# Draft Sampling Plan We Energies’
Pleasant Prairie Power Station Pleasant Prairie, WI
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

May 3, 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 ........................................................................................ 2-2

2.2 FGD Wastewater Trea tment System ................................................................... 2-3

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 the FGD Wastewater Treatment System (SP-1) .................... 3-3

3.3.2 Effluent from FGD Wastewater Treatment System (SP-2) ..................... 3-8 3.4 Sample Preservation, Shi pping, and Analysis ................................................... 3-17 3.5 Field Measurements and Engineering Data Collection ..................................... 3-18 3.6 Sample Labeling ................................................................................................ 3-19 3.7 Traffic Reports ................................................................................................... 3-19 3.8 Quality Assurance/Quality Control .................................................................... 3-20 3.9 Sample Splitting ................................................................................................. 3-22

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 Pleasant Prairie Power Plant 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 ...................................... 6-1 6.2.1 Work Assignment Manager ..................................................................... 6-2TABLE OF CONTENTS (Continued)

Page

ii 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 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 Pleasa nt Prairie Power Plant ........................................................ 3-23

3-2 Analytical Methods ........................................................................................................ 3-24

3-3 Summary of Sample Containers and Planned Preservation ........................................... 3-25

3-4 Sampling Point Field Measurements ............................................................................. 3-25

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

LIST OF FIGURES

Page

2.1 FGD Wastewater Treatment System, Pleasant Prairie Power Plant ................................ 2-6

3-1 Sample Preservation Log Sheet ..................................................................................... 3-26

3-2 Field Sampling Log Sheet .............................................................................................. 3-2 7

3-3 Engineering Data Collection Sheet (Page 1 of 3) .......................................................... 3-28

3-4 Engineering Data Collection Sheet (Page 2 of 3) .......................................................... 3-29

3-5 Engineering Data Collection Sheet (Page 3 of 3) .......................................................... 3-30

3-6 Example Traffic Report ................................................................................................. 3- 311-1 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 plan, de veloped for the We Energies’ Pleasant Prairie Power Station (Pleasant Prairie), located in Pleas ant Prairie, Wisconsin, 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 its recently completed detailed st udy 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 wast e streams contributing these toxic loadings are associated with wet flue gas desulfurization (F GD) systems present at coal-fired power plants.

This sampling plan will focus on charact erizing wastewaters and treatment system discharges at Pleasant Prairie. For a general de scription of the steam el ectric process and the wastewaters generated during the operation of a coal-fired st eam electric power plant, see Chapters 3 and 4 of the Steam Electric Power Generating Point Source Category: Final Detailed 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 a chemical prec ipitation FGD wastewater treatment system. A chemical precipitation system utilizes physical a nd chemical treatment to remove heavy metals using hydroxide precipitation, or a combina tion of hydroxide and sulfide precipitation.

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?

 What are the effluent concentrations for pollutants present in treated FGD

wastewater?1-2  What are the pollutant loadings associat ed with discharges of FGD wastewater following treatment?

EPA conducted a one-day presampling site vi sit at Pleasant Prai rie on March 2, 2010, 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 develop the sampling plan; and

 Information on potential sampling points.

The sampling program will consist of four-day sampling episodes at selected plants. The sampling will characterize the wastewater genera ted by the wet FGD scrubbers and the treatment performance of the systems used to treat th e FGD scrubber purge wastewater. EPA will also collect field quality control (QC) samples cons isting of bottle blanks, field blanks, equipment blanks, duplicate samples, and laboratory QC sa mples 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 proc ess configurations and characteristics of the plants.

Pleasant Prairie was selected by EPA for sampling based on the following site

characteristics:

 The plant is a coal-fired pow er plant that burns powder river basin (PRB) coal in each of its two generating units;

 The plant operates limestone forced oxidation wet FGD systems on both units;

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

— Equalization,

— pH adjustment (lime addition),

— Primary clarification,

— Organosulfide addition,

— Ferric chloride addition,

— Polymer addition,

— Secondary clarification;1-3  The plant operates selective catalytic reduction (SCR) systems on both generating units; and

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

Pleasant Prairie operates two steam electric generating units and each has a coal-fired boiler. Units 1 and 2 each have a capacity of 615 megawatts (MW), and came online in 1980 and 1985, respectively. The plant is located in Pleasant Prairie, Wisconsin, about 5 miles from Lake Michigan.

Pleasant Prairie burns approximately 5.5 milli on tons of PRB coal each year. The plant also burns bottom and fly ash from older power pl ants to reclaim some of the carbon in the ash. The old ash is burned at approxi mately one to two percent wei ght of the total fuel burned.

Approximately three years ago, Pleasant Prai rie retrofitted both un its with FGD scrubber systems to control th e sulfur dioxide (SO 2 ) releases from the plant. The Unit 1 FGD system was installed in November 2006, and the Unit 2 FGD system was installed in March 2007. The wet FGD scrubbers remove approximately 97 to 98 percent of the SO 2 from the flue gas. In addition to the FGD scrubber systems, Pleasant Prairie inst alled an FGD wastewater treatment system to control the discharges of the wastewater gene rated during the operation of the FGD scrubbers.

Sections 2.1 and 2.2 further discuss the F GD scrubber systems and the FGD wastewater treatment system, respectively.

Pleasant Prairie retrofit ted Units 1 and 2 with SCR systems in 2006 and 2003, respectively. The plant operates the SCR systems, which are used to control nitrogen oxide (NO X ) emissions, year round.

The electrostatic precipitators (ESPs) at Plea sant Prairie are particulate control devices that are designed to remove 99.7 percent of the fly ash and other particulates from the flue gas.

Pleasant Prairie utilizes ESPs to remove the fly ash from both units. The fly ash and other particulates are collected in hoppers and pneumatically conveyed to storage silos. Pleasant Prairie markets the fly ash produced. There is no wa stewater discharge associated with the ESPs.

Pleasant Prairie recently installed a calciu m bromide injection system in November 2009 and began continuous calcium bromide in jection in January 2010. [QUESTION FOR PLEASANT PRAIRIE: When was the bromide inj ection system added?] The system injects a solution of calcium bromide on to the coal prio r to it being pulverized. Adding the calcium

bromide to coal enhances the oxidation of the me rcury in the boiler and, therefore, results in better removals of mercury in the downstream FGD system. Since the addition of the injection system, Pleasant Prairie has noticed an increase in the mercury concentrations present in the gypsum, as well as the sludge generated from the FGD wastewater treatment system.

Units 1 and 2 each have the following configuration:

 Boiler;

 SCR system;

 ESP; and

 FGD scrubber system.2-2 2.1 FGD Scrubber Systems

Pleasant Prairie operates two identical wet F GD scrubber systems that treat the flue gas from Units 1 and 2. The plant uses limestone slurry as the sorbent for SO 2 absorption. Limestone and service water are fed to on-site ball mills, wh ich pulverize the limestone to create the slurry. From the ball mills, the slurry is transferred to hydrocyclones to collect limestone particles that are too large to use in the FGD scrubber sy stem. The underflow from the hydrocyclones is returned to the ball mill for additional processi ng. The overflow from the hydrocyclones, which is approximately 40 to 50 percent solids (by weight), is transferre d to a limestone slurry storage tank and used as fresh limestone slurry in the absorber.

The fresh limestone slurry is fed to the r eaction tank of the FGD scrubber system and the recycle pumps pump the slurry to the various le vels of the FGD scrubbe r (typically two of the three spray levels are operating at one time). Th e slurry is pressurized and sprayed downward into the scrubber vessel through the spray nozzles. As the slurry falls downward and the flue gas flows countercurrent 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 spray droplets flow downward until they reach th e dual flow tray, which forms a layer of slurry that the flue gas must pass thr ough to exit the FGD scrubber system . The tray has small holes in it that allow the flue gas to bubble through the limestone slurry layered on the tray, which provides additional contact between the limestone slurry and the flue gas. The spray droplets

continue to flow downward in the scrubber until they reach the reaction tank. Pleasant Prairie bubbles air through the reaction tank to oxidize th e calcium sulfite to calcium sulfate (i.e., gypsum).

The SO 2 removal in the FGD systems is optimized at a pH of 5.9 and the limestone slurry feed rate is adjusted to main tain this pH. In addition, the pl ant operates the FGD systems to

maintain a solids concentration in the scrubbe r of 15 to 18 percent so lids. When the solids concentration exceeds 18 percent, the plant bl ows down from the FGD system. The blow down from each FGD system lasts for about eight to ten hours each day and is transferred to the gypsum dewatering operations. The plant sta ggers the blow down from the two units.

Pleasant Prairie also maintains the chloride concentration in the FGD scrubber systems between 3,000 and 10,000 ppm. The maximum desi gn chlorides concentr ation is 15,000 ppm, but the plant tries to keep the ch lorides concentration around 6,000 ppm.

The gypsum slurry for each scrubber is pumped to its primary hydrocyclone, where the solid gypsum is separated from the water by cen trifugal force. The solid gypsum is forced outward to the walls of the hydrocyclones and fa lls downward, while the wa ter exits the top of the hydrocyclones. The gypsum from the primar y hydrocyclones, which is approximately 50 percent solids, is transferred to the vacuum belt filters for fina l dewatering. The overflow from both the Unit 1 and Unit 2 primary hydrocyclones are commingled and transferred to a common secondary hydrocyclone. [QUESTION FOR PLEA SANT PRAIRIE: Is there a collection tank between the primary hydrocyclones and the s econdary hydrocyclone where the streams are commingled?] The overflow from the second hydroc yclone is transferred to the FGD wastewater

treatment system.2-3 Pleasant Prairie washes the gypsum sent to th e vacuum filter belts wi th service water, as the gypsum slurry is poured onto the belts. The v acuum filter belts dry the gypsum to a moisture content less than 10 percent. Pleasant Prairie sells the gypsum for use in wallboard manufacturing or for agricultur al purposes. Pleasant Prairie gene rates approximately 45,000 tons of gypsum per hour, when the plant is dewatering the gypsum.

The filtrate from the vacuum belt filters is collected and transferred back to the FGD scrubber systems. Typically, the filtrate is tran sferred back to the Unit 1 FGD scrubber system; however, the plant has the capability to send the filtrate to the Unit 2 FGD scrubber system.

2.2 FGD Wastewater Treatment System

The Pleasant Prairie FGD wastewater treatment system is designed to receive intermittent

transfers of wastewater from the FGD scr ubber system, which consists of secondary hydrocyclone overflow, at a flow rate of a pproximately 40 gallons per minute (gpm). The intermittent transfers are expected to o ccur for 6 to 12 hours per day. [QUESTION FOR

PLEASANT PRAIRIE: What is th e typical duration fo r a single transfer from the secondary hydrocyclone to the FGD wastewater treatment syst em? For example, is there one transfer a day, for 6 to 12 hours? Or are there multiple tran sfer each day for shorte r durations?] The FGD wastewater treatment system is a chemical pr ecipitation system and contains the following treatment operations:

 Equalization tank;

 pH adjustment (lime addition);

 Primary clarification and polymer addition;

 Organosulfide and hydrochl oric acid addition;

 Ferric chloride addition;

 Mixing tank;

 Flocculation tank;

 Secondary clarification; and

 pH adjustment (hydrochloric acid addition).

Figure 2-1, located at the end of this secti on, presents the process flow diagram of the FGD wastewater treatment syst em, as well as the planned sampling locations for EPA’s sampling episode. Pleasant Prairie estimates that the total residence time of the FGD wastewater treatment system is approximately 55 hours.

The secondary hydrocyclone overflow from the scrubbers is transferred directly to the equalization tank at the start of th e wastewater treatment system. This wastewater is expected to contain approximately 0.5 to 1.0 percent solids an d have a pH of 5.6 S.U. The equalization tank also receives water from the filtrate sump, which includes the filtrate from the treatment system sludge filter presses.

From the equalization tank, the wastewater enters reaction tank 1, where hydrated lime is added to raise the pH of the wastewater from 5.6 to 8.5 S.U. to precipitate the soluble metals as insoluble hydroxides and oxyhydroxides. The reacti on tank also desaturates the gypsum in the wastewater, which prevents gypsum scale forma tion in the downstream wastewater treatment2-4 equipment. To desaturate the gypsum, some of the sludge from the downstream primary clarifier is recycled back to reacti on tank 1 to provide seed crys tals for gypsum nucleation.

From reaction tank 1, the wastewater flows to the primary clarifier, where polymer is added to aid in the settling of the solids. Pleasant Prairie stated that 96 per cent of the solids settle out of the wastewater in the pr imary clarifier. The overflow from the primary clarifier flows to reaction tank 2, where the plant adds organosulfi de and hydrochloric acid. When the plant first began operating the treatment system , they used TMT 15® as the or ganosulfide. Since that time, the plant has switched to using Nalmet 1689®, wh ich is an organosulfide that has a longer polymer chain, and therefore, a higher molecula r weight, which helps aid in the settling of precipitates. Pleasant Prairie also began addi ng hydrochloric acid to reaction tank 2, which

wasn’t in the initial de sign of the system; because the plant de termined that they achieve better removals of mercury when the system is operate d at a lower pH. The pH in reaction tank 2 is targeted at 7.0 to 7.2 S.U.

From reaction tank 2, the wastewater flows to reaction tank 3, where ferric chloride is

added to the wastewater. The effluent from r eaction tank 3 flows to the flash mix tank, where polymer is added to the wastewater. From th e flash mix tank, the wastewater flows to the flocculation tank. Gentle mixing in the floccu lation tank allows dens er floc to form.

The wastewater from the flocculation ta nk flows to the secondary clarifier. The secondary clarifier settle s the solids that were formed duri ng the chemical conditioning steps. Pleasant Prairie operates an inclined-plate lamella separator type clarifier. Hydrochloric acid may be added to the overflow from the secondary clarifie r to readjust the pH valu e, if needed, to meet effluent limits. From the secondary clarifier, water flows to the effluent tank and is then commingled with other waste st reams (e.g., cooling tower blowdow n) prior to discharging to Lake Michigan. Pleasant Prairie commingles the effluent from the FGD wastewater treatment plant with other plant wastewater to meet the fi nal outfall mercury and chloride limits. To meet the effluent mercury limit, Pleasa nt Prairie must dilute the FGD wastewater at a 30:1 ratio.

The sludge from the primary and secondary cl arifiers is transfe rred to sludge holding tanks using sludge transfer pumps. A portion of the clarifier sludge is recycled from the sludge holding tank to reaction tank 1, while the majority is pumped to a filter press for dewatering. The filter press uses hydraulic power from compressors to remove water. The solids are then stacked on-site prior to being transferred to an off-site la ndfill. The filtrate is transferred to the filtrate sump, the contents of which are recy cled back to the equalization tank.

Pleasant Prairie typically operates the FGD wastewater treatment system Monday through Saturday. The system is shut down Sunday to perform weekly cleaning and maintenance. This weekly maintenance includes draining and flushing of the secondary clarifier to avoid buildup from floccula tion. [NOTE TO PLEASANT PRAIRI E: Can the weekly cleaning and maintenance be rescheduled the Sunday be fore the sampling episode (e.g., performed on Saturday instead) to allow EPA/ERG to test th e sampling configurations on Sunday, which is the set-up day for the sampling episode? An swer – Yes, see related comment]

Pleasant Prairie has made the following modi fications to the FGD wastewater treatment system since the system first began operating in early 2007:2-5  Changed the type of organosulfide used in the system from TMT 15® to Nalmet® 1689 (described previously);

 Added a hydrochloric acid addition point to reaction tank 2 be cause the system removes more mercury at a lower pH (described previously);

 Bypassed a set of sand filter s that were located after the secondary clarifiers because of scaling issues (the sand filt ers are not shown in Figure 2-1); and

 Added the capability to use cartridge filtr ation to remove colloidal particles from

the wastewater after the sec ondary clarifier, which may build up in the system if the plant recirculates the wastewater without discha rging for several weeks; however the cartridge filtration is not used regularly (the cartridge filters are not shown in Figure 2-1).2-6SecondaryHydrocycloneOverflowLimeOrganosulfideFerricChloridePolymerHydrochloricAcidTreatedEffluent toDischargeTo Sludge DisposalEqualizationTankReaction Tank 1Primary ClarifierReactionTank 2ReactionTank 3FlashMix TankFlocculationTankSecondaryClarifierTreatedWastewaterStorageTanksSludge HoldingTankFilter PressFiltrateSumpSP-1SP-2Indicates a Sampling PointTreatedEffluentRecyclePolymerHydrochloricAcidFigure 2.1. FGD Wastewater Treatment System, Pleasant Prairie Power Plant3-1 3. S AMPLING P ROCEDURES

This section discusses th e planned sampling procedures to be followed during the sampling episode at Pleasant Prairi e. This section also provides th e necessary information to plan for the logistics of this sampling episode. All tabl es and figures in this section are presented at

the end of the section.

3.1 Sampling Point Selection

EPA’s sampling point selection includes trea tment system influent and effluent sampling

locations for the FGD wastewater treatmen t system and sampling related to Quality Assurance/Quality Control (QA/QC) samples. A total of five sampling points were defined for this plant:

 SP-1 Influent to the FGD Wa stewater Treatment System;

 SP-2 Effluent from the FGD Wa stewater Treatment System;

 SP-3 Duplicate of Effluent from the FGD Wastewater Treatment System (SP-2);

 SP-4 Influent to the FGD Wastewater Tr eatment System (SP-1) Field Blank;

and

 SP-5 Effluent from the F GD Wastewater Treatment Sy stem (SP-2) Field Blank.

3.2 Analyte Selection

Analytes that will be included in EPA’s Pleasant Prairie 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;

 Total metals:

— Aluminum, antimony, arsenic, barium, beryllium, boron, cadmium, calcium, chromium, cobalt, copper , iron, lead, magnesium, manganese,3-2 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 the FGD wa stewater treatment system (SP-1) and the

effluent from the FGD wa stewater treatment system (SP-2) at Pleasant Prairie, the sampling team will use varying methods to collect the samples depending on the sampling point and pollutant parameters. This subsection describes in detail the sample collection 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. The masks are used during sampling to prevent contamination of the mercury samples and ar e not required for re spiratory protection.

Sample containers and bottles will be pur chased precleaned and certified and will not require rinsing with sample. ERG will follow prot ocols described in EPA Method 1669 to collect metal sample fractions. All sampling equipment (e .g., tubing) and sample bottles will be cleaned according to the procedures described in EP A Method 1669. Samplers will use “clean hands / dirty hands” sample collection t echniques when collecting metal sa mple fractions, as described

in EPA Method 1669.

For this sampling episode, ERG will collect in dividual grab samples at the influent to the FGD wastewater treatment system sampling point for all analytes. At the effluent from the FGD wastewater treatment system, ERG will collect 24-hour composite samples for most analytes; however, cyanide will be collected as a single grab sample and mercury will be collected as four grab samples. ERG will collect one sample at each sampling point each day over four consecutive 24-hour periods (mercury will be coll ected as four grab samples each day for the

effluent from the FGD wa stewater treatment syst em sampling point).3-3 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 the FGD Wastewat er Treatment System (SP-1)

The influent to the FGD wastewater treatment system (SP-1) has a sample tap located on the secondary hydrocyclone. ERG w ill collect the sample prior to the wastewater entering the equalization tank because the FGD scrubber purge is commingled with recycled wastewater in the equalization tank and, therefore, the sampli ng point upstream of the tank provides the best representation of the FGD scrubber purge from the Pleasant Prairie FGD scrubber system. Because the flow through the secondary hydrocyc lone is not continuous, ERG will need to coordinate closely with Pleasan t Prairie 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 system). ERG will follo w protocols described in EPA Method 1669 to collect metal sample fractions from SP-1.

ERG plans to collect split samples with Pl easant Prairie (or its representative), where possible; therefore, ERG plans to attach a piece of silicone tubing to the sample tap with a “Y” splitter at the other end of the tubing to allow ERG and Pleasan t Prairie (or its representative) to collect samples simultaneously. The sample tap located at the secondahttp://webapps4/msdgen/pds/archi ves/pds/default/004 00307.pdfry hydrocyclone currently has a large diameter tubi ng that flows to a drain. For the sample collection, the plant

will need to install a 3/8 inch hose barb to the sample tap for ERG to attach its tubing. [QUESTION FOR PLEASANT PRAIRIE: Please confirm that the plant will be able to remove the current tubing and install a 3/ 8 inch hose barb to the sample tap. Yes, confirmed.] If problems occur during the collection 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 Pleasant Prairie or its representative. For all analyses (except dissolved metals and hexavalent chromium), the samplers will collect samples through the tubing directly into the specified containers. For th e dissolved metals (excluding mercury) and hexavalent chromium samples, the samplers will fill one 10-L container, allow the solids to settle for one hour, and then pump the aqueous porti on of the sample through a 0.45- μ m filter and then through a “Y” splitte r into the specified containers; therefore, the dissolved metals and hexavalent chromium samples will be collected as split samples.

The influent sample at Pleasant Prairie is expected to contain approximately 0.5 to 1.0 percent suspended solids, but TSS levels in FGD pur ge at other plants have been observed in the range of 1 to 5 percent. If the TSS content of the sample is greater than one percent, then the laboratory will separate the aqueous and solid por tions of the sample and analyze both for the analyte of interest (i.e., biphasic samples). In this instance, Group I (chl oride and sulfate only), Group II (ammonia as nitrogen, nitrate/nitrite as nitrogen, and total phos phorus only), and total metals (including mercury, but not hexavalent chro mium because it is filtered in the field during sample collection) samples will be analyzed as biphasic samples. Group I (TSS and TDS only), Group II (COD only), BOD 5 , hexavalent chromium, and dissolv ed metals (including mercury)3-4 samples will not be analyzed as biphasic samples. Scrubber purge samples with less than one percent TSS will not require biphasic separation and analysis.

The samples for the influent to the FGD wa stewater 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- μ m filter;

 Funnel;

 Peristaltic pump;

 Small table;

 Cleanbox;

 Tyvek® suits (for metals samples);

 Masks (for mercury samples); and

 Sample containers.

ERG will follow all procedures and protocol s described in EPA Method 1669 to clean all metals sampling equipment and to collect metal sample fractions. Two or more ERG samplers (one designated as “clean hands” and the othe r as “dirty hands”) wi ll follow the protocols described in the steps below to set up the samp ling point, collect the field blank samples, and collect wastewater samples. This section describe s the set-up of the samp le point and collection of the EPA samples 1

.

1. Samplers remove the bags containing the gloves and high-density polyethelene (HDPE) plastic wrap from the coolers or storage containers in which they are packed. Samplers identify which cool ers or boxes contai n the double-bagged sample bottles, precleaned tubing, bla nk water, and cleanbox. Depending on the condition of the sample tap, samplers may n eed to wipe the tap with a clean paper towel to remove any buildup on the tap that could potentially fall in the sample bottles during sample collection.

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

3. “Dirty hands” opens the outer bag of the cleanbox and “clean hands” opens the inner bag. “Clean hands” places the 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 the plant’s 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 during only 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. “Clean hands” fills the 10-L container with sample to be analyzed for dissolved metals and hexavalent chromium, which is required to be filtered for these analyses. The samplers will allow the solid s to settle for one hour while collecting the remaining samples. “Clean hands” pl aces the lid back on the 10-L container, places the plastic bag over the end of the silicone tubing, and places the tubing

into the cleanbox. ”Clean hands” screws the lid on the 10-L container and closes the inner bag. “Dirty hands” closes the out er 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 follow 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 at the influent to the FGD wastewater treatment system during only 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 Effluent from FGD Wastewater Treatment System (SP-2)

The effluent from the FGD wastewater tr eatment system (SP-2) will be collected

downstream of the two effluent tanks. Pleasan t Prairie has a sample tap located on the wastewater piping downstream of the effluent tanks. Pleasant Prairie uses the tap to collect samples associated with its NPDES internal monitoring point. The sample tap located downstream of the effluent tanks currently has a fiberglass fitting with a larger diameter than ERG’s tubing can accommodate. Plea sant Prairie personnel stated that the current sample tap could be replaced with a new flanged fitting with a sample tap that would accommodate the ERG sample tubing configuration. ERG will follow protocols described in EPA Method 1669 to collect metal sample fractions from SP-2.

ERG will collect the effluent from the F GD wastewater treatment system composite samples using two automatic compositors that w ill be programmed to collect individual sample volumes into two large containers (e.g., two 20-lit er HPDE containers). To collect sufficient sample volume, ERG will calculate the total volum e 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 programme d to be collected in one-hour intervals during the 24-hour composite period. Following the com posite 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.3-9 ERG has two approaches for collecting the total and dissolved me rcury grab samples; however, the approach used will depend on how Pleasant Prairie is able to configure the sample taps. The preferred approach for the mercury coll ection is to have a third tap available at the sampling point (i.e., one tap for the metals compos itor, one tap for the classicals compositor, and one tap for mercury grab samples). If Pleasant Pr airie can accommodate 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 configuration is not possible, then ERG will collect the samples from the composite tubi ng line that discharges to the sump/drain, described in more detail in the steps below. For both of these collection approaches, ERG will not be able to collect split samples with Pleas ant Prairie (or its repres entative); therefore, duplicate samples will be collected.

[QUESTION FOR PLEASANT PRAIRIE: Please confirm that the plant will be able to replace the current fiberglass fitting with a new flanged f itting. Also, would the plant be able to set up the flanged fitting to have a three-way splitter a ttached with each splitter having a 3/8 inch hose barb and having its own valve to cont rol flow? Yes. We expect to be able to fabricate this item.]

When pumping off the composite samples that have been collected, a “Y” splitter will be used with two pieces of silicone tubing attach ed to the “Y” splitter to allow ERG and Pleasant Prairie (or its representative) to collect samples simultaneously. If problems occur during the collection of split samples (e.g., the splitters b ecome clogged and the flow is split unevenly between the sampling crews), then EPA may stop th e split sample collection and offer instead to collect duplicate samples with Pleasan t Prairie (or its representative).

As described previously, to meet their permit limits, Pleasant Prairie must dilute the FGD

wastewater treatment effluent wi th other process wastewaters at the plant, mainly cooling tower

blowdown. Pleasant Prairie does not discharge cooling tower blowdown when the plant is chlorinating the cooling system; therefore, the pl ant may be unable to discharge FGD wastewater from the treatment system during the chlorination period if there is not sufficient volume from other wastewater discharges for the required dilution. During the summer, Pleasant Prairie chlorinates the cooling system Monday, Wednesd ay, and Thursday from 8:00 AM to 2:00 PM; therefore, during the sampling episode, ERG will be unable to pull volume for the 24-hour composite during these time periods if the plant will not be discharging from the effluent tanks. During the presampling site visit, EPA, ERG, and Pleasant Prairie personnel discussed this potential issue. As part of th e discussion, Pleasant Prairie personne l stated that the plant could continuously operate the effluent pumps, and the flow could be transferred to a storage tank during the chlorination period. This operation would allow ERG to collect effluent samples for the entire 24-hour period. Pleasant Prairie also stated that the treat ed effluent collected could be sent back to the scrubber as make-up wate r and, therefore, would not impact the FGD wastewater treatment system performance. ER G and EPA agreed with this approach for collecting samples of the effluent from the FGD wastewater treatment system.

[QUESTION FOR PLEASANT PRAIRIE: Please confirm that the plant will be able to operate the FGD wastewater treatment system, as desc ribed above, for chlorination periods during the sampling episode. Yes – See related comment.]3-10 For all analytes, ERG will collect QC samples at the effluent from the FGD wastewater treatment system (SP-2) during one day of the sampling episode. In addition, for all analytes, ERG will collect a duplicate sample of the efflue nt from FGD wastewater treatment system (SP3) during one day of the sampling episode.

The sample of the effluent from the FGD wastewater treatment 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- μ m 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 4

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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

4 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 the plant’s samples is not described.3-11 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 colle ct 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 lids, and places each in its inner bag. “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 field blank sample bottle in the outer bag and “dirty 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 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 the3-12 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 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 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.

5 ERG will collect field blank samples at the effluent fr om the FGD wastewater treatment system during only one day of the sampling episode.3-13 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 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 the sample tap and adjusts the flow. “Cl ean hands” opens 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 to collect 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 to co llect 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 Pleasant Prairie (or its repr esentative), but wi ll be collected as duplicate samples. The total mercury duplicate sample for Pleasant Prairie (or its representative) will be collected immediately after ERG collects the total mercury3-14 sample. ERG will not collect the dissolved mercury sample until after Pleasant Prairie (or its representative) collects its total mercury duplicate sample. Pleasant Prairie (or its respresentative) will colle ct its dissolved mercury duplicate sample immediately after ERG collects its dissolved mercury sample.

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 third sample tap, if available. If the third sample tap is not available, samplers will collect a total cyanide grab sample out of the tubing that is discharging into the sump/drain at the sample location. The samplers will fill the bottle directly from the tap or the tubing used for the classicals composite co ntainer; therefore, the cyanide sample will not be collected as a split sample with Pleasant Prairie (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 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-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 collecting the composite samples, the sampling team then needs to 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 which3-15 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 peristaltic 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 t ubing, a “Y” splitter, and two additional pieces of silicone tubi ng. “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 and then stops the pump. “Clean hands” closes the lid on the sample bottle and closes the inne r bag. “Clean hands” places the inner bag and bottle in the outer bag and “dir ty 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 blank3-16 water from the field blank composite cont ainer. “Clean hands” places the end of the silicone tubing in the cleanbox, opens the inner bag of the dissolved metals field blank sample bottle, and removes the lid. “Dirty hands” operates the pump to

collect the dissolved metals field blank sample and then 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 hexavalent chromium field blank samples 6 . “Clean hands” closes the inner bag of the field blank composite container and “dirty hands” closes th e outer bag. Note: 750 mL of blank water does not need to be purged for each sample, just at the beginning of each new filter. If a new filter is needed, “clean hands” removes the used filter and samplers follow step 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 and then 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 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 for the hexavalent chromium samples. During one day of the sampling episode, the samp lers will collect additional sample volume for the duplicate samples. The samplers will also collect additional sample volume for the laboratory QC an alyses 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.

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 and th en stops the pump. “Clean hands” places

the end of the silicone tu bing back in the cleanbox.

6 ERG will collect field blank samples at the effluent fr om the FGD wastewater treatment system during only one day of the sampling episode. ERG will collect the dissolve d mercury sample using the same technique as the total mercury sample, but the dissolved sample will be filtered at the laboratory. A dissolved mercury field blank will be performed by the laboratory to assess any mercury 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.3-17 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 t ubing and then 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 FGD wastewater treatment system (SP-2) 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 FGD3-18 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 at 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 preservation 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 and SP-2). The samplers will measure temperature and pH when the automatic composite samplers are initially set up and every 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 present, the samplers will

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 fact or of 3 (2:1). They will continue this process 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 collected3-19 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.

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 will be completed in indelible ink and contain 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 each3-20 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 the 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 collection at Pleasant Prairie 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-3)

of the effluent from the FGD wa stewater treatment system (SP-2) . The duplicate samples will be collected as separate aliquots in the field. Resu lts of the duplicate analyses will be used to evaluate precision, including variability in sample collection, handling, prep aration, 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.3-21 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).

ERG will prepare field blanks for each of the total and dissolved metals analyses at each of the two sampling points during one day of the sampling episode 7 . 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 effluent from the FGD wastew ater treatment system sampling point 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 mercur y field blank at the e ffluent from the FGD

wastewater treatment system sa mpling point will be prepared by either pouring ASTM Type 1 water directly into the sample bottles or pum ping ASTM Type 1 water through the tubing that discharges to the sump/drain and into the sample bottles. The dissolved metals field blank at the influent to the FGD wastewater treatment system sampling points will be prepared by gravityfeeding ASTM Type 1 water through the silicon e tubing set into a large composite container where it will be held for approximately one hour, then pumping the ASTM Type 1 water from the large composite containe r through the Teflon® and si licone tubing, through a 0.45- μ m filter, and into the sample bottles. The dissolved meta ls field blank at the effluent from the FGD wastewater treatment system sampling points will be prepared by pumping ASTM Type 1 water through the composite tubing set in to a large composite container 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- μ m filter, and into the sample

bottles. The field blanks will determine if th ere 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., matrix spike (MS)/matrix spike duplicate (MSD) sample) will be collected for every 10 samples collected at a sampling event, excluding field blank samples. For classical analyses, EPA will collect one QC sample volume at the effluent fr om the FGD wastewater tr eatment system (SP-2)

7 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 by the laboratory.3-22 sample point at each episode. For all analytes requiring laboratory QC volumes, the sampling team will collect QC sample volume from the effluent from the FGD wastewater treatment system (SP-2) during one da y of the sampling episode.

3.9 Sample Splitting

Pleasant Prairie or its repres entative has elected to colle ct split samples (or duplicate samples, as appropriate) at each of the sampling poi nts. Pleasant Prairie or its representative will supply all of the personnel, equipment, glassware, and reagents required to collect the split and duplicate samples and to coordinate the analysis of samples. For each of the sampling points, excluding the mercury (total and di ssolved) and total cyanide grab samples at SP-2, the sampling crew will attempt to collect split samples with Pleasant Prairie or its representative as described in this plan; however, if problem s occur (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 sample s with Pleasant Prairie or its representative. For the mercury (total and dissolved) and total cyanide grab sample s at SP-2, ERG will not be able to collect split samples with Pleasant Prairie due to sample confi guration issues discussed previously in Section 3.3.2; therefore, duplicate samples will be collected.3-23Table 3-1. Sample Collection at Pleasant Prairie Power PlantSamplingPointNumberSampling 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 BOD 5 Group I

a Group II b Total CyanideSP-1 Influent to the FGD WastewaterTreatment System4 4 4 4 4 4 4 4 4SP-2 Effluent from the FGD WastewaterTreatment System4+1QC 4+1QC 41+1QC 4+1QC4+1QC 4+1QC 4+1QC 4+1QC4+1QCSP-3 Duplicate of the Effluent from FGDWastewater Treatment System1 1 1 1 1 1 1 11SP-4 Influent to the FGD WastewaterTreatment System Field Blank1 1 1 1SP-5 Effluent from the FGD WastewaterTreatment System Field Blank1 1 1 1Total Number of Samples 11+1QC 11+1QC 11+1QC 9+1QC 11+1QC 9+1QC 9+1QC 9+1QC 9+1QCa – 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.3-24 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.)3-25 Table 3-3. Summary of Sample Cont ainers 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 NaOH to pH >10, dilution until sulfide is not present, NaAsO 2 until total chlorine is not present, ≤ 6  C

Metals

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

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

Total mercury One 250-mL glass bottle (ultraclean),fluoropolymerlined cap One 250-mL glass bottle (ultraclean),fluoropolymerlined cap 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 )3-26 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 Sheet3-27 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 Sheet3-28Plant 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 Make-upWater SourceSO2RemovalPercentageType ofSolidsSeparationNote changes in operation over the past month (e.g., turned off SCRs on October 1 or burned 5 percent petroleum coke previous week);Figure 3-3. Engineering Data Collection Sheet (Page 1 of 3)3-29 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:

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 3-4. Engineering Data Co llection Sheet (Page 2 of 3)3-30Plant 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) ________________Figure 3-5. Engineering Data Collection Sheet (Page 3 of 3)3-31 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 3-6. 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 shippi ng activities while at Pleasant Prairie. 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. Af ter EPA review, the report will be forwarded to

Pleasant Prairie for review.

4.2 Presampling Preparation

On March 2, 2010, ERG and EPA conducted a site visit at Pleasant Prairie. The site visit and subsequent follow-up telephone calls to Pl easant Prairie representa tives provided ERG and EPA the necessary information to prepare for th e sampling episode and to create this sampling plan.

As part of preparing the team for the sampli ng episode at Pleasant Prairie, 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 Pleasant

Prairie. The crew chief will also give copies of this sampling pl an to Pleasant Prairie 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 Pleasant Pr airie, the ERG crew chief, in conjunction with the EPA representatives, will meet with Pleasant Prairie personnel to determine whether 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 descrip tions of the proposed sampling points, if necessary, in consulta tion with EPA and Pleasant Prairie personnel. If necessary, the crew chief will obtain additional equipment. Th e revised sampling description 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 recommended4-2 revisions to the proposed health and safety pr ocedures. Together, the crew chief and HSC willreview the proposed health and safety procedures. The crew chief will incorporate any plantspecific 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 Pleasant Prairie co ntacts, analytical labo ratory contacts and addresses, and sampling team personnel and support functions.

4.4.1 Pleasant Prairie Power Plant Contacts

David Lee, Manager – Water Qual ity Environmental Department We Energies

333 W. Everett St. Milwaukee, WI 53203 (414) 221-2158

Pete Kutzora, Chemical Engineer – Fossil Operations Business Unit We Energies 231 W. Michigan Street – P145 Milwaukee, WI 53203 (414) 221-3926

Rob Muehlenkamp

Pleasant Prairie Power Plant

8000 95 th Street Pleasant Prairie, WI 53158 (262) 947-5344

[QUESTION FOR PLEASANT PRAI RIE: Who will be the plant contact for the sampling episode, including the point of contact for shipping 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 (4 miles from plant) 9740 76th St, Suite 104 Pleasant Prairie, WI 53158 (262) 697-8422 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 Office Print & Ship Center (4 miles from plant)

6411 Grand Ave Gurnee, IL 60031 (847) 856-8020 Hours of Operation: Mon. – Fr i.: 7:00 a.m. to 11:00 p.m.

Last Express Drop-off: Mon. – Fri.: 8:00 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 shippe d in accordance with U.S. 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, sa mples collected at Pleasant Prairie 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. Wrap each glass sample bottle with two layers of “bubble wrap” (or place bottle in two “bubble bags”). The bubble wrap mu st fit snugly and completely cover the sample bottle. Enclose each “bubble-wrappe d” container and plastic container in an individual sealable plastic freezer bag.

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

6. Place sample bottles in garbage bags in the cooler with proper end up, close the interior garbage bag by tying or with a twist-tie. If the samples do not require

≤ 6°C preservation, close the outer ba g by tying or using a twist-tie.

7. For samples requiring ≤ 6°C preservation, add ice to c ooler to keep samples cold during shipment. Arrange blue ice or sealed plastic freezer bags filled with wet ice on top of the sample bottles (if samples require ≤ 6°C preservation). If using wet ice, place the ice inside two one-gallon s ealable freezer bags. Put at least 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 ambient temperatures are very high. Place the ice inside the second garbage bag and close the second garbage bag by tying or with a twist-tie.

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 Pleasant Prairi e. This section provides general 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

Pleasant Prairie has first aid kits availabl e throughout the plant. In addition, ERG will also bring a first aid kit. In case of an em ergency, EPA/ERG will immediately call the control room for safety response.

6.1.2 Site Evacuation/Emergency Response Plan

The sampling team will be informed of th e Pleasant Prairie 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 Aurora Medical Center, located in Kenosha, WI, and is approximately 2.4 miles from Pleasant Prairi e Power Station. The hospital address is:

Aurora Medical Center: Hospital

10400 75 th St. Kenosha, WI 53142

[QUESTION FOR PLEASANT PRAIRIE: Is this the closest hospital listing for the area? Yes]

When on-site call the plant control room at 262-947-5350 or -5351. When off-site, the local emergency phone number in Kenosha, WI 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 Pleasant Prairie personnel to ensure that all potential hazards ha ve been identified.

The crew chiefs have the authority to en force ERG’s health and safety requirements contained in this plan, and any facility-specifi c requirements. Changes to this plan or the sampling plan can be made if the crew chief, 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 half-hour safety cour se given by Pleasant Prairie personnel prior to conducti ng sampling activities at Pleasant Prairie. This safety course will review plant-specific health and safety procedures, including:

 Locations of on-site first aid/descript ions of 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 PLEASANT PRAIRI E: Please confirm this information is correct. Yes, confirmed]

6.4 Safety Procedures

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

6.4.1 PPE

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

 Steel-toed safety shoes;

 Long sleeves (when sampling) and pants;

 Hard hat, where required by Pleasant Prairie;

 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, and when required by Pleasant Prairie.

For all phases of sample collection, disposab le PPE will be used, so decontamination of the PPE may not be necessary. If gloves become to rn 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 chemical and physical hazards. A Pleasant Prairie 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 Pleasant Prairie 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 and SP-2 due to the location 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 collecting 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 Pleasant Prairie 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.

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:

— Pale, cool, moist, clammy skin

— Heavy sweating6-6 — 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 Material Safety Data Sh eets (MSDS) for the chemical involved. If an

incident occurs and MSDSs are not availabl e for a particular hazardous chemical (e.g., wastewater), the following general firs t 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 Pleasant Prairie are cuts and bruises; 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 (longsleeved cotton coveralls or uncoated Tyvek®, safety glasses with side sh ields or splash goggles,6-8 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 the FGD Wastewater Treatment System Steel-toed boots, hard hats, gloves, safety glasses, and face shield/goggles while connecting and disconnecting tubing from the sample tap. Splash hazard: Potential for splashing from the sample tap. Sample tap will be above waist

level.

SP-2 Effluent from the FGD Wastewater Treatment System Steel-toed boots, hard hats, gloves, safety glasses, and face shield/goggles while connecting and disconnecting tubing from the sample tap. Splash hazard: Potential for splashing from the sample tap. Sample tap will be above 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. Gene ric 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/st eam/finalreport.pdf. DCN

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