Site Visit Notes and 

Sampling Episode Report 

Enel’s Power Plants 

Italy 

Sampling Episode 6576 

 

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 9-29 
 

i

CONTENTS 

Page 

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

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

1.2 Power Plant Site Selection ................................................................................... 1-1

1.3 Sampling Episode Overview................................................................................ 1-2

2. SITE VISITS ....................................................................................................................... 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. SAMPLE COLLECTION ....................................................................................................... 3-1

3.1 Sampling 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. LABORATORY ANALYTICAL RESULTS AND DISCUSSION ................................................... 4-1

5. DATA QUALITY ................................................................................................................. 5-1

5.1 Analytical Quality 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. REFERENCES ..................................................................................................................... 6-1

Appendix A: ANALYTICAL RESULTS

Appendix B: DATA REVIEW NARRATIVES

Appendix C: PICTURES FROM THE SAMPLING EPISODE
 

ii

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 Point 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 Treatment 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-6
 

LIST 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 

Analytical 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-31
 

iv

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-4
 

1-1

1. INTRODUCTION

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-fired steam electric power plants and 

evaluate treatment technologies and best management practices used to reduce pollutant 

discharges. This report describes the site visits that took place at Enel’s Federico II Power Plant 

(Brindisi), located in Brindisi Italy, 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, 

2011, at Brindisi (Sampling Episode 6576). The focus of Episode 6576 was to characterize the 

purge stream entering the flue gas desulfurization (FGD) 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 Background

Metals 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. 

1.2 Power Plant Site Selection

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

configurations and characteristics of the plants. 

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, 

— Polyelectrolyte 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 Sampling Episode Overview

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

On Monday, April 4, 2011, EPA arrived at Brindisi to meet with plant personnel, 

participate in a site visit 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, 2011). The following 

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. SITE VISITS

 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 Brindisi Facility Overview

The Brindisi plant was built in 1993 and is located in Cerano-Tuturano (Brindisi), Italy. 

There are 309 employees and 171 operators at 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 usually include starting 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 planned for April 5, 

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

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 conveyor 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. These 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 electrostatic precipitators (ESPs) on Units 1, 2, and 4 to control 

particulate releases from the plant. The plant operates a fabric filter on Unit 3. The plant is in the 

process of converting the remaining three ESPs into fabric filters. 

Brindisi also operates selective 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 Research 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 laboratory-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 (CO2) 

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

2-2

Additionally, Brindisi is researching CO2 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 CO2. 

Other research topics at Brindisi include the following: 

 Environmental Impact Source Apportionment: the evaluation of the effect of 

Enel-fired plants on ambient air in reference 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: established by the numerical aspersion model, this technology 

screens filter samples using morphological recognition to determine the chemical 

composition of air particles. 

 Point Source Apportionment: mobile 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 services a 10,000 normal cubic meters per hour (Nm3/hr) flue gas slip stream from Unit 4. 

The pilot system is designed to treat approximately 2-3 MW-equivalent and capture 2.5 metric 

tons of CO2 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 CO2 separation since 

starting the system. Figure 2-1, located at the end of this section, presents the process flow 

diagram of the pilot-scale CCS system. 

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

heater. Pretreatment includes additional desulfurization (DeSOx), where the flue gas is washed 

with a limestone slurry to remove sulfur trioxide (SO3) and reduce sulfur dioxide (SO2) levels to 

below 20 mg/Nm3

. Immediately downstream of the DeSOx 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 SO2, which would require additional sorbent. 

The pretreated flue gas then enters the CO2 absorber. The absorber 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 m3

/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 CO2 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 the bottom of the CO2 absorber is the CO2-rich MEA solution. The MEA and 

CO2 solution is sent through a heat exchanger to increase the temperature of the solution and 

then sent to a high-pressure steam stripper where the CO2 is stripped from the solution. CO2 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 CO2 gas to separate from the water. 

The condensed water is transferred back to the stripper and the CO2 is captured. Currently, the 

captured CO2 is returned to the stack. 

Exiting the bottom of the stripper is the water and MEA solution, which ranges from a 

20– 40% MEA solution. A portion of the bottoms is transferred to the reboiler, where steam is 

used to heat the solution. The solution is then returned to the stripper and provides the necessary 

heat to strip the CO2 from the CO2-rich MEA solution. The remainder of the bottoms, which is 

the CO2-lean MEA solution is sent through the heat exchanger to heat the CO2-rich MEA 

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

to transfer through mechanical and activated carbon filters to avoid particles going through the 

CO2 absorber. After passing through the filters, the stream is combined with the portion that was 

not filtered and is transferred to the CO2 absorber where it absorbs the CO2 from the flue gas. 

Plant personnel stated that the pilot-scale system also has a reclaimer at the bottom of the 

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

Because of the different chemicals 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)) is 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 have 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 recycled water. Although the plant does not 

treat the recirculation 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 SO2 from the units. Each FGD system consists of both a prescrubber and 
 

2-4

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 designed to have the same SO2 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 m3

/hr 

(264 gal/min) for the two units combined. The Unit 3 and 4 prescrubber blowdown is 

approximately 80 m3

/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 ranges 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 gasgas 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 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. 

Finally, the flue gas is heated to its exit temperature, 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 and 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 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 limestone slurry is pressurized and sprayed into the absorbers; the 

spray droplets absorb the SO2, 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 the 
 

2-5

absorber. The plant continues to blowdown until the solids concentration 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 filters 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 primary 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. Wastewater from the Units 1 and 2 FGD sump is 

typically transferred to the FGD wastewater treatment system at a flow rate of 20 m3

/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 were 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 limestone slurry is pressurized and sprayed into the absorber; the 

spray droplets absorb the SO2, 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 FGD absorber to control 

the solids concentration in the scrubbers. The plant initiates a blow down 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. There 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. 

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

the gypsum byproduct to a moisture content of less than 10 percent. Brindisi sells the gypsum for 
 

2-6

use in wallboard manufacturing. The filtrate from the vacuum 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 designed 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 were 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 typically transferred to the FGD 

wastewater treatment system at a flow rate of 100 m3

/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 

blowdown 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, 

 Lime, sodium sulfide, and caustic soda addition (pH adjustment/metal hydroxide 

precipitation), 

 Ferric chloride addition, 

 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 presents a diagram of the pretreatment system, which includes the chemical 
 

2-7

precipitation portion of the system. Figure 2-3 presents a diagram of the evaporation portion of 

the wastewater treatment system. Figure 2-4 presents a diagram of the crystallization portion of 

the wastewater treatment system. 

The prescrubber blowdown, the Units 1 and 2 FGD sump transfers, and the Units 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 m3

 (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 stream 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 m3

 (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 the transfers from the bottom ash treatment basin to the FGD wastewater treatment 

tanks?] 

The FGD wastewater treatment tanks feed the 1st stage of the neutralization basin, which 

is a large concrete basin that has three divided compartments. In the 1st compartment, the plant 

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

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

where a polyelectrolyte is added. 

The overflow from the third compartment of the 1st 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 

filtrate from the filter presses transferred?] The overflow from the clarifier is sent to the 2nd

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); these solids are pumped back to the FGD process as make-up to 

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

clearwell. 

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 m3

/hr, with 140 m3/hr to 

be recycled and 140 m3/hr to be sent to the softening tank. However, 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 m3

/hr back to the FGD system and transferring 50 m3/hr to the softening tank. 

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

complete the softening process. The overflow from the softening tanks is then transferred to the 
 

2-8

evaporation and crystallization system. As described above, the original design for the system 

was for the softening tank to receive 140 m3/hr of wastewater, but only 70 m3/hr was supposed to 

be transferred to the evaporation system, while 70 m3/hr was supposed to be recycled back to the 

FGD system. Because of the reduced flow to the softening tanks, the entire 50 m3

/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 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 prior to the evaporation system. From the evaporator feed tank, the wastewater is 

split into two streams and both are sent to heat exchangers to bring the wastewater to its boiling 

point. The distillate stream from the brine concentrator and the condensate stream from the 

crystallizer are the streams used to transfer heat to the wastewater. From the heat exchangers, 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 between the compressed vapor and the 

brine solution causes the compressed vapor to transfer heat to the brine solution, which flashes to 

a vapor. As heat is transferred to the brine, the compressed vapor cools and condenses as distilled 

water. 

The condensed vapor from the brine concentrator is collected and transferred to a 

distillate tank. The distillate is 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 brine slurry from the brine concentrator tubes falls into the sump and is 

recycled with the feed (i.e., FGD wastewater) back to the top of the brine concentrator, while a 

small amount is continuously withdrawn from the sump and transferred to a set of 

hydrocyclones. To prevent scaling within the brine concentrator as a result of the gypsum present 

in the FGD wastewater, the brine concentrator is seeded with calcium sulfate. The calcium salts 

preferentially precipitate onto the seed crystals instead of the tube surfaces of the brine 

concentrator. The hydrocyclones recover the calcium sulfate seed crystals in the underflow and 

recycle the seed to the recirculation stream entering the top of the brine concentrator. 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 crystallizer feed tank, the wastewater is combined 

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

2-9

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

level of slurry in the bottom of the system. Within the system, the water is evaporated and exits 

the top of the crystallizer as steam. Some of the steam is diverted to a thermocompressor where 

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

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

recirculated in the crystallizer, 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 

distillate 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. The 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 Brindisi 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 transfers the wastewater to the distillate tank. 

2.2 Torrevaldaliga Nord Facility Overview

The Torrevaldaliga Nord plant originally started operation 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. There 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 

starting the unit with natural gas. The coal-fired units at the plant began operation in the 

following months: 
 

2-10

 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. The 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, which 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 

between 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 

to control particulate releases from the plant. The removal 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 the 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 cement 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 boiler 

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 using 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 SO2 from the units. All three FGD systems were 

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

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

2-11

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 SO2, 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 used 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 prevalent 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 scrubber. [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 blowdown 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 

dewatering. 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 eventually 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 hydrocyclones 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 secondary 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 from each of the three FGD 

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

2-12

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

wastewater treatment system contains the following treatment operations: 

 Equalization, 

 Lime 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 FGD 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 4,000 m3

 (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 reaction 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 back 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 content 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% crystallization 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 prior 
 

2-13

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 and 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 between the compressed vapor and the 

brine solution causes the compressed vapor to transfer heat to the brine solution, which flashes to 

a vapor. As heat is transferred to the brine, the compressed vapor cools and condenses as distilled 

water. 

The condensed vapor from the brine concentrator is collected and transferred to a 

distillate tank. [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 brine slurry from the brine concentrator tubes falls into the sump and is 

recycled with the feed (i.e., FGD wastewater) back to the top of the brine concentrator, while a 

small amount is continuously withdrawn from the sump and transferred to a set of 

hydrocyclones. To prevent scaling within the brine concentrator as a result of the gypsum present 

in the FGD wastewater, the brine concentrator is seeded with calcium sulfate. The calcium salts 

preferentially precipitate onto the seed crystals instead of the tube surfaces of the brine 

concentrator. The hydrocyclones recover the calcium sulfate seed crystals in the underflow and 

recycle the seed to the recirculation stream entering the top of the brine concentrator. 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 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 slurry in the bottom of the system. Within the system, the water is evaporated and exits 

the top of the crystallizer as steam. Some of the steam is diverted to a thermocompressor where 

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

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

recirculated in the crystallizer, 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 

distillate in the distillate tank. [QUESTION FOR ENEL: What is the flow rate of the condensate 
 

2-14

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-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. The 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 
2-16 

Clearwell

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

Power Plant 
2-17 Hydrochloric Acid

Feed/Crystallizer 

Heat Exchanger

Distillate 

Tank

Deaerator

Brine Concentrator 

Vent to 

Atmosphere

Brine 

Solution

Brine 

Recycle

Distillate

Softening 

Tank

From 

Pretreatment 

Soda Ash

To Limestone 

Preparation

Evaporator 

Feed Tank

Anti-Scalant

Feed/Distillate 

Heat Exchanger

Condensate from 

Crystallizer

Make-up 

Steam

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 

Power Plants 
2-18 

Figure 2-4. Diagram of the Crystallization Portion of the FGD Wastewater Treatment System, Brindisi a

Nord Power Plants 
2-19 

Figure 2-5. Diagram of the Chemical Precipitation Portion of the FGD Wastewater Treatment System, T

Power Plant
 

3-1 

3. SAMPLE COLLECTION

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 data collected during 

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

activities. 

3.1 Sampling Points, Sample Collection Methods, and Field Measurements

This section describes the sampling points, sample collection methods, 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. 

Table 3-1 lists 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 the 

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® 

coveralls 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 opened, 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 and 
 

3-2 

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 sample 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 system (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 transfers 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 sample collection. 

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

treatment system (SP-1)1

, the sampling team collected field blanks (SP-4) for total mercury and 

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

the influent to the FGD wastewater treatment system. 

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

system, the samplers attached 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 attached 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-cleaned 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. 

 

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: 

 Total mercury; 

 Total metals by 200.8; and 

 Total metals by 200.7. 

The sampling team collected an aliquot of sample for field testing. Sample pH and 

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 Concentrator (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. Brindisi 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 the sample collection. 

ERG collected 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 container with 21 liters of sample2

. Following the 

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

containers. 

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. 

Samplers set up the compositor by attaching a T-splitter tubing set to one of the taps on 

the two-way splitter. The T-splitter tubing set consisted of three silicone tubes attached to a Tsplitter. 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 

 

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 

period3

. For every manual composite sample, the sample tap was opened and the flow was 

directed to 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 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 container was placed into a plastic bin, and maintained 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-3, in Appendix C, is a picture of the composite sampling setup at the distillate from the brine concentrator. 

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 description of the field blank sample collection procedures at the distillate 

from the 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 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 every two hours thereafter over the fourhour period, for 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. Table 3-3 presents 

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

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

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

up. A closed 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. 

The 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 used 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 end of the Teflon® tubing into the 20-liter composite container filled with the 

distillate from the brine concentrator. After the tubing was purged with 1-2 liters of sample, 

samplers 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 avoid 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. Group 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, prior 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 the 

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 outside (see Figure 2-4 for the sampling location for SP-3). There were 

no wind or rain concerns during the sample collection. 

ERG collected 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 sample4

. Following the 

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

containers. 

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. 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 collection procedures at the condensate from the 

crystallizer. 

Samplers set up the compositor by attaching a T-splitter tubing set to one of the taps on 

the two-way splitter. The T-splitter tubing set consisted of three silicone tubes attached to a Tsplitter. 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 

period5

. For every manual composite sample, the sample tap was opened and the flow was 

 

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 constraints with available FedEx shipments from the plant. 

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 the 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 container was placed into a plastic bin, and maintained 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 setup 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 description 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 every two hours thereafter over the fourhour 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 collected in the composite container, ERG followed “clean 

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

up. A closed 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. 

The 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 used 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 end of the Teflon® tubing into the 20-liter composite container filled with condensate 

from the crystallizer. After the tubing was purged with 1-2 liters of sample, samplers collected 

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

 Total metals by 200.8; and 

 Total metals by 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 Group II samples were immediately placed on ice 
 

3-7 

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

sample bottle immediately after the other. 

On Day 1 only, prior to collecting any samples of the condensate from the crystallizer, 

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 the condensate from the 

crystallizer. 

3.2 List of Analytes and Sample Preservation

Samples collected at Brindisi were analyzed for the following parameters: 

 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 Metals: 

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

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

mercury, molybdenum, nickel, selenium, silver, sodium, thallium, tin, 

titanium, vanadium, and zinc. 

The analytes selected 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 

samples 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 cool 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 Plant Operational Data

During the EPA sampling episode, Brindisi plant personnel provided the sampling team 

with operational data for 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 information 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. 

3.4 Deviations from the Sampling and Analysis Plan

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

described below: 

 Collection of grab samples at SP-1 (Day 1): On day 1 of sample collection at 

the influent the FGD wastewater treatment system (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 

Day 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 

manual 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 collection to three separate samples collected every two hours 

over a four-hour period. 

 Collection of first manual composite 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 sample 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 mercury 
 

3-9 

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

transferred the label to a new bottle and collected another sample. 

 

 Total mercury field blank samples 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 collection. 

 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 kept 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 1006b

Influent to FGD Wastewater Treatment 

System – Day 3 

Grab 4/7/11 1006b

SP-2 Distillate from the Brine Concentrator – 

Day 1 

Composite 4/5/11 0840c, 1042c, 1303c, 

1438d

Grab 4/5/11 0857e, 1050f, 1311g

Distillate from the Brine Concentrator – 

Day 2 

Composite 4/6/11 0708c, 0908c, 1112c, 

1207d

Grab 4/6/11 0722e, 0917f, 1121g

Distillate from the Brine Concentrator – 

Day 3 

Composite 4/7/11 0713c, 0906c, 1110c, 

1213d

Grab 4/7/11 0725e, 0915f, 1117g

SP-3 Condensate from the Crystallizer – Day 1 Composite 4/5/11 0931c, 1133c, 1329c, 

1504d

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

Condensate from the Crystallizer – Day 2 Composite 4/6/11 0739c, 0926c, 1131c, 

1231d

Grab 4/6/11 0749e, 0934f, 1140g

Condensate from the Crystallizer – Day 3 Composite 4/7/11 0743c, 0924c, 1134c, 

1232d

Grab 4/7/11 0754e, 0931f, 1142g

SP-4 Influent to FGD Wastewater Treatment 

System Field Blank, Day 1 

Grab 4/5/11 a 1216h

SP-5 Distillate from the Brine Concentrator 

Field Blank – Day 1 

Composite 4/5/11 0811i, 1431j

Grab 4/5/11 0850k

Distillate from the Brine Concentrator 

Field Blank – Day 2 

Grab 4/6/11 0717k

Distillate from the Brine Concentrator 

Field Blank – Day 3 

Grab 4/7/11 0720k

SP-6 Condensate from the Crystallizer Field 

Blank – Day 1 

Composite 4/5/11 0918i, 1500j

Grab 4/5/11 0937k

Condensate from the Crystallizer Field 

Blank – Day 2 

Grab 4/6/11 0744k

Condensate from the Crystallizer Field 

Blank – Day 3 

Grab 4/7/11 0749k
 

3-11 

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 team 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 collection of the total metals samples (total metals by 200.7 and total metals by 200.8) total 

mercury, and classicals (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 collection of total metals samples (total metals by 200.7 and total metals by 200.8) and classicals 

(Group I and Group II). 

e Start time for the collection of the total 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

 Start 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 and 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 Name 

Total Metals 

(EPA Method 200.8 with 

collision cell)

Total Metals 

(EPA Method 200.7) 

Total Mercury 

a

SP-1 Influent to the FGD Wastewater Treatment System 2 2 2 SP-2 Distillate from the Brine Concentrator 3+1QC 3+1QC 3+1QC 3+SP-3 Condensate from the Crystallizer 3+1QC 3+1QC 3+1QC 3+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+2QC 11+2QC 15+2QC 8+2

a – Group I includes total suspended solids (TSS), total dissolved solids (TDS), sulfate, and chloride. b – Group II includes ammonia as nitrogen, nitrate/nitrite as nitrogen, total Kjeldahl nitrogen (TKN), chemical oxygen demand (COD), and total phosp
3-13 

Table 3-3. Field Measurements, Brindisi 

Sampling Point 

Number Sampling Point Description Date Time 

Temperat

(°C) 

SP-1 Influent to FGD Wastewater Treatment System – Day 2 4/6/11 1006 32 

Influent to FGD Wastewater Treatment System – Day 3 4/7/11a 1006 31 

SP-2 Distillate from the Brine Concentrator – Day 1 4/5/11 0857 82 

4/5/11 1050 80 4/5/11 1311 85 

Distillate from the Brine Concentrator – Day 2 4/6/11 0722 86 

4/6/11 0918 86 4/6/11 1121 90 

Distillate from the Brine Concentrator – Day 3 4/7/11 0725 82 

4/7/11 0915 87 4/7/11 1117 86 

SP-3 Condensate from the Crystallizer – Day 1 4/5/11 0942 72 

4/5/11 1143 64 4/5/11 1338 71 

Condensate from the Crystallizer – Day 2 4/6/11 0749 69 

4/6/11 0934 69.5 4/6/11 1140 71 

Condensate from the Crystallizer – Day 3 4/7/11 0754 61 

4/7/11 0931 70 4/7/11 1142 79 

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

after the field blank collection. The SP-1 samples planned to be collected on day 1 were actually collected on day 3 of sampling; howevnot informed of the clogged pipe until after the field blank samples were collected. Therefore, the field blank samples were collected owastewater 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 

72523 SP-6, Day 1 Condensate from the Crystallizer Field Blank - Day 1 

72524 SP-6, Day 2 Condensate from the Crystallizer Field Blank - Day 2 

72525 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 team 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 oxygen demand (COD) EPA 410.4 28 days 

Total suspended solids (TSS) SM 2540 D 7 days 

Total dissolved solids (TDS) SM 2540 C 7 days 

Sulfate EPA 300.0 28 days 

Chloride EPA 300.0 28 days 

Ammonia as nitrogen EPA 350.1 28 days 

Nitrate/nitrate as nitrogen EPA 353.2 28 days 

Total Kjeldahl nitrogen (TKN) EPA 351.2 28 days 

Total phosphorus EPA 365.1 28 days 

Total Metals

Mercury EPA 1631E 90 days b

Antimony, arsenic, 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 

bottles 

Two 1-L plastic 

bottles 

H2SO4 to pH <2, ≤6C 

Metals 

Total metals (EPA Method 200.8 with 

collision cell) 

One 500-mL 

plastic bottle 

No additional 

volume needed 

None 

(acid preserve at laboratory) 

Total metals (EPA Method 200.7) One 500-mL 

plastic bottle 

No additional 

volume needed 

None 

(acid preserve at laboratory) 

Total mercury: None 

Manual composite grab samples Three 125-mL (acid preserve at laboratory) 

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 H2SO4 8.5 < 2 20 

72513 Group II Volume 2 4/5/11 H2SO4 8.5 < 2 20 

72516 Group II Volume 1 4/5/11 H2SO4 8.5 < 2 24 

72516 Group II Volume 2 4/5/11 H2SO4 8.5 < 2 20 

72512 Group II Volume 1 4/6/11 H2SO4 2.5 < 2 25 

72512 Group II Volume 2 4/6/11 H2SO4 2.5 < 2 25 

72514 Group II Volume 1 4/6/11 H2SO4 8.5 < 2 30 

72514 Group II Volume 2 4/6/11 H2SO4 8.5 < 2 30 

72514 Group II Volume 1 - QC 4/6/11 H2SO4 8.5 < 2 30 

72514 Group II Volume 2 - QC 4/6/11 H2SO4 8.5 < 2 30 

72517 Group II Volume 1 4/6/11 H2SO4 8.5 < 2 20 

72517 Group II Volume 2 4/6/11 H2SO4 8.5 < 2 23 

72511 Group II Volume 1 4/7/11 H2SO4 4.5 < 2 25 

72511 Group II Volume 2 4/7/11 H2SO4 4.5 < 2 25 

72515 Group II Volume 1 4/7/11 H2SO4 8.5 < 2 25 

72515 Group II Volume 2 4/7/11 H2SO4 8.5 < 2 22 

72518 Group II Volume 1 4/7/11 H2SO4 8.5 < 2 25 

72518 Group II Volume 2 4/7/11 H2SO4 8.5 < 2 25 

72518 Group II Volume 1 - QC 4/7/11 H2SO4 8.5 < 2 25 

72518 Group II Volume 2 - QC 4/7/11 H2SO4 8.5 < 2 25 

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

pH meter calibrated at 08:30 on 4/6/11. 

pH meter calibrated at 08:30 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 

S

Rem

Perce

BS1 Yes Bishoff a Yes Limestone None Recovered ZLD water Recovered ZLD water 84BS2 Yes Bishoff a Yes Limestone None Recovered ZLD water Recovered ZLD water 84BS3 Yes Mitsubishi a Yes Limestone None Recovered ZLD water Recovered ZLD water 84BS4 Yes Mitsubishi a Yes Limestone None Recovered ZLD water Recovered ZLD water 84

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 ththat there must be some other sources of water used in the prescrubber and FGD makeup, such as intake water. Please specify other souprocesses.] 
 

3-20

Table 3-8. Coal Usage during Sample Collection, Brindisi 

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 Operating 
 

3-21

Table 3-9. Scrubber Slurry Information during Sample Collection, Brindisi

Day of 

Sampling 

FGD 

System IDa

Associated 

Unit IDs 

Slurry Blowdown 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 

collected 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 represent?] 
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.) 

Hy

Ac

1 4000 ppm 200 ppm 28 ppm 120 ppm 2 ppm 15 ppm 8 m3/h 30 2 4000 ppm 200 ppm 28 ppm 120 ppm 2 ppm 15 ppm 8 m3/h 30 3 4000 ppm 200 ppm 28 ppm 120 ppm 2 ppm 15 ppm 8 m3/h 30 

a Estimated on daily consumption.
 

4-1 

4. LABORATORY ANALYTICAL RESULTS AND DISCUSSION

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

the FGD wastewater treatment system, the distillate from the brine concentrator, and the 

condensate from the crystallizer. 

Appendix A provides all analytical results for all samples collected at Brindisi, 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 two 

days of sampling 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 the 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 the 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” followed 

by the sample-specific quantitation limit in parentheses. 

Tables 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 the 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 quantitation limit

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 

value. B – Analyte was found in the blank and sample. Est – Estimated value. 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 Syste

Day 2 Day 3 

Classicals Ammonia mg/L 350.1 12.0 12 Est Nitrate Nitrite as N mg/L 353.2 56.0 46 Est Nitrogen, Total Kjeldahl mg/L 351.2 3.60 Est 11 B, Est Chemical Oxygen Demand mg/L 410.4 110 100 Est Chloride mg/L 300.0 6,400 6,200 Sulfate mg/L 300.0 7,000 5,700 Est Total Dissolved Solids mg/L 2540C 13,000 15,000 Total Suspended Solids mg/L 2540D 2,600 F, Est 3,600 Phosphorus, Total mg/L 365.1 0.0840 6 Est Total Metals Aluminum ug/L 200.7 70,000 B 120,000 B Antimony ug/L 200.8 11.0 14 Arsenic ug/L 200.8 53.0 55 Barium ug/L 200.7 1,400 1,200 Beryllium ug/L 200.7 9.10 11 Boron ug/L 200.7 83,000 100,000 Cadmium ug/L 200.8 6.30 6 Calcium ug/L 200.7 1,700,000 1,300,000 Chromium ug/L 200.8 190 290 Cobalt ug/L 200.7 44.0 59 Copper ug/L 200.8 87.0 110 Iron ug/L 200.7 26,000 44,000 Lead ug/L 200.8 53.0 82 Magnesium ug/L 200.7 98,000 80,000 Manganese ug/L 200.7 990 1,000 Mercury ng/L 1631E 26,900 21,100 Molybdenum ug/L 200.7 85.0 110 Nickel ug/L 200.8 140 160 Selenium ug/L 200.8 220 290 
4-3 

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 quantitation limit

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 

value. B – Analyte was found in the blank and sample. Est – Estimated value. 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 Syste

Day 2 Day 3 

Silver ug/L 200.8 ND (2.00) ND (2.00) Sodium ug/L 200.7 5,700,000 B 6,900,000 B Thallium ug/L 200.8 2.00 2.1 Tin ug/L 200.7 NQ (200) NQ (200) Titanium ug/L 200.7 4,400 7,500 Vanadium ug/L 200.8 620 670 Zinc ug/L 200.7 670 430 
4-4 

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

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 

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 

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 

ClassicalsAmmonia mg/L 350.1 21.0 19.0 15.0 Est Nitrate Nitrite as N mg/L 353.2 0.110 0.130 0.160 Est Nitrogen, Total Kjeldahl mg/L 351.2 20.0 18.0 4 16.0 B, Est Chemical Oxygen Demand mg/L 410.4 ND (20.0) ND (20.0) F NQ (20.0) Chloride mg/L 300.0 ND (3.00) NQ (3.00) F ND (3.00) Sulfate mg/L 300.0 ND (5.00) ND (5.00) ND (5.00) Total Dissolved Solids mg/L 2540C 13.0 10.0 NQ (10.0) Total Suspended Solids mg/L 2540D ND (4.00) ND (4.00) ND (4.00) Phosphorus, Total mg/L 365.1 ND (0.0500) ND (0.0500) ND (0.0500) Total MetalsAluminum ug/L 200.7 NQ (200) B NQ (200) B NQ (200) B Antimony ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) Arsenic ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) Barium ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) Beryllium ug/L 200.7 ND (2.00) ND (2.00) ND (2.00) Boron ug/L 200.7 3,600 6,200 4 3,100 Cadmium ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) Calcium ug/L 200.7 ND (400) NQ (400) NQ (400) Chromium ug/L 200.8 ND (8.00) ND (8.00) ND (8.00) Cobalt ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) Copper ug/L 200.8 ND (4.00) NQ (4.00) ND (4.00) Iron ug/L 200.7 ND (200) ND (200) ND (200) Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) Magnesium ug/L 200.7 ND (400) NQ (400) ND (400) Manganese ug/L 200.7 ND (20.0) NQ (20.0) ND (20.0) Mercury ng/L 1631E 3.98 3.13 2.89 Molybdenum ug/L 200.7 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 quND – 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 quantitation limit

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 

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 

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 

Nickel ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) Selenium ug/L 200.8 ND (4.00) ND (4.00) NQ (4.00) Silver ug/L 200.8 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 Thallium ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) Tin ug/L 200.7 ND (200) ND (200) ND (200) Titanium ug/L 200.7 ND (20.0) ND (20.0) NQ (20.0) Vanadium ug/L 200.8 ND (10.0) ND (10.0) ND (10.0) Zinc ug/L 200.7 NQ (40.0) 71.0 ND (40.0) 
4-6 

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

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 

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 limits are 

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 

ClassicalsAmmonia mg/L 350.1 26.0 43.0 22.0 4, Est Nitrate Nitrite as N mg/L 353.2 NQ (0.100) NQ (0.100) 0.100 Est Nitrogen, Total Kjeldahl mg/L 351.2 25.0 37.0 Est 25.0 B,4, Est Chemical Oxygen Demand mg/L 410.4 ND (20.0) ND (20.0) NQ (20.0) Chloride mg/L 300.0 ND (3.00) ND (3.00) ND (3.00) Sulfate mg/L 300.0 ND (5.00) ND (5.00) ND (5.00) Total Dissolved Solids mg/L 2540C 10.0 22.0 NQ (10.0) Total Suspended Solids mg/L 2540D ND (4.00) ND (4.00) ND (4.00) Phosphorus, Total mg/L 365.1 ND (0.0500) ND (0.0500) ND (0.0500) Total MetalsAluminum ug/L 200.7 NQ (200) B NQ (200) B ND (200) Antimony ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) Arsenic ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) Barium ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) Beryllium ug/L 200.7 ND (2.00) ND (2.00) ND (2.00) Boron ug/L 200.7 3,200 3,100 3,300 Cadmium ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) Calcium ug/L 200.7 ND (400) ND (400) ND (400) Chromium ug/L 200.8 ND (8.00) ND (8.00) ND (8.00) Cobalt ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) Copper ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) Iron ug/L 200.7 ND (200) ND (200) ND (200) Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) Magnesium ug/L 200.7 ND (400) ND (400) ND (400) Manganese ug/L 200.7 NQ (20.0) ND (20.0) ND (20.0) Mercury ng/L 1631E 20.4 20.7 10.9 Molybdenum ug/L 200.7 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 quND – 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 quantitation limit

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 

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 limits are 

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 

Nickel ug/L 200.8 NQ (4.00) ND (4.00) NQ (4.00) Selenium ug/L 200.8 NQ (4.00) 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 NQ (10,000) B NQ (10,000) B NQ (10,000) B Thallium ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) Tin ug/L 200.7 ND (200) ND (200) ND (200) Titanium ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) Vanadium ug/L 200.8 ND (10.0) ND (10.0) ND (10.0) Zinc ug/L 200.7 ND (40.0) NQ (40.0) ND (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 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 quantitation 

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 quantit

one result is a J-value. 

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

Analyte Unit Method

Influent to FGD Wastewater 

Treatment System (SP-1) 

2-Day Average 

Distillate from Brine 

Concentrator (SP-2) 

3-Day Average 

C

C

ClassicalsAmmonia mg/L 350.1 12.0 18.3 Nitrate Nitrite as N mg/L 353.2 51.0 0.133 Nitrogen, Total Kjeldahl mg/L 351.2 7.30 18.0 Chemical Oxygen Demand mg/L 410.4 105 NQ (20.0) Chloride mg/L 300.0 6,300 NQ (3.00) Sulfate mg/L 300.0 6,350 ND (5.00) Total Dissolved Solids mg/L 2540C 14,000 < 9.33 Total Suspended Solids mg/L 2540D 3,100 ND (4.00) Phosphorus, Total mg/L 365.1 3.04 ND (0.0500) 
4-9 

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

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 

value. 

Table 4-5. Metal Pollutants Average Data Summary for FGD Wastewater Treatment System, B

Analyte Unit Method 

Influent to FGD Wastewater 

Treatment System (SP-1) 

2-Day Average 

Distillate from Brine 

Concentrator (SP-2) 

3-Day Average 

Condensa

3-

Total Metals Aluminum ug/L 200.7 95,000 NQ (200) Antimony ug/L 200.8 12.5 ND (2.00) Arsenic ug/L 200.8 54.0 ND (4.00) Barium ug/L 200.7 1,300 ND (20.0) Beryllium ug/L 200.7 10.1 ND (2.00) Boron ug/L 200.7 91,500 4,300 Cadmium ug/L 200.8 6.15 ND (4.00) Calcium ug/L 200.7 1,500,000 NQ (400) Chromium ug/L 200.8 240 ND (8.00) Cobalt ug/L 200.7 51.5 ND (20.0) Copper ug/L 200.8 98.5 NQ (4.00) Iron ug/L 200.7 35,000 ND (200) Lead ug/L 200.8 67.5 ND (2.00) Magnesium ug/L 200.7 89,000 NQ (400) Manganese ug/L 200.7 995 NQ (20.0) Mercury ng/L 1631E 24,000 3.33 Molybdenum ug/L 200.7 97.5 ND (40.0) Nickel ug/L 200.8 150 ND (4.00) Selenium ug/L 200.8 255 NQ (4.00) Silver ug/L 200.8 ND (2.00) ND (2.00) Sodium ug/L 200.7 6,300,000 NQ (10,000) NThallium ug/L 200.8 2.05 ND (2.00) Tin ug/L 200.7 NQ (200) ND (200) Titanium ug/L 200.7 5,950 NQ (20.0) Vanadium ug/L 200.8 645 ND (10.0) Zinc ug/L 200.7 550 < 37.0 
 

5-1

5. DATA QUALITY

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 Appendix A. QC practices used 

for this sampling episode include the analysis of matrix spikes, blanks, and QC standard checks. 

5.1 Analytical Quality Control

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. Data review chemists at ERG 

prepared written data review narratives describing any qualifications of the analytical data from 

this episode. The data review narratives are included in Appendix B. 

5.2 Field Quality Control

This section discusses the bottle blanks, equipment blanks, and field blanks results. 

Section 3.8 of the Sampling Plan discusses field QC specifications. 

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 precleaned bottles, Frontier Global Sciences. 

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 Sciences then analyzed the samples using 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 samples using EPA Method 1631E. 

Albion Environmental collected the bottle blanks 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 period, 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 blanks, except for nickel being detected in the 500-

mL plastic bottles 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 the analytical 
 

5-2

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 techniques 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 collected 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 through 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 

described 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 possible 

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 pumping ASTM Type 1 water through the silicone tubing used for sample 

collection. To prevent potential atmospheric deposition, the sampling team placed the sample 

bottles in a “cleanbox.” 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 

Enel, 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 representative 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 sample 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 composite 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 

same 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 ASTM 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 sample 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 total metals field blank samples 

(Methods 200.7 and 200.8). No metals were detected in the field blank samples above the 

quantitation limit, indicating that there was no contamination from the sample collection 

technique. Appendix Tables A-10 through A-16 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. REFERENCES

1. Eastern Research Group, Inc., 2011. Sampling Plan, Enel’s Federico II Power Plant. 

March 21. DCN SE01184. 

2. Eastern Research Group, Inc., 2010. Quality Assurance Project Plan for the Steam 

Electric Effluent Guidelines Rulemaking. (October). DCN SE00058. 
 

Appendix A 

ANALYTICAL RESULTS 
ND – 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, Brin

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific 

MDL 

SampleSpecific QL 

Classicals Ammonia 350.1 mg/L 2 0.11 2 Nitrate Nitrite as N 353.2 mg/L 20 0.38 2 Nitrogen, Total Kjeldahl 351.2 mg/L 1 0.077 1 Chemical Oxygen Demand 410.4 mg/L 1 4.1 20 Chloride 300.0 mg/L 200 51 600 Sulfate 300.0 mg/L 200 46 1,000 Total Dissolved Solids 2540C mg/L 1 94 200 Total Suspended Solids 2540D mg/L 1 11 40 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 50 240 5,000 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 1Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 
ND – 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, Brin

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific 

MDL 

SampleSpecific QL 

Iron 200.7 ug/L 50 800 5,000 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 4,000 965 2,020 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 50 4,600 250,000 5Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 50 41 500 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 
ND – 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, Brin

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Classicals Ammonia 350.1 mg/L 2 0.11 2 Nitrate Nitrite as N 353.2 mg/L 10 0.19 1 Nitrogen, Total Kjeldahl 351.2 mg/L 1 0.38 5 Chemical Oxygen Demand 410.4 mg/L 1 4.1 20 Chloride 300.0 mg/L 200 51 600 Sulfate 300.0 mg/L 200 46 1,000 Total Dissolved Solids 2540C mg/L 1 94 200 Total Suspended Solids 2540D mg/L 1 11 40 Phosphorus, Total 365.1 mg/L 10 0.05 0.5 Total MetalsAluminum 200.7 ug/L 50 240 5,000 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 50 170 5,000 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 50 1,700 10,000 1Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 
ND – 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, Brin

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 4,000 965 2,020 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 50 4,600 250,000 6Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 
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-3. Influent to FGD Wastewater Treatment System, Day 1 Analytical Results, Brin

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Classicals Ammonia 350.1 mg/L 4 0.22 4 Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 Chemical Oxygen Demand 410.4 mg/L 1 4.1 20 Chloride 300.0 mg/L 1 0.25 3 Sulfate 300.0 mg/L 1 0.23 5 Total Dissolved Solids 2540C mg/L 1 4.7 10 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 
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 quantitation limit). 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 1 0.24 0.51 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 
ND – 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 

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 

SampleSpecific MDL Sample- Specific QL 

Classicals Ammonia 350.1 mg/L 4 0.22 4 Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 Chemical Oxygen Demand 410.4 mg/L 1 4.1 20 Chloride 300.0 mg/L 1 0.25 3 Sulfate 300.0 mg/L 1 0.23 5 Total Dissolved Solids 2540C mg/L 1 4.7 10 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 
ND – 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 

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 

SampleSpecific MDL Sample- Specific QL 

Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 1 0.24 0.51 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 
ND – 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 

SampleSpecific MDL Sample- Specific QL 

Classicals Ammonia 350.1 mg/L 2 0.11 2 Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 Nitrogen, Total Kjeldahl 351.2 mg/L 2 0.15 2 Chemical Oxygen Demand 410.4 mg/L 1 4.1 20 Chloride 300.0 mg/L 1 0.25 3 Sulfate 300.0 mg/L 1 0.23 5 Total Dissolved Solids 2540C mg/L 1 4.7 10 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 NTotal MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 
ND – 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 

SampleSpecific MDL Sample- Specific QL 

Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 1 0.24 0.51 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 
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-6. Condensate from Crystallizer, Day 1 Analytical Results, Brindisi 

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Classicals Ammonia 350.1 mg/L 5 0.27 5 Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 Chemical Oxygen Demand 410.4 mg/L 1 4.1 20 Chloride 300.0 mg/L 1 0.25 3 Sulfate 300.0 mg/L 1 0.23 5 Total Dissolved Solids 2540C mg/L 1 4.7 10 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 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-6. Condensate from Crystallizer, Day 1 Analytical Results, Brindisi 

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Mercury 1631E ng/L 10 2.44 5.1 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 
ND – 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 

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Classicals Ammonia 350.1 mg/L 5 0.27 5 Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 Chemical Oxygen Demand 410.4 mg/L 1 4.1 20 Chloride 300.0 mg/L 1 0.25 3 Sulfate 300.0 mg/L 1 0.23 5 Total Dissolved Solids 2540C mg/L 1 4.7 10 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 Total MetalsAluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 
ND – 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 

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 10 2.44 5.1 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 Zinc 200.7 ug/L 2 9.1 40 
ND – 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 

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 

SampleSpecific 

MDL 

SampleSpecific QL 

Classicals Ammonia 350.1 mg/L 4 0.22 4 Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 Chemical Oxygen Demand 410.4 mg/L 1 4.1 20 Chloride 300.0 mg/L 1 0.25 3 Sulfate 300.0 mg/L 1 0.23 5 Total Dissolved Solids 2540C mg/L 1 4.7 10 Total Suspended Solids 2540D mg/L 1 1.1 4 Phosphorus, Total 365.1 mg/L 1 0.005 0.05 NTotal MetalsAluminum 200.7 ug/L 2 9.4 200 NAntimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 NBeryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 NChromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 NCopper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 N
ND – 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 

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 

SampleSpecific 

MDL 

SampleSpecific QL 

Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 NManganese 200.7 ug/L 2 0.51 20 NMercury 1631E ng/L 10 2.44 5.1 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 NTitanium 200.7 ug/L 2 1.6 20 NVanadium 200.8 ug/L 2 1.7 10 NZinc 200.7 ug/L 2 9.1 40 N
 

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 

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) 

Nickela 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 – Bottle 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 Resu

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Total Metals Aluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 1 0.24 0.5 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 
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 Resu

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Zinc 200.7 ug/L 2 9.1 40 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Total Metals Aluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 1 0.24 0.5 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 
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-11. Distillate from Brine Concentrator Field Blank, Day 1 Analytical Results, Bri

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Zinc 200.7 ug/L 2 9.1 40 
Table A-12. Distillate from Brine Concentrator Field Blank, Day 2 Analytical Results, Bri

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Total Metals Mercury 1631E ng/L 1 0.24 0.5 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Total Metals Mercury 1631E ng/L 1 0.24 0.5 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Total Metals Aluminum 200.7 ug/L 2 9.4 200 Antimony 200.8 ug/L 2 0.72 2 Arsenic 200.8 ug/L 2 1.2 4 Barium 200.7 ug/L 2 2.5 20 Beryllium 200.7 ug/L 2 0.71 2 Boron 200.7 ug/L 2 6.7 200 Cadmium 200.8 ug/L 2 1.2 4 Calcium 200.7 ug/L 2 69 400 Chromium 200.8 ug/L 2 3.3 8 Cobalt 200.7 ug/L 2 1.1 20 Copper 200.8 ug/L 2 0.96 4 Iron 200.7 ug/L 2 32 200 Lead 200.8 ug/L 2 0.73 2 Magnesium 200.7 ug/L 2 21 400 Manganese 200.7 ug/L 2 0.51 20 Mercury 1631E ng/L 1 0.24 0.5 Molybdenum 200.7 ug/L 2 1.6 40 Nickel 200.8 ug/L 2 0.89 4 Selenium 200.8 ug/L 2 0.62 4 Silver 200.8 ug/L 2 0.59 2 Sodium 200.7 ug/L 2 180 10,000 Thallium 200.8 ug/L 2 0.47 2 Tin 200.7 ug/L 2 4.8 200 Titanium 200.7 ug/L 2 1.6 20 Vanadium 200.8 ug/L 2 1.7 10 
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-14. Condensate from Crystallizer Field Blank, Day 1 Analytical Results, Brind

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Zinc 200.7 ug/L 2 9.1 40 
Table A-15. Condensate from Crystallizer Field Blank, Day 2 Analytical Results, Brind

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Total Metals Mercury 1631E ng/L 1 0.24 0.5 

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

Analyte Method Unit 

Dilution 

Factor 

SampleSpecific MDL Sample- Specific QL 

Total Metals Mercury 1631E ng/L 1 0.24 0.5 

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 NARRATIVES 
1

MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD 

CC: Jezebele Alicea, Alternate Work Assignment Manager, EPA EAD 

 Deb Bartram, ERG 

 TJ Finseth, ERG 

From: Randy Mercurio, ERG 

Date: 9/21/2011

Subject: TestAmerica Data Review Narrative for Total Metals by 200.8 – Episode 6576

TestAmerica generated analytical data for total metals (antimony, arsenic, cadmium, 

chromium, copper, lead, nickel, selenium, silver, thallium and vanadium) for Sample 

Episode 6576. The samples were analyzed according to EPA Method 200.8. 

Table 1 summarizes the samples TestAmerica extracted and analyzed for total metals by 

EPA Method 200.8.

Table 1. EPA Episode 6576 Total Metals – Sample Identification 

EPA 

Sample 

# EPA Sample Description 

Lab Sample 

ID # 

Sample 

Matrix 

Sampling 

Date 

Receipt 

Date 

72511 FGD Influent, Day 3 280-14451-1 Aqueous 4/7/2011 4/11/2011

72512 FGD Influent, Day 2 280-14362-1 Aqueous 4/6/2011 4/8/2011

72513 Distillate from Brine Concentrator, Day 1 280-14362-3 Aqueous 4/5/2011 4/8/2011

72514 Distillate from Brine Concentrator, Day 2 280-14362-7 Aqueous 4/6/2011 4/8/2011

72515 Distillate from Brine Concentrator, Day 3 280-14451-2 Aqueous 4/7/2011 4/11/2011

72516 Condensate from Crystallizer, Day 1 280-14362-5 Aqueous 4/5/2011 4/8/2011

72517 Condensate from Crystallizer, Day 2 280-14362-8 Aqueous 4/6/2011 4/8/2011

72518 Condensate from Crystallizer, Day 3 280-14451-3 Aqueous 4/7/2011 4/11/2011

72519 FGD Influent Field Blank, Day 1 280-14362-2 Aqueous 4/5/2011 4/8/2011

72520 Distillate from BC Field Blank, Day 1 280-14362-4 Aqueous 4/5/2011 4/8/2011

72523 Condensate from Crystallizer Field 

Blank, Day 1 

280-14362-6 Aqueous 4/5/2011 4/8/2011

SUMMARY 

The samples were prepared for total metals analysis according to TestAmerica’s “FGD 

ICP/MS SOP: Inductively Coupled Plasma Mass Spectrometry for Trace Element 

Analysis in Flue Gas Desulfurization Wastewaters,” dated October 6, 2010, based on 

EPA Method 200.8, by ICP/MS analysis. 
2

There were no findings from the data review that required additional data qualifiers 

(excluding those identified by the laboratory) in this dataset. 

INTERNAL STANDARDIZATION 

All internal standards used by TestAmerica were within the method criteria. 

INITIAL CALIBRATION 

TestAmerica performed the initial calibrations on each analysis day. The initial 

calibration for the ICP-MS analysis consisted of a blank and four calibration standards. 

INITIAL AND CONTINUING CALIBRATION VERIFICATION (ICV/CCV) 

The initial calibration verifications (ICV) and continuing calibration verifications (CCV) 

performed by TestAmerica all had recoveries within the method criteria. 

METHOD/INSTRUMENT BLANKS 

All the method blanks were less than the reporting limit. No additional qualifiers were 

required for method blanks. 

All instrument blanks (ICB and CCB) were less than the reporting limit; however, some 

elements were above the MDL and flagged with a “J” qualifier. No additional qualifiers 

were required for instrument blanks. 

REPORTING LIMIT VERIFICATION STANDARD (CRI) 

All CRI samples passed TestAmerica’s SOP control limits of 50–150% recovery. 

LABORATORY CONTROL SAMPLES (LCS) 

All LCS samples passed the method QC limits of 85–115% recovery. 

SYNTHETIC FGD INTERFERENCE CHECK SOLUTION (ICSA) 

Based on TestAmerica’s SOP, all interference check sample A (ICSA) results had 

analytes of interest with concentrations less than the RL or less than five times the RL 

when known inherent contaminants are present in the stock solution used to make the 

ICS. 

All interference check sample B (ICSAB) synthetic spikes recovered within 

TestAmerica’s SOP criteria of 70–130% of the true value. 
3

SERIAL DILUTION (SRD) 

The serial dilution performed for the total sample 72514 Distillate from Brine 

Concentrator, Day 2 (280-14362-7) met Test America’s requirement of ±10% difference. 

FIELD DUPLICATES 

Field duplicates were not collected for this sampling episode. 

MATRIX SPIKE AND MATIX SPIKE DUPLICATES (MS/MSD) 

Matrix spikes (MS) and matrix spike duplicates (MSD) were performed on the total 

samples of 72514 Distillate from Brine Concentrator, Day 2 (280-14362-7 MS/MSD) and 

72518 Condensate from Crystallizer, Day 3 (280-14451-3 MS/MSD). The MS/MSD of 

both samples passed the method control limits of 70–130% recovery and the RPD control 

limits of ±20% from the FGD ICP/MS SOP. No additional data qualifiers were required 

for MS/MSD samples. 

POST DIGESITON SPIKES 

A post digestion spike was performed on sample 72514 Distillate from Brine 

Concentrator, Day 2 (280-14362-7 PDS), which passed TestAmerica’s control limits of 

85–115% recovery. No additional data qualifiers were required. 

DETECTION LIMITS 

The laboratory performed an MDL study in the synthetic FGD wastewater matrix, instead 

of reagent water. 
1

MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD 

CC: Jezebele Alicea, Alternate Work Assignment Manager, EPA EAD 

 Deb Bartram, ERG 

 TJ Finseth, ERG 

From: Randy Mercurio, ERG 

Date: 9/21/2011

Subject: TestAmerica Data Review Narrative for Total Metals by 200.7 – Episode 6576

TestAmerica generated analytical data for total metals (aluminum, boron, barium, 

beryllium, calcium, cobalt, iron, magnesium, manganese, molybdenum, sodium, tin, 

titanium, and zinc). The samples were analyzed according to EPA Method 200.7. 

Table 1 summarizes the samples TestAmerica extracted and analyzed for total metals by 

EPA Method 200.7.

Table 1. EPA Episode 6576 Total Metals – Sample Identification 

EPA 

Sample 

# EPA Sample Description 

Lab Sample 

ID # 

Sample 

Matrix 

Sampling 

Date 

Receipt 

Date 

72511 FGD Influent, Day 3 280-14451-1 Aqueous 4/7/2011 4/11/2011

72512 FGD Influent, Day 2 280-14362-1 Aqueous 4/6/2011 4/8/2011

72513 Distillate from Brine Concentrator, 

Day 1 

280-14362-3 Aqueous 4/5/2011 4/8/2011

72514 Distillate from Brine Concentrator, 

Day 2 

280-14362-7 Aqueous 4/6/2011 4/8/2011

72515 Distillate from Brine Concentrator, 

Day 3 

280-14451-2 Aqueous 4/7/2011 4/11/2011

72516 Condensate from Crystallizer, Day 1 280-14362-5 Aqueous 4/5/2011 4/8/2011

72517 Condensate from Crystallizer, Day 2 280-14362-8 Aqueous 4/6/2011 4/8/2011

72518 Condensate from Crystallizer, Day 3 280-14451-3 Aqueous 4/7/2011 4/11/2011

72519 FGD Influent Field Blank, Day 1 280-14362-2 Aqueous 4/5/2011 4/8/2011

72520 Distillate from BC Field Blank, Day

1 

280-14362-4 Aqueous 4/5/2011 4/8/2011

72523 Condensate from Crystallizer Field 

Blank, Day 1 

280-14362-6 Aqueous 4/5/2011 4/8/2011
2

SUMMARY 

The samples were prepared for total metals analysis according to Test America’s SOP for 

ICP Analysis for Trace Metals by Method 200.7. Any significant findings are 

summarized below. No additional data qualifiers were required for this data set. 

• The post digestion spike (PDS) for total sodium for sample 72514 failed the 

method criteria of 85–115%. 

• The post digestion spike (PDS) for total boron for sample 72514 failed the 

method criteria of 85–115%, but was not qualified because the sample 

concentration was greater than 4 times the spike concentration. 

SAMPLE RECEIPT, HANDLING AND STORAGE ISSUES 

No issues were found with sample receipt, handling, or storage. 

INTERNAL STANDARDIZATION 

While the internal standard (ISTD) Yttrium was used for these analyses, no checks on the 

ISTD recoveries in the ±30% criterion of the calibration blank as per Section 9.11 of the 

SOP were seen. All ISTD were within the control limits. 

INITIAL CALIBRATION 

TestAmerica performed the initial calibrations on each analysis day. The initial 

calibration for the ICP analysis consisted of a blank and one calibration standard. 

INITIAL AND CONTINUING CALIBRATION VERIFICATIONS 

The initial calibration verifications (ICV) and continuing calibration verifications (CCV) 

performed by TestAmerica all had recoveries within the method criteria. In some cases 

the CCVs failed the method criteria, but the affected samples were re-analyzed. 

METHOD/INSTRUMENT BLANKS 

All the method blanks were less than the reporting limit; however, some had levels above 

the MDL and were flagged with the “J” qualifier. 

All instrument blanks (ICB and CCB) were less than the reporting limit; however, some 

elements were above the MDL and were flagged with the “J” qualifier. 

REPORTING LIMIT VERIFICATION STANDARD (CRI) 

All CRI samples passed Test America’s SOP control limits of 50–150% recovery. 
3

LABORATORY CONTROL SAMPLES (LCS) 

All LCS passed the method control limits of 85–115% recovery. 

INTERFERENCE CHECK SOLUTIONS 

Interference checks were performed using the synthetic matrix as the check solution. All 

recoveries met the method-specified criteria. 

SERIAL DILUTION (SRD) 

The serial dilution performed for the total sample 72514 Distillate from Brine 

Concentrator, Day 2 (280-14362-7) met Test America’s requirement of ±10% difference. 

FIELD DUPLICATES 

Field duplicates were not collected for this sampling episode. 

MATRIX SPIKE AND MATIX SPIKE DUPLICATES (MS/MSD) 

Matrix spikes (MS) and matrix spike duplicates (MSD) were performed on the total 

samples of 72514 Distillate from Brine Concentrator, Day 2 (280-14362-7 MS/MSD) and 

72518 Condensate from Crystallizer, Day 3 (280-14451-3 MS/MSD). 

The MS of sample 72514 failed EPA Method 200.7 spike recovery control limits of 70–

130% for boron, but was flagged with a “4” qualifier indicating that the concentration in 

the parent sample was greater than 4 times the spike and could not be reliably calculated. 

Otherwise, the MS/MSD spike recoveries were always within the control limits of 70-

130% for both samples. The relative percent difference (RPD) for the MS/MSD of 

samples 72514 and 72518 passed TestAmerica’s SOP requirement of ± 20%. 

POST DIGESTION SPIKE 

A PDS of total sample 72514 Distillate from Brine Concentrator, Day 2 (280-14362-7 

PDS) failed the method criteria of 85–115% for sodium, which was qualified with a “W”. 

Boron also failed at 158% recovery but was not qualified because the sample 

concentration was greater than 4 times the spike concentration. Boron, did however, pass 

the serial dilution criteria for this sample demonstrating that there was no significant 

matrix interference. No additional data qualifiers are required. 

DETECTION LIMITS 

The laboratory performed an MDL study in the synthetic FGD wastewater matrix, instead 

of reagent water. 
1

MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD

CC: Jezebele Alicea, Alternate Work Assignment Manager, EPA EAD 

 Deb Bartram, ERG 

 TJ Finseth, ERG 

From: Ariel Atkinson, ERG 

 Donna Tedder, ERG 

Date: 9/21/2011

Subject: FGS Data Review Narrative for Total Mercury – Episode 6576

Frontier Global Sciences (FGS) generated analytical data for total mercury. The samples 

were analyzed according to EPA Method 1631E for total mercury by Cold Vapor Atomic 

Fluorescence Spectrometry (CVA-FS) analysis. 

Table 1 summarizes the 15 samples (excluding laboratory prep blanks) FGS extracted 

and analyzed for total mercury. 

Table 1. EPA Episode 6576 Total Mercury – Sample Identification 

EPA 

Sample # 

Lab Sample 

ID # 

Sample 

Matrix Sample Description 

Sampling 

Date 

72511 1104114-13 Aqueous FGD Influent, Day 3 04/07/2011 

72512 1104114-01 Aqueous FGD Influent, Day 2 04/06/2011 

72513 1104102-04RE2 Aqueous Distillate from Brine Concentrator, Day 1 04/05/2011 

72514 1104103-04RE2 Aqueous Distillate From Brine Concentrator, Day 2 04/06/2011 

72515 1104114-06 Aqueous Distillate From Brine Concentrator, Day 3 04/07/2011 

72516 1104102-09 Aqueous Condensate from Crystallizer, Day 1 04/05/2011 

72517 1104103-09 Aqueous Condensate from Crystallizer, Day 2 04/06/2011 

72518 1104114-11RE1 Aqueous Condensate From Crystallizer, Day 3 04/07/2011 

72519 1104114-02 Aqueous FGD Influent Field Blank, Day 1 04/05/2011 

72520 1104102-05 Aqueous Distillate from BC Field Blank, Day 1 04/05/2011 

72521 1104103-05 Aqueous Distillate from BC Field Blank, Day 2 04/06/2011 

72522 1104114-07 Aqueous Distillate From BC Field Blank, Day 3 04/07/2011 

72523 1104102-10 Aqueous Cond. from Crystlzr., Field Blank, Day 1 04/05/2011 

72524 1104103-10 Aqueous Cond. from Crystlzr., Field Blank, Day 2 04/06/2011 

72525 1104114-12 Aqueous Cond. From Crystlzr., Field Blank, Day 3 04/07/2011 
2

SUMMARY 

The samples were prepared according to EPA Method 1631E to be analyzed by CVAFS. 

There were no findings from the data review that required additional qualifiers in this 

dataset. 

SAMPLE RECEIPT, HANDLING, AND STORAGE ISSUES 

The FGD Influent Day 2 sample ID was wrong on the chain of custody; the sample 

number was given as 72511 when it should have been 72512. There were no other sample 

receipt issues in this data package. 

INITIAL CALIBRATION 

FGS performed the initial calibrations on the analysis day. The initial calibration for the 

CVAFS analysis consisted of a blank and five calibration standards with a correlation 

coefficient ≥0.995. All method-specified criteria were met. 

INITIAL AND CONTINUING CALIBRATION VERIFICATIONS 

All initial and continuing calibration verifications (ICVs, CCVs) met method-specified 

criteria. 

BLANKS 

All the preparation blanks or laboratory reagent blanks (LRBs) and the continuing 

calibration blanks (CCBs) met method-specified criteria. There was an FGD Influent 

field blank (FB) on Day 1, while the Influent samples were collected on Days 2 and 3.

DUPLICATES 

No field duplicate samples were collected with these sampling episodes. One sample was 

analyzed as a laboratory duplicate, Condensate from Crystallizer, Day 3 (sample 72518). 

The RPD was 5.62%. The laboratory’s RPD criteria between analytical duplicates is 

24%. 

LABORATORY CONTROL SAMPLES 

All laboratory control samples were within Frontier’s control limits of 80-120% recovery 

and 24% RPD. 

MATRIX SPIKE AND MATIX SPIKE DUPLICATES (MS/MSD) 
3

Matrix spikes (MS) and matrix spike duplicates (MSD) were performed on samples 

72518 and 72514. All aqueous MS/MSD recoveries were within method specifications of 

71-125%. All RPDs met method-specified criteria. 

DETECTION LIMITS 

The laboratory MDL in the synthetic matrix was 0.239 ng/L. Results below this MDL 

were reported as not detected (ND). 
1 

MEMORANDUM

To: Ron Jordan, Work Assignment Manager, EPA EAD 

CC: Jezebele Alicea, Alternate Work Assignment Manager, EPA EAD 

 Deb Bartram, ERG 

 TJ Finseth, ERG 

From: Donna Tedder, ERG 

Date: 9/21/2011 

Subject: TestAmerica Data Review Narrative for Classicals Analyses – Episode 6576 

TestAmerica Denver Laboratory generated analytical data for classical wet chemistry 

analyses for Sample Episode 6576. All samples were tested for the following analytes: 

• Ammonia by EPA method 350.1, 

• Chloride and Sulfate by EPA method 300.0, 

• Chemical Oxygen Demand (COD) by EPA method 410.4, 

• Nitrate/Nitrite by EPA method 353.2, 

• Phosphorus (total) by EPA method 365.1, 

• Total Dissolved Solids (TDS) by SM 2540C, 

• Total Kjeldahl Nitrogen (TKN) by EPA method 351.2, and 

• Total Suspended Solids (TSS) by SM 2540D. 

Table 1 summarizes the 11 samples that TestAmerica analyzed for the above analytes. 

Table 1. EPA Episode 6576 Classical Analytes – Sample Identification 

EPA 

Sample # 

Sample 

Matrix Sample Description 

Sampling 

Date 

72511 Water FGD Influent, Day 3 4/7/11 

72512 Water FGD Influent, Day 2 4/6/11 

72513 Water Distillate From Brine Concentrator, Day 1 4/5/11 

72514 Water Distillate From Brine Concentrator, Day 2 4/6/11 

72515 Water Distillate From Brine Concentrator, Day 3 4/7/11 

72516 Water Condensate From Crystallizer, Day 1 4/5/11 

72517 Water Condensate From Crystallizer, Day 2 4/6/11 

72518 Water Condensate From Crystallizer, Day 3 4/7/11 

72519 Water FGD Influent Field Blank, Day 1 4/5/11 

72520 Water Distallate From BC Field Blank, Day 1 4/5/11 

72523 Water Conds. From Crystllzr Field Blank, Day 1 4/5/11 
2 

SUMMARY 

All samples were analyzed within the holding time specified in 40 CFR 136 Table II. All 

samples were preserved appropriately unless otherwise specified below. Group I and 

Group II samples 72511, 72515, and 72518 were received at 15.4°C and 17.1°C due to 

international shipping issues. The client was notified and analyses performed. 

 

If applicable, the appropriate number of standards was used to create a calibration curve. 

If sample results were above the highest standard used to create the curve, the sample was 

diluted and reanalyzed. All sample results were between the lowest and highest standards 

unless noted below. Additionally, unless otherwise noted, all calibration blanks and 

calibration verification samples met the criteria specified in the method. 

If required by the method, the quality control sample (QCS), a secondary source standard 

used to verify calibration, was always within the control limits specified by the method. 

As described below, the analyte of interest was detected above the method detection limit 

(MDL) in some laboratory reagent blanks (LRB). However, the analyte of interest was 

never detected above the reporting limit (RL) in the LRBs. If required by the method, all 

laboratory fortified blanks (LFB) met the criteria specified in the method unless specified 

below. 

If required by the method, a matrix spike (MS) sample was analyzed on samples 72514 

and 72518 for each analyte to check for matrix interferences. For some analytes, 

TestAmerica spiked more samples than required. All MS samples analyzed met the 

criteria specified in the method unless described below. 

DATA NOTES/ISSUES 

Ammonia 

Samples 72511, 72515, and 72518 were received at 15.4°C and 17.1°C. The method 

requires samples to be maintained at 4°C between collection and analysis. The results for 

these samples were qualified as estimated values. 

The MS/MSD analysis on sample 72518 yielded percent recoveries for the MS and MSD 

of 100% and 94%, respectively. Since the sample concentration was greater than 4 times 

the spike amount in the MS and MSD samples, TestAmerica stated that the percent 

recoveries and RPDs could not be reliably calculated and the results were flagged with a 

“4”. 

BOD5 

No BOD was analyzed for this sampling episode. 
3 

Chloride and Sulfate 

Samples 72511, 72515, and 72518 were received at 15.4°C and 17.1°C. The method 

requires samples to be maintained at 4°C between collection and analysis for sulfate (no 

temperature requirements for chloride analysis). Sulfate in samples 72515 and 72518 

was not detected, and therefore, does not need additional qualification. Sample 72511 

was qualified as an estimated value. 

The MS/MSD chloride recoveries for sample 72514 were above the EPA Method 300.0 

control limits and qualified with an “F”. The LFB associated with this sample met the 

method criteria. There was no need for additional qualifiers for the sample. 

Sample 72514 and its laboratory duplicate had results below the lowest calibration 

standard and the RL, but above the MDL. This result was flagged with a “J,” and does 

not need additional qualification. 

COD 

Samples 72511, 72515, and 72518 were received at 15.4°C and 17.1°C. The method 

requires samples to be maintained at 4°C between collection and analysis. Samples 

72515 and 72518 have been qualified with a “J”, and do not need additional qualification. 

Sample 72511 was qualified as an estimated value. 

The MS/MSD recoveries for sample 72514 were above the control limits of 90-110% 

required by EPA method 410.4 with recoveries at 122% and 112%, respectively. The 

RPD between the MS and MSD was 11%, which is also outside the method control 

limits. COD for sample 72514 was not detected, and the MS and MSD results were 

qualified with an “F.” The LFB percent recoveries associated with this sample met the 

method criteria. There was no need for additional qualifiers for the sample. 

Sample 72515 had a result below the lowest calibration standard and the RL, but above 

the MDL. This result was flagged with a “J,” and does not need additional qualification. 

Cyanide 

No cyanide was analyzed for this sampling episode. 

Nitrate/Nitrite 

Samples 72511, 72515, and 72518 were received at 15.4°C and 17.1°C. The method 

requires samples to be maintained at 4°C between collection and analysis. Samples 

72511, 72515, and 72518 were qualified as estimated values. 
4 

Phosphorus 

Samples 72511, 72515, and 72518 were received at 15.4°C and 17.1°C. The method 

requires samples to be maintained at 4°C between collection and analysis. Phosphorus in 

samples 72515 and 72518 was not detected, and therefore, does not need additional 

qualification. Sample 72511 was qualified as an estimated value. 

TDS 

Constant weight was not achieved after 3 drying cycles for sample 72517. The samples 

were not qualified, but results may be biased high. 

The RPD for the laboratory duplicate for sample 72518 was 43%, which is greater than 

10% as required by SM 2540C. Because the RPD was greater than the method control 

limits, sample 72518 should be qualified as an estimated value. However, this sample is 

already qualified with a “J” meaning that the result is less than the RL but greater than or 

equal to the MDL and the concentration is an approximate value. Therefore, no additional 

qualifier is needed. The RPD for the sample 72514 laboratory duplicate was within 

method limits. 

TKN 

The ammonia concentrations were greater than the TKN, particularly for samples 72512 

and 72517, and were re-analyzed for confirmation. Since TKN is a sum of free ammonia 

and organic nitrogen compounds, the ammonia concentrations should be less than the 

TKN numbers. The method states that in samples with high nitrate levels the TKN may 

be biased low. The TKN results for samples 72512 and 72517 were qualified as 

estimated values. 

Samples 72511, 72515, and 72518 were received at 15.4°C and 17.1°C. The method 

requires samples to be maintained at 4°C between collection and analysis. These results 

were qualified as estimated values. 

 

TestAmerica performed MS/MSD analysis on sample 72514. The percent recoveries for 

the MS and MSD samples were 85% and 78%, respectively. These did not meet the 

method control limits of 90-110%, but did meet the laboratory control limits of 54-131%. 

Since the sample concentration was greater than 4 times the spike amount in the MS and 

MSD samples, TestAmerica stated that the percent recoveries and RPDs could not be 

reliably calculated. Therefore, sample 72514 was not additionally qualified because it is 

not possible to determine if the failure was a result of matrix interferences or caused by 

spiking the sample with too little analyte. 

TKN was detected at 0.124 mg/L in the LRB associated with samples 72511, 72514, and 

72518. This blank result was greater than the MDL (0.077 mg/L), but less than the RL 

(1.0 mg/L). Because the blank result was less than the RL, no samples were qualified 

based on the LRB result. 
5 

TSS 

Constant weight was not achieved after 3 drying cycles for sample 72512 and the 

laboratory duplicate. 

The RPD for the laboratory duplicate of sample 72512 was 33%. This RPD was greater 

than the method control criteria of 10%. Sample 72512 was qualified as an estimated 

value. The RPD for the laboratory duplicates of samples 72514 and 72518 could not be 

calculated because all results were not detected. 

Table 2. Data Review Summary Table 

Sample Analyte Qualifier/Action Reason Level Detected

72511 Sulfate Estimated Value Sample received at > 4°C 5700 mg/L 

72511 Ammonia Estimated Value Sample received at > 4°C 12 mg/L 

72515 Ammonia Estimated Value Sample received at > 4°C 15 mg/L 

72518 Ammonia Estimated Value Sample received at > 4°C 22 mg/L 

72511 COD Estimated Value Sample received at > 4°C 100 mg/L 

72511 Nitrate/nitrite Estimated Value Sample received at > 4°C 46 mg/L 

72515 Nitrate/nitrite Estimated Value Sample received at > 4°C 0.16 mg/L 

72518 Nitrate/nitrite Estimated Value Sample received at > 4°C 0.1 mg/L 

72511 Phosphorus Estimated Value Sample received at > 4°C 6 mg/L 

72511 TKN Estimated Value Sample received at > 4°C 11 mg/L 

72512 TKN Estimated Value TKN value < Ammonia 

value 

3.6 mg/L 

72515 TKN Estimated Value Sample received at > 4°C 16 mg/L 

72517 TKN Estimated Value TKN value < Ammonia 

value 

37 mg/L 

72518 TKN Estimated Value Sample received at > 4°C 25 mg/L 

72512 TSS Estimated Value Lab duplicate RPD > 

method-specified criteria 

2600 mg/L 
Appendix C 

PICTURES FROM THE SAMPLING EPISODE 
C-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 Sytem 
C-3 

Figure C-3. Sample Collection Set-Up at the Distillate from the Brine Concentrator 
C-4 

Figure C-4. Sample Collection Set-Up at the Condensate from the Crystallizer