# Final
S ampling Plan RRI Energy’s Keystone Generating Station Shelocta, PA
Sampling Episode 6563

Prepared for:



## U.S. Environmental Protection Agency

Engineering and Analysis Division
Office of Water 1200 Pennsylvania Avenue, NW Washington, D.C. 204 60

Prepared by:



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

September 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

- 1

2.2 FGD Wastewater Treatment System

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

- 2

3. S AMPLING P ROCEDURES

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

- 1

3.1 Sampling Point Selection

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

- 1

3.2 Analyte Selection

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

- 1

3.3 Sample Collection Procedures

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

- 2

3.3.1 In fluent 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 Samp le Preservation, Shipping, and Analysis

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

- 16

3.5 Field Measurements and Engineering Data Collection

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

- 17

3.6 Sample Labeling

................................ ................................ ................................ 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 Keystone Generating Station Contacts

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

- 2

4.4.2 EPA Contacts

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

- 2

4.4.3 An alytical Laboratories

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

- 3

4.4.4 ERG Contacts

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

- 3

4.4.5 Freight Forwarders

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

- 3

5. S AMPLE S HIPMENT

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

- 1

5.1 Sample Set Preparation

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

- 1

5.2 Sample Packing

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

- 1

6. S ITE

- S PECIFIC H EALTH AND S AFETY P ROCEDURES

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

- 1

6.1 Emergency/Medical Procedures

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

- 1

6.1.1 First Ai d 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 W ork Assignment Manager

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

- 2TABLE OF CONTENTS (Continued)

Page

ii 6.2.2 Crew Chief

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

- 2

6.2.3 Sampling Team Members

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

- 2

6.3 Briefings

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

- 2

6.3.1 Off

- Site Briefings

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

- 2

6.3.2 On

- Site Briefings

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

- 3

6.4 Safety Procedures

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

- 3

6.4.1 PPE 6

- 3

6.4.2 Safety Practices

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

- 3

6.4.3 Safe Work Practices

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

- 4

6.5 Sampling

- Point

- Specific Safety Procedures

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

- 4

6.5.1 Physical Haz ards

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

- 4

6.5.2 Thermal Hazards

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

- 5

6.5.3 Chemical Hazards

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

- 5

6. 6 Temperature Extremes

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

- 5

6.6.1 Heat Stress

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

- 5

6.6.2 Heat Stress Monitoring

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

- 6

6.7 First Aid

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

- 7

6.8 Sample Preservation and Safety Considerations

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

- 7

6.9 Training and Medical Monitoring Re quirements

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

- 8

6.10 Shift Work Protocol

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

- 9

7. R EFERENCES

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

- 1iii LIST OF TABLES

Page

3

- 1 Sample Collection at Keystone Generating Station

................................ ....................... 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 Simplified Diagram of the FGD Was tewater Treatment System, Keystone Generating

Station

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

- 5

2

- 2 Detailed Diagram of the FGD Wastewater Treatment System, Keystone Generating

Station

................................ ................................ ................................ .............................. 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 Ag ency (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 RRI Energy’s Keystone Generating Station ( Keystone )

, located in Shelocta, Pennsylvania

, provides plant

- specific sampling procedures and methods EPA and its contractors wi ll follow when conducting sampling activities

. Sampling will be performed by EPA’s technical contractor, Eastern Research Group, Inc. (ERG), under Contract No. 68

- C

- 02

- 095

. This document, in combination with the Generic Sampling and Analysis Plan for Coal

- Fired Steam Electric Power Plants [ 1 ] , is intended to serve as a guide to the ERG field sa mpling crew, a review mechanism for EPA personnel, and a source of procedural information for plant personnel

.

1.1

During its recently completed detailed st udy of the steam electric industry, EPA identified metals and certain other constituents present in the wastewater discharges from steam electric power plants that are contributing the majority of the toxic loadings for the industry. Additionally, EPA dete rmined that one of the waste streams contributing most of 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 sy stem discharges at Keystone

. For a general description of the steam electric process and the wastewaters generated during the operation of a coal

- fired steam electric power plant, see Chapters 3 and 4 of the Steam Electric Power Generating Point Source Cat egory: Final Detailed Study Report [ 2 ].

1.2

EPA and ERG are preparing to collect and analyze samples to characterize wastewater streams generated at coal

- fired steam electric power plants. This sampling plan descri bes the approach EPA and ERG 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 an d chemical treatment to remove heavy metals using hydroxide, or a combination of hydroxide and sulfide precipitation. Objectives and Scope

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

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

**•** What are the effluent concentrations for pollutants present in treated FGD

wastewater?1

- 2 **•** What are the pollutant load ings associated with discharges of FGD wastewater following treatment?

EPA and ERG conduct ed a one

- day presampling site visit at Keystone on February 1,

2010

, and collected t he following information :

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

results ;

**•** P rocess

- specific information ;

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

**•** P lant

- specific information to tailor sampling plans ; and

**•** Information on potential sampling points

.

The sampling prog ram 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 and ERG wi ll also collect field quality control (QC) samples consisting of bottle blanks, field blanks, equipment blanks, field duplicate samples, and laboratory QC aliquot s 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 and ERG will collect information regarding system design and day

- to

- day op eration

.

1.3

EPA expects to select up to seven coal

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

Keystone was selected by EPA for samp ling based on the following site characteristics :

**•** The plant is a coal

- fired power plant that burns eastern bituminous 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,

— L ime addition ( pH adjustment /metal hydroxide precipitation)

— Organosulfide addition,

— Ferric chloride addition,

— Polymer addition,

— Clarification,

— Hydrochloric acid addition (pH adjustment),1

- 3 — Antiscalant addition,

— Heat exchange, and

— Filtration (sand filters and polishing filters); and

**•** The plant operates selective catalytic re duction (SCR) systems on both generating

units

.2

- 1 2. F ACILITY O VERVIEW

Keys tone operates two steam electric units and each has a coal

- fired boiler. Units 1 and 2,

which came on line in 19 67 and 19 68 , respectively, each have a net capacity of 850 megawatts (MW) ( 900 MW gross capacity)

. Both generating units burn e astern b ituminous coal. The Keystone plant and supporting facilities are located on approximately 1,000 acres in Shelocta,

P ennsylvania

.

Keystone recently retrofitted both units with a wet FGD scrubber system to control the sulfur dioxide (SO 2 ) releases from the plant. The Unit 1 FGD system was installed in September

200 9 , and the Unit 2 FGD system was installed in November 200 9 . With the recent addition of the FGD scrubber systems, Keystone also installed an FGD wastewater treatment system to control the discharges of t he wastewater generated during the operation of the FGD scrubbers. The FGD scrubber systems are discussed further in Section 2.1 and the FGD wastewater treatment system is discussed further in Section 2.2.

In 2003, Keystone retrofitted Units 1 and 2 with selective catalytic reduction (SCR) systems to control nitrogen oxide (NO

x ) releases from the plant. I n January 200 9

, Keystone began operating the SCR system s year

- round. Keystone also uses low NO

x burners on Units 1 and 2, which were installed in 1994 a nd 1995 respectively, to control NO

x releases from the plant.

The electrostatic precipitators ( ESPs ) at Keystone are particulate control devices that remove the fly ash and other particulates from the flue gas. Keystone utilizes cold

- side ESPs to

remove the fly ash from both units. The ESPs are designed to remove 99.5 percent of the fly ash from the flue gas. The fly ash and other particulates are collected in hoppers and are pneumatically transferred to fly ash silos.

Units 1 and 2 have the following configuration:

**•** Boiler;

**•** SCR system;

**•** Air heater;

**•** ESP ; and

**•** FGD scrubber system.

2.1

Keystone operates two forced oxidation wet FGD scrubber system s (one per unit) to control the emission of sulfur dioxide from the unit. The plant uses lim estone slurry as the sorbent for sulfur dioxide 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 trans ferred to hydro cy clones to collect limestone particles that are too large for use in the FGD system

. The

underflow from t he hydrocyclones is sent back to the ball mill s for processing. The overflow from the hydro cy clones , which ranges from 25 to 35 percent solids (by weight), is transferred to

the li mestone slurry storage tank and then used as fresh limestone slurry in the absorber

. FGD Scrubber Systems2

- 2 The fresh limestone slurry is fed to the reaction tank of the FGD system s where the slurry is pumped to the various levels of the FGD scrubber s with the recycle pumps

. Both absorbers

have five spray levels, but the plant does not always operate all of them at the same time. The slurry is pressurized and sprayed downward into the scrubber vessel through spray nozzles. As the slurry falls downward and the flue gas flows co unter

- current 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 settle on the tray, forming a layer of slurry that the flue gas must pass through to exit the FGD system. The tray has small holes in it that allow the flue gas to bubble through the limestone slurry layered on the tray, which provides additional contact between the limestone slurry and the flue gas. The spray droplets continue to flow downward in the scrubber until it reaches the reaction tank. Keystone bubbles air through the reaction tank to oxidize the calcium sulfite to calcium sulfate (i.e., gypsum).

Keystone intermittently blows down the gypsum slurry from the reaction tank to control

the solids and chlorides concentration in each of the scrubbers. Blowdown from a scrubber

occurs when t he chlorides concentration is between 1 8,000 and 2 0,000 ppm and/or when the

solids level i s between 18 and 22 percent. Keystone transfers the blowdown from the scrubber

absorber to the gypsum dewatering operations.

The scrubber blowdown is pumped to the primary hydrocyclones where the solid gypsum is separated from the water by centrifugal f orce. 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 underflow from the primary hydrocyclones is transferred to the vacuum filter belts. The

overflow from the primary hydrocyclone s is monitored. If the chloride concentration in the primary hydroclone overflow is less than 16,000 ppm, then the waste stream is recycled back to the absorber. Otherwise, the overflow is transferred to a holding tank, and then pumped to the secondary hydrocyclones. The underflow from the secondary hydrocyclones is returned to the

absorber . The overflow from the secondary hydrocyclones is sent to the purge tank and then pumped to the FGD wastewater treatment system. The secondary hydro cyclone overflow is never recycled back to the absorber.

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

gypsum is poured onto the belts. The vacuum filter belts dry the gypsum to a moisture content of

less than 10 p ercent. The chloride concentration in the dry gypsum is less than 120 ppm. Keystone transfers the gypsum to an on

- site ash landfill for disposal. Fly ash, bottom ash, and dewatered sludge from the FGD wastewater treatment plant are also sent to this landfi ll. The landfill is lined and has a leachate collection system. The leachate collection system produces a continuous waste stream. Although Keystone is attempting to market gypsum, the plant currently has no p ro spective clients. Keystone produce s approxima tely 2,000 tons of gypsum every day.

2.2

The FGD wastewater treatment system is designed to receive intermittent transfers of FGD wastewater from the purge tank, which contains secondary hydrocyclone overflow

. The daily (24 ho ur) average flow rate is 260 gallons per minute (gpm). The plant attempts to keep the flow rate constant by staggering the operation of the scrubbers. However, the flow rate can range FGD Wastewater Treatment System2

- 3 from no flow (if neither scrubber is operating) up to 400

- 450 gpm if bot h scrubbers are operating. The design maximum flow rate for the treatment system is 450 gpm.

Keystone operates the FGD wastewater treatment system 24 hours per day

, 7 days per

week . The wastewater treatment system was installed to treat the FGD scrubber purge

wastewater to meet the plant’s permit limits, which includes limits for total suspended solids (TSS), total selenium, oil and grease, BOD 5 , beryllium, copper, lead, mercury, silver, temperature, and pH

. Keystone’s FGD wastewater treatment system cont ains the following treatment operations:

**•** Equalization ;

**•** L ime addition ( pH adjustment /metal hydroxide precipitation) ;

**•** Organosulfide addition ;

**•** Ferric chloride addition ;

**•** Polymer addition ;

**•** Clarification ;

**•** Hydrochloric acid addition (pH adjustment) ;

**•** Antiscalant addition ;

**•** Heat exchange ; and

**•** Filtration (s and filters and polishing filters)

.

Figures 2

- 1 and 2

- 2 located at the end of this section, present process flow diagrams of the FGD wastewater treatment system, as well as the planned sampling locations for EPA ’s sampling episode. Figure 2

- 1 presents a simplified diagram of the FGD wastewater treatment system. Figure 2

- 2 pr esents a more complex diagram providing more detail on the chemical precipitation treatment operations.

The secondary hydrocyclone overflo w from the scrubbers is transferred to the purge tank and then sent to the equalization tank at the start of the wastewater treatment system. This wastewater is expected to contain approximately 2.0 percent solids and have a pH of 6.0 to 7.0

S.U. The equal ization tank also receives waste water from the wastewater treatment sump and

effluent from the FGD wastewater treatment system, which the plant recirculates to maintain a steady flow of wastewater through the system

.

From the equalization tank, the waste water enters three reaction tanks in series. First

, the

wastewater flows into the desaturation tank

, in which a lime slurry consisting of 10% lime is

added to encourage metal hydroxide precipitation and to increase the pH to between 8. 0 and 8.5

S.U. The pH is optimal at this range because a higher pH would cause magnesium hydroxide to precipitate. From the desaturation tank, the wastewater flows to the heavy metals reaction tank where organosulfide (TMT

- 15) is added. T he wastewater then flows to the flow sp litter tank

where ferric chloride is added.

After the flow splitter tank, polymer is injected into the wastewater as it flows to the clarifiers. Keystone operates two solid contact clarifiers in parallel , which contain a sludge bed

that attracts the sol ids in the wastewater. On average, approximately 65 percent of the sludge from the clarifier is recycled back to the desaturation tank, while the remainder is transferred to a sludge tank and then pumped to a filter press for dewatering ; however, the perce nt distribution2

- 4 varies throughout the day depending of the sludge level in the clarifier. T he dewatered sludge is

sent to the on

- site ash landfill. The wastewater is sent to the filtrate sump. All wastewater in the filtrate sump is recycled back to the equ alization tank.

The clarifier overflow is transferred to the heat exchanger feed tank. Hydrochloric acid

and an antiscalant are added to the wastewater as it is transferred to the heat exchangers. The heat exchangers lower the temperature of the wastew ater from 120°F to 85

- 90°F.

From the heat exchangers, the wastewater is transferred to three continuous backwash sand filters operating in parallel. The sand filters reduce the level of total suspended solids in the

wastewater . Backwash from the sand fil ters is transferred to the wastewater treatment sump. After the sand filters, the wastewater flows by gravity to the effluent tank.

From the effluent tank , the wastewater is sent to the polishing filters , which contain a

Teflon® media

. The polishing filt ers are continuous backwash filters. Backwash from the filters is sent to the filtrate sump. Wastewater in the filtrate sump flows back to the equalization tank.

T he FGD wastewater treatment system was originally designed s uch that the plant could bypass

t he polishing filters if the TSS level after the sand filters met the plant’s permit limit. However, Keystone has found that using the polishing filters full time is necessary to keep the TSS

concentration below the ir permit limit , which is 10 mg/L (monthl y average) and 20 mg/L (daily maximum)

. Therefore, Keystone plans to use the polishing filters full time even though the design of their system allow s them to skip this final step. The hydraulic residence time of the FGD wastewater treatment system ranges from 16 to 18 hours.

Figure 2

- 2 shows the planned sampling points for the sampling episode at Keystone . The influent sampling point at Keystone ’s FGD wastewater treatment system is located downstream of the purge tank and upstream of the equalization t ank. Thus, the influent sampling point is upstream of any chemical addition and before the influent is mixed with any recycle streams

. Although Keystone attempts to maintain a constant flow rate by staggering the operation of the scrubbers, flow at the inf luent sampling point will likely be intermittent. The FGD wastewater

treatment effluent sampling point is located in the discharge pump house downstream of the polishing filters. This point is where the plant collects its compliance monitoring 24

- hour

comp osite sample s . Keystone maintain s a relatively constant flow of 180

- 220 gpm at this sample point.

Discharge from the FGD wastewater treatment system is regulated by I nternal O utfall

101. Keystone currently discharges all plant wastewater, with the exce ption of Internal Outfalls

101 and 201 , to Crooked Creek or Plum Creek

. B ecause the water quality criteria for trace

elements such as cadmium could not be met, Keystone installed 16 miles of piping to allow the discharge of this effluent directly to the A llegheny River via Outfall 001

. The FGD effluent from

Internal Outfall 101 is first combined with effluent from the “ Pigging ” wastewater treatment system ( I nternal O u t fall 201 ) , when the wastewater from the Pigging Treatment facility is ready to discharge. The Pigging wastewater treatment facility treats via filtration wastewater generated from cleaning (i.e., “ pigging ” ) the 16 mile pipeline.2-5

Phys / Chem Separation 16 Mile Pipe FGD Scrubber Purge Internal
Outfall 101 Final
Outfall 001 Effluent from Pigging Wastewater Treatment System

Allegheny

River Internal
Outfall 201

Figure 2

- 1

. Simplified Diagram of the FGD Wastewater Treatment System, Keystone Gene rating Station2-6 FGD Scrubber Purge ( from Purge Tank ) Lime

Desaturation

Tank Heavy Metals

Reaction Tank SP

- 1

Indicates a Sampling Point Sand

Filter

2 Clarifier 1

Sludge Storage

Tank Filter Press

Sump Sand

Filter

1

Solids to On

site Ash

Landfill Wastewater Flow

Sludge Flow Intermittent Wastewater Flow Clarifier Sludge

Clarifier 2 Sand

Filter

3

Sand Filter Backwash Flow Splitter

Tank Organosulfide Ferric Chloride

Heat Exchanger

Feed Tank Cooling Water

Cooling Water

Return

Effluent

Tank Equalization

Tank

Polishing

Filters

Polishing Filter Backwash Effluent Recycle

Allegheny

River Wastewater from Sump

SP

- 2

Effluent Recycle Polymer

Hydrochloric

Acid Antiscalant

Figure 2

- 2. Detailed Diagram of the FGD Wastewater Treatment System, Keystone Generati ng Station3

- 1 3. S AMPLING P ROCEDURES

This section discusses the planned sampling procedures to be followed during the sampling epi sode at Keystone

. 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 and ERG selected the f ollowing five sampling points for this plant ( the two proposed sampling locations for Keystone ’s FGD wastewater treatment system as well as the

related Quality Assurance/Quality Control (QA/QC) samples ) : Sampling Point Selection

**•** SP

- 1 Influent to the FGD Wastewater Treatment Syste m;

**•** SP

- 2 Effluent from the FGD Wastewater Treatment System ;

**•** SP

- 3 Field Duplicate of Effluent from the FGD Wastewater Treatment System ( same location as SP

- 2 );

**•** SP

- 4 Field Blank for Influent to the FGD Wastewater Treatment System ( same location as SP

- 1); and

**•** SP

- 5 Field Blank for Effluent from the FGD Wastewater Treatment System ( same location as SP

- 2)

.

3.2

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

**•** Classicals :

— Biochemical oxygen demand, 5

- day (BOD 5 ),

— Chemical oxygen demand (COD)

,

— Total suspended solids (TSS),

— Total dissolved solids (TDS),

— Sulfate,

— Chloride,

— Total Kjeldahl nitrogen (TKN),

— Ammonia as nitrogen,

— Nitrate/nitrite as nitrogen,

— Total phosphorus

,

— Total c yanide;

**•** Total m etals:

— Aluminum, antimony, arsenic, barium, beryllium, boron, cadmium, calcium, chromium, cobalt, copper, iron, lead, magnesium, manganese,3

- 2 mercury, molybdenum, nickel, selenium, silver, sodium, thallium, tin, titanium, vanadium, and zinc

.

**•** Dissolved 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 sorbent s, treatment chemicals, and other sources. Table 3

- 1 lists the potential analytes for each sampling point, Table

3

- 2 lists the analytical methods that will be used, and Table 3

- 3 lists the sample container and volume and planned on

- site preservation for ea ch 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 Keystone , the sampling team will

use varying met hods to collect the samples depending on the sampling point and pollutant parameters. This sub section describes in detail the sample collection techniques. Sample Collection Procedures

Samples will be collected as a series of “fractions,” or bottles designated for particular analys es requiring the same preservation. The comprehensive sample set will consist 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, T DS, sulfate, and chloride) and Group II analytes (ammonia as nitrogen, COD, nitrate/nitrite as nitrogen, TKN, and total phosphorus).

In general, samplers will work in teams of two to ensure that proper sampling techniques are followed and adequate notes are taken at each sampling location. Samplers will wear disposable gloves, Tyvek® suits, masks (when sampling for mercury by EPA Method 1631E ),

steel

- toed boots, hard hats, and safety eyewear, and will observe precautions while collecting samples, remaini ng aware of their surroundings. Note that the use of masks is to prevent contamination of the mercury samples and not for respiratory protection.

Sample containers and bottles will be purchased precleaned and certified and will not require rinsing with s ample. The sample bottles for the metals analyses will be cleaned according

to EPA Method 1669. For this sampling episode, ERG will collect 24

- hour composite samples at

the effluent from the FGD wastewater treatment system sampling point 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 individual grab samples at the influent to the FGD wastewater treatment system sampling point for all analytes

. ERG will collec t 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 )

. ERG will follow protocols described in EP A Method 1669 to collect metal sample fractions. All sampling equipment (e.g., tubing) and sample bottles will be cleaned according to the procedures

described in EPA Method 1669. Samplers will use “clean hands / dirty hands” sample collection techniques w hen collecting metal sample fractions, as described in EPA Method 1669.3

- 3 Samplers will take care not to touch the insi des of bottles or lids/caps during sampling. Samples that require cooling to ≤6 **°** C for preservation will be cooled immediately in an ice

- water bath and then placed into coolers containing bagged ice throughout sample storage, shipment, and receipt at the an alytical laboratories. The Crew Chief will confirm that samples are actually

≤6 **°** C before being packed for shipment to the laboratory and the temperature reading will be documented in the traffic report for the samples. Samples that require cooling to ≤6 **°** C shall not be shipped until that temperature is reached. In addition, the length of time required for the samples to reach ≤6 **°** C shall be documented in the field log sheet.

3.3.1 Influent to the FGD Wastewater Treatment System (SP

- 1)

The influent to the FGD was tewater treatment system (SP

- 1) ha s a sample tap located downstream of the purge tank and upstream of the equalization tank

. ERG will collect the sample prior to the wastewater entering the equalization tank because the FGD scrubber purge is commingled wit h recycled wastewater in the equalization tank

. T herefore, the sampling point upstream of the tank provides the best representation of the FGD scrubber purge from the Keystone FGD scrubber system

. Because the flow from the purge tank may not be continuous,

ERG will need to coordinate closely with Keystone 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 describe d in EPA Method 1669 to collect metal sample fractions from SP

- 1

.

ERG plans to collect split samples with Keystone (or its representative) , where possible; therefore, ERG plans to attach a piece of silicone tubing to the sample tap with a “Y” splitter at the other end of the tubing to allow ERG and Keystone (or its representative) to collect samples simultaneously

. The sample tap located upstream of the equalization tank c urrently has a large diameter tubing ; for the sample collection, Keystone has agreed to install a 3/8 inch hose barb to the sample tap for ERG to attach its tubing

. To prevent potential contamination from the hose barb, ERG will flush sample through the hose barb for at least two minutes prior to collecting any samples. 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 offer instead to collect duplicate samples with Keystone or its

represe ntative

. For all analyses (except dissolved metals and hexavalent chromium) , the samplers will collect samples through the tubing directly into the specified containers

. For the dissolved

metals (excluding mercury) and hexavalent chromium samples, the samp lers will fill one 10

- L container, allow the solids to settle for approximately 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 metal s and hexavalent chromium samples will be collected as split samples.

Due to the high suspended solids content (1 to 5 percent) of the samples collected at the influent to the FGD wastewater treatment system, EPA may analyze the samples as biphasic

samp les. If the TSS content of the sample 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. 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 will3

- 4 be analyzed as biphasic samples. Grou p 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 an d analysis.

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

- 1) will be

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

**•** Colorless, electronic

- grade, non

- nitrile gloves;

**•** Silicone tubing with “Y” s plitter;

**•** 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. In addition to the specific instances noted in the steps below, the samplers will change gloves any time that the sampler has reason to believe his/her gloves have

become contaminated. 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 co ntain the double

- bagged sample bottles, precleaned tubing, blank water, and cleanbox

. Depending on the condition of the sample tap, samplers may need to wipe the tap with a clean paper towel to remove any buildup on the tap that could potentially fall in t he 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 sur face.

1 For the sample collection, the samples will be split with the plant (or the plant’s representative) and, therefore, the sample set

- up descri bes equipment needed for split samples. However, EPA is not responsible for the collection of the split samples collected by the plant and, therefore, the collection of the plant’s samples is not described in this plan.3

- 5 3. “Dirty hands” opens the outer bag of the cleanbox and “clean hands” opens the inner bag

. “Clean hands” places the cleanbox at the point of sample collection and secures it open with the clips located inside the box.

4. “Dirty hands” opens the outer ba g containing a length of precleaned silicone tubing

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

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

5. “Dirty hands” opens the outer bag of the funnel and “cle an 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 blank sample bottles

. “Clean hands” opens the inner bag for the

field b lank water, unscrews the lid and places it in the inner bag

. “Clean hands” passes the funnel end of the tubing with a plastic bag shrouding the funnel to another “clean hands” person to hold outside the cleanbox

. “Clean hands” removes the inner bag for the total mercury field blank sample bottle and places it

in the cleanbox

. “Clean hands” holds the end of the silicone tubing outside the cleanbox over a bucket, with the plastic bag still covering the end of the tubing

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

. After the tubing has been purged with sufficient volume, “clean hands” places the silicone tubing back in the cleanbox

. Working inside the cleanbox, “clean hands” unscrews the lid of the field blank sample bottle, removes the tubing from the plastic bag, and prepares to fill the field blank sample bottle

. “Dirty hands” pours field blank water into the funnel and tubing, and “clean hands” fills the total

mercury field blank sample bottle

. “Clean hands” places the end of the sil icone tubing into the plastic bag, replaces the lid on the sample bottle, and closes the inner bag

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

. “Dirty hands” closes the outer bag

. The samplers repeat this procedure

fo r 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 the end of the silicone tubing at the mouth of the 10

- L container and re moves the lid. “Dirty hands” pours field blank water through the funnel and tubing, and “clean hands”

fills the 10

- L container with enough field blank water to collect the dissolved metals field blank samples. “Clean hands” places the lid back on the 10

- L container, places the plastic bag over the end of the silicone tubing, and places the tubing in the cleanbox. “Clean hands” screws the lid on the 10

- L container and closes the inner bag. “Dirty hands” closes the outer bag of the 10

- L container.

2 ERG will collect field blank sampl es at the influent to the FGD wastewater treatment system on Day 1 of the sampling episode. Because ERG will collect the dissolved mercury sample using the same techni que as the total mercury sample and will send the sample to the laboratory where it will be filtered to yield the dissolved fraction, the laboratory will be responsible for analyzing a filter blank sample to assess any mercury contamination from the filtering performed at the laboratory. Ther efore, ERG does not need to collect a separate disso lved mercury field blank sample in the field.3

- 6 8. After col lecting 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. “Clean hands” holds the opposite end of the silicone tubing outside the cl eanbox over a bucket, with the plastic bag covering the end of the tubing

. “Dirty hands” opens the valve to the sample tap to purge the piping for a minimum of 2 minutes

. “Clean hands” places the end of the silicone tubing back in the cleanbox.

10. “Dirty han ds” opens the outer bag for the total mercury sample bottle

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

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

. “Clean hands” removes the plastic bag from the tubing and fills the sample bottle

. “Clean hands” places the tubing back in the plastic bag, replaces the lid on the sample bottle and closes the inner bag

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

. “Dirty hands” closes the oute r bag

. The samplers repeat this procedure

for the d issolved mercury and total metals samples.

11. “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

sil icone 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 analyzed for dissolved

metals and hexavalent chromium, which is required to be filtered for these analyses. The samplers will allow the solids to settle for one hour while collecting the remaining samples

. “Clean hands” places the lid back on the 10

- L container, places the plastic bag over the end o f the silicone tubing , and places the tubing

into the cleanbox. ”Clean hands” screws the lid on the 10

- L container and closes the inner bag. “Dirty hands” closes the outer bag of the 10

- Liter container. Both samplers change their gloves.

12. “Dirty hands” p l a ces an ERG label on the outer bags of the sample bottles.

13. “Clean hands” holds the tubing outside the cleanbox over a bucket and removes the plastic bag covering the end of the tubing. “Dirty hands” opens the lid of a 1

- L plastic container for field measu rements and holds the bottle above the bucket while “clean hands” fills the bottle with sample from the tubing. T he samplers will give the container to another sampling team member to measure the temperature and pH

.

14. “Dirty hands” opens the lid of the BOD 5 sample container and holds the bottle above the bucket while “clean hands” fills the bottle with sample from the tubing. The samplers repeat this procedure for the Group I, Group II , and total cyanide samples.3

- 7 15. Immediately after all samples have been c ollected, t he samplers test the total cyanide samples for sulfides and oxidants and preserve the samples according to the preservation protocols outlined in Section s 3.4 and 3.5

.

Dissolved Metals Sample Collection

16. Samplers allow the 10

- L sample container to settle for approximately one hour following sample collect ion

.

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

- bagged sample bottles within easy access on the covered

surface.

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

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

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

19. “Dirty hands” opens the opening on th e peristaltic pump head so the tubing can be placed in the pump head

. “Dirty hands” opens the outer bag containing a length of precleaned Teflon® tubing attached to a 5

- foot length of precleaned silicone tubing, a “Y” splitter, and two additional pieces of precleaned silicone tubing

. “Clean hands” moves the tubing into the cleanbox, opens the inner bag

, and removes the tubing

. “Clean hands” places a clean plastic bag over the end s of the

Teflon® and silicone tubing.

20. “Dirty hands” threads the silicone tubin g into the peristaltic pump head.

21. Both samplers change gloves.

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

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

. “Clean hands” attaches the capsule filter to the silicone tubing just before the “Y” splitter.

23. “Dirty hands” opens the outer bag of the 10

- L container that was used to collect the field blank water for the dissolved metals fractions. “Clean hands” opens the inner bag of the 10

- L container. “Clean hands” removes the Teflon® tubing from the cleanbox, opens the lid of the 10

- L plastic container, removes the plastic bag from the Teflon® tubing, and places the Teflon® into the 10

- L container. “Dirty hands” opens the dissolved metals field blank sample bottle

. “Clean hands”

remove s the dissolved metals field blank sample bottle and places it in the

cleanbox

. “Clean hands” holds the end of the silicone tubing outside the cleanbox over a bucket, with the plastic bag still covering the end of the tubing and “dirty hands” operates the pump to pump about 750 mL of blank water from the field

blank water bottle

. “Clean hands” places the end of the silicone tubing in the cleanbox, opens the inner bag of the dissolved metals field blank sample bottle,

and removes the lid

. “Dirty hands” opera tes the pump to collect the dissolved metals field blank sample and then stops the pump . The samplers repeat the3

- 8 procedure for the dissolved metals and hexavalent chromium field blank samples. If a new filter is needed, “clean hands” removes the used filte r and samplers follow step 2 1 to replace the filter 3

.

24. Both samplers change gloves.

25. “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 cont ainer

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

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

and then stops the pump.

26. “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 di ssolved metals sample and then stops the pump

. “Clean hands” closes the lid on the sample bottle and closes the inner bag. “Clean hands” places the inner bag and bottle in the outer bag and “dirty hands” closes the outer bag

. The samplers repeat this proce dure for the di ssolved metals and hexavalent

chromium samples

.

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

EPA and ERG plan to collect samples at the i nfluent to the FGD w astewater t reatment

s ystem (SP

- 1) on four consecut ive 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 in the

wastewater treatment building on the discharge side of the polishing filters. Keystone has a sample tap located on the wastewater piping downstream of the polishing filters

. The sample tap located downstream of the polishing filters currently has a large diameter t ubing; for the sample collection, the plant will need to install a three

- way splitter with 3/8 inch hose barbs on each splitter. Keystone has agreed to install a three

- way splitter on the sample tap that will have three separate taps to collect samples fro m 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 b e programmed to collect individual sample volumes into two large containers (e. g. , two 20

- liter HPDE containers). ERG will collect 20

- liters of sample volume for the metals compositor and 20 liters of sample for the classicals compositor, which will provid e sufficient sample volume to collect all EPA samples as well as

3 ERG will collect field blank samples at the influent to the FGD wastewater treatment system only during Day 1 of the sampling episode.3

- 9 plant split sample s and 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.

F ollowing the composite period, ERG will pump off the specific sample volumes into the individual sample containers.

ERG will use one automatic compositor to collect sample volume for the metals analyses (excluding mercury) and another automatic composit or 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 samples every six hours durin g each compositing period. ERG will also collect one grab sample for cyanide during each compositing period.

ERG plans to collect split samples with Keystone (or its representative), where possible; therefore, when pump ing off the composite samples, a “Y ” splitter will be used with two pieces of silicone tubing attached to the “Y” splitter to allow ERG and Keystone (or its representative)

to collect samples simultaneously. I f problems occur during the collection of split samples (e.g., the splitters becom e 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 Keystone ( or its representative ).

ERG will collect the total and dissolved mercury gr ab samples by shrouding one of the three taps on the three

- way splitter (the other two taps are used for the two compositors) and 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 Keystone (or its representative); therefore, duplicate samples will be collected.

For all analytes, ERG will collect laboratory QC aliquots at the effluent from the FGD

wastewater treatment system (SP

- 2 ) on Day 3 of the sampl ing episode . In addition, for all analytes, ERG will collect a field duplicate sample of the effluent from FGD wastewater

treatment system (SP

- 3 ) on Day 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;

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

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

**•** Sample containers.3

- 10 All metals sampling equipment will be specially cleaned according to t he procedures

described in EPA Method 1669. The supplier of the cleaned bottles, tubing, and composite containers will prepare and analyze bottle blanks and equipment blanks to evaluate possible

contamination. ERG will follow protocols described in EPA Met hod 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. In addition to the specific instances noted in the steps below, the samplers will change gloves any time that the sampler has reason to believe his/her gloves have become contaminated. This section describes the set up of the sample point and

collection of th e 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 contain the double

- bagged composite containers, precleaned

tubi ng , 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 composite containers within easy access on the covered surface.

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

collection. “Clean hands” opens the cleanbox and secures it open with the clips

located inside the box.

4. “Dirty hands” opens up the peristaltic pump portion of the automatic compositor so the tubing can be added. “Dirty hands” opens the outer bag containing a length

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

. “Clean hands” takes the inner bag containing the tubing and moves it into

the cleanbox. “Clean hands” opens the inner bag and removes the tubing. “Clean hands” places a clean plastic bag over each end of the silicone tubing. The tubing configuration will be set up such that one end will be connected to the sample tap, one end will be threaded through the automatic compositor and connected to the large composite container, and one end will be placed next to a sump/drain near the sampling point. To collect t he 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. Additiona lly, 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 responsible for the collection of the split samples collected by the plant and therefore, the collection of the plant’s samples is not described.3

- 11 5. “Dirty hands” threads one portion of the silicone tubing through the peristaltic pump portion of the automatic compositor.

6. Both samplers change gloves.

7. “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 water, unscrews the lid

, and places it in the inner bag. “Clean hands” then places

one end of the silicone tubing into the blank water. “Clean hands” also opens the inner bag for the field blank composite container and loosens the lid. “Clean hands” holds the silicone tubing with the plastic bag covering the end out o f 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 silicone tubing at the mouth of the field blank composite containe r and fills the composite container with sufficient volume to the collect the total and dissolved metals field blank samples at the pump

- off

location. “Dirty hands” stops the pump. During the purging of the tubing and collection of the field blank sample v olume, “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 with blank water during the pumping process. “Clean hands” places the plastic bag over the end of the silicone tubing, replaces the lid on the field blank composite container, places the silicone tubing back in the cleanbox, and closes the inner bag of the field blank composite container. “ Dirty hands” closes the outer bag of the field blank composite container 5

.

8. Both samplers work together to move the sampling tubing, automatic compositor, and composite containers into position for the sample collection. Samplers will ensure that the tubing will stay in place during t he 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 the end of the tubing. “Dirty hands” places the end of the sili cone tubing near the sump/drain and opens the sample tap valve to allow the wastewater to flow through the tubing. “Dirty hands” operates the pump to purge the pump portion of the tubing for a minimum of 2 minutes.

11. “Dirty hands” programs the automatic com positor to collect the 20 liters of sample over a 24

- hour time period in one

- hour intervals (i.e., collect 8 3 0 mL of sample every hour)

. “Dirty hands” calibrates the compositor to ensure that approximately 8 3 0 mL is collected for each individual grab.

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

system.3

- 12 12. “Di rty hands” opens the outer bag of the large composite container. “Clean hands” opens the inner bag and connects the silicone tubing to the port on the composite container, securing the connection with a cable tie. “Clean hands” closes the inner bag around the composite bottle, and “dirty hands” closes the outer bag. The samplers put ice around the composite container to keep the samples cold during the compositing time period.

13. Samplers repeat steps 1

- 1 2 to set up the automatic compositor for the classical analy t es (skipping step 7). Samplers will use another composite container.

14. “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 samplers to work in with their hands. “Dirty hands” then opens the outer bag of the mercury field blank water and the total mercury field blank sample bottle. “Clean hands” opens the inner bag for the field blank wa ter 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 tot al mercury field blank sample bottle in the outer bag and “dirty hands” closes the outer bag.

15. “ 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 o pens the outer bag of the total mercury sample bottle. “Clean hands” takes the bottles and positions himself/herself at the tap with the bottle under the shrouding and opens the inner bag. “Dirty hands” opens the sample tap and adjusts the flow.

“Clean han ds” opens the lid of the total mercury sample bottle and places the bottle under the flowing stream to fill the bottle. “Clean hands” then closes the lid on the bottle and closes the inner bag. “Dirty hands” closes the sample tap. “Clean hands” places the bottle in the outer bag and “dirty hands” closes the outer bag. The samplers repeat this procedure to collect the dissolved mercury sample.

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 with Keystone (or its representative), but will be collected as duplicate samples.

16. The samplers will collect total and dissolved mercury grab samples every six hours during the compositing time period.

17. Samplers coll ect a total cyanide grab sample from the same sample tap used for the mercury sample collection

. The samplers will fill the bottle directly from the

tap ; therefore, the cyanide sample will not be collected as a split sample with Keystone (or its representa tive). Immediately after collection, the samplers need to test for sulfides and oxidants and preserve the sample according to the preservation protocols outlined in Section s 3.4 and 3.5

.3

- 13 18. Samplers fill a 1

- L jar for the field measurements. The samplers wil l give the jar to another sampling team member to measure the temperature and pH.

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 u sed 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 bag and detaches th e 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 individu al 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 p ump

- 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

- Of f 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

, precleaned tubing , and

cl eanbox

.

23. Both samplers put on Tyvek® suits and gloves. “Dirty hands” covers work surfaces with HDPE plastic wrap and places the double

- bagged sample bottles

and precleaned tubing within easy access on the covered surface.

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

collection. “Clean hands” opens the cleanbox and secures it open with the clips

located inside the box.

25. “Dirty hands” opens the perista ltic 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 tubin g

. “Clean hands” moves the tubing into3

- 14 the cleanbox and opens the inner bag and removes the tubing. “Clean hands” places a clean plastic bag over the end of the Teflon® and silicone tubing.

26. “Dirty hands” threads the silicone tubing into the peristaltic pu mp 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 l ean hands” opens the inner bag of the field blank composite container. “Clean hands” removes the lid from

the field blank composite container and places the end of the Teflon® tubing in

the blank water. “Clean hands” holds the end of the silicone tubing ou tside 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 the silicone

tubin g 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 bo ttle and closes the inner bag. “Clean hands” places the inner bag and bottle in the outer bag and “dirty hands” closes the outer bag.

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

.

30. “Dirty hands” opens the outer bag of the dissolved me t als field blank sample

bottle. “Clean hands” removes the dissolved metals field blank sample bottle and

p laces 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

water from the fiel d blank composite container

. “Clean hands” places the end of the silicone tubing in the cleanbox, opens the inner bag of the dissolved metals field blank sample bottle, and removes the lid. “Dirty hands” operates the pump to

collect the dissolved metals fi eld blank sample and then stops the pump. “Clean hands” closes the lid on the sample bottle and closes the inner bag. “Clean hands” places the inner bag and bottle in the outer bag and “dirty hands” closes the outer bag. The samplers repeat this procedure for the hexavalent chromium field blank samples 6

6 ERG will collect field blank samples at the influent to the FGD wastewater treatment system on Day 1 of the sampling episode. Because ERG will collect the dissolved mercury sample using the same technique as the total mercury sample and will send the sample to the laboratory where it will be filtered to yield the dissolved fraction, the laboratory will be responsible for analyzing a filter blank sample to assess any mercury contamination from the filtering performed at the laboratory. Therefore, ERG does not need to collect a separate dissolved mercury field blank sample in the field. . “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, just at the beginnin g of each new3

- 15 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 “clean hands” opens th e inner bag. “Clean hands” transfers the Teflon® tubing from the field blank composite container to the metals sample composite container. “Clean hands” holds the end of the silicone tubing outside the cleanbox over a bucket, with the plastic bag still cov ering 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

hands” removes the in ner bag and bottle and places it in the cleanbox. “Clean hands” opens the inner bag and removes the lid. “Dirty hands” operates the pump to collect the dissolved metals sample and then stops the pump. “Clean hands” closes the lid on the sample bottle and c loses 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 Day 2 of the sampling episode, the samplers will coll ect additional sample

volume for the field duplicate samples and during Day 3 of the sampling episode,

t he samplers will collect additional sample volume for the laboratory QC analyses

.

33. “Clean hands” removes the capsule filter from the sample tubing confi guration 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 st ops 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 hands”

opens the inner bag and removes the lid. “Dirty hands” operates the pump to

collect the total metals sample and then stops the pump. “Clean hands” closes the lid on the sample bottle and closes the inner bag. “Clean hands” places the inner bag and bottle in the outer bag and “dirty hands” closes the outer bag. D uring Day

2 of the sampling episode, the samplers will collect additional sample volume for

the field duplicate samples and during Day 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 for the composite container

. “Clean hands” opens the inner bag and transfers the Teflon® tubing from the metals composite container to the composite container for the classical analytes.3

- 16 38. “Clean hands” holds the silicone tubing outside the cleanbox over a bucket and removes 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. “Dirty hands” opens the lid of a 1

- L plastic container for field measurements and

holds the bottle above the bucket while “clean hands” fills the bottle with sample from the tubing. T he samplers will give the container to another sampling team member to measure the temperature and pH

.

40. “Dirty hands” opens the lid of the BOD 5 sample container and holds the bo ttle above the bucket while “clean hands” fills the bottle with sample from the tubing. The samplers repeat this procedure for the Group I, Group II , and total cyanide samples. During Day 2 of the sampling episode, the samplers will collect

additional sam ple volume for the field duplicate samples and during Day 3 of the sampling episode, the samplers will collect additional sample volume for the laboratory QC analyses.

41. Immediately after all samples have been collected, the samplers test the total cyanide samples for sulfides and oxidants and preserve the samples according to the preservation protocols outlined in Section 3.4.

EPA and ERG plan to collect samples at the effluent from the FGD wastewater treatment system (SP

- 2 ) on four consecutive days. The sample collection setup and sampling technique for each day of sampling will be the same.

3.4

All samples will be maintained on ice immediately upon collection (except metals samples that do not require cooling). Because the classical and hexavalent chromium samples are required to be cooled, all composite containers will be maintained on ice. After pumping off the composite samples into the individual sample containers, the classical and hex avalent 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 will be filtered upon receipt at the laboratory. All metals samples, ex cept 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. If the hexavalent chromium samples do not reach the required pH (9.3 to 9.7 S.U.) after 3 mL of ammonium sulfate buffer addition, the samplers will add ammonium hydroxide to achieve the required pH. Samplers will filter samples within 15 minutes

after the compositing period ends (or as soon thereafter as possible). The dis solved samples of

the FGD influent will be filtered approximately one hour after they are collected to allow for solids settling because the samples’ high solids content that would clog the filter.3

- 17 The total cyanide grab samples will be preserved accordi ng to the method

- specific protocols immediately following collection. During a presampling set

- up day , the samplers will test the wastewater at each sampling point for sulfide using lead acetate test strips. If sulfide is present, the samplers will use the procedure identified in Section 3.5 to determine the minimal amount of dilution necessary to reduce sulfide to a nondetectable concentration. After determining this minimal dilution factor for the sampling point, the samplers will dilute all samples colle cted at this sampling point using blank water . After dilution, the samplers will retest the sample for sulfides. If sulfides are still detected, the sample will be diluted further using the same technique as identified in Section 3.5 to ensure that the sam ple is not over

diluted. The samplers will then test the diluted sample for the presence of oxidants (i.e., chlorine) using potassium

- iodide starch paper. If total chlorine is present, the samplers will add sodium

arsenite in small increments until the oxi dants are at nondetectable concentrations in the sample

. The samplers will then carefully adjust the pH to >10 S.U. using sodium hydroxide and place the sample on ice. The preservation, including the amount of dilution, will be reported to the

lab oratory o n the traffic reports.

Table 3

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

- site preservation requirements for each type of analysis. The type and amount of preservation used will be recorded on sample preservation log sheets (Figure 3

- 1). With the exception of total cyanide samples, if 10 percent of the sample volume is added and the required pH is not achieved

, ERG

will discontinue preservation to prevent the sample from being diluted any further and the final pH will be noted it on the tr affic 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

During the 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 reduc e the sulfide concentration to below detection by the lead acetate test strips. To identify the minimal amount of dilution, the samplers

will dilute the sample by a factor of two (1:1) and retest for sulfide. If sulfide is still detected, the samplers will dilute the original sample by a factor of 3 (2:1). They will continue 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 sampling point. The samplers will also test both the original (i.e., nondiluted) and diluted sample for the presence of oxidants (e.g., chlorine) during the presampling set

- up day using potassium

- iodide starch paper. Field Measurements and Engineering Data Collection

T emperature

, pH , sulfide

, and oxidants will be measured and recorded by the sampling crew at each sampling point (SP

- 1 and SP

- 2 )

. The samplers will measure temperature and pH

when the automatic composite samplers are initially set up and every six hours dur ing 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

- liter3

- 18 glass jar with sample and test the wastewater immedi ately after collect ing the aliquot. For sulfide and oxidants, the samplers will fill the cyanide sample bottle directly and test for sulfide and oxidants using test strips immediately after sample collection.

Samplers will follow applicable test kit cal ibration 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 and ERG

will collect flow rate data for each sampled waste stream. The flow rates for all the sampling points will be collected from the plant’s existing flow recorders.

Field sampling log sheets (Figure 3

- 2) will be completed at each sampling point. This sheet will record the sampling methodology , names of the samplers, sample collection time, field measurements, and any notes and observations.

Samplers will also collect e ngineering information with regard to design and operation of the plant. For example, they will collect information such as c oal usage, plant capacity, wastewater flow rates, sludge generation rates (if applicable), and retention times in wastewater treatment process stages. Engineering data collection sheets (Figures 3

- 3, 3

- 4, and 3

- 5) will be completed for the plant. This info rmation 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 label ed 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;

**•** Sampl ing episode number;

**•** Sampling point/description;

**•** Date of sample collection;

**•** Analysis to be performed;

**•** Sample bottle type; and

**•** Required preservation.

If any of the preprinted information is incorrect, it will be revised using indelible ink

. In particular, if a required preservation is not used, it will be marked out (additional preservation details will be noted on the traffic report)

. Once applied to the sample container, labels are covered with clear tape to prevent tampering, abrasion, smearing, or loss during transit

. For metal samples, the samplers will not label the sample bottles, but will label the outer plastic bag of the sample bottle.

3.7

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

, samplers will complete a traffic report for each sample set at each Traffic Reports3

- 19 sampling location

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

. T raffic report forms will be completed f or 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 transmitt ed with the samples to the analytical laboratory.

In addition to the transfer of custody, the traffic report provides information to the analytical laboratory on the sample number, type of water sample (in

- line process, untreated wastewater, treated effl uent), 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 o r instructions to the laboratory, such as whether samples have been filtered on site or how to composite separate samples prior to analysis

. The sampling team will also comment if sample bottles are not completely filled (i.e., less than 75 percent full)

. In addition, the comments section

will be used to note deviations from standard sampling protocols (for example, if a sample could

not be acid

- preserved because of excessive buffering).

3.8

The QA/QC pro gram for sample collection at Keystone will include the following: Quality Assurance/Quality Control

**•** Documentation for samples through laboratory traffic reports;

**•** Collection of field 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 aliquot s for matrix spike/matrix spike duplicate and laboratory duplicate analyses

.

Field d uplicate sample sets will be collected as part of the quality assur ance program for sampling. During Day 2 of the sampling episode, ERG will collect one field duplicate sample (SP

- 3 ) of the effluent from the FGD wastewater treatment system (SP

- 2 ). The field duplicate samples will be collected as separate aliquots in the f ield. Results of the field 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 cle aned metals bottles will prepare and analyze the bottle blanks prior to shipping the equipment to the sampling episode.3

- 20 Field blanks will be used to evaluate possible contamination caused by sampling equipment or by sampling equipment decontamination pro cedures. Field blanks will be prepared in the field prior to sample collection and analyzed for all sampling equipment, other than sample bottles, that come into direct contact with samples (e.g., tubing or filters).

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

of the two sampling points during Day 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 wastewater treatment system will be prepared by gravity

- feeding ASTM Type 1 water through the silicone tubing into the sample bottles. The total metals field blanks (excluding mercury) at the effluent from th e 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 fr om the large composite container through the Teflon® and silicone tubing and into the sample bottles. The total mercury field blank at the effluent from the FGD wastewater treatment system sampling point will be prepared by pouring ASTM Type 1 water direct ly 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 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. 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 laboratory QC analyses. The sampling team will collect, label, and ship the necessary laboratory QC volumes. L aboratory QC volumes (e.g.

, 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

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

- 21 laborat ory QC volumes , the sampling team will collect laboratory QC aliquots from the effluent

from the FGD wastewater treatment system (SP

- 2 ) during Day 3 of the sampling episode

.

3.9

Keystone or it s representative has elect ed to collect split samples at each of the sampling points

. Keystone or its representative will supply all of the personnel, equipment, glassware, and reagents required to collect the split samples and to coordinate the analysis of samples

. For each

of the sampling points , excluding the total and dissolved mercury grab sample at SP

- 2, the sampling crew will attempt to collect split samples with Keystone or its representative as described in this plan ; however, if problems occur (e.g., the splitters become c logged 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 Keystone o r its representative

. For the total and dissolved mercury grab samples at SP

- 2, E RG will not be able to collect split samples with Keystone due to sample configuration issues discussed previously is Section 3.3.2 ;

t herefore, duplicate samples will be collected. Sample Splitting3-22 Table 3

- 1 . Sample Collect ion at Keystone Generating Station

Sampling

Point

Number Sampling Point NameTotal Metals(EPA Method 200.8 withcollision cell)Total Metals(EPA Method 200.7)Dissolved Metals(EPA Method 200.8 withcollision cell)Dissolved Metals(EPA Method 200.7)Total 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 Field 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 fr om 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 14+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), and total phosphorus.3

- 23 Table 3

- 2

. Analytical Methods

Paramet er Method Number Maximum Holding

Time a

Classicals

Biochemical o xygen d emand (BOD 5 ) SM 5210 B 48 hours

Chemical o xygen d emand (COD) EPA 410. 4 28 days

Total s uspended s olids (TSS) SM 2540 D 7 days

Total d issolved s olids (TDS) SM 2540 C 7 days

Sulfat e EPA 300.0 28 days

Chloride EPA 300.0 28 days

Ammonia as n itrogen EPA 350.1 28 days

Nitrate/ n itrate as n itrogen EPA 353.2 28 days

Total Kjeldahl n itrogen (TKN) EPA 351.2 28 days

Total p hosphorus EPA 365. 1 28 days

Total c yanide SM 4500 CN E 14 days

Total and Dissolved Metals

Mercury EPA 1631 E 90 days b

Hexavalent c hromium (dissolved only) EPA 218.6 28 days

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

collision cell 6 months

Aluminum, barium, beryllium, boron, calcium, cobalt, iron, magnesium, manganese, molybdenum, sodium, tin, titanium , and zinc EPA 200.7 6 months

a The holding times are based on the on

- site field preservation identified in Table 3

- 3.

b The dissolved merc ury samples must be filtered in the laboratory within 24 hours after sample collection.

Additionally, the samples must be preserved by the laboratory within 48 hours after sample collection.3

- 24 Table 3

- 3

. Summ ary of Sample Container s and Planned Preservation

Parameter Sample

Container and

Volume Laboratory 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 One 1

- L plastic

bottle ≤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 NaOH to pH >10, dilution until sulfide is not p resent, 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 plastic bottle No additional

volume needed None (acid preserve at laboratory)

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

- mL plast ic 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 isso lved metals (EPA Method 200.7) One 5 0 0

- mL plastic bottle No additional

volume needed 0.45

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

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

- mL glass bo ttle 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, nitrate/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

- )

Oxi dants (i.e., chlorine) P otassium

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

- 26 Sampling Episode

____________

Preservation Chemicals

– List Strength of Solution from Bottle and Lot Number

H 2 SO 4

_____________________ NH 4 SO 4

________________________

NaOH

_____________________

Sample

Number Ana lysis Date Time Name Chemical Initial pH Final pH Number of Drops

Figure 3

- 1

. Sample Preservation Log Sheet3

- 27 Sampling Episode:

________________________________ _

Sampling Point :

________________________________ ___

Sample Numbers :

________________________________ __

Date :

Manual Composite 

## □ Grab 

## □

Automatic Composite 

## □

Time of Grab Sample Collection:

Start Time 

## □ AM 

## □ PM

End Time 

## □ AM 

## □ PM

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 generating units and FGD systems operating at the plant based on all four days of t he sampling episode. Note any changes in operation that occur during the four

- day period. Provide actual data if possible. If actu al 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 rea sonably 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 E SP, or BH)

a The electricity production 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 mo nth (e.g., turned off SCRs on October 1 or burned 5 percent petroleum coke previous week);

Figure 3

- 3

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

- 29 Plant Name:

________________________________ ________________________________ _______________ Plant Contact:

________________________________ ________________________________ ______________ Dates of Sample Collection:

________________________________ ________________________________ ___ Data Collected by:

________________________________ ________________________________ __________

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

Coal Infor mation

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 S crubber Slurry

Blowdown Flow Rate Scrubber

S lurry

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 trea tment system for each day of the sampling episode and the 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 specific information. Some of the data requested may not be susceptible to estimation. Enter “URE” for “unable to reasonably estimate.” Otherwise, specify whether data provided are actual or estimated by wr iting in “ACT” or EST” wherever appropriate.

FGD Wastewater Treatment System Operation Information

Day of Sampling Scrubber Purge Chemical Usage (specify units)

Flow Rate

(gpm) Duration Lime Ferric

Chloride Organo

- sulfide

_________ (specify product ) Po lymer:

_________ (specify product ) Acid:

_________ (specify product )

1

2

3

4

Volume of equalization tank:

________________ Volume of reaction tanks: 1)

________________ 2)

________________ 3)

________________ Volu me 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 organiz ation, sampling preparation, and sampling activities.

4.1

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

one EPA representative

. The crew chief will be responsible for all health and safety, sampl e collection, preservation, and shipping activities while at Keystone

. 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 r eport will be forwarded to Keystone for review. Sampling Team Organization

4.2

On February 1, 2010 , ERG and EPA conducted a site visit at Keystone

. The site visit and subsequent follow

- up telephone calls to Keystone representatives provided ERG and EPA the

nece ssary information to prepare 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 Keystone , the ERG crew chief

will distribute this s ampling p lan to each team member and ensure they are com pletely familiar with the sampling plan and the health and safety requirements specific to Keystone

. The crew chief will also give copies of this sampling plan to Keystone personnel before sampling begins

.

The ERG crew chief will also coordinate the pro curement and shipment of all necessary sampling and health and safety equipment

.

4.3

Upon arrival at Keystone , the ERG crew chief , in conjunction with the EPA representative

, will meet with Keystone personnel to determine whether samples can be collected as planned at each of the planned sampling points

. Upon confirming the methods to collect samples, the ERG crew chief will update the descriptions of the proposed sampling points, if necessary, in consultation with EPA and Keystone personnel

. The changes to the sampling point collection techniques will be described in the trip report prepared by ERG after the sampling episode, described in Section 4.1. If necessary, the crew chief will obtain additional equipmen t

. 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 and safety procedures.

Prior to sampling, the ERG crew chief will notify the ERG Health and Safety Coordinator (HS C) of any revised sampling activity descriptions along with recommended4

- 2 revisions to the proposed health and safety procedures

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

. The crew chief will incorporate any plan t

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

All sample bottles will be labeled, 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 Traffic Report forms will be completed and placed in plastic sleeves inside the coolers

. The coolers will then be

taken to the nearest Federal Express office and shipped to the analytical laboratories

. At the conclusion of the sampling episode, the sampling equipment will be prepared for return shipping.

4.4

This sub sect i on summarizes Keystone co ntacts, analytical laboratory contacts and addresses, and sampling team personnel and support functions. Logistics

4.4.1 Keystone Generating Station Contacts

Sara Marie Baldi RRI Energy 121 Champion Way Suite 200 Canonsburg, PA 15317 (724) 597

- 8633

Mark J Jacklin Keyst one Power Plant 313 Keystone Dr. Shelocta, PA 15774 (724) 354

- 5475

4.4.2 EPA Contacts

Ron Jordan Engineering and Analysis Division

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

. 20460 (202) 566

- 1003

J ezebele Alicea

E ngineering and Analysis Division U.S. Environmental Protection Agency 1200 Pennsylvania Avenue, NW (4303T) Washington, D.C

. 20460 (202) 566

- 1 7554

- 3 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 E RG Contacts

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

- 1698

Jess Wolford (Crew Chief) Eastern Research Group, Inc. 14555 Avion Parkway, Suite 200 Chantilly, VA 20151 (703) 6 33

- 1681

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

- 1669

4.4.5 Freight Forwarders

Federal Express (FedEx) General Information (800) 463

- 3339

FedEx Express Ship Center ( 26 miles from plant)

5 Commerce Dr Plum, PA 15239

H ours of Operation: Mon.

– Fri.: 8:30 a.m. to 7:30 p.m. Last E xpress Drop

- off: Mon.

– Fri.: 7:30 p.m.4

- 4 FedEx Office Print & Ship Center ( 26 miles from plant) 5109 Rte 30, Suite E Greensburg, PA 15601 (724) 8 53

- 7072 Hours of Operation: Mon.

– Fri.: 7:30 a.m. to 9:00 p.m. Last E xpress Drop

- off: Mon.

– Fri.: 6:0 0 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 form s

. Custody will be maintained by the sampling crew chief from sample collection until samples are delivered to Federal Express.

All samples will be packaged and shipped in accordance with U.S. Department of Transportation ( DOT ) or International Air Trans port 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 o uter packaging during normal conditions of transport

. Cushioning material must not react dangerously with the contents of the inner packaging

. Any leakage of the contents must not substantially impair the protective properties of the cushioning

material

. U nless otherwise provided in this paragraph or in the Packing Instructions, liquids in Classes, 3, 4, 5, 6, or 8 of Packing Groups I or II in glass or earthenware inner packaging, must be packaged using material capable of absorbing the liquid

. Absorbent ma terial must not react dangerously 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 permane nt distortion of the receptacle will occur as a result of an expansion of the liquid caused by temperatures likely to prevail during transport

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

55 ° C (130 ° F).” (IATA Dangerous Goods Regulatio ns, 5.0.12).

The packing and labeling procedures in the following subsections may be used for nonhazardous samples

. Hazardous samples will be identified based on consultation with the

hazardous shipments contact, Steve Strackbein (ERG), and appropriate h azardous shipping procedures will be followed

. Based on process considerations, samples collected at Keystone will not be classified as IATA dangerous goods.

5.1

Samples will be collected as a series of “fractions ,” or bottles designated for particular analyses requiring the same preservation

. The comprehensive water sample set will consist of sample fractions for all pollutants listed in Section 3.2, collected as grab samples directly into the individual sample co ntainers or composite samples that are transferred 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 each sample bottle

. If a required preservation is not used, cross it off with

indelible ink

. Cover the label with clear tape to protect this information

. Do not

label m etal sample bottles , but the outer plastic b ag 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 contam ination into the sample

. Clean the sample bottle 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 coo l.

4. When each sample requiring ≤6 ° C preservation has reached the desired temperature, wrap each glass sample bottle with two layers of “bubble wrap” (or place bottle in two “bubble bags”)

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

. Enclose e ach “bubble

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

.

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

6. Place sample bottles in garbage bags in the cooler with proper end up, close the

in terior garbage bag by tying or with a twist

- tie.

7. Add ice to cooler to keep samples cold during shipment

. Arrange blue ice or sealed plastic freez er 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 with a twist

tie.

8. Fill in around the bottles and any fre e 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 inside of the cooler lid.

11. Close cooler.

12. Make several wraps with tape around the cooler perpendicular to the seal to ensure that the lid will remain closed if the latch is accidentally released or damaged.5

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

14. Place a completed address label on the lid of the cooler including name, address, and telephone number of the receiving laboratory and the return address and telephone number of the shipper.6

- 1 6. S ITE

- S PECIFIC H EALTH AND S AFET Y P ROCEDURES

This section specifies the health and safety procedures and practices to be used by the sampling team during sampling at Keystone . This section provides general health and safety information for this sampling episode. The sampling team is obl igated 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

Keystone has first aid ki ts available throughout the plant. In addition, ERG will also bring a first aid kit. In case of an emergency, EPA/ERG will immediately call the control room for safety response. The plant does have a first responder team; however, they are only available

d uring day shift hours. EPA/ERG will have access to the first responders if the first responders

are on site.

6.1.2 Site Evacuation/Emergency Response Plan

The sampling team will be informed of the Keystone evacuation procedures and routes by plant personnel

.

6.1.3 Emergency Showers and Eye Washes

Emergency showers and eye wash stations are located throughout the plant

. Before collecting samples at any point, sampling team members will locate the nearest operating safety shower and eye wash station.

6.1.4 Local Hospita l

The nearest hospital is Indiana Regional Medical Center: Safety and Security

, located in Home, PA , and is approximately 14 miles from Keystone Power Plant

. The hospital address is:

Indiana Regional Medical Center: Safety and Security

1221 Potts Road

Ho me, PA 15747

The local emergency phone number in Shelocta, PA is 911.

6.2

The ERG Work Assignment Manager (WAM), crew chief, and sampling team members have different responsibilities to maintain a safe s ampling 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 regul ations and corporate guidelines, that proper health and safety procedures have been initiated, and that all ERG activities are conducted in accordance with the health and safety plan

. The ERG WAM will also ensure that proper resources are allocated so that the project is conducted in a safe manner, and that the crew chief is competent in his ability to oversee health and safety during the sampling episode.

6.2.2 Crew Chief

The ERG crew chief, Jess Wolford , is responsible for ensuring that ERG sampling team

memb ers 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 Coo rdinator (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 and review sample collection procedures with the Keystone personnel to ensure that all potential

hazar ds 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 facility

- specific requirements

. Changes to this plan or the sampling plan can be made if the crew chief

, the Chant illy HSC , and EPA representative agree that the changes are appropriate.

6.2.3 Sampling Team Members

All field personnel are responsible for following the requirements of this plan, adhering to plant

- specific health and safety procedures, and donning required/ recommended personal protective equipment (PPE). They are also responsible for bringing health and safety issues to

the attention of the crew chiefs.

6.3

ERG sampling t e am personnel will attend on

- and off

- site health and safety briefings. Briefings

6.3.1 Off

- Sit e 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 require d 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 participating in field sampling activities.6

- 3 6.3.2 On

- Site Briefings

ERG samplin g team personnel must attend a half

- hour sa fety course given by Keystone personnel prior to conducting sampling activities at Keystone

. This safety course will review plant

- specific 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

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

6.4

ERG personnel will follow g eneral 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 Keystone :

**•** Steel

- toed safety shoes;

**•** Long sleeves (when collecting sa mpl es ) and pants;

**•** Hard hat, where required by Keystone ;

**•** Hearing protection, where needed;

**•** Nitrile or noncolored, electronic grade gloves, when collecting or preserving samples ; and

**•** Safety glasses with side shields or chemical splash goggles, when collectin g or preserving samples

.

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, inclu ding gloves, will be removed, b agged, and left at

the site in a controlled manner.

6.4.2 Safety Practices

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

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

. Each worker will maintain visual contact with at least one other worker at all times

. This buddy system will ensure against an employee becoming injured or contaminated with chemicals

without a c oworker being aware of his or her condition

. Workers should “watch out” for each other while working close to potential chemical and physical hazards

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

. This arrangement will be agreed to an d acknowledged by the employee

.6

- 4 ERG employees will not enter any permit

- required confined 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 re quired;

**•** Staying within designated areas;

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

**•** Keeping long hair in hard hat or tied back;

**•** Not eating in the sampling or staging areas; and

**•** Not smoking in the sampling or staging areas

.

6.5

All sampling team members will be advised of any sampling

- point

- specific safety protocols during the on

- site health and safety briefing

. Table 6

- 1 summarizes all potential sampling

- point

- specific safety hazards as well as the PPE required at each sampling point

. During the day shift, t he sampling team health and safety officer (HSO) for this sampling episode is the crew chief, Jess Wolford (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 Keystone personnel. Sampling

- Point

- Specific Safety Pro cedures

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 S P

- 2 due to the location of the sample tap s

. To prevent splashing, ERG personnel will ensure that the sample tubing is connected securely to the sample tap and will open the sample valve slowly when collecting samples

. Other potential hazards may include

fa lling 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 ma y be a hazard in certain areas of the facility

. The sampling team will use h earing 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 necessa ry by the Keystone personnel or ERG crew chief

.6

- 5 6.5.2 Thermal Hazards

Heat stres s may be a concern during the sampling episode

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

.

Wastewater sampling points are not expected to be too ho t 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 ar e chemicals used to preserve samples

. All sampling team members will be advised of any potential chemical hazards at each sampling point as well as any special PPE recommendations during the formal health and safety briefing

. If the sample tap (i.e., the p oint from which the wastewater flows) is above waist height, a face shield or goggles must be worn during sample collection

. To avoid ingesting chemicals, sampling team members will be required to wash hands thoroughly before eating or drinking

. ERG person nel will not be permitted to enter areas where the facility has determined that respiratory protection equipment is necessary to protect against inhalation hazards

.

6.6

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

. ERG personnel will take precautions to avoid injuries 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 h eat 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®.

**•** H eat cramps that are caused by heavy sweating and inadequate electrolyte replacement

. Many times, cramps may not occur until after work or until the worker is sleeping

. Signs and symptoms include muscle spasms and pain in the hands, feet, and abdomen

.

**•** Tre atment: Gently stretch and massage muscles and replace fluids. Have worker

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

d ehydration

. Signs and symptoms include:

— Pale, cool, moist, clammy skin

— Heavy sweating6

- 6 — Headache and dizziness

— Nausea

— Fainting or fatigue

— Elevated pulse rate (above 150)

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

. Pla ce worker in cool air and seek medical care.

**•** Heat stroke is the most serious form of heat stress

. Temperature regulation fails

and the body temperature rises to critical levels

. Immediate action must be taken to cool the body before serious injury and dea th occur

. Competent medical help

must be obtained

. Signs and symptoms are:

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

— Lack of or reduced perspiration

— Nausea

— Headache, dizziness, and confusion

— Strong, rapid pulse

— Coma

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

6.6.2 H eat Stress Monitoring

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

area

. The individual should not return to work until symptoms are no longer recognizable

. If symptoms appear critical, persist, or get worse, the crew chief will seek immediate medical attention for the employee

. If the individual does resume work, he/she will be monitored for any

increase in heart rate for the remainder of his/her shift

. In addition, the worker will be requested to consume electrolyte fluid or cool water every hour.

The crew chief will visually monitor workers hourly when:

**•** Symptoms of heat stress are reported or observed;

**•** Ambient tempera tures exceed 70 ° F and workers are dressed in impervious clothing; or

**•** Ambient temperatures exceed 90 ° F and workers are dressed in normal clothing.

For sampling on this project , work periods will be considered to be approximately two hours in length , with a 20 minute break after the two hour period

.6

- 7 At ambient temperatures of 87 ° F and above, workers will be monitored for heat stress conditions by measuring the heart rate (HR) by radial (wrist) pulse for 30 seconds after one

minute of rest

. The HR after o ne minute of rest should not exceed 110 beats per minute

. If the

heart beat is higher, the next work period will be shortened by 33 percent , while the length of rest period remains the same

. If the pulse rate is still higher than 110 beats per minute after one minute of rest in the next rest period, the following work cycle will be sho rtened by another 33

percent

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

6.7

First ai d procedures in response to chemical exposures will be conducted in accordance with the appropriate Material Safety Data Sheets ( MSDS ) for the chemical involved

. If an incident occurs and MSDSs are not available for a particular hazardous chemical (e.g., wastewater), the following general first aid procedures will be performed: 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 are a

. The

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

**•** Adhesive bandages;

**•** Antiseptic wipes;

**•** A compress;

**•** An eyewash solution;

**•** Gauze pads;

**•** A cold pack; and

**•** A triangular bandage.

The injuries most likely to be encountered at Keystone are cuts an d 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 a cid (HCl), sodium hydroxide (NaOH), an ammonium sulfate buffer solution (NH 4 SO 4 ) , and/or sodium arsenite (NaAsO 2 ) before shipment to the analytical laboratory

. Nitrile gloves and splash goggles must be worn when handling these corrosive chemicals to preven t chemical burns

. Sample preservation must be performed in a well

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

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

sleeved cotton coveralls or uncoated Tyvek®, safety glasses with side shields or splash goggles, Sample Preservation and Safety Considerations6

- 8 and nitrile gloves). Sodium arsenite is a known carcinogen and toxic so extra care should be taken when handling any solutions containing sodium arsenite.

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

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

. For instance, if acids are added to a wastewater sample containing cyanide or sulfides, dangerous and toxic vapors wil l be emitted

. If the sample reacts violently, notify the crew chief and stop preserving the sample immediately.

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

**•** Don protective clothing (nitrile gloves as a minimum).

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

**•** Use spill control pillows or prepared neutralizers to contain/clean up spill

. Do not

add water to acid.

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

site for di sposal information.

**•** Notify the crew chief of the spill and the procedures used.

At any time, if personnel do not feel comfortable about cleaning up the spilled material or if a large quantity has been spilled, notify site personnel

. The site may have an emergency response team who will respond to the chemical spill.

In the case of fire, notify the site contact

. If the fire can be easily extinguished using a portable fire extinguisher, and personnel have received fire extinguisher training, extinguish the fire using the portable extinguisher.

6.9

All ERG sampling crew personnel have participated in ERG's annual eight

- hour health and safety training program as specified by ERG's Corporate H ealth and Safety Policy. Training and Medical Monitoring Requirements

This training includes:

**•** Toxicology;

**•** Exposure limits;

**•** Chemical, biological, and physical hazards;

**•** Heat and cold stress;

**•** Confined spaces;

**•** PPE;

**•** Decontamination; and

**•** Emergency plans and procedures.

All ERG personnel involved with sa mple collection and preservation are active participants in the Medical Monitoring Program

. Field sampling personnel have received a

baseline medical information review

.6

- 9 6.10

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

. It is important to remember extended work schedules will contribute to poor production and motivation

. All field teams will rotate to ensure that sampling team

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

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 consec utive 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 Numb er Sampling Point Description PPE Required a Potential Physical Hazards b

SP

- 1 Influent to the FGD

Wastewater Treatment System Steel

- toed boots, hard hats,

g loves

, safety glasses , and face shield while connecting and disconnecting tubing from the sample t ap. 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 while connecting and

disconne cting tubing from the sample tap. Splash hazard: Potential for splashing from the sample tap

. Sample tap will be above waist

level.

a

– Splash protection ( face shield) required if sampling port is waist high or above

. Hearing protection (ear plugs)

will b e 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 Analysi s Plan for

Coal

- Fired Steam Electric Power Plants

. (February)

.

2. U.S. EPA. 200 9

. Steam Electric Power 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. DCN

SE00003

.