# Final
S ampling Plan

W e Energies ’
Pleasant Prairie Power Station Pleasant Prairie, WI
Sampling Episode 6559

Prepared for:



## U.S. Environmental Protection Agency

Engineering and Analysis Division
Office of Water 1200 Pennsylvania Avenue, NW Washingto n, D.C. 20460

Prepared by:



### Eastern Research Group, Inc. 14555 Avion Parkway
Suite 200 Chantilly, VA 20151

June 3

, 20 10

EPA Contract No. 68

- C

- 02

- 095 Work Assignment 7

- 2 9i TABLE OF CONTENTS

Page

1. I NTRODUCTION

................................ ................................ ................................ ................. 1

- 1

1.1 Background

................................ ................................ ................................ .......... 1

- 1

1.2 Objectives and Scope

................................ ................................ ........................... 1

- 1

1.3 Plant Selection

................................ ................................ ................................ ..... 1

- 2

2. F ACILITY O VERVIEW

................................ ................................ ................................ ........ 2

- 1

2.1 FGD Scrubber Systems

................................ ................................ ........................ 2

- 2

2.2 FGD Wastewater Treatment System

................................ ................................ ... 2

- 3

3. S AMPLING P ROCEDURES

................................ ................................ ................................ ... 3

- 1

3.1 Sampling Point Selection

................................ ................................ ..................... 3

- 1

3.2 Analyte Selection

................................ ................................ ................................ . 3

- 1

3.3 Sample Collection Procedures

................................ ................................ ............. 3

- 2

3. 3.1 Influent to the FGD Wastewater Treatment System (SP

- 1)

.................... 3

- 3

3.3.2 Effluent from FGD Wastewater Treatment System (SP

- 2)

..................... 3

- 8

3. 4 Sample Preservation, Shipping, and Analysis

................................ ................... 3

- 16

3.5 Field Measurements and Engineering Data Collection

................................ ..... 3

- 17

3.6 Sample Labeli ng

................................ ................................ ................................ 3

- 18

3.7 Traffic Reports

................................ ................................ ................................ ... 3

- 18

3.8 Quality Assurance/Quality Control

................................ ................................ .... 3

- 19

3.9 Sample Splitting

................................ ................................ ................................ . 3

- 21

4. S AMPLING A CTIVITIES

................................ ................................ ................................ ...... 4

- 1

4.1 Sampling Team Organization

................................ ................................ .............. 4

- 1

4.2 Presampling Preparation

................................ ................................ ...................... 4

- 1

4.3 Field Sampling Activities

................................ ................................ .................... 4

- 1

4.4 Logistics

................................ ................................ ................................ ............... 4

- 2

4.4.1 Pleasant Prairie Power Plant Contacts

................................ ..................... 4

- 2

4.4.2 EPA Contacts

................................ ................................ ........................... 4

- 2

4 .4.3 Analytical Laboratories

................................ ................................ ............ 4

- 3

4.4.4 ERG Contacts

................................ ................................ ........................... 4

- 3

4.4.5 Freight Forwarders

................................ ................................ ................... 4

- 3

5. S AMPLE S HIPMENT

................................ ................................ ................................ ........... 5

- 1

5.1 Sample Set Preparation

................................ ................................ ........................ 5

- 1

5.2 Sample Packing

................................ ................................ ................................ .... 5

- 1

6. S ITE

- S PECIFIC H EALTH AND S AFETY P ROCEDURES

................................ .......................... 6

- 1

6.1 Emergency/Medical Procedures

................................ ................................ .......... 6

- 1

6.1.1 F irst Aid 6

- 1

6.1.2 Site Evacuation/Emergency Response Plan

................................ ............. 6

- 1

6.1.3 Emergency Showers and Eye Washes

................................ ..................... 6

- 1

6.1.4 Local Hospital

................................ ................................ .......................... 6

- 1

6.2 ERG Health and Safety Responsibilities and Authority

................................ ...... 6

- 1

6.2.1 Work Assignment Manager

................................ ................................ ..... 6

- 2TABLE OF CONTENTS (Continued)

Page

ii 6.2.2 Crew Chief

................................ ................................ ............................... 6

- 2

6.2.3 Sampling Team Members

................................ ................................ ........ 6

- 2

6.3 Briefings

................................ ................................ ................................ ............... 6

- 2

6.3.1 Off

- Site Briefings

................................ ................................ ..................... 6

- 2

6.3.2 On

- Site Briefings

................................ ................................ ..................... 6

- 3

6.4 Safety Procedures

................................ ................................ ................................ . 6

- 3

6.4.1 PPE 6

- 3

6.4.2 Safety Practices

................................ ................................ ........................ 6

- 3

6.4.3 Safe Work Practices

................................ ................................ ................. 6

- 4

6.5 Sampling

- Point

- Specific Safety Procedures

................................ ........................ 6

- 4

6.5.1 Physi cal Hazards

................................ ................................ ...................... 6

- 4

6.5.2 Thermal Hazards

................................ ................................ ...................... 6

- 4

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 Monito ring Requirements

................................ ................ 6

- 8

6.10 Shift Work Protocol

................................ ................................ ............................. 6

- 8

7. R EFERENCES

................................ ................................ ................................ ..................... 7

- 1iii LIST OF TABLES

Page

3

- 1 Sample Collection at Pleasant Prairie Power Plant

................................ ........................ 3

- 22

3

- 2 Analytical Methods

................................ ................................ ................................ ........ 3

- 23

3

- 3 Summary of Sample Containers and Planned Preservation

................................ ........... 3

- 24

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

- 311

- 1 1. I NTRODUCTION

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 W e 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

Gr oup, 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 sa mpling crew, a review mechanism fo r EPA personnel, and a source of procedural information for plant personnel

.

1.1

During its recently completed detailed study of the steam electric industry, EPA identified metals and certain other constituents present in the wastewater discharge s 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. Background

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 th e 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

EPA is preparing to collect and analyz e 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. Objectives and Scope

Generall y, 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 conduct ed a one

- day presampling site visit at Plea sant Prairie on March 2, 2010

, and

collected t he following information :

**•** I nformation about the plant’s operations , including existing sampling data and

results ;

**•** P rocess

- specific information ;

**•** I nformation on pollution prevention and wastewater treatment o per ations ;

**•** P lant

- 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

EPA expects to select up to seven coal

- fired steam electric plants for FGD wastewater sampling , basing the plant selectio n on the process configurations and characteristics of the plants. Plant Selection

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

characteristics :

**•** The plant is a coal

- fired power plant that burns p owder r iver b asin (PRB) coal in

each of its two generating units;

**•** The plant operates limestone forced oxidation wet FGD system s on both units ;

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

— Equalization

,

— pH adjustment (lime addition)

,

— Prima ry 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 gy psum by

- pr oduct.2

- 1 2. F ACILITY O VERVIEW

Pleasant Prairie operates two steam elec tric generating units and each has a co a l

- fired boiler. Units 1 and 2 each have a capacity of 615 megawatts (MW), and came online in 1980 and 1985, respectively. The p lant 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 i n 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 (SO 2 ) releases from the p lant . The Unit 1 FGD system was

installed in November 2006

, and the Unit 2 FGD system was installed in March 2007. The wet FGD scrubbers remove approximately 97 to 98 percent of the SO 2 from the flue gas. In addition

to the FGD scrubber systems, Pleasant P rair i e installed a n FGD wastewater treatment system to control the discharges of the wastewater generated during the operation of the FGD scrubbers.

Section s 2.1 and 2.2 further discuss the FGD scrubber systems and the FGD wastewater

treatment syste m, resp ectively.

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 (NO X ) emissions, year round.

The electrostatic precipitators (ESPs) at P leasant 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 c ollected 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 installed a calcium bromide injection system in November 2009 and began continuous calcium bromide injection in January 2010 . The system injects a solution of

calcium bromide on to the coal prior to it being pulverized. A dd ing the calcium bromide to the

coal enhances the oxidation of the mercury in the boiler and

, ther efore, 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 FG D wastewater treatment system

.

Units 1 and 2 each have the following configuration:

**•** Boiler ;

**•** SCR system;

**•** ESP; and

**•** FGD scrubber system

.2

- 2 2.1

Pleasant Prairie operates two identical wet FGD scrubber systems that treat the flue gas

from U nits 1 and 2. The plant uses limestone slurry as the sorbent for SO 2 absorption. Limestone

and service water are fed to on

- site ball mills, which pulverize the limestone to create the slurry. From the ball mills, the slurry is transferred to hydrocyclone s to collect limestone particles that are too large to use in the FGD scrubber system. The underflow from the hydrocyclone s is returned to the ball mill for additional processing. The overflow from the hydrocyclone s, which is approximately 40 to 50 percent s olids (by weight), is transferred to a limestone slurry storage tank and used as fresh limestone slurry in the absorber

. FGD Scrubber System s

The fresh limestone slurry is fed to the reaction tank of the FGD scrubber system and the recycle pumps pump the slurry to the vario us 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

flow s counte rcurrent to the slurry, the spray droplets of the limestone slurry contact the flue gas

and absorb the SO 2 , which reacts with the limestone particles and produces calcium sulfite. The spray droplets flow downward until they reach 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 li mestone slurry and the flue gas. The spray droplets

continue to flow d ownward 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 SO 2 removal in the FGD systems is optimized at a pH of 5.9 ; however the plant operates the FGD systems at a pH of 5.6 to 5.7 to reduce the scaling potential in the system. The limestone slurry feed rate is adjusted to maintain th e pH in the system at 5.6 t o 5.7 . 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 sy stem lasts for about eight to ten hours each day and is transferred to the gypsum dewatering operations . The plant stagger s 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 th e plant tries to keep the chlorides concentration around 6,000 ppm.

The gypsum slurry for each scrubber is pumped to its primary hydro cy clone, 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 5 0 percent solids, is transferred to the vacuum belt filters for final dewatering. The overflow from

both the Unit 1 and Unit 2 primary hydrocyclone s are commingled in the secondary hydrocyclone feed tank and transferred to a common secondary hydro cy clone. The overflow from the second hydro cy clone 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 belt s 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 4 5,000 tons of gypsum per hour, when the plant is dewat ering 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 fi ltrate to the Unit 2 FGD scrubber system.

2.2

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

transfers of wastewater from the FGD scrubber system, which consists of secondary hydrocycl one overflow, at a flow rate of approximately 40 gallons per minute ( gpm )

. The

intermittent transfers are expected to occur twice per day. According to plant personnel, the secondary hydrocyclone typically operates for ten hours and is then off for six ho urs and then operates for ten hours again. The FGD wastewater treatment system is a chemical precipitation

system and contains the following treatment operations: FGD Wastewater Treatment System

**•** 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, present s the process flow d iagram 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 equaliza tion tank also receives water from the filtrate sump, which includes the filtrate from the treatment system sludge filter press es

.

From the equalization tank, the wastewater enters reaction tank 1 , where hydrated lime is

added to raise the pH of the wast ewater 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 equipment . To desaturat e the gypsum

, some of the sludge from the downstream primary clarifier is recycled back to r eaction t ank 1 to provide seed crystals for gypsum nucleation.2

- 4 From reaction tank 1, the wastewater flows to the primary clarifier, where polymer i s 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 therefor e, 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

.

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

added to the wastewater. The pH in reaction tank 3 is targeted at 7.0 to 7.2 S.U. The effluent

from re action 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 flocc ulation 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 t he 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 t o discharging to Lake Michigan. Pleasant Prairie commingles the effluent from the FGD wastewater treatment plant with o ther plant wastewater to meet the final outfall mercury and chloride limits. To meet the effluent mercury limit, Pleasant Prairie must di lute the FGD wastewater at a 30:1 ratio.

The sludge from the primary and secondary clarifier s is transferred to sludge holding

tank s 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

maintena nce. This weekly maintenance includes draining and flushing of the secondary clarifier to avoid buildup from flocculation. Pleasant Prairie personnel stated that the weekly maintenance will be performed on the Thursday prior to the EPA sampling episode so plant can verify the system performance on Friday and have it available for the sampling episode on Monday.

Pleasant Prairie has made the following modifications to the FGD wastewater treatment system since the system first began operating in early 200 7:

**•** Changed the type of organosulfide used in the system from TMT 15 ® to Nalmet ®

1689 (described previously) ;2

- 5 **•** Added a hydrochloric acid addition point to reaction tank 2 because the system

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

**•** Bypass ed 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 aft er 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

Treated

Effluent to Discharge

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

SP

- 2

Indicates a Sampling Point Treated

Effluent Recycle Polymer Hydrochloric

Acid

Figure 2.1

. FGD Wastewater Treatment System, Pleasant Prairie Power Plant3

- 1 3. S AMPLING P ROCEDURES

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

EPA ’s s ampling point selection includes treatment system infl uent 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 : Sampling Point Selection

**•** SP

- 1 Influent to the FGD Wastewater Treat ment 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 FG D Wastewater Treatment System (SP

- 2) Field Blank

.

3.2

Analytes that will be included in EPA’s Pleasant Prairie sampling episode include those in the following classes of pollutants: Analyte Selection

**•** Classicals:

— Biochemical oxygen demand, 5

- day (BOD 5 ),

— Chem ical 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 c yanide;

**•** Total m etals:

— Aluminum, antimony, ar senic, 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 m etals:

— 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. Tabl e 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

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 o n the sampling point and pollutant parameters. This sub section describes in detail the sample collection techniques. Sample Colle ction Procedures

Samples are collected as a series of “fractions,” or bottles designated for particular analyses requiring the same preservation. The com prehensive 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 analyte s (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. T he masks are u sed 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 protoc ols 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 coll ection 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 b ottles 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) ha s a sample tap loc ate d on

the secondary hydrocyclone

. ERG will collect the sample prior to the wastewater entering the

equ alization 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 s crubber 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 possib le; 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 se condary hydrocyclone c urrently

has a large diameter tubing that flows to a drain . F or 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. I f problems occur during the collection of spl it 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 ana lyses (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 1 0

- 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 0. 8 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 sam ple is greater than one percent , the n the laboratory will separate the aqueous and solid portion s 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), BOD 5 , hexavalent chromium, and dissolved metals (including mercury ) samples will not be analyzed as biphasic samples. Scrubber purge samples with less than one percent TSS will not require biphasic separation and analysi s.3

- 4 The samples for the influent to the FGD wastewater treatment system (SP

- 1) will be

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

**•** Colorless, electronic

- 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 me tals samples);

**•** Masks (for mercury samples); and

**•** Sample containers.

ERG will follow all procedures and protocols described in EPA Method 1669 to clean a ll metals sampling equ ipment 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, an d collect wastewater samples. This section describes the set

- up of the sample point and collection of the EPA samples 1

.

1. Samplers remove the bags containing the gloves and high

- density polyethelene ( HDPE ) plastic wrap from the coolers or storage containers in which they are packed

. Samplers identify which 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

t owel 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 double

bagged 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 wi th the clips located inside the box.

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 sili cone tubing.

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 s plit samples collected by the plant and, therefore, the collection of the plant’s samples is not described in this plan.3

- 5 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 tota l

mercury field b lank 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

merc ury 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

. “Di rty hands” closes the outer bag

. The samplers repeat this procedure

for the total metals field blank samples 2

.

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 th e 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

meta ls 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

.

9. “Cle an 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” p laces the end of the silicone tubing back in the cleanbox.

2 ERG will collect field blank samples at the influent to the FGD wastewater treatment system on Day 1 of the sampling episode. Additio nally, 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 10. “Dirty hands” opens the outer bag for a precleaned 10

- L container

. “Clean hands”

op e ns 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” fill s the 10

- L container with sample to be analy z ed for dissolved metals and hexavalent chromium, which is required to be f iltered 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 th e 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 mercu ry 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 tu bing 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

f

or the d issolved mercury and total metals samples.

12. “Dirty hands” p l aces 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 t he temperature and pH

.

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

.

16. “Dirty hands” cove rs the work surfaces (ground or table) with HDPE plastic wrap and places the double

- bagged sample bottles within easy access on the covered

surface.

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

. “Clean hands” pl aces the cleanbox at the point of sample collection

. “Clean hands” secures the cleanbox open with the clips located inside the box.3

- 7 18. “Dirty hands” opens the opening on the peristaltic pump head so the tubing can be placed in the pump head

. “Dirty hands” op ens 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 t he inner bag

, and removes the tubing

. “Clean hands” places a clean plastic bag over the end s 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 t he 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 pla stic 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 han ds” 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 pum p . 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 2 1 to replace the filter 3

.

23. Both samplers change gloves.

24. “ Dirty hands” opens the outer bag of one of the 10

- L containers

. “Clean hands” opens the inner bag, removes the lid, and places the end of the Teflon® tubing

into the container

. “Clean hands” holds the end of the silicone tubing outside the cleanbox, with t he plastic bag still covering the end of the tubing

. “Dirty hands” starts the pump and passes approximately 7 50 mL through the tubing and filter

and then stops the pump.

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 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 sam ple 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 di ssolved 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 i nfluent to the FGD w astewater t reatment s ystem (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 tank s

. Pleasant Prairie has a sample tap located on the wastewater piping downs tream of the effluent tank s

. 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 large r 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. Pleasant Prairie has also agreed to install a t hree

- way splitter on the sample tap that will have three separate taps to collect the samples from the sampling point. 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) an d another automatic compositor to collect sample volume for all classical analytes (i.e., BOD 5 , Group I, and Group II). In addition to collecting automatic composite samples for the analytes listed above, ERG will collect total and dissolved mercury grab s amples every six hours during each compositing period. ERG will also collect one grab sample for cyanide during each compositing period.

ERG will collect the total and dissolved mercury grab samples by shrouding one of the three taps on the three way spl itter (the other two taps are used for the two compositors) and3

- 9 collecting the samples directly from the tap. Because the samples are collected directly from the

tap , ERG will not be able to collect split samples with Pleasant Prairie (or its representativ e); therefore, duplicate samples will be collected.

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 re presentative) to collect samples simultaneously. I f 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 offe r 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, ma inly 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 peri od 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 epis ode, 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 is sue . 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 the Metal Cleaning

Basin 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. E RG and EPA agreed with this approach for

collect ing samples of the effluent from the FGD wastewater treatment system.

For all analytes, ERG will collect QC samples at the effluent from the FGD wastewater

treatment system (SP

- 2 ) on D ay 3 of the sampling episode . In addition, for all analytes, ERG will collect a duplicate sample of the effluent from FGD wastewater treatment system (SP

- 3 ) on D ay 2 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;3

- 10 **•** Tyvek® suits (for me tals samples);

**•** Masks (for mercury samples); and

**•** Sample containers.

All metals sampling equipment will be specially cleaned according to the proced ures 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 samples 4

.

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 c ontain 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 double

bagged co mposite containers within easy access on the covered surface.

3. “Dirty hands” opens the outer bag of the cleanbox and “clean hands” opens the clear inner bag. “Clean hands” places the cleanbox at the point of sample

collection. “Clean hands” opens the clean box 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 e ach 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 pla ced 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 flow ing 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.

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 responsib le 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 5. “Dirty hands” threads one portion of the silicone tubing thr ough the peristaltic pump portion of the automatic compositor.

6. Both samplers change gloves.

7. “D irty 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

w ater, 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 t he silicone tubing with the plastic bag covering the end out of the

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

water through the tubing

. After the tubing has been purged with sufficient volume, “clean hands” holds the sili cone 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 pu rging of the tubing and collection of the field blank sample volume, “dirty hands” holds t he 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 wit h 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 fi eld blank composite container. “ Dirty hands” closes the outer bag of the field blank composite container 5

.

8. Both samplers work together to move the sampling tubing, automatic compositor, and composite containers into position for the sample collection. Sa mplers will ensure that the tubing will stay in place during the 24

- hour sample collection period.

9. “Dirty hands” changes gloves.

10. “Clean hands” holds the end of the silicone tubing outside the cleanbox over a bucket, with the plastic bag still covering t he 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 m inimum of 2 minutes.

11. 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 for all metals at the effluent from the FGD wastewater treatment system during o n Day 1 of the sampling episode. Additionally, ERG will collect a total mercury field blank sample during one of the grab samples for each day of sample collection at the effluent from the FGD wastewater treatment

system.3

- 12 12. “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 8 33 mL of sample every hour)

. “Dirty hands” calibrates the compositor to ensure that approximately 8 33 mL is collected for each individual grab.

13. “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” clo ses the outer bag. The samplers put ice around the composite container to keep the samples cold during the compositing time period.

14. Samplers repeat steps 1

- 1 3 to set up the automatic compositor for the classical analy t es (skipping step 7). Samplers will u se another composite container.

15. “ Dirty hands” and “clean hands” then work to collect the total mercury field blank sample. “Dirty hands” shrouds the sample tap with a clear plastic bag that covers the end of the sample tap and provides enough room for sam plers 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

16. “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 samp le 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 sampl e 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” cl oses 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; therefore, the total and dissolved mercury samples will not be collected as split samples wi th 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 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 coll ects its dissolved mercury sample

.3

- 13 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 from the same sample tap used for the mercury sample co llection

. The samplers will fill the bottle directly from the

tap ; 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 sample tap used for the mercury collection

.

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 ba g 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. S amplers 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 sample bottles

, preclean ed 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.3

- 14 24. “Dirty hands” op ens 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 con taining 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 t he peristaltic pump head.

27. Both samplers change gloves.

28. “Dirty hands” opens the outer bag of the field blank composite container and total

me t als field blank sample bottle. “Clean hands” removes the total metals field blank sample bottle and places it in the cleanbox. “C lean 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 s ilicone tubing outside the cleanbox over a bucket, with the plastic bag still covering the end of the tubing

and “ d irty hands” operates the pump to pump about 75 0 mL of blank water from

the field blank composite container

. “Clean hands” places the end of t he 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 th e 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 me t als field blank sample

bottle. “Clean hands” removes the dissolved metals field blank sa mple 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 “ d irty hands” operates the pump to pump about 75 0 mL of blank

wa ter 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 di ssolved 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 repea t this procedure for the hexavalent chromium field blank3

- 15 samples 6

. “Clean hands” closes the inner bag of the field blank composite container and “dirty hands” closes the outer bag. Note: 75 0 mL of blank water does not need to be purge d for each sample, jus t at the beginning of each new

filter. If a new filter is needed, “clean hands” removes the used filt er 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 “clea n 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 plas tic bag still covering the end of the tubing and “ d irty 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

hand s” 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 sa mple 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

D ay 2 of the sampling episode, the s amplers will collect additional sample volume for the duplicate samples

. The samplers will also collect additional sample volume for the laboratory QC analyses during D ay 3 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.

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 h ands” 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 bo ttle in the outer bag and “dirty hands” closes the outer bag. D uring D ay 2 of the sampling episode, the samplers will collect additional sample volume for

6 ERG will collect field blank sam ples for all metals samples at the effluent from the FGD wastewater treatment system during Day 1 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 samp le in the

field.3

- 16 the duplicate samples and during D ay 3 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 f or 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 b ucket, 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 BOD 5 , Group I, and Group II samples. During D ay 2 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 D ay 3 of the sampling episode.

EPA plans to collect samples at the effluent from the F GD 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

All samples will be maintain ed 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 Sample Preservation, Shipping, and Analysis

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 wil l be filtered upon receipt at the laboratory. All metals samples, except hexavalent chromium, will be acid

- preserved prior to extraction at the laboratory. H exavalent 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

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

wastew ater 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 of3

- 17 dilution necessary to reduce sulfide to a nondetectable concentr ation. 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 d etected, 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

- io dide 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 hydroxi de and place the sample on ice. The preservation, including the amount of dilution, will be reported to the lab oratory on the traffic reports.

Table 3

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

- site preservation requirements for each typ e 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 s top diluting the sample s by discontinuing preservation and not ing 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

Temperature

, pH , sulfide

, and oxidants will be measured and recorded by the sampli ng 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 collect ing the aliquot. For sulfide and oxidants, the samplers will f ill the cyanide sample bottle directly and test for sulfide and oxidants using test strips immediately after sample collection. Field Measurements and Engineering Data 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

dete ction 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 o f 3 (2:1). They will continue t his 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 dilu te all samples collected

at the sampl ing 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 c alibration 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 collect3

- 18 flow rate data for each sample d 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, name s of the samplers, sample collection time, field measurements, and any notes and observations.

Samplers will also collect e ngineering information with regard to design and operation of the plant. For example, they will collect information such as coal us age, 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 informatio n will be used to determine if the specific design or operational criteria of the steam electric operations affect the wastewater characteristics.

3.6

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, al though they may also be completed by hand

. Each self

- adhesive label will be completed in indelible ink and contain the following information: Sample Labeling

**•** Sample number;

**•** Sampling ep isode 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 r equired 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

To maintain a record of sample collection, transfer between personnel, shipment, and receipt by the laboratory

, samplers will complete a traffic report for each sample set at each sampling location

. These forms are used to document sample custody transfer from the field to the laboratory

. T raffic 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 wit h the samples to the analytical laboratory. Traffic Reports3

- 19 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 t he comment section to provide special notes or

inst ructions 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 add ition, 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

The QA/QC program f or sample collection at Pleasant Prairie will include the following: Quality Assurance/Quality Control

**•** 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 m etals;

**•** 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 D a y 2 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 bottl e blanks prior to shipping the equipment to the sampling episode.

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 pr ior 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).3

- 20 E RG will prepare field blanks for each of the total and dissolved metals analyses at each

of the two sampling points during D ay 1 of the sampling episode 7

. Additionally, ERG will collect total mercury field blanks at the effluent from the FGD wastewater treatment system sampling point during the collection of one of the grab samples each day of the sampling episode. 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 wastew ater 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® a nd 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 pouring ASTM Type 1 water directly into the sample bottles. The dissolved metals field blank at the influent to the FGD wastewater treatment system sampling points will be prepared by gravity

feeding ASTM Type 1 water through the silicone tubing set into a large composite container where it will be held for approximately one hour, then pump ing 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. T he 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 containe r 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 determin e 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 contaminati on 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 , ma trix 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 necessa ry laboratory QC volumes. L aboratory 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 all analytes requiring laboratory QC volu mes , the sampling team will collect QC sample volume from the effluent

from the FGD wastewater treatment system (SP

- 2 ) during D ay 3 of the sampling episode

.

7 ERG will not collect a field blank for dissolved mercury because a filter blank will be prepared and analyzed by the laboratory.3

- 21 3.9

Pleasant Prairie or it s representative has elected to col lect 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 sample s 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 duplica te samples with Pleasant P rairie o r 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 i n Section

3.3.2 ; t heref ore, duplicate samples will be collected. Sample Splitting3-22 Table 3

- 1

. Sample Collection at Pleasant Prairie Power Plant

Sampling

Point

Number Sampling Point NameTotal Metals(EPA Method200.8 withcollision cellTotal Metals(EPA Method 200.7Dissolved Metals(EPA Method 200.8 withcollision cellDissolved Metals(EPA Method 200.7Total MercuryDissolved MercuryHexavalent ChromiumBOD5Group IaGroup IIbTotal Cyanide

SP

- 1 Influent to the FGD Wastewater Treatment System 4 4 4 4 4 4 4 4 4 4 4

SP

- 2 Effluent from the FGD Wastewater Treatment System 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+1QC 4+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 1 1 1 1

SP

- 4 Influent to the FGD Wastewater Treatment System Field Blank 1 1 1 1 1 1

SP

- 5 Effluent from the FGD Wastewater Treatment System

Field Blank 1 1 1 1 4 1

Total Number of Samples 11+1QC 11+1QC 11+1QC 11+1QC 1 4 +1QC 9+1QC 11+1QC 9+1QC 9 +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 (CO D), a nd total phosphorus.3

- 23 Table 3

- 2

. Analytical Methods

Parameter Method Number

Classicals

Biochemical o xygen d emand (BOD 5 ) SM 5210 B

Chemical o xygen d emand (COD) EPA 410. 4

Total s uspended s olids (TSS) SM 2 540 D

Total d issolved s olids (TDS) SM 2540 C

Sulfate EPA 300.0

Chloride EPA 300.0

Ammonia as n itrogen EPA 350.1

Nitrate/ n itrate as n itrogen EPA 353.2

Total Kjeldahl n itrogen (TKN) EPA 351.2

Total p hosphorus EPA 365. 1

Total c yanide SM 4500 CN E

T otal and Dissolved Metals

Mercury EPA 1631 E

Hexavalent c hromium (dissolved only) EPA 218.6

A ntimony, a rsenic, cadmium, chromium, copper, lead, manganese, nickel, selenium, silver, thallium, vanadium, and zinc EPA 200.8 with collision cell

Aluminum, b arium, beryllium, boron, calcium, cobalt, iron, magnesium, molybdenum, sodium, tin, and titanium EPA 200.73

- 24 Table 3

- 3

. Summary of Sample Container s and Planned Preservation

Parameter Sample

Container and

Volume QC Sample

Container and

Volume On

- Site Preservation

Classicals

BOD 5 One 1

- L plastic

bottle One 1

- L plastic

bottle ≤6 **°** C

Group I a One 1

- L plastic

bottle s One 1

- L plastic

bottle s ≤6 **°** C

Group II b Two 1

- L plastic

bottle s Two 1

- L plastic

bottle s H 2 SO 4 to pH <2, ≤6 **°** C

Total c yanide One 1

- L plastic

bottle One 1

- L plastic

bottle s NaOH to pH >10, dilution until sulfide is not present, NaAsO 2 until total chlorine is not present, ≤6 **°** C

Metals

T otal metals (EPA Method 200.8 with collision cell) One 5 0 0

- mL

p lastic bottle No additional

volume needed None (acid preserve at laboratory)

T otal metals (EPA Method 200.7) One 5 0 0

- mL plastic bottle No additional

volume needed None (acid preserve at laboratory)

D issolved metals (EPA Method 200.8 with collision cell) One 5 0 0

- mL plastic bottle No additional

volume needed 0.45

- μm filter (performed in field) (acid preserve at laboratory)

D issolved metals (EPA Method 200.7) One 5 0 0

- mL plastic bottle No additional

volume needed 0.45

- μm filter (performed in field) (acid pre serve at laboratory)

T otal mercury : None (acid preserve at laboratory) Manual composite grab samples Four 125

- mL glass bottle No additional

volume needed

Influent samples and field blank samples Two 250

- mL glass bottle No additional

volume needed

D issolved mercury : None ( filter and acid preserve at laboratory) Manual composite grab samples Four 125

- mL glass bottle No additional

volume needed

Influent samples One 250

- mL glass bottle No additional

volume needed

Hexavalent chromium One 2 50

- mL plastic bottle No additional

volume needed 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, ni trate/nitrite as nitrogen, TKN, and total phosphorus.3

- 25 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 L ead acetate test strip >50 mg/L sulfide (S 2

- )

Oxidants (i.e., chlorine) P otassium

- iodide starch paper >1 mg/L free chlorine ( Cl 2 )3

- 26 Sampling Episode

____________

Preserv ation Chemicals

– List Strength of Solution from Bottle and Lot Number

H 2 SO 4

_____________________ NH 4 SO 4

________________________

NaOH

_____________________

Sample

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

Figure 3

- 1

. Sample Preservation Log Sheet3

- 27 Sampling Episode:

________________________________ _

Sampling Point :

________________________________ ___

Sample Numbers :

________________________________ __

Dat e :

Manual Composite 

## □ Grab 

## □

Automatic Composite 

## □

Time of Grab Sample Collection:

Start Time 

## □ AM 

## □ PM

End Time 

## □ AM 

## □ PM

Time of Automatic Sample Collection:

Start Time 

## □ AM 

## □ PM

End Time 

## □ AM 

## □ PM

Equipment Used: _________________________________________________

Samplers’ Names: ________________________________________________

Grab Sample Time Temp

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

1

2

3

4

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

______________________________________________________________________________

______________________________________________________________________________

______________________________________________________________________________

______________________________________________________________________________

______________________________________________________________________________

Figure 3

- 2

. Field Sampling Log Sheet3-28 Plant Name:

________________________________ ________________________________ _______________ Plant Contact:

________________________________ ________________________________ ______________ Dates of Sample Collection :

________________________________ ________________________________ ___ Data Collected by:

________________________________ ________________________________ __________

Instructions: In the tables below, fill out information on the gener ating units and FGD systems operating at the plant based on all four days of the sampling episode. Note any changes in operation that occur during the four

- day period. 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 reasona bly estimate.” Otherwise, specify 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 prod uction should be measured on a daily basis from midnight of the 1 st day of sample collection to 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 SO 2 Removal Percentage Type of

Solids Separation

Note changes in operation over the past month (e.g., turned off SCRs on October 1 or burne d 5 percent petroleum coke previous week);

Figure 3

- 3

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

- 29 Plant Name:

________________________________ ________________________________ _______________ Plant Contact:

________________________________ ________________________________ ______________ Dates of Sample Collection:

________________________________ ________________________________ ___ Data Collected by:

________________________________ ________________________________ __________

Instructions: In the tables below, provi de 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 n ot 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 T ype Amount of

Coal Used

During Day of Sampling Source of Coal ( Coal

Region

and/or

S tate) 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 ID s Scrubber Slurry

Blowdown Flow Rate Scrubber

S lurr y P ercent
S olids Time of Dewatering

During Sampling Day Percent

Filtrate Recycled

Back to

S crubber 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 epi sode and t he volumes of the FGD wastewater treatment system tanks and reactors. If possible, provide the name of the acid and polymer used during the samplin g episode. Provide actual data if possible. If actual data are not available, provide estimates for the speci fic 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.

FGD Waste water 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 ) Acid:

_________ (spec ify product )

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

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

SAMPLE

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

Comments: United States


# EPA Environmental Protection Agency
Washington, DC 20460

TRAFFIC REPORT P.O. BOX 1407

USEPA ENGINEERING AND ANALYSIS DIVISION ALEXANDRIA, VA 22313

SAMPLE CONTROL CENTER (703) 519-1140

INDUSTRIAL FIRM SAMPLED SHIPPING & INFORMATION

SAMPLE POINT DESCRIPTION SAMPLE ANALYSES Eastern Research Group, Inc. 14555 Avion Parkway, Suite 200 Chantilly, VA 20151

Figure 3

- 6

. Example Traffic Report4

- 1 4. S AMPLING A CTIVITIES

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

4.1

The sampling crew will consist of a crew chief a nd 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 whi le at Pleasant Prairie

. Following the sampling episode

, ERG will collate the analytical results from each laboratory and summarize and transmit

t his information in a trip report to EPA

. After EPA review, the report will be forwarded to

Pleasant Prairie for review. S ampling Team Organization

4.2

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 prepa re for the sampling episode and to create this s ampling

p lan

. Pre s ampling Preparation

As part of preparing the team for the sampling episode at Pleasant Prairie , the ERG crew

chief will distribute this s ampling p lan to each team member and ensure they are completely

familiar w ith 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 procu rement and shipment of all necessary sampling and health and safety equipment

.

4.3

Upon arrival at Pleasant Prairie , the ERG crew chief , in conjunction with the EPA representative s
, will meet with Pleasant Pra irie 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, i n consultation with EPA and Pleasant Prairie personnel

. If necessary, the

crew chief will obtain additional equipment

. The revised sampling description will include: Field Sampling Activities

**•** 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 a nd 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 recommended4

- 2 revisions to the proposed health and safety procedures

. Together, th e crew chief and HSC will review the proposed health and safety procedures

. The crew chief will incorporate any plant

specific changes indicated by the HSC and receive approval for sampling from the HSC before proceeding with sampling activities.

All sam ple bottles will be labeled, collected, and preser v ed, according to method protocols

. Sample fractions requiring ≤6 o C preservation will be placed on ice

. Sample fractions will then be sealed, and placed in coolers for shipment to the laboratory

. The Traffi c 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 equi pment will be prepared for return shipping.

4.4

This sub sect i on summarizes Pleasant Prairie contacts, analytical laboratory contacts and addresses, and sampling team personnel and support functions. Logistics

4.4.1 Pleasant Prairie Power Pla nt Contacts

David Lee, Manager

– Water Quality Environmental Department

W e Energies

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

- 2158

Pete Kutzora , Chemical Engineer

– Fossil Operations Business Unit

W e Energies 231 W. Michigan Street

– P145

Mil waukee, WI 53203 (414) 221

- 3926

Ed Morris

Pleasant Prairie Power Plant

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

- 5 625

4.4.2 EPA Contacts

Ron Jordan Engineering and Analysis Division

U.S. Environmental Protection Agency 1200 Pennsylvania Avenu e, NW (4303T) Washington, D.C

. 20460 (202) 566

- 10034

- 3 J ezebele Alicea Engineering and Analysis Division U.S. Environmental Protection Agency 1200 Pennsylvania Avenue, NW (4303T) Washington, D.C

. 20460 (202) 566

- 1 755

4.4.3 Analytical Laboratories

Classicals and Metals by 200.7 and 200.8 with Collision Cell TestAmerica, Inc. :

4955 Yarrow Street Arvada, CO 80002 Phone: (303) 736

- 0138 Contact: Elizabeth Eichelberger

Frontier GeoSciences, Inc. Mercury and Dissolved Hexavalent Chromium :

414 Pontius Ave. North

Seattle , WA 98109 Phone: (206) 957

- 1428

Contact: Patrick Garcia

- Strickland

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 Rese arch 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 Pra irie, WI 53158 (262) 697

- 8422 Hours of Operation: Mon.

– Fri.: 7:30 a.m. to 9:00 p.m.4

- 4 Last E xpress Drop

- off: Mon.

– Fri.: 7:3 0 p.m.

FedEx Office Print & Ship Center ( 4 miles from plant)

6411 Grand Ave Gurnee, IL 60031 (847) 856

- 8020

H ours of Operati on: Mon.

– Fri.: 7:00 a.m. to 11:00 p.m.

Last E xpress Drop

- off: Mon.

– Fri.: 8:00 p.m.5

- 1 5. S AMPLE S HIPMENT

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

. All samples will be tracked using Traffic Report forms

. Custody will be main tained 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 n ormal 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 provide d 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 d angerously with the liquid

. Abso rbent 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 re ceptacle 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 pack ing 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

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

ana lyses 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 transfer red to individual sample containers using a pump

- off approach

. Sample Set Preparation

5.2

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): Sample Packing5

- 2 1. Label eac h 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 m etal 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 bottl e with a cloth rag or paper towel

. Do not clean t he bottle

threads for the metals sample bottles.

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

ice chest with wet ice to cool.

4. W rap each glass sample bottle with two laye rs of “bubble wrap” (or place bottle in two “bubble bags”)

. The bubble wrap must fit snugly and completely cover the sample bottle

. Enclose e ach “bubble

- wrapped” container and plastic container in an individual sealable plastic freezer bag

.

5. Place two garb age 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, a dd 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 m ore ice when ambient temperatures are very high

. Place t he ice inside the second garbage bag and c lose 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 s ufficient 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 ins ide 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. Pl ace a completed address label on the lid of the cooler including name, address, and telephone number of the receiving laboratory and the return address and telephone number of the shipper.6

- 1 6. S ITE

- S PECIFIC H EALTH AND S AFETY P ROCEDURES

This section specifie s 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

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

situation

. Emergency/Medical Procedures

6.1.1 First Aid

Pleasant Prairie has first aid kits available through out 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 Prair ie 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 oper ating 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 75 th St. Kenosha, WI 53142

When on

- site call the plant control room at 262

- 947

- 5350 or

- 5351. When off

- site, t he local emergency phone number in Kenosha, WI is 911.

6.2

The ERG Work Assignment Man ager (WAM), crew chief, and sampling team members have different responsibilities to maintain a safe sampling environment

. These responsibilities

are described below. ERG Health and Safety Responsibilities and Authority6

- 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 wit h 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 cr e w 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 chief s will inspect all sampling points an d review sample collection procedures with the Pleasant Prairie personnel to ensure that all potential hazards have been identified.

The crew chief s ha ve the authority to enforce ERG’s health and safety requirements contained in this plan, and any facili ty

- 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 t he 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

ERG sampling t e am personnel will attend on

- and off

- site health and safety briefings. 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 th e sampling plan and the proposed sample collection activities. All ERG employees will be required to sign a health and safety sign

off sheet stating that they have read, understood, and agree with this health and safety plan prior to participat ing in field sampling activities.6

- 3 6.3.2 On

- Site Briefings

ERG samplin g team personnel must attend a half

- hour safety course given by Pleasan t
Prairie personnel prior to conducting sampling activities at Pleasant Prairie

. This safety course will review plant

- sp ecific health and safety procedures, including:

**•** Locat ions 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

**•** O ther site safety requirements and procedures that ERG personnel must follow.

6.4

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

6.4.1 PPE

The PPE listed below will be worn by ERG personnel at all tim es 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 gr ade 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 sam ple collection, disposa b l e 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, b agged, and left at

the site in a controlled manner.

6.4.2 Safety Prac tices

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 c ontact 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 wo rking close to potential chemical and physical hazards

. A Pleasant Prairie or EPA employee may be used as a buddy by ERG personnel

. This arrangement will be agreed to and acknowledged by the employee

.6

- 4 ERG employees will not enter any permit

- required con fined space areas

.

6.4.3 Safe Work Practices

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

**•** Wearing PPE, where required;

**•** Staying within designated areas;

**•** Not wearing loose clothing or jewelry;

**•** Keepin g 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

All sampling team members will be advised of any sampling

- point

- specific safet y 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, t he 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 identi fied hazards may affect the plant ’s personnel, the HSO will notify the appropriate Pleasant Prairie personnel. Sampling

- Point

- Specific Safety Procedures

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

hazard s at SP

- 1 and SP

- 2 due to the location of the sample tap s

. To prevent splashing, ERG personnel w ill 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 h earin g 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

.

6.5.2 Thermal Hazards

Heat s tres s may be a concern during the sampling episode

. S amplers may be suited in Tyvek® and temperatures could reach extremes

.6

- 5 Wastewater sampling points are not expected to be too hot for safe handling using typical

PP E

. Thicker nitrile gloves may be used during sampling if sample bottles are too hot to hold

. S amplers will handle extremely hot samples with heat

- resistant gloves.

6.5.3 Chemical Hazards

The only chem i cal hazards expected are chemicals used to preserve samples

. All sampling team members will be a dvised 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

shiel d 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 determine d that respiratory protection equipment is necessary to protect against inhalation hazards

.

6.6

Extremely hot temperatures can be a health and safety hazard for this sampling episode

. ERG personnel will take precautions to avoid injurie s due to extreme temperatures. Temperature Extremes

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

r eplacement

. 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 worke r rest in a cool shaded area.

**•** Heat exhaustion that occu r s 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

— H eavy sweating

— Headache and dizziness

— Nausea

— Fainting or fatigue

— Elevated pulse rate (above 150)6

- 6 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 ser ious 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 we t 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 wi ll 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

**•** Amb ient 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.

At ambient temperatures of 87 ° F and above, workers will be monitored for he at 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 shorten ed 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 one6

- 7 minute of rest in the next rest period, the following work cycle will be sho rtened by another 33

percent

. This shorten ing of the work period must continue until the worker's HR is no greater than 110 beats per minute.

6.7

First ai d procedures in response to chemical exposures will be conducted in accordance with the appropriate Material Safet y 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: First Aid

**•** Skin Contact

– Rinse t he affected area thoroughly and copiously with clean water

. Seek medical attention if irritation is experienced after cleaning.

**•** Eye Contact

– Flush t he eyes thoroughly at the nearest eyewash station for 15

minutes

. Follow up with medical attention.

**•** Ingestion

– Notify t he 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 eyewa sh 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

Water samples to be analyzed for various contaminants may be preserved with sulfuric acid (H 2 SO 4 ), hydrochloric acid (HCl), sodium hydroxide (NaOH), an ammonium sulfate buffer solution (NH 4 SO 4 ) , and/or sodium arsenite (NaAsO 2 ) b efore 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 well

ventilated area (preferably an operational lab ho od) to avoid potential accumulation and inhalation of any toxic vapors

. When pouring samples, skin protection must also be worn (long

sleeved cotton coveralls or uncoated Tyvek®, safety glasses with side shields or splash goggles, and nitrile gloves). Sodi um arsenite is a known carcinogen and toxic so extra care should be taken when handling any solutions containing sodium arsenite. Sample Preservation and Safety Considerat ions

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

reaction ( i.e., generation of heat or rel ease of toxic vapors )

. For instance, if acids are added to a6

- 8 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.

I n 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

. I f 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

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. Training and Medical Monitoring Requirements

This training includes:

**•** Toxicology;

**•** Exposure limits;

**•** Chemical, biological, and physical h azards;

**•** 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 personne l have received a

baseline medical information review

.

6.10

This sub section provides guidance for field personnel project schedules and field work, particularly overtime

. It is important to remember extended work sch edules will contribute to Shift Work Protocol6

- 9 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 Trea tment System Steel

- toed boots, hard hats,

g loves

, 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

. Sampl e 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. R EFERENCES

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

Coal

- Fired Steam Electric Power Plants

. (February)

.

2. U.S. EPA. 200 9

. Steam Electric Powe r Generating Point Source Category: Final Detailed Study Report . EPA 821

- R

- 0 9

- 0 08 . Washington, DC. ( Octob er).

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

SE00003

.