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 7-29
i

TABLE OF CONTENTS 

Page 

1. INTRODUCTION ................................................................................................................. 1-1 

1.1 Background .......................................................................................................... 1-1 

1.2 Objectives and Scope ........................................................................................... 1-1 

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

2. FACILITY OVERVIEW ........................................................................................................ 2-1 

2.1 FGD Scrubber Systems ........................................................................................ 2-2 

2.2 FGD Wastewater Treatment System ................................................................... 2-3 

3. SAMPLING PROCEDURES ................................................................................................... 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, Shipping, 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. SAMPLING ACTIVITIES ...................................................................................................... 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. SAMPLE SHIPMENT ........................................................................................................... 5-1 

5.1 Sample Set Preparation ........................................................................................ 5-1 

5.2 Sample Packing .................................................................................................... 5-1 

6. SITE-SPECIFIC HEALTH AND SAFETY PROCEDURES .......................................................... 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 ..................................................................... 6-2 
TABLE 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 Monitoring Requirements ................................................ 6-8 

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

7. REFERENCES ..................................................................................................................... 7-1 
iii

LIST OF TABLES 

Page 

3-1 Sample Collection at Pleasant 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 .............................................................................................. 3-27 

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 ................................................................................................. 3-31 
1-1

1. INTRODUCTION

 The Engineering and Analysis Division (EAD) of the U.S. Environmental Protection 

Agency (EPA) is currently conducting a sampling 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 technologies and best management practices used to 

reduce pollutant discharges. This sampling plan, developed for the We Energies’ Pleasant Prairie 

Power Station (Pleasant Prairie), located in Pleasant 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 ERG field sampling crew, a review mechanism for EPA personnel, and 

a source of procedural information for plant personnel. 

1.1 Background

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

identified metals and certain other constituents present 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 waste streams contributing these toxic loadings are 

associated with wet flue gas desulfurization (FGD) systems present at coal-fired power plants. 

 This sampling plan will focus on characterizing wastewaters and treatment system 

discharges at Pleasant Prairie. For a general description of the steam electric process and the 

wastewaters generated during the operation of a coal-fired steam electric power plant, see 

Chapters 3 and 4 of the Steam Electric Power Generating Point Source Category: Final 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 electric power plants. This sampling 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 precipitation FGD wastewater treatment system. A 

chemical precipitation system utilizes physical and chemical treatment to remove heavy metals 

using hydroxide precipitation, or a combination 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., pollutants present, pollutant concentrations, flow 

rate/volume) of untreated FGD scrubber purge wastewater? 

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

wastewater? 
1-2

 What are the pollutant loadings associated with discharges of FGD wastewater 

following treatment? 

 EPA conducted a one-day presampling site visit at Pleasant Prairie 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 and 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 generated by the wet FGD scrubbers and the treatment 

performance of the systems used to treat the FGD scrubber purge wastewater. EPA will also 

collect field quality control (QC) samples consisting of bottle blanks, field blanks, equipment 

blanks, duplicate samples, and laboratory QC samples used for matrix spike/matrix spike 

duplicate analyses. 

 EPA’s sampling program will provide data to perform an engineering assessment of the 

design, operation, and performance of treatment systems at steam electric power plants. In 

addition to sampling the wastewater, EPA will collect information regarding system design and 

day-to-day operation. 

1.3 Plant Selection

 EPA expects to select up to seven coal-fired steam electric plants for FGD wastewater 

sampling, basing the plant selection on the process 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 power 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 commercial-grade gypsum by-product. 
2-1

2. FACILITY OVERVIEW

 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 million tons of PRB coal each year. The plant 

also burns bottom and fly ash from older power plants to reclaim some of the carbon in the ash. 

The old ash is burned at approximately one to two percent weight of the total fuel burned. 

 Approximately three years ago, Pleasant Prairie retrofitted both units with FGD scrubber 

systems to control the sulfur dioxide (SO2) 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 SO2 from the flue gas. In addition 

to the FGD scrubber systems, Pleasant Prairie installed an FGD wastewater treatment system to 

control the discharges of the wastewater generated during the operation of the FGD scrubbers. 

Sections 2.1 and 2.2 further discuss the FGD scrubber systems and the FGD wastewater 

treatment system, respectively. 

 Pleasant Prairie retrofitted 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 

(NOX) emissions, year round. 

 The electrostatic precipitators (ESPs) at Pleasant 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 wastewater discharge associated with the ESPs. 

 Pleasant Prairie recently installed a calcium bromide injection system in November 2009 

and began continuous calcium bromide injection in January 2010. [QUESTION FOR 

PLEASANT PRAIRIE: When was the bromide injection system added?] The system injects a 

solution of calcium bromide on to the coal prior to it being pulverized. Adding the calcium 

bromide to coal enhances the oxidation of the mercury 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 FGD scrubber systems that treat the flue gas 

from Units 1 and 2. The plant uses limestone slurry as the sorbent for SO2 absorption. Limestone 

and service water are fed to on-site ball mills, which 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 system. The underflow from the hydrocyclones is 

returned to the ball mill for additional processing. The overflow from the hydrocyclones, which 

is approximately 40 to 50 percent solids (by weight), is transferred to a limestone slurry storage 

tank and used as fresh limestone slurry in the absorber. 

 The fresh limestone slurry is fed to the reaction tank of the FGD scrubber system and the 

recycle pumps pump the slurry to the various levels of the FGD scrubber (typically two of the 

three spray levels are operating at one time). The 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 SO2, which reacts with the limestone particles and produces calcium sulfite. The 

spray droplets flow downward until they reach the dual flow tray, which forms a layer of slurry 

that the flue gas must pass through 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 the calcium sulfite to calcium sulfate (i.e., 

gypsum). 

The SO2 removal in the FGD systems is optimized at a pH of 5.9 and the limestone slurry 

feed rate is adjusted to maintain this pH. In addition, the plant operates the FGD systems to 

maintain a solids concentration in the scrubber of 15 to 18 percent solids. When the solids 

concentration exceeds 18 percent, the plant blows 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 staggers 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 design chlorides concentration is 15,000 ppm, 

but the plant tries to keep the chlorides 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 centrifugal force. The solid gypsum is forced 

outward to the walls of the hydrocyclones and falls downward, while the water exits the top of 

the hydrocyclones. The gypsum from the primary hydrocyclones, which is approximately 50 

percent solids, is transferred to the vacuum belt filters for final dewatering. The overflow from 

both the Unit 1 and Unit 2 primary hydrocyclones are commingled and transferred to a common 

secondary hydrocyclone. [QUESTION FOR PLEASANT PRAIRIE: Is there a collection tank 

between the primary hydrocyclones and the secondary hydrocyclone where the streams are 

commingled?] The overflow from the second hydrocyclone is transferred to the FGD wastewater 

treatment system. 
2-3

 Pleasant Prairie washes the gypsum sent to the vacuum filter belts with service water, as 

the gypsum slurry is poured onto the belts. The vacuum 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 agricultural purposes. Pleasant Prairie generates 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 transferred 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 scrubber system, which consists of secondary 

hydrocyclone overflow, at a flow rate of approximately 40 gallons per minute (gpm). The 

intermittent transfers are expected to occur for 6 to 12 hours per day. [QUESTION FOR 

PLEASANT PRAIRIE: What is the typical duration for a single transfer from the secondary 

hydrocyclone to the FGD wastewater treatment system? For example, is there one transfer a day, 

for 6 to 12 hours? Or are there multiple transfer each day for shorter durations?] The FGD 

wastewater treatment system is a chemical precipitation system and contains the following 

treatment operations: 

 Equalization tank; 

 pH adjustment (lime addition); 

 Primary clarification and polymer addition; 

 Organosulfide and hydrochloric 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 section, presents the process flow diagram of the 

FGD wastewater treatment system, 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 the wastewater treatment system. This wastewater is expected to 

contain approximately 0.5 to 1.0 percent solids and 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 reaction tank also desaturates the gypsum in the 

wastewater, which prevents gypsum scale formation in the downstream wastewater treatment 
2-4

equipment. To desaturate the gypsum, some of the sludge from the downstream primary clarifier 

is recycled back to reaction tank 1 to provide seed crystals 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 percent of the solids settle 

out of the wastewater in the primary clarifier. The overflow from the primary clarifier flows to 

reaction tank 2, where the plant adds organosulfide and hydrochloric acid. When the plant first 

began operating the treatment system, they used TMT 15® as the organosulfide. Since that time, 

the plant has switched to using Nalmet 1689®, which is an organosulfide that has a longer 

polymer chain, and therefore, a higher molecular weight, which helps aid in the settling of 

precipitates. Pleasant Prairie also began adding hydrochloric acid to reaction tank 2, which 

wasn’t in the initial design of the system; because the plant determined that they achieve better 

removals of mercury when the system is operated 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 reaction tank 3 flows to the flash mix tank, where 

polymer is added to the wastewater. From the flash mix tank, the wastewater flows to the 

flocculation tank. Gentle mixing in the flocculation tank allows denser floc to form. 

 The wastewater from the flocculation tank flows to the secondary clarifier. The 

secondary clarifier settles the solids that were formed during 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 clarifier to readjust the pH value, if needed, to meet 

effluent limits. From the secondary clarifier, water flows to the effluent tank and is then 

commingled with other waste streams (e.g., cooling tower blowdown) prior to discharging to 

Lake Michigan. Pleasant Prairie commingles the effluent from the FGD wastewater treatment 

plant with other plant wastewater to meet the final outfall mercury and chloride limits. To meet 

the effluent mercury limit, Pleasant Prairie must dilute the FGD wastewater at a 30:1 ratio. 

 The sludge from the primary and secondary clarifiers is transferred 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 landfill. The filtrate is transferred to the filtrate 

sump, the contents of which are recycled 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 flocculation. [NOTE TO PLEASANT PRAIRIE: Can the weekly cleaning 

and maintenance be rescheduled the Sunday before the sampling episode (e.g., performed on 

Saturday instead) to allow EPA/ERG to test the sampling configurations on Sunday, which is the 

set-up day for the sampling episode? Answer – Yes, see related comment] 

 Pleasant Prairie has made the following modifications 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 because the system 

removes more mercury at a lower pH (described previously); 

 Bypassed a set of sand filters that were located after the secondary clarifiers 

because of scaling issues (the sand filters are not shown in Figure 2-1); and 

 Added the capability to use cartridge filtration to remove colloidal particles from 

the wastewater after the secondary clarifier, which may build up in the system if 

the plant recirculates the wastewater without discharging for several weeks; 

however the cartridge filtration is not used regularly (the cartridge filters are not 

shown in Figure 2-1). 
2-6 

Secondary 

Hydrocyclone 

Overflow

Lime

Organosulfide

Ferric 

Chloride Polymer Hydrochloric 

Acid

To Sludge Disposal

Equalization 

Tank Reaction Tank 1

Primary Clarifier

Reaction 

Tank 2

Reaction 

Tank 3

Flash 

Mix Tank

Flocculation 

Tank

Secondary 

Clarifier

Treated 

Wastewater 

Storage 

Tanks

Sludge Holding 

Tank

Filter Press

Filtrate 

Sump

SP-1

S

Indicates a Sampling Point

Treated 

Effluent 

Recycle

Polymer Hydrochloric 

Acid

Figure 2.1. FGD Wastewater Treatment System, Pleasant Prairie Power Plant
3-1 

3. SAMPLING PROCEDURES

 This section discusses the planned sampling procedures to be followed during the 

sampling episode at Pleasant Prairie. This section also provides the necessary information to plan 

for the logistics of this sampling episode. All tables and figures in this section are presented at 

the end of the section. 

3.1 Sampling Point Selection

 EPA’s sampling point selection includes treatment system influent and effluent sampling 

locations for the FGD wastewater treatment 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 Wastewater Treatment System; 

 SP-2 Effluent from the FGD Wastewater Treatment System; 

 SP-3 Duplicate of Effluent from the FGD Wastewater Treatment System 

(SP-2); 

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

and 

 SP-5 Effluent from the FGD Wastewater Treatment System (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 (BOD5), 

— 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 contributions from coal, scrubber 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 used, 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 wastewater treatment system (SP-1) and the 

effluent from the FGD wastewater 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 series of “fractions,” or bottles designated for particular 

analyses requiring the same preservation. The comprehensive sample set consists of sample 

fractions for all pollutant classes listed in Section 3.2. Note that some sample fractions will be 

collected in the same sample bottle, such as Group I analytes (TSS, TDS, sulfate, and chloride) 

and Group II analytes (ammonia as nitrogen, COD, nitrate/nitrite 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 eyewear, 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 are not required for respiratory protection. 

 Sample containers and bottles will be purchased precleaned and certified and will not 

require rinsing with sample. ERG will follow protocols described in EPA Method 1669 to collect 

metal sample fractions. All sampling equipment (e.g., tubing) and sample bottles will be cleaned 

according to the procedures described in EPA Method 1669. Samplers will use “clean hands / 

dirty hands” sample collection techniques when collecting metal sample fractions, as described 

in EPA Method 1669. 

 For this sampling episode, ERG will collect individual 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 collected as four grab samples each day for the 

effluent from the FGD wastewater treatment system 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 bagged ice throughout sample storage, shipment, 

and receipt at the analytical laboratories. 

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

 The influent to the FGD wastewater treatment system (SP-1) has a sample tap located on 

the secondary hydrocyclone. ERG will 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 sampling 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 hydrocyclone is not continuous, ERG will need to 

coordinate closely with Pleasant 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 follow protocols described in EPA Method 1669 to 

collect metal sample fractions from SP-1. 

 ERG plans to collect split samples with Pleasant 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 Pleasant Prairie (or its representative) to 

collect samples simultaneously. The sample tap located at the 

secondahttp://webapps4/msdgen/pds/archives/pds/default/00400307.pdfry hydrocyclone 

currently has a large diameter tubing 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 the 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 portion of the sample through a 0.45-μm 

filter and then through a “Y” splitter 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 purge 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 portions of the sample and analyze both for the 

analyte of interest (i.e., biphasic samples). In this instance, Group I (chloride and sulfate only), 

Group II (ammonia as nitrogen, nitrate/nitrite as nitrogen, and total phosphorus only), and total 

metals (including mercury, but not hexavalent chromium because it is filtered in the field during 

sample collection) samples will be analyzed as biphasic samples. Group I (TSS and TDS only), 

Group II (COD only), BOD5, hexavalent chromium, and dissolved 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 wastewater treatment system (SP-1) will be 

collected from a sample tap. The sampling equipment will consist of the following: 

 Colorless, electronic-grade, non-nitrile gloves; 

 Silicone tubing with “Y” splitter; 

 10-L containers; 

 Teflon® tubing; 

 Silicone tubing; 

 0.45-μm 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 protocols 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 other as “dirty hands”) will follow the protocols 

described in the steps below to set up the sampling point, collect the field blank samples, and 

collect wastewater samples. This section describes the set-up of the sample point and collection 

of the EPA samples1. 

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 coolers or boxes contain the double-bagged 

sample bottles, precleaned tubing, blank water, and cleanbox. Depending on the 

condition of the sample tap, samplers may need to wipe the tap with a clean paper 

towel to remove any buildup on the tap that could potentially fall in the sample 

bottles during sample collection. 

2. Both samplers put on Tyvek® suits, masks, 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 clips located inside the box. 

 

1

 For the sample collection, the samples will be split with the 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 containing a length of precleaned silicone 

tubing. “Clean hands” opens the inner bag inside of the cleanbox, removes the 

tubing, and places clean plastic bags over the ends of the silicone tubing. 

5. “Dirty hands” opens the outer bag of the funnel and “clean hands” opens the inner 

bag inside of the cleanbox 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. “Clean 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 mercury 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 covering the end of the tubing. 

“Dirty hands” pours field blank water through the funnel and tubing. After the 

tubing has been purged with sufficient volume, “clean hands” places the silicone 

tubing back in the cleanbox. Working inside the cleanbox, “clean hands” 

unscrews the lid of the field blank sample 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 tubing, and “clean hands” fills the total 

mercury field blank sample bottle. “Clean hands” places the end of the silicone 

tubing into the plastic bag, replaces the lid on the sample bottle, and closes the 

inner bag. “Clean hands” removes the bottle from the cleanbox and places it in the 

outer bag. “Dirty hands” closes the outer bag. The samplers repeat this procedure 

for the total metals field blank samples2

. 

7. “Dirty hands” opens the outer bag for a precleaned 10-L container. “Clean hands” 

opens the inner bag and loosens the lid. “Clean hands” holds the end of the 

silicone tubing at the mouth of the 10-L container and removes the lid. “Dirty 

hands” pours field blank water through the funnel and tubing, and “clean hands” 

fills the 10-L container with enough field 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” screws 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” work to attach the end 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 blank 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 plastic bag covering the end of the tubing. “Dirty hands” 

opens the valve to the sample tap to purge 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 container. “Clean hands” 

opens the inner bag and loosens the lid. “Clean hands” holds the end of the 

silicone tubing at the mouth of the 10-L container and removes the lid. “Dirty 

hands” opens the sample valve to allow sample to flow into the 10-L container. 

“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 solids to settle for one hour while collecting 

the remaining samples. “Clean hands” places the lid back on the 10-L container, 

places the plastic bag over the end of the 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 outer bag of the 10-Liter container. Both 

samplers change their gloves. 

11. “Dirty hands” opens the outer bag for the total mercury sample bottle. “Clean 

hands” removes the inner bag and bottle and places it in the cleanbox. “Clean 

hands” opens the inner bag and bottle lid. “Clean hands” removes the plastic bag 

from the tubing and fills the sample bottle. “Clean hands” places the tubing back 

in the plastic bag, replaces the lid on the sample bottle and closes the inner bag. 

“Clean hands” removes the sample bottle from the cleanbox and places it in the 

outer bag. “Dirty hands” closes the outer bag. The samplers 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 measurements. The samplers will give the jar 

to another sampling team member to measure the temperature and pH. 

14. Both samplers collect the BOD5, 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 the samples immediately after sample 

collection, according to the preservation 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 bottles within easy access on the covered 

surface. 
3-7 

17. “Dirty hands” opens the outer bag of the clean box and “Clean hands” opens the 

inner bag. “Clean hands” places the cleanbox 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 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 attached to a 5-foot length of precleaned 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 clean plastic bag over the ends of the 

Teflon® and silicone tubing. 

19. “Dirty hands” threads the silicone tubing 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. “Clean 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 was used to collect 

the field blank water for the dissolved metals 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 Teflon® into the 10-L container. “Dirty 

hands” opens the 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 the plastic bag still covering the end 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 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. The samplers repeat the 

procedure for the dissolved metals and hexavalent chromium field blank samples. 

If a new filter is needed, “clean hands” removes the used filter and samplers 

follow step 21 to replace the filter3

. 

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, and places the end of the Teflon® tubing 

into the container. “Clean hands” holds the end of the silicone tubing outside the 

cleanbox, with the plastic bag still covering 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 closes the inner bag. “Clean hands” places 

the inner bag and bottle in the outer bag and “dirty hands” closes the outer bag. 

The samplers repeat this procedure for the dissolved metals and hexavalent 

chromium samples. 

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

 EPA plans to collect samples at the influent 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 treatment system (SP-2) will be collected 

downstream of the two effluent tanks. Pleasant 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. Pleasant 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 FGD wastewater treatment system composite 

samples using two automatic compositors that will be programmed to collect individual sample 

volumes into two large containers (e.g., two 20-liter HPDE containers). To collect sufficient 

sample volume, ERG will calculate the total volume required for ERG sample collection as well 

as plant split sample collection and also add additional volume for purging tubing and 

contingencies. The volume will then be programmed to be collected in one-hour intervals during 

the 24-hour composite period. Following the composite period, ERG will pump off the specific 

sample volumes into the individual sample containers. 

 ERG will use one automatic compositor to collect sample volume for the metals analyses 

(excluding mercury) and another automatic compositor to collect sample volume for all classical 

analytes (i.e., BOD5, Group I, and Group II). In addition to collecting automatic composite 

samples for the analytes listed above, ERG will collect 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 mercury 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 collection is to have a third tap available at the 

sampling point (i.e., one tap for the metals compositor, one tap for the classicals compositor, and 

one tap for mercury grab samples). If Pleasant Prairie 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 tubing 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 Pleasant Prairie (or its representative); 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 fitting. Also, would the plant be able to set up 

the flanged fitting to have a three-way splitter attached with each splitter having a 3/8 inch hose 

barb and having its own valve to control 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 attached 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 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). 

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

wastewater treatment effluent with 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 plant 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, Wednesday, 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 the discussion, Pleasant Prairie personnel 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 treated effluent collected could be 

sent back to the scrubber as make-up water and, therefore, would not impact the FGD 

wastewater treatment system performance. ERG 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 described 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 effluent 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-grade, 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-μm filter; 

 Cleanbox; 

 Tyvek® suits (for metals samples); 

 Masks (for mercury samples); and 

 Sample containers. 

 All metals sampling equipment will be specially cleaned according to the procedures 

described in EPA Method 1669. 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 described 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 steps 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 samples4

. 

1. Samplers remove the bags containing the gloves and HDPE plastic wrap from the 

coolers or storage containers in which they are packed. Samplers identify which 

coolers or boxes contain the double-bagged composite containers, precleaned 

tubing, blank water, and cleanbox. 

2. Both samplers put on Tyvek® suits, masks, 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 the 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. 
3-11 

collection. “Clean hands” opens the cleanbox and secures it open 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 inner 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 will 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 and 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 the flowing stream between each individual 

sample aliquot. 

5. “Dirty hands” threads one portion of the silicone tubing through the peristaltic 

pump portion of the automatic compositor. 

6. Both samplers change gloves. 

7. “Dirty hands” and “clean hands” then collect the total mercury field blank sample. 

The total mercury field blank sample collection will depend on the sampling 

configuration for mercury, so both configurations are described in this plan. 

Collection from third sample tap: “Dirty hands” shrouds the sample tap with a 

clear plastic bag that covers the end of the sample tap and provides enough room 

for samplers to work in with their hands. “Dirty hands” then opens the outer bag 

of the mercury field blank water and the total mercury field blank sample bottle. 

“Clean hands” opens the inner bag for the 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 water into the field blank sample bottle, 

closes the lids, and closes the inner bags. “Clean hands” places the total mercury 

field blank sample bottle in the outer bag and “dirty hands” closes the outer bag. 

Collection from compositor tubing 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 the 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, unscrews the lid, places it in the inner bag and 

places the end of the silicone tubing into blank water. “Dirty hands” operates the 
3-12 

pump to pump blank water through the tubing. 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 field blank sample. “Clean hands” closes the 

lid on the sample bottle, closes the inner 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 the 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 blank water. “Clean hands” also opens the 

inner bag for the field blank composite container and loosens the lid. “Clean 

hands” holds the silicone tubing with the plastic bag covering the end out of the 

cleanbox and over a bucket and “dirty hands” operates the pump to pump blank 

water through the tubing. After the tubing 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 the tubing configuration from filling with 

blank water during the pumping process. “Clean hands” places the plastic bag 

over the end of the silicone tubing, replaces the lid on the field blank composite 

container, places the silicone tubing back in the cleanbox, and closes the inner bag 

of the field blank composite container. “Dirty hands” closes the outer bag of the 

field blank composite container5

. 

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 place during the 24-hour sample collection 

period. 

10. “Dirty hands” changes gloves. 

11. “Clean hands” holds the end of the silicone tubing outside the cleanbox over a 

bucket, with the plastic bag still covering the end of the tubing. “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 the tubing for a minimum of 2 minutes. 

12. Samplers fill a 1-L jar for the field measurements. 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 from the FGD wastewater treatment system during only one 

day of the sampling episode. 
3-13 

13. “Dirty hands” programs the automatic compositor 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” calibrates 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 connection 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 the automatic compositor for the classical 

analytes (skipping steps 7 and 8). Samplers will use another composite 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 collection 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 the outer bag of the total mercury sample 

bottle. “Clean hands” takes the bottles and 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. “Clean 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 closes the inner bag. 

“Dirty hands” closes the sample tap. “Clean 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 tubing 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 the 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. “Dirty hands” closes the outer bag. The 

samplers repeat this procedure to collect the dissolved mercury sample. 

The samplers will fill the bottle directly from the sample tap (or tubing); 

therefore, the total and dissolved mercury samples will not be collected as split 

samples with Pleasant Prairie (or its representative), but will 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 mercury 
3-14 

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 collect its dissolved mercury duplicate sample 

immediately after ERG collects its dissolved mercury sample. 

17. The samplers will collect total and dissolved 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 container; 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 measurement samples every six hours during the 

compositing time period. The field measurement samples will be collected from 

the tubing that is discharging into the 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-off 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 within the tubing, which could lead to greater 

concentrations in the dissolved metals fractions. 

Sample Pump-Off Procedures 

22. Samplers remove the bags containing the gloves and HDPE plastic wrap from the 

coolers or storage containers in which they are packed. Samplers identify which 
3-15 

coolers or boxes contain the double-bagged 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 places 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 cleanbox and secures it open 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 tubing, a “Y” splitter, 

and two additional pieces of silicone tubing. “Clean hands” moves the tubing into 

the cleanbox and opens the inner bag and removes the tubing. “Clean hands” 

places a clean plastic bag over the end of the Teflon® and silicone tubing. 

26. “Dirty hands” threads the silicone tubing 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 container. “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 covering 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 inner bag. “Clean hands” places the inner bag 

and bottle in the outer bag and “dirty hands” closes the outer bag. 

29. “Dirty hands” opens the outer bag of a capsule filter. “Clean hands” opens the 

inner bag and removes the capsule filter. “Clean hands” attaches the capsule filter 

to the silicone tubing just before the “Y” splitter. 

30. “Dirty hands” opens the outer bag of the 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 the plastic bag still covering the end of 

the tubing and “dirty hands” operates the pump to pump about 750 mL of blank 
3-16 

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 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 

samples6

. “Clean hands” closes the inner bag of the field blank composite 

container and “dirty hands” closes the outer bag. Note: 750 mL of blank water 

does not need to be purged for each sample, just at the beginning of each new 

filter. If a new filter is needed, “clean hands” removes the used filter and samplers 

follow step 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 inner bag. “Clean hands” transfers the 

Teflon® tubing from the field blank composite container to the metals sample 

composite container. “Clean hands” holds the end of the silicone tubing outside 

the cleanbox over a bucket, with the plastic bag still covering the end of the 

tubing and “dirty hands” operates the pump to 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 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 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. 

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 tubing outside the cleanbox over a bucket, with 

the plastic bag covering the end of the tubing. “Dirty hands” pumps about one 

liter of sample through the tubing and then stops the pump. “Clean hands” places 

the end of the silicone tubing back in the cleanbox. 

 

6

 ERG will collect field blank samples at the effluent from the FGD wastewater treatment system during only one 

day of the sampling episode. ERG will collect the dissolved mercury sample using the same technique as the total 

mercury sample, but the dissolved sample will be filtered at the laboratory. A dissolved mercury field blank will be 

performed by the laboratory to assess any mercury contamination from the filtering performed at the laboratory. 

Therefore, ERG does not need to collect a dissolved mercury field blank sample in the field. 
3-17 

35. “Dirty hands” opens the outer bag of the total 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 total metals 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. During one 

day of the sampling episode, the samplers will collect additional sample volume 

for the duplicate samples and during another 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 composite container for the classical analytes. 

38. “Clean hands” holds the silicone tubing outside the cleanbox over a bucket, with 

the plastic bag covering the end of the tubing. “Dirty hands” pumps about one 

liter of sample through the tubing and then stops the pump. 

39. Both samplers collect the BOD5, 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 containers, the classical and hexavalent chromium 

samples will be put in an ice-water bath; however, 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 chromium samples will be preserved on site, according 

to the method-specified protocols. Samplers will filter samples within 15 minutes after the 

compositing period ends (or as soon thereafter as possible). The dissolved samples of the FGD 
3-18 

influent will be filtered approximately one hour after they are collected to allow for solids 

settling because the samples’ high solids 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 for sulfide using lead acetate test strips. If sulfide is present, 

the samplers will use the procedure identified in Section 3.5 to determine the minimal amount of 

dilution necessary to reduce sulfide to a nondetectable concentration. After 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 samplers 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 sample is not over-diluted. The samplers will then 

test the diluted sample for the presence of oxidants (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 laboratory on the traffic reports. 

 Table 3-3 lists the parameters, bottle types, sample volume, and on-site preservation 

requirements for each type of analysis. The type and amount of preservation used will be 

recorded on sample preservation log sheets (Figure 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 preservation and noting it on the traffic report. 

The wastewater samples, except metals samples that 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 via Federal Express to laboratories. 

3.5 Field Measurements and Engineering Data Collection

 Temperature, pH, sulfide, and oxidants will 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 wastewater 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 immediately after collecting the aliquot. For sulfide 

and oxidants, the samplers will fill the cyanide sample bottle directly and test for sulfide and 

oxidants using test strips immediately after sample collection. 

 During a presampling set-up day (i.e., the day before the sampling episode begins), the 

samplers will test the wastewater at each sampling point for sulfide using lead acetate test strips 

to determine if preservation is needed for cyanide. If sulfide is present, the samplers will 

determine the minimal amount of dilution necessary to reduce the sulfide concentration to below 

detection by the lead acetate test strips. To identify the minimal amount of dilution, the samplers 

will dilute the sample by a factor of two (1:1) and retest for sulfide. If sulfide is still detected, the 

samplers will dilute the original sample by a factor of 3 (2:1). They will continue this process 

until sulfide is not detected in the sample. After this minimal dilution factor is determined for the 

sampling point, the samplers will use this minimal dilution factor to dilute all samples collected 
3-19 

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., chlorine) during the presampling set-up day using 

potassium-iodide starch paper. 

 Samplers will follow applicable test kit calibration procedures specified by the 

manufacturer. Table 3-4 summarizes the field measurements, the method to be used for the 

measurement, and the detection range of each field 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 information with regard to design and operation of 

the plant. For example, they will collect information such as coal usage, plant capacity, 

wastewater flow rates, sludge generation rates (if applicable), and retention times in wastewater 

treatment process stages. Engineering data collection 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 the 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 printed prior to arrival in the field, 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 incorrect, 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 traffic report). Once applied to the sample container, labels are 

covered with clear tape to prevent tampering, abrasion, smearing, or loss during transit. For 

metal samples, the samplers will not label the sample bottles, but will label the outer plastic bag 

of the sample bottle. 

3.7 Traffic Reports

 To maintain a record of sample collection, transfer between personnel, shipment, and 

receipt by the laboratory, samplers will complete a traffic report for each sample set at each 
3-20 

sampling location. These forms are used to document 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, the traffic report provides information to the 

analytical laboratory on the sample number, type of water sample (in-line process, untreated 

wastewater, treated effluent), sample description, whether the sample 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 provide 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 sampling 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 through 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 for 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 wastewater treatment system (SP-2). The duplicate samples will be 

collected as separate aliquots in the field. Results of the duplicate analyses will be used to 

evaluate precision, including variability in sample collection, handling, preparation, and analysis. 

 Bottle blanks will be used to evaluate possible contamination from the sample bottles. 

The bottle blank will consist of an analyte-free matrix (Ultra Pure Blank Water DI+TM) poured 

into the appropriate sample bottles (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 equipment to the sampling episode. 
3-21 

 Field blanks will be used to evaluate possible contamination caused by sampling 

equipment or by sampling equipment decontamination procedures. Field blanks will be prepared 

in the field prior to sample collection and analyzed 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 episode7

. 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 field blanks (including mercury) 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 bottles. The total metals field blanks (excluding 

mercury) at the effluent from the FGD wastewater treatment system sampling point will be 

prepared by pumping ASTM Type 1 water through the composite tubing set into 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 

and into the sample bottles. The total mercury field blank at the effluent from the FGD 

wastewater treatment system sampling point will be prepared by either pouring ASTM Type 1 

water directly into the sample bottles or pumping 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 silicone 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 container through the Teflon® and silicone tubing, through a 0.45-μm filter, 

and into the sample bottles. The dissolved metals 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 into 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-μm filter, and into the sample 

bottles. The field blanks will determine if there is any contamination from the sampling 

equipment, atmospheric contamination, or other contamination from the surroundings. 

 EPA Method 1669 requires that equipment blanks also be prepared and analyzed for 

metals to evaluate possible contamination of metals caused by the sampling equipment. The 

supplier of the tubing and composite containers will prepare and analyze these equipment blanks 

and provide a report certifying the equipment as clean. 

 As part of standard laboratory quality control, matrix effects on analytical performance 

are assessed through the analysis of matrix spikes and laboratory duplicates. Consequently, 

additional sample volume must be collected for these QC analyses. The sampling team will 

collect, label, and ship the necessary laboratory 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 from the FGD wastewater treatment 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 day of the sampling episode. 

3.9 Sample Splitting

 Pleasant Prairie or its representative has elected to collect split samples (or duplicate 

samples, as appropriate) at each of the sampling points. 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 dissolved) 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 problems 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 samples with Pleasant Prairie or its representative. For the mercury 

(total and dissolved) and total cyanide grab samples at SP-2, ERG will not be able to collect split 

samples with Pleasant Prairie due to sample configuration issues discussed previously in Section 

3.3.2; therefore, duplicate samples will be collected. 
3-23 

Table 3-1. Sample Collection at Pleasant Prairie Power Plant 

Sampling 

Point 

Number Sampling 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

SP-1 Influent to the FGD Wastewater 

Treatment System 

4 4 4 4 4 4 4 

SP-2 Effluent from the FGD Wastewater 

Treatment System 

4+1QC 4+1QC 41+1QC 4+1QC 4+1QC 4+1QC 4+1QC 

SP-3 Duplicate of the Effluent from FGD 

Wastewater Treatment System 

1 1 1 1 1 1 1 

SP-4 Influent to the FGD Wastewater 

Treatment System Field Blank 

1 1 1 1 

SP-5 Effluent from the FGD Wastewater 

Treatment System Field Blank 

1 1 1 1 

Total Number of Samples 11+1QC 11+1QC 11+1QC 9+1QC 11+1QC 9+1QC 9+1QC 

a – 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 phosp
3-24

Table 3-2. Analytical Methods 

Parameter Method Number 

Classicals

Biochemical oxygen demand (BOD5) SM 5210 B (or other 40 CFR Part 136-approved method 

Chemical oxygen demand (COD) EPA 410.3 (or other 40 CFR Part 136-approved method) 

Total suspended solids (TSS) SM 2540 D (or other 40 CFR Part 136-approved method) 

Total dissolved solids (TDS) SM 2540 C (or other 40 CFR Part 136-approved method) 

Sulfate ASTM D516-90 (or other 40 CFR Part 136-approved 

method) 

Chloride SM 4500–Cl–C (or other 40 CFR Part 136-approved 

method) 

Ammonia as nitrogen SM 4500—NH3 B, F (or other 40 CFR Part 136-approved 

method) 

Nitrate/nitrate as nitrogen SM 4500—NO3 -H (or other 40 CFR Part 136-approved 

method) 

Total Kjeldahl nitrogen (TKN) SM 4500—NH3 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 Containers and Planned Preservation 

Parameter 

Sample 

Container and 

Volume 

QC Sample 

Container and 

Volume On-Site Preservation 

Classicals 

BOD5 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 

H2SO4 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, NaAsO2 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, TDS, sulfate, and chloride. 

b – Group II includes ammonia as nitrogen, COD, nitrate/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 (S2-)

Oxidants (i.e., chlorine) Potassium-iodide starch paper >1 mg/L free chlorine (Cl2) 
3-26

Sampling Episode ____________ 

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

H2SO4 _____________________ NH4SO4 ________________________ 

NaOH _____________________ 

Sample 

Number Analysis Date Time Name Chemical 

Initial 

pH Final pH 

Number of 

Drops 

 

Figure 3-1. Sample Preservation Log Sheet 
3-27

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 pictures if necessary) 

______________________________________________________________________________

______________________________________________________________________________

______________________________________________________________________________

______________________________________________________________________________

______________________________________________________________________________

______________________________________________________________________________ 

Figure 3-2. Field Sampling Log Sheet 
3-28 

Plant Name: _______________________________________________________________________________ Plant Contact: ______________________________________________________________________________ Dates of Sample Collection: ___________________________________________________________________ Data Collected by: __________________________________________________________________________ Instructions: In the tables below, fill out information on the generating units and FGD systems operating at the plant based on all four depisode. Note any changes in operation that occur during the four-day period. Provide actual data if possible. If actual data are not availfor the specific information. Some of the data requested may not be susceptible to estimation. Enter “URE” for “unable to reasonably especify whether data provided are actual or estimated by writing in “ACT” or EST” wherever appropriate. 

Generating Unit Operating Characteristics During Sample Collection 

Unit 

ID Boiler Type 

Capacity 

(MW) 

Electricity 

Production 

(MW) 

(or Percent 

Capacity %)a 

SCR 

(No, On, 

Off) 

Particulate 

Control System 

(HS/CS ESP, or 

BH) 

a The electricity production should be measured on a daily basis from midnight of the 1st day o

midnight of the last day of sample collection. 

FGD System Operating Characteristics During Sample Collection 

Unit 

ID 

Wet FGD 

System 

(Yes/No) 

Type of 

Scrubber 

Forced 

Oxidation 

(Yes/No) Sorbent 

Additives 

(DBA, formic 

acid, etc.) 

FGD Make-up 

Water Source 

SO2

Removal 

Percentage 

Typ

So

Sepa

Note changes in operation over the past month (e.g., turned off SCRs on October 1 or burned 5 percent petroleum coke pr

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 possible. 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 Collection Sheet (Page 2 of 3)
3-30 

Plant Name: ________________________________________________________________________________ Plant Contact: ______________________________________________________________________________ Dates of Sample Collection: ___________________________________________________________________ Data Collected by: ___________________________________________________________________________ Instructions: In the table below, provide information on the FGD wastewater treatment system for each day of the sampling episode and wastewater treatment system tanks and reactors. If possible, provide the name of the acid and polymer used during the sampling episod

possible. If actual data are not available, provide estimates for the specific information. Some of the data requested may not be suscepti“URE” for “unable to reasonably estimate.” Otherwise, specify whether data provided are actual or estimated by writing in “ACT” or Eappropriate. 

FGD Wastewater Treatment System Operation Information 

Day of 

Sampling 

Scrubber Purge 

Chemical Usage 

(specify units) 

Flow Rate 

(gpm) Duration Lime 

Ferric 

Chloride 

Organo-sulfide 

_________ 

(specify product) 

Polymer: 

_________ 

(specify product) 

_

(spe

1 2 3 4 

Volume 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 

NUMBER

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

ADDITIONAL 

SAMPLE 

DESCRIPTION

PH LEVELPRESERVED (Y/N)G=GRAB / C=COMPOSITESAMPLE COLLECTION TIME / 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 Report 
4-1

4. SAMPLING ACTIVITIES

 This section discusses the sampling team organization, sampling preparation, and 

sampling activities. 

4.1 Sampling Team Organization

 The sampling crew will consist of a crew chief and four crew members from ERG and 

two EPA representatives. The crew chief will be responsible for all health and safety, sample 

collection, preservation, and shipping activities while at 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. After 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 Pleasant Prairie representatives provided ERG and 

EPA the necessary information to prepare for the sampling episode and to create this sampling 

plan. 

 As part of preparing the team for the sampling 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 plan to Pleasant Prairie personnel 

before sampling begins. 

 The ERG crew chief will also coordinate the procurement and shipment of all necessary 

sampling and health and safety equipment. 

4.3 Field Sampling Activities

 Upon arrival at Pleasant Prairie, 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 descriptions of the proposed sampling 

points, if necessary, in consultation with EPA and Pleasant Prairie personnel. If necessary, the 

crew chief will obtain additional equipment. The revised sampling description will include: 

 A sampling point description and collection 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 associated 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 revised sampling activity descriptions along with recommended 
4-2

revisions to the proposed health and safety procedures. Together, the crew chief and HSC will 

review 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, collected, and preserved, according to method 

protocols. Sample fractions requiring ≤6o

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 sleeves inside the coolers. The coolers will then be 

taken to the nearest Federal Express office and shipped to the analytical 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 contacts, analytical laboratory contacts and 

addresses, and sampling team personnel and support functions. 

4.4.1 Pleasant Prairie Power Plant Contacts 

David Lee, Manager – Water Quality 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 95th Street 

Pleasant Prairie, WI 53158 

(262) 947-5344 

[QUESTION FOR PLEASANT PRAIRIE: 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) 566-1003 
4-3

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. – Fri.: 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. – Fri.: 7:00 a.m. to 11:00 p.m. 

Last Express Drop-off: Mon. – Fri.: 8:00 p.m. 
5-1

5. SAMPLE SHIPMENT

 All sample containers will be labeled with ERG's standard address labels. All samples 

will be tracked using Traffic Report forms. Custody will be maintained by the sampling crew 

chief from sample collection until samples are delivered to Federal Express. 

 All samples will be packaged and shipped in accordance with U.S. Department of 

Transportation (DOT) or International Air Transport Association (IATA) regulations. The 

general IATA packaging requirements for air shipment are as follows: 

 “Inner packaging must be so packed, secured or cushioned as to prevent their 

breakage or leakage and so as to control their movement within the outer 

packaging during normal conditions of transport. Cushioning material must not 

react dangerously with the contents of the inner packaging. Any leakage of the 

contents must not substantially impair the protective properties of the cushioning 

material. Unless otherwise provided in this paragraph or in the Packing 

Instructions, liquids in Classes, 3, 4, 5, 6, or 8 of Packing Groups I or II in glass or 

earthenware inner packaging, must be packaged using material capable of 

absorbing the liquid. Absorbent material must not react dangerously with the 

liquid. Absorbent material is not required...” (IATA Dangerous Goods 

Regulations, 5.0.16). 

 “When filling receptacles for liquids, sufficient ullage (outage) must be left to 

ensure that neither leakage nor permanent distortion of the receptacle will occur 

as a result of an expansion of the liquid caused by temperatures likely to prevail 

during transport. Liquids must not completely fill a receptacle at a temperature of 

55°C (130°F).” (IATA Dangerous 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 hazardous shipping procedures will be followed. 

Based on process considerations, samples collected at Pleasant Prairie will not be classified as 

IATA dangerous goods. 

5.1 Sample Set Preparation

 Samples are collected as a series of “fractions,” or bottles designated for particular 

analyses requiring the same preservation. The comprehensive water sample set consists of 

sample fractions for all pollutants listed in Section 3.2, collected as grab samples directly into the 

individual sample containers or composite samples 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 liquid 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 the 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 must fit snugly and completely cover the 

sample bottle. Enclose each “bubble-wrapped” 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 bag by tying or using a twist-tie. 

7. For samples requiring ≤6°C preservation, add ice to cooler 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 sealable 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 space with additional cushioning material. 

Use sufficient packing material so that the 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 the inside of the cooler lid. 

11. Close cooler. 

12. Make several wraps with tape 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. SITE-SPECIFIC HEALTH AND SAFETY PROCEDURES

 This section specifies the health and safety procedures and practices to be used by the 

sampling team during sampling at Pleasant Prairie. 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 available throughout the plant. In addition, ERG will 

also bring a first aid kit. In case of an emergency, 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 the 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 members 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 Prairie Power Station. The hospital address is: 

Aurora Medical Center: Hospital 

10400 75th 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 responsibilities 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 overall responsibility to ensure that these 

health and safety procedures are developed and implemented in accordance with regulations and 

corporate guidelines, that proper health and safety procedures have 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 conducted in a safe manner, 

and that the crew chief is competent in his ability to oversee health and safety during the 

sampling episode. 

6.2.2 Crew Chief 

 The ERG crew chief, TJ Finseth, is responsible for ensuring that ERG sampling team 

members adhere to this plan. The ERG crew chief and ERG night crew chief are responsible for 

overseeing all activities. The crew chiefs must report any accident, near miss, or injury to any 

sampling team member to the ERG Chantilly Office Health and Safety Coordinator (HSC), 

Kevin Sikora, verbally within eight hours, or sooner. 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 program will be modified to avoid similar accidents 

in the future. 

 At the start of the sampling visit, the crew chiefs will inspect all sampling points and 

review sample collection procedures with the Pleasant Prairie personnel to ensure that all 

potential hazards have been identified. 

 The crew chiefs have the authority to enforce ERG’s health and safety requirements 

contained in this plan, and any facility-specific 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 following the requirements of this plan, adhering 

to plant-specific health and safety procedures, and donning required/recommended personal 

protective equipment (PPE). They are also responsible 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 the 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 will be required to sign a health and safety signoff sheet stating that they have read, understood, and 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 course given by Pleasant 

Prairie personnel prior to conducting sampling activities at Pleasant Prairie. This safety course 

will review plant-specific health and safety procedures, including: 

 Locations of on-site first aid/descriptions 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 procedures that ERG personnel must follow. 

[QUESTION FOR PLEASANT PRAIRIE: 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 gloves, when collecting or preserving; and 

 Safety glasses with side shields or chemical splash goggles, when collecting or 

preserving samples, and when required by Pleasant Prairie. 

 For all phases of sample collection, disposable PPE will be used, so decontamination of 

the PPE may not be necessary. If gloves become torn or degraded, they will be thrown away and 

replaced with a new pair. Disposable PPE, including gloves, will be removed, bagged, and left at 

the site in a controlled 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 other 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 her condition. Workers should “watch out” for each 

other while working close to potential chemical and physical hazards. A Pleasant Prairie or EPA 
6-4

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 permit-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 advised of any sampling-point-specific safety 

protocols during the on-site health and safety briefing. Table 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 determined at a later date). 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. Where 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 physical hazards present while on site. Physical 

hazards may arise from using catwalks, hitting low-hanging overhead piping, and working 

around moving equipment or vehicles. ERG personnel 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 operation of large trucks 

and machinery in the vicinity of the sample collection 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 they are having trouble hearing or being heard 

when standing three feet or less away from another 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 sampling episode. Samplers may be suited in 

Tyvek® and temperatures could reach extremes. 

 Wastewater sampling points are not expected to be too hot for 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 samples with heat-resistant gloves. 

6.5.3 Chemical Hazards 

 The only chemical hazards expected are chemicals 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 health 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 sample 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 areas 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 avoid injuries due to extreme temperatures. 

6.6.1 Heat Stress 

 Heat stress is not only a concern in hot/humid outdoor environments, it is a concern due 

to the thermal or radiant heat generated by equipment and/or processes. Sampling team personnel 

will monitor each other for the following symptoms: 

 Heat rash that may result from continuous 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 muscles and replace fluids. Have worker 

rest in a cool shaded area. 

 Heat exhaustion that occurs from increased stress on various body organs 

including inadequate blood circulation due to cardiovascular insufficiency or 

dehydration. Signs and symptoms include: 

— Pale, cool, moist, clammy skin 

— Heavy sweating 
6-6

— 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 serious injury and death occur. 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 clothes with cold water, wrap 

worker in wet cold sheets (if possible), monitor ABC (airway, breathing, 

circulation), treat for shock, and call emergency 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 requested to consume electrolyte fluid or cool 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 worse, 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/her shift. In addition, the worker will be requested 

to consume electrolyte fluid 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 workers are dressed in normal clothing. 

 For sampling on this project, work periods will 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 for 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 beats per minute after one 

minute of rest in the next rest period, the following work cycle will be shortened by another 33 

percent. This shortening of the work period must continue until the worker's HR is no greater 

than 110 beats per minute. 

6.7 First Aid

 First aid procedures in response to chemical exposures will be conducted in accordance 

with the appropriate Material Safety Data Sheets (MSDS) for the chemical involved. If an 

incident occurs and MSDSs are not available for a particular hazardous chemical (e.g., 

wastewater), the following general first aid procedures will be performed: 

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

Seek medical attention if irritation 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 contaminants may be preserved with sulfuric 

acid (H2SO4), hydrochloric acid (HCl), sodium hydroxide (NaOH), an ammonium sulfate buffer 

solution (NH4SO4), and/or sodium arsenite (NaAsO2) 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 lab hood) to avoid potential accumulation and 

inhalation of any toxic vapors. When pouring samples, skin protection must also be worn (longsleeved cotton coveralls or uncoated Tyvek®, safety glasses with side shields or splash goggles, 
6-8

and nitrile gloves). Sodium arsenite is a known carcinogen and toxic so extra care should be 

taken when handling any solutions containing sodium arsenite. 

 In some instances, the use of these preservation chemicals could create a chemical 

reaction (i.e., generation of heat or release of toxic vapors). For instance, 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 chief and stop preserving the sample immediately. 

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

 Don protective clothing (nitrile gloves as a minimum). 

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

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

add water to acid. 

 Place spilled material in a heavy plastic container, label the container, and contact 

site for disposal information. 

 Notify the crew chief of the spill and the procedures used. 

 At any time, if personnel do not feel comfortable 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 portable extinguisher. 

6.9 Training and Medical Monitoring Requirements

 All ERG sampling crew personnel have participated 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 preservation are active 

participants in the Medical Monitoring Program. 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 schedules and field work, 

particularly overtime. It is important to remember extended work schedules will contribute to 

poor production and motivation. All field teams will rotate to ensure that sampling team 

members receive sufficient rest to avoid injuries resulting from fatigue or inattention. 

 It is common practice to perform 12-hour work days under project management direction. 

If this work schedule is exceeded, the 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 three 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 health and safety briefing. 

Updates to this table will be made as needed. 
7-1 

7. REFERENCES

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

Coal-Fired Steam Electric Power Plants. (February). 

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

Detailed Study Report. EPA 821-R-09-008. Washington, DC. (October). 

Available online at: http://www.epa.gov/guide/steam/finalreport.pdf. DCN 

SE00003.