity %)aSCR(No, On,Off)ParticulateControl System(HS/CS ESP, orBH)aThe electricity production should be measured on a daily basis from midnight of the 1stday of sample collection tomidnight of the last day of sample collection.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 5percent petroleum coke previous week);Figure 3-3. Engineering Data Collection Sheet (Page 1 of 4)3-37 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.” Otherwise, 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:

Figure 3-4. Engineering Data Co llection Sheet (Page 2 of 4)3-38 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 3-5. Engineering Data Co llection Sheet (Page 3 of 4)3-39Plant 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 product)Polymer:_________(specify product)Acid:_________(specify product)1234Volume of equalization tank: ________________Volume of reaction tanks: 1) ________________ 2) ________________ 3) ________________Volume of clarifiers: 1) ________________ 2) ________________Volume of first-stage bioreactors: ________________Volume of second-stagebioreactors:________________Figure 3-6. Engineering Data Collection Sheet (Page 4 of 4)3-40 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

NUMBERSOURCE WATER(city, river, well)IN LINE PROCESSUNREATED EFFLUENT(raw wastewater)TREATED EFFLUENTOTHER(specify) ADDITIONAL

SAMPLE

DESCRIPTIONPH LEVELPRESERVED (Y/N)G=GRAB / C=COMPOSITESAMPLE COLLECTIONTIME / DATE

Comments: 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 ANALYSES Eastern Research Group, Inc. 14555 Avion Parkway, Suite 200 Chantilly, VA 20151

Figure 3-7. Example Traffic Report4-1 4. S AMPLING A CTIVITIES

This section discusses the sampling t eam organization, sampling preparation, and sampling activities.

4.1 Sampling Team Organization

The sampling crew will consist of a crew chief and four crew members from ERG and two EPA representatives. The crew chief will be responsible for all health and safety, sample collection, preservation, and shipping activities while at Allen. Following the sampling episode, ERG will collate the analytical results from each laboratory and summarize and transmit this information in a trip report to EPA. After EPA review, the report will be forwarded to Allen for

review.

4.2 Presampling Preparation

On October 22, 2009, ERG and EPA conducted a si te visit at Allen. The site visit and subsequent follow-up telephone calls to Alle n representatives provi ded ERG and EPA the necessary information to prepare for the sampli ng episode and to create this sampling plan.

As part of preparing the team for the samp ling episode at Allen, the ERG crew chief will distribute this sampling plan to each team member and ensure they are completely familiar with the sampling plan and the health and safety requirements specific to Allen. The crew chief will also give copies of this sampling plan to Allen personnel before sampling begins.

The ERG crew chief will also coordinate th e procurement and shipment of all necessary sampling and health and safety equipment.

4.3 Field Sampling Activities

Upon arrival at Allen, the ERG crew chief, in conjunction with the EPA representatives, will meet with Allen personnel to determine whethe r samples can be collected as planned at each of the planned sampling points. Upon confirming the methods to collect samples, the ERG crew chief will update the descriptions of the proposed sampling points, if necessary, in consultation with EPA and Allen personnel. If necessary, th e crew chief will obtain additional equipment. The revised sampling desc ription will include:

 A sampling point description and collec tion procedure for each sampling point;

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

 A list of potential physical hazards (e .g., pH, temperature, and potentially hazardous equipment);

 A list of potential chemical hazards asso ciated with each sampling point; and

 A list of proposed health and safety procedures.

Prior to sampling, the ERG crew chief will notify the ERG Health and Safety Coordinator (HSC) of any revi sed sampling activity descript ions along with recommended revisions to the proposed health and safety pr ocedures. Together, the crew chief and HSC will review the proposed health and safety procedures. The crew chief will incorporate any plant-4-2 specific changes indicated by the HSC and receive 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 o C preservation will be placed on ice. 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 sleeve s inside the coolers. The coolers will then be taken to the nearest Federal Expr ess office and shipped to the an alytical laboratories. At the conclusion of the sampling episode, the sampling equipment will be prepared for return shipping.

4.4 Logistics

This subsection summarizes Allen contacts, an alytical laboratory c ontacts and addresses, and sampling team personnel and support functions.

4.4.1 Allen Steam Station Contacts

Robert Wylie Duke Energy Carolinas

526 S. Church Street Charlotte, NC 28201 (704) 382-4669

Contact Name - TBD Duke Energy Carolinas

Allen Steam Station

253 Plant Allen Road Belmont, NC 28012 (704) 825-2022

[QUESTION FOR ALLEN: Who will be the plan t contact for the sampling episode, including the point of contact for shi pping supplies to the plant?]

4.4.2 EPA Contacts

Ron Jordan Engineering and Analysis Division U.S. Environmental Protection Agency 1200 Pennsylvania Avenue, NW (4303T) Washington, D.C. 20460 (202) 566-10034-3 Jezebele Alicea Engineering and Analysis Division U.S. Environmental Protection Agency 1200 Pennsylvania Avenue, NW (4303T) Washington, D.C. 20460 (202) 566-1755

4.4.3 Analytical Laboratories

TBD

4.4.4 ERG Contacts

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

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

4.4.5 Freight Forwarders

Federal Express (FedEx) General Information (800) 463-3339

FedEx Office Print & Ship Center (5 miles from plant) 2908 Oak Lake Blvd, Suite 107 Charlotte, NC 28208 Hours of Operation: Mon. – Fr i.: 7:30 a.m. to 9:00 p.m.

Last Express Drop-off: Mon. – Fri.: 7:30 p.m.

FedEx Express Airport Facil ity (6 miles from plant) 4831/4850 Express Dr Charlotte, NC 28208 Hours of Operation: Mon. – Fr i.: 8:30 a.m. to 9:30 p.m.

Last Express Drop-off: Mon. – Fri.: 9:30 p.m.5-1 5. S AMPLE S HIPMENT

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

All samples will be packaged and shi pped in accordance with Department of Transportation (DOT) or International Air Tr ansport Association (IA TA) 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 permanen t 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, samples collecte d at Allen will not be classified as IATA dangerous goods.

5.1 Sample Set Preparation

Samples are collected as a se ries of “fractions,” or bottl es designated for particular analyses requiring the same preservation. The comprehensive water sample set consists of sample fractions for all pollutants listed in Sectio n 3.2, collected as grab samples directly into the individual sample containers or composite samp les that are transferred to individual sample containers using a pump-off approach.

5.2 Sample Packing

All dilute samples from the plant will be packed according to the following guidelines (there is no limit on the amount of liqui d each sample container may contain):5-2 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. Do not label metal sample bottles, but the outer plastic bag for each bottle instead.

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. Do not clean the bottle threads for the metals sample bottles.

3. Prior to packaging, place each sample bottle requiring ≤ 6°C preservation into an

ice chest with wet ice 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. En close each “bubble-wrapped” container and plastic container in an individual sealable plastic freezer bag. Place VOA vials in VOA bricks in a 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 tyi ng 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 leas t 4 × 1⁄2 gallons of ice (4 × 2.5 pounds of ice) in each large cooler and 2 × 1⁄2 gallons of ice (2 × 2.5 pounds of ice) in each

small cooler. Use more ice when ambien t temperatures are very high. Place the ice inside the second garbag e bag and close the second garbage bag with a twisttie.

8. Fill in around the bottles and any free sp ace with additional cushioning material. Use sufficient packing material so that th e sample containers will not shift during shipment.

9. Seal the Traffic Report form in a plastic zip-lock bag and tape it securely to the

inside of the cooler lid.

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.5-3 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.6-1 6. S ITE -S PECIFIC H EALTH AND S AFETY P ROCEDURES

This section specifies the health and safety procedures and practices to be used by the sampling team during sampling at Allen. This se ction provides genera l health and safety information for this sampling episode. The sampling team is obligated to follow all safety procedures specified in this section.

6.1 Emergency/Medical Procedures

The following procedures will be followed in the event of a medical or other emergency

situation.

6.1.1 First Aid

Allen has first aid kits ava ilable throughout the plant. In addition, ERG will also bring a first aid kit. [QUESTION FOR ALLEN: Does the plant have a first responder team and would

EPA/ERG have access to the team if necessary?]

6.1.2 Site Evacuation/Emergency Response Plan

The sampling team will be informed of th e Allen evacuation procedures and routes by plant personnel.

6.1.3 Emergency Showers and Eye Washes

Emergency showers and eye wash stations are located throughout the plant. Before collecting samples at any point, sampling team me mbers will locate the nearest operating safety shower and eye wash station.

6.1.4 Local Hospital

The nearest hospital is Gaston Memorial Ho spital, located in Gastonia, NC, and is approximately 12 miles from Allen Steam Station. The hospital address is:

Gaston Memorial Hospital

2525 Court Drive Gastonia, NC 28054

The local emergency phone number in Belmont, NC is 911.

6.2 ERG Health and Safety Responsibilities and Authority

The ERG Work Assignment Manager (WAM), crew chief, and sampling team members have different responsibili ties to maintain a safe sampling environment. These responsibilities

are described below.6-2 6.2.1 Work Assignment Manager

The ERG WAM, Deborah Bartram, has the ove rall responsibility to ensure that these health and safety procedures are developed a nd implemented in accordance with regulations and corporate guidelines, that proper health and safety procedures ha ve been initiated, and that all

ERG activities are conducted in accordance with the health and safety plan. The ERG WAM will also ensure that proper resources are allocated so that the project is condu cted in a safe manner, and that the crew chief is competent in his ab ility to oversee health and safety during the sampling episode.

6.2.2 Crew Chief

The ERG crew chief, TJ Finseth, is res ponsible for ensuring that ERG sampling team members adhere to this plan. The ERG crew chie f and ERG night crew ch ief are responsible for overseeing all activities. The crew chiefs must re port any accident, near miss, or injury to any sampling team member to the ERG Chantilly O ffice Health and Safety Coordinator (HSC), Kevin Sikora, verbally within eight hours, or so oner. The HSC will investigate the incident to identify the cause of the accident, near miss, or injury. If sufficient cause exists, ERG’s general health and safety plan and in-house training prog ram will be modified to avoid similar accidents

in the future.

At the start of the sampling visit, the cr ew chiefs will inspect all sampling points and review sample collection procedures with the Alle n personnel to ensure that all potential hazards

have been identified.

The crew chiefs have the authority to en force ERG’s health and safety requirements contained in this plan, and any facility-specific re quirements. Changes to this plan can be made if the crew chiefs, the Chantilly HSC, and EPA representative agree that the changes are appropriate.

6.2.3 Sampling Team Members

All field personnel are responsible for follo wing the requirements of this plan, adhering to plant-specific health and safety pro cedures, and donning required/recommended personal protective equipment (PPE). They are also respon sible for bringing health and safety issues to

the attention of the crew chiefs.

6.3 Briefings

ERG sampling team personnel will attend on- and off-site health and safety briefings.

6.3.1 Off-Site Briefings

Prior to arriving on site, all members of th e sampling team will receive a copy of this sampling plan and attend a presampling meeting to review the sampling plan and the proposed sample collection activities. All ERG employees w ill be required to sign a health and safety signoff sheet stating that they have read, understood, a nd agree with this health and safety plan prior to participating in field sampling activities.6-3 6.3.2 On-Site Briefings

ERG sampling team personnel must attend a one- to two-hour safe ty course given by Allen personnel prior to conducti ng sampling activities at Allen. Th is safety course will review plant-specific health and sa fety procedures, including:

 Locating on-site first aid/emergency medical procedures;

 Required PPE;

 High hazard areas and other specific areas or hazards of concern;

 Emergency alarms and evacuation procedures; and

 Other site safety requirements and pro cedures that ERG personnel must follow.

[QUESTION FOR ALLEN: Please confir m this information is correct.]

6.4 Safety Procedures

ERG personnel will follow general safety procedures, which include wearing PPE and engaging in safe work practices.

6.4.1 Personal Protective Equipment (PPE)

The PPE listed below will be worn by ERG personnel at all times while inside the premises of Allen:

 Steel-toed safety shoes;

 Long sleeves (when sampling) and pants;

 Hard hat, where required by Allen;

 Hearing protection, where needed;

 Nitrile or noncolored, electronic grade gl oves, when collecting or preserving; and

 Safety glasses with side shields or ch emical splash goggles, when collecting or preserving samples.

For all phases of sample collection, disposal PPE will be used, so decontamination of the PPE may not be necessary. If glove s become torn or degraded, they will be thrown away and replaced with a new pair. Disposable PPE, includ ing gloves, will be removed, bagged, and left at

the site in a c ontrolled manner.

6.4.2 Safety Practices

ERG personnel will conduct themselves at all times in a manner judged to be safe by site supervisors.

All sample collection will be scheduled so that no ERG employee collects samples alone.

Each worker will maintain visual contact with at least one othe r worker at all times. This buddy system will ensure against an employee becoming injured or contaminated with chemicals without a coworker being aware of his or he r condition. Workers should “watch out” for each other while working close to potential chem ical and physical hazards. An Allen or EPA6-4 employee may be used as a buddy by ERG personnel. This arrangement will be agreed to and acknowledged by the employee.

ERG employees will not enter any pe rmit-required confined space areas.

6.4.3 Safe Work Practices

ERG samplers will obey the following safety rules while working in the facility:

 Wearing PPE, where required;

 Staying within designated areas;

 Not wearing loose clothing or jewelry;

 Keeping long hair in hard hat or tied back;

 Not eating in the sampling or staging areas; and

 Not smoking in the sampling or staging areas.

6.5 Sampling-Point-Specific Safety Procedures

All sampling team members will be advi sed of any sampling-point-specific safety protocols during the on-site he alth and safety briefing. Tabl e 6-1 summarizes all potential sampling-point-specific safety hazards as well as the PPE required at each sampling point. During the day shift, the sampling team health and safety officer (HSO) for this sampling episode is the crew chief, TJ Finseth (ERG). During the night shift, the HSO for this sampling episode is the ERG night crew chief (to be de termined at a later da te). The HSO and the sampling team will inspect each sampling point area to identify unique or additional hazards not already covered in this plan or during the formal health and safety briefing. If additional hazards are found, the sampling team will be informed of each hazard and required control measures prior to the start of work. Wh ere identified hazards may affect the plant’s personnel, the HSO will notify the appropriate Allen personnel.

6.5.1 Physical Hazards

ERG personnel will be alert for all physic al hazards present wh ile on site. Physical hazards may arise from using catwalks, hitting low-hanging overhead piping, and working around moving equipment or vehicles. ERG personne l will be aware of the potential splash hazards at SP-1, SP-2, and SP-3 due to the locati on of the sample taps. To prevent splashing, ERG personnel will ensure that the sample tubing is connected securely to the sample tap and will open the sample valve slowly when collecti ng samples. Other potential hazards may include falling hazards during sample collection, tripping on metal grates, or oper ation of large trucks and machinery in the vicinity of the sample co llection area. See Table 6-1 for potential hazards that may be associated with specific sampling points.

Noise may be a hazard in certain areas of the facility. The sampling team will use hearing protection where required by the plant, when th ey are having trouble h earing or being heard when standing three feet or less away from a nother person, or when deemed necessary by the Allen personnel or ERG crew chief.6-5 6.5.2 Thermal Hazards

Heat stress may be a concern during the sa mpling episode. Samplers may be suited in Tyvek® and temperatures could reach extremes. Of particular concern is SP-1, which is located outside. The sampling team members will consume plen ty of fluids prior to the start of sampling,

and will monitor each other for symptoms of heat stress.

Wastewater sampling points are not expected to be too hot fo r safe handling using typical PPE. Thicker nitrile gloves may be used during sampling if sample bottles are too hot to hold. Samplers will handle extremely hot sa mples with heat-resistant gloves.

6.5.3 Chemical Hazards

The only chemical hazards expected are ch emicals used to preserve samples. All sampling team members will be advised of any potential chemical hazards at each sampling point as well as any special PPE recommendations during the formal heal th and safety briefing. If the sample tap (i.e., the point from which the wastewater flows) is above waist height, a face shield or goggles must be worn during samp le collection. To avoid ingesting chemicals, sampling team members will be required to wash hands thoroughly before eating or drinking. ERG personnel will not be permitted to enter ar eas where the facility has determined that respiratory protection equipment is necessary to protect against inhalation hazards.

6.6 Temperature Extremes

Extremely hot temperatures can be a health and safety hazard for this sampling episode. ERG personnel will take precautions to avoi d injuries due to extreme temperatures.

6.6.1 Heat Stress

Heat stress is not only a concern in hot/hum id outdoor environments , it is a concern due to the thermal or radiant heat generated by equi pment and/or processes. Sampling team personnel will monitor each other for the following symptoms:

 Heat rash that may result from con tinuous exposure to heat or humid air. Treatment: Wear cotton clothing under coveralls or Tyvek®.

 Heat cramps that are caused by heavy sweating and inadequate electrolyte replacement. Many times, cramps may not occur until after work or until the worker is sleeping. Signs and symptoms include muscle spasms and pain in the hands, feet, and abdomen:

Treatment: Gently stretch and massage mu scles and replace fluids. Have worker

rest in a cool shaded area.

 Heat exhaustion that occurs from in creased stress on various body organs including inadequate blood circulation due to cardiova scular insufficiency or dehydration. Signs and symptoms include:6-6 — Pale, cool, moist, clammy skin

— Heavy sweating

— Headache and dizziness

— Nausea

— Fainting or fatigue

— Elevated pulse rate (above 150)

Treatment: Replace fluids, pour cool water over face, neck, hands, arms, and legs.

Place worker in cool air and seek medical care.

 Heat stroke is the most serious form of heat stress. Temperature regulation fails and the body temperature rises to critical levels. Immediate action must be taken to cool the body before se rious injury and death occu r. Competent medical help

must be obtained. Signs and symptoms are:

— Red, hot, usually dry skin, body core temperature 108°F (oral)

— Lack of or reduced perspiration

— Nausea

— Headache, dizziness, and confusion

— Strong, rapid pulse

— Coma

Treatment: Remove worker to cool area, saturate clothe s with cold water, wrap worker in wet cold sheets (if possi ble), monitor ABC (airway, breathing, circulation), treat for shock, and call em ergency services for basic life support (BLS) or advanced life support (ALS).

6.6.2 Heat Stress Monitoring

A worker who exhibits any of the above symptoms will be immediately relieved of responsibilities and reques ted to consume electrolyte fluid or c ool water while resting in a shaded

area. The individual should not return to work until symptoms are no longer recognizable. If symptoms appear critical, persist, or get wo rse, the crew chief will seek immediate medical attention for the employee. If the individual does resume work, he/she will be monitored for any

increase in heart rate for the remainder of his/he r shift. In addition, the worker will be requested to consume electrolyte flui d or cool water every hour.

The crew chief will visually monitor workers hourly when:

 Symptoms of heat stress are reported or observed;

 Ambient temperatures exceed 70°F and workers are dressed in impervious clothing; or

 Ambient temperatures exceed 90°F and wo rkers are dressed in normal clothing.

For sampling on this project, work periods wi ll be considered to be approximately two hours in length.6-7 At ambient temperatures of 87°F and above, workers will be monitored for heat stress conditions by measuring the heart rate (HR) by radial (wrist) pulse fo r 30 seconds after one

minute of rest. The HR after one minute of rest should not exceed 110 beats per minute. If the heart beat is higher, the next work period will be shortened by 33 percent, while the length of rest period remains the same. If the pulse rate is still higher than 110 b eats per minute after one minute of rest in the next rest period, the fo llowing work cycle will be shortened by another 33 percent. This shortening of the work period must continue until the work er's HR is no greater than 110 beats per minute.

6.7 First Aid

First aid procedures in response to chemi cal exposures will be conducted in accordance with the appropriate MSDS for the chemical invol ved. If an incident occurs and MSDSs are not available for a particular hazardous chemical (e.g., wastewater), the following general first aid procedures will be performed:

 Skin Contact – Rinse the affected area t horoughly and copiously with clean water.

Seek medical attention if irrita tion is experienced after cleaning.

 Eye Contact – Flush the eyes thoroughly at the nearest eyewash station for 15 minutes. Follow up with medical attention.

 Ingestion – Notify the hospital and carry out any procedures recommended.

The first aid kit will be maintained on each site in the equipment staging area. The

contents of the first aid kit will include at a minimum:

 Adhesive bandages;

 Antiseptic wipes;

 A compress;

 An eyewash solution;

 Gauze pads;

 A cold pack; and

 A triangular bandage.

The injuries most likely to be encountered at Allen are cuts and brui ses; the first aid kit will be maintained and stocked accordingly.

6.8 Sample Preservation and Safety Considerations

Water samples to be analyzed for various c ontaminants may be preserved with sulfuric acid (H 2 SO 4 ), hydrochloric acid (HCl), sodium hydroxi de (NaOH), an ammonium sulfate buffer solution (NH 4 SO 4 ), and/or sodium arsenite (NaAsO 2 ) before shipment to the analytical laboratory. Nitrile gloves and splash goggles must be worn when handling these corrosive chemicals to prevent chemical burns. Sample preservation must be performed in a wellventilated area (preferably an operational la b hood) to avoid pote ntial accumulation and inhalation of any toxic vapors. When pouring samples, skin prot ection must also be worn (long-6-8 sleeved cotton coveralls or uncoated Tyvek®, safety glasses with side sh ields or splash goggles, and nitrile gloves). Sodium arsenite is a known carcinogen and toxic so ex tra care should be taken when handling any solutions containing sodium arsenite.

In some instances, the use of these pres ervation chemicals could create a chemical reaction (i.e., generation of heat or release of toxic vapors). For in stance, if acids are added to a wastewater sample containing cyanide or sulfides, dangerous and toxic vapors will be emitted. If the sample reacts violently, notify the crew chie f and stop preserving the sample immediately.

In the case of a chemical spill, the following procedures must be followed:

 Don protective clothing (nitr ile gloves as a minimum).

 Ventilate area (open doors, window s, or turn on ventilation).

 Use spill control pillows or prepared neutra lizers to contain/clean up spill. Do not

add water to acid.

 Place spilled material in a heavy plastic co ntainer, label the container, and contact site for disposal information.

 Notify the crew chief of the sp ill and the procedures used.

At any time, if personnel do not feel comforta ble about cleaning up the spilled material or if a large quantity has been spilled, notify site personnel. The site may have an emergency response team who will respond to the chemical spill.

In the case of fire, notify the site contact. If the fire can be easily extinguished using a portable fire extinguisher, and personnel have received fire extinguisher training, extinguish the fire using the por table extinguisher.

6.9 Training and Medical Monitoring Requirements

All ERG sampling crew personnel have partic ipated in ERG's annual eight-hour health and safety training program as specified by ERG's Corporate Health and Safety Policy. This training includes:

 Toxicology;

 Exposure limits;

 Chemical, biological, and physical hazards;

 Heat and cold stress;

 Confined spaces;

 PPE;

 Decontamination; and

 Emergency plans and procedures.

All ERG personnel involved with sample collection and pres ervation are active participants in the Medical Monitoring Pr ogram. Field sampling personnel have received a

baseline medical information review.6-9 6.10 Shift Work Protocol

This subsection provides guidance for field personnel project sche dules and field work, particularly overtime. It is important to reme mber extended work schedules will contribute to poor production and motivation. All field teams w ill rotate to ensure that sampling team members receive sufficient rest to avoid inju ries resulting from fati gue or inattention.

It is common practice to perform 12-hour wo rk days under project management direction. If this work schedule is exceeded, th e following guidelines will be recognized:

1. A maximum work day will be 15 hours, provided that it does not occur on consecutive days, or more than th ree times in ANY SEVEN-DAY PERIOD.

2. Each shift will be followed by nine hours off per 24-hour period, excluding driving time to and from the hotel.

3. No more than seven consecutive days of work will be allowed without a

minimum of 24 hours off.

4. Each work day will be reviewed as a 24- hour cycle to assure all field workers receive adequate time off.6-10 Table 6-1. Sample-Point-Specific PPE and Potential Hazards

Sampling

Point Number Sampling Point Description PPE Required a Potential Physical Hazards b

SP-1 Influent to FGD Wastewater Treatment System Steel-toed boots, hard hats, gloves and safety glasses Splash hazard: Potential for splashing from the sample tap. Sample tap will be below waist

level.

SP-2/SP-4 Infl uent to Bioreactor System Steel-toed boots, hard hats, gloves, and safety glasses Splash hazard: Potential for splashing from the sample tap. Sample tap will be below waist

level.

SP-3/SP-5 Effluent from Bioreactor System Steel-toed boots, hard hats, gloves, and safety glasses Splash hazard: Potential for splashing from the sample tap. Sample tap will be below waist

level.

a – Splash protection (face shield) required if sampling port is waist high or above. Hearing protection (ear plugs)

will be worn if needed. b – Additional physical hazards, if any, will be identified during the formal on-site he alth and safety briefing. Updates to this table will be made as needed.7-1 7. R EFERENCES

1. Eastern Research Group, Inc. 2009. Generic Sampling and Analysis Plan for Coal-Fired

Steam Electric Power Plants . (February).

2. U.S. EPA. 2009. Steam Electric Power Generating Point Source 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

.