# Site Visit Notes and

Sampling Episode Report

Enel’s Power Plants

Italy

Sampling Episode 657 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

1 March 2012

EPA Contract No. 68

- C

- 02

- 095

Work Assignment 9

- 29i CONTENTS

Page

1. I NTRODUCTION

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

- 1

1.1 Background

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

- 1

1.2 Power Plant Site Selection

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

- 1

1.3 Sampling Episode Overview

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

- 2

2. S ITE V ISITS

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

- 1

2.1 Brindisi Facility Overview

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

- 1

2.1.1 Enel Research and Development

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

- 1

2.1.2 Pilot

- Scale Carbon Capture and Storage System

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

- 2

2.1.3 Ash Handling Procedures

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

- 3

2. 1.4 FGD Scrubber Systems

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

- 3

2.1.5 FGD Wastewater Treatment System

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

- 6

2.2 Torrevaldaliga Nord Facility Overview

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

- 9

2.2.1 Ash Handling Procedures

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

- 10

2. 2.2 FGD Scrubber Systems

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

- 10

2.2.3 FGD Wastewater Treatment System

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

- 11

3. S AMPLE C OLLECTION

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

- 1

3.1 Sampli ng Points, Sample Collection Methods, and Field Measurements

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

- 1

3.1.1 Influent to FGD Wastewater Treatment System

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

- 2

3.1.2 Distillate from the Brine Concentrator (SP

- 2)

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

- 3

3.1.3 Condensate from the Crystallizer

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

- 5

3.2 List of Analytes and Sample Preservation

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

- 7

3.3 Plant Operational Data

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

- 8

3.4 Deviations from the Sampling and Analysis Plan

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

- 8

4. L ABORATORY A NALYTICAL R ESULTS AND D ISCUSSION

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

- 1

5. D ATA Q UALITY

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

- 1

5.1 Analytical Q uality Control

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

- 1

5.2 Field Quality Control

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

- 1

5.2.1 Bottle Blanks

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

- 1

5.2.2 Equipment Blanks

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

- 2

5.2.3 Field Blanks

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

- 2

6. R EFERENCES

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

- 1

Appendix A: A NALYTICAL R ESULTS

Appendix B : D ATA R EVIEW N ARRATIVES

Appendix C : P ICTURES F ROM THE S AMPLING E PISODEii LIST OF TABLES

Page

Table 3

- 1. Sample Collection Information, Brindisi

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

- 10

Table 3

- 2. Sample Collection at Brindisi

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

- 12

Table 3

- 3. Field Measurements, Brindisi

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

- 13

Table 3

- 3. Crosswalk of Sample Number to Sampling Poi nt and Day, Brindisi

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

- 14

Table 3

- 4. Analytical Methods, Brindisi

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

- 15

Table 3

- 5. Summary of Sample Containers and Planned Preservation, Brindisi

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

- 16

Table 3

- 6. Sample Preservation Summary, Brindisi

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

- 17

Table 3

- 7. Generating Unit Operating Characteristics during Sample Collection, Brindisi

..... 3

- 18

Table 3

- 8. FGD Scrubber System Operating Characteristics, Brindisi

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

- 19

Table 3

- 9. Coal Usage during Sample Collection, Brindisi

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

- 20

Table 3

- 10. Scrubber Slurry Information during Sample Collection, Brindisi

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

- 21

Table 3

- 11. FGD Wastewater Tr eatment System Operation Information, Brindisi

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

- 22

Table 4

- 1. Influent to FGD Wastewater Treatment System, Brindisi

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

- 2

Table 4

- 2. Distillate from Brine Concentrator, Brindisi

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

- 4

Table 4

- 3. Condensate from Crystallizer, Brindisi

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

- 6

Table 4

- 4. Classical Pollutants Average Data Summary for FGD Wastewater Treatment

System, Brindisi

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

- 8

Table 4

- 5. Metal Pollutants Average Data Summary for FGD Wastewater Treatment

System, Brindisi

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

- 9

Table A

- 1. Influent to FGD Wastewater Treatment System, Day 2 Analytical Results,

Brindisi

................................ ................................ ................................ ............................ A

- 2

Table A

- 2. Influent to FGD Wastewater Treatment System, Day 3 Analytical Results,

Brindisi

................................ ................................ ................................ ............................ A

- 4

Table A

- 3. Influent to FGD Wastewater Treatment System, Day 1 Analytical Results,

Brindisi

................................ ................................ ................................ ............................ A

- 6LI ST OF TABLES (Continued)

Page

iii Table A

- 4. Distillate from Brine Concentrator, Day 2 Analytical Results, Brindisi

................. A

- 8

Table A

- 5. Distillate from Brine Concentrator, Day 3 Analytical Results, Brindisi

............... A

- 10

Table A

- 6. Condensate from Crystallizer, Day 1 Analytical Results, Brindisi

....................... A

- 12

Table A

- 7. Condensate from Crystallizer, Day 2 Analytical Results, Brindisi

....................... A

- 14

Table A

- 8. Condensate from Crystallizer, Day 3 Analytical Results, Brindisi

....................... A

- 16

Table A

- 9. Bottle Blank and Equipment Blank Analytical Data, Brindisi

............................... A

- 18

Table A

- 10. Influent to FGD Wastewater Treatment System Field Blank, Day 1

A nalytical Results, Brindisi

................................ ................................ .......................... A

- 22

Table A

- 11. Distillate from Brine Concentrator Field Blank, Day 1 Analytical Results,

Brindisi

................................ ................................ ................................ .......................... A

- 24

Table A

- 12. Distillate from Brine Concentrator Field Blank, Day 2 Analytical Results,

Brindisi

................................ ................................ ................................ .......................... A

- 26

Table A

- 13. Distillate from Brine Concentrator Field Blank, Day 3 Analytical Results,

Brindisi

................................ ................................ ................................ .......................... A

- 27

Table A

- 14. Condensate from Crystallizer Field Blank, Day 1 Analytical Results,

Brindisi

................................ ................................ ................................ .......................... A

- 28

Table A

- 15. Condensate from Crystallizer Field Blank, Day 2 Analytical Results,

Brindisi

................................ ................................ ................................ .......................... A

- 30

Table A

- 16. Condensate from Crystallizer Field Blank, Day 3 Analytical Results,

Brindisi

................................ ................................ ................................ .......................... A

- 31iv LIST OF FIGURES

Page

Figure 2

- 1. Diagram of the Pilot

- Scale Carbon Capture and Storage System, Brindisi

Power Plant

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

- 15

Figure 2

- 2. Diagram of the Chemical Precipitation and Softening Portion of the FGD

Wastewater Treatment System, Brindisi Power Plant

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

- 16

Figure 2

- 3. Diagram of the Evaporation Portion of the FGD Wastewater Treatment

System, Brindisi and Torrevaldaliga Nord Power Plants

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

- 17

Figure 2

- 4. Diagram of the Crystallization Portion of the FGD Wastewater Treatment

System, Brindisi and Torrevaldaliga Nord Power Plants

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

- 18

Figure 2

- 5. Diagram of the Chemical Precipitation Portion of the FGD Wastewater

Treatment System, Torrevaldaliga Nord Power Plant

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

- 19

Figure C

- 1. Sampler Working Inside a “Cleanbox”

................................ ................................ .... C

- 1

Figure C

- 2. Picture of Sampling Location and Tubing Attached to the PVC Pipe at the

Influent to the FGD Wastewater Treatment Sytem

................................ ......................... C

- 2

Figure C

- 3. Sample Collection Set

- Up at the Distillate from the Brine Concentrator

................ C

- 3

Figure C

- 4. Sample Collection Set

- Up at the Condensate from the Crystallizer

........................ C

- 41

- 1 1. I NTRODUCTION

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

Agency (EPA) is conducting a sampling program at steam electric power plants . The sampling

program will characterize wastewaters generated by coal

- fi red steam electric power plants and

evaluate treatment technologies and best management practices used to reduce pollutant

discharges. This r eport describes the site visits that took place at Enel’s Federico II Power Pl ant

(Brindisi), located in Brin disi I taly, on February 14 and April 4, 2011 ; the site visit that took

place at Enel’s Torrevaldaliga Nord Power Station ( Torrevaldaliga Nord ), located in

Civitavecchia, Italy , on March 31, 2011 ; and the sampling activities that took place April 5

- 7

, 201 1 , at Brindisi (Sampling Episode 65 76 ). The focus of Episode 65 76 was to characterize the

purge stream entering the flue gas desulfurization (F GD) wastewater treatment system , the

distillate from the brine concentrator, and the condensate from the crystallizer of the FGD

mechanical vapor compression treatment system

.

1.1

M etals and certain other constituents present in the wastewater discharges from steam

electric power plants substantially contribute to the toxic loadings for the industry. Additionally,

EPA has 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.

Based on these findings, EPA has focused the sampling program on characterizing the untreated

FGD wastewaters and effluent quality from technologies designed to treat the wastewater. Background

1.2

EPA selected steam electric plants for FGD wastewater sampling based on the process

configurations and char acteristics of the plants. Power Plant Site 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 systems 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)

,

— Ferric chloride addition,

— Polyelectrolyt e addition,

— Clarification,

— Ferrous chloride and soda ash addition (softening),

— Clarification,

— Evaporation (brine concentrator), and

— Crystallization; and

**•** The plant operates selective catalytic reduction (SCR) systems on all four units.1

- 2 1.3

EPA ’s technical contractor, Eastern Research Group, Inc. (ERG)

, conduct ed a one

- day

pre

- sampling site visit at Brindisi on February 14, 2011

. The information collected during the

pre

- sampling site visit was used to create Sampling Plan, Enel’s Federico II Power Plant

(Sampling Plan) [1], which describes the sample collection procedures used during the sampling

episode. Sampling Episode Overview

O n Monday

, April 4 , 20 1 1 , EPA arrived at Brindisi to meet with plant personnel,

participate in a site vis it at the facility, receive on

- site safety training, review the sampling points,

and determine the set

- up for the sample collection. EPA and ERG collected the samples

specified in the Sampling Plan on Tuesday through Thursday ( April 5

– 7 , 20 1 1 ) . The follo wing

personnel participated in EPA’s sample collection activities:

**•** Ron Jordan, EPA/EAD;

**•** TJ Finseth, ERG;

**•** Elizabeth Sabol, ERG; and

**•** Tracey Footer, ERG.

In addition, during the sample collection, EPA collected duplicate samples with Enel

personnel

.2

- 1 2. S ITE V IS I TS

EPA conducted site visits at two of Enel’s power plants in Italy prior to the sampling

episode at Brindisi. This summarizes the facility information gathered from the site visits at

Brindisi on February 14 and April 4, 2011 and the site visit at Torrevaldaliga Nord on March 31,

2011.

2.1

The Brindisi plant was built in 1993 and is located in Cerano

- Tuturano (Brindisi), Italy.

There are 309 employees and 171 operators a t the plant

. Brindisi operates four steam electric

units and each has a coal

- fired boiler. All four units have a capacity of 660 megawatts (MW) and

can operate with a 100 percent coal fuel source or a mix of coal and oil. Regular start

- up

operations usuall y include start ing the unit with oil as the fuel source until it is at 40 percent

capacity, then the fuel source switches to coal to optimize combustion

. At the time of the site

visit on April 4, 2011 , Unit 1 was operating on oil, with the switch to coal p lanned for April 5,

2011, Unit 2 was not operating , and Units 3 and 4 were operating on coal. Brindisi Facility Overview

Brindisi receives approximately 5 million tons of coal per year from the Costa Morena

port , which is transported to the plant via two 15 kilometer ( km ) covered co nveyor belts. Each

conveyor belt can transfer up to 1,500 tons of coal per hour. Brindisi can also transport coal via

truck pending any issues with the conveyor belt system. Coal is imported from several different

countries, including South Africa, Columbia, Indonesia, or the United States. T he se coals are

generally low sulfur coal (1 percent sulfur). Brindisi also burns bituminous coal occasionally;

however, plant personnel noted that it can cause issues with the conveyor belt system

.

Currently, Brindisi burns 20,000 tons of coal per day between its four steam electric

generating units. Brindisi estimates that this results in approximately 600,000 tons of ash per

year. Brindisi operates electrosta tic precipitators (ESPs) on Units 1, 2, and 4 to control

particulate releases from the plant

. The plant operates a fabric filter on Unit 3. T he plant is in the

process of converting the remaining three ESPs into fabric filters

.

Brindisi also operates selec tive catalytic reduction (SCR) systems to control the NOx

emissions from the plant. The plant injects ammonia into the flue gas in the system to convert

the NOx to nitrogen gas with the aid of the catalyst layers. The SCR system achieves

approximately 80 percent removal of NOx from the flue gas.

2.1.1 Enel R esearch and Development

Enel has three research centers for research and development (R&D) activities, one of

which is located at the Brindisi plant. The Brindisi research center focuses largely on residues,

environmental impact analyses, and renewable energy.

Currently, the Brindisi research center has a lab oratory

- scale carbon capture and storage

system (CCS) and a pilot

- scale CCS is in operation at the Brindisi plant. See Section 2.1.2 for

further information on the pilot

- scale CCS at Brindisi. Enel is researching carbon dioxide (CO 2 )

post

- combustion capture and the ability to retrofit existing plants with such a system.2

- 2 Additionally, Brindisi is researching CO 2 geo

- sequestration and is in the process of trying to

identify a geological storage site on Italian territory that consists of an impermeable substrate to

prevent the release of captured CO 2

.

Other research topics at Brindisi include the following :

**•** Environmental Impact Source Apportionment: the evaluation of the effect of

Enel

- fired plant s on ambient air in r eference to particulate matter using mass

spectrometry.

**•** Wind Power Forecast: the development of a short

- or medium

- term wind power

prediction model to improve the compatibility of wind power production to the

grid using historical data.

**•** Biomass Energetic Valorization: the evaluation of the economic impact and

sustainability of biomass , including availability and competitiveness of different

supply chains.

**•** CALPUFF Model: e stablished by the numerical aspersion model, this technology

screens filter samples using morphological recognition to determine the chemical

composition of air partic le s.

**•** Point Source Apportionment: m obile equipment performing real

- time analyses

using ion chromatography.

2.1.2 Pilot

- Scale Carbon Capture and Storage System

The Brindisi plant recently installed a pilot

- scale post

- combustion carbon capture plant

that service s a 10,000 normal cubic meters per hour (Nm 3 /hr) flue gas slip stream from Unit 4.

The pilot system is designe d to treat approximately 2

- 3 MW

- equivalent and capture 2.5 metric

tons of CO 2 per hour. The pilot system started up in June 2010 and took approximately one year

for construction of the system. It took less than two years to get the first CO 2 separation since

starting the system. Figure 2

- 1

, located at the end of this section, present s the process flow

diagram of the pilot

- scale CCS system

.

The slip stream of f lue gas from Unit 4 is first pretreated after the FGD and gas/gas

heater

. Pretreatment include s additional desulfurization ( DeSO

x ) , where the flue gas is washed

with a limestone slurry to remove sulfur trioxide ( SO 3 ) and reduce sulfur dioxide ( SO 2 ) levels to

below 20 mg/Nm 3

. Immediately downstream of the DeSO

x system, is a wet ESP to remove any

additional particulate matter. This pretreatment is required because the sorbent used in the

carbon capture system will also react with the SO 2 , which would require additional sorbent.

The pretreated flue gas then enters the CO 2 absorber. The absorb er is approximately 1.5

meters in diameter and contains three structural packing sections. Monoethanolamine (MEA)

solution is fed into the absorber at the three different packing sections at flow rates ranging from

20

- 80 m 3 /hour . The absorber was designed with three different levels to experiment with the

amount of surface area exposed to the MEA solution and/or solvent used in the process. The

cleaned flue gas exiting the top of the CO 2 absorber exits out the stack. Prior to exiting through

the stack, the flue gas is washed to remove any leftover solvent particles and to control the

temperature of the flue gas.2

- 3 Existing t he bottom of the CO 2 absorber is the CO 2

- rich MEA solution. The MEA and

CO 2 solution is sent through a heat exchanger to increase the tem perature of the solution and

then sent to a high

- pressure steam stripper where the CO 2 is stripped from the solution. CO 2 and

water vapor exit the top of the stripper and go through a condenser where the water vapor is

condensed and then transferred to a separator to allow the CO 2 gas to separate from the water.

The condensed water is transferred back to the stripper and the CO 2 is captured. Currently, the

captured CO 2 is returned to the stack.

Exiting the bottom of the stripper is the water and MEA sol ution, whic h ranges from a

20

– 4 0% MEA solution. A portion of the bottoms is transferred to the reboiler, where steam is

used to heat the solution . T he solution is then returned to the stripper and provide s the necessary

heat to strip the CO 2 from the CO 2

- rich MEA solution

. The remainder of the bottoms, which is

the CO 2

- lean MEA solution is sent through the heat exchanger to heat the CO 2

- rich MEA

solution prior to it entering the stripper. This solution is then split to allow some of the solution

to transf er through mechanical and activated carbon filters to avoid particles going through the

CO 2 absorber. After passing through the filters, the stream is combined with the portion that was

not filtered and is transferred to the CO 2 absorber where it absorbs t he CO 2 from the flue gas.

Plant personnel stated that the pilot

- scale system also has a recla imer at the bottom of the

stripper ; however, the plant does not normally operate the equipment with the system

.

Because of the different chemic als in the flue gas , Brindisi is working with several

different patented sorbents and operating conditions (temperature and pressure) to determine the

optimal capture/stripping phase.

2.1.3 Ash Handling Procedures

The fly ash generated at the Brindisi plant is collected in ESPs (Units 1, 2, 4) or a fabric

filter (Unit 3) and is transported to silos via dry vacuum. Brindisi operates four temporary silos

(one per unit) which feed into two storage silos. From the storage silos, the fly ash is sent to the

market via truck. All of the fly ash is marketed assuming that the carbon content of the ash (loss

on ignition (LOI)) i s between 2 and 5 percent and meets the conditions of the European Quality

Management 450 Rule for selling fly ash to the concrete industry. Additionally, the plant does

have the capability to sluice the fly ash to ships if the ash will be transported by barge.

Bottom ash is wet sluiced to hydrobins . The overflow from the hydrobins is recirculated

back to the bottom ash sluicing system. Currently, Brindisi does not h ave problems reusing the

overflow from the hydrobins as source water for the bottom ash sluicing system. Brindisi does

not operate a chemical addition system to treat the rec ycled water. Although the plant does not

treat the recirc ulation water, problems with low pH are sometimes identified with the overflow

from the hydrobins. When pH levels drop, the plant adds makeup water from the fresh water

intake to raise the pH. Bottom ash solids are sold to the concrete industry and are also used for

porcelain production.

2.1.4 FGD Scrubber Systems

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 and2

- 4 a main scrubber. Brindisi has two different types of FGD scrubber 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 desi gned to have the same SO 2 removal efficiency; however, the Bishoff scrubbers are

bigger than the Mitsubishi scrubbers and have achieved greater removal efficiencies.

The prescrubbers for each FGD system operate similarly, using a water scrubber to help

remove the additional particulates from the flue gas (i.e., carry

- over fly ash from the ESPs) prior

to the FGD system. Additionally, the prescrubbers remove chlorides from the flue gas prior to

the main scrubber. Each prescrubber has a continuous blowdown that is fed to the FGD

wastewater 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 prescrubbe r blowdown is

approximately 80 m 3 /hr (352 gal/min) for the two units combined.

The main scrubbers for each unit have some similarities, including the following:

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

**•** The solids concentration in the scrubbers r anges from 18 to 24% solids;

**•** The chlorides concentration in the scrubbers is approximately 5,000 ppm ; and

**•** The systems include gas

- gas heaters (described below).

The scrubbed flue gas exiting the absorber passes through the mist eliminators and a gas

gas heater prior to entering the stack and being emitted to the atmosphere. The system used at

Brindisi is a leakage

- free gas

- gas heater where the heating medium is used to cool the flue gas

entering the FGD system in the heat recovery section. By cooling t he flue gas, the heating

medium has extracted heat from the flue gas. The heating medium is then pumped to the

reheater section, where the heating medium heats the cleaned flue gas exiting the FGD system.

Finally, the flue gas is heated to its exit tempe rature, using a steam coil gas heater. The desired

exit temperature provides better diffusion of the exhaust gas and prevents the white steam cloud

prevalent with FGD system stacks.

Section 2.1.1 describes the operation of the Bishoff scrubbers (Units 1 a nd 2) and Section

2.1.2 describes the operation of the Mitsubishi scrubbers (Units 3 and 4).

2.1.4.1 Units 1 and 2 FGD Scrubber Systems

The Units 1 and 2 FGD scrubber systems were both manufactured by Bishoff and have

an identical design. Each unit is equipped wit h two FGD absorber modules

, with each absorber

receiving approximately 50 percent of the flue gas. T he FGD systems use limestone as the

sorbent in the system. The limestone slurry is pressurized and sprayed into the absorbers ; 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 absorber 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 absorber to control the

solids concentration. The plant initiates a blow down once the solids reach 24% within the2

- 5 absorber . The plant continues to blowdown until the solids concentrat ion is reduced to 18%

within the absorber

.

The blowdown from each of the Units 1 and 2 FGD absorbers is transferred to the

primary hydrocyclones. There is one set of primary hydrocyclones for each absorber ; therefore,

there are two sets of primary hydrocyclones for each unit. The underflow from each of the

primary hydrocyclones (i.e., the gypsum slurry) is transferred to vacuum belt filters for

dewatering. Brindisi washes the gypsum as it is applied to the vacuum belt filters. The vacuum

belt filter s dry the gypsum byproduct to a moisture content of less than 10 percent. Brindisi sells

the gypsum for use in wallboard manufacturing. The filtrate from the vacuum belt filters is

transferred to the Units 1 and 2 FGD sump.

The overflow from the two primar y hydrocyclones for each unit is combined in a storage

tank (a separate storage tank for each unit) and then transferred to the secondary 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 Units 1 and 2 FGD sump.

The Units 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 Units 1 and 2 FGD sump is periodically transferred to the FGD wastewater

treatment system based on sump level control. Wastewa ter from the Units 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.

2.1.4.2 Units 3 and 4 FGD Scrubber Systems

The Units 3 and 4 FGD scrubber systems wer e both manufactured by Mitsubishi and

have an identical design. Each unit is equipped with two FGD absorber modules , with each

absorber receiving approximately 50 percent of the flue gas. The FGD systems use limestone as

the sorbent in the system. The lime stone slurry is pressurized and sprayed into the absorber ; 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 absorber where air is

in

jected 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 absorber to control

the solids concentration in the scrubbers. The plant initiates a blow do wn once the solids reach

24% within the absorber . The plant continues to blowdown until the solids concentration is

reduced to 18% within the absorber

.

The blowdown from each of the Units 3 and 4 FGD absorbers is transferred to the

primary hydrocyclones. T here is one set of primary hydrocyclones for each absorber ; therefore,

there are two sets of primary hydrocyclones for each unit. The underflow from the primary

hydrocyclones (i.e., the gypsum slurry) is transferred to vacuum belt filters for dewatering.

B rindisi 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 the gypsum for2

- 6 use in wallboard manufacturing. The filtrate from the vacuu m belt filters is transferred to the

Units 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

absorber are transferred to the Units 3 and 4 FGD sump, which means that the clarifier is

essentially acting as a holding tank and is not being used to remove suspended solids

. According

to plant personnel, the Units 3 and 4 FGD scrubber systems were initially desi gned with

centrifuges, which are a solids separation process that is not as efficient as hydrocyclones ;

therefore, the clarifiers were needed to achieve additional solids settling. However, when the

plant started using the hydrocyclones, the clarifiers wer e no longer needed.

The Units 3 and 4 FGD sump also receives rainfall, stormwater runoff from the

surrounding area, and other wash waters from the FGD process area. The Units 3 and 4 FGD

sump is periodically transferred to the FGD wastewater treatment system based on sump level

control. Wastewater from the Units 3 and 4 FGD sump is typ ically 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.

2.1.5 FGD Wastewater Treatment System

The FGD wastewater treatment system at Brindisi is designed to receive continuous

blo wdown flow from the eight prescrubber units and intermittent transfers from the Units 1 and 2

FGD sump and the Units 3 and 4 FGD sump.

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, and

crystallization system which allows the entire plant to achieve zero liquid discharge , with the

exception of cooling water discharges . The Brindisi FGD wastewater treatment system contains

the following treatment operations:

**•** Settling;

**•** Equalization,

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

precipitation),

**•** Ferric chloride a ddition,

**•** Polyelectrolyte addition,

**•** Clarification,

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

**•** Clarification,

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

**•** Crystallization (added in 2008).

Figures 2

- 2, 2

- 3, and 2

- 4 , located at the end of this section, present process flow diagrams

of the FGD wastewater treatment system and the sampling locations for EPA’s sampling

episode. Figure 2

- 2 pre sents a diagram of the pretreatment system, which includes the chemical2

- 7 precipitation portion of the system. Figure 2

- 3 presents a diagram of the evaporation portion o f

the wastewater treatment system. Figure 2

- 4 presents a diagram of the crystallization portion of

the wastewater treatment system.

The prescrubber 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 concrete settling

basins, each with a capacity of 600 m 3 (158,500 gallons). The plant only operates one settling

basin at a time because while one is operating, the other is being dredged and cleaned out.

During the sampling episode, the wastewater sampled from the settling basin (i.e., where the

influent strea m enters the basin) was found to contain less than 0. 4 percent solids, had a pH

between 2 and 2.5 S.U., and a temperature between 30 and 35 °C.

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 equalization of the

wastewater. Brindisi also transfers the overflow from the bottom ash treatment basins to the FGD

wastewater treatment tanks. [QUESTION FOR ENEL: What is the typical flow rate and

duration of t he transfers from the bottom ash treatment basin 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. In the 1 st comp artment , the plant

adds lime, sodium sulfide, and caustic soda. Overflow from the 1 st compartment feeds the 2 nd

compartment where ferric chloride is added. The wastewater then flows to the 3 rd compartment

where a polyelectrolyte is added.

The overflow from the third compartment of the 1 st stage 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. [QUESTION FOR ENEL: Where is the

filt rate from the filter presses transferred?] The overflow 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 from 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); th ese 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.

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 treatment. The original design for the system

was for the pretreatment system (i.e., neutralization basins) to treat 280 m 3 /hr

, with 140 m 3 /hr to

be recycled and 140 m 3 /hr to be sent to the softening tank. Howeve r, the plant attempts to

maximize the amount 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 back to the FGD system a nd transferring 50 m 3 /hr to the softening tank.

The wastewater sent to the softening tank is treated with additional sodium carbonate to

c omplete the softening process. The overflow from the softening tanks is then transferred to the2

- 8 evaporati on and crysta llization 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 softening 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.

Brindisi operates two identical parallel trains of the evaporation and crystallization

system. However, because of the reduced flow to the system compared to the design, the plant

typically only operates one of the trains at a given time. The wastewater from the softening tank

is transferred to the evapo rator feed tank, where the wastewater is equalized 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 waste water 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 th e wastewater. From the heat exchangers, the

two wastewater streams 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 su mp 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

introduced to the she ll 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, whic h 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 then pumped throug h 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

combined with the cond ensate 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 withdr awn 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 p recipitate onto the seed crystals instead of the tube surfa ces 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 concentrat or. The

overflow from the hydrocyclones is the concentrate that is transferred to the crystallizer feed

tank.

The crystallizer feed tank also receives the filtrate from the filter presses that dewater the

solids generated in the crystallizer. From the crys tallizer feed tank, the wastewater is combined

with some of the slurry recirculation from the bottom of the crystallizer and then combined with2

- 9 the reheated slurry recycle and fed into the crystallizer. The crystallizer is operated with a certain

level of slurr y 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

- p ressure steam is

transferred to the forced circulation heat exchanger where it transfers its heat to the slurry that is

recirculated in the crystallizer, which 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

dist illate in the distillate tank. [QUESTION FOR ENEL: What are the flow rates of the distillate

and condensate streams?] 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 transferred 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. The 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. T he filtrate

from the filter presses is recycled back to the crystallizer feed tank and the solids are transferred

to a mine as fill.

2.1.5.1 Sampling Points

Figures 2

- 2, 2

- 3, and 2

- 4 show the sampling points for the B rindisi sampling episode;

they are summarized below:

**•** A sample of the purge stream from the settling basin at the point where the Units

1&2 and 3&4 sumps transfer line and prescrubber lines enter the basin, upstream

of the FGD wastewater treatment system (i.e., the sample was collected prior to

any equalization, chemical addition or mixing with recycle streams);

**•** A sample of the distillate from the brine concentrator

, upstream of the first

distillate tank and downstream of the heat exchanger ; and

**•** A sample of the condensate from the crystallizer on the discharge side of the

pump that transfer s the wastewater to the distillate tank

.

2.2

The Torrevaldaliga Nord plant originally started operat ion in 1984 as an oil

- fired plant

with four 660

- megawatts (MW) oil

- fired units. In 2003, Enel started the conversion project that

converted the plant to three 660

- MW coal

- fired units. The Torrevaldaliga Nord plant is located

in Civitavecchia, Italy. Ther e are approximately 400 Enel employees at the plant, with an

additional 300 other staff working at the plant. All three units have a capacity of 660 MW and

can operate with a 100 percent coal fuel source. Regular start

- up operations usually include

startin g the unit with natural gas. The coal

- fired units at the plant began operation in the

following months: Torrevaldaliga Nord Facility Overview2

- 10 **•** Unit 4

– June 2009;

**•** Unit 3

– January 2010; and

**•** Unit 2

– September 2010.

Torrevaldaliga Nord burns approximately 4.5 million tons of coal per year. T he coal

arrives on ships and is unloaded at one of the two jetties. The plant has two unloaders, each with

an unloading capacity of 1,500 tons/ hour, which are continuous

- bucket unloaders. From the

unloaders, the coal enters the closed vacuum conveyors, w hich prevent fugitive dust emissions

during the transport of the coal. The conveyors transport the coal to one of two closed

- dome

storage areas, each with a capacity of 150,000 tons. The use of the closed domes prevents the

generation of coal pile runoff at the plant. According to plant personnel, the domes contain

approximately 20 days supply of coal and one dome is generally full while the other is loading or

unloading.

Torrevaldaliga Nord burns approximately 15,000 tons of bituminous coal per day

be tween its three steam electric generating units. Torrevaldaliga Nord estimates that this results

in approximately 500,000 tons of ash per year. The plant operates fabric filters on all three units

t o control particulate releases from the plant . The remova l efficiency of the fabric filters is 99.9

percent.

Torrevaldaliga Nord also operates a selective catalytic reduction (SCR) system to control

the NOx emissions from the plant. The plant uses urea, which it converts to ammonia, for use in

the SCR system . The SCR was built with four catalyst layer compartments, but the plant began

installation with only three layers for each unit. The SCR system achieves approximately 80

percent removal of NOx from the flue gas.

2.2.1 Ash Handling Procedures

The fly ash generated at the Torrevaldaliga Nord plant is collected in fabric filters and is

transported to silos via a dry pressure system

. Torrevaldaliga Nord operates three silos , which are

shared among the three units and are classified based on the quality of th e ash. From the storage

silos, the fly ash is transferred to storage ships via a pressure system to be marketed for use in

cement manufacturing. [ QUESTION FOR ENEL: Please confirm that the fly ash is marketed to

the c ement industry. ] Additionally, the plant does have the capability to moisture the fly ash in a

pugmill to approximately 20 percent moisture content prior to transporting it to the ships

.

Torrevaldaliga Nord operates completely dry bottom ash systems, meaning that the boile r

does not have a water quench bath for the bottom ash. This system uses extraction cooling with

air to cool the bottom ash. From the collection system, the bottom ash is ground as fine as the fly

ash and transferred to the silos along with the fly ash u sing the same pressure system.

2.2.2 FGD Scrubber Systems

Torrevaldaliga Nord operates three limestone forced oxidation wet FGD scrubber

systems (one per unit) to control the emission of SO 2 from the units. All three FGD systems were

manufactured by MHI (Mitsu bishi) and operate similarly. They achieve approximately 97

percent removal of sulfur dioxide. Unlike the FGD systems at Brindisi, the FGD systems at2

- 11 Torrevaldaliga Nord do not have prescrubbers. The FGD systems are double

- contact

- flow

scrubbers, where the limestone slurry is sprayed upward into the FGD system, in the same

direction as the flue gas, and then the spray falls downward, thereby contacting the flue gas in

both directions. During contact with the flue gas, 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 ).

The scrubbed flue gas then passes through the mist eliminators and a gas

- gas heater prior

to entering the stack and being emitted to the atmosphere. The system used at Torrevaldaliga

Nord is a leakage

- free gas

- gas heater where the heating medium is use d to cool the flue gas

entering the FGD system from 140°C to 97°C in the heat recovery section. By cooling the flue

gas, the heating medium has extracted heat from the flue gas. The heating medium is then

pumped to the reheater section, where the heating medium heats the cleaned flue gas exiting the

FGD system from 49°C to 90°C. Finally, the flue gas is heated to 110°C, using a steam coil gas

heater. This exit temperature provides better diffusion of the exhaust gas and prevents the white

steam cloud pr evalent with FGD system stacks.

Torrevaldaliga Nord intermittently blows down the gypsum slurry from each FGD

system to control the solids concentration in the scrubbers. The plant initiates a blow down when

the solids begin approaching 50% within the scru bber. [ QUESTION FOR ENEL: Please

confirm the solids content in the scrubber is 50% ] The chlorides concentration in the scrubbers

ranges from 15,000 to 25,000 parts per million (ppm), with a maximum allowable chlorides

concentration of 30,000 ppm.

The blow down from each of the FGD scrubbers is transferred to primary hydrocyclones.

There is one set of primary hydrocyclones for each FGD system. The underflow from the

primary hydrocyclones (i.e., the gypsum slurry) is transferred to vacuum belt filters for

dew atering. Torrevaldaliga Nord 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.

The gypsum is transferred to a covered gypsum storage area and even tually sold for use in

wallboard manufacturing. The filtrate from the vacuum belt filters is transferred to the process

water storage tanks and either reused for limestone preparation or transferred back to the

scrubbers.

The overflow from the primary hydr ocyclones is transferred to the secondary

hydrocyclones. The underflow from the secondary hydrocyclones is transferred to the process

water storage and either reused for limestone preparation or transferred back to the scrubbers.

The overflow from the se condary hydrocyclones is transferred to the FGD wastewater treatment

system.

2.2.3 FGD Wastewater Treatment System

The FGD wastewater treatment system at Torrevaldaliga Nord is designed to receive

intermittent transfers of the secondary hydrocyclone overflow fr om each of the three FGD

systems. [QUESTION FOR ENEL: What is the flow rate and duration of the secondary2

- 12 hydrocyclone transfers to the FGD wastewater treatment system?] The Torrevaldaliga Nord FGD

wastewater treatment system contains the following treatm ent operations:

**•** Equalization,

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

**•** Ferric chloride addition,

**•** Polyelectrolyte addition,

**•** Clarification,

**•** Soda ash addition (softening),

**•** Clarification, [ QUESTION FOR ENEL: What type of operation is the softened

water tank (e.g., clarifier, thickener, etc.)? ]

**•** Evaporation (brine concentrator), and

**•** Crystallization.

Figures 2

- 5, 2

- 3, and 2

- 4 , located at the end of this section, present the process flow

diagrams of the Torrevaldaliga Nord F GD wastewater treatment system. Figure 2

- 5 presents a

diagram of the pretreatment system, which includes the chemical precipitation portion of the

system. Figure 2

- 3 presents a diagram of the evaporation portion of the wastewater treatment

system , which is identical to the Brindisi system

. Figure 2

- 4 presents a diagram of the

crystallization portion of the wastewater treatment system, which is identical to the Brindisi

system.

The secondary hydrocyclone overflow from the FGD systems is transferred to the FGD

wastewater treatment tanks, which consist of two 4,0 00 m 3 (1,056,000 gallons) tanks used for

equalization of the wastewater. The FGD wastewater treatment tanks feed reaction tank 1, where

the plant adds lime to the wastewater to adjust the pH and desaturate the gypsum. Overflow from

reaction tank 1 feeds re action tank 2 where lime and sodium sulfide are added. The wastewater

then flows to reaction tank 3 where ferric chloride is added.

The overflow from reaction tank 3 is transferred to the clarifier, where a polyelectrolyte

is added. The underflow from the clarifier is transferred to a thickener for additional settling.

The underflow from the thickener is transferred to a filter presses for dewatering. The dewatered

solids are sent to a landfill for disposal. The overflow from the thickener is transferred b ack to

reaction tank 1. The filtrate from the filter press is combined with the clarifier overflow and

transferred to the softener.

In the softener, the plant adds sodium carbonate (soda ash) and polyelectrolyte to the

wastewater to reduce the calcium con tent of the wastewater. The underflow from the softener,

which is primarily calcium carbonate ( limestone), is reused in the limestone preparation process.

The overflow from the softener is either reused as soda ash make

- up or sent to the evaporation

and crystallization system. [QUESTION FOR ENEL: What is the flow rate of the FGD

wastewater transferred to the evaporation and crystallization system?]

Torrevaldaliga Nord operates two identical 50% parallel trains of the evaporation system

and one 100% cr ystallization system. The wastewater from the softening tank is transferred to

the evaporator feed tank, where the wastewater is equalized prior to being fed to the evaporation

system. Additionally, the plant adds hydrochloric acid and an anti

- scalant to the wastewater prior2

- 13 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 an d the condensate stream from the crystallizer are

the streams used to transfer heat to the wastewater. From the heat exchangers, the two

wastewater streams 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

introduced to the shell side of the brine concentrator (i.e., the outside of the tubes), along with

additional make

- up steam. The temperature difference b etween 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. [QUESTION FOR ENEL: What is the flow rate of the distillate stream?] The

distillate is then 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 combined with the

condensate from the crystallizer.

The concentrated br ine 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

hydroc yclones. 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 tub e surfa ces 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. The

overflow from the hydrocyclones is the conce ntrate that is transferred to the crystallizer feed

tank.

The crystallizer feed tank also receives the filtrate from the filter presses that dewater the

solids generated in the crystallizer. From the crystallizer feed tank, the wastewater is combined

with some of the slurry recirculation from the bottom of the crystallizer and then combined with

the reheated slurry recycle and fed into the crystallizer. The crystallizer is operated with a certain

level of slurr y in the bottom of the system. Within the syste m, 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 circulati on heat exchanger where it transfers its heat to the slurry that is

recirculated in the crystallizer, which 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

was tewater entering the deaerator. The condensate is then combined with the brine concentrator

dist illate in the distillate tank. [QUESTION FOR ENEL: What is the flow rate of the condensate2

- 14 stream?] 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 transferred through the forced

circulation heat exchanger where it is heated by the high

- press ure 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. The evaporation of the water also concentrates the solids

present and allows the solids t o 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. T he filtrate

from the filter presses is recycled back to the crystallizer feed tank and the solids are transferred

to a mine as fill.

According to the plant personnel, the cost of the FGD wastewater treatment system was

approximately €10 million. The costs for the system were broken out as follows:

**•** Wastewater storage: €0.7 million;

**•** Pretreatment: €1. 7 million;

**•** Brine concentrators: €4.7 million; and

**•** Crystallizer: €2.9 million.2-15

Figure 2

- 1 . Diagram of the Pilot

- Scale Carbon Capture and Storage System

, Brindisi Power Plant2-16 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

Compartment 2 nd

Compartment 3 rd

Compartment

1 st Stage Neutralization Basin Lime

NaOH

Sodium

Sulfide Ferric Chloride

Polyelectrolyte

1 st

Compartment Lamella

Clarifier

2 nd Stage Neutralization

Basin Ferrous

Chloride Soda

AshClearwell To Softening /

Evaporation /

Crystallization

FGD System

Make Up

Figure 2

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

Power Plant2-17 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 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

- 3 . Diagram of the Evaporation Portion of the FGD Wastewater Treatment System, Brindisi and Torrevaldaliga Nord

Power Plants2-18 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

- 4 . Diagram of the Crystallization Portion of the FGD Wastewater Treatment System, Brindisi and Torrevaldaliga

Nord Power Plants2-19 Secondary Hydrocyclone

Overflow FGD

Wastewater

Treatment

Tank A

Filter Press Clarifier

Solids to Landfill FGD

Wastewater

Treatment

Tank B Reaction

Tank 1 Reaction

Tank 2 Reaction

Tank 3 Lime Sodium

Sulfide Ferric

Chloride

Polyelectrolyte

To Softening /

Evaporation /

Crystallization Lime

Thickener

Figure 2

- 5 . Diagram of the Chemical Precipitation Portion of the FGD Wastewater Treatment System, Torrevaldaliga Nord

Power Plant3

- 1 3. S AMPLE C OLLECTION

During the Brindisi sampling episode, the sampling team followed the collection

protocols specified in the Sampling Plan. Section 3.1 describes the sampling points, sample

collection methods, and field measurements. Section 3.2 describes the list of analytes and the

sample preservation procedures. Section 3.3 discusses the plant operational da ta collected during

the sampling episode. Finally, Section 3.4 discusses any deviations from the planned sampling

activities.

3.1

This section describes the sampling points, sample collection me thods , and field

measurements

. Additional details are available in Section 3 of the Sampling Plan. Figures 2

- 2 , 2

-

3

, and 2

- 4 of this report present flow diagrams of the plant’s wastewater treatment system,

including sampling point locations. Sampling Points, Sample Collection Methods, and Field Measurements

Table 3

- 1 l ists the sampling points, sampling point descriptions, type of sample

collection, and sample collection dates and times. Table 3

- 2 lists the sampling point numbers and

descriptions, the number of samples collected, and the pollutant parameters for which th e

samples were analyzed. Table 3

- 3 presents the field measurement data collected from each

sampling point. Table 3

- 4 presents a crosswalk between the sample numbers used for laboratory

sample identification and the sample points for each day.

The sampling points for this episode were:

**•** SP

- 1 Influent to FGD Wastewater Treatment System;

**•** SP

- 2 Distillate form the Brine Concentrator ;

**•** SP

- 3 Condensate from the 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 )

.

For all the sampling points, EPA collected duplicate samples with Enel’ s samplers by

filling one bottle immediately after the other for each sample

.

At each of the sampling points, EPA collected metals sample fractions following EPA

Method 1669 collection protocols. To collect these samples, EPA samplers donned Tyvek®

coverall s and dust masks (dust masks were worn until all mercury samples had been collected).

In addition, EPA set up a “cleanbox,” which consists of a portable plastic rectangular box with a

shallow lip and a flip

- top lid that secures itself open with clips. The “cleanbox” is double

- bagged

with a clear inner bag, enclosed in a translucent outer bag. The “cleanbox” is handled using

“clean hands / dirty hands” techniques, whereby the inner bag is handled only by the “clean

hands” sampler. When the “cleanbox” is open ed, the sampler is able to position his/her hands in

the box and pull the bag over the opening of the box, but is still able to see the sample bottles and3

- 2 tubing. The “cleanbox” minimizes potential atmospheric contamination during sample

collection. Figure C

- 1, in Appendix C, is a picture of a sampler working inside a “cleanbox.”

The metals s ample bottles were also double

- bagged. To collect the metals samples, EPA

placed the sample bottles (while still in its sealed inner bag) into the “cleanbox” following the

protocols specified in Method 1669, also referred to as “clean hands / dirty hands” protocols.

Sampling staff filled the sample container, then closed the sample bottle lid and sealed the inner

bag as quickly as possible within the “cleanbox.” The bagged sample bottles were then removed

from the “cleanbox” and placed into the outer bag following the “clean hands / dirty hands”

protocols.

3.1.1 Influent to FGD Wastewater Treatment System

The influent to FGD wastewater treatment s ystem (SP

- 1) was collected directly from the

settling basin at the point the Units 1&2 and Units 3&4 sump transfer lines and the prescrubber

blowdown lines enter the settling basin . Figure 2

- 2 identifies the sampling location for SP

- 1.

Because the transfer s from the sumps were not continuous, ERG coordinated with Brindisi

personnel to determine when wastewater from both sumps was being transferred to the FGD

wastewater treatment system. This sample was collected as a grab sample because the sumps

only have periodic discharges of the FGD wastewater; therefore, EPA wanted to make sure that

all waste streams were captured by the samples

.

The sampling point was located outside, on the platform over a portion of the settling

basin . There was no rain during the sa mple collection

.

On Day 1 only, p rior to collecting the samples at the influent to the FGD wastewater

treatment system (SP

- 1) 1

To collect the wastewater samples at the influent to the FGD wastewater treatment

system , the samplers attach ed a length of pre

- cleaned Teflon ® tubing (which was connected to a

10

- foot length of pre

- cleaned silicone tubing ) to a piece of PVC pipe to easily control the

position of the tubing in the basin. Zipties were used to secure the Teflon ® tubing to the PVC

pipe. Samplers lowered the PVC pipe and att ached Teflon ® tubing into the settling basin so that

the tubing end was beneath the surface

. Figure C

- 2, in Appendix C, is a picture of the tubing

attached to the PVC pipe inserted into the settling basin

. The samplers threaded the 10

- foot

length of pre

- cl eaned silicone tubing through a peristaltic pump to pump the wastewater out of

the settling basin to collect the samples. Samplers purged the line for two minutes before

beginning to fill sample containers. Samplers operated the pump accordingly to collect all

samples. , the sampling team collected field blanks (SP

- 4 ) for total mercury and

total metals. See Section 5.2.3 for a description of the f ield blank sample collection procedures at

the influent to the FGD wastewater treatment system.

1 During Day 1 of sampling, the sump pump discharge pipe (inlet to the settling basin) was clogged; therefore,

samplers were unable to collect samples at SP

- 1 after the field blank collection. SP

- 1 field blanks were still collected

on Day 1 because the sump pump clog was not detected until after the field blank samples were taken. Day 1, SP

- 1

samples were collected on Day 3.3

- 3 The samplers collected the following samples using a “cleanbox,” as described in Section

3.1 :

**•** T otal mercury ;

**•** T otal metals by 200.8; and

**•** Total metals by 200.7.

T he sampling team collected an aliquot of sample for field testing. Sample pH a nd

temperature were measured immediately at the sampling point using four

- color pH paper and a

thermometer. Table 3

- 3 presents the field measurement data for the influent to the FGD

wastewater treatment system.

The samplers then filled containers for Group I and Group II samples directly from the

tubing without using a “cleanbox.” See Table 3

- 6 for a list of Group I and Group II analytes.

Group I and Group II were immediately placed on ice after sample collection.

3.1.2 Distillate from the Brine Concentrato r (SP

- 2)

The distillate from the brine concentrator (SP

- 2) was 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. Brind isi installed a two

- way splitter

on the sample tap, which had two separate taps to collect samples from the sampling point. The

sample tap was located outside (see Figure 2

- 3 for the sampling location for SP

- 2 )

. There were

no wind or rain concerns during t he sample collection.

ERG collect ed the distillate from the brine concentrator as manual composite samples

collected into one 20

- liter container. ERG manually collected seven liters of sample, every two

hours, for a four

- hour period to fill the 20

- liter co ntainer with 21 liters of sample 2

ERG used the manual composite sample to collect sample volume for the metals analyses

(excluding mercury) and classical analytes (i.e., Group I and Group II). In addition to collecting

manual composite samples for the analytes listed above, ERG collected total mercury grab

samples every two hours during each compositing period. . Following the

composite period, ERG pumped off the specific sample volumes into the individual sample

containers.

Samplers set up the compositor by attaching a T

- splitter tubing set to o ne of the tap s on

the two

- way splitter

. The T

- splitter tubing set consisted of three silicone tubes attached to a T

splitter. The tubing configuration was set up such that one end was connected to the sample tap,

o ne end was connected to the 20

- liter composite container, and one end was placed next to a

sump/drain near the sampling point. The samplers attached the silicone tubing to the sample tap,

opened the valve

, and allowed sample to flow through both sets of tu bing before the tubing was

attached to a vented cap on a 20

- liter composite container

. The tubing attached to the vented cap

on the container was pinched shut and secured with a ziptie during the four

- hour composite

2 ERG did not collect five liters of sample, every two hours, for a six hour period, originally discussed in the

Sampling Plan, due to time constraints with available FedEx shipments from the plant.3

- 4 period 3

The 20

- liter composite container was placed into a plastic bin , and main tained on ice for

the entire four

- hou r compositing period. A plastic bag was placed on top of the trash cans to

minimize contamination. Figure C

- 3 , in Appendix C, is a picture of the composite sampling set

up at the distillate from the brine concentrator. . For every manual composite samp le, the sample tap was opened and the flow was

directed t o the tubing leading to the drain . After purging the line for two minutes, samplers

simultaneously pinched the tubing leading to the drain and unpinched the tubing connected to the

composite containe r. The samplers allowed the container to fill with seven liters of samples then

re

- pinched the tubing leading to the composite container.

Immediately after setting up the compos itor, ERG collected the first total mercury grab

sample. At the first grab sample every day, ERG collected field blanks for total mercury samples.

See Section 5.2.3 for a description of the field blank sample collection procedures at the distillate

from th e brine concentrator

.

For mercury collection, samplers shrouded one of the two taps on the two

- way splitter

(the other tap was being used by the compositor ) with a clean plastic bag by puncturing a hole in

the bottom of the bag with the end of the tap an d then securing it to the tap with a ziptie. After

purging the tap for two minutes, the samples were collected directly from the tap into the sample

bottles . ERG collected another total mercury sample every two hours thereafter over the four

hour period , f or a total of three grab samples

. The plastic shroud was replaced for each mercury

grab sample. After collecting each mercury grab, ERG filled a field test bottle and tested for pH

and temperature using four

- colored pH paper , pH meter, and a thermometer. T able 3

- 3 presents

the field measurement data for the distillate from the brine concentrator.

After the third aliquot was collected in the composite c ont ai ner , ERG followed “clean

hands / dirty hands” sampling techniques to disassemble the compositor from t he sampling set

up. A c losed cap was placed on the composite container and the composite container was moved

to the pump

- off area where it remained on ice until individual sample bottles were filled

.

T he sampling team transferred the wastewater collected in the 20

- liter container into the

individual sample containers at the pump

- off area

. For this sampling point, ERG use d a sample

pump

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

.

The pump

- off station consisted of a length of Teflon® tubing attached to a length of

silicone tubing, which was threaded through an ISCO peristaltic pump. The sampling team

placed the en d of the Teflon® tubing into the 2 0

- liter composite container filled with the

distillate from the brine co ncentrator

. After the t ubing was purged with 1

- 2 liters of sample

,

s amplers collected the following samples using a “cleanbox,” as described in Section 3.1 :

**•** Total metals by 200.8; and

**•** Total metals by 200.7.

3 Samplers secured the pinched tubing of the composite container with a ziptie for the entire length of the composite

period, excluding the times when actual samples were being taken, to avoi d any sample entering the container if the

valves from the sample tap did not have a completely tight seal.3

- 5 After the metal samples had been collected, the samplers filled containers for Group I and

Group II samples directly from the tubing without using a “cleanbox.” See Table 3

- 6 for a list of

Group I and Group II analytes. G roup I and Group II samples were immediately placed on ice

after sample collection. EPA collected duplicate samples with Enel personnel by filling one

sample bottle immediately after the other.

On Day 1 only, p rior to collecting any samples of the distillate from the brine

concentrator , the samplers collected a field blank sample (SP

- 5 ) for total metals. See Section

5.2.3 for a description of the dissolved and total metals field blank sample collection at th e

distillate from the brine concentrator

.

3.1.3 Condensate from the Crystallizer

The condensate from the crystallizer (SP

- 3) was collected from the discharge side of the

pump that transfers the wastewater to the distillate tank. Brindisi installed a two

- way splitter on

the sample tap to provide two separate taps for collecting samples from the sampling point. The

sample tap was located outsi de (see Figure 2

- 4 for the sampling location for SP

- 3). T here were

no wind or rain concerns during the sample collection.

ERG collect ed the condensate from the crystallizer as manual composite samples

collected into one 20

- liter container. ERG manually collected seven liters of sample, every two

hours, for a four

- hour period to fill the 20

- liter container with 21 liters of sample 4

ERG used the manual composite sample to collect sample volume for the metals analyses

(excluding mercury) and classical analytes (i.e., Group I and Group II). In addition to collecting

manual composite samples for the analytes listed above, ERG colle cted total mercury grab

samples every two hours during each compositing period. On day 1 only, ERG collected field

blank samples (SP

- 6 ) for total metals by 200.7, and total metals by 200.8. See Section 5.2.3 for a

description of the field blank sample coll ection procedures at the condensate from the

crystallizer

. . Following the

composite period, ERG pump ed off the specific sample volumes into the individual sample

contain ers.

Samplers set up the compositor by attaching a T

- splitter tubing set to one of the tap s on

the two

- way splitter

. The T

- splitter tubing set consisted of three silicone tubes attached to a T

splitter. The tubing configuration was set up such that one end was connected to the sample tap,

one end was connected to the 20

- liter composite container, and one end was placed next to a

sump/drain near the sampling point. The samplers attached the silicone tubing to the sample tap,

opened the valve

, and allowed sample to flow through both sets of tubing before the tubing was

attached to a vented cap on a 20

- liter composite container. The tubing attached to the vented cap

on the container was pinched shut and secured with a ziptie during the four

- hour composite

period 5

4 ERG did not collect five liters of sample, every two hours, for a six hour period, originally discussed in the

Sampling Plan, due to time constra ints with available FedEx shipments from the plant. . For every manual composite sample, the sample tap was opened and the flow was

5 Samplers secured the pinched tubing of the composite container with a ziptie for the entire length of the composite

period, excluding the times when actual samples were being taken, to avoid any sample entering the container if the

valves from the sample tap did not have a completely tight seal.3

- 6 directed through the tubing to the drain. After purging the line for two minutes, samplers

simultaneously pinched t he tubing leading to the drain and unpinched the tubing connected to the

composite container. The samplers allowed the container to fill with seven liters of samples then

re

- pinched the tubing leading to the composite container.

The 20

- liter composite co ntainer was placed into a plastic bin , and main tained on ice for

the entire four

- hour compositing period. A plastic bag was placed on top of the trash cans to

minimize contamination. Figure C

- 4 , in Appendix C, is a picture of the composite sampling set

up at the condensate from the crystallizer.

Immediately after setting up the compositor, ERG collected the first total mercury grab

sample. At the first grab sample every day, ERG collected field blanks for total mercury samples.

See Section 5.2.3 for a desc ription of the field blank sample collection procedures at the

condensate from the crystallizer

.

For mercury collection, samplers shrouded one of the two taps on the two

- way splitter

(the other tap was being used by the compositor) with a clean plastic bag by puncturing a hole in

the bottom of the bag with the end of the tap and then securing it to the tap with a ziptie . After

purging the tap for two minutes, the samples were collected directly from the tap into the sample

bottles

. ERG collected another total mercury sample e very two hours thereafter over the four

hour period , for a total of three grab samples

. The plastic shroud was replaced for each mercury

grab sample. After collecting each mercury grab sample , ERG filled a field test bottle and tested

for pH and temperature using four

- colored pH paper , pH meter, and a thermometer. Table 3

- 3

presents the field measurement data for the condensate from the crystallizer.

After the third aliquot was colle cted in the composite container , ERG followed “clean

hands / dirty hands” sampling techniques to disassemble the compositor from the sampling set

up. A c losed cap was placed on the composite container and the composite container was moved

to the pump

- off area where it remained on ice until individual sample bottles were filled

.

T he sampling team then transferred the wastewater collected in the 20

- liter container into

the individual sample containers at the pump

- off area

. For this sampling point, ERG use d a

sample pump

- off approach to transfer the composite s amples to the individual sample bottles

.

The pump

- off station consisted of a length of Teflon® tubing attached to a length of

silicone tubing, which was threaded through an ISCO peristaltic pump. The sampling team

placed the en d of the Teflon® tubing into the 2 0

- liter composite container filled with condensate

from the crystallizer

. After the tubing was purged with 1

- 2 liters of sample , s amplers collected

the following samples using a “cleanbox,” as described in Section 3.1 :

**•** Total metals by 200.8; and

**•** Tota l metals b y 200.7.

After the metal samples had been collected, the samplers filled containers for Group I and

Group II samples directly from the tubing without using a “cleanbox.” See Table 3

- 6 for a list of

Group I and Group II analytes. Group I and Grou p II samples were immediately placed on ice3

- 7 after sample collection. EPA collected duplicate samples with Enel personnel by filling one

sample bottle immediately after the other.

On Day 1 only, p rior to collecting any samples of the condensate from the cr ystallizer

, the samplers collected a field blank sample (SP

- 6 ) for total metals. See Section 5.2.3 for a

description of the dissolved metals field blank sample collection at th e condensate from the

crystallizer

.

3.2

Samples collected at Brindisi were analyzed for the following parameters : List of Analytes and Sample Preservation

**•** 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 ;

**•** Total M e tals:

— Aluminum, antimony, arsenic, barium, beryllium, boron, cadmium,

calcium, chromium, cobalt, copper, iron, lead, magnesium, manganese,

mercury, molybdenum, nickel, selenium, silver, sodium, t hallium, tin,

titanium, vanadium, and zinc.

The analytes selected reflect the current understanding of coal

- fired power plant air

pollution control wastewaters, including contributions from coal, scrubber sorbents, treatment

chemicals, and other sources

. Table 3

- 5 lists the analytical methods used to determine pollutant

concentrations.

Table 3

- 6 lists the containers used for sample collection and the preservation

requirements for each sample. Table 3

- 7 summarizes the chemical preservation for each of the

s amples that were preserved on site. The sampling team preserved samples in accordance with

procedures described in Section 3.4 of the Sampling Plan. Immediately following sample

collection, the samplers placed the Group I and Group II samples on ice to coo l the samples to

<6°C. The sampling team did not place the total metals or the total mercury samples on ice

, which comports with the requirements of Methods 200.7, 200.8

, and 1631E

. The Group II

samples were preserved with sulfuric acid to a pH of <2 S.U. in the staging area, and the pH was

confirmed with four

- color pH strips.3

- 8 3.3

During the EPA sampling episode

, Brindis i plant personnel provided the sampling team

with operational data f or each of the generating units and the FGD scrubber system, as well as

operational and flow data for the FGD wastewater treatment system. Table 3

- 8 presents the unit

operating characteristics, Table 3

- 9 presents the FGD scrubber system operating characteristics

, Table 3

- 10 presents informa tion on the coal burned during the sampling episode, Table 3

- 11

presents information on the FGD scrubber slurry generation during the sampling episode, and

Table 3

- 12 presents the FGD wastewater treatment system operating characteristics

. Plant Operational Data

3.4

The sampling episode proceeded as specified in the Sampling Plan with the exceptions

described below: Deviations from the Sampling and Analysis Plan

**•** Collection of grab samples at SP

- 1 (Day 1) : On day 1 of sample collection at

the influent the FGD wastewater treatment syst em (SP

- 1)

, Brindisi personnel

informed the sampling team that the sump pump discharge pipe (inlet to the

settling basin) was clogged, delaying the collection of the SP

- 1 samples

. Therefore, SP

- 1 samples were collected on Days 2 and 3 instead of Day 1 and

D ay 2 . However, the sampling team was not informed about the clogged pipe

until after the field blank samples were collected and due to limited amount of

blank water available, the field blank samples collected on Day 1 were retained

for analysis by the laboratory.

**•** Collection of grab samples at SP

- 1 (Day 2) : On Day 2 of sample collection at

the influent to the FGD wastewater treatment system (SP

- 1), the sample line

connection between the silicone and Teflon ® portion of the tubing came apart

while attaching the tubing to the PVC pipe. The Teflon ® portion of the tubing

came in contact with the floor of the platform over the settling basin.

**•** Composite time period for SP

- 2 and SP

- 3 : ERG had planned on collecting the

manua l composite samples at SP

- 2 and SP

- 3 as four separate samples collected

every two hours over a six

- hour period; however, because of the limited time

available for preparing international shipments to meet courier schedules , ERG

revised the sample collectio n to three separate samples collected every two hours

over a four

- hour period.

**•** Collection of first manual c omposite sample at SP

- 2 (Day 1) : On Day 1 of

sample collection at the distillate from the brine concentrator (SP

- 2)

, Brindisi

personnel opened the s ample valve too far and the high flow through the sample

tap blew the sample tubing off the tap . The tubing fell to the ground , but was

immediately picked up by the sampling team.

**•** Total mercury grab sample at SP

- 2 (Day 2): On Day 2 of sample collection at

the distillate from the brine concentrator (SP

- 2), the cap for a total mercury3

- 9 sample bottle (grab #2) broke when recapping after sample collection. ERG

transferred the label to a new bottle and collected another sample

.

**•** Total mercury f ield blank sample s at SP

- 2 (Day 3): On Day 3 of sample

collection at the distillate from the brine concentrator (SP

- 2), the sample valve

line was not fully closing. ERG observed a slow, single droplet leak from sample

pipe during field blank colle ction.

**•** Day 1 Sample Shipment: After the completion of sample collection on Day 1,

the sampling team prepared the samples for shipment to the laboratories;

however, the samples were not ready in time for the FedEx shipment. Therefore

, the sampling team kep t the samples in coolers on ice overnight and shipped the

samples with the Day 2 samples the following day. When the sampling team

arrived at the plant on Day 2, the samples were still cold and ice still remained in

the coolers. The sampling team put more ice on the samples to keep them cold

until the samples were prepared for shipment.3

- 10 Table 3

- 1 . Sample Collection Information, Brindisi

Sampling

Point

Number Sampling Point Description Type of

Sample Sample Collection

Date Sample Collection

Time

SP

- 1 Influent to FGD Wastewater Treatment

System

– Day 2 Grab 4/6/11 1006 b

Influent to FGD Wastewater Treatment

System

– Day 3 Grab 4/7/11 1006 b

SP

- 2 Distillate from the Brine Concentrator

– Day 1 Composite 4/5/11 0 840 c , 1042 c , 1303 c

, 1438 d

Grab 4/5/11 0 857 e , 1050 f , 1311 g

Distillate from the Brine Concentrator

– Day 2 Composite 4/6/11 0 708 c , 0908 c , 1112 c

, 1207 d

Grab 4/6/11 0 722 e

, 0 917 f , 1121 g

Distillate from the Brine Concentrator

– Day 3 Composite 4/7/11 0 713 c

, 0 906 c , 1110 c

, 1213 d

Grab 4/7/11 0 725 e

, 0 915 f , 1117 g

SP

- 3 Condensate from the Crystallizer

– Day 1 Composite 4 /5/11 0 931 c , 1133 c , 1329 c

, 1504 d

Grab 4 /5/11 0942 e , 1143 f , 1338 g

Condensate from the Crystallizer

– Day 2 Composite 4/6/11 0 739 c

, 0 926 c , 1131 c

, 1231 d

Grab 4/6/11 0 749 e

, 0 934 f , 1140 g

Condensate from the Crystallizer

– Day 3 Composite 4/7/11 0 743 c

, 0 924 c , 1134 c

, 1232 d

Grab 4/7/11 0 754 e

, 0 931 f , 1142 g

SP

- 4 Influent to FGD Wastewater Treatment

System Field Blank , Day 1 Grab 4/5/11 a 1216 h

SP

- 5 Distillate from the Brine Concentrator

Field Blank

– Day 1 Composite 4 /5/11 0 811 i , 1431 j

Grab 4 /5/11 0 850 k

Distillate from the Brine Concentrator

Field Blank

– Day 2 Grab 4/6/11 0 717 k

Distillate from the Brine Concentrator

Field Blank

– Day 3 Grab 4/7/11 0 720 k

SP

- 6 Condensate from the Crystallizer Field

Blank

– Day 1 Composite 4 /5/11 0 918 i , 1500 j

Grab 4 /5/11 0 937 k

Condensate from the Crystallizer Field

Blank

– Day 2 Grab 4/6/11 0 744 k

Condensate from the Crystallizer Field

Blank

– Day 3 Grab 4/7/11 0 749 k3

- 11 a During Day 1 of sampling, the sump pump discharge pipe (inlet to the settling basin) was clogged; therefore,

samplers were unable to collect samples at SP

- 1 after the field blank collection. The SP

- 1 samples planned to be

collected on day 1 were actually collected on day 3 of sampling ; however, the sampling te am was not informed of

the clogged pipe until after the field blank samples were collected. Therefore, the field blank samples were

collected on Day 1, while the wastewater samples were collected on Days 2 and 3

. b Start time for the c ollection of the total metals samples ( total metals by 200.7 and total metals by 200.8 ) total

mercury, and classical s (Group I, Group II)

.

c Start time for the collection of the manual composite samples. Manual composite samples (7L) were collected

every two hours for a four

- hour composite period.

d Start time for the c ollection of total metals samples (total metals by 2 00.7 and total metals b y 200.8) and classicals

(Group I and Group II).

e Start time for the collection of the t otal mercury Grab 1 sample

. f Start time for the collection of the total mercury Grab 2 sample

.

g Start time for the collection of the total mercury Grab 3 sample

. h St art time for the collection of total mercury, total metals by 200.7, and total metals by 200.8 field blank samples.

i Filled 20

- liter field blank composite container with blank water.

j Start time for the collection of total metals (total metals by 200.7 a nd total metals by 200.8) field blank samples.

k Start time for the collection of total mercury field blank samples.3-12 Table 3

- 2

. Sample Collection at Brindisi

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.3-13 Table 3

- 3. Field Measurements, Brindisi

Sampling Point

Number Sampling Point Description Date Time Temperature

(°C) pH

(S.U.)

SP

- 1 Influent to FGD Wastewater Treatment System

– Day 2 4/6/11 1006 32 2.0

Influent to FGD Wastewater Treatment System

– Day 3 4/7/11 a 1006 31 2.0

SP

- 2 Distillate from the Brine Concentrator

– Day 1 4/5/11 0 857 82 8.0

4/5/11 1050 80 8.5

4/5/11 1311 85 8.0

Distillate from the Brine Concentrator

– Day 2 4/6/11 0 722 86 8.0

4/6/11 0 918 86 8.0

4/6/11 1121 90 8.5

Distillate from the Brine Concentrator

– Day 3 4/7/11 0 725 82 8.0

4/7/11 0 915 87 8.0

4/7/11 1117 86 8.0

SP

- 3 Condensate from the Crystallizer

– Day 1 4/5/11 0 942 72 8.0

4/5/11 1143 64 8.5

4/5/11 1338 71 8.5

Condensate from the Crystallizer

– Day 2 4/6/11 0 749 69 8.5

4/6/11 0 934 69.5 8.5

4/6/11 1140 71 8.5

Condensate from the Crystallizer

– Day 3 4/7/11 0 754 61 8.5

4/7/11 0 931 70 8.5

4/7/11 1142 79 8.0

a During Day 1 of sampling, the sump pump discharge pipe (inlet to the settling basin) was clogged; therefore, samplers were unable to collect samples at SP

- 1

after the field blank collection. The SP

- 1 samples planned to be collected on day 1 were actually collected on day 3 of sampling ; however, the sampling te am was

not informed of the clogged pipe until after the field blank samples were collected. Therefore, the field blank samples were collected on Day 1, while the

wastewater samples were collected on Days 2 and 3

.3

- 14 Table 3

- 3

. Crosswalk of Sample Number to Sampling Point and Day

, Brindisi

Sample Number Sample Point Sample Description

72511 SP

- 1, Day 3 Influent to FGD Wastewater Treatment System

- Day 3 a

72512 SP

- 1, Day 2 Influent to FGD Wastewater Treatment System

- Day 2

72513 SP

- 2, Day 1 Distillate from the Brine Concentrator

- Day 1

72514 SP

- 2, Day 2 Distillate from the Brine Concentrator

- Day 2

72515 SP

- 2, Day 3 Distillate from the Brine Concentrator

- Day 3

72516 SP

- 3, Day 1 Condensate from the Crystallizer

- Day 1

72517 SP

- 3, Day 2 Condensate from the Crystallizer

- Day 2

72518 SP

- 3, Day 3 Condensate from the Crystallizer

- Day 3

72519 SP

- 4 , Day 1 Influent to FGD Wastewater Treatment System Field Blank

- Day 1

72520 SP

- 5

, Day 1 Distillate from the Brine Concentrator Field Blank

- Day 1

72521 SP

- 5 , Day 2 Distillate from the Brine Concentrator Field Blank

- Day 2

72522 SP

- 5 , Day 3 Distillate from the Brine Concentrator Field Blank

- Day 3

7252 3 SP

- 6 , Day 1 Condensate from the Crystallizer Field Blank

- Day 1

7252 4 SP

- 6 , Day 2 Condensate from the Crystallizer Field Blank

- Day 2

7252 5 SP

- 6 , Day 3 Condensate from the Crystallizer Field Blank

- Day 3

a During Day 1 of sampling, the sump pump discharge pipe (inlet to the settling basin) was clogged; therefore,

samplers were unable to collect samples at SP

- 1 after the field blank collection. The SP

- 1 samples planned to be

collected on day 1 were actually collected on day 3 of sampling ; however, the sampling te am was not informed of

the clogged pipe until after the field blank samples were collected. Therefore, the field blank samples were

collected on Day 1, while the wastewater samples were collected on Days 2 and 3

.3

- 15 Table 3

- 4 . Analytical Methods, Brindisi

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

- 16 Table 3

- 5

. Summary of Sample Containers and Planned Preservation, Brindisi

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 Three 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

- 17 Table 3

- 6

. Sample Preservation Summary, Brindisi

Sampling Point

Number Analysis Date Chemical

Added Initial pH

(S.U.) Final pH

(S.U.) Amount

Added

(drops)

72513 Group II Volume 1 4/5/11 H 2 SO 4 8.5 < 2 20

72513 Group II Volume 2 4/5/11 H 2 SO 4 8.5 < 2 20

72516 Group II Volume 1 4/5/11 H 2 SO 4 8.5 < 2 24

72516 Group II Volume 2 4/5/11 H 2 SO 4 8.5 < 2 20

72512 Group II Volume 1 4/6/11 H 2 SO 4 2.5 < 2 25

72512 Group II Volume 2 4/6/11 H 2 SO 4 2.5 < 2 25

72514 Group II Volume 1 4/6/11 H 2 SO 4 8.5 < 2 30

72514 Group II Volume 2 4/6/11 H 2 SO 4 8.5 < 2 30

72514 Group II Volume 1

- QC 4/6/11 H 2 SO 4 8.5 < 2 30

72514 Group II Volume 2

- QC 4/6/11 H 2 SO 4 8.5 < 2 30

72517 Group II Volume 1 4/6/11 H 2 SO 4 8.5 < 2 20

72517 Group II Volume 2 4/6/11 H 2 SO 4 8.5 < 2 23

72511 Group II Volume 1 4/7/11 H 2 SO 4 4.5 < 2 25

72511 Group II Volume 2 4/7/11 H 2 SO 4 4.5 < 2 25

72515 Group II Volume 1 4/7/11 H 2 SO 4 8.5 < 2 25

72515 Group II Volume 2 4/7/11 H 2 SO 4 8.5 < 2 22

72518 Group II Volume 1 4/7/11 H 2 SO 4 8.5 < 2 25

72518 Group II Volume 2 4/7/11 H 2 SO 4 8.5 < 2 25

72518 Group II Volume 1

- QC 4/7/11 H 2 SO 4 8.5 < 2 25

72518 Group II Volume 2

- QC 4/7/11 H 2 SO 4 8.5 < 2 25

pH meter calibrated at 13:45 on 4/4/11.

pH meter calibrated at 0 8:30 on 4/6/11.

pH meter calibrated at 0 8:30 on 4/7/11.3

- 18 Table 3

- 7

. Generating Unit Operating Characteristics during Sample Collection, Brindisi

Unit ID Boiler Type Capacity

(MW) Electricity Production

(MW)

(or Percent Capacity %) SCR

(No, On, Off) Particulate Control System

(HS/CS ESP, or BH)

BS1 Universal

Pressure 660 436.6 On ESP

BS2 Universal

Pressure 660 0 On ESP

BS3 Universal

Pressure 660 357.2 On Bag

- House

BS4 Universal

Pressure 660 349.9 On ESP

[ QUESTION FOR ENEL: Please clarify what the electricity production numbers provided represent (e.g., average

MW over the course of the 3

- day sampling event ). Additionally, based on the coal consumption data included in

Table 3

- 9, the difference between the reported MWs in this table seems incorrect because Unit 3 burned three times

more coal than Unit 4, but that isn’t represented in the information above. ]3-19 Table 3

- 7

. FGD Scrubber System Operating Characteristics, Brindisi

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

BS1 Yes Bishoff a Yes Limestone None Recovered

ZLD water Recovered

ZLD water 84% Hydrocyclones

BS2 Yes Bishoff a Yes Limestone None Recovered

ZLD water Recovered

ZLD water 84% Hydrocyclones

BS3 Yes Mitsubishi a Yes Limestone None Recovered

ZLD water Recovered

ZLD water 84% Hydrocyclones

BS4 Yes Mitsubishi a Yes Limestone None Recovered

ZLD water Recovered

ZLD water 84% Hydrocyclones

a Wet limestone/gypsum forced oxidation open spray tower with pre

- scrubber

. [QUESTION FOR ENEL: Based on the amount of water consumed by a scrubber and that only a portion of the wastewater is sent to the ZLD system, it s eems

that there must be some other sources of water used in the prescrubber and FGD makeup, such as intake water. Please specify o ther sources used in these

processes.]3

- 20 Table 3

- 8 . Coal Usage during Sample Collection, B rindisi

Day of

Sampling Unit

ID Coal Type Amount of

Coal Used

During Day

of Sampling

(tpd) Source of Coal

(Coal Region

and/or State) Percent

Sulfur in

Coal

(%) Chlorine Content

of Coal

(ppm)

1 BS1 Bituminous 4,840 60% South African 0.56 0.004

40% Colombian 0.58 0.0082

BS2 Not Operating

BS3 Bituminous 2,755 60% South African 0.56 0.004

40% Colombian 0.58 0.0082

BS4 Bituminous 3,340 60% South African 0.56 0.004

40% Colombian 0.58 0.0082

2 BS1 Bituminous 4,007 60% South African 0.56 0.004

40% Colombian 0.58 0.0082

BS2 Not Operating

BS3 Bituminous 3,360 60% South African 0.56 0.004

40% Colombian 0.58 0.0082

BS4 Not Operating

3 BS1 Bituminous 4,802 60% South African 0.56 0.004

40% Colombian 0.58 0.0082

BS2 Not Operating

BS3 Bituminous 3,710 60% South African 0.56 0.004

40% Colombian 0.58 0.0082

BS4 Not Operating3

- 21 Table 3

- 9 . Scrubber Slurry Information during Sample Collection, Brindisi

Day of

Sampling FGD

System ID a Associated

Unit IDs Slurry B lowdown Flow Rate

Percent

Solids Time of

Dewatering

During Sampling

Day Flow Rate

(gpm) Duration

1 C1 BS1 132 Continuous 0.035%

-

C2 BS2

- - - -

C3 BS3 176 Continuous 0.050%

-

C4 BS4 176 Continuous 0.286%

-

D12 BS1, BS2 66 7.5% at 880 gpm URE b 5 h/day

D34 BS3, BS4 425 40% at 1056 gpm URE b 5 h/day

2 C1 BS1 132 Continuous 0.040%

-

C2 BS2

- - - -

C3 BS3 176 Continuous 0.040

-

C4 BS4

- - - -

D12 BS1, BS2 66 7.5% at 880 gpm URE b 5 h/day

D34 BS3, BS4 321 30% at 1056 gpm URE b 5 h/day

3 C1 BS1 132 Continuous 0.027%

-

C2 BS2

- - - -

C3 BS3 176 Continuous 0.036%

-

C4 BS4

- - - -

D12 BS1, BS2 66 7.5% at 880 gpm URE b 5 h/day

D34 BS3, BS4 220 21% at 1056 gpm URE b 5 h/day

a IDs from C1 to C4 identify Continuous blow

- downs from Pre

- scrubbers; IDs D12 and D34 identify Discontinuous

blow

- downs from FGD sumps.

b No sample was taken. Absorber density is not representative for sump solid content, since other solid sources are

coll ected into the sumps, ( i.e. off

- line washings, FGD tanks overflows ) and therefore should be considered.

[QUESTION FOR ENEL: In the slurry blowdown flow rate, duration column, a percentage is provided along with

the flow rate. What does this percentage rep resent?]3-22 Table 3

- 10 . FGD Wastewater Treatment System Operation Information , Brindisi

Day of

Sampling Chemical Usage

(Quantity added

- specify units)

Lime Caustic

Soda Sodium

Sulfide Ferric

Chloride Polyelectrolyte Ferrous

Chloride Soda Ash

(10% sol.) Hydrochloric

Acid (30%)

(EST) a Anti

Scalant

1 4000 ppm 200 ppm 28 ppm 120 ppm 2 ppm 15 ppm 8 m3/h 30 ton/day No

2 4000 ppm 200 ppm 28 ppm 120 ppm 2 ppm 15 ppm 8 m3/h 30 ton/day No

3 4000 ppm 200 ppm 28 ppm 120 ppm 2 ppm 15 ppm 8 m3/h 30 ton/day No

a Estimated on daily consumption.4

- 1 4. L ABORATORY A NALYTICAL R ESULTS AND D ISCUSSION

This section summarizes the laboratory results of analyses of samples for the influent to

the FGD wastewater treatment system , the distillate from the brin e concentrator, and the

condensate from the crystallizer.

Appendix A provides all analytical results for all samples collected at B rindisi , including

all qualified results and all results that were measured above the method detection limit, but

below the quantitation limit (i.e., results flagged as J

- values by the laboratory ).

Table 4

- 1 presents the analytical results for all classical and metal parameters for the t wo

days of samp ling at the influent to the FGD wastewater treatment system (SP

- 1), as well as the

calculated 2

- day average result for each analyte. Tables 4

- 2 and 4

- 3 present the analytical results

for all classical and metal analytes for the three days of sampling at th e distillate from the brine

concentrator (SP

- 2) and the condensate from the crystallizer (SP

- 3), and the 3

- day average for

each analyte

. All results are rounded to three significant digits. If an analyte was not detected at

a concentration higher than th e method detection limit, the result is reported as “ND” followed

by the sample

- specific quantitation limit in parentheses. If an analyte was measured above the

method detection limit, but below the quantitation limit, the result is reported as “NQ” follow ed

by the sample

- specific quantitation limit i n parentheses.

Table s 4

- 4 and 4

- 5 compare the average results for classical and metal analytes for SP

- 1,

SP

- 2 and SP

- 3

. The data presented in this report are not paired results, meaning that the sample

collection across the treatment system was not timed to reflect the amount of time it takes the

wastewater to pass through the system.

Appendix Tables A

- 1 through A

- 8 present all th e analytical results for each sample point

, including J

- values.4-2

ND

– Not detected (number in parentheses is the quantitation limit).

NQ

– Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the q uantitation limit). The analytical resul t is

presented in Appendix A with a J flag designation. A “NQ” for the 2

- day average result indicates that all results were below the quantitation limit, but at least one result is a J

value.

B

– Analyte was found in the blank and sample.

Est

– Estimated v alue.

F

– MS and/or MSD not within laboratory control limits. Table 4

- 1

. Influent to FGD Wastewater Treatment System

, Brindisi

Analyte Units Method Influent to FGD Wastewater Treatment System (SP

- 1)

Day 2 Day 3 2

- Day Average

Classicals

Ammonia mg/L 350.1 12.0 12 Est 12.0

Nitrate Nitrite as N mg/L 353.2 56.0 46 Est 51.0

Nitrogen, Total Kjeldahl mg/L 351.2 3.60 Est 11 B, Est 7.30

Chemical Oxygen Demand mg/L 410.4 110 100 Est 105

Chloride mg/L 300.0 6,400 6,200 6,300

Sulfate mg/L 300.0 7,000 5,700 Est 6,350

Total Dissolved Solids mg/L 2540C 13,000 15,000 14,000

Total Suspended Solids mg/L 2540D 2,600 F, Est 3,600 3,100

Phosphorus, Total mg/L 365.1 0.0840 6 Est 3.04

Total Metals

Aluminum ug/L 200.7 70,000 B 120,000 B 95,000

Antimony ug/L 200.8 11.0 14 12.5

Arsenic ug/L 200.8 53.0 55 54.0

Barium ug/L 200.7 1,400 1,200 1,300

Beryllium ug/L 200.7 9.10 11 10.1

Boron ug/L 200.7 83,000 100,000 91,500

Cadmium ug/L 200.8 6.30 6 6.15

Calcium ug/L 200.7 1,700,000 1,300,000 1,500,000

Chromium ug/L 200.8 190 290 240

Cobalt ug/L 200.7 44.0 59 51.5

Copper ug/L 200.8 87.0 110 98.5

Iron ug/L 200.7 26,000 44,000 35,000

Lead ug/L 200.8 53.0 82 67.5

Magnesium ug/L 200.7 98,000 80,000 89,000

Manganese ug/L 200.7 990 1,000 995

Mercury ng/L 1631E 26,900 21,100 24,000

Molybdenum ug/L 200.7 85.0 110 97.5

Nickel ug/L 200.8 140 160 150

Selenium ug/L 200.8 220 290 2554-3

ND

– Not detected (number in parentheses is the quantitation limit).

NQ

– Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the q uantitation limit). The analytical resul t is

presented in Appendix A with a J flag designation. A “NQ” for the 2

- day average result indicates that all results were below the quantitation limit, but at least one result is a J

value.

B

– Analyte was found in the blank and sample.

Est

– Estimated v alue.

F

– MS and/or MSD not within laboratory control limits. Table 4

- 1

. Influent to FGD Wastewater Treatment System

, Brindisi

Analyte Units Method Influent to FGD Wastewater Treatment System (SP

- 1)

Day 2 Day 3 2

- Day Average

Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00)

Sodium ug/L 200.7 5,700,000 B 6,900,000 B 6,300,000

Thallium ug/L 200.8 2.00 2.1 2.05

Tin ug/L 200.7 NQ (200) NQ (200) NQ (200)

Titanium ug/L 200.7 4,400 7,500 5,950

Vanadium ug/L 200.8 620 670 645

Zinc ug/L 200.7 670 430 5504-4

<

- Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).

ND

– Not detected (number in parentheses is the quantitation limit).

NQ

– Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the q uantitation limit). The analytical result is

presented in Appendix A with a J flag designation. A “NQ” for the 3

- day average result indicates that all results were below the quantitation limit, but at least one result is a J

- value.

4

– MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control l imits are not applicable.

B

– Analyte was found in the blank and sample.

Est

– Estimated value.

F

– MS and/or MSD not within laboratory control limits. Table 4

- 2 . Distillate from Brine Concentrator, Brindisi

Analyte Units Method Distillate from the Brine Concentrator (SP

- 2)

Day 1 Day 2 Day 3 3

- Day Average

Classicals

Ammonia mg/L 350.1 21.0 19.0 15.0 Est 18.3

Nitrate Nitrite as N mg/L 353.2 0.110 0.130 0.160 Est 0.133

Nitrogen, Total Kjeldahl mg/L 351.2 20.0 18.0 4 16.0 B, Est 18.0

Chemical Oxygen Demand mg/L 410.4 ND (20.0) ND (20.0) F NQ (20.0) NQ (20.0)

Chloride mg/L 300.0 ND (3.00) NQ (3.00) F ND (3.00) NQ (3.00)

Sulfate mg/L 300.0 ND (5.00) ND (5.00) ND (5.00) ND (5.00)

Total Dissolved Solids mg/L 2540C 13.0 10.0 NQ (10.0) < 9.33

Total Suspended Solids mg/L 2540D ND (4.00) ND (4.00) ND (4.00) ND (4.00)

Phosphorus, Total mg/L 365.1 ND (0.0500) ND (0.0500) ND (0.0500) ND (0.0500)

Total Metals

Aluminum ug/L 200.7 NQ (200) B NQ (200) B NQ (200) B NQ (200)

Antimony ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00)

Arsenic ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.00)

Barium ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.0)

Beryllium ug/L 200.7 ND (2.00) ND (2.00) ND (2.00) ND (2.00)

Boron ug/L 200.7 3,600 6,200 4 3,100 4,300

Cadmium ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.00)

Calcium ug/L 200.7 ND (400) NQ (400) NQ (400) NQ (400)

Chromium ug/L 200.8 ND (8.00) ND (8.00) ND (8.00) ND (8.00)

Cobalt ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.0)

Copper ug/L 200.8 ND (4.00) NQ (4.00) ND (4.00) NQ (4.00)

Iron ug/L 200.7 ND (200) ND (200) ND (200) ND (200)

Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00)

Magnesium ug/L 200.7 ND (400) NQ (400) ND (400) NQ (400)

Manganese ug/L 200.7 ND (20.0) NQ (20.0) ND (20.0) NQ (20.0)

Mercury ng/L 1631E 3.98 3.13 2.89 3.33

Molybdenum ug/L 200.7 ND (40.0) ND (40.0) ND (40.0) ND (40.0)4-5

<

- Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).

ND

– Not detected (number in parentheses is the quantitation limit).

NQ

– Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the q uantitation limit). The analytical result is

presented in Appendix A with a J flag designation. A “NQ” for the 3

- day average result indicates that all results were below the quantitation limit, but at least one result is a J

- value.

4

– MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control l imits are not applicable.

B

– Analyte was found in the blank and sample.

Est

– Estimated value.

F

– MS and/or MSD not within laboratory control limits. Table 4

- 2 . Distillate from Brine Concentrator, Brindisi

Analyte Units Method Distillate from the Brine Concentrator (SP

- 2)

Day 1 Day 2 Day 3 3

- Day Average

Nickel ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.00)

Selenium ug/L 200.8 ND (4.00) ND (4.00) NQ (4.00) NQ (4.00)

Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00)

Sodium ug/L 200.7 NQ (10,000) B NQ (10,000) B NQ (10,000) B NQ (10,000)

Thallium ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00)

Tin ug/L 200.7 ND (200) ND (200) ND (200) ND (200)

Titanium ug/L 200.7 ND (20.0) ND (20.0) NQ (20.0) NQ (20.0)

Vanadium ug/L 200.8 ND (10.0) ND (10.0) ND (10.0) ND (10.0)

Zinc ug/L 200.7 NQ (40.0) 71.0 ND (40.0) < 37.04-6

<

- Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).

ND

– Not detected (number in parentheses is the quantitation limit).

NQ

– Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the q uantitation limit). The analytical result is

presented in Appendix A with a J flag designation. A “NQ” for the 4

- day average result indicates that all results were below the quantitation limit, but at least one result is a J

value.

4

– MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control l imits are not applicable.

B

– Analyte was found in the blank and sample.

Est

– Estimated value. Table 4

- 3

. Condensate from Crystallizer, Brindisi

Analyte Units Method Condensate from the Crystallizer (SP

- 3)

Day 1 Day 2 Day 3 3

- Day Average

Classicals

Ammonia mg/L 350.1 26.0 43.0 22.0 4, Est 30.3

Nitrate Nitrite as N mg/L 353.2 NQ (0.100) NQ (0.100) 0.100 Est < 0.0667

Nitrogen, Total Kjeldahl mg/L 351.2 25.0 37.0 Est 25.0 B,4, Est 29.0

Chemical Oxygen Demand mg/L 410.4 ND (20.0) ND (20.0) NQ (20.0) NQ (20.0)

Chloride mg/L 300.0 ND (3.00) ND (3.00) ND (3.00) ND (3.00)

Sulfate mg/L 300.0 ND (5.00) ND (5.00) ND (5.00) ND (5.00)

Total Dissolved Solids mg/L 2540C 10.0 22.0 NQ (10.0) < 12.3

Total Suspended Solids mg/L 2540D ND (4.00) ND (4.00) ND (4.00) ND (4.00)

Phosphorus, Total mg/L 365.1 ND (0.0500) ND (0.0500) ND (0.0500) ND (0.0500)

Total Metals

Aluminum ug/L 200.7 NQ (200) B NQ (200) B ND (200) NQ (200)

Antimony ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00)

Arsenic ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.00)

Barium ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.0)

Beryllium ug/L 200.7 ND (2.00) ND (2.00) ND (2.00) ND (2.00)

Boron ug/L 200.7 3,200 3,100 3,300 3,200

Cadmium ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.00)

Calcium ug/L 200.7 ND (400) ND (400) ND (400) ND (400)

Chromium ug/L 200.8 ND (8.00) ND (8.00) ND (8.00) ND (8.00)

Cobalt ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.0)

Copper ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00)

Iron ug/L 200.7 ND (200) ND (200) ND (200) ND (200)

Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00)

Magnesium ug/L 200.7 ND (400) ND (400) ND (400) ND (400)

Manganese ug/L 200.7 NQ (20.0) ND (20.0) ND (20.0) NQ (20.0)

Mercury ng/L 1631E 20.4 20.7 10.9 17.3

Molybdenum ug/L 200.7 NQ (40.0) NQ (40.0) NQ (40.0) NQ (40.0)4-7

<

- Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).

ND

– Not detected (number in parentheses is the quantitation limit).

NQ

– Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the q uantitation limit). The analytical result is

presented in Appendix A with a J flag designation. A “NQ” for the 4

- day average result indicates that all results were below the quantitation limit, but at least one result is a J

value.

4

– MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control l imits are not applicable.

B

– Analyte was found in the blank and sample.

Est

– Estimated value. Table 4

- 3

. Condensate from Crystallizer, Brindisi

Analyte Units Method Condensate from the Crystallizer (SP

- 3)

Day 1 Day 2 Day 3 3

- Day Average

Nickel ug/L 200.8 NQ (4.00) ND (4.00) NQ (4.00) NQ (4.00)

Selenium ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00)

Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00)

Sodium ug/L 200.7 NQ (10,000) B NQ (10,000) B NQ (10,000) B NQ (10,000)

Thallium ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00)

Tin ug/L 200.7 ND (200) ND (200) ND (200) ND (200)

Titanium ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.0)

Vanadium ug/L 200.8 ND (10.0) ND (10.0) ND (10.0) ND (10.0)

Zinc ug/L 200.7 ND (40.0) NQ (40.0) ND (40.0) NQ (40.0)4-8

<

- Average result includes at least one value measured below the quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).

ND

– Not detected (number in parentheses is the quantitation limit).

NQ

– Analyte was measured above the method detection limit, but below the quantit ation limit (number shown in parentheses is the quantitation limit). The analytical

result is presented in Appendix A with a J flag designation. A “NQ” for the 4

- day average result indicates that all results were below the quantitation limit, but at least

one result is a J

- value. Table 4

- 4

. Classical Pollutants Average Data Summary for FGD Wastewater Treatment System, Brindis i

Analyte Unit Method Influent to FGD Wastewater

Treatment System (SP

- 1)

2

- Day Average Distillate from Brine

Concentrator (SP

- 2)

3

- Day Average Condensate from

Crystallizer (SP

- 3)

3

- Day Average

Classicals

Ammonia mg/L 350.1 12.0 18.3 30.3

Nitrate Nitrite as N mg/L 353.2 51.0 0.133 < 0.0667

Nitrogen, Total Kjeldahl mg/L 351.2 7.30 18.0 29.0

Chemical Oxygen Demand mg/L 410.4 105 NQ (20.0) NQ (20.0)

Chloride mg/L 300.0 6,300 NQ (3.00) ND (3.00)

Sulfate mg/L 300.0 6,350 ND (5.00) ND (5.00)

Total Dissolved Solids mg/L 2540C 14,000 < 9.33 < 12.3

Total Suspended Solids mg/L 2540D 3,100 ND (4.00) ND (4.00)

Phosphorus, Total mg/L 365.1 3.04 ND (0.0500) ND (0.0500)4-9

<

- Average result includes at least one value measured below the quantita t ion limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).

ND

– Not detected (number in parentheses is the quantitation limit).

NQ

– Analyte was measured above the method detection limit, but below the quantitation limit (number shown in parentheses is the q uantitation limit). The analytical result is

presented in Appendix A with a J flag de signation. A “NQ” for the 4

- day average result indicates that all results were below the quantitation limit, but at least one result is a J

value. Table 4

- 5

. Metal Pollutants Average Data Summary for FGD Wastewater Treatment System, Brindisi

Analyte Unit Method Influent to FGD Wastewater

Treatment System (SP

- 1)

2

- Day Average Distillate from Brine

Concentrator (SP

- 2)

3

- Day Average Condensate from Crystallizer

(SP

- 3)

3

- Day Average

Total Metals

Aluminum ug/L 200.7 95,000 NQ (200) NQ (200)

Antimony ug/L 200.8 12.5 ND (2.00) ND (2.00)

Arsenic ug/L 200.8 54.0 ND (4.00) ND (4.00)

Barium ug/L 200.7 1,300 ND (20.0) ND (20.0)

Beryllium ug/L 200.7 10.1 ND (2.00) ND (2.00)

Boron ug/L 200.7 91,500 4,300 3,200

Cadmium ug/L 200.8 6.15 ND (4.00) ND (4.00)

Calcium ug/L 200.7 1,500,000 NQ (400) ND (400)

Chromium ug/L 200.8 240 ND (8.00) ND (8.00)

Cobalt ug/L 200.7 51.5 ND (20.0) ND (20.0)

Copper ug/L 200.8 98.5 NQ (4.00) NQ (4.00)

Iron ug/L 200.7 35,000 ND (200) ND (200)

Lead ug/L 200.8 67.5 ND (2.00) ND (2.00)

Magnesium ug/L 200.7 89,000 NQ (400) ND (400)

Manganese ug/L 200.7 995 NQ (20.0) NQ (20.0)

Mercury ng/L 1631E 24,000 3.33 17.3

Molybdenum ug/L 200.7 97.5 ND (40.0) NQ (40.0)

Nickel ug/L 200.8 150 ND (4.00) NQ (4.00)

Selenium ug/L 200.8 255 NQ (4.00) NQ (4.00)

Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00)

Sodium ug/L 200.7 6,300,000 NQ (10,000) NQ (10,000)

Thallium ug/L 200.8 2.05 ND (2.00) ND (2.00)

Tin ug/L 200.7 NQ (200) ND (200) ND (200)

Titanium ug/L 200.7 5,950 NQ (20.0) ND (20.0)

Vanadium ug/L 200.8 645 ND (10.0) ND (10.0)

Zinc ug/L 200.7 550 < 37.0 NQ (40.0)5

- 1 5. D ATA Q UALITY

Quality assurance/quality control ( QA/QC ) procedures applicable to the Brindisi

sampling episode are outlined in the Quality Assurance Project Plan for the Steam Electric

Rulemaking (QAPP) [ 2 ]. This section describes the QC procedures used to assess the precision

and accuracy of the analytical data presented in Section 4 and Appendi x A . QC practices used

for this sampling episode include the analysis of matrix spikes, blanks, and QC standard checks.

5.1

ERG contracted directly with analytical laboratories for the analysis of samples collected

during this episode

. ERG verified that the performance of the laboratories selected was

acceptable by conducting QC checks of the analytical data. D ata review chemists at ERG

prepared written data review narratives describing any qualifications of the analytical data from

th is episode. The data review narratives are included in Appendix B

. Analytical Quality Control

5.2

This section discusses the bottle blanks, equipment blanks, and field blanks results.

Section 3.8 of the Sampling Plan discusses field QC specifications. Field Quality Control

5.2.1 Bottle Blanks

ERG collects bottle blanks to evaluate possible contamination from the sample collection

bottles. Bottle blanks were collected and analyzed for metals (EPA Method 200.8, 200.7, and

1631E) by the supplier of the pre cleaned bottles, Frontier Global Sc iences

.

Frontier Global Sciences collected the bottle blanks for the metals sample bottles by

filling the precleaned bottle with reagent water and preserving the sample with nitric acid to a pH

<2 S.U

. Frontier Global S ciences then analyzed the samples usi ng EPA Method 1638.

Frontier Global Sciences collected the bottle blanks for the mercury sample bottles by

filling the precleaned bottle with reagent water and preserving the sample with bromine

monochloride. Frontier Global Sciences then analyzed the sam ples using EPA Method 1631E.

Albion Environmental collected the bottle blank s for the 20

- liter composite container by

filling the container with approximately two liters of ASTM Type 1 water and allowing it to soak

for approximately 24 hours. During this p eriod, the laboratory shook the container periodically

and changed its orientation to expose all surfaces of the container to the ASTM Type 1 water.

Albion Environmental then shook the 20

- liter container and poured a representative sample into

a precleaned LDPE sample bottle. The blank samples were then preserved and analyzed

according to the analytical methods (i.e., EPA Method 1638 )

.

No metals were detected in the bottle blank s

, except for nickel being detected in the 500

- mL plastic bottle s at a concentration of 0.14 ug/L

. This concentration is well below the

quantitation limit used for the sample analyses (i.e., 4.0 ug/L); therefore, the contamination did

not affect the results of the sampling episode. Appendix Table A

- 9 presents all of t he analytical5

- 2 results from the bottle blank analyses for the bottles used to collect the metals and mercury

samples.

5.2.2 Equipment Blanks

EPA collects equipment blanks to evaluate possible contamination from the equipment

used for sample collection. The techni que s used to collect field blanks for this sampling episode

(as described in Section 5.2.3) include the sampling equipment and therefore would identify

whether the sampling equipment was introducing contamination . In addition, Frontier Global

Sciences coll ected and analyzed equipment blanks for metals (EPA Method 1638 and 1631E) for

each type of precleaned equipment supplied for the episode.

Frontier Global Sciences collected the equipment blanks for the fabricated tubing sets by

pumping reagent water thro ugh the cleaned and fully assembled equipment sets into a cleaned

bottle (an HDPE bottle for metals and a glass bottle for mercury). The blank samples were then

preserved and analyzed according to the analytical methods (EPA Method 1638 and 1631E), as

desc ribed in Section 5.2.1 for the bottle blank samples.

No metals were detected in the equipment blanks, indicating that there was no

contamination from the sampling equipment. Appendix Table A

- 9 presents all of the analytical

results from the bottle blank and equipment blank analyses for all of the equipment used for the

collection of metals and mercury samples.

5.2.3 Field Blanks

The sampling team collected field blanks (SP

- 4 , SP

- 5

, and SP

- 6 ) to evaluate poss ible

contamination from sampling equipment, sampling equipment decontamination procedures,

sample collection procedures, or atmospheric contamination. EPA analyzed the field blank

samples for total metals and total mercury

.

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

- 4 )

were collected by p ump ing ASTM Type 1 water through the silicone tubing used for sample

collection. To prevent potential atmospheric deposition, t he sampling team placed the sample

bottles in a “cleanb ox.” Prior to filling the sample bottles, the tubing was purged with

approximately 1 liter of blank water

. The ASTM Type 1 water was then pumped through the

tubing into the sample bottles. EPA collected the field blank samples as duplicate samples with

Ene l , using the same procedure discussed in the sample collection description (Section 3.1).

As described in Section 3.4, the field blank samples for the influent to the FGD

wastewater treatment system (SP

- 4) were collected on Day 1 of sample collection, but the

influent samples were collected on Days 2 and 3 because the discharge pipe was clogged on Day

1 and the sampling team was not informed of the clogged pipe until after the field blanks were

collected. The procedures for the field blank collection would not have changed based on the

sample collection day and there were no weather conditions of concern (e.g., rain) on any of the

sampling days. Therefore, the day of the field blank collection did not impact the results of the

field blanks and is represent ative of the other two days of sample collection at SP

- 1.5

- 3 The total mercury field blank sample for the distillate from the brine concentrator (SP

- 5 )

and the condensate from the crystallizer (SP

- 6 ) were collected by shrouding one of the two taps

on the samp le tap splitter with a clear plastic bag. Before purging the sample tap , ASTM Type 1

water was poured directly into the sample bottles under the clear plastic bag.

The metals field blank samples (Methods 200.7 and 200.8) for the distillate from the

brine concentrator (SP

- 5) and the condensate from the crystallizer (SP

- 6) were collected by

filling a 20

- liter composite container with approximately five liters of ASTM Type 1 water. The

same T

- splitter tubing used to collect the composite sample at each sample point was first used to

collect the field blank. Prior to attaching the tubing to the sample tap, it was placed directly into

the bottle of ASTM Type 1 water. The other end of the tubing was attached to the vented cap on

the 20

- liter field blank com posite container. After enough volume was pumped into the 20

- liter

field blank composite container

, the vented cap was replaced with a closed cap and the field

blank container was placed on ice. The vented cap used for the field blank collection was the

sa me cap subsequently used when collecting the composite sample

.

After four hours, the ASTM Type 1 water in the 20

- liter field blank composite container

was pumped into the individual sample bottles

. The sample bottles were placed in a “cleanbox”

and the AST M Type 1 water was pumped through the tubing and into the sample bottles. EPA

collected the field blank samples as duplicate samples with Enel , using the same procedure

discussed in the sample collection description (Section 3.1). Prior to filling the samp le bottles,

the tubing was purged with approximately one liter of ASTM Type 1 water. Then the samplers

placed the sample bottles in a “cleanbox” and collected the t otal metals field blank samples

(Methods 200.7 and 200.8)

. No metals were detected in the fi eld blank samples above the

quantitation limit, indicating that there was no contamination from the sample collection

technique

. Appendix Tables A

- 10 through A

- 1 6 present the analytical results for the field blanks

from each of the sampling points , including all qualified results and all results that were

measured above the method detection limit, but below the quantitation limit (i.e., J

- values).6

- 1 6. R EFERENCES

1. Ea stern Research Group, Inc., 2011

. Sampling Plan, Enel’ s Federico II Power Plant

. Ma rch 21 . DCN SE 01184

.

2. Eastern Research Group, Inc., 20 10

. Quality Assurance Project Plan for the Steam

Electric Effluent Guidelines Rulemaking . ( October ). DCN SE00058.Appendix A

ANALYTICAL RESULTSND

– Not detected (number in parentheses is the quantitation limit).

B

– Analyte was found in the blank and sample.

Est

– Estimated value.

F

– MS and/or MSD not within laboratory control limits.

J

– Result measured above the MDL, but less than the quantitation limit.

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit). Table A

- 1

. Influent to FGD Wastewater Treatment System, Day 2 Analytical Results, Brindisi

Analyte Method Unit Dilution

Factor Sample

Specific

MDL Sample

Specific QL Concentration

Classicals

Ammonia 350.1 mg/L 2 0.11 2 12

Nitrate Nitrite as N 353.2 mg/L 20 0.38 2 56

Nitrogen, Total Kjeldahl 351.2 mg/L 1 0.077 1 3.6 Est

Chemical Oxygen Demand 410.4 mg/L 1 4.1 20 110

Chloride 300.0 mg/L 200 51 600 6,400

Sulfate 300.0 mg/L 200 46 1,000 7,000

Total Dissolved Solids 2540C mg/L 1 94 200 13,000

Total Suspended Solids 2540D mg/L 1 11 40 2,600 F, Est

Phosphorus, Total 365.1 mg/L 1 0.005 0.05 0.084

Total Metals

Aluminum 200.7 ug/L 50 240 5,000 70,000 B

Antimony 200.8 ug/L 2 0.72 2 11

Arsenic 200.8 ug/L 2 1.2 4 53

Barium 200.7 ug/L 2 2.5 20 1,400

Beryllium 200.7 ug/L 2 0.71 2 9.1

Boron 200.7 ug/L 50 170 5,000 83,000

Cadmium 200.8 ug/L 2 1.2 4 6.3

Calcium 200.7 ug/L 50 1,700 10,000 1,700,000

Chromium 200.8 ug/L 2 3.3 8 190

Cobalt 200.7 ug/L 2 1.1 20 44

Copper 200.8 ug/L 2 0.96 4 87ND

– Not detected (number in parentheses is the quantitation limit).

B

– Analyte was found in the blank and sample.

Est

– Estimated value.

F

– MS and/or MSD not within laboratory control limits.

J

– Result measured above the MDL, but less than the quantitation limit.

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit). Table A

- 1

. Influent to FGD Wastewater Treatment System, Day 2 Analytical Results, Brindisi

Analyte Method Unit Dilution

Factor Sample

Specific

MDL Sample

Specific QL Concentration

Iron 200.7 ug/L 50 800 5,000 26,000

Lead 200.8 ug/L 2 0.73 2 53

Magnesium 200.7 ug/L 2 21 400 98,000

Manganese 200.7 ug/L 2 0.51 20 990

Mercury 1631E ng/L 4,000 965 2,020 26,900

Molybdenum 200.7 ug/L 2 1.6 40 85

Nickel 200.8 ug/L 2 0.89 4 140

Selenium 200.8 ug/L 2 0.62 4 220

Silver 200.8 ug/L 2 0.59 2 ND (2) U

Sodium 200.7 ug/L 50 4,600 250,000 5,700,000 B

Thallium 200.8 ug/L 2 0.47 2 2

Tin 200.7 ug/L 2 4.8 200 14 J

Titanium 200.7 ug/L 50 41 500 4,400

Vanadium 200.8 ug/L 2 1.7 10 620

Zinc 200.7 ug/L 2 9.1 40 670ND

– Not detected (number in parentheses is the quantitation limit).

B

– Analyte was found in the blank and sample.

Est

– Estimated value.

J

– Result measured above the MDL, but less than the quantitation limit.

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit). Table A

- 2

. Influent to FGD Wastewater Treatment System, Day 3 Analytical Results, Brindisi

Analyte Method Unit Dilution

Factor Sample

Specific MDL Sample

Specific QL Concentration

Classicals

Ammonia 350.1 mg/L 2 0.11 2 12 Est

Nitrate Nitrite as N 353.2 mg/L 10 0.19 1 46 Est

Nitrogen, Total Kjeldahl 351.2 mg/L 1 0.38 5 11 B, Est

Chemical Oxygen Demand 410.4 mg/L 1 4.1 20 100 Est

Chloride 300.0 mg/L 200 51 600 6,200

Sulfate 300.0 mg/L 200 46 1,000 5,700 Est

Total Dissolved Solids 2540C mg/L 1 94 200 15,000

Total Suspended Solids 2540D mg/L 1 11 40 3,600

Phosphorus, Total 365.1 mg/L 10 0.05 0.5 6 Est

Total Metals

Aluminum 200.7 ug/L 50 240 5,000 120,000 B

Antimony 200.8 ug/L 2 0.72 2 14

Arsenic 200.8 ug/L 2 1.2 4 55

Barium 200.7 ug/L 2 2.5 20 1,200

Beryllium 200.7 ug/L 2 0.71 2 11

Boron 200.7 ug/L 50 170 5,000 100,000

Cadmium 200.8 ug/L 2 1.2 4 6

Calcium 200.7 ug/L 50 1,700 10,000 1,300,000

Chromium 200.8 ug/L 2 3.3 8 290

Cobalt 200.7 ug/L 2 1.1 20 59

Copper 200.8 ug/L 2 0.96 4 110

Iron 200.7 ug/L 2 32 200 44,000

Lead 200.8 ug/L 2 0.73 2 82

Magnesium 200.7 ug/L 2 21 400 80,000ND

– Not detected (number in parentheses is the quantitation limit).

B

– Analyte was found in the blank and sample.

Est

– Estimated value.

J

– Result measured above the MDL, but less than the quantitation limit.

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit). Table A

- 2

. Influent to FGD Wastewater Treatment System, Day 3 Analytical Results, Brindisi

Analyte Method Unit Dilution

Factor Sample

Specific MDL Sample

Specific QL Concentration

Manganese 200.7 ug/L 2 0.51 20 1,000

Mercury 1631E ng/L 4,000 965 2,020 21,100

Molybdenum 200.7 ug/L 2 1.6 40 110

Nickel 200.8 ug/L 2 0.89 4 160

Selenium 200.8 ug/L 2 0.62 4 290

Silver 200.8 ug/L 2 0.59 2 ND (2) U

Sodium 200.7 ug/L 50 4,600 250,000 6,900,000 B

Thallium 200.8 ug/L 2 0.47 2 2.1

Tin 200.7 ug/L 2 4.8 200 24 J

Titanium 200.7 ug/L 2 1.6 20 7,500

Vanadium 200.8 ug/L 2 1.7 10 670

Zinc 200.7 ug/L 2 9.1 40 430ND

– Not detected (number in parentheses is the quantitation limit).

B

– Analyte was found in the blank and sample.

J

– Result measured above the MDL, but less than the quantitation limit.

U

– Result below the MDL. (Number shown in parentheses is the quantitat ion limit). Table A

- 3

. Influent to FGD Wastewater Treatment System, Day 1 Analytical Results, Brindisi

Analyte Method Unit Dilution

Factor Sample

Specific MDL Sample

Specific QL Concentration

Classicals

Ammonia 350.1 mg/L 4 0.22 4 21

Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 0.11

Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 20

Chemical Oxygen Demand 410.4 mg/L 1 4.1 20 ND (20) U

Chloride 300.0 mg/L 1 0.25 3 ND (3) U

Sulfate 300.0 mg/L 1 0.23 5 ND (5) U

Total Dissolved Solids 2540C mg/L 1 4.7 10 13

Total Suspended Solids 2540D mg/L 1 1.1 4 ND (4) U

Phosphorus, Total 365.1 mg/L 1 0.005 0.05 ND (0.05) U

Total Metals

Aluminum 200.7 ug/L 2 9.4 200 10 B

Antimony 200.8 ug/L 2 0.72 2 ND (2)

Arsenic 200.8 ug/L 2 1.2 4 ND (4)

Barium 200.7 ug/L 2 2.5 20 ND (20)

Beryllium 200.7 ug/L 2 0.71 2 ND (2)

Boron 200.7 ug/L 2 6.7 200 3,600

Cadmium 200.8 ug/L 2 1.2 4 ND (4)

Calcium 200.7 ug/L 2 69 400 ND (400)

Chromium 200.8 ug/L 2 3.3 8 ND (8)

Cobalt 200.7 ug/L 2 1.1 20 ND (20)

Copper 200.8 ug/L 2 0.96 4 ND (4)

Iron 200.7 ug/L 2 32 200 ND (200)

Lead 200.8 ug/L 2 0.73 2 ND (2)

Magnesium 200.7 ug/L 2 21 400 ND (400)ND

– Not detected (number in parentheses is the quantitation limit).

B

– Analyte was found in the blank and sample.

J

– Result measured above the MDL, but less than the quantitation limit.

U

– Result below the MDL. (Number shown in parentheses is the quantitat ion limit). Table A

- 3

. Influent to FGD Wastewater Treatment System, Day 1 Analytical Results, Brindisi

Analyte Method Unit Dilution

Factor Sample

Specific MDL Sample

Specific QL Concentration

Manganese 200.7 ug/L 2 0.51 20 ND (20)

Mercury 1631E ng/L 1 0.24 0.51 3.98

Molybdenum 200.7 ug/L 2 1.6 40 ND (40)

Nickel 200.8 ug/L 2 0.89 4 ND (4)

Selenium 200.8 ug/L 2 0.62 4 ND (4)

Silver 200.8 ug/L 2 0.59 2 ND (2) U

Sodium 200.7 ug/L 2 180 10,000 290 B

Thallium 200.8 ug/L 2 0.47 2 ND (2)

Tin 200.7 ug/L 2 4.8 200 ND (200) J

Titanium 200.7 ug/L 2 1.6 20 ND (20)

Vanadium 200.8 ug/L 2 1.7 10 ND (10)

Zinc 200.7 ug/L 2 9.1 40 21ND

– Not detected (number in parentheses is the quantitation limit).

4

– MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are not applicable.

B

– Analyte was found in the blank and sample.

F

– MS and/or MSD not within laboratory control limits.

J

– Result measured above the MDL, but less than the quantitation limit.

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit). Table A

- 4. Distillate from Brine Concentrator, Day 2 Analytical Results, Brindisi

Analyte Method Unit Dilution

Factor Sample

Specific MDL Sample

Specific QL Concentration

Classicals

Ammonia 350.1 mg/L 4 0.22 4 19

Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 0.13

Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 18 4

Chemical Oxygen Demand 410.4 mg/L 1 4.1 20 ND (20) U,F

Chloride 300.0 mg/L 1 0.25 3 0.34 J, F

Sulfate 300.0 mg/L 1 0.23 5 ND (5) U

Total Dissolved Solids 2540C mg/L 1 4.7 10 10

Total Suspended Solids 2540D mg/L 1 1.1 4 ND (4) U

Phosphorus, Total 365.1 mg/L 1 0.005 0.05 ND (0.05) U

Total Metals

Aluminum 200.7 ug/L 2 9.4 200 33 J,B

Antimony 200.8 ug/L 2 0.72 2 ND (2) U

Arsenic 200.8 ug/L 2 1.2 4 ND (4) U

Barium 200.7 ug/L 2 2.5 20 ND (20) U

Beryllium 200.7 ug/L 2 0.71 2 ND (2) U

Boron 200.7 ug/L 2 6.7 200 6,200 4

Cadmium 200.8 ug/L 2 1.2 4 ND (4) U

Calcium 200.7 ug/L 2 69 400 220 J

Chromium 200.8 ug/L 2 3.3 8 ND (8) U

Cobalt 200.7 ug/L 2 1.1 20 ND (20) U

Copper 200.8 ug/L 2 0.96 4 2.7 J

Iron 200.7 ug/L 2 32 200 ND (200) U

Lead 200.8 ug/L 2 0.73 2 ND (2) U

Magnesium 200.7 ug/L 2 21 400 25 JND

– Not detected (number in parentheses is the quantitation limit).

4

– MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are not applicable.

B

– Analyte was found in the blank and sample.

F

– MS and/or MSD not within laboratory control limits.

J

– Result measured above the MDL, but less than the quantitation limit.

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit). Table A

- 4. Distillate from Brine Concentrator, Day 2 Analytical Results, Brindisi

Analyte Method Unit Dilution

Factor Sample

Specific MDL Sample

Specific QL Concentration

Manganese 200.7 ug/L 2 0.51 20 1.4 J

Mercury 1631E ng/L 1 0.24 0.51 3.13

Molybdenum 200.7 ug/L 2 1.6 40 ND (40) U

Nickel 200.8 ug/L 2 0.89 4 ND (4) U

Selenium 200.8 ug/L 2 0.62 4 ND (4) U

Silver 200.8 ug/L 2 0.59 2 ND (2) U

Sodium 200.7 ug/L 2 180 10,000 480 J,B

Thallium 200.8 ug/L 2 0.47 2 ND (2) U

Tin 200.7 ug/L 2 4.8 200 ND (200) U

Titanium 200.7 ug/L 2 1.6 20 ND (20) U

Vanadium 200.8 ug/L 2 1.7 10 ND (10) U

Zinc 200.7 ug/L 2 9.1 40 71ND

– Not detected (number in parentheses is the quantitation limit).

B

– Analyte was found in the blank and sample.

Est

– Estimated value.

J

– Result measured above the MDL, but less than the quantitation limit.

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit). Table A

- 5

. Distillate from Brine Concentrator, Day 3 Analytical Results, Brindisi

Analyte Method Unit Dilution

Factor Sample

Specific MDL Sample

Specific QL Concentration

Classicals

Ammonia 350.1 mg/L 2 0.11 2 15 Est

Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 0.16 Est

Nitrogen, Total Kjeldahl 351.2 mg/L 2 0.15 2 16 B, Est

Chemical Oxygen Demand 410.4 mg/L 1 4.1 20 6.4 J

Chloride 300.0 mg/L 1 0.25 3 ND (3) U

Sulfate 300.0 mg/L 1 0.23 5 ND (5) U

Total Dissolved Solids 2540C mg/L 1 4.7 10 7 J

Total Suspended Solids 2540D mg/L 1 1.1 4 ND (4) U

Phosphorus, Total 365.1 mg/L 1 0.005 0.05 ND (0.05) U

Total Metals

Aluminum 200.7 ug/L 2 9.4 200 12 J,B

Antimony 200.8 ug/L 2 0.72 2 ND (2) U

Arsenic 200.8 ug/L 2 1.2 4 ND (4) U

Barium 200.7 ug/L 2 2.5 20 ND (20) U

Beryllium 200.7 ug/L 2 0.71 2 ND (2) U

Boron 200.7 ug/L 2 6.7 200 3,100

Cadmium 200.8 ug/L 2 1.2 4 ND (4) U

Calcium 200.7 ug/L 2 69 400 89 J

Chromium 200.8 ug/L 2 3.3 8 ND (8) U

Cobalt 200.7 ug/L 2 1.1 20 ND (20) U

Copper 200.8 ug/L 2 0.96 4 ND (4) U

Iron 200.7 ug/L 2 32 200 ND (200) U

Lead 200.8 ug/L 2 0.73 2 ND (2) U

Magnesium 200.7 ug/L 2 21 400 ND (400) UND

– Not detected (number in parentheses is the quantitation limit).

B

– Analyte was found in the blank and sample.

Est

– Estimated value.

J

– Result measured above the MDL, but less than the quantitation limit.

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit). Table A

- 5

. Distillate from Brine Concentrator, Day 3 Analytical Results, Brindisi

Analyte Method Unit Dilution

Factor Sample

Specific MDL Sample

Specific QL Concentration

Manganese 200.7 ug/L 2 0.51 20 ND (20) U

Mercury 1631E ng/L 1 0.24 0.51 2.89

Molybdenum 200.7 ug/L 2 1.6 40 ND (40) U

Nickel 200.8 ug/L 2 0.89 4 ND (4) U

Selenium 200.8 ug/L 2 0.62 4 0.67 J

Silver 200.8 ug/L 2 0.59 2 ND (2) U

Sodium 200.7 ug/L 2 180 10,000 1,200 J,B

Thallium 200.8 ug/L 2 0.47 2 ND (2) U

Tin 200.7 ug/L 2 4.8 200 ND (200) U

Titanium 200.7 ug/L 2 1.6 20 1.6 J

Vanadium 200.8 ug/L 2 1.7 10 ND (10) U

Zinc 200.7 ug/L 2 9.1 40 ND (40) UND

– Not detected (number in parentheses is the quantitation limit).

B

– Analyte was found in the blank and sample.

J

– Result measured above the MDL, but less than the quantitation limit.

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit). Table A

- 6

. Condensate from Crystallizer, Day 1 Analytical Results, Brindisi

Analyte Method Unit Dilution

Factor Sample

Specific MDL Sample

Specific QL Concentration

Classicals

Ammonia 350.1 mg/L 5 0.27 5 26

Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 0.061 J

Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 25

Chemical Oxygen Demand 410.4 mg/L 1 4.1 20 ND (20) U

Chloride 300.0 mg/L 1 0.25 3 ND (3) U

Sulfate 300.0 mg/L 1 0.23 5 ND (5) U

Total Dissolved Solids 2540C mg/L 1 4.7 10 10

Total Suspended Solids 2540D mg/L 1 1.1 4 ND (4) U

Phosphorus, Total 365.1 mg/L 1 0.005 0.05 ND (0.05) U

Total Metals

Aluminum 200.7 ug/L 2 9.4 200 19 J,B

Antimony 200.8 ug/L 2 0.72 2 ND (2) U

Arsenic 200.8 ug/L 2 1.2 4 ND (4) U

Barium 200.7 ug/L 2 2.5 20 ND (20) U

Beryllium 200.7 ug/L 2 0.71 2 ND (2) U

Boron 200.7 ug/L 2 6.7 200 3,200

Cadmium 200.8 ug/L 2 1.2 4 ND (4) U

Calcium 200.7 ug/L 2 69 400 ND (400) U

Chromium 200.8 ug/L 2 3.3 8 ND (8) U

Cobalt 200.7 ug/L 2 1.1 20 ND (20) U

Copper 200.8 ug/L 2 0.96 4 1.1 J

Iron 200.7 ug/L 2 32 200 ND (200) U

Lead 200.8 ug/L 2 0.73 2 ND (2) U

Magnesium 200.7 ug/L 2 21 400 ND (400) U

Manganese 200.7 ug/L 2 0.51 20 0.64 JND

– Not detected (number in parentheses is the quantitation limit).

B

– Analyte was found in the blank and sample.

J

– Result measured above the MDL, but less than the quantitation limit.

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit). Table A

- 6

. Condensate from Crystallizer, Day 1 Analytical Results, Brindisi

Analyte Method Unit Dilution

Factor Sample

Specific MDL Sample

Specific QL Concentration

Mercury 1631E ng/L 10 2.44 5.1 20.4

Molybdenum 200.7 ug/L 2 1.6 40 2.9 J

Nickel 200.8 ug/L 2 0.89 4 1.1 J

Selenium 200.8 ug/L 2 0.62 4 1.1 J

Silver 200.8 ug/L 2 0.59 2 ND (2) U

Sodium 200.7 ug/L 2 180 10,000 240 J,B

Thallium 200.8 ug/L 2 0.47 2 ND (2) U

Tin 200.7 ug/L 2 4.8 200 ND (200) U

Titanium 200.7 ug/L 2 1.6 20 ND (20) U

Vanadium 200.8 ug/L 2 1.7 10 ND (10) U

Zinc 200.7 ug/L 2 9.1 40 ND (40) UND

– Not detected (number in parentheses is the quantitation limit).

B

– Analyte was found in the blank and sample.

Est

– Estimated value.

J

– Result measured above the MDL, but less than the quantitation limit.

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit). Table A

- 7

. Condensate from Crystallizer, Day 2 Analytical Results, Brindisi

Analy te Method Unit Dilution

Factor Sample

Specific MDL Sample

Specific QL Concentration

Classicals

Ammonia 350.1 mg/L 5 0.27 5 43

Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 0.02 J

Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 37 Est

Chemical Oxygen Demand 410.4 mg/L 1 4.1 20 ND (20) U

Chloride 300.0 mg/L 1 0.25 3 ND (3) U

Sulfate 300.0 mg/L 1 0.23 5 ND (5) U

Total Dissolved Solids 2540C mg/L 1 4.7 10 22

Total Suspended Solids 2540D mg/L 1 1.1 4 ND (4) U

Phosphorus, Total 365.1 mg/L 1 0.005 0.05 ND (0.05) U

Total Metals

Aluminum 200.7 ug/L 2 9.4 200 12 J,B

Antimony 200.8 ug/L 2 0.72 2 ND (2) U

Arsenic 200.8 ug/L 2 1.2 4 ND (4) U

Barium 200.7 ug/L 2 2.5 20 ND (20) U

Beryllium 200.7 ug/L 2 0.71 2 ND (2) U

Boron 200.7 ug/L 2 6.7 200 3,100

Cadmium 200.8 ug/L 2 1.2 4 ND (4) U

Calcium 200.7 ug/L 2 69 400 ND (400) U

Chromium 200.8 ug/L 2 3.3 8 ND (8) U

Cobalt 200.7 ug/L 2 1.1 20 ND (20) U

Copper 200.8 ug/L 2 0.96 4 3.1 J

Iron 200.7 ug/L 2 32 200 ND (200) U

Lead 200.8 ug/L 2 0.73 2 ND (2) U

Magnesium 200.7 ug/L 2 21 400 ND (400) UND

– Not detected (number in parentheses is the quantitation limit).

B

– Analyte was found in the blank and sample.

Est

– Estimated value.

J

– Result measured above the MDL, but less than the quantitation limit.

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit). Table A

- 7

. Condensate from Crystallizer, Day 2 Analytical Results, Brindisi

Analy te Method Unit Dilution

Factor Sample

Specific MDL Sample

Specific QL Concentration

Manganese 200.7 ug/L 2 0.51 20 ND (20) U

Mercury 1631E ng/L 10 2.44 5.1 20.7

Molybdenum 200.7 ug/L 2 1.6 40 2.3 J

Nickel 200.8 ug/L 2 0.89 4 ND (4) U

Selenium 200.8 ug/L 2 0.62 4 0.92 J

Silver 200.8 ug/L 2 0.59 2 ND (2) U

Sodium 200.7 ug/L 2 180 10,000 250 J,B

Thallium 200.8 ug/L 2 0.47 2 ND (2) U

Tin 200.7 ug/L 2 4.8 200 ND (200) U

Titanium 200.7 ug/L 2 1.6 20 ND (20) U

Vanadium 200.8 ug/L 2 1.7 10 ND (10) U

Zinc 200.7 ug/L 2 9.1 40 9.2 JND

– Not detected (number in parentheses is the quantitation limit).

4

– MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are not applicable.

B

– Analyte was found in the blank and sample.

Est

– Estimated value.

J

– Result measured above the MDL , but less than the quantitation limit.

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit). Table A

- 8

. Condensate from Crystallizer, Day 3 Analytical Results, Brindisi

Analyte Method Unit Dilution

Factor Sample

Specific

MDL Sample

Specific QL Concentration

Classicals

Ammonia 350.1 mg/L 4 0.22 4 22 4, Est

Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 0.1 Est

Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 25 B,4, Est

Chemical Oxygen Demand 410.4 mg/L 1 4.1 20 9.6 J

Chloride 300.0 mg/L 1 0.25 3 ND (3) U

Sulfate 300.0 mg/L 1 0.23 5 ND (5) U

Total Dissolved Solids 2540C mg/L 1 4.7 10 9 J

Total Suspended Solids 2540D mg/L 1 1.1 4 ND (4) U

Phosphorus, Total 365.1 mg/L 1 0.005 0.05 ND (0.05) U

Total Metals

Aluminum 200.7 ug/L 2 9.4 200 ND (200) U

Antimony 200.8 ug/L 2 0.72 2 ND (2) U

Arsenic 200.8 ug/L 2 1.2 4 ND (4) U

Barium 200.7 ug/L 2 2.5 20 ND (20) U

Beryllium 200.7 ug/L 2 0.71 2 ND (2) U

Boron 200.7 ug/L 2 6.7 200 3,300

Cadmium 200.8 ug/L 2 1.2 4 ND (4) U

Calcium 200.7 ug/L 2 69 400 ND (400) U

Chromium 200.8 ug/L 2 3.3 8 ND (8) U

Cobalt 200.7 ug/L 2 1.1 20 ND (20) U

Copper 200.8 ug/L 2 0.96 4 3.7 J

Iron 200.7 ug/L 2 32 200 ND (200) UND

– Not detected (number in parentheses is the quantitation limit).

4

– MS and/or MSD did not meet laboratory criteria, but sample concentration is four times greater than the matrix spike amount, so control limits are not applicable.

B

– Analyte was found in the blank and sample.

Est

– Estimated value.

J

– Result measured above the MDL , but less than the quantitation limit.

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit). Table A

- 8

. Condensate from Crystallizer, Day 3 Analytical Results, Brindisi

Analyte Method Unit Dilution

Factor Sample

Specific

MDL Sample

Specific QL Concentration

Lead 200.8 ug/L 2 0.73 2 ND (2) U

Magnesium 200.7 ug/L 2 21 400 ND (400) U

Manganese 200.7 ug/L 2 0.51 20 ND (20) U

Mercury 1631E ng/L 10 2.44 5.1 10.9

Molybdenum 200.7 ug/L 2 1.6 40 1.7 J

Nickel 200.8 ug/L 2 0.89 4 1.1 J

Selenium 200.8 ug/L 2 0.62 4 1.6 J

Silver 200.8 ug/L 2 0.59 2 ND (2) U

Sodium 200.7 ug/L 2 180 10,000 230 J,B

Thallium 200.8 ug/L 2 0.47 2 ND (2) U

Tin 200.7 ug/L 2 4.8 200 ND (200) U

Titanium 200.7 ug/L 2 1.6 20 ND (20) U

Vanadium 200.8 ug/L 2 1.7 10 ND (10) U

Zinc 200.7 ug/L 2 9.1 40 ND (40) Ua Nickel was detected in one bottle blank for the 500

- mL plastic bottles at 0.14 ug/L.

ND

– Not detected (number in parentheses is the quantitation limit). Table A

- 9

. Bottle Blank and Equipment Blank Analytical Data, Brindisi

Analyte Method Process Units Concentration

HDPE 500 ml Plastic Bottles

– Bottle Blank (for metals samples)

Aluminum EPA 1638 Total Recoverable ug/L ND (4.0)

Antimony EPA 1638 Total Recoverable ug/L ND (0.020)

Arsenic EPA 1638 Total Recoverable ug/L ND (0.15)

Barium EPA 1638 Total Recoverable ug/L ND (0.20)

Beryllium EPA 1638 Total Recoverable ug/L ND (0.060)

Boron EPA 1638 Total Recoverable ug/L ND (3.0)

Cadmium EPA 1638 Total Recoverable ug/L ND (0.020)

Calcium EPA 1638 Total Recoverable ug/L ND (40)

Chromium EPA 1638 Total Recoverable ug/L ND (0.10)

Cobalt EPA 1638 Total Recoverable ug/L ND (0.10)

Copper EPA 1638 Total Recoverable ug/L ND (0.10)

Iron EPA 1638 Total Recoverable ug/L ND (10)

Lead EPA 1638 Total Recoverable ug/L ND (0.040)

Magnesium EPA 1638 Total Recoverable ug/L ND (2.5)

Manganese EPA 1638 Total Recoverable ug/L ND (0.10)

Molybdenum EPA 1638 Total Recoverable ug/L ND (0.060)

Nickel a EPA 1638 Total Recoverable ug/L 0.14

Selenium EPA 1638 Total Recoverable ug/L ND (0.60)

Silver EPA 1638 Total Recoverable ug/L ND (0.020)

Sodium EPA 1638 Total Recoverable ug/L ND (20)

Thallium EPA 1638 Total Recoverable ug/L ND (0.0050)

Tin EPA 1638 Total Recoverable ug/L ND (0.10)

Titanium EPA 1638 Total Recoverable ug/L ND (0.50)

Vanadium EPA 1638 Total Recoverable ug/L ND (0.10)

Zinc EPA 1638 Total Recoverable ug/L ND (0.20)

125 ml Glass Bottles

– Bottle Blank (for mercury composite samples)

Mercury EPA 1631E Total Recoverable ug/L ND (0.00050)

250 ml Glass Bottles

– Bot tle Blank (for mercury grab samples)

Mercury EPA 1631E Total Recoverable ug/L ND (0.00050)

LDPE 20 L Composite Bottles

– Bottle Blank (sample composite bottle for dissolved/filtration pump

- off)

Aluminum EPA 1638 Dissolved ug/L ND (2.0)

Antimony EPA 1638 Dissolved ug/L ND (0.50)

Arsenic EPA 1638 Dissolved ug/L ND (0.50)

Barium EPA 1638 Dissolved ug/L ND (0.10)

Beryllium EPA 1638 Dissolved ug/L ND (0.10)

Cadmium EPA 1638 Dissolved ug/L ND (0.10)

Chromium EPA 1638 Dissolved ug/L ND (1.0)

Cobalt EPA 1638 Dissolved ug/L ND (0.10)a Nickel was detected in one bottle blank for the 500

- mL plastic bottles at 0.14 ug/L.

ND

– Not detected (number in parentheses is the quantitation limit). Table A

- 9

. Bottle Blank and Equipment Blank Analytical Data, Brindisi

Analyte Method Process Units Concentration

Copper EPA 1638 Dissolved ug/L ND (0.30)

Lead EPA 1638 Dissolved ug/L ND (0.050)

Manganese EPA 1638 Dissolved ug/L ND (0.50)

Molybdenum EPA 1638 Dissolved ug/L ND (0.50)

Nickel EPA 1638 Dissolved ug/L ND (0.50)

Selenium EPA 1638 Dissolved ug/L ND (2.0)

Silver EPA 1638 Dissolved ug/L ND (0.10)

Thallium EPA 1638 Dissolved ug/L ND (0.050)

Vanadium EPA 1638 Dissolved ug/L ND (1.0)

Zinc EPA 1638 Dissolved ug/L ND (0.50)

Influent Tubing Set

– Equipment Blank ( 15 feet of #73 silicone tubing for sample collection for mercury and

metals directly from the wastewater basin )

Aluminum EPA 1638 Total Recoverable ug/L ND (4.0)

Antimony EPA 1638 Total Recoverable ug/L ND (0.020)

Arsenic EPA 1638 Total Recoverable ug/L ND (0.15)

Barium EPA 1638 Total Recoverable ug/L ND (0.20)

Beryllium EPA 1638 Total Recoverable ug/L ND (0.060)

Boron EPA 1638 Total Recoverable ug/L ND (3.0)

Cadmium EPA 1638 Total Recoverable ug/L ND (0.020)

Calcium EPA 1638 Total Recoverable ug/L ND (40)

Chromium EPA 1638 Total Recoverable ug/L ND (0.10)

Cobalt EPA 1638 Total Recoverable ug/L ND (0.10)

Copper EPA 1638 Total Recoverable ug/L ND (0.10)

Iron EPA 1638 Total Recoverable ug/L ND (10)

Lead EPA 1638 Total Recoverable ug/L ND (0.040)

Magnesium EPA 1638 Total Recoverable ug/L ND (2.5)

Manganese EPA 1638 Total Recoverable ug/L ND (0.10)

Mercury EPA 1631E Total Recoverable ug/L ND (0.00050)

Molybdenum EPA 1638 Total Recoverable ug/L ND (0.060)

Nickel EPA 1638 Total Recoverable ug/L ND (0.10)

Selenium EPA 1638 Total Recoverable ug/L ND (0.60)

Silver EPA 1638 Total Recoverable ug/L ND (0.020)

Sodium EPA 1638 Total Recoverable ug/L ND (20)

Thallium EPA 1638 Total Recoverable ug/L ND (0.0050)

Tin EPA 1638 Total Recoverable ug/L ND (0.10)

Titanium EPA 1638 Total Recoverable ug/L ND (0.50)

Vanadium EPA 1638 Total Recoverable ug/L ND (0.10)

Zinc EPA 1638 Total Recoverable ug/L ND (0.20)a Nickel was detected in one bottle blank for the 500

- mL plastic bottles at 0.14 ug/L.

ND

– Not detected (number in parentheses is the quantitation limit). Table A

- 9

. Bottle Blank and Equipment Blank Analytical Data, Brindisi

Analyte Method Process Units Concentration

Pump

- Off Tubing Set

– Equipment Blank (Three feet of Teflon® tubing, 10 feet of #73 silicone tubing, and 5

feet of #24 silicone tubing for total metals sample collection)

Aluminum EPA 1638 Total Recoverable ug/L ND (4.0)

Antimony EPA 1638 Total Recoverable ug/L ND (0.020)

Arsenic EPA 1638 Total Recoverable ug/L ND (0.15)

Barium EPA 1638 Total Recoverable ug/L ND (0.20)

Beryllium EPA 1638 Total Recoverable ug/L ND (0.060)

Boron EPA 1638 Total Recoverable ug/L ND (3.0)

Cadmium EPA 1638 Total Recoverable ug/L ND (0.020)

Calcium EPA 1638 Total Recoverable ug/L ND (40)

Chromium EPA 1638 Total Recoverable ug/L ND (0.10)

Cobalt EPA 1638 Total Recoverable ug/L ND (0.10)

Copper EPA 1638 Total Recoverable ug/L ND (0.10)

Iron EPA 1638 Total Recoverable ug/L ND (10)

Lead EPA 1638 Total Recoverable ug/L ND (0.040)

Magnesium EPA 1638 Total Recoverable ug/L ND (2.5)

Manganese EPA 1638 Total Recoverable ug/L ND (0.10)

Mercury EPA 1631E Total Recoverable ug/L ND (0.00050)

Molybdenum EPA 1638 Total Recoverable ug/L ND (0.060)

Nickel EPA 1638 Total Recoverable ug/L ND (0.10)

Selenium EPA 1638 Total Recoverable ug/L ND (0.60)

Silver EPA 1638 Total Recoverable ug/L ND (0.020)

Sodium EPA 1638 Total Recoverable ug/L ND (20)

Thallium EPA 1638 Total Recoverable ug/L ND (0.0050)

Tin EPA 1638 Total Recoverable ug/L ND (0.10)

Titanium EPA 1638 Total Recoverable ug/L ND (0.50)

Vanadium EPA 1638 Total Recoverable ug/L ND (0.10)

Zinc EPA 1638 Total Recoverable ug/L ND (0.20)

T

- Splitter Tubing Set

– Equipment Blank ( Ten feet of #73 silicone tubing, T

- splitter, six feet of #73 silicone

tubing, and 15 feet of #73 silicone tubing for total metals composite sample collection)

Aluminum EPA 1638 Total Recoverable ug/L ND (4.0)

Antimony EPA 1638 Total Recoverable ug/L ND (0.020)

Arsenic EPA 1638 Total Recoverable ug/L ND (0.15)

Barium EPA 1638 Total Recoverable ug/L ND (0.20)

Beryllium EPA 1638 Total Recoverable ug/L ND (0.060)

Boron EPA 1638 Total Recoverable ug/L ND (3.0)

Cadmium EPA 1638 Total Recoverable ug/L ND (0.020)

Calcium EPA 1638 Total Recoverable ug/L ND (40)

Chromium EPA 1638 Total Recoverable ug/L ND (0.10)

Cobalt EPA 1638 Total Recoverable ug/L ND (0.10)a Nickel was detected in one bottle blank for the 500

- mL plastic bottles at 0.14 ug/L.

ND

– Not detected (number in parentheses is the quantitation limit). Table A

- 9

. Bottle Blank and Equipment Blank Analytical Data, Brindisi

Analyte Method Process Units Concentration

Copper EPA 1638 Total Recoverable ug/L ND (0.10)

Iron EPA 1638 Total Recoverable ug/L ND (10)

Lead EPA 1638 Total Recoverable ug/L ND (0.040)

Magnesium EPA 1638 Total Recoverable ug/L ND (2.5)

Manganese EPA 1638 Total Recoverable ug/L ND (0.10)

Mercury EPA 1631E Total Recoverable ug/L ND (0.00050)

Molybdenum EPA 1638 Total Recoverable ug/L ND (0.060)

Nickel EPA 1638 Total Recoverable ug/L ND (0.10)

Selenium EPA 1638 Total Recoverable ug/L ND (0.60)

Silver EPA 1638 Total Recoverable ug/L ND (0.020)

Sodium EPA 1638 Total Recoverable ug/L ND (20)

Thallium EPA 1638 Total Recoverable ug/L ND (0.0050)

Tin EPA 1638 Total Recoverable ug/L ND (0.10)

Titanium EPA 1638 Total Recoverable ug/L ND (0.50)

Vanadium EPA 1638 Total Recoverable ug/L ND (0.10)

Zinc EPA 1638 Total Recoverable ug/L ND (0.20)ND

– Not detected (number in parentheses is the quantitation limit).

B

– Analyte was found in the blank and sample.

J

– Result measured above the MDL, but less than the quantitation limit.

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit). Table A

- 10 . Influent to FGD Wastewater Treatment System Field Blank, Day 1 Analytical Results, Brindisi

Analyte Method Unit Dilution

Factor Sample

Specific MDL Sample

Specific QL Concentration

Total Metals

Aluminum 200.7 ug/L 2 9.4 200 13 J,B

Antimony 200.8 ug/L 2 0.72 2 ND (2) U

Arsenic 200.8 ug/L 2 1.2 4 ND (4) U

Barium 200.7 ug/L 2 2.5 20 ND (20) U

Beryllium 200.7 ug/L 2 0.71 2 ND (2) U

Boron 200.7 ug/L 2 6.7 200 ND (200) U

Cadmium 200.8 ug/L 2 1.2 4 ND (4) U

Calcium 200.7 ug/L 2 69 400 ND (400) U

Chromium 200.8 ug/L 2 3.3 8 ND (8) U

Cobalt 200.7 ug/L 2 1.1 20 ND (20) U

Copper 200.8 ug/L 2 0.96 4 ND (4) U

Iron 200.7 ug/L 2 32 200 ND (200) U

Lead 200.8 ug/L 2 0.73 2 ND (2) U

Magnesium 200.7 ug/L 2 21 400 ND (400) U

Manganese 200.7 ug/L 2 0.51 20 ND (20) U

Mercury 1631E ng/L 1 0.24 0.5 ND (0.5) U

Molybdenum 200.7 ug/L 2 1.6 40 ND (40) U

Nickel 200.8 ug/L 2 0.89 4 ND (4) U

Selenium 200.8 ug/L 2 0.62 4 ND (4) U

Silver 200.8 ug/L 2 0.59 2 ND (2) U

Sodium 200.7 ug/L 2 180 10,000 370 J,B

Thallium 200.8 ug/L 2 0.47 2 ND (2) U

Tin 200.7 ug/L 2 4.8 200 ND (200) U

Titanium 200.7 ug/L 2 1.6 20 ND (20) U

Vanadium 200.8 ug/L 2 1.7 10 ND (10) UND

– Not detected (number in parentheses is the quantitation limit).

B

– Analyte was found in the blank and sample.

J

– Result measured above the MDL, but less than the quantitation limit.

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit). Table A

- 10 . Influent to FGD Wastewater Treatment System Field Blank, Day 1 Analytical Results, Brindisi

Analyte Method Unit Dilution

Factor Sample

Specific MDL Sample

Specific QL Concentration

Zinc 200.7 ug/L 2 9.1 40 ND (40) U

ND

– Not detected (number in parentheses is the quantitation limit).

B

– Analyte was found in the blank and sample.

J

– Result measured above the MDL, but less than the quantitation limit.

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit).ND

– Not detected (number in parentheses is the quantitation limit).

B

– Analyte was found in the blank and sample.

J

– Result measured above the MDL, but less than the quantitation limit.

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit). Table A

- 1 1 . Distillate from Brine Concentrator Field Blank, Day 1 Analytical Results , Brindisi

Analyte Method Unit Dilution

Factor Sample

Specific MDL Sample

Specific QL Concentration

Total Metals

Aluminum 200.7 ug/L 2 9.4 200 13 J,B

Antimony 200.8 ug/L 2 0.72 2 ND (2) U

Arsenic 200.8 ug/L 2 1.2 4 ND (4) U

Barium 200.7 ug/L 2 2.5 20 ND (20) U

Beryllium 200.7 ug/L 2 0.71 2 ND (2) U

Boron 200.7 ug/L 2 6.7 200 ND (200) U

Cadmium 200.8 ug/L 2 1.2 4 ND (4) U

Calcium 200.7 ug/L 2 69 400 ND (400) U

Chromium 200.8 ug/L 2 3.3 8 ND (8) U

Cobalt 200.7 ug/L 2 1.1 20 ND (20) U

Copper 200.8 ug/L 2 0.96 4 ND (4) U

Iron 200.7 ug/L 2 32 200 77 J

Lead 200.8 ug/L 2 0.73 2 0.73 J

Magnesium 200.7 ug/L 2 21 400 ND (400) U

Manganese 200.7 ug/L 2 0.51 20 ND (20) U

Mercury 1631E ng/L 1 0.24 0.5 ND (0.5) U

Molybdenum 200.7 ug/L 2 1.6 40 ND (40) U

Nickel 200.8 ug/L 2 0.89 4 ND (4) U

Selenium 200.8 ug/L 2 0.62 4 ND (4) U

Silver 200.8 ug/L 2 0.59 2 ND (2) U

Sodium 200.7 ug/L 2 180 10,000 270 J,B

Thallium 200.8 ug/L 2 0.47 2 ND (2) U

Tin 200.7 ug/L 2 4.8 200 ND (200) U

Titanium 200.7 ug/L 2 1.6 20 ND (20) U

Vanadium 200.8 ug/L 2 1.7 10 ND (10) UND

– Not detected (number in parentheses is the quantitation limit).

B

– Analyte was found in the blank and sample.

J

– Result measured above the MDL, but less than the quantitation limit.

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit). Table A

- 1 1 . Distillate from Brine Concentrator Field Blank, Day 1 Analytical Results , Brindisi

Analyte Method Unit Dilution

Factor Sample

Specific MDL Sample

Specific QL Concentration

Zinc 200.7 ug/L 2 9.1 40 ND (40) UTable A

- 1 2 . Distillate from Brine Concentrator Field Blank, Day 2 Analytical Results, Brindisi

Analyte Method Unit Dilution

Factor Sample

Specific MDL Sample

Specific QL Concentration

Total Metals

Mercury 1631E ng/L 1 0.24 0.5 ND (0.5) U

ND

– Not detected (number in parentheses is the quantitation limit).

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A

- 1 3 . Distillate from Brine Concentrator Field Blank, Day 3 Analytical Results, Brindisi

Analyte Method Unit Dilution

Factor Sample

Specific MDL Sample

Specific QL Concentration

Total Metals

Mercury 1631E ng/L 1 0.24 0.5 ND (0.5) U

ND

– Not detected (number in parentheses is the quantitation limit).

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit).ND

– Not detected (number in parentheses is the quantitation limit).

B

– Analyte was found in the blank and sample.

J

– Result measured above the MDL, but less than the quantitation limit.

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit). Table A

- 1 4 . Condensate from Crystallizer Field Blank, Day 1 Analytical Results, Brindisi

Analyte Method Unit Dilution

Factor Sample

Specific MDL Sample

Specific QL Concentration

Total Metals

Aluminum 200.7 ug/L 2 9.4 200 14 J,B

Antimony 200.8 ug/L 2 0.72 2 ND (2) U

Arsenic 200.8 ug/L 2 1.2 4 ND (4) U

Barium 200.7 ug/L 2 2.5 20 ND (20) U

Beryllium 200.7 ug/L 2 0.71 2 ND (2) U

Boron 200.7 ug/L 2 6.7 200 ND (200) U

Cadmium 200.8 ug/L 2 1.2 4 ND (4) U

Calcium 200.7 ug/L 2 69 400 ND (400) U

Chromium 200.8 ug/L 2 3.3 8 ND (8) U

Cobalt 200.7 ug/L 2 1.1 20 ND (20) U

Copper 200.8 ug/L 2 0.96 4 1 J

Iron 200.7 ug/L 2 32 200 ND (200) U

Lead 200.8 ug/L 2 0.73 2 ND (2) U

Magnesium 200.7 ug/L 2 21 400 ND (400) U

Manganese 200.7 ug/L 2 0.51 20 ND (20) U

Mercury 1631E ng/L 1 0.24 0.5 ND (0.5) U

Molybdenum 200.7 ug/L 2 1.6 40 ND (40) U

Nickel 200.8 ug/L 2 0.89 4 ND (4) U

Selenium 200.8 ug/L 2 0.62 4 ND (4) U

Silver 200.8 ug/L 2 0.59 2 ND (2) U

Sodium 200.7 ug/L 2 180 10,000 260 J,B

Thallium 200.8 ug/L 2 0.47 2 ND (2) U

Tin 200.7 ug/L 2 4.8 200 ND (200) U

Titanium 200.7 ug/L 2 1.6 20 ND (20) U

Vanadium 200.8 ug/L 2 1.7 10 ND (10) UND

– Not detected (number in parentheses is the quantitation limit).

B

– Analyte was found in the blank and sample.

J

– Result measured above the MDL, but less than the quantitation limit.

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit). Table A

- 1 4 . Condensate from Crystallizer Field Blank, Day 1 Analytical Results, Brindisi

Analyte Method Unit Dilution

Factor Sample

Specific MDL Sample

Specific QL Concentration

Zinc 200.7 ug/L 2 9.1 40 ND (40) UTable A

- 1 5

. Condensate from Crystallizer Field Blank, Day 2 Analytical Results, Brindisi

Analyte Method Unit Dilution

Factor Sample

Specific MDL Sample

Specific QL Concentration

Total Metals

Mercury 1631E ng/L 1 0.24 0.5 ND (0.5) U

ND

– Not detected (number in parentheses is the quantitation limit).

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A

- 1 6

. Condensate from Crystallizer Field Blank, Day 3 Analytical Results, Brindisi

Analyte Method Unit Dilution

Factor Sample

Specific MDL Sample

Spec ific QL Concentration

Total Metals

Mercury 1631E ng/L 1 0.24 0.5 ND (0.5) U

ND

– Not detected (number in parentheses is the quantitation limit).

U

– Result below the MDL. (Number shown in parentheses is the quantitation limit).Appendix B

DATA REVIEW NARRATIVESAppendix C

PICTURES FROM THE SAMPLING EPISODEC

- 1 Figure C

- 1. Sampler Working Inside a “Cleanbox”C

- 2 Figure C

- 2

. Picture of Sampling Location and Tubing Attached to the PVC Pipe at the

Influent to the FGD Wastewater Treatment SytemC

- 3 Figure C

- 3

. Sample Collection Set

- Up at the Distillate from the Brine ConcentratorC

- 4 Figure C

- 4

. Sample Collection Set

- Up at the Condensate from the Crystallizer