# 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. I NTRODUCTION 

### ................................................................................................................. 1-1

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

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

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

2. S ITE 

### V ISITS 

### ....................................................................................................................... 2-1

2.1 Brindisi Facility Overview ................................................................................... 2-1

2.1.1 Enel Research and Development ............................................................. 2-1

2.1.2 Pilot-Scale Carbon Capture and Storage System ..................................... 2-2

2.1.3 Ash Handling Procedures ........................................................................ 2-3

2.1.4 FGD Scrubber Systems ............................................................................ 2-3

2.1.5 FGD Wastewater Trea tment 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 Trea tment System ..................................................... 2-11

3. S AMPLE 

### C OLLECTION 

### ....................................................................................................... 3-1

3.1 Sampling Points, Sample Collection Me thods, and Field Measurements ........... 3-1

3.1.1 Influent to FGD Wastewater Treatment System ...................................... 3-2

3.1.2 Distillate from the Brine Concentrator (SP-2) ......................................... 3-3

3.1.3 Condensate from the Crystallizer ............................................................. 3-5

3.2 List of Analytes and Sample Preservation ........................................................... 3-7

3.3 Plant Operational Data ......................................................................................... 3-8

3.4 Deviations from the Sampling and Analysis Plan ............................................... 3-8

4. L ABORATORY 

### A NALYTICAL 

### R ESULTS AND 

### D ISCUSSION 

### ................................................... 4-1

5. D ATA 

### Q UALITY 

### ................................................................................................................. 5-1

5.1 Analytical 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. R EFERENCES 

### ..................................................................................................................... 6-1

Appendix A: A NALYTICAL 

### R ESULTS



### Appendix B: D ATA 

### R EVIEW 

### N ARRATIVES



### Appendix C: P ICTURES 

### F ROM THE 

### S AMPLING 

### E PISODE

### 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 ................................................................................... 3-1 3

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 Preserva tion, Brindisi ...................... 3-16

Table 3-6. Sample Preservati on Summary, Brindisi .................................................................. 3-17

Table 3-7. Generating Unit Operating Characteris tics during Sample Coll ection, Brindisi ..... 3-18

Table 3-8. FGD Scrubber System Operat ing Characteristics, Brindisi ..................................... 3-19

Table 3-9. Coal Usage during Samp le Collection, Brindisi ....................................................... 3-20

Table 3-10. Scrubber Slurry Information du ring Sample Collection, Brindisi .......................... 3-21

Table 3-11. FGD Wastewater Tr eatment System Operation Information, Brindisi .................. 3-22

Table 4-1. Influent to FGD Wastewater Treatment System, Brindisi ......................................... 4-2

Table 4-2. Distillate from Brin e Concentrator, Brindisi .............................................................. 4-4

Table 4-3. Condensate from Crys tallizer, Brindisi ...................................................................... 4-6

Table 4-4. Classical Pollutants Average Da ta 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 Resu lts, Brindisi ................. A-8

Table A-5. Distillate from Brine Concentrator , Day 3 Analytical Resu lts, 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 Bl ank 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 Concentrat or Field Blank, Day 1 Analytical Results,

Brindisi ...................................................................................................................... .... A-24

Table A-12. Distillate from Brine Concentrat or Field Blank, Day 2 Analytical Results,

Brindisi ...................................................................................................................... .... A-26

Table A-13. Distillate from Brine Concentrat or 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 Car bon Capture and Storag e System, Brindisi

Power Plant ................................................................................................................... . 2-15

Figure 2-2. Diagram of the Chemical Precip itation and Softening Portion of the FGD Wastewater Treatment System, Brindisi Power Plant ................................................... 2-16

Figure 2-3. Diagram of the Evaporation Po rtion of the FGD Wastewater Treatment System, Brindisi and Torrevaldal iga Nord Power Plants .............................................. 2-17

Figure 2-4. Diagram of the Crystallization Po rtion of the FGD Wastewater Treatment System, Brindisi and Torrevaldal iga Nord Power Plants .............................................. 2-18

Figure 2-5. Diagram of the Chemical Preci pitation 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 Wastew ater Treatment Sytem .........................................................C-2

Figure C-3. Sample Collection Set-Up at the Distillate from the Br ine Concentrator ................C-3

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

### 1-1 1. I NTRODUCTION



### The Engineering and Analysis Division (EAD) of the U.S. Environmental Protection Agency (EPA) is conducting a sampling program at steam electric power plants. The sampling program will characterize wastewaters generated by coal-fired steam electric power plants and evaluate treatment technologies and best mana gement practices used to reduce pollutant discharges. This report describes th e 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 fo cus of Episode 6576 was to characterize the purge stream entering the flue gas desulfuriz ation (FGD) wastewater treatment system, the

distillate from the brine con centrator, and the condensate from the crystallizer of the FGD mechanical vapor compression treatment system.

1.1 Background

Metals and certain other constituents presen t 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 stream s 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 sa mpling program on characterizing the untreated

FGD wastewaters and effl uent quality from technologies desi gned to treat the wastewater.

1.2 Power Plant Site Selection

EPA selected steam electric plants for F GD wastewater sampling based on the process configurations and characte ristics of the plants.

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

 

### The plant is a coal-fired power plant;

 

### The plant operates limestone forced oxid ation 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 s oda 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 Bri ndisi on February 14, 2011. The in formation 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 Br indisi to meet with plant personnel, participate in a site visit at th e facility, receive on-site safety training, review the sampling points, and determine the set-up for the sample co llection. EPA and ERG collected the samples specified in the Sampling Plan on Tuesday th rough 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, EP A collected duplicate samples with Enel personnel.

### 2-1 2. S ITE 

### V ISITS



### EPA conducted site visits at two of Enel’s power plants in Italy prior to the sampling episode at Brindisi. This summari zes the facility information gath ered 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 lo cated in Cerano-Tuturano (Brindisi), Italy. There are 309 employees and 171 operators at the plant. Brindisi operate s four steam electric

units and each has a coal-fired bo iler. All four units have a capa city 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 s ource 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 approximatel y 5 million tons of coal per year from the Costa Morena port, which is transported to the plant via tw o 15 kilometer (km) covered conveyor belts. Each conveyor belt can transfer up to 1,50 0 tons of coal per hour. Brindi si 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, Indone sia, or the United States. These coals are generally low sulfur coal (1 pe rcent sulfur). Brindisi also bur ns bituminous coal occasionally; however, plant personnel noted that it can cau se 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 precip itators (ESPs) on Units 1, 2, and 4 to control particulate releases from the plant. The plant oper ates 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 ammo nia 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 Bri ndisi research center fo cuses largely on residues, environmental impact analyses, and renewable energy.

Currently, the Brindisi resear ch center has a laboratory-scal e carbon capture and storage system (CCS) and a pilot-scale CCS is in opera tion at the Brindisi pl ant. See Section 2.1.2 for further information on the pilot-scale CCS at Br indisi. Enel is resear ching carbon dioxide (CO 2 

### ) post-combustion capture and the ability to retr ofit existing plants with such a system.

### 2-2 Additionally, Brindisi is researching CO 2 

### geo-sequestration and is in the process of trying to identify a geological storage site on Italian territory that consists of an impermeable substrate to prevent the release of captured CO 2



### .

Other research topics at Br indisi include the following:

 

### Environmental Impact Source Apportionmen t: the evaluation of the effect of Enel-fired plants on ambient air in re ference to particulate matter using mass

spectrometry.

 

### Wind Power Forecast: the development of a short- or medium-term wind power prediction model to improve the compa tibility 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 numeri cal aspersion model, this technology screens filter samples using morphological recognition to determine the chemical composition of air particles.

 

### Point Source Apportionment: mobile equi pment performing real-time analyses using ion chromatography.

2.1.2 Pilot-Scale Carbon Capture and Storage System

The Brindisi plant recently installed a p ilot-scale post-combustion carbon capture plant that services a 10,000 normal cubic meters per hour (Nm 3 

### /hr) flue gas slip stream from Unit 4. The pilot system is designed to treat approxima tely 2-3 MW-equivalent and capture 2.5 metric

tons of CO 2 

### per hour. The pilot system st arted up in June 2010 and took approximately one year for construction of the system. It took less than two years to get the first CO 2 

### separation since starting the system. Figure 2-1, located at the e nd of this section, pres ents 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 a dditional desulfur ization (DeSO

x 

### ), where the flue gas is washed with a limestone slurry to remove sulfur trioxide (SO 3 

### ) and reduce sulfur dioxide (SO 2 

### ) levels to below 20 mg/Nm 3 

### . Immediately downstream of the DeSO

x 

### system, is a wet ESP to remove any additional particulate matter. This pretreatment is required because the sorbent used in the carbon capture system will also react with the SO 2 

### , which would require additional sorbent.

The pretreated flue gas then enters the CO 2 

### absorber. The absorber is approximately 1.5

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

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

20-80 m 3 

### /hour. The absorber was designed with three different levels to experiment with the amount of surface area exposed to the MEA soluti on and/or solvent used in the process. The cleaned flue gas exiting the top of the CO 2 

### absorber exits out the stack. Prior to exiting through the stack, the flue gas is washed to remove any leftover solven t particles and to control the temperature of the flue gas.

### 2-3 Existing the bottom of the CO 2 

### absorber is the CO 2 

### -rich MEA solution. The MEA and

CO 2 

### solution is sent through a heat exchanger to increase the te mperature of the solution and then sent to a high-pressure steam stripper where the CO 2 

### is stripped from the solution. CO 2 

### and water vapor exit the top of the stripper and go through a condens er where the water vapor is

condensed and then transferred to a separator to allow the CO 2 

### gas to separate from the water.

The condensed water is transferre d back to the st ripper and the CO 2 

### is captured. Currently, the captured CO 2 

### is returned to the stack.

Exiting the bottom of the stripper is the wa ter 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 CO 2 

### from the CO 2 

### -rich MEA solution. The remainder of the bottoms, which is

the CO 2 

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

### -rich MEA solution prior to it entering the stripper. This so lution is then split to allow some of the solution to transfer through mechanical and activated ca rbon filters to avoid pa rticles going through the

CO 2 

### absorber. After passing through th e filters, the stream is combined with the portion that was

not filtered and is transferred to the CO 2 

### absorber where it absorbs the CO 2 

### from the flue gas. Plant personnel stated that the pilot-scale syst em also has a reclaime r 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 fl ue 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 Brin disi plant is collected in ESPs (Units 1, 2, 4) or a fabric filter (Unit 3) and is transporte d to silos via dry vacuum. Brindi si operates four temporary silos (one per unit) which feed into two storage silos. From the storage si los, 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. Addi tionally, 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 ove rflow from the hydrobins is recirculated back to the bottom ash sluicing system. Currentl y, 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 sy stem to treat the recycled wa ter. Although the plant does not treat the recirculation water, problems with lo w 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 for ced oxidation wet FGD scrubber systems (two per unit) to

control the emission of SO 2 

### from the units. Each FGD system consists of both a prescrubber and

### 2-4 a main scrubber. Brindisi has two different type s 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). Accordi ng to plant personnel, each of the scrubbers was designed to have the same SO 2 

### removal efficiency; however , the Bishoff scrubbers are bigger than the Mitsubishi sc rubbers and have achieved gr eater removal efficiencies.

The prescrubbers for each FGD system operate similarly, using a water scrubber to help remove the additional particulates from the flue gas (i.e., carry-over fly ash from the ESPs) prior to the FGD system. Additionally, the prescrubbers remove chlorides from the flue gas prior to the main scrubber. Each prescrubber has a continuous blowdown that is fed to the FGD wastewater treatment system. The Unit 1 and 2 prescrubber blowdown is approximately 60 m 3 

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

### /hr (352 gal/min) for the two units combined.

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

 The systems are limestone forced oxidation scrubbers;

 The solids concentration in the scrubbers ranges from 18 to 24% solids;

 The chlorides concentration in the sc rubbers is approximately 5,000 ppm; and

 The systems include gas-gas heaters (described below).

The scrubbed flue gas exiting the absorber pa sses 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-ga s heater where the heating medium is used to cool the flue gas entering the FGD system in the heat recovery s ection. 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 heat s the cleaned flue gas exiting the FGD system. Finally, the flue gas is heated to its exit temper ature, using a steam coil gas heater. The desired exit temperature provides better diffusion of th e exhaust gas and prevents the white steam cloud prevalent with FGD system stacks.

Section 2.1.1 describes the operation of the Bis hoff scrubbers (Units 1 and 2) and Section 2.1.2 describes the operation of the Mits ubishi scrubbers (Units 3 and 4).

2.1.4.1 Units 1 and 2 FGD Scrubber Systems

The Units 1 and 2 FGD scrubber systems we re both manufactured by Bishoff and have an identical design. Each unit is equipped with two FGD absorber modules, with each absorber receiving approximately 50 percen t 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 SO 2 

### , which reacts with the limestone particles and produces calcium sulfite. The spray droplets fall to the reaction tank at the bottom of the absorber where air is injected and the slurry is mixe d 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 prim ary 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 c ontent of less than 10 pe rcent. Brindisi sells the gypsum for use in wallboard manufacturing. Th e filtrate from the vacuum belt filters is transferred to the Units 1 and 2 FGD sump.

The overflow from the two primary hydrocyclone s 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 thic kener). 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 peri odically transferred to the FGD wastewater treatment system based on sump level control. Wa stewater from the Units 1 and 2 FGD sump is typically transferred to the FGD wastewater treatment system at a flow rate of 20 m 3 

### /hr (88 gal/min) for 15 to 20 minutes every two hours.

2.1.4.2 Units 3 and 4 FGD Scrubber Systems

The Units 3 and 4 FGD scrubber systems were both manufactured by Mitsubishi and have an identical design. Each unit is equippe d with two FGD absorber modules, with each absorber receiving approximately 50 percent of th e 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 SO 2 

### , which reacts with the limestone particles and produces calcium sulfite. The spray droplets fall to the reaction tank at the bottom of the absorber where air is injected and the slurry is mixe d 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 dow n 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 prim ary 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 tran sferred to vacuum belt filters for dewatering. Brindisi washes the gypsum as it is applied to th e 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 be ing used to remove suspended solids. According to plant personnel, the Units 3 and 4 FGD sc rubber systems were in itially designed with centrifuges, which are a solids separation process that is not as effici ent as hydrocyclones; therefore, the clarifiers were needed to achie ve 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 transferre d to the FGD wastewater treatm ent system based on sump level

control. Wastewater from the Units 3 and 4 F GD sump is typically transferred to the FGD

wastewater treatment system at a flow rate of 100 m 3 

### /hr (440 gal/min) for 10 to 15 minutes every

30 minutes.

2.1.5 FGD Wastewater Treatment System

The FGD wastewater treatment system at Br indisi is designed to receive continuous blowdown flow from the eight prescrubber units a nd intermittent transfers from the Units 1 and 2 FGD sump and the Units 3 and 4 FGD sump.

The FGD wastewater treatment system was orig inally installed to treat the FGD scrubber purge wastewater to meet the plant’s permit lim its prior to discharge. However, in 2008, the plant upgraded the FGD wastewater treatment sy stem to include a softening, evaporation, and crystallization system which allows the entire plant to achieve zero liqui d discharge, with the exception of cooling water discharges. The Brindi si 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 a ddition (softening (a dded 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 a nd the sampling locations for EPA’s sampling episode. Figure 2-2 presents a diagram of the pr etreatment 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 presen ts a diagram of the cr ystallization 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 se ttling basin. Brindisi ha s two concrete settling basins, each with a capacity of 600 m 3 

### (158,500 gallons). The plant on ly 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 samp led from the settling basin (i.e., where the influent stream enters the basin) was found to contain less than 0.4 pe rcent solids, had a pH between 2 and 2.5 S.U., and a te mperature between 30 and 35 °C.

The overflow from the settling basins is transferred to the FGD wastewater treatment tanks, which consist of two 2,000 m 3 

### (528,000 gallons) tanks used for equalization of the

wastewater. Brindisi also transf ers 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 tr eatment basin to the FGD wastewater treatment tanks?]

The FGD wastewater treatment tanks feed the 1 st 

### stage of the neutra lization basin, which is a large concrete basin that has three divided compartments. In the 1 st 

### compartment, the plant adds lime, sodium sulfide, and caustic soda. Overflow from the 1 st 

### compartment feeds the 2 nd


### compartment where ferric chloride is a dded. The wastewater then flows to the 3 rd 

### compartment where a polyelectrolyte is added.

The overflow from the third compartment of the 1 st 

### stage basin is transferred to the

clarifier. The underflow from the clarifier is transferred to fi lter 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 2 nd


### stage of the neutralizatio n basin, which has two divided compartments. In the first compartment, the plant adds ferrous chloride and sodium carbonate (soda ash) to the wast ewater for softening. The overflow from the first compartment is tran sferred 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 pu mped 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 e ither recycled back to the FGD system as make-up or sent to the softening tank for furthe r treatment. The original design for the system was for the pretreatment system (i.e., neutralization basi ns) to treat 280 m 3 

### /hr, with 140 m 3 

### /hr to be recycled and 140 m 3 

### /hr to be sent to the softening ta nk. However, the plant attempts to maximize the amount of recycle because the lower the flow to the evapor ation system, the less expensive it is to operate the system. Therefore, the plant cu rrently operates the system by recycling 230 m 3 

### /hr back to the FGD system and transferring 50 m 3 

### /hr to the softening tank.

The wastewater sent to the softening tank is treated with additional sodium carbonate to complete the softening process. The overflow from the softening tanks is then transferred to the

### 2-8 evaporation and crystallization system. As described above, the original design for the system was for the softening tank to receive 140 m 3 

### /hr of wastewater, but only 70 m 3 

### /hr was supposed to

be transferred to the eva poration system, while 70 m 3 

### /hr was supposed to be recycled back to the FGD system. Because of the reduced flow to the softening tanks, the entire 50 m 3 

### /hr entering the softening tanks is transferred to the evaporation system with no recycle back to the FGD system.

Brindisi operates two identical parallel trai ns 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 aci d and an anti-scalant to the wastewater prior to the evapora tion system. From the evaporator feed tank, the wastewater is split into two streams and both are sent to heat ex changers to bring the wa stewater to its boiling point. The distillate st ream 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 se nt to the deaerator, where the noncondensable

materials such as carbon dioxide an d 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 concen trator and enters the heat transfer tubes. While falling down the heat transfer tubes, part of th e solution is vaporized and then compressed and

introduced to the shell side of the brine concentr ator (i.e., the outside of the tubes), along with additional make-up steam. The temperature di fference between the compressed vapor and the brine solution causes the compresse d vapor to transfer heat to th e 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 concentr ator is collected and transferred to a distillate tank. The distillate is then pumped th rough 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 contin ues to the second dist illate tank where it is combined with the condensate from the crystallizer.

The concentrated brine slurry from the brine co ncentrator 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 fr om the sump and transferred to a set of hydrocyclones. To prevent scaling within the brin e concentrator as a result of the gypsum present in the FGD wastewater, the brine concentrator is seeded with cal cium sulfate. The calcium salts preferentially precipitate onto the seed crystals instead of the tube surfaces of the brine concentrator. The hydrocyclones r ecover the calcium sulf ate 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 crys tallizer feed tank, the wa stewater is combined with some of the slurry recircul ation from the bottom of the crysta llizer and then combined with

### 2-9 the reheated slurry recycle and fed into the crysta llizer. The crystallizer is operated with a certain level of slurry in the bottom of the system. Within the system, th e water is evaporated and exits the top of the crystallizer as steam. Some of th e steam is diverted to a thermocompressor where the low-pressure steam is converted to high pr essure 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 transfe rred 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 ta nk. [QUESTION FOR ENEL: What are th e flow rates of the distillate and condensate streams?] The rest of the steam that exits the top of the crysta llizer 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 cr ystallizer is tr ansferred 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 pr esent in the slurry to evaporate and exit the crystallizer as steam. The evapora tion 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 wh ere 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 pres crubber 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 br ine concentrator, upstream of the first

distillate tank and downstream of the heat exchanger; and

 

### A sample of the condensate from the crys tallizer on the discharge side of the pump that transfers the wastew ater to the distillate tank.

2.2 Torrevaldaliga Nord Facility Overview

The Torrevaldaliga Nord plant originally st arted 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 th ree 660-MW coal-fired units. The To rrevaldaliga 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 sour ce. Regular start-up opera tions usually include starting the unit with natural gas. The coal-f ired units at the plan t 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 mi llion tons of coal per year. The coal arrives on ships and is unloaded at one of the tw o jetties. The plant has two unloaders, each with an unloading capacity of 1,500 tons/hour, which ar e 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. To rrevaldaliga Nord estimates that this results in approximately 500,000 tons of ash per year. The plant operates fabric fi lters 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 selectiv e 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 ca talyst layer compartments, but the plant began installation with only three layers for each un it. 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. To rrevaldaliga Nord operates three silos, which are shared among the three units and are classified ba sed 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 ha ve the capability to moisture the fly ash in a pugmill to approximately 20 percent moisture cont ent 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 th e fly ash using the same pressure system.

2.2.2 FGD Scrubber Systems

Torrevaldaliga Nord operates three limes tone forced oxidation wet FGD scrubber systems (one per unit) to control the emission of SO 2 

### from the units. All three FGD systems were manufactured by MHI (Mitsubishi ) and operate similarly. Th ey 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 ar e double-contact-flow scrubbers, where the limestone slurry is spra yed upward into the FGD system, in the same direction as the flue gas, and then the spray falls downward, ther eby contacting the flue gas in both directions. During contac t with the flue gas, the spray droplets absorb the SO 2 

### , which reacts with the limestone particles and produces calcium sulfite. The spray droplets fall to the reaction

tank at the bottom of the scrubber where air is in jected and the slurry is mixed to oxidize the

calcium sulfite to calcium sulfate (i.e., gypsum).

The scrubbed flue gas then passes through the mi st eliminators and a gas-gas heater prior to entering the stack and being em itted 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 extr acted heat from the flue gas. The heating medium is then pumped to the reheater section, where the heatin g 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 diff usion 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 c oncentration 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 concentr ation 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 th e 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 vac uum belt filters is transferred to the process water storage tanks and either reused for limes tone preparation or transferred back to the

scrubbers.

The overflow from the primary hydrocyclo nes is transferred to the secondary hydrocyclones. The underflow from the secondar y hydrocyclones is transferred to the process water storage and either reused for limestone prep aration or transferred b ack 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 th e flow rate and durat ion of the secondary

### 2-12 hydrocyclone transfers to the FGD wastewater tr eatment system?] The Torrevaldaliga Nord FGD wastewater treatment system contains the following treatment operations:

 Equalization,

 Lime and sodium sulfide addition (pH ad justment/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, locat ed at the end of this sect ion, present the process flow diagrams of the Torrevaldaliga Nord FGD wastew ater treatment system. Figure 2-5 presents a diagram of the pretreatment system, which incl udes the chemical preci pitation portion of the

system. Figure 2

- 3 presents a diagram of the evaporati on 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 treatmen t system, which is identical to the Brindisi

system.

The secondary hydrocyclone overflow from th e FGD systems is transferred to the FGD wastewater treatment tanks, which consist of two 4,000 m 3 

### (1,056,000 gallons) tanks used for equalization of the wastewater. The FGD wastewat er treatment tanks feed reaction tank 1, where the plant adds lime to the wastew ater to adjust the pH and desa turate 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 wh ere ferric chloride is added.

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

is added. The underflow from the clarifier is tran sferred 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 th ickener 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 carbona te (soda ash) and polyelectrolyte to the

wastewater to reduce the calcium content of th e 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 evapora tion and crystallization system?]

Torrevaldaliga Nord operates two identical 50% parallel trains of th e evaporation system and one 100% crystallization system. The wastewat er from the softening tank is transferred to the evaporator feed tank, where the wastewater is equalized prior to bein g fed to the evaporation system. Additionally, the plant adds hydrochloric aci d and an anti-scalant to the wastewater prior

### 2-13 to the evaporation system. From the evaporator feed tank, the wastewat er 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 a nd the condensate stream from the crystallizer are

the streams used to transfer heat to the wa stewater. From the heat exchangers, the two

wastewater streams are recombined and sent to the deaerator, where the noncondensable

materials such as carbon dioxide an d 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 concen trator and enters the heat transfer tubes. While falling down the heat transfer tubes, part of th e solution is vaporized and then compressed and

introduced to the shell side of the brine concentr ator (i.e., the outside of the tubes), along with additional make-up steam. The temperature di fference between the compressed vapor and the brine solution causes the compresse d vapor to transfer heat to th e 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 concentr ator is collected and transferred to a distillate tank. [QUESTION FOR EN EL: What is the flow rate of the distillate stream?] The distillate is then pumped through one of the feed h eat exchangers where it tr ansfers its heat to the incoming wastewater and at the same time cool ing 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 co ncentrator 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 fr om the sump and transferred to a set of hydrocyclones. To prevent scaling within the brin e concentrator as a result of the gypsum present in the FGD wastewater, the brine concentrator is seeded with cal cium sulfate. The calcium salts preferentially precipitate onto the seed crysta ls instead of the tube surfaces of the brine concentrator. The hydrocyclones r ecover the calcium sulf ate 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 crys tallizer feed tank, the wa stewater is combined with some of the slurry recircul ation from the bottom of the crysta llizer and then combined with the reheated slurry recycle and fed into the crysta llizer. The crystallizer is operated with a certain level of slurry in the bottom of the system. Within the system, th e water is evaporated and exits the top of the crystallizer as steam. Some of th e steam is diverted to a thermocompressor where the low-pressure steam is converted to high pr essure 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 transfe rred 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 ta nk. [QUESTION FOR ENEL: What is th e flow rate of the condensate

### 2-14 stream?] The rest of the steam that exits the t op 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 cr ystallizer is tr ansferred 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 pr esent in the slurry to evaporate and exit the crystallizer as steam. The evapora tion 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 wh ere 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.

### 2-15Figure 2-1. Diagram of the Pilot-Scale Carbon Capture and Storage System, Brindisi Power Plant

### 2-16 ClearwellFigure 2-2. Diagram of the Chemical Precipitation and Softening Portion of the FGD Wastewater Treatment System, BrindisiPower Plant

### 2-17HydrochloricAcidFeed/CrystallizerHeat ExchangerDistillateTankDeaeratorBrine ConcentratorCompressorVent toAtmosphereBrineSolutionBrineRecycleDistillateLiquid StreamLegendGas StreamSofteningTankFromPretreatmentSoda AshTo LimestonePreparationEvaporatorFeed TankAnti-ScalantFeed/DistillateHeat ExchangerCondensate fromCrystallizerMake-upSteamConcentrate toCrystallizer Feed TankDistillateTankTo Plant forReuseIndicates a sampling pointSP-2Figure 2-3. Diagram of the Evaporation Portion of the FGD Wastewater Treatment System, Brindisi and Torrevaldaliga NordPower Plants

### 2-18Figure 2-4. Diagram of the Crystallization Portion of the FGD Wastewater Treatment System, Brindisi and TorrevaldaligaNord Power Plants

### 2-19Figure 2-5. Diagram of the Chemical Precipitation Portion of the FGD Wastewater Treatment System, Torrevaldaliga NordPower Plant

### 3-1 3. S AMPLE 

### C OLLECTION



### During the Brindisi sampling episode, th e sampling team followed the collection protocols specified in the Sa mpling Plan. Section 3.1 describes the sampling points, sample collection methods, and field measurements. Secti on 3.2 describes the list of analytes and the sample preservation procedures. Section 3.3 discu sses the plant operational data collected during the sampling episode. Finally, Section 3.4 discusse s any deviations from the planned sampling

activities.

3.1 Sampling Points, Sample Collectio n Methods, and Field Measurements

This section describes the sampling point s, 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, sampli ng point descriptions, type of sample collection, and sample collection dates and times. Table 3-2 list s 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 th e field measurement data collected from each sampling point. Table 3-4 presents a crosswalk be tween 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 th e 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 th at secures itself ope n with clips. The “cleanbox” is double-bagged with a clear inner bag, enclosed in a translu cent outer bag. The “cleanbo x” is handled using “clean hands / dirty hands” techniques, where by the inner bag is ha ndled 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 open ing of the box, but is still able to see the sample bottles and

### 3-2 tubing. The “cleanbox” minimizes potential at mospheric contamination during sample collection. Figure C-1, in Appendix C, is a pictur e 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 seal ed 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 cl osed the sample bottle lid and sealed the inner bag as quickly as possible with in 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 syst em (SP-1) was collected directly from the settling basin at the point the Units 1&2 and Un its 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, EP A wanted to make sure that all waste streams were captured by the samples.

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

basin. There was no rain duri ng the sample collection.

On Day 1 only, prior to collecting the sample s at the influent to the FGD wastewater treatment system (SP-1) 1 

### , the sampling team collected field bl anks (SP-4) for total mercury and total metals. See Section 5.2.3 for a description of the field blank sample co llection 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 (whi ch 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 se ttling 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. Sa mplers 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 fi eld 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 pla ced 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 tr ansfers the wastewater from the distillate tank through the heat exch anger and to the other di stillate tank. Brindisi in stalled 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 contai ner. ERG manually collected seve n liters of sample, every two hours, for a four-hour period to fill the 20-lite r container with 21 liters of sample 2 

### . 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 list ed 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-splitte r tubing set consisted of three silicone tube s attached to a Tsplitter. The tubing confi guration was set up such that one en d 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 tu bing to the sample tap, opened the valve, and allowed sample to flow through both sets of tubi ng before the tubing was attached to a vented cap on a 20-liter composite c ontainer. The tubing attach ed to the vented cap on the container was pinched shut and secured with a ziptie during the four-hour composite

2 ERG did not collect five liters of sample, every two hours, for a six hour period, originally discussed in the Sampling Plan, due to time constraints with available FedEx shipments from the plant.

### 3-4 period 3 

### . 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 li ne 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, ER G collected the first total mercury grab sample. At the first grab sample every day, ERG co llected field blanks for total mercury samples. See Section 5.2.3 for a description of the field blank sample collection procedur es 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) w ith 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 co llected directly from the tap into the sample bottles. ERG collected another total mercury sa mple 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 co llected in the composite c ontainer, ERG followed “clean hands / dirty hands” sampling techniques to di sassemble the compositor from the sampling set up. A closed cap was placed on the composite co ntainer and the composite container was moved to the pump-off area where it remained on ice un til individual sample bo ttles 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 indivi dual 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 usi ng a “cleanbox,” as descri bed in Section 3.1:

 

### Total metals by 200.8; and

 

### Total metals by 200.7.

3 Samplers secured the pinched tubing of the composite cont ainer 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, th e samplers filled containers for Group I and Group II samples directly from the tubing without using a “cleanbox.” See Ta ble 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 co llected duplicate samples with Enel personnel by filling one sample bottle immediately after the other.

On Day 1 only, prior to co llecting any samples of the distillate from the brine concentrator, the samplers collected a field blan k 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) wa s collected from the discharge side of the pump that transfers the wastewat er to the distillate tank. Brindi si installed a two-way splitter on the sample tap to provide two separate taps fo r 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 cr ystallizer as manual composite samples

collected into one 20-liter contai ner. ERG manually collected seve n liters of sample, every two hours, for a four-hour period to fill the 20-lite r container with 21 liters of sample 4 

### . 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 list ed above, ERG collected total mercury grab samples every two hours during each compositi ng 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-splitte r tubing set consisted of three silicone tube s attached to a Tsplitter. The tubing confi guration was set up such that one en d 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 tu bing to the sample tap, opened the valve, and allowed sample to flow through both sets of tubi ng before the tubing was attached to a vented cap on a 20-liter composite c ontainer. The tubing attach ed to the vented cap on the container was pinched shut and secured with a ziptie during the four-hour composite period 5 

### . 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 cont ainer 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. Afte r 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, ER G collected the first total mercury grab sample. At the first grab sample every day, ERG co llected field blanks for total mercury samples. See Section 5.2.3 for a description of the field blank sample collecti on 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) w ith 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 co llected directly from the tap into the sample bottles. ERG collected another total mercury sa mple 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 pa per, pH meter, and a thermometer. Table 3-3 presents the field measurement data for the condensate from the crystallizer.

After the third aliquot was co llected in the composite c ontainer, ERG followed “clean hands / dirty hands” sampling techniques to di sassemble the compositor from the sampling set up. A closed cap was placed on the composite co ntainer and the composite container was moved to the pump-off area where it remained on ice un til individual sample bo ttles were filled.

The sampling team then transferred the wastewat er 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 compos ite 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 containe r filled with condensate from the crystallizer. After the tubing was purged with 1-2 liters of sample, samplers collected the following samples using a “clean box,” as described in Section 3.1:

 

### Total metals by 200.8; and

 

### Total metals by 200.7.

After the metal samples had been collected, th e samplers filled containers for Group I and Group II samples directly from the tubing without using a “cleanbox.” See Ta ble 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 co llected duplicate samples with Enel personnel by filling one sample bottle immediately after the other.

On Day 1 only, prior to colle cting any samples of the conde nsate 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 bla nk sample collection at the condensate from the crystallizer.

3.2 List of Analytes and Sample Preservation

Samples collected at Bri ndisi 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, in cluding contributions from coal , scrubber sorb ents, treatment chemicals, and other sources. Table 3-5 lists the analytical methods used to determine pollutant

concentrations.

Table 3-6 lists the containers used fo r 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 sampli ng 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 Gr oup 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 sulfur ic 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 F GD scrubber system, as well as operational and flow data for the FGD wastewater treatment system. Tabl e 3-8 presents the unit operating characteristics, Table 3-9 presents th e 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 slu rry generation during th e sampling episode, and Table 3-12 presents the FGD wastewater tr eatment 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 treatme nt system (SP-1), Brindisi personnel informed the sampling team that the sump pump discharge pi pe (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 sa mples 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 treat ment system (SP-1), the sample line

connection between the silicone and Te flon® 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 th e 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 sh ipments to meet courier schedules, ERG revised the sample collection to three se parate samples collected every two hours over a four-hour period.

 

### Collection of first manual comp osite 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 ta p. 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 concentrat or (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 brin e 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 we re still cold and ice still remained in the coolers. The sampling team put more ice on the samples to keep them cold until the samples were prepared for shipment.

### 3-10 Table 3-1. Sample Collection Information, Brindisi

Sampling

Point

Number Sampling Point Description Type of Sample Sample Collection

Date Sample Collection

Time

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

Influent to FGD Wa stewater Treatment System – Day 3 Grab 4/7/11 1006 b

SP-2 Distillate from the Brine Concentrator – Day 1 Composite 4/5/11 0840 c , 1042 c , 1303 c

, 1438 d

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

Distillate from the Brine Concentrator – Day 2 Composite 4/6/11 0708 c , 0908 c , 1112 c

, 1207 d

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

Distillate from the Brine Concentrator – Day 3 Composite 4/7/11 0713 c , 0906 c , 1110 c

, 1213 d

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

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

, 1504 d

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

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

, 1231 d

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

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

, 1232 d

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

SP-4 Influent to FGD Wastewater Treatment System Field Blank, Day 1 Grab 4/5/11 a 1216 h

SP-5 Distillate from the Brine Concentrator Field Blank – Day 1 Composite 4/5/11 0811 i , 1431 j

Grab 4/5/11 0850 k

Distillate from the Brine Concentrator Field Blank – Day 2 Grab 4/6/11 0717 k

Distillate from the Brine Concentrator Field Blank – Day 3 Grab 4/7/11 0720 k

SP-6 Condensate from the Crystallizer Field Blank – Day 1 Composite 4/5/11 0918 i , 1500 j

Grab 4/5/11 0937 k

Condensate from the Crystallizer Field Blank – Day 2 Grab 4/6/11 0744 k

Condensate from the Crystallizer Field Blank – Day 3 Grab 4/7/11 0749 k

### 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 th e 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.

### 3-12Table 3-2. Sample Collection at BrindisiSamplingPointNumberSampling Point Name Total Metals (EPA Method 200.8 with collision cell) Total Metals (EPA Method 200.7) Total Mercury Group I

a Group II bSP-1 Influent to the FGD Wastewater Treatment System 2 2 2 2 2SP-2 Distillate from the Brine Concentrator 3+1QC 3+1QC 3+1QC 3+1QC 3+1QCSP-3 Condensate from the Crystallizer 3+1QC 3+1QC 3+1QC 3+1QC 3+1QCSP-4 Influent to the FGD Wastewater Treatment System Field Blank 1 1 1SP-5 Distillate from the Brine Concentrator Field Blank 1 1 3SP-6 Condensate from the Crystallizer Field Blank 1 1 3Total Number of Samples 11+2QC 11+2QC 15+2QC 8+2QC 8+2QCa – 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 phosphorus.

### 3-13Table 3-3. Field Measurements, BrindisiSampling PointNumberSampling Point DescriptionDateTimeTemperature(°C)pH(S.U.)SP-1 Influent to FGD Wastewater Treatment System – Day 2 4/6/11 1006322.0Influent to FGD Wastewater Treatment System – Day 3 4/7/11a1006312.0SP-2 Distillate from the Brine Concentrator – Day 14/5/11 0857828.04/5/11 1050808.54/5/11 1311858.0Distillate from the Brine Concentrator – Day 2 4/6/11 0722868.04/6/11 0918868.04/6/11 1121908.5Distillate from the Brine Concentrator – Day 3 4/7/11 0725828.04/7/11 0915878.04/7/11 1117868.0SP-3 Condensate from the Crystallizer – Day 14/5/110942728.04/5/111143648.54/5/111338718.5Condensate from the Crystallizer – Day 2 4/6/110749698.54/6/11093469.58.54/6/111140718.5Condensate from the Crystallizer – Day 3 4/7/11 0754618.54/7/11 0931708.54/7/11 1142798.0aDuring 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-1after the field blank collection. The SP-1 samples planned to becollected on day 1 were actuallycollected on day 3 of sampling; however, the sampling team wasnot informed of the clogged pipe until after the field blank samples were collected. Therefore,the field blank samples were collected on Day 1, while thewastewater 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 Wastewat er 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 th e 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 nitr ogen 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 an d 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 H 2 SO 4 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 (acid preserve at laboratory) Manual composite grab samples Three 125-mL glass bottle No additional

volume needed

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

volume needed

a Group I includes TSS, TDS, sulfate, and chloride.

b Group II includes ammonia as nitrogen, COD, nitr ate/nitrite as ni trogen, TKN, and total phosphorus.

### 3-17 Table 3-6. Sample Preservation Summary, Brindisi

Sampling Point

Number Analysis Date Chemical

Added Initial pH (S.U.) Final pH (S.U.) Amount

Added (drops)

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

pH meter calibrated at 13:45 on 4/4/11. pH meter calibrated at 08:30 on 4/6/11. pH meter calibrated at 08:30 on 4/7/11.

### 3-18 Table 3-7. Generating Unit Operating Charac teristics 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 wh at 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 re ported MWs in this table seems incorr ect because Unit 3 bu rned three times more coal than Unit 4, but that isn’t represented in the information above.]

### 3-19Table 3-7. FGD Scrubber System Operating Characteristics, BrindisiUnit IDWet FGDSystem(Yes/No)Type ofScrubberForcedOxidation(Yes/No)SorbentAdditives(DBA, formicacid, etc.)PrescrubberWater SourceFGD Make-upWater SourceSO2RemovalPercentageType of SolidsSeparationBS1 Yes BishoffaYes Limestone NoneRecoveredZLD waterRecoveredZLD water84% HydrocyclonesBS2 Yes BishoffaYes Limestone NoneRecoveredZLD waterRecoveredZLD water84% HydrocyclonesBS3 Yes MitsubishiaYes Limestone NoneRecoveredZLD waterRecoveredZLD water84% HydrocyclonesBS4 Yes MitsubishiaYes Limestone NoneRecoveredZLD waterRecoveredZLD water84% HydrocyclonesaWet limestone/gypsum forced oxidation open spray tower with pre-scrubber.[QUESTION FOR ENEL: Based on the amount of water consumed by a scrubber and that only a portion of the wastewater is sent to the ZLD system, it seemsthat there must be some other sources ofwater used in the prescrubber and FGD makeup, such as intake water. Please specify other sources used in theseprocesses.]

### 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 ID a 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 representa tive 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?]

### 3-22Table 3-10. FGD Wastewater Treatment System Operation Information, BrindisiDay ofSamplingChemical Usage(Quantity added - specify units)LimeCausticSodaSodiumSulfideFerricChloridePolyelectrolyteFerrousChlorideSoda Ash(10% sol.)HydrochloricAcid (30%)(EST)aAntiScalant1 4000 ppm 200 ppm 28 ppm 120 ppm 2 ppm 15 ppm 8 m3/h 30 ton/day No2 4000 ppm 200 ppm 28 ppm 120 ppm 2 ppm 15 ppm 8 m3/h 30 ton/day No3 4000 ppm 200 ppm 28 ppm 120 ppm 2 ppm 15 ppm 8 m3/h 30 ton/day NoaEstimated on daily consumption.

### 4-1 4. L ABORATORY 

### A NALYTICAL 

### R ESULTS AND 

### D ISCUSSION



### This section summarizes the laboratory results of analyses of samples for the influent to the FGD wastewater treatment system, the dist illate 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 fla gged 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 wast ewater treatment system (SP-1), as well as the calculated 2-day average result for each analyte. Tables 4-2 and 4-3 presen t the analytical results for all classical and metal analytes for the three da ys of sampling at the di stillate 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 si gnificant 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 parent heses. 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 result s for classical and metal analytes for SP-1, SP-2 and SP-3. The data presented in this report ar e not paired results, meaning that the sample collection across the treatment sy stem was not timed to reflect the amount of time it takes the wastewater to pass through the system.

Appendix Tables A-1 through A-8 present all th e analytical results for each sample point, including J-values.

### 4-2ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 2-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.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, BrindisiAnalyteUnitsMethodInfluent to FGD Wastewater Treatment System (SP-1)Day 2Day 32-Day AverageClassicalsAmmonia mg/L 350.1 12.0 12 Est 12.0Nitrate Nitrite as N mg/L 353.2 56.0 46 Est 51.0Nitrogen, Total Kjeldahl mg/L 351.2 3.60 Est 11 B, Est 7.30Chemical Oxygen Demand mg/L 410.4 110 100 Est 105Chloride mg/L 300.0 6,400 6,200 6,300Sulfate mg/L 300.0 7,000 5,700 Est 6,350Total Dissolved Solids mg/L 2540C 13,000 15,000 14,000Total Suspended Solids mg/L 2540D 2,600 F, Est 3,600 3,100Phosphorus, Total mg/L 365.1 0.0840 6 Est 3.04Total MetalsAluminum ug/L 200.7 70,000 B 120,000 B 95,000Antimony ug/L 200.8 11.0 14 12.5Arsenic ug/L 200.8 53.0 55 54.0Barium ug/L 200.7 1,400 1,200 1,300Beryllium ug/L 200.7 9.10 11 10.1Boron ug/L 200.7 83,000 100,000 91,500Cadmium ug/L 200.8 6.30 6 6.15Calcium ug/L 200.7 1,700,000 1,300,000 1,500,000Chromium ug/L 200.8 190 290 240Cobalt ug/L 200.7 44.0 59 51.5Copper ug/L 200.8 87.0 110 98.5Iron ug/L 200.7 26,000 44,000 35,000Lead ug/L 200.8 53.0 82 67.5Magnesium ug/L 200.7 98,000 80,000 89,000Manganese ug/L 200.7 990 1,000 995Mercury ng/L 1631E 26,900 21,100 24,000Molybdenum ug/L 200.7 85.0 110 97.5Nickel ug/L 200.8 140 160 150Selenium ug/L 200.8 220 290 255

### 4-3ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 2-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.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, BrindisiAnalyteUnitsMethodInfluent to FGD Wastewater Treatment System (SP-1)Day 2Day 32-Day AverageSilver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00)Sodium ug/L 200.7 5,700,000 B 6,900,000 B 6,300,000Thallium ug/L 200.8 2.00 2.1 2.05Tin ug/L 200.7 NQ (200) NQ (200) NQ (200)Titanium ug/L 200.7 4,400 7,500 5,950Vanadium ug/L 200.8 620 670 645Zinc ug/L 200.7 670 430 550

### 4-4< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 3-day average result indicates that all results were below the quantitation limit, but at least one result is a J-value.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.Table 4-2. Distillate from Brine Concentrator, BrindisiAnalyteUnitsMethodDistillate from the Brine Concentrator (SP-2)Day 1Day 2Day 33-Day AverageClassicalsAmmonia mg/L 350.1 21.0 19.0 15.0 Est 18.3Nitrate Nitrite as N mg/L 353.2 0.110 0.130 0.160 Est 0.133Nitrogen, Total Kjeldahl mg/L 351.2 20.0 18.0 4 16.0 B, Est 18.0Chemical Oxygen Demand mg/L 410.4 ND (20.0) ND (20.0) F NQ (20.0) NQ (20.0)Chloride mg/L 300.0 ND (3.00) NQ (3.00) F ND (3.00) NQ (3.00)Sulfate mg/L 300.0 ND (5.00) ND (5.00) ND (5.00) ND (5.00)Total Dissolved Solids mg/L 2540C 13.0 10.0 NQ (10.0) < 9.33Total Suspended Solids mg/L 2540D ND (4.00) ND (4.00) ND (4.00) ND (4.00)Phosphorus, Total mg/L 365.1 ND (0.0500) ND (0.0500) ND (0.0500) ND (0.0500)Total MetalsAluminum ug/L 200.7 NQ (200) B NQ (200) B NQ (200) B NQ (200)Antimony ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00)Arsenic ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.00)Barium ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.0)Beryllium ug/L 200.7 ND (2.00) ND (2.00) ND (2.00) ND (2.00)Boron ug/L 200.7 3,600 6,200 4 3,100 4,300Cadmium ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.00)Calcium ug/L 200.7 ND (400) NQ (400) NQ (400) NQ (400)Chromium ug/L 200.8 ND (8.00) ND (8.00) ND (8.00) ND (8.00)Cobalt ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.0)Copper ug/L 200.8 ND (4.00) NQ (4.00) ND (4.00) NQ (4.00)Iron ug/L 200.7 ND (200) ND (200) ND (200) ND (200)Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00)Magnesium ug/L 200.7 ND (400) NQ (400) ND (400) NQ (400)Manganese ug/L 200.7 ND (20.0) NQ (20.0) ND (20.0) NQ (20.0)Mercury ng/L 1631E 3.98 3.13 2.89 3.33Molybdenum ug/L 200.7 ND (40.0) ND (40.0) ND (40.0) ND (40.0)

### 4-5< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 3-day average result indicates that all results were below the quantitation limit, but at least one result is a J-value.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.Table 4-2. Distillate from Brine Concentrator, BrindisiAnalyteUnitsMethodDistillate from the Brine Concentrator (SP-2)Day 1Day 2Day 33-Day AverageNickel ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.00)Selenium ug/L 200.8 ND (4.00) ND (4.00) NQ (4.00) NQ (4.00)Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00)Sodium ug/L 200.7 NQ (10,000) B NQ (10,000) B NQ (10,000) B NQ (10,000)Thallium ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00)Tin ug/L 200.7 ND (200) ND (200) ND (200) ND (200)Titanium ug/L 200.7 ND (20.0) ND (20.0) NQ (20.0) NQ (20.0)Vanadium ug/L 200.8 ND (10.0) ND (10.0) ND (10.0) ND (10.0)Zinc ug/L 200.7 NQ (40.0) 71.0 ND (40.0) < 37.0

### 4-6< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.Table 4-3. Condensate from Crystallizer, BrindisiAnalyteUnitsMethodCondensate from the Crystallizer (SP-3)Day 1Day 2Day 33-Day AverageClassicalsAmmonia mg/L 350.1 26.0 43.0 22.0 4, Est 30.3Nitrate Nitrite as N mg/L 353.2 NQ (0.100) NQ (0.100) 0.100 Est < 0.0667Nitrogen, Total Kjeldahl mg/L 351.2 25.0 37.0 Est 25.0 B,4, Est 29.0Chemical Oxygen Demand mg/L 410.4 ND (20.0) ND (20.0) NQ (20.0) NQ (20.0)Chloride mg/L 300.0 ND (3.00) ND (3.00) ND (3.00) ND (3.00)Sulfate mg/L 300.0 ND (5.00) ND (5.00) ND (5.00) ND (5.00)Total Dissolved Solids mg/L 2540C 10.0 22.0 NQ (10.0) < 12.3Total Suspended Solids mg/L 2540D ND (4.00) ND (4.00) ND (4.00) ND (4.00)Phosphorus, Total mg/L 365.1 ND (0.0500) ND (0.0500) ND (0.0500) ND (0.0500)Total MetalsAluminum ug/L 200.7 NQ (200) B NQ (200) B ND (200) NQ (200)Antimony ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00)Arsenic ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.00)Barium ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.0)Beryllium ug/L 200.7 ND (2.00) ND (2.00) ND (2.00) ND (2.00)Boron ug/L 200.7 3,200 3,100 3,300 3,200Cadmium ug/L 200.8 ND (4.00) ND (4.00) ND (4.00) ND (4.00)Calcium ug/L 200.7 ND (400) ND (400) ND (400) ND (400)Chromium ug/L 200.8 ND (8.00) ND (8.00) ND (8.00) ND (8.00)Cobalt ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.0)Copper ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00)Iron ug/L 200.7 ND (200) ND (200) ND (200) ND (200)Lead ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00)Magnesium ug/L 200.7 ND (400) ND (400) ND (400) ND (400)Manganese ug/L 200.7 NQ (20.0) ND (20.0) ND (20.0) NQ (20.0)Mercury ng/L 1631E 20.4 20.7 10.9 17.3Molybdenum ug/L 200.7 NQ (40.0) NQ (40.0) NQ (40.0) NQ (40.0)

### 4-7< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.Table 4-3. Condensate from Crystallizer, BrindisiAnalyteUnitsMethodCondensate from the Crystallizer (SP-3)Day 1Day 2Day 33-Day AverageNickel ug/L 200.8 NQ (4.00) ND (4.00) NQ (4.00) NQ (4.00)Selenium ug/L 200.8 NQ (4.00) NQ (4.00) NQ (4.00) NQ (4.00)Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00)Sodium ug/L 200.7 NQ (10,000) B NQ (10,000) B NQ (10,000) B NQ (10,000)Thallium ug/L 200.8 ND (2.00) ND (2.00) ND (2.00) ND (2.00)Tin ug/L 200.7 ND (200) ND (200) ND (200) ND (200)Titanium ug/L 200.7 ND (20.0) ND (20.0) ND (20.0) ND (20.0)Vanadium ug/L 200.8 ND (10.0) ND (10.0) ND (10.0) ND (10.0)Zinc ug/L 200.7 ND (40.0) NQ (40.0) ND (40.0) NQ (40.0)

### 4-8< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analyticalresult is presented in Appendix A with a Jflag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at leastone result is a J-value.Table 4-4. Classical Pollutants Average Data Summary for FGD Wastewater Treatment System, BrindisiAnalyteUnitMethodInfluent to FGD WastewaterTreatment System (SP-1)2-Day AverageDistillate from BrineConcentrator (SP-2)3-Day AverageCondensate fromCrystallizer (SP-3)3-Day AverageClassicalsAmmonia mg/L 350.1 12.0 18.3 30.3Nitrate Nitrite as N mg/L 353.2 51.0 0.133 < 0.0667Nitrogen, Total Kjeldahl mg/L 351.2 7.30 18.0 29.0Chemical Oxygen Demand mg/L 410.4 105 NQ (20.0) NQ (20.0)Chloride mg/L 300.0 6,300 NQ (3.00) ND (3.00)Sulfate mg/L 300.0 6,350 ND (5.00) ND (5.00)Total Dissolved Solids mg/L 2540C 14,000 < 9.33 < 12.3Total Suspended Solids mg/L 2540D 3,100 ND (4.00) ND (4.00)Phosphorus, Total mg/L 365.1 3.04 ND (0.0500) ND (0.0500)

### 4-9< - Average result includes at least one value measured belowthe quantitation limit. (Calculation uses 1⁄2 the quantitation limit for values below the quantitation limit).ND – Not detected (number in parentheses is the quantitation limit).NQ – Analyte was measured above the method detection limit, butbelow the quantitation limit (number shown in parentheses is the quantitation limit). The analytical result ispresented in Appendix A with a J flag designation. A “NQ” for the 4-day average result indicates that all results were below the quantitation limit, but at least one result is a Jvalue.Table 4-5. Metal Pollutants Average Data Summaryfor FGD Wastewater Treatment System, BrindisiAnalyteUnitMethodInfluent to FGD WastewaterTreatment System (SP-1)2-Day AverageDistillate from BrineConcentrator (SP-2)3-Day AverageCondensate from Crystallizer(SP-3)3-Day AverageTotal MetalsAluminum ug/L 200.7 95,000 NQ (200) NQ (200)Antimony ug/L 200.8 12.5 ND (2.00) ND (2.00)Arsenic ug/L 200.8 54.0 ND (4.00) ND (4.00)Barium ug/L 200.7 1,300 ND (20.0) ND (20.0)Beryllium ug/L 200.7 10.1 ND (2.00) ND (2.00)Boron ug/L 200.7 91,500 4,300 3,200Cadmium ug/L 200.8 6.15 ND (4.00) ND (4.00)Calcium ug/L 200.7 1,500,000 NQ (400) ND (400)Chromium ug/L 200.8 240 ND (8.00) ND (8.00)Cobalt ug/L 200.7 51.5 ND (20.0) ND (20.0)Copper ug/L 200.8 98.5 NQ (4.00) NQ (4.00)Iron ug/L 200.7 35,000 ND (200) ND (200)Lead ug/L 200.8 67.5 ND (2.00) ND (2.00)Magnesium ug/L 200.7 89,000 NQ (400) ND (400)Manganese ug/L 200.7 995 NQ (20.0) NQ (20.0)Mercury ng/L 1631E 24,000 3.33 17.3Molybdenum ug/L 200.7 97.5 ND (40.0) NQ (40.0)Nickel ug/L 200.8 150 ND (4.00) NQ (4.00)Selenium ug/L 200.8 255 NQ (4.00) NQ (4.00)Silver ug/L 200.8 ND (2.00) ND (2.00) ND (2.00)Sodium ug/L 200.7 6,300,000 NQ (10,000) NQ (10,000)Thallium ug/L 200.8 2.05 ND (2.00) ND (2.00)Tin ug/L 200.7 NQ (200) ND (200) ND (200)Titanium ug/L 200.7 5,950 NQ (20.0) ND (20.0)Vanadium ug/L 200.8 645 ND (10.0) ND (10.0)Zinc ug/L 200.7 550 < 37.0 NQ (40.0)

### 5-1 5. D ATA 

### Q UALITY



### Quality assurance/quality control (QA/QC) procedures applicable to the Brindisi sampling episode are outlined in the Quality Assurance Project Plan for the Steam Electric Rulemaking (QAPP) [2]. This section describes the QC pr ocedures 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 labor atories for the analysis of samples collected during this episode. ERG verified that the pe rformance of the laboratories selected was acceptable by conducting QC checks of the analytical data. Data review chemists at ERG prepared written data review narr atives describing any qualifications of the analytical data from this episode. The data review narrat ives are included in Appendix B.

5.2 Field Quality Control

This section discusses the bot tle blanks, equipment blanks, and field blanks results. Section 3.8 of the Sampling Plan di scusses field QC specifications.

5.2.1 Bottle Blanks

ERG collects bottle blanks to evaluate possibl e 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 precleane d bottles, Frontier Global Sciences.

Frontier Global Sciences collected the bottl e blanks for the metals sample bottles by filling the precleaned bottle with reagent water and pr eserving the sample with nitric acid to a pH

<2 S.U. Frontier Global Sciences then an alyzed the samples using EPA Method 1638.

Frontier Global Sciences collected the bottl e blanks for the mercury sample bottles by filling the precleaned bottle with reagent wate r and preserving the sample with bromine

monochloride. Frontier Global Sciences then analyzed the samples using EPA Method 1631E.

Albion Environmental collected the bottle blan ks 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 contai ner and poured a repres entative sample into a precleaned LDPE sample bot tle. The blank samples were th en 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 concen tration of 0.14 ug/L. This c oncentration 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. Ap pendix Table A-9 presents all of the analytical

### 5-2 results from the bottle blank an alyses 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 introduci ng contamination. In a ddition, Frontier Global Sciences collected and analyzed equipment bl anks for metals (EPA Method 1638 and 1631E) for each type of precleaned equipment supplied for the episode.

Frontier Global Sciences collected the equipm ent blanks for the fabricated tubing sets by pumping reagent water through the cleaned and fu lly 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 anal ytical methods (EPA Method 1638 and 1631E), as described in Section 5.2.1 for the bottle blank samples.

No metals were detected in the equipm ent blanks, indicating that there was no contamination from the sampling equipment. Appe ndix 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, samp ling 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 de position, 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 th e field blank samples as duplicate samples with Enel, using the same procedure discussed in the sample collection de scription (Section 3.1).

As described in Section 3.4, the field bla nk samples for the influent to the FGD wastewater treatment system (SP-4) were co llected on Day 1 of samp le 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 c oncern (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 representa tive of the other two days of sample collection at SP-1.

### 5-3 The total mercury field blank sample for the di stillate 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 ba g. Before purging the sample tap, ASTM Type 1 water was poured directly into the sa mple 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 crystalli zer (SP-6) were collected by filling a 20-liter composite container with approxim ately 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 at taching 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 pum ped into the 20-liter field blank composite container, the vented cap was replaced w ith 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 bla nk 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 throug h 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 collecti on description (Section 3.1). Prior to filling the sample bottles, the tubing was purged with approximately one lite r of ASTM Type 1 water. Then the samplers placed the sample bottles in a “cleanbox” and co llected the total metals field blank samples (Methods 200.7 and 200.8). No metals were detect ed 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. R EFERENCES



### 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 RESULTSND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-1. Influent to FGD Wastewater TreatmentSystem, Day 2 Analytical Results, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecificMDLSampleSpecific QLConcentrationClassicalsAmmonia 350.1 mg/L 2 0.11 2 12Nitrate Nitrite as N 353.2 mg/L 20 0.38 2 56Nitrogen, Total Kjeldahl 351.2 mg/L 1 0.077 1 3.6 EstChemical Oxygen Demand 410.4 mg/L 1 4.1 20 110Chloride 300.0 mg/L 200 51 600 6,400Sulfate 300.0 mg/L 200 46 1,000 7,000Total Dissolved Solids 2540C mg/L 1 94 200 13,000Total Suspended Solids 2540D mg/L 1 11 40 2,600 F, EstPhosphorus, Total 365.1 mg/L 1 0.005 0.05 0.084Total MetalsAluminum 200.7 ug/L 50 240 5,000 70,000 BAntimony 200.8 ug/L 2 0.72 2 11Arsenic 200.8 ug/L 2 1.2 4 53Barium 200.7 ug/L 2 2.5 20 1,400Beryllium 200.7 ug/L 2 0.71 2 9.1Boron 200.7 ug/L 50 170 5,000 83,000Cadmium 200.8 ug/L 2 1.2 4 6.3Calcium 200.7 ug/L 50 1,700 10,000 1,700,000Chromium 200.8 ug/L 2 3.3 8 190Cobalt 200.7 ug/L 2 1.1 20 44Copper 200.8 ug/L 2 0.96 4 87ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.Est – Estimated value.F – MS and/or MSD not within laboratory control limits.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-1. Influent to FGD Wastewater TreatmentSystem, Day 2 Analytical Results, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecificMDLSampleSpecific QLConcentrationIron 200.7 ug/L 50 800 5,000 26,000Lead 200.8 ug/L 2 0.73 2 53Magnesium 200.7 ug/L 2 21 400 98,000Manganese 200.7 ug/L 2 0.51 20 990Mercury 1631E ng/L 4,000 965 2,020 26,900Molybdenum 200.7 ug/L 2 1.6 40 85Nickel 200.8 ug/L 2 0.89 4 140Selenium 200.8 ug/L 2 0.62 4 220Silver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 50 4,600 250,000 5,700,000 BThallium 200.8 ug/L 2 0.47 2 2Tin 200.7 ug/L 2 4.8 200 14 JTitanium 200.7 ug/L 50 41 500 4,400Vanadium 200.8 ug/L 2 1.7 10 620Zinc 200.7 ug/L 2 9.1 40 670ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.Est – Estimated value.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-2. Influent to FGD Wastewater TreatmentSystem, Day 3 Analytical Results, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia 350.1 mg/L 2 0.11 2 12 EstNitrate Nitrite as N 353.2 mg/L 10 0.19 1 46 EstNitrogen, Total Kjeldahl 351.2 mg/L 1 0.38 5 11 B, EstChemical Oxygen Demand 410.4 mg/L 1 4.1 20 100 EstChloride 300.0 mg/L 200 51 600 6,200Sulfate 300.0 mg/L 200 46 1,000 5,700 EstTotal Dissolved Solids 2540C mg/L 1 94 200 15,000Total Suspended Solids 2540D mg/L 1 11 40 3,600Phosphorus, Total 365.1 mg/L 10 0.05 0.5 6 EstTotal MetalsAluminum 200.7 ug/L 50 240 5,000 120,000 BAntimony 200.8 ug/L 2 0.72 2 14Arsenic 200.8 ug/L 2 1.2 4 55Barium 200.7 ug/L 2 2.5 20 1,200Beryllium 200.7 ug/L 2 0.71 2 11Boron 200.7 ug/L 50 170 5,000 100,000Cadmium 200.8 ug/L 2 1.2 4 6Calcium 200.7 ug/L 50 1,700 10,000 1,300,000Chromium 200.8 ug/L 2 3.3 8 290Cobalt 200.7 ug/L 2 1.1 20 59Copper 200.8 ug/L 2 0.96 4 110Iron 200.7 ug/L 2 32 200 44,000Lead 200.8 ug/L 2 0.73 2 82Magnesium 200.7 ug/L 2 21 400 80,000ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.Est – Estimated value.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-2. Influent to FGD Wastewater TreatmentSystem, Day 3 Analytical Results, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationManganese 200.7 ug/L 2 0.51 20 1,000Mercury 1631E ng/L 4,000 965 2,020 21,100Molybdenum 200.7 ug/L 2 1.6 40 110Nickel 200.8 ug/L 2 0.89 4 160Selenium 200.8 ug/L 2 0.62 4 290Silver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 50 4,600 250,000 6,900,000 BThallium 200.8 ug/L 2 0.47 2 2.1Tin 200.7 ug/L 2 4.8 200 24 JTitanium 200.7 ug/L 2 1.6 20 7,500Vanadium 200.8 ug/L 2 1.7 10 670Zinc 200.7 ug/L 2 9.1 40 430ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-3. Influent to FGD Wastewater TreatmentSystem, Day 1 Analytical Results, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia 350.1 mg/L 4 0.22 4 21Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 0.11Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 20Chemical Oxygen Demand 410.4 mg/L 1 4.1 20 ND (20) UChloride 300.0 mg/L 1 0.25 3 ND (3) USulfate 300.0 mg/L 1 0.23 5 ND (5) UTotal Dissolved Solids 2540C mg/L 1 4.7 10 13Total Suspended Solids 2540D mg/L 1 1.1 4 ND (4) UPhosphorus, Total 365.1 mg/L 1 0.005 0.05 ND (0.05) UTotal MetalsAluminum 200.7 ug/L 2 9.4 200 10 BAntimony 200.8 ug/L 2 0.72 2 ND (2)Arsenic 200.8 ug/L 2 1.2 4 ND (4)Barium 200.7 ug/L 2 2.5 20 ND (20)Beryllium 200.7 ug/L 2 0.71 2 ND (2)Boron 200.7 ug/L 2 6.7 200 3,600Cadmium 200.8 ug/L 2 1.2 4 ND (4)Calcium 200.7 ug/L 2 69 400 ND (400)Chromium 200.8 ug/L 2 3.3 8 ND (8)Cobalt 200.7 ug/L 2 1.1 20 ND (20)Copper 200.8 ug/L 2 0.96 4 ND (4)Iron 200.7 ug/L 2 32 200 ND (200)Lead 200.8 ug/L 2 0.73 2 ND (2)Magnesium 200.7 ug/L 2 21 400 ND (400)ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-3. Influent to FGD Wastewater TreatmentSystem, Day 1 Analytical Results, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationManganese 200.7 ug/L 2 0.51 20 ND (20)Mercury 1631E ng/L 1 0.24 0.51 3.98Molybdenum 200.7 ug/L 2 1.6 40 ND (40)Nickel 200.8 ug/L 2 0.89 4 ND (4)Selenium 200.8 ug/L 2 0.62 4 ND (4)Silver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 290 BThallium 200.8 ug/L 2 0.47 2 ND (2)Tin 200.7 ug/L 2 4.8 200 ND (200) JTitanium 200.7 ug/L 2 1.6 20 ND (20)Vanadium 200.8 ug/L 2 1.7 10 ND (10)Zinc 200.7 ug/L 2 9.1 40 21ND – Not detected (number in parentheses is the quantitation limit).4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.F – MS and/or MSD not within laboratory control limits.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-4. Distillate from Brine Concentrator, Day 2 Analytical Results, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia 350.1 mg/L 4 0.22 4 19Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 0.13Nitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 18 4Chemical Oxygen Demand 410.4 mg/L 1 4.1 20 ND (20) U,FChloride 300.0 mg/L 1 0.25 3 0.34 J, FSulfate 300.0 mg/L 1 0.23 5 ND (5) UTotal Dissolved Solids 2540C mg/L 1 4.7 10 10Total Suspended Solids 2540D mg/L 1 1.1 4 ND (4) UPhosphorus, Total 365.1 mg/L 1 0.005 0.05 ND (0.05) UTotal MetalsAluminum 200.7 ug/L 2 9.4 200 33 J,BAntimony 200.8 ug/L 2 0.72 2 ND (2) UArsenic 200.8 ug/L 2 1.2 4 ND (4) UBarium 200.7 ug/L 2 2.5 20 ND (20) UBeryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 2 6.7 200 6,200 4Cadmium 200.8 ug/L 2 1.2 4 ND (4) UCalcium 200.7 ug/L 2 69 400 220 JChromium 200.8 ug/L 2 3.3 8 ND (8) UCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 2.7 JIron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 2 21 400 25 JND – Not detected (number in parentheses is the quantitation limit).4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.F – MS and/or MSD not within laboratory control limits.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-4. Distillate from Brine Concentrator, Day 2 Analytical Results, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationManganese 200.7 ug/L 2 0.51 20 1.4 JMercury 1631E ng/L 1 0.24 0.51 3.13Molybdenum 200.7 ug/L 2 1.6 40 ND (40) UNickel 200.8 ug/L 2 0.89 4 ND (4) USelenium 200.8 ug/L 2 0.62 4 ND (4) USilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 480 J,BThallium 200.8 ug/L 2 0.47 2 ND (2) UTin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 ND (10) UZinc 200.7 ug/L 2 9.1 40 71ND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.Est – Estimated value.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-5. Distillate from Brine Concentrator, Day 3 Analytical Results, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia 350.1 mg/L 2 0.11 2 15 EstNitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 0.16 EstNitrogen, Total Kjeldahl 351.2 mg/L 2 0.15 2 16 B, EstChemical Oxygen Demand 410.4 mg/L 1 4.1 20 6.4 JChloride 300.0 mg/L 1 0.25 3 ND (3) USulfate 300.0 mg/L 1 0.23 5 ND (5) UTotal Dissolved Solids 2540C mg/L 1 4.7 10 7 JTotal Suspended Solids 2540D mg/L 1 1.1 4 ND (4) UPhosphorus, Total 365.1 mg/L 1 0.005 0.05 ND (0.05) UTotal MetalsAluminum 200.7 ug/L 2 9.4 200 12 J,BAntimony 200.8 ug/L 2 0.72 2 ND (2) UArsenic 200.8 ug/L 2 1.2 4 ND (4) UBarium 200.7 ug/L 2 2.5 20 ND (20) UBeryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 2 6.7 200 3,100Cadmium 200.8 ug/L 2 1.2 4 ND (4) UCalcium 200.7 ug/L 2 69 400 89 JChromium 200.8 ug/L 2 3.3 8 ND (8) UCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 ND (4) UIron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 2 21 400 ND (400) UND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.Est – Estimated value.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-5. Distillate from Brine Concentrator, Day 3 Analytical Results, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationManganese 200.7 ug/L 2 0.51 20 ND (20) UMercury 1631E ng/L 1 0.24 0.51 2.89Molybdenum 200.7 ug/L 2 1.6 40 ND (40) UNickel 200.8 ug/L 2 0.89 4 ND (4) USelenium 200.8 ug/L 2 0.62 4 0.67 JSilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 1,200 J,BThallium 200.8 ug/L 2 0.47 2 ND (2) UTin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 1.6 JVanadium 200.8 ug/L 2 1.7 10 ND (10) UZinc 200.7 ug/L 2 9.1 40 ND (40) UND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-6. Condensate from Crystallizer,Day 1 Analytical Results, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia 350.1 mg/L 5 0.27 5 26Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 0.061 JNitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 25Chemical Oxygen Demand 410.4 mg/L 1 4.1 20 ND (20) UChloride 300.0 mg/L 1 0.25 3 ND (3) USulfate 300.0 mg/L 1 0.23 5 ND (5) UTotal Dissolved Solids 2540C mg/L 1 4.7 10 10Total Suspended Solids 2540D mg/L 1 1.1 4 ND (4) UPhosphorus, Total 365.1 mg/L 1 0.005 0.05 ND (0.05) UTotal MetalsAluminum 200.7 ug/L 2 9.4 200 19 J,BAntimony 200.8 ug/L 2 0.72 2 ND (2) UArsenic 200.8 ug/L 2 1.2 4 ND (4) UBarium 200.7 ug/L 2 2.5 20 ND (20) UBeryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 2 6.7 200 3,200Cadmium 200.8 ug/L 2 1.2 4 ND (4) UCalcium 200.7 ug/L 2 69 400 ND (400) UChromium 200.8 ug/L 2 3.3 8 ND (8) UCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 1.1 JIron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 2 21 400 ND (400) UManganese 200.7 ug/L 2 0.51 20 0.64 JND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-6. Condensate from Crystallizer,Day 1 Analytical Results, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationMercury 1631E ng/L 10 2.44 5.1 20.4Molybdenum 200.7 ug/L 2 1.6 40 2.9 JNickel 200.8 ug/L 2 0.89 4 1.1 JSelenium 200.8 ug/L 2 0.62 4 1.1 JSilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 240 J,BThallium 200.8 ug/L 2 0.47 2 ND (2) UTin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 ND (10) UZinc 200.7 ug/L 2 9.1 40 ND (40) UND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.Est – Estimated value.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-7. Condensate from Crystallizer,Day 2 Analytical Results, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationClassicalsAmmonia 350.1 mg/L 5 0.27 5 43Nitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 0.02 JNitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 37 EstChemical Oxygen Demand 410.4 mg/L 1 4.1 20 ND (20) UChloride 300.0 mg/L 1 0.25 3 ND (3) USulfate 300.0 mg/L 1 0.23 5 ND (5) UTotal Dissolved Solids 2540C mg/L 1 4.7 10 22Total Suspended Solids 2540D mg/L 1 1.1 4 ND (4) UPhosphorus, Total 365.1 mg/L 1 0.005 0.05 ND (0.05) UTotal MetalsAluminum 200.7 ug/L 2 9.4 200 12 J,BAntimony 200.8 ug/L 2 0.72 2 ND (2) UArsenic 200.8 ug/L 2 1.2 4 ND (4) UBarium 200.7 ug/L 2 2.5 20 ND (20) UBeryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 2 6.7 200 3,100Cadmium 200.8 ug/L 2 1.2 4 ND (4) UCalcium 200.7 ug/L 2 69 400 ND (400) UChromium 200.8 ug/L 2 3.3 8 ND (8) UCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 3.1 JIron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 2 21 400 ND (400) UND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.Est – Estimated value.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-7. Condensate from Crystallizer,Day 2 Analytical Results, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationManganese 200.7 ug/L 2 0.51 20 ND (20) UMercury 1631E ng/L 10 2.44 5.1 20.7Molybdenum 200.7 ug/L 2 1.6 40 2.3 JNickel 200.8 ug/L 2 0.89 4 ND (4) USelenium 200.8 ug/L 2 0.62 4 0.92 JSilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 250 J,BThallium 200.8 ug/L 2 0.47 2 ND (2) UTin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 ND (10) UZinc 200.7 ug/L 2 9.1 40 9.2 JND – Not detected (number in parentheses is the quantitation limit).4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-8. Condensate from Crystallizer,Day 3 Analytical Results, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecificMDLSampleSpecific QLConcentrationClassicalsAmmonia 350.1 mg/L 4 0.22 4 22 4, EstNitrate Nitrite as N 353.2 mg/L 1 0.019 0.1 0.1 EstNitrogen, Total Kjeldahl 351.2 mg/L 5 0.38 5 25 B,4, EstChemical Oxygen Demand 410.4 mg/L 1 4.1 20 9.6 JChloride 300.0 mg/L 1 0.25 3 ND (3) USulfate 300.0 mg/L 1 0.23 5 ND (5) UTotal Dissolved Solids 2540C mg/L 1 4.7 10 9 JTotal Suspended Solids 2540D mg/L 1 1.1 4 ND (4) UPhosphorus, Total 365.1 mg/L 1 0.005 0.05 ND (0.05) UTotal MetalsAluminum 200.7 ug/L 2 9.4 200 ND (200) UAntimony 200.8 ug/L 2 0.72 2 ND (2) UArsenic 200.8 ug/L 2 1.2 4 ND (4) UBarium 200.7 ug/L 2 2.5 20 ND (20) UBeryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 2 6.7 200 3,300Cadmium 200.8 ug/L 2 1.2 4 ND (4) UCalcium 200.7 ug/L 2 69 400 ND (400) UChromium 200.8 ug/L 2 3.3 8 ND (8) UCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 3.7 JIron 200.7 ug/L 2 32 200 ND (200) UND – Not detected (number in parentheses is the quantitation limit).4 – MS and/or MSD did not meet laboratorycriteria, but sample concentration is fourtimes greater thanthe matrix spike amount, so control limits are not applicable.B – Analyte was found in the blank and sample.Est – Estimated value.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-8. Condensate from Crystallizer,Day 3 Analytical Results, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecificMDLSampleSpecific QLConcentrationLead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 2 21 400 ND (400) UManganese 200.7 ug/L 2 0.51 20 ND (20) UMercury 1631E ng/L 10 2.44 5.1 10.9Molybdenum 200.7 ug/L 2 1.6 40 1.7 JNickel 200.8 ug/L 2 0.89 4 1.1 JSelenium 200.8 ug/L 2 0.62 4 1.6 JSilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 230 J,BThallium 200.8 ug/L 2 0.47 2 ND (2) UTin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 ND (10) UZinc 200.7 ug/L 2 9.1 40 ND (40) Ua Nickel was detected in one bottle blank for the 500-mL plastic bottles at 0.14 ug/L. ND – Not detected (number in parentheses is the quantitation limit). 

### Table A-9. Bottle Blank and Equipmen t Blank Analytical Data, Brindisi

Analyte Method Process Units Concentration

HDPE 500 ml Plastic Bottles – Bottle Blank (for metals samples)

Aluminum EPA 1638 Total Recoverable ug/L ND (4.0)

Antimony EPA 1638 Total Recoverable ug/L ND (0.020)

Arsenic EPA 1638 Total Recoverable ug/L ND (0.15)

Barium EPA 1638 Total Recoverable ug/L ND (0.20)

Beryllium EPA 1638 Total Recoverable ug/L ND (0.060)

Boron EPA 1638 Total Recoverable ug/L ND (3.0)

Cadmium EPA 1638 Total Recoverable ug/L ND (0.020)

Calcium EPA 1638 Total Recoverable ug/L ND (40)

Chromium EPA 1638 Total Recoverable ug/L ND (0.10)

Cobalt EPA 1638 Total Recoverable ug/L ND (0.10)

Copper EPA 1638 Total Recoverable ug/L ND (0.10)

Iron EPA 1638 Total Recoverable ug/L ND (10)

Lead EPA 1638 Total Recoverable ug/L ND (0.040)

Magnesium EPA 1638 Total Recoverable ug/L ND (2.5)

Manganese EPA 1638 Total Recoverable ug/L ND (0.10)

Molybdenum EPA 1638 Total Recoverable ug/L ND (0.060)

Nickel a EPA 1638 Total Recoverable ug/L 0.14

Selenium EPA 1638 Total Recoverable ug/L ND (0.60)

Silver EPA 1638 Total Recoverable ug/L ND (0.020)

Sodium EPA 1638 Total Recoverable ug/L ND (20)

Thallium EPA 1638 Total Recoverable ug/L ND (0.0050)

Tin EPA 1638 Total Recoverable ug/L ND (0.10)

Titanium EPA 1638 Total Recoverable ug/L ND (0.50)

Vanadium EPA 1638 Total Recoverable ug/L ND (0.10)

Zinc EPA 1638 Total Recoverable ug/L ND (0.20)

125 ml Glass Bottles – Bottle Blank (for mercury composite samples)

Mercury EPA 1631E Total Recoverable ug/L ND (0.00050)

250 ml Glass Bottles – Bottle Bl ank (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 Equipmen t 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 Equipmen t 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 #7 3 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 Equipmen t 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 SystemField Blank, Day 1 Analytical Results, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsAluminum 200.7 ug/L 2 9.4 200 13 J,BAntimony 200.8 ug/L 2 0.72 2 ND (2) UArsenic 200.8 ug/L 2 1.2 4 ND (4) UBarium 200.7 ug/L 2 2.5 20 ND (20) UBeryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 2 6.7 200 ND (200) UCadmium 200.8 ug/L 2 1.2 4 ND (4) UCalcium 200.7 ug/L 2 69 400 ND (400) UChromium 200.8 ug/L 2 3.3 8 ND (8) UCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 ND (4) UIron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 2 21 400 ND (400) UManganese 200.7 ug/L 2 0.51 20 ND (20) UMercury 1631E ng/L 1 0.24 0.5 ND (0.5) UMolybdenum 200.7 ug/L 2 1.6 40 ND (40) UNickel 200.8 ug/L 2 0.89 4 ND (4) USelenium 200.8 ug/L 2 0.62 4 ND (4) USilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 370 J,BThallium 200.8 ug/L 2 0.47 2 ND (2) UTin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 ND (10) UND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-10. Influent to FGD Wastewater Treatment SystemField Blank, Day 1 Analytical Results, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationZinc 200.7 ug/L 2 9.1 40 ND (40) UND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).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, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsAluminum 200.7 ug/L 2 9.4 200 13 J,BAntimony 200.8 ug/L 2 0.72 2 ND (2) UArsenic 200.8 ug/L 2 1.2 4 ND (4) UBarium 200.7 ug/L 2 2.5 20 ND (20) UBeryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 2 6.7 200 ND (200) UCadmium 200.8 ug/L 2 1.2 4 ND (4) UCalcium 200.7 ug/L 2 69 400 ND (400) UChromium 200.8 ug/L 2 3.3 8 ND (8) UCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 ND (4) UIron 200.7 ug/L 2 32 200 77 JLead 200.8 ug/L 2 0.73 2 0.73 JMagnesium 200.7 ug/L 2 21 400 ND (400) UManganese 200.7 ug/L 2 0.51 20 ND (20) UMercury 1631E ng/L 1 0.24 0.5 ND (0.5) UMolybdenum 200.7 ug/L 2 1.6 40 ND (40) UNickel 200.8 ug/L 2 0.89 4 ND (4) USelenium 200.8 ug/L 2 0.62 4 ND (4) USilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 270 J,BThallium 200.8 ug/L 2 0.47 2 ND (2) UTin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 ND (10) UND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-11. Distillate from Brine Concentrator Field Blank, Day 1 Analytical Results, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationZinc 200.7 ug/L 2 9.1 40 ND (40) UTable A-12. Distillate from Brine Concentrator Field Blank, Day 2 Analytical Results, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsMercury 1631E ng/L 1 0.24 0.5 ND (0.5) UND – 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, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsMercury 1631E ng/L 1 0.24 0.5 ND (0.5) UND – 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 FieldBlank, Day 1 AnalyticalResults, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsAluminum 200.7 ug/L 2 9.4 200 14 J,BAntimony 200.8 ug/L 2 0.72 2 ND (2) UArsenic 200.8 ug/L 2 1.2 4 ND (4) UBarium 200.7 ug/L 2 2.5 20 ND (20) UBeryllium 200.7 ug/L 2 0.71 2 ND (2) UBoron 200.7 ug/L 2 6.7 200 ND (200) UCadmium 200.8 ug/L 2 1.2 4 ND (4) UCalcium 200.7 ug/L 2 69 400 ND (400) UChromium 200.8 ug/L 2 3.3 8 ND (8) UCobalt 200.7 ug/L 2 1.1 20 ND (20) UCopper 200.8 ug/L 2 0.96 4 1 JIron 200.7 ug/L 2 32 200 ND (200) ULead 200.8 ug/L 2 0.73 2 ND (2) UMagnesium 200.7 ug/L 2 21 400 ND (400) UManganese 200.7 ug/L 2 0.51 20 ND (20) UMercury 1631E ng/L 1 0.24 0.5 ND (0.5) UMolybdenum 200.7 ug/L 2 1.6 40 ND (40) UNickel 200.8 ug/L 2 0.89 4 ND (4) USelenium 200.8 ug/L 2 0.62 4 ND (4) USilver 200.8 ug/L 2 0.59 2 ND (2) USodium 200.7 ug/L 2 180 10,000 260 J,BThallium 200.8 ug/L 2 0.47 2 ND (2) UTin 200.7 ug/L 2 4.8 200 ND (200) UTitanium 200.7 ug/L 2 1.6 20 ND (20) UVanadium 200.8 ug/L 2 1.7 10 ND (10) UND – Not detected (number in parentheses is the quantitation limit).B – Analyte was found in the blank and sample.J – Result measured above the MDL, but less than the quantitation limit.U – Result below the MDL. (Number shown in parentheses is the quantitation limit).Table A-14. Condensate from Crystallizer FieldBlank, Day 1 AnalyticalResults, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationZinc 200.7 ug/L 2 9.1 40 ND (40) UTable A-15. Condensate from Crystallizer FieldBlank, Day 2 AnalyticalResults, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsMercury 1631E ng/L 1 0.24 0.5 ND (0.5) UND – 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 FieldBlank, Day 3 AnalyticalResults, BrindisiAnalyteMethodUnitDilutionFactorSampleSpecific MDLSample-Specific QLConcentrationTotal MetalsMercury 1631E ng/L 1 0.24 0.5 ND (0.5) UND – Not detected (number in parentheses is the quantitation limit).U – Result below the MDL. (Number shown in parentheses is the quantitation limit).

### 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

7 2511 FGD Influent, Day 3 280

- 14451

- 1 Aqueous 4/7 /201 1 4/11 /201 1

72512 FGD Influent, Day 2 280

- 14362

- 1 Aqueous 4/ 6 /2011 4/8 /201 1

7 2513 Distillate from Brine Concentrator, Day 1 280

- 14362

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

7 2514 Distillate from Brine Concentrator, Day 2 280

- 14362

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

7 2515 Distillate from Brine Concentrator, Day 3 280

- 14451

- 2 Aqueous 4/7 /201 1 4/11 /201 1

7 2516 Condensate from Crystallizer

, Day 1 280

- 14362

- 5 Aqueous 4/5/2011 4/8/2011

7 2517 Condensate from Crystallizer

, Day 2 2 80

- 14362

- 8 Aqueous 4/ 6 /2011 4/8/2011

72518 Condensate from Crystallizer, Day 3 280

- 14451

- 3 Aqueous 4/7 /201 1 4/11 /201 1

7 2519 FGD Influent Field Blank, Day 1 280

- 14362

- 2 Aqueous 4/ 5 /2011 4/8/2011

72 520 Distillate from BC Field Blank, Day

1 280

- 14362

- 4 Aqueous 4/5/2011 4/8/2011

7 2523 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.

M ATRIX 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”.

BOD 5



### 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