# S ampling Plan Enel ’s Federico II Power Plant Brindisi

, Italy Sampling Episode 65 7 6

Prepared for:


## U.S. Environmental Protection Agency Engineering and Analysis Division Office of Water 1200 Pennsylvania Avenue, NW Washington, D.C. 20460

Prepared by:


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

March 21

, 20 1 1

EPA Contract No. 68

- C

- 02

- 095 Work Assignment 8

- 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 2.1.1 Units 1 and 2 FGD Scrubber Systems

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

- 2 2.1.2 Units 3 and 4 FGD Scrubber Systems

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

- 3 2.2 FGD Wastewater Treatment System

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

- 3

3. S AMPLING P ROCEDURES

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

- 1 3.1 Sampling Point Selection

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

- 1 3.2 Analyte Selection

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

- 1 3.3 Sample Collection Procedures

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

- 2 3.3.1 Influent to the FGD Wastewater Treatment System (SP

- 1)

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

- 3 3.3.2 Distillate from the Brine Concentrator (SP

- 2)

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

- 5 3.3.3 Condensate from the Crystallizer (SP

- 3)

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

- 11 3.4 Sample Preservation, Shipping, and Analysis

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

- 17 3.5 Field Measurements and Engineering Data Collection

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

- 18 3.6 Sample Labeling

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

- 18 3.7 Traffic Reports

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

- 19 3.8 Quality Assurance/Quality Control

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

- 19

4. S AMPLING A CTIVITIES

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

- 1 4.1 Samp ling 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 Federico II Power Plant

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

- 2 4.4.2 EPA Contacts

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

- 2 4.4.3 Analyt ical Laboratories

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

- 3 4.4.4 ERG Contacts

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

- 3 4.4.5 Freight Forwarders

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

- 3

5. S AMPLE S HIPMENT

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

- 1 5.1 Sample Set Preparation

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

- 1 5.2 Sample Packing

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

- 1

6. S ITE

- S PECIFIC H EALTH AND S AFETY P ROCEDURES

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

- 1 6.1 Emergency/Medical Procedures

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

- 1 6.1.1 First Aid

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

- 1 6.1.2 Site Evacu ation/Emergency Response Plan

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

- 1 6.1.3 Emergency Showers and Eye Washes

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

- 1 6.1.4 Local Hospital

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

- 1TABLE OF CONTENTS (Continued)

Page

ii 6.2 ERG Health and Safety Responsibilities and Authority

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

- 1 6.2.1 Work Assignment Manager

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

- 1 6.2.2 Crew Chief

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

- 2 6.2.3 Sampling Team Members

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

- 2 6.3 Briefings

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

- 2 6.3.1 Off

- Site Briefings

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

- 2 6.3.2 On

- Site Briefings

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

- 3 6.4 Safety Procedures

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

- 3 6.4.1 PPE

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

- 3 6.4.2 Safety Practices

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

- 3 6.4.3 Safe Work Practices

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

- 4 6.5 Sampling

- Point

- Specific Safety Procedures

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

- 4 6.5.1 Physical Hazards

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

- 4 6.5.2 Th ermal Hazards

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

- 4 6.5.3 Chemical Hazards

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

- 5 6.6 Temperature Extremes

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

- 5 6.6.1 Heat Stress

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

- 5 6.6.2 Heat Stress Monitoring

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

- 6 6.7 First Aid

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

- 7 6.8 Sample Preserv ation and Safety Considerations

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

- 7 6.9 Training and Medical Monitoring Requirements

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

- 8 6.10 Shift Work Protocol

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

- 8

7. R EFERENCES

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

- 1iii LIST OF TABLES

Page

3

- 1. Sample Collection at Brindisi Power Plant

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

- 21

3

- 2. Analytical Methods

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

- 22

3

- 3. Summary of Sample Containers and Planned Preservation

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

- 23

3

- 4. Sampling Point Field Measurements

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

- 24

6

- 1. Sample

- Point

- Specific PPE and Potential Hazards

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

- 10

LIST OF FIGURES

Page

2

- 1. Diagram of the Chemical Precipitation and Softening Portion of the FGD Wastewater Treatment System, Brindisi Power Plant

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

- 7

2

- 3. Diagram of the Crystallization Portion of the FGD Wastewater Treatment System, Brindisi Power Plant

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

- 9

3

- 1. Sample Preservation Log Sheet

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

- 25

3

- 2. Field Sampling Log Sheet

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

- 26

3

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

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

- 27

3

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

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

- 28

3

- 5. Engineering Data Collectio n Sheet (Page 3 of 3)

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

- 29

3

- 6. Example Traffic Report

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

- 301

- 1 1. I NTRODUCTION

The Engineering and Analysis Division (EAD) of the U.S. Environmental Protection Agency (EPA) is curr ently 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 Enel Federico II Power Plant ( Brindisi )

, located in Brindisi

, Italy

, provides plant

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

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

- C

- 02

- 095

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

- Fired Steam Electric Power Plants [ 1 ] , is intended to serve as a guide to the ERG field

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

.

1.1

During its recen tly completed detailed study of the steam electric industry, EPA identified metals and certain other constituents present in the wastewater discharges from steam electric power plants in the United States that are contributing the majority of the toxic loadings for the industry. Additionally, EPA determined 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 system discharges at Brindisi

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

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

1.2

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 describes the approach EPA and ERG will use to collect and analyze samples to characterize untreated FGD

sc rubber purge and treated FGD wastewater from a n FGD wastewater treatment system consisting of chemical precipitation followed by mechanical vapor

- compression evaporation . A chemical precipitation system utilizes physical and chemical treatment to remove he avy metals using hydroxide, or a combination of hydroxide and sulfide precipitation. A mechanical vapor

compression evaporation system uses a falling

- film evaporator to produce a concentrated wastewater stream and a reusable distillate stream. The concentrated wastewater stream may be further processed in a crystallizer, in which a solid product is generated along with a reusable conden sate stream. 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 untrea ted FGD scrubber purge wastewater?1

- 2 **•** What are the effluent concentrations for pollutants present in treated FGD wastewater?

**•** What are the pollutant loadings associated with discharges of FGD wastewater following treatment?

ERG conduct ed a one

- day presampli ng site visit at Brindisi on February 14 , 201 1

, and collected t he following information :

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

**•** P rocess

- specific information ;

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

**•** P lant

- specific information to tailor sampling plans ; and

**•** Information on potential sampling points

.

The sampling program will consist of three

- or 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 will 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 operation

.

1.3

EPA expects to select up to eight coal

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

Brindisi was selected by EPA for sampling based on the following site characteristics :

**•** The plant is a coal

- fired power plant ;

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

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

— Settling;

— Equalization,

— Lime , sodium sulfide, and caustic soda addition (pH adjustment/metal hydroxide precipitation)

,1

- 3 — Ferric chloride addition,

— Polyelectrolyte addition,

— Clarification,

— Ferrous chloride and soda ash addition (softening),

— Clarification,

— Evaporation (brine concentrator), and

— Crystallization; and

**•** The plant operates selective c atalytic re duction (S CR) system s on all four u nit s

.2

- 1 2. F ACILITY O VERVIEW
Brindisi operates four steam electric units and each has a coal

- fired boiler. All four units have a capacity of 660 megawatts (MW). Each unit burns a coal with 0.6% sulfur content. The Brindisi plant is located in Cerano

- Tuturano (Brindisi), Italy.

Brindisi retrofitted all four units with wet FGD scrubber systems in the early 1990s to control the sulfur dioxide (SO 2 ) releases from the plant. With the addition of the FGD scrubber system, Brindisi also installed an FGD wastewater treatment system to control the discharges of the wastewater generated during the operation of the FGD scrubbers. In 2008, Brindisi upgraded the FGD wastewater treatment system to include a vapor

- compression evaporation system which allows the plant to operate as a zero liquid discharge plant. The FGD scrubber systems are discussed further in Section 2.1 and the FGD wastewater treatment syste m is discussed further in Section 2.2.

At the time the FGD scrubber systems were installed, Brindisi also installed selective catalytic reduction (SCR) systems on all four units to control nitrogen oxide (NO x ) releases from the plant.

Brindisi operates electrostatic precipitators (ESPs) on three of the four units to control particulate releases from the plant. The plant operates a baghouse on the other unit. According to plant personnel, Brindisi is in the process of converting the remaining three ESPs into baghouses. The plant almost exclusively handles the fly ash dry and trucks the ash to mines for use as structural fill; however, the plant does have the capability to sluice the fly ash to ships if the ash will be transported by barge.

Bri ndisi operates a wet bottom ash handling system which sluices the bottom ash to a segregated wastewater treatment basin. The overflow from the bottom ash basin is mixed with the FGD wastewater and treated by the vapor

- compression evaporation system.

2.1

Brindisi operates eight forced oxidation wet FGD scrubber systems (two per unit) to control the emission of SO 2 from the units. Each FGD system consists of both a prescrubber and a main scrubber. Brindisi has two different types of FGD sc rubber systems for the four units. The Unit 1 and 2 FGD systems were manufactured by Bishoff and the Unit 3 and 4 FGD systems were manufactured by MHI (Mitsubishi). According to plant personnel, each of the scrubbers was designed to have the same SO 2 removal efficiency; however, the Bishoff scrubbers are bigger than the Mitsubishi scrubbers and have achieved greater removal efficiencies. FGD S crubber Systems

The prescrubbe r s for each FGD system operate similarly, using a water scrubb er to help remove the additional partic ulates from the flue gas (i.e., carry

- over fly ash from the ESPs) prior to the FGD system. Additionally, t he prescrubbers remove chlorides from the flue gas prior to the main scrubber. Each prescrubber has a continuous blowdown that is fed to the FGD

was tewater treatment system. The Unit 1 and 2 prescrubber blowdown is approximately 60

m 3 /hr (264 gal/min) for the two units combined. The Unit 3 and 4 prescrubber blowdown is approximately 80 m 3 /hr (352 gal/min) for the two units combined.2

- 2 The main scrubbe rs for each unit have some similarities, including the following:

**•** The systems are limestone forced oxidation scrubbers;

**•** The solids concentration in the scrubbers ranges from 18 to 24% solids; and

**•** The chlorides concentration in the scrubbers is approximatel y 5,000 ppm.

However, due to the differences between the Bishoff and Mitsubishi designs, Section 2.1.1 describes the operation of the Bishoff scrubbers (i.e., Units 1 and 2) and Section 2.1.2 describes the operation of the Mitsubishi scrubbers (i.e., Unit s 3 and 4).

2.1.1 Unit s 1 and 2 FGD Scrubber Systems

The Unit s 1 and 2 FGD scr ubber systems were both manufactured by Bishof f and have an identical design. Each unit is equipped with two FGD scrubber systems , with each system receiving approximately 50 percent of the flue gas. The FGD systems use limestone as the sorbent in the system. The limestone slurry is pressurized and sprayed into the scrubber ; the spray droplets absorb the SO 2 , which reacts with the limestone particles and produces calcium sulfite. The spray droplets fall to the reaction tank at the bottom of the scrubber where air is injected and the slurry is mixed to oxidize the calcium sulfite to calcium sulfate (i.e., gypsum).

Brindisi intermittently blows down the gypsum slurry from each FGD syste m to control the solids concentration in the scrubbers. The plant initiates a blow down once the solids reach 24% within the scrubber. The plant continues to blowdown until the solids concentration is reduced to 18% within the scrubber.

The blowdown from each of the Unit s 1 and 2 FGD scrubbers is transferred to the primary hydrocyclones . There is o ne set of hydro cy clones for each FGD system; therefore

, there

are two sets of hydrocyclones for each unit. The underflow from each of the primary hydrocyclones is transferred to vacuum belt fi lters for dewatering. Brindisi washes the gypsum as it is applied to the vacuum belt filters. The vacuum belt filters dry the gypsum byproduct to a moisture content of less than 10 percent. Brindisi sells th e gypsum for use in wallboard manufacturing. The filtrate from the vacuum belt filters is transferred to the Unit s 1 and 2 FGD
sump.

The overflow from the two primary hyrdrocyclones for each unit is combined in a storage tank and then transferred to the s econdary hydrocyclones (one set for each unit). The overflow from the secondary hydrocyclones is transferred to a thickener for settling (each unit has its own thickener). The overflow from the thickener is recycled back to the FGD scrubber systems. The underflow from the thickeners is transferred to the Unit s 1 and 2 FGD sump.

The Unit s 1 and 2 FGD sump also receives rainfall, stormwater runoff from the surrounding area, and other wash waters from the FGD process area. The wastewater that collects in the Unit s 1 and 2 FGD sump is periodically transferred to the FGD wastewater treatment system based on sump level control. Wastewater from the Unit s 1 and 2 FGD sump is typically transferred to the FGD wastewater treatment system at a flow rate of 20 m 3 / hr (88 gal/min) for 15 to 20 minutes every two hours.2

- 3 2.1.2 Unit s 3 and 4 FGD Scrubber Systems

The Unit s 3 and 4 FGD scrubber systems were both manufactured by Mitsubishi and have an identical design. Each unit is equipped with two FGD scrubber systems, with e ach system receiving approximately 50 percent of the flue gas. The FGD systems use limestone as the sorbent in the system. The limestone slurry is pressurized and sprayed into the scrubber ; the spray droplets absorb the SO 2 , which reacts with the limeston e particles and produces calcium sulfite. The spray droplets fall to the reaction tank at the bottom of the scrubber where air is injected and the slurry is mixed to oxidize the calcium sulfite to calcium sulfate (i.e., gypsum).

Brindisi intermittently bl ows down the gypsum slurry from each FGD system to control the solids concentration in the scrubbers. The plant initiates a blow down once the solids reach 24% within the scrubber. The plant continues to blowdown until the solids concentration is reduced to 18% within the scrubber.

The blowdown from each of the Unit s 3 and 4 FGD scrubbers is transferred to the primary hydrocyclones. There is one set of hydrocyclones for each FGD system; therefore, there are two sets of hydrocyclones for each unit. The u nderflow from the primary hydrocyclones is transferred to vacuum belt filters for dewatering. Brindisi washes the gypsum as it is applied to the vacuum belt filters. The vacuum belt filters dry the gypsum byproduct to a moisture content of less than 10 p ercent. Brindisi sells the gypsum for use in wallboard manufacturing. The filtrate from the vacuum belt filters is transferred to the Unit s 3 and 4 FGD sump.

The overflow from each primary hydrocyclone is transferred to an intermediate storage tank and then to a clarifier. Both the overflow and the underflow from the clarifier for each FGD system are transferred to the Unit s 3 and 4 FGD sump , which means that the clarifier is not really acting as a cla rifier but like a holding tank. According to plant personnel, the Unit s 3 and 4 FGD scrubber systems were initially designed with centrifuges, which are a solids separation process that is not as efficient as hyrdrocyclones ; therefore, the clarifiers were needed to achieve additional solids settling. However, when the plant started using the hydrocyclones, the clarifiers were no longer needed.

The Unit s 3 and 4 FGD sump also receives rainfall, stormwater runoff from the surrounding area, and other wash wa ters from the FGD process area. The Unit s 3 and 4 FGD sump is periodically transferred to the FGD wastewater treatment system based on sump level control. Wastewater from the Unit s 3 and 4 FGD sump is typically transferred to the FGD
wastewater treatment system at a flow rate of 100 m 3 /hr (440 gal/min) for 10 to 15 minutes every 30 minutes.

2.2

The FGD wastewater treatment system at Brindisi is designed to receive continuous blowdown flow from the eight prescrubber units and in termittent transfers from the Unit s 1 and 2 FGD sump and the Unit s 3 and 4 FGD sump. FGD Wastewater Treatment System

The FGD wastewater treatment system was originally installed to treat the FGD scrubber purge wastewater to meet the plant’s permit limits prior to discharge. However, in 2008, the plant upgraded the FGD wastewater treatment system to include a softening, evaporation

, and2

- 4 crystallization system which allows the entire plant to achieve zero liquid discharge. The Brindisi FGD wastewater treatment system contains the followin g treatment operations:

**•** Settling;

**•** Equalization,

**•** L ime , sodium sulfide, and caustic soda addition ( pH adjustment /metal hydroxide precipitation),

**•** Ferric chloride addition,

**•** Polyelectrolyte addition,

**•** Clarification,

**•** Ferrous chloride and soda ash addition (softe ning (added in 2008) ),

**•** Clarification,

**•** Evaporation (brine concentrator) (added in 2008) , and

**•** Crystallization (added in 2008)

. Figures 2

- 1 , 2

- 2, and 2

- 3

, 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 diagram of the pretreatment system, which includes the chemical precipitation portion of the system. Figure 2

- 2 pr esents a diagram of the evaporation portion of the wastewater treatment system

. Figure 2

- 3 presents a diagram of the crystallization portion of the wastewater treatment system.

The pres crubber blowdown, the Unit s 1 and 2 FGD sump transfers, and the Unit s 3 and 4 FGD sump transfers are first treated in the settling basin. Brindisi has two settling basins, each with a capacity of 600 m 3 (158,500 gallons). The plant only operates one sett ling basin at a time because while one is operat ing, the other is being dredged and cleaned out.

The overflow from the settling basins is transferred to the FGD wastewater treatment tanks, which consist of two 2,000 m 3 (528,000 gallons) tanks used for equa lization of the wastewater. Brindisi also transfers the overflow from the bottom ash treatment basins to the FGD wastewater treatment tanks.

The FGD wastewater treatment tanks feed the 1 st stage of the neutralization basin, which is a large concrete basin that has three divided compartments/basins. In the 1 st basin, the plant adds lime, sodium sulfide, and caustic soda. Overflow from the 1 st basin feeds the 2 nd basin where ferric chloride is added. The wastewater then flows to the 3 rd basin where a polyelectrolyte is added.

The overflow from the third basin is transferred to the clarifier. The underflow from the clarifier is transferred to filter presses for dewatering. The dewatered solids are sent to a landfill for disposal. The o verflow from the clarifier is sent to the 2 nd stage of the neutralization basin, which has two divided compartments. In the first compartment, the plant adds ferrous chloride and sodium carbonate (soda ash) to the wastewater for softening. The overflow f rom the first compartment is transferred to the second compartment, which is a lamella type clarifier. The solids that settle at the bottom of the lamella clarifier consist of calcium carbonate (limestone) ; these solids are pumped back to the FGD process as make

- up to the FGD limestone preparation. The overflow from the lamella clarifier is transferred to the clearwell

.2

- 5 From the clearwell, the FGD wastewater is either recycled back to the FGD system as make

- up or sent to the softening tank for further tre atment. The original design for the system was for the pretreatment system (i.e., neutralization basins) to treat 280 m 3 /hr and 140 m 3 /hr would be recycled and 140 m 3 /hr would be sent to the softening tank. However, the plant attempts to maximize the amo unt of recycle because the lower the flow to the evaporation system, the less expensive it is to operate the system. Therefore, the plant currently operates the system by recycling 230 m 3 /hr and transferring 50 m 3 /hr to the softening tank.

The wastewater sent to the softening tank is treated with additional sodium carbonate to complete the softening process. The overflow from the softening tanks is then transferred to the evaporation and crystallization system. As described above, the original design for the system was for the softening tank to receive 140 m 3 /hr of wastewater, but only 70 m 3 /hr was supposed to be transferred to the evaporation system, while 70 m 3 /hr was supposed to be recycled back to the FGD system. Because of the reduced flow to the so ftening tanks, the entire 50 m 3 /hr entering the softening tanks is transferred to the evaporation system with no recycle back to the FGD system.

The wastewater from the softening tank is transferred to the evaporator feed tank, where the wastewater is equa lized prior to being fed to the evaporation system. Additionally, the plant adds hydrochloric acid and an anti

- scalant to the wastewater prior to the evaporation system. From the evaporator feed tank, the wastewater is split into two streams and both are sent to heat exchangers to bring the wastewater to its boiling point. The distillate stream from the brine concentrator and the condensate stream from the crystallizer are the streams used to transfer heat to the wastewater. From the heat exchangers, th e wastewaters are recombined and sent to the deaerator, where the noncondensable materials such as carbon dioxide and oxygen are vented to the atmosphere.

From the deaerator, the wastewater enters the sump of the brine concentrator. Brine from the sump is pumped to the top of the brine concentrator and enters the heat transfer tubes. While falling down the heat transfer tubes, part of the solution is vaporized and then compressed and introdu ced to the shell side of the brine concentrator (i.e., the outside of the tubes) , along with additional make

- up steam . The temperature difference between the compressed vapor and the brine solution causes the compressed vapor to transfer heat to the brine solution, which flashes to a vapor. As heat is transferred to the brine, the compressed vapor cools and condenses as distilled
water.

The condensed vapor from the brine concentrator is collected and transferred to a distillate tank. The distillate is the n pumped through one of the feed heat exchangers where it transfers its heat to the incoming wastewater and at the same time cooling the distillate stream. From the heat exchanger, the distillate continues to the second distillate tank where it is combine d with the condensate from the crystallizer.

The concentrated brine slurry from the brine concentrator tubes falls into the sump and is recycled with the feed ( i.e., FGD wastewater ) back to the top of the brine concentrator, while a small amount is continuously withdrawn from the sump and transferred to a set of hydrocyclones. To prevent scaling within the brine concentrator as a result of the gypsum present in the FGD wastewater, the brine concentrator is seeded with calcium sulfate. The calcium salts preferentially precipitate onto the seed crystals instead of the tube surfaces of the brine concentrator. The hydrocyclones recover the calcium sulfate seed crystals in the underflow and recycle the seed to the recirculation stream entering the top of the brine concentrator. The2

- 6 overflow from the hydrocyclones is the concentrate that is transferred to the crystallizer feed tank.

The crystallizer feed tank also receives the filtrate f rom the filter presses that dewater the solids generated in the crystallizer. From the crystallizer feed tan k, the wastewater is combined with the some of the slurry recirculation from the bottom of the crystallizer and then combined with the reheated slu rry recycle and fed into the crystallizer. The crystallizer is operated with a certain level of slurry in the bottom of the system. Within the system, the water is evaporated and exits the top of the crystallizer as steam. Some of the steam is diverted to a thermocompressor where the low

- pressure steam is converted to high pressure steam. This high

pressure steam is transferred to the forced circulation heat exchanger where it transfers its heat to the slurry that is recirculated in the crystallizer, wh ich provides the heat for the water to vaporize in the system. The condensed steam is transferred to one of the feed heat exchangers to heat the FGD wastewater entering the deaerator. The condensate is then combined with the brine concentrator distillate in the distillate tank. The rest of the steam that exits the top of the crystallizer is diverted to a condenser where it is cooled with cooling water and transferred to a condensate tank.

Some of the slurry from the bottom of the crystallizer is transfer red through the forced circulation heat exchanger where it is heated by the high

- pressure steam and fed back to the crystallizer. The heat transferred to the slurry allows the water present in the slurry to evaporate and exit the crystallizer as steam. T he evaporation of the water also concentrates the solids present and allows the solids to crystallize. There is a continuous bleed of the slurry from the crystallizer that is fed to the filter presses where the crystallized solids are dewatered. The filt rate from the filter presses is recycled back to the crystallizer feed tank and the solids are transferred to a mine as fill.2-7 Secondary Hydrocyclone Overflow

FGD Wastewater Treatment

Tank A

Filter Press SP

- 1

Indicates a Sampling Point Clarifier

Solids to Landfill Prescrubber Blowdown Unit 1

Prescrubber Blowdown Unit 2

Prescrubber Blowdown Unit 3

Prescrubber Blowdown Unit 4

Unit 1 & 2 FGD Sump Transfer

Unit 3 & 4 FGD Sump Transfer Settling Basin A

Settling Basin B FGD Wastewater Treatment

Tank B Bottom Ash Treatment Basin Overflow

1 st Basin 2 nd Basin 3 rd Basin

1 st Stage Neutralization Basin Lime
NaOH Sodium Sulfide Ferric Chloride

Polyelectrolyte

1 st Basin Lamella Clarifier

2 nd Stage Neutralization Basin Ferrous Chloride Soda AshClearwell To Softening / Evaporation / Crystallization

FGD System

Make Up

Figure 2

- 1

. Diagram of the C hemical Precipitation and Softening Portion of the FGD Wastewater Treatment System, Brindisi Power Plant2-8 Hydrochloric Acid

Feed / Crystallizer Heat Exchanger Distillate Tank Deaerator Brine Concentrator Compressor Vent to Atmosphere

Brine Solution Brine Recycle

Distillate

Liquid Stream Legend

Gas Stream Softening

Tank From Pretreatment

Clearwell Soda Ash

To Limestone Preparation Evaporator Feed Tank Anti

- Scalant Feed / Distillate Heat Exchanger

Condensate from Crystallizer Make

- up Steam

Concentrate to Crystallizer Feed Tank Distillate

Tank To Plant for

Reuse

Indicates a sampling point SP

- 2

Figure 2

- 2

. Diagram of the Evaporation Portion of the FGD Wastewater Treatment System, Brindisi Power Plant2-9 Concentrate from Brine Concentrator

Liquid Stream Legend

Gas Stream Crystallizer Feed Tank Feed / Distillate Heat Exchanger

Crystallizer Forced

Circulation Heat

Exchanger E

- 29 Crystallizer Thermocompressor Make

- up Steam

Cooling Water

Condenser

Condensate Tank

Solid Stream Solids to Disposal Filter Press

Indicates a sampling point Condensate to Distillate Tank

SP

- 3

Condensate to Distillate Tank

Figure 2

- 3

. Diagram of the Crystallization Portion of the FGD Wastewater Treatment System, Brindisi Power Plant3

- 1 3. S AMPLING P ROCEDURES
This section discusses the planned sampling procedures to be followed during the sampling episode at Brindisi

. 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 following six sampling points for Brindisi ( the three proposed sampling loca tions for the plant’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 System;

**•** SP

- 2 Distillate from the Brine Concentrator ;

**•** SP

- 3 Condensate from th e Crystallizer ;

**•** SP

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

- 1 );

**•** SP

- 5 Field Blank for Distillate from the Brine Concentrator ( same location as SP

2 ); and

**•** SP

- 6 Field Blank for Condensate from the Crystallizer ( same location as SP

- 3 )

.

3.2

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

**•** Classicals:

— 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, and

— Total phosphorus ;3

- 2 **•** Total m etals:

— Aluminum, antimony, arsenic, barium, beryllium, boron, cadmium, calcium, chromium, cobalt, copper, iron, lead, magnesium, manganese, mercury, molybdenum, nickel, selenium, silver, sodium, thallium, tin, titanium, vanadium, and zinc.

The analytes selected for analysis reflect the current understanding of coal

- fired power plant FGD wastewaters, i ncluding contributions from coal, scrubber sorbents, treatment chemicals, and other sources. Table 3

- 1 lists the potential analytes for each sampling point, Table 3

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

- 3 lists the sample container and volume and planned on

- site preservation for each parameter or parameter group.

3.3

To characterize the influent to the FGD wastewater treatment system (SP

- 1 ) , the distillate from the brine concentrator (SP

- 2), and the condensate from the crystallizer (SP

- 3 ) at Brindisi

, the sampling team will use varying methods 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 analyses 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 fracti ons will be collected in the same sample bottle , such as Group I analytes (TSS, TDS, sulfate, and chloride) and Group II analytes (ammonia as nitrogen, COD, nitrate/nitrite as nitrogen, TKN, and total phosphorus).

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

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

Sample containers and bottles w ill be purchased precleaned and certified and will not require rinsing with sample. The sample bottles for the metals analyses will be cleaned according to EPA Method 1669. For this sampling episode, ERG will collect six

- hour composite samples at the disti llate from the brine concentrator and condensate from the crystallizer sampling point s for most analytes; however, mercury will be collected as four grab samples. ERG will collect individual grab samples at the influent to the FGD wastewater treatment syst em sampling point for all analytes

. ERG will collect one sample at the influent to the FGD wastewater treatment system sampling point for two consecutive days. ERG will collect one sample at the distillate from the brine concentrator and condensate from t he crystallizer sampling points for three consecutive days ( mercury will be collected as four grab samples over a six

- hour period each day for both the distillate from the brine concentrator and condensate from the crystallizer sampling points). ERG will follow protocols described in EPA Method 1669 to collect metal sample fractions. All sampling equipment (e.g., tubing) and sample bottles will be cleaned according to3

- 3 the procedures described in EPA Method 1669. Samplers will use “clean hands / dirty hands ” sample collection techniques when collecting metal sample fractions, as described in EPA Method 1669.

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

- water bath and then placed into coolers containing bagged ice throughout sample storage, shipment, and receipt at the analytical laboratories. 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 wastewater treatment system (SP

- 1) will be collected directly from the settling basin at the point where the Un it s 1&2 and Unit s 3&4 sump transfer lines and the prescrubber blowdown lines enter the settling basin. Because the transfers from the sumps

are not continuous, ERG will need to coordinate closely with Brindisi personnel during the sampling episode to dete rmine when grab samples can be collected (i.e., when wastewater from both sumps is being transferred to the FGD wastewater treatment system ). ERG will follow protocols described in EPA Method 1669 to collect metal sample fractions from SP

- 1

.

For all analytes, the samplers will pump the samples directly from the settling basin into the specified containers using a peristaltic pump and tubing. The sampling equipment will consist of the following:

**•** Colorless, electronic

- grade, non

- nitrile gloves;

**•** Teflon® tubing;

**•** Silicone tubing;

**•** PVC piping ;

**•** 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

m etals sampling equipment and to collect metal sample fractions. Two or more ERG samplers ( one designated as “clean hands” and the other as “dirty hands”) will follow the protocols described in the steps below to set up the sampling point, collect the field blank samples, and collect wastewater samples. 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.3

- 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 d o uble

- bagged sample bottles, pre

- cleaned tubing

, and cleanbox

.
2) Both samplers put on Tyvek® suits , g loves , and masks . “Dirty hands” covers work surfaces ( tables and platform ) with HDPE plastic wrap and places the double

- bagged sample bottles and Teflon® tubing 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 secu res it open with the clips located inside the box.

4) “Dirty hands” opens the opening on the peristaltic pump head so the tubing can be placed in the pump head. “Dirty hands” opens the outer bag containing a length of pre

- cleaned Teflon® tubing attached to a 10

- foot length of pre

- cleaned 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 the Teflon® and silicone ends of the tubing
set.

5) “Dirty hands” threads the silicone tubing into the peristaltic pump head

.
6) Both samplers change gloves.

7) “Dirty hands” opens the outer bags of the blank water and total mercury field blank sample bo ttles. “Clean hands” opens the inner bag for the field blank water, unscrews the lid and places it in the inner bag. “Clean hands” then places the Teflon® end of the tubing into the blank water. “Clean hands” removes the total mercury field blank sample bottle and places it in the cleanbox. Working inside the cleanbox, “clean hands” opens in the inner bag and unscrews the lid of the total mercury field blank sample bottle

. “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. “ D irty hands” operates the pump to pump blank
water through the tubing

. After the tubing has been purged with sufficient volume, “clean hands” places the silic one tubing back in the clean box and fills the total mercury field blank sample bottle. “Dirty hands” stops the pump. “Clean hands” places the plastic bag over the end of the silicone tubing, replaces the lid on the sample bottle, and closes the inner bag. “Clean hands” removes the bottle from the cleanbox and places it in the outer bag. “Dirty hands” closes the outer bag. The samplers repeat this procedure for the total metals field blank samples

.
8) After collecting all of the total metals field blank samples, “clean hands” and “d irty hands” work together to place the Teflon® end of the tubing into the settling basin , taking care that the end of the tubing does not touch anything other3

- 5 than the sample water. The samplers will secure the Teflon® tubing to a piece of PVC piping so t he samplers can easily control the position of the tubing in the basin

.
9) Both samplers change 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 and “ d ir ty hands” operates the pump to purge the tubing for a minimum of 2 minutes. After the tubing is purged, “Dirty hands” turns off the pump. “Clean hands” places the end of the silicon e tubing back in the cleanbox.

11) “Dirty hands” opens the outer bag for the total mercury sample bottle s . “Clean hands” removes the inner bag and bottle and places it in the cleanbox. “Clean hands” opens the inner bag and bottle lid. “Dirty hands” operates the pump and “Clean hands” fills the sample bottle. “Dirty hands” stop s the pump. “Clean hands” replaces the lid on the sample bottle and closes the inner bag. “Clean hands” removes the sample bottle from the cleanbox and places it in the outer bag. “Dirty hands” closes the outer bag. The samplers repeat this procedure f or the total metals samples

.
12) “ Dirty hands” places 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 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

.
14) “Dirty hands” opens the lid of the Group I 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 II samples

.
15) Immediately after all samples have been collected, the samplers preserve the samples according to the preservation protocols outlined in Sections 3.4 and 3.5

.

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

s ystem (SP

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

.

3.3.2 Distillate from the Brine Concentrator (SP

- 2 )

The dis tillate from the brine concentrator (SP

- 2 ) will be collected from the sample tap located on the discharge side of the pump that transfers the wastewater from the distillate tank through the heat exchanger and to the other distillate tank. For the sample collection, the plant will need to install a two

- way splitter with 3/8 inch hose barbs on each splitter. Brindisi has3

- 6 agreed to install a two

- way splitter on the sample tap that will have two separate taps to collect samples from the samplin g point. ERG will follow protocols described in EPA Method 1669 to collect metal sample fractions from SP

- 2

.

ERG will collect the distillate from the brine concentrator as manual composite samples collect ed into a large container (e. g. , a 20

- liter HPDE car boy ). ERG will collect a total of 20 liters of sample volume, which will provide sufficient sample volume to collect all EPA samples

, as well as volume for purging tubing and contingencies. ERG will collect five liters of sample every two hours for a six

- h our period to collect the 20 liters of sample. Following the composite period, ERG will pump off the specific sample volumes into the individual sample containers.

ERG will use one 20

- liter carboy to collect sample volume for the metals analyses (excludin g mercury) and all classical analytes (i.e., Group I and Group II). In addition to collecting manual composite samples for the analytes listed above, ERG will collect total
mercury grab samples every two hours during the compositing period.

ERG will collect the total mercury grab samples by shrouding one of the two taps on the
two

- way splitter (the other tap is used for the compositor) and collecting the samples directly from the tap.

For all analytes, ERG will collect laboratory QC aliquot s at the distillate from the brine
concentrator (SP

- 2 ) on Day 2 of the sampling episode

. The sample of the distillate from the brine concentrator (SP

- 2 ) will be collected from a sample tap. The sampling equipment will consist of the following:

**•** Colorless, el ectronic

- grade, non

- nitrile gloves;

**•** Large composite container (i.e., 20

- liter carboy);

**•** Peristaltic pump;

**•** “T” splitter;

**•** Teflon® tubing;

**•** Silicone tubing;

**•** Cleanbox;

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

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

**•** Sample containers.

All metals sampling equipment will be specially cleaned according to the procedures described in EPA Method 1669. The supplier of the cleaned bottles, tubing, and composite containers will prepare and analyze bottle blanks and equipment blanks to evaluate possible contamination. ERG will follow protocols described in EPA Method 1669 to collect metal sample fractions. Two or more ERG samplers (“clean hands” and “dirty hands”) will follow the protocols described in the steps below to set up the sampling point , collect the field blank samples, and collect wastewater samples. 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

.3

- 7 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 b oxes contain the double

- bagged composite containers, precleaned tubing , blank water, and cleanbox

.
2) Both samplers put on Tyvek® suits, masks, and gloves. “Dirty hands” covers work surfaces (ground or table) with HDPE plastic wrap and places the double

bag ged composite container 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 an automatic compositor so the tubing can be added. “Dirty hands” opens the outer bag containing a length of precleaned silicone tub ing , 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 ov er 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 connected to the large composite container, and one end will be placed next to a sump/drain near the sampling point. To collect the manual composite samples, the sample rs will pinch the piece of tubing leading to the large composite container by folding a length of tubing over itself and holding it. The samplers will then open the sample tap , which will allow th e sample to flow to the drain. The samplers will let the tap purge with sample for two minutes and will then pinch the piece of tubing leading to the drain and at the same time unpinch the tubing leading to the compositor. The samplers will allow the

com positor to fill with five liters of sample and will then repinch the tubing leading to the compositor

.
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 of the cleanbox and over a buck et 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 container and fills the composite cont ainer with sufficient volume to3

- 8 collect the total metals field blank samples at the pump

- off location. “Dirty hands” stops the pump. During the purging of the tubing and collection of the field blank sample volume, “dirty hands” pinches t he silicone tubing that will be placed by the sump/drain 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 bla nk 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 1

.
8) “Dirty hands” removed the silicone tubing from the peristaltic pump.

9) Both samplers work together to move the sampling tubing, automatic compositor, and composite container into position for the sample collection. Samplers will ensure that the tubing will stay in place during the six

- hour sample collection period.

10) “Dirty hands” changes gloves.

11) “Clean hands” holds the end of the silicone tubing outside the cleanbox over a bucket, with the plastic bag still covering the end of the tubing. “Dirty hands” places the end of the silicone tubing near the sump/drain and opens the sample tap valve to allow the wastewater to flow through the tubing. “Dirty hands” pinches the tubing leading to the drain which allows the sample to flow through the tubing that will be connected to the compositor. The samplers purge this portion of the tubing for a minimum of 2 minutes.

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

.
13) “Dirty hands” pinches the tubing leading to the composite container and opens the sample tap to allow the wastewater to flo w to the drain for two minutes. “Dirty hands” then unpinches the tubing leading to the composit e container as another “dirty hands” sampler then pinches the tubing leading to the drain. The samplers allow the composite container to fill with approximately five liters of sample and then “Dirty hand” pinches the tubing leading to the composite contai ner while the other “dirty hands” sampler unpinches the tubing leading to the drain.

1 ERG will collect field blank samples for all metals samples at the distillate from the brine concentrator on Day 1 of the sampling episode. Additionally, ERG will collect a total mercury field blank sample during one of the grab samples for each day of sa mple collection at the distillate from the brine concentrator.3

- 9 14) “Dirty hands” zipties the tubing leading to the composite container such that it remains pinched until the next manual composite sample collection.

15) “Dirty hands” closes the sample tap and allows the wastewater to drain out of the sample tubing. “Dirty hands” pinches the tubing leading to the drain.

16) “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 water and the total mercury field blank sample bottle, unscrews the lids, and places each in its inner bag. “Clean hands” pours the field blank water into the field blank sample bottle, closes the lids, and closes the inner bags. “Clean hands” places the total mercury field blank sample bottle in the outer bag and “dirty hands” closes the outer bag.

17) “ Dirty hands” positions a bucket under the sample tap, opens the valve and purges the valve for at least two minute s

. “ Dirty hands” then opens the outer bag of the total mercury sample bottle. “Clean hands” takes the bottles and positions himself/herself at the tap with the bottle under the shrouding and opens the inner bag. “Clean hands” opens the lid of the total mercury sample bottle and places the bottle under the flowing stream to fill the bottle. “Clean hands” then closes the lid on the bottle and closes the inner bag. “Dirty hands” closes the sample tap. “Clean hands” places the bottle in the outer bag and “dirty hands” closes the outer bag.

18) Samplers fill a 1

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

19) The samplers will collect five liters into the large composite c ontainer, total mercury grab samples , and a field test jar every two hours during the six

- hour compositing time period.

20) After the fourth manual composite sample is collected, “dirty hands” opens the outer bag of the composite container. “ C lean hands” open s the inner bag and detaches the used tubing from the composite container and covers the port with a closed lid. The samplers transport the composite container s , including the field blank composite container, to the pump

- off area to pump off the samples in to the specified containers.

After collecting the composite samples

, the sampling team then needs to transfer the sample into the individual sample containers at the pump

- off area

. For this sampling point, ERG will use a sample pump

- off approach to transf er the composite samples to the individual sample bottles

.3

- 10 Sample Pump

- Off Procedures

21) 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 cleanbox

.
22) 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 wit hin easy access on the covered surface.

23) “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 ope n with the clips located inside the box.

24) “Dirty hands” opens the peristaltic pump head so the tubing can be placed in the pump head. “Dirty hands” opens the outer bag con taining a length of precleaned Teflon® tubing connected to a length of precleaned si licone tubing. “Clean hands” moves the tubing into the cleanbox and opens the inner bag and removes the tubing. “Clean hands” places a clean plastic bag over the end of the Teflon® and silicone tubing.

25) “Dirty hands” threads the silicone tubing into the pe ristaltic pump head.

26) Both samplers change gloves.

27) “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 c leanbox. “C lean hands” opens the inner bag of the field blank composite container. “Clean hands” removes the lid from the field blank composite container and places the end of the Teflon® tubing in the blank water. “Clean hands” holds the end of the 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 field blank composite containe r

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

28) “Dirty hands” shakes the large composite container to mix the sample. “Dirty hands” opens the outer bag for the composite container and “clean hands” opens the inner bag. “Clean hands” transfers the Teflon® tubing from the field blank composite container to the metals s ample composite container. “Clean hands”3

- 11 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 one liter of sample through the tu bing and then stops the
pump

.
29) “ 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 D ay 2 of the sampling episode, the samplers will collect additional sample volume for the laboratory QC analyses

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

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

. “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

.
32) “Dirty hands” opens the lid of the Group I sample container and holds the bottle above the bucket while “clean hands” fills the bottle with sample from the tu bing. The samplers repeat this procedure for the Group II samples. During Day 2 of the sampling episode, the samplers will collect additional sample volume for the laboratory QC analyses.

33) Immediately after all samples have been collected, the samplers pr eserve the samples according to the preservation protocols outlined in Section 3.4.

34) EPA and ERG plan to collect samples at the distillate from the brine concentrator (SP

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

3.3.3 Condensate from the Crystallizer (SP

- 3 )

The condensate from the crystallizer (SP

- 3 ) will be collected from the sample tap located on the discharge side of the pump that transfers the wastewater to the distillate tan k. For the sample collection, the plant will need to install a two

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

- way splitter on the sample tap that will have two separate taps to collect samples from the sam pling point. ERG will follow protocols described in EPA Method 1669 to collect metal sample fractions from SP

- 3

.

ERG will collect the condensate from the crystallizer as manual composite samples collect ed into a large container (e. g. , a 20

- liter HPDE carboy ). ERG will collect a total of 203

- 12 liters of sample volume, which will provide sufficient sample volume to collect all EPA samples, as well as volume for purging tubing and contingencies. ERG will collect five liters of sample every two hours for a si x

- hour period to collect the 20 liters of sample. Following the composite period, ERG will pump off the specific sample volumes into the individual sample containers.

ERG will use one 20

- liter carboy to collect sample volume for the metals analyses (exclu ding mercury) and all classical analytes (i.e., Group I and Group II). In addition to collecting manual composite samples for the analytes listed above, ERG will collect total mercury grab samples every two hours during the compositing period.

ERG will co llect the total mercury grab samples by shrouding one of the two taps on the
two

- way splitter (the other tap is used for the compositor) and collecting the samples directly from the tap.

For all analytes, ERG will collect laboratory QC aliquot s at the cond ensate from the crystallizer (SP

- 3 ) on Day 3 of the sampling episode

. The sample of the condensate from the crystallizer (SP

- 3 ) will be collected from a sample tap. The sampling equipment will consist of the following:

**•** Colorless, electronic

- grade, non

- nit rile gloves;

**•** Large composite container (i.e., 20

- liter carboy);

**•** Peristaltic pump;

**•** “T” splitter;

**•** Teflon® tubing;

**•** Silicone tubing;

**•** Cleanbox;

**•** Tyvek® suits (for metals samples);

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

**•** Sample containers.

All metals sampling equipment will be specially cleaned according to the procedures described in EPA Method 1669. The supplier of the cleaned bottles, tubing, and composite containers will prepare and analyze bottle blanks and equipment blanks to evaluate possible contaminati on. ERG will follow protocols described in EPA Method 1669 to collect metal sample fractions. Two or more ERG samplers (“clean hands” and “dirty hands”) will follow the protocols described in the steps below to set up the sampling point, collect the field blank samples, and collect wastewater samples. 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 t he set up of the sample point and collection of the EPA samples

. 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 do uble

- bagged composite containers, precleaned tubing, blank water, and cleanbox.3

- 13 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 container 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 an automatic composito r 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 c leanbox. “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 connected to the large composite container, and one end will be placed next to a sump/drain near the sampling point. To collect the manual composite samples, the samplers will pinch the piece of tubing leading to the large composite container and open the sample tap, which will allow the sample to flow to the drain. The samplers will let the tap purge with sample for two minutes and will then pinch the piece of tubing leading to the drain and at the same time unpinch the tubing leading to the compositor. The samplers will allow the compositor to fill with five liters of sample and will then repinch the tubing leading to the compositor.

5) “Dirty hands” threads one portion of the silicone tubing through the peristaltic pump portion of the automatic composito r.

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. “Cle an hands” then places one end of the silicone tubing into the blank water. “Clean hands” also opens the inner bag for the field blank composite container and loosens the lid. “Clean hands” holds the silicone tubing with the plastic bag covering the end out of the cleanbox and over a bucket and “ 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 contai ner and fills the composite container with sufficient volume to collect the total metals field blank samples at the pump

- off location. “Dirty hands” stops the pump. During the purging of the tubing and collection of the field blank sample volume, “dirty ha nds” pinches the silicone tubing that will be placed by the sump/drain 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, r eplaces the lid on the field blank3

- 14 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 2

.
8) “Dirty hands” removed the silicone tubing from the peristaltic pump.

9) Both samplers work together to move the sampling tubing, automatic compositor, and composite container into position for the sample collection. Samplers will ensure that the tubing will stay in place during the six

- hour sample collection period.

10) “Dirty hands” changes gloves.

11) “Clean hands” holds the end of the silicone tubing outside the cleanbox over a bucket, with the plastic bag still covering the end of the tubing. “Dirty hands” pl aces the end of the silicone tubing near the sump/drain and opens the sample tap valve to allow the wastewater to flow through the tubing. “Dirty hands” pinches the tubing leading to the drain which allows the sample to flow through the tubing that will be connected to the compositor. The samplers purge this portion of the tubing for a minimum of 2 minutes.

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

13) “Dirty hands” pinches the tubing leading to the composite container and opens the sample tap to allow the wastewater to flow to the drain for two minutes. “Dirty hands” then unpinches the tubing leading to the composite container as another “dirty hands” sampler then pinches the tubing leading to the drain. The samplers allow the composite container to fill with approximately five liters of sample and then “Dirty hand” pinches the tub ing leading to the composite container while the other “dirty hands” sampler unpinches the tubing leading to the drain.

14) “Dirty hands” zipties the tubing leading to the composite container such that it remains pinched until the next manual composite sample collection.

15) “Dirty hands” closes the sample tap and allows the wastewater to drain out of the sample tubing. “Dirty hands” pinches the tubing leading to the drain.

2 ERG will collect field blank samples for all metals samples at the condensate from the crystallizer on Day 1 of the sampling episode. Additionally, ERG will collect a total mercury field blan k sample during one of the grab samples for each day of sample collection at the condensate from the crystallizer.3

- 15 16) “Dirty hands” and “clean hands” then work to collect the total mercury field blank sampl e. “Dirty hands” shrouds the sample tap with a clear plastic bag that covers the end of the sample tap and provides enough room for samplers to work in with their hands. “Dirty hands” then opens the outer bag of the mercury field blank water and the total mercury field blank sample bottle. “Clean hands” opens the inner bag for the field blank water and the total mercury field blank sample bottle, unscrews the lids, and places each in its inner bag. “Clean hands” pours the field blank water into the field bl ank sample bottle, closes the lids, and closes the inner bags. “Clean hands” places the total mercury field blank sample bottle in the outer bag and “dirty hands” closes the outer bag.

17) “Dirty hands” positions a bucket under the sample tap, opens the valve and purges the valve for at least two minutes. “Dirty hands” then opens the outer bag of the total mercury sample bottle. “Clean hands” takes the bottles and positions himself/herself a t the tap with the bottle under the shrouding and opens the inner bag. “Clean hands” opens the lid of the total mercury sample bottle and places the bottle under the flowing stream to fill the bottle. “Clean hands” then closes the lid on the bottle and clo ses 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.

18) Samplers fill a 1

- L jar for the field measurements. The samplers will give the jar to another sampling team me mber to measure the temperature and pH.

19) The samplers will collect a manual composite sample (i.e., five liters into the large composite container )

, a total mercury grab sample , and a field test sample every two hours during the six

- hour compositing time p eriod.

20) After the fourth manual composite sample is collected, “dirty hands” opens the outer bag of the composite container. “Clean hands” opens the inner bag and detaches the used tubing from the composite container and covers the port with a closed lid. The samplers transport the composite containers, including the field blank composite container, to the pump

- off area to pump off the samples into the specified containers.

After collecting the composite samples

, the sampling team then needs to transfer th e sample into the individual sample containers at the pump

- off area

. For this sampling point, ERG will use a sample pump

- off approach to transfer the composite samples to the individual sample bottles

. Sample Pump

- Off Procedures

21) 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 sample bottles, precleaned tubing, and cleanbox.3

- 16 22) 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.

23) “Dirty hands” opens the outer bag of the cleanbox and “clean hands” op ens 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.

24) “Dirty hands” opens the peristaltic pump head so the tubing can be p laced 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. “Clean hands” moves the tubing into the cleanbox and opens the inner bag and removes the tubing. “Clean hands” places a clean plastic bag over the end of the Teflon® and silicone tubing.

25) “Dirty hands” threads the silicone tubing into the peristaltic pump head.

26) Both samplers change gloves.

27) “Dirty hands” opens the outer bag of the field blank compos ite container and total

me t als field blank sample bottle. “Clean hands” removes the total metals field blank sample bottle and places it in the cleanbox. “C lean hands” opens the inner bag of the field blank composite container. “Clean hands” removes the li d from the field blank composite container and places the end of the Teflon® tubing in the blank water. “Clean hands” holds the end of the silicone tubing outside the cleanbox over a bucket, with the plastic bag still covering the end of the tubing and “ d i rty 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 tubing in the cleanbox, opens the inner bag of the total metals field blank sample bottle, and removes t he lid. “Dirty hands” operates the pump to collect the total metals field blank sample and then stops the pump. “Clean hands” closes the lid on the sample bottle and closes the inner bag. “Clean hands” places the inner bag and bottle in the outer bag and “ dirty hands” closes the outer bag.

28) “Dirty hands” shakes the large composite container to mix the sample. “Dirty hands” opens the outer bag for the composite container and “clean hands” opens the inner bag. “Clean hands” transfers the Teflon® tubing from t he field blank composite container to the metals sample composite container. “Clean hands” holds the end of the silicone tubing outside the cleanbox over a bucket, with the plastic bag still covering the end of the tubing and “ d irty hands” operates the
pum p to pump about one liter of sample through the tubing and then stops the
pump

.
29) “ 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 inne r bag and removes the lid. “Dirty hands” operates the pump to3

- 17 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 ba g and “dirty hands” closes the outer bag. During Day 3 of the sampling episode, the samplers will collect additional sample volume for the laboratory QC analyses.

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

31) “Clean hands” ho lds the silicone tubing outside the cleanbox over a bucket, with the plastic bag covering the end of the tubing . “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

.
32) “Dirty hands” opens the lid of the Group I 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 II samples. During Day 3 of the sampling episode, the samplers will collect additional sample volume for the laboratory QC analyses.

33) Immediately after all samples have been collected, the samplers preserve the samples according to the preservation protocols outlined in Section 3.4.

EPA and ERG plan to collect samples at the condensate from the crystallizer (SP

- 3 ) on three consecutive d ays. 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 t hat do not require cooling). Because the classical 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 samples will be put in an ice

- water bath; however, the m etals samples, which do not require cooling, will Sample Preservation, Shipping, and Analysis

not

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 pres ervation log sheets ( be placed on ice. The classical grab samples collected at the FGD influent sampling point will also be placed on ice immediately after collection. All metals samples will be acid

- preserved prior to extraction at the laboratory.

Figure 3

- 1 ). I f 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 on the traffic report . The wastewater samples, except metals samples that do not require cooling , will be packed in ice chests with a sufficient qu antity of ice to maintain a temperature of ≤6 **°** C. All samples will be prepared for overnight shipment via Federal Express to laboratories.3

- 18 3.5

Temperature and pH will be measured and recor ded by the sampling crew at each sampling point (SP

- 1

, SP

- 2 , and SP

- 3 )

. For SP

- 1, the samplers will measure the temperature and pH at the time the samples are collected. For SP

- 2 and SP

- 3, t he samplers will measure temperature and pH each time a mercury g rab sample is collected, which is every two hours during the compositing period. T he samplers will fill a 1

- liter plastic bottle with sample and test the wastewater for temperature and pH immediately after collect ing the aliquot. Field Measurements and Engineering Data Collection

Samplers will follow applicable test kit calibration procedures specified by the manufacturer. Table 3

- 4 summarizes the field measurements, the method to be used for the measurement, and the detection range of each field test instrument. In addition, EPA 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 recorder s.
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 col lection time, field measurements, and any notes and observations.

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

- 3, 3

- 4, and 3

- 5) will be completed for the plant. This information will be used to determine if the specific design or operational criteria of the steam electric operations affect the wastewater characteristics.

3.6

Each sample will be coded with a unique sample number and labeled at the time of collection

. Typically , labels are printed prior to arrival in the field, al though they may also be completed by hand

. Each self

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

**•** Sample number;

**•** Sampling 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 samp les, the samplers will not label the sample bottles, but will label the outer plastic bag of the sample bottle.3

- 19 3.7

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

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

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

. T raffic report forms will be completed for all samples sent to all laboratories

. Traffic Reports

Figure 3

- 6 includes an example of a traffic report

. At the time of sample shipment, a copy of the traffic report will be sent to ERG , another copy will be kept by sampling personnel, and two copies will be transmitted with the samples to the analytical laboratory.

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

- line process, untreated wastewater, treated effluent), sample description, whether the sample is preserved, pH of the sample after preservation, type of sample (grab, composite), sample collection date and time, and the analyses requested

. Sam plers will use t he comment section to provide special notes or instructions to the laboratory, such as whether samples have been filtered on site or how to composite separate samples prior to analysis

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

. In addition, the comments section will be used to note deviations from standard sampling protocols (for example, if a sample could not be acid

- preserved because of excessive buffering).

3.8

The QA/QC program for sample collection at Brindisi will include the following: Quality Assurance/Quality Control

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

**•** 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

. Bottle blanks will be used to evaluate possible contamination fr om 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 laborator y . The supplier of the cleaned metals bottles will prepare and analyze the bottle blanks prior to shipping the equipment to the sampling episode.

Field blanks will be used to evaluate possible contamination caused by sampling equipment or by sampling equip ment decontamination procedures. Field blanks will be prepared in the field prior to sample collection and analyzed for all sampling equipment, other than sample bottles, that come into direct contact with samples (e.g., tubing or filters).3

- 20 E RG will prepare field blanks for each of the total metals analyses at each of the t hree sampling points during Day 1 of the sampling episode. Additionally, ERG will collect total mercury field blanks at the distillate from the brine concentrator and condensat e from the crystallizer sampling point s 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 pumping ASTM Type 1 water through the Teflon® and silicone tubing into the sample bottles. The total metals field blanks (excluding mercury) at the distillate from the brine concentrator and condensate from the crystallizer sampling point s will be prepared by pumping ASTM Type 1 water through the composite tubing set into a large composite container where it will be h eld for the six

- hour compositing period, then pumping the ASTM Type 1 water from the large composite container through the Teflon® and silicone tubing and into the sample bottles. The total mercury field blank s at the distillate from the brine concentrator and condensate from the crystallizer sampling point s will be prepared by pouring ASTM Type 1 water directly into the sample bottles. The field blanks will determine if there is any contamination from the sampling equipment, atmospheric contamination

, or o ther contamination from the surroundings.

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

. As part of standard laboratory quality control , matrix effects on analytical performance are assessed through the analysis of matrix spikes and la boratory 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 laboratory QC volumes , the sampling team will collect laboratory QC aliquots from the distillate from t he brine concentrator (SP

- 2 ) during Day 2 of the sampling episode

. The sampling team will also collect laboratory QC aliquots from the condensate from the crystallizer (SP

- 3) during Day 3 of the sampling episode.3-21 Table 3

- 1

. Sample Collection at Brindisi Power Plant

Sampling Point Number Sampling Point NameTotal Metals(EPA Method 200.8 withcollision cell)Total Metals(EPA Method 200.7)Total MercuryGroup IaGroup IIb

SP

- 1 Influent to the FGD Wastewater Treatment System 2 2 2 2 2

SP

- 2 Distillate from the Brine Concentrator 3 +1QC 3 +1QC 3 +1QC 3 +1QC 3 +1QC

SP

- 3 Condensate from the Crystallizer 3 +1QC 3 +1QC 3 +1QC 3 +1QC 3 +1QC

SP

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

SP

- 5 Distillate from the Brine Concentrator Field Blank 1 1 3

SP

- 6 Condensate from the Crystallizer Field Blank 1 1 3 Total Number of Samples 11+ 2 QC 11+ 2 QC 15+2QC 8 + 2 QC 8 + 2 QC

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

- 22 Table 3

- 2

. Analytical Methods

Parameter Method Number Maximum Holding Time a

Classicals
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
Sulfate 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 Metals Mercury EPA 1631 E 90 days b

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 T he mercury samples must be preserved by the laboratory within 48 hours after sample collection.3

- 23 Table 3

- 3

. Summary of Sample Container s and Planned Preservation

Parameter Sample Container and Volume Laboratory QC Sample Container and Volume On

- Site Preservation
Classicals 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

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 plastic bottle No additional volume needed None (acid preserve at laboratory)

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

- mL glass bottle No additional volume needed Influent samples and field blank samples Two 250

- mL glass bottle No additional volume needed

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

- 24 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.3

- 25 Sampling Episode

____________

Preservation Chemicals

– List Strength of Solution from Bottle and Lot Number

H 2 SO 4

_____________________ NH 4 SO 4

________________________

NaOH

_____________________

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

Figure 3

- 1

. Sample Preservation Log Sheet3

- 26 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 Sheet3-27 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 the sampling episode. Note any changes in operation that occur during the four

- day period. Provide actual data if possible. If actual data are not available, provide estimates for the s pecific information. Some of the data requested may not be susceptible to estimation. Enter “URE” for “unable to reasonably e stimate.” Otherwise, specify whether data provided are actual or estimated by writing in “ACT” or EST” wherever appropriate.

Gener ating Unit Operating Characteristics During Sample Collection

Unit ID Boiler Type Capacity (MW) Electricity Production

(MW) (or Percent Capacity % ) a SCR (No, On,

Off) Particulate Control System (HS/CS ESP, or BH)

a The electricity production should be measured on a daily basis from midnight of the 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.) Prescrubber Water Source FGD Make

up Water

Source SO 2 Removal Percentage Type of Solids Separation

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

Figure 3

- 3

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

- 28 Plant Name:

________________________________ ________________________________ _______________ Plant Contact:

________________________________ ________________________________ ______________ Dates of Sample Collection:

________________________________ ________________________________ ___ Data Collected by:

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

Day of Sampling Unit ID Coal Type Amount of Coal Used

During Day of Sampling Source of Coal (Coal

Region and/or State) Percent Su lfur in

Coal Chlorine Content of Coal

1

2

3

Note changes in operation over the past month (e.g., turned off SCRs on October 1 or burned 5% petroleum coke previous week) as well as conditions and changes during the sampling episode:

Scrubber Slurry Information

Day of Sampling FGD System ID Associated Unit IDs Scrubber Slurry Blowdown Flow Rate Scrubber Slurry Percent Solids Time of Dewatering

During Sampling Day Flow Rate

(gpm) Duration

1

2

3

4

Figure 3

- 4

. Engineering Data Collection Sheet (Page 2 of 3)3-29 Plant Name:

________________________________ ________________________________ ________________ Plant Contact:

________________________________ ________________________________ ______________ Dates of Sample Collection:

________________________________ ________________________________ ___ Data Collected by:

________________________________ ________________________________ ___________

Instructions: In the table below, provide information on the FGD wastewater treatment system for each day of the sampling episode and 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 e stimates for the specific information. Some of the data requested may not be susceptible to estimation. Enter “URE” for “unable to reasonably estimate.” Otherwise, specify whether data provided are actual or estimated by writing in “ACT” or EST” wherever

a ppropriate.

FGD Wastewater Treatment System Operation Information

Day of Sampling Chemical Usage ( Quantity added

- specify units)

Lime Caustic Soda Sodium Sulfide Ferric Chloride Polyelectrolyte Ferrous Chloride Soda Ash Hydrochloric Acid Anti

- Scalant
1

2

3

Volume of equalization tank: 1)

________________ 2)

________________ Volume of neutralization basins : 1)

________________ 2)

________________ 3)

________________ 4 Volume of clarifiers: 1)

________________ 2)

________________ )

________________ Volume of softening tanks: 1)

________________ 2)

________________

Figure 3

- 5

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

- 30 Figure 3

- 6

. Example Traffic Report 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 201514

- 1 4. S AMPLING A CTIVITIES
This section discusses the sampling team organization, sampling preparation, a nd sampling activities.

4.1

The sampling crew will consist of a crew chief a nd one crew member from ERG and one EPA representative

. The crew chief will be responsible for all health and safety, sample collection, preservation, and shipping activities while at Brindisi

. Following the sampling episode

, ERG will collate the analytical results from each laboratory and summarize and transmi t
t his information in a trip report to EPA

. After EPA review, the report will be forwarded to Brindisi for review. Sampling Team Organization

4.2

On February 1 4 , 201 1 , ERG conducted a site visit at Brindisi

. The site visit and subsequent follow

- up telephone calls to Brindisi representatives provided ERG and EPA the necessary 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 Brindisi , the ERG crew chief will distribute this s ampling p lan to each team member and ensure they are completely familiar with the sampling plan and the health and safety requirements specific to Brindisi

.

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

.

4.3

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

, will meet with Brindisi personnel to determine whether samples can be collected as plan ned 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 Brindisi personnel

. The changes to the s ampling 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 equipment

. The revised sampling description will include: Field Sampling Activities

**•** A s ampling point description and collection procedure for each sampling point ;

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

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

**•** A list of potential chemical hazards associated with each sampling point ; and

**•** A list of proposed health and safety procedures.

Prior to sampling, the ERG crew chief will notify the ERG Health and Safety Coordinator (HSC) of any revised sampling activity descriptions along with recommended 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 plant

-4

- 2 specific changes indicated by the HSC and receive app roval 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 picked up by FedEx 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 Brindisi contacts, analytical laboratory contacts and addresses, and sampling team personnel and support functions. Logistics

4.4.1 Federico II Power Plant

Claudio Mosti Enel Produzione SpA Via Carlo Bini 2 Florence

, Italy 50134 +39 0555234086

Adolfo De Leo Enel Produzione SpA Centrale termoelettrica Federico II Cerano (Brindisi), Italy, 72100 +39 0831254007

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 Engineering 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 :

414 Pontius Ave. North Seattle, WA 98109 Phone: (206) 957

- 1428 Contact: Patrick Garcia

- Strickland

4.4.4 ERG Contacts

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

- 1698

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

- 1669

4.4.5 Freight Forwarders

Federal Express (FedEx) General Info rmation (800) 463

- 3339 Customer Service (Italy): 199

- 151

- 1195

- 1 5. S AMPLE S HIPMENT
All sample containers will be labeled with ERG's standard address labels

. All samples will be tracked using Traffic Report forms

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

All samples will be packaged and shipped in accordance with U.S. Department of Transportation ( DOT ) or International Air Transport Association ( IATA ) regulations

. The general IATA packaging requirements for air shipment are as follows:

**•** “Inner packaging must be so packed, secured or cushioned as to prevent their breakage or leakage and so as to control their movement within the outer packaging duri ng normal conditions of transport

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

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

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

. Absorbent material must not rea ct 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 permanent distortion of th e receptacle will occur as a result of an expansion of the liquid caused by temperatures likely to prevail during transport

. Liquids must not completely fill a receptacle at a temperature of 55 ° C (130 ° F).” (IATA Dangerous Goods Regulations, 5.0.12).

The p acking 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 hazardous shipping
pr ocedures will be followed

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

5.1

Samples will be collected as a series of “fractions,” or bottles designat ed 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 containers 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 samp le 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 bag for each bottle instead

.
2) Tighten the lid on each filled sample bottle, being careful not to overtighten the lid

. If bottle threads are dirty to where the lid is impeded from closing, clean the threads on the bottle being careful to not introduce contamination int o 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 cool.

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 bottle

. Encl ose 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 interior ga rbage 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 freezer bags filled with wet ice on top of the sample bottles (if samples require ≤6 ° C preservation)

. If using wet ice, place the ice inside two one

gallon sealable freezer bags

. Put at least 4 × 1⁄2 gallons of ice (4 × 2.5 pounds of ice) in each large cooler and 2 × 1⁄2 gallons of ice (2 × 2.5 pounds of ice) in each small cooler

. Use m ore ice when ambient temperatures are very high

. Place t he ice inside the second garbage bag and c lose the second garbage bag with a twist

tie.

8) Fill in around the bottles and any free space with additional cushioning material

. Use s ufficient packing material so that the sample containers will not shift during shipment.

9) Seal the Traffic Report form in a plastic zip

- lock bag and tape it securely to the inside of the cooler lid.

10) Place a "Return to ..." label on the inside of the cooler lid.

11) Close cooler.

12) Make several wraps with tape around the c ooler 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.

15) Attach customs forms to the package, including commercial invoices and packing lists.6

- 1 6. S ITE
- S PECIFIC H EALTH AND S AFETY P ROCEDURES
This section specifies the health and safety procedures and practices to be used by the sampling team during sampling at Brindisi . This section provides general health and safety information for this sampling episode. The sampling team is obliga ted 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

Brindisi has first aid kits available throughout the plant. In addition, ERG will also bring a first aid kit. In case of an emergency, EPA/ERG will immediately call the control room for safety response. Brindisi has first aid responders that are trained in CPR an d emergency response and will respond to an emergency.

6.1.2 Site Evacuation/Emergency Response Plan

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

.

6.1.3 Emergency Showers and Eye Washes

Emergency showers and eye wash stations are located throughout the plant

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

6.1.4 Local Hospital

The nearest hospital is Medicasa Italia

, located in Brin disi, Italy , and is approximately 12 miles from Federico II Power Plant

. The hospital address is:

Medicasa Italia Corso Giuseppe Garibaldi, 53 72100 Brindisi, Italy 0831 529920

6.2

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

. These responsibilities are described below. ERG Health and Safety Responsibilities and Authority

6.2.1 Work Assignment Manager

The ERG WAM, Deborah Bartram, has the overall responsibility t o ensure that these health and safety procedures are developed and implemented in accordance with regulations and6

- 2 corporate guidelines, that proper health and safety procedures have been initiated, and that all ERG activities are conducted in accordance wi th the health and safety plan

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

6.2.2 Crew Chief

The ERG crew chief, TJ Finseth , is responsible for ensuring that ERG sampling team members adhere to this plan

. The ERG cr e w chief is responsible for overseeing all activities. The crew chief must report any accident, near miss, or injury to an y sampling team member to the ERG Chantilly Office Health and Safety Coordinator (HSC), Kevin Sikora, verbally within eight hours, or sooner

. The HSC will investigate the incident to identify the cause of the accident, near miss, or injury

. If sufficient c ause 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 will inspect all sampling points and review sample collection proc edures with the Brindisi personnel to ensure that all potential hazards have been identified.

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

- specific requirements

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

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

6.2.3 Sampling Team Members

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

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

6.3

ERG sampling t e am personnel will attend on

- and off

- site health and safety briefings. Briefings

6.3.1 Off

- Site Briefings

Prior to arriving on site, all members of the sampling team will receive a copy of this sampling plan and attend a presampling meeting to review th e sampling plan and the proposed sample collection activities. All ERG employees will be required to sign a health and safety sign

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

- 3 6.3.2 On

- Site Briefings

ERG samplin g team personnel must attend a half

- hour safety course given by Brindisi personnel prior to conducting sampling activities at Brindisi

. This safety course will review plant

- specific health and safety proced ures, 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 an d procedures that ERG personnel must follow.

6.4

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

6.4.1 PPE

The PPE listed below will be worn by ERG personnel at all tim es while inside the premises of Hatfield’s Ferry :

**•** Steel

- toed safety shoes;

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

**•** Hard hat, where required by Hatfield’s Ferry ;

**•** 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 collecting 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 neces sary

. If gloves become torn or degraded, they will be thrown away and replaced with a new pair

. Disposable PPE, including gloves, will be removed, b agged, and left at the site in a controlled manner.

6.4.2 Safety Practices

ERG personnel wil l 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 tim es

. This buddy system will ensure against an employee becoming injured or contaminated with chemicals without a coworker being aware of his or her condition

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

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

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

.6

- 4 ERG employees will not enter any permit

- required 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 required;

**•** Staying within designated areas;

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

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

**•** Not eating in the samp ling 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

. Sampling

- Point

- Specific Safety Procedures

Table 6

- 1 summarizes all potential sampling

- point

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

. T he sampling team health and safety offic er (HSO) for this sampling episode is the crew chief, TJ Finseth (ERG)

. 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 bri efing

. 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 Brindisi pers onnel.

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

- 2 and SP

- 3 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 collect ing samples

. Other potential hazards may include falling hazards during sample collection, tripping on metal grates, or operation of large trucks and machinery in the vicinity of the sample collection area

. See Table 6

- 1 for potential hazards that may be a ssociated with specific sampling points.

Noise may 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 necessary by the Brindisi personnel or ERG crew chief

.

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

.6

- 5 The w astewa ter at SP

- 2 and SP

- 3 sampling points is expected to be extremely hot; therefore, during collection of the mercury grab samples at these locations, samplers will wear heat

- res istant gloves.

6.5.3 Chemical Hazards

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

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

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

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

. ERG personnel will no t 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 this sampling e pisode

. 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 heat generated b y equipment and/or processes

. Sampling team personnel will monitor each other for the following symptoms:

**•** Heat rash that may result from continuous exposure to heat or humid air

. Treatment: Wear cotton clothing under coveralls or Tyvek®.

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

**•** Treatment: Gently s tretch and massage muscles and replace fluids. Have worker rest in a cool shaded area.

**•** Heat exhaustion that occurs from increased stress on various body organs including inadequate blood circulation due to cardiovascular insufficiency or dehydration. Sign s and symptoms include:

— Pale, cool, moist, clammy skin

— Heavy sweating

— Headache and dizziness

— Nausea

— Fainting or fatigue

— Elevated pulse rate (above 150)6

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

. Place worker in cool air and seek medical care.

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

. Temperature regulation fails and the body temperature rises to critical levels

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

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

6.6.2 Heat Stress Mo nitoring

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 n o longer recognizable

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

. If the individual does resume work, he/she will be monitored for any increase in heart rate for the remainder of his/her shift

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

**•** The crew chief will visually monitor workers hourly when:

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

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

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

For sampling on this project , work periods will be considered to be approximately two hours in length.

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

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

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

. If the pulse rate is still higher than 110 beats per minute after one6

- 7 minute of rest in the next rest period, the following wo rk 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 area

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

**•** Adhesive bandages;

**•** Antiseptic wipes;

**•** A compress;

**•** An eyewash solution;

**•** Gauze pads;

**•** A cold pack; and

**•** A triangular bandage.

The injuries most likely to be encountered at Hatfield’s Ferry are cuts and bruises; the first aid kit will be maintained and stocked accordingly.

6.8

Water samples to be analyzed for various contaminants may be preserved with sulfuric acid (H 2 SO 4 ) before shipment to the analytical laboratory

. Nitrile gloves and splash gogg les must be worn when handling these corrosive chemicals to prevent chemical burns

. Sample preservation must be performed in a well

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

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

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

In some instances, 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 sampl e containing cyanide or sulfides, dangerous and toxic vapors will be emitted

. If the sample reacts violently, notify the crew chief and stop preserving the sample immediately.6

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

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

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

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

. Do not add water to acid.

**•** Place spilled material in a heavy plastic container, label the container, and contact site for disposal information.

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

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

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

In the case of fire, notify the site contact

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

6.9

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

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

This training includes:

**•** Toxicology;

**•** Exposure limits;

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

**•** Heat and cold stress;

**•** Confined spaces;

**•** PPE;

**•** Decontamination; and

**•** Emergency plans and procedures.

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

. Field sampling personnel have received a baseline medical information review

.

6.10

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

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

. All field teams will rotate to ensure that sampling team members receive sufficient rest to avoid injuries resulting from fatigue or inattention. Shift Work Protocol6

- 9 It is common practice to perform 12

- hour work days under project management direction

. If this work schedule is exceeded

, the following gu idelines 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 ti me to and from the hotel.

3) No more than seven consecutive days of work will be allowed without a minimum of 24 hours off.

4) Each work day will be reviewed as a 24

- hour cycle to assure all field workers receive adequate time off.6

- 10 Table 6

- 1

. Sample

- Point

- Specific PPE and Potential Hazards

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

SP

- 1 Influent to the FGD Wastewater Treatment System Steel

- toed boots, hard hats,
g loves

, and safety glasses

. Fall and trip hazard: Potential for falling and tripping because one sampler will need to stand on a catwalk holding the tubing in the settling basin during sample collection

. SP

- 2 Distillate from the Brine Concentrator Steel

- toed boots, hard hats, gloves, safety glasses , and heat

resistant gloves while collecting the mercury grab samples

. Thermal hazard: Potential for burns from the extremely hot temperatures of the samples.

SP

- 3 Condensate from the Crystallizer Steel

- toed boots, hard hats, gloves, safety glasses , and heat

resistant gloves while collecting the mercury grab samples. Thermal hazard: Potential for burns from the extremely hot temperatures of the samples.

a

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

. Hearing protection (ear plugs) will be worn if needed. b

– Additional physical hazards, if any, will be identified during the formal on

- site health and safety briefing

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

- 1 7. R EFERENCES

1. Eastern Research Group, Inc. 20 10

. Generic Sampling and Analysis 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

.