Crystals

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Effluent Quality Assessment

Crystals (Mastertaste Purchasing Company)

Hillsborough County NPDES #FL0037389 Sampled July 28, 2008

November 2008

Biology Section Bureau of Laboratories Division of Environmental Assessment and Restoration Quality Manual No. 870346G NELAC Certification No. E31780

Crystals, 1111 W. Dr. Martin Luther King Boulevard, Plant City, Hillsborough County, Florida 33566. NPDES #FL0037389. Effluent samples for this facility were collected on July 28, 2008.

Introduction Crystals is a food processing facility which manufactures food crystals by vacuum-enhanced dehydration utilizing barometric assemblies, which induces a vacuum by contacting cooling water (the source of cooling water is ground water) with steam. Effluent discharge from the facility is continuous. The facility has a permitted maximum discharge of 4.02 million gallons per day (MGD). The monthly average discharge from the facility from August 2007 through July 2008 was 2.105 MGD. The monthly maximum discharge was 3.98 MGD. The wastewater treatment system consists of: • •

a splash box at the outlet of the 0.46 m (18 inch) outfall pipe; and, splash plates.

The splash box is a mechanical aeration device consisting of subsurface propellers that are mounted on the side of the barometric condenser hot well tanks pipe. The splash box serves to increase the dissolved oxygen content of the effluent. The splash plates provide additional agitation. The wastewater stream consists of cooling water which has been mixed with the process water. This wastewater is further combined with the facility grounds stormwater runoff and then discharged through Outfall D-001 into an unnamed ditch, then to Westside canal and thence into the Class III freshwaters of Pemberton Creek. The point of discharge for Outfall D-001 is located approximately at latitude 28º 00’ 41.3” N, longitude 82º 08’ 01.2” W. The facility has no Administrative Orders, Consent Orders or mixing zones. A review of Discharge Monitoring Report (DMR) data for the past year, revealed only one permit violation (July 2008 – dissolved oxygen value 4.1 mg/L; permitted value ≥ 5 mg/L monthly minimum). The DMR review found the facility to be operating within permitted limits except as noted above for dissolved oxygen. (Facility information provided by Peter Wenner FDEP Southwest District).

Methods Samples were collected from the EFF-1 NPDES sampling point for Outfall D-001 by Pete Wenner and Jason Cohen (FDEP Southwest District) following DEP-SOP-001/01 FS 2400 Wastewater Sampling. All DEP SOPs are available on the web at: http://www.floridadep.org/labs/qa/sops.htm. See Appendix A for the completed chain of custody form. The 48-hour acute screening toxicity tests and algal growth potential test were performed following internal DEP SOPs TA07_01, TA07_02, and TA08_01 through TA08_09. All internal DEP SOPs are available on the web at: http://www.floridadep.org/labs/cgi-bin/sop/biosop.asp. Although the 48-hour acute screening toxicity test does not reflect the required permit conditions, passing test results provide confidence that the required permit conditions would likely be met.

Toxicity Test Results Tests were performed July 29-31, 2008. Ceriodaphnia dubia 48-hour acute screening bioassay –

LC50 > 100%, 0% mortality* in 100% sample at 48 hours

Cyprinella leedsi 48-hour acute screening bioassay –

LC50 > 100%, 5% mortality* in 100% sample at 48 hours

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The bioassay samples were not acutely toxic to the test organisms. See Appendix B for bioassay bench sheets. See Appendix C for results of the last 20 standard reference toxicant (SRT) tests and the bench sheets and statistical analyses of the SRT tests that correspond to these facility tests. See Appendix D for test organism receipts. *NOTE: In a 48-hour acute screening test of 100% effluent, mortality of 50% indicates that the effluent fails to meet the minimum requirement to discharge to waters of the state (Rule 624.244(3)(a), F.A.C.).

Algal Growth Potential The effluent Algal Growth Potential (AGP) was 12.3 mg dry wt/L of the unicellular green alga, Pseudokirchneriella subcapitata, formerly known as Selenastrum capricornutum. Raschke and Shultz (1987) found that AGP values above 5.0 mg dry weight/L represent a “problem” threshold for fresh receiving waters, implying nutrient enrichment. The analytical chemistry suggests that the effluent is nitrogen-limited. The predicted AGP based on inorganic nitrogen concentrations was 6.7 (±20%) mg dry wt/L (Table 1; Miller et al. 1978). See Table 1 for AGP results.

Chemistry Results Total residual chlorine and total ammonia were not detected in the bioassay sample in the laboratory. The total ammonia concentration in the sample collected and preserved for chemical analysis was 0.17 mg/L. Based on the pH, salinity, and temperature of the effluent as collected, the calculated unionized ammonia concentration was < 0.02 mg/L. No substances of concern were detected in the effluent. Iron was detected between the laboratory method detection limits (MDL) and practical quantitation limits (PQL). See Table 2 for results of analytes detected in the effluent, and corresponding limits. See Appendix E for a complete list of chemical analyses performed. See Appendix F for bioassay instruments.

Conclusion The effluent sample collected from the EFF-1 NPDES sampling point for Outfall D-001 for this facility on July 28, 2008, was not acutely toxic to either test species during the 48-hour acute screening bioassays. The effluent AGP result exceeded the "problem” threshold for fresh receiving waters. Effluent water quality samples did not exceed any applicable water quality standards or violate any permit conditions.

Literature Cited Miller, W. E., T. E. Maloney, and J. C. Greene. 1978. The Selenastrum capricornutum Printz algal assay bottle test. EPA-600/9-78-018. U. S. EPA, Cincinnati, Ohio. 126 p.

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Table 1. Measured and predicted algal growth potential (AGP; mg dry weight/L) for total soluble inorganic nitrogen (TSIN) and total nitrogen (TN) limitation of the freshwater species Pseudokirchneriella subcapitata and ratios of nitrogen to phosphorus for samples collected from the Crystals facility on July 28, 2008. Crystals (Mastertaste Purchasing Company) Location Effluent

AGP (measured) 12.3

Predicted AGP (TSIN) ± 20% 6.7 ± 1.3

Predicted AGP (TN) ± 20% 7.8 ± 1.6

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Inorganic N:P ratio 4.5

Total N:P ratio 4.5

Table 2. Effluent limits, Class III Freshwater Criteria, and chemical and microbiological data for samples collected from the Crystals facility on July 28, 2008. Crystals (Mastertaste Purchasing Company) NPDES# FL0037389 Organic Constituents (µg/L) None Detected Metals (µg/L unless otherwise noted) Aluminum Arsenic Cadmium Calcium (mg/L) Chromium-III Copper Iron Lead Magnesium (mg/L) Nickel Selenium Silver Zinc Nutrients (mg/L) Ortho-phosphate Total Phosphorus Total Ammonia Un-ionized Ammonia Nitrate and Nitrite Total Kjeldahl Nitrogen Organic Nitrogen Total Nitrogen General Physical and Chemical Parameters Dissolved Oxygen (mg/L) pH (SU) Conductivity (µmhos/cm) Temperature °C Total Residual Chlorine (mg/L) Chlorophyll a (µg/L) - Corrected Phaeophytin (µg/L) CBOD, 5 day (mg/L), N - inhibited Flow (MGD) Hardness (mg CaCO3)

Class III Criteria

Effluent Limits

Effluent

-

-

None Detected

≤ 50 ≤ 0.4 b ≤ 144.4 b ≤ 16.0 b ≤ 1,000 ≤ 7.1 b ≤ 88.9 b ≤ 5.0 ≤ 0.07 ≤ 204.4 b

-

60 0.5 0.02 57.1 0.5 0.5 53 0.2 11 0.25 0.5 0.025 5

≤ 0.02 s -

≤ 0.02 s -

0.039 0.046 0.17 ≤ 0.02 0.005 0.2 0.03 0.205

≥ 5.0 6.0 - 8.5 ≤ 1,275 ≤ 0.01 Microbiology (Number of colony forming units/100ml) # ≤ 400s Fecal Coliforms

U U U A U U I U A U U U U

I c I J c c

≥ 5.0 s 6.0 - 8.5 s ≤ 33.3 s ≤ 4.02 -

7.5 7.9 374 30.1 0.03 UQ£ 0.55 U 0.24 U 0.2 U 2.105 m 187.88 c

-

1

U

Value exceeds the Class III Water Quality Criteria or permit limits a - Annual average b - Value is calculated based on hardness c - Value is calculated m - Monthly average daily flow s - Single sample A - Value reported is the mean of two or more determinations I - The reported value is between the laboratory method detection limit and the laboratory practical quantitation limit Q - Sample held beyond normal holding time J - Estimated value U - Material analyzed for but not detected; value reported is the method detection limit # - If 10 or fewer samples are taken within a month, the single sample limit is 400 CFU (62-302.530(6), F.A.C.) £ - Analysis performed in bioassay lab

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Appendix A. Chain of Custody Form

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Appendix B. Bench Sheets

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Appendix B. (continued)

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Appendix B. (continued)

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Appendix B. (continued)

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Appendix B. (continued)

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Appendix C. SRT Bench Sheets and Statistical Analysis Florida Department of Environmental Protection Bureau of Laboratories Standard Reference Toxicant (SRT) Test Data - 48-hour Acute Toxicity Ceriodaphnia dubia (water flea) - Sodium Chloride (NaCl) LC50 2.22 2.39 1.92 2.37 1.78 1.69 2.28 1.99 1.94 1.95 2.04 2.35 2.13 1.92 2.25 2.15 2.50 2.19 1.91 2.21

Date 01/16/07 02/13/07 03/13/07 04/03/07 05/08/07 05/29/07 06/06/07 07/03/07 07/31/07 09/04/07 10/02/07 10/30/07 12/04/07 01/22/08 02/05/08 03/04/08 04/01/08 05/06/08 06/03/08 07/08/08

Mean LC50 2.19 2.31 2.18 2.20 2.18 2.06 2.16 2.14 2.14 2.13 2.11 2.11 2.09 2.08 2.08 2.08 2.11 2.11 2.10 2.11

Std Dev 0.17 0.17 0.18 0.18 0.21 0.23 0.22 0.22 0.22 0.22 0.21 0.21 0.20 0.20 0.20 0.20 0.22 0.22 0.22 0.22

Lower Control Limit Upper Control Limit 1.85 2.52 1.97 2.54 1.82 2.55 1.83 2.57 1.77 2.59 1.70 2.60 1.71 2.60 1.70 2.58 1.71 2.58 1.70 2.57 1.68 2.53 1.68 2.54 1.67 2.51 1.66 2.50 1.68 2.48 1.68 2.49 1.68 2.55 1.68 2.55 1.66 2.54 1.67 2.55

Means are of the last 20 SRT tests. Lower Control Limit = mean - 2 * Std Dev Upper Control Limit = mean + 2 * Std Dev

CV = 10.35 EPA reference 75th quartile CV = 29%

Standard Reference Toxicant Data Ceriodaphnia dubia 48 hour LC50

2.50

2.00

Test Date LC50

Mean LC50

Lower Control Limit

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Upper Control Limit

07/08/08

06/03/08

05/06/08

04/01/08

03/04/08

02/05/08

01/22/08

12/04/07

10/30/07

10/02/07

09/04/07

07/31/07

07/03/07

06/06/07

05/29/07

05/08/07

04/03/07

03/13/07

02/13/07

1.50 01/16/07

g/L NaCl

3.00

Appendix C. (continued) Florida Department of Environmental Protection Bureau of Laboratories Standard Reference Toxicant (SRT) Test Data - 48-hour Acute Toxicity Cyprinella leedsi (bannerfin shiner) - Sodium Chloride (NaCl) Date 01/16/07 02/14/07 03/14/07 04/03/07 05/08/07 05/30/07 07/03/07 07/10/07 08/01/07 09/05/07 10/02/07 10/30/07 12/04/07 01/08/08 02/05/08 03/04/08 04/01/08 05/15/08 06/03/08 07/08/08

LC50 8.47 8.92 7.75 8.50 9.07 8.85 8.67 8.52 7.7 9.06 8.55 8.72 7.71 8.7 8.92 7.89 8.24 8.1 8.21 8.04

Mean LC50 8.04 8.70 8.38 8.41 8.22 8.59 8.33 8.36 8.31 8.34 8.43 8.43 8.36 8.35 8.42 8.42 8.42 8.39 8.37 8.33

Std Dev 0.47 0.32 0.59 0.49 0.52 0.48 0.50 0.49 0.51 0.54 0.47 0.47 0.47 0.47 0.46 0.46 0.45 0.51 0.51 0.50

Lower Control Limit Upper Control Limit 7.11 8.98 7.12 9.10 7.16 9.09 7.19 9.12 7.18 9.25 7.23 9.32 7.34 9.32 7.38 9.34 7.29 9.34 7.26 9.42 7.45 9.35 7.48 9.37 7.41 9.31 7.41 9.30 7.50 9.33 7.50 9.33 7.51 9.33 7.36 9.41 7.34 9.40 7.32 9.33

Means are of the last 20 SRT tests. Lower Confidence Limit = mean - 2 * Std Dev Upper Confidence Limit = mean + 2 * Std Dev

CV = 6.03 EPA reference 75th quartile CV = 19%

Standard Reference Toxicant Data Cyprinella leedsi 48-hour LC50

8

6

07/08/08

06/03/08

05/15/08

04/01/08

03/04/08

02/05/08

01/08/08

12/04/07

10/30/07

10/02/07

09/05/07

08/01/07

07/10/07

07/03/07

05/30/07

05/08/07

04/03/07

03/14/07

02/14/07

4 01/16/07

g/L NaCl

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Test Date LC50

Mean LC50

Lower Control Limit

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Upper Control Limit

Appendix C. (continued)

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Appendix C. (continued)

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Appendix C. (continued)

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Appendix C. (continued)

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Appendix C. (continued) Ceriodaphnia dubia Acute Standard Reference Toxicant Test

DATE: 7-8-08 DURATION: 48 hr SPECIES: Ceriodaphnia dubia RAW DATA: Concentration (g/L) .00 1.50 2.00 2.50 3.00 4.00 SPEARMAN-KARBER TRIM:

TOXICANT : NaCl

Number Exposed 20 20 20 20 20 20

Mortalities 0 0 1 20 20 20

.00%

SPEARMAN-KARBER ESTIMATES: LC50: 2.21 95% LOWER CONFIDENCE: 2.15 95% UPPER CONFIDENCE: 2.26 __________________________________________________________ Cyprinella leedsi Acute Standard Reference Toxicant Test DATE: 7-8-08 DURATION: 48 hr SPECIES: Cyprinella leedsi RAW DATA:

Concentration (g/L) 0.00 6.00 7.00 8.00 9.00 10.00

SPEARMAN-KARBER TRIM:

TOXICANT : NaCl

Number Exposed 20 20 20 20 20 20

Mortalities 0 2 3 9 16 20

0.00%

SPEARMAN-KARBER ESTIMATES: LC50: 8.04 95% LOWER CONFIDENCE: 7.64 95% UPPER CONFIDENCE: 8.47

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Appendix D. Test Organism Receipt(s)

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Appendix D. (continued)

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Appendix E. Chemical Analyses performed on the effluent from the Crystal facility Outfall D-001, sampled on July 28, 2008. Date Sampled 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00

Field ID Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent

Analysis AGP/LN Chlorophyll/Grain Size/BOD Chlorophyll/Grain Size/BOD Chlorophyll/Grain Size/BOD Overflow Toxicology Toxicology Metals Metals Metals Metals Metals Metals Metals Metals Metals Metals Metals Metals Metals Metals Metals Nutrients Nutrients Nutrients Nutrients Nutrients Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides

Component Algal Growth Potential Biochemical Oxygen Demand-5 Day,N-Inhib Chlorophyll-a, Corrected Phaeophytin-a Fecal Coliforms-Membrane Filter Bioassay-Acute-Screen-FW-Fish, LC50 Bioassay-Acute-Screen-FW-C.dubia, LC50 Aluminum Magnesium Arsenic Beryllium Lead Calcium Iron Zinc Antimony Chromium Nickel Selenium Cadmium Silver Copper NO2NO3-N Ammonia-N O-Phosphate-P Total-P Kjeldahl Nitrogen Fonofos Ethoprop Butylate Parathion Ethyl Bromacil Metalaxyl

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Result 12.3 0.2 0.55 0.24 1 100 100 60 11 0.5 0.025 0.2 57.1 53 5 0.5 0.5 0.25 0.5 0.02 0.025 0.5 0.005 0.17 0.039 0.046 0.2 0.1 0.1 0.2 0.15 0.2 0.25

Remark Units mg DryWt/L U mg/L U ug/L U ug/L U #/100 mL L LC50 L LC50 U ug/L A mg/L U ug/L U ug/L U ug/L A mg/L I ug/L U ug/L U ug/L U ug/L U ug/L U ug/L U ug/L U ug/L U ug/L I mg N/L mg N/L mg P/L I mg P/L J mg N/L U ug/L U ug/L U ug/L U ug/L U ug/L U ug/L

MDL 0.3 0.2 0.55 0.24 1

PQL 0.9 2 1.7 0.71

60 0.04 0.5 0.025 0.2 0.075 30 5 0.5 0.5 0.25 0.5 0.02 0.025 0.5 0.004 0.01 0.004 0.02 0.08 0.1 0.1 0.2 0.15 0.2 0.25

240 0.16 2 0.1 0.8 0.3 120 20 2 2 1 2 0.08 0.1 2 0.01 0.02 0.01 0.06 0.2 0.4 0.4 0.8 0.6 0.8 1

Appendix E. (continued) Date Sampled 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00

Field ID Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent

Analysis Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants

Component Chlorpyrifos Methyl Atrazine Ametryn Prometryn Parathion Methyl Naled Metolachlor Chlorpyrifos Ethyl Alachlor Simazine Phorate Mevinphos Fenamiphos Ethion Azinphos Methyl Metribuzin Diazinon Hexazinone Malathion Norflurazon 2,4-Dinitrophenol 2-Nitrophenol 4-Bromophenyl phenyl ether Benzidine Pyrene beta-BHC 2-Chlorophenol Acenaphthylene Bis(2-ethylhexyl)phthalate Di-n-octyl phthalate Fluorene Hexachlorocyclopentadiene 2,4-Dichlorophenol 4,4'-DDT

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Result 0.1 0.05 0.05 0.15 0.1 0.8 0.5 0.05 0.6 0.05 0.05 0.2 0.2 0.05 0.2 0.1 0.05 0.1 0.15 0.15 14 0.96 0.96 96 0.96 1.4 0.96 0.96 14 0.96 0.96 2.9 0.96 1.4

Remark U U U U U UJ U U U U U U U U U U UJ U U U U U U U U U U U U U U U U U

Units ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L

MDL 0.1 0.05 0.05 0.15 0.1 0.8 0.5 0.05 0.6 0.05 0.05 0.2 0.2 0.05 0.2 0.1 0.05 0.1 0.15 0.15 14 0.96 0.96 96 0.96 1.4 0.96 0.96 14 0.96 0.96 2.9 0.96 1.4

PQL 0.4 0.2 0.2 0.6 0.4 3.2 2 0.2 2.4 0.2 0.2 0.8 0.8 0.2 0.8 0.4 0.2 0.4 0.6 0.6 58 3.8 3.8 380 3.8 5.8 3.8 3.8 58 3.8 3.8 12 3.8 5.8

Appendix E. (continued) Date Sampled 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00

Field ID Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent

Analysis Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants

Component Benzo(a)pyrene Bis(2-chloroethyl)ether Endosulfan II Endrin gamma-BHC 2-Chloronaphthalene Diethyl phthalate Hexachlorobutadiene Indeno(1,2,3-cd)pyrene Isophorone N-Nitrosodi-n-propylamine N-Nitrosodimethylamine delta-BHC 2,6-Dinitrotoluene 2-Methyl-4,6-dinitrophenol 4-Nitrophenol Benzo(g,h,i)perylene Chrysene Endosulfan sulfate Endrin aldehyde 2,4,6-Trichlorophenol 2,4-Dimethylphenol 2,4-Dinitrotoluene 3,3'-Dichlorobenzidine 4,4'-DDD Benzo(a)anthracene Benzo(k)fluoranthene Bis(2-chloroethoxy)methane Bis(2-chloroisopropyl)ether Butyl benzyl phthalate Dibenzo(a,h)anthracene Dimethyl phthalate Nitrobenzene Pentachlorophenol

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Result 0.96 0.96 3.8 1.4 1.4 0.96 0.96 2.9 0.96 0.96 1.9 1.9 1.4 0.96 2.9 14 0.96 0.96 1.4 3.8 0.96 9.6 0.96 38 1.4 0.96 0.96 0.96 2.9 4.8 0.96 9.6 1.9 2.9

Remark U U UJ U U U U U U U U U U U U U U U U UJ U U U U U U U U U U U UJ U UJ

Units ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L

MDL 0.96 0.96 3.8 1.4 1.4 0.96 0.96 2.9 0.96 0.96 1.9 1.9 1.4 0.96 2.9 14 0.96 0.96 1.4 3.8 0.96 9.6 0.96 38 1.4 0.96 0.96 0.96 2.9 4.8 0.96 9.6 1.9 2.9

PQL 3.8 3.8 15 5.8 5.8 3.8 3.8 12 3.8 3.8 7.7 7.7 5.8 3.8 12 58 3.8 3.8 5.8 15 3.8 38 3.8 150 5.8 3.8 3.8 3.8 12 19 3.8 38 7.7 12

Appendix E. (continued) Date Sampled 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:00 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15

Field ID Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Effluent Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank

Analysis Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Field Parameter Field Parameter Field Parameter Field Parameter Chlorophyll/Grain Size/BOD Metals Metals Metals Metals Metals Metals Metals Metals Metals

Component 1,2,4-Trichlorobenzene 4,4'-DDE 4-Chlorophenyl phenyl ether Anthracene Dieldrin Fluoranthene Hexachlorobenzene Phenanthrene alpha-BHC 4-Chloro-3-methylphenol Acenaphthene Aldrin Benzo(b)fluoranthene Di-n-butyl phthalate Endosulfan I Heptachlor Heptachlor epoxide Hexachloroethane Naphthalene Phenol Specific Conductance Dissolved Oxygen Temperature pH Biochemical Oxygen Demand-5 Day,N-Inhib Lead Zinc Aluminum Magnesium Copper Silver Chromium Beryllium Arsenic

23

Result 0.96 1.4 1.9 0.96 1.4 0.96 0.96 0.96 1.4 0.96 0.96 1.4 0.96 4.8 3.8 1.4 1.4 2.9 0.96 0.96 374 7.53 30.11 7.86 0.2 0.2 5 60 0.04 0.5 0.025 0.5 0.025 0.5

Remark U U U U U U U U U U U UJ U U U U U U U U

Units ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L umhos/cm mg/L C

MDL 0.96 1.4 1.9 0.96 1.4 0.96 0.96 0.96 1.4 0.96 0.96 1.4 0.96 4.8 3.8 1.4 1.4 2.9 0.96 0.96

PQL 3.8 5.8 7.7 3.8 5.8 3.8 3.8 3.8 5.8 3.8 3.8 5.8 3.8 19 15 5.8 5.8 12 3.8 3.8

U U U U U U U U U U

mg/L ug/L ug/L ug/L mg/L ug/L ug/L ug/L ug/L ug/L

0.2 0.2 5 60 0.04 0.5 0.025 0.5 0.025 0.5

2 0.8 20 240 0.16 2 0.1 2 0.1 2

Appendix E. (continued) Date Sampled 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15

Field ID Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank

Analysis Metals Metals Metals Metals Metals Metals Nutrients Nutrients Nutrients Nutrients Nutrients Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides Pesticides

Component Calcium Antimony Iron Selenium Nickel Cadmium Kjeldahl Nitrogen NO2NO3-N Total-P Ammonia-N O-Phosphate-P Prometryn Atrazine Fenamiphos Hexazinone Metribuzin Ethoprop Simazine Phorate Naled Mevinphos Malathion Ethion Ametryn Parathion Ethyl Metalaxyl Parathion Methyl Azinphos Methyl Metolachlor Diazinon Chlorpyrifos Methyl Butylate Fonofos Alachlor

Result 0.075 0.5 30 0.5 0.25 0.02 0.08 0.004 0.02 0.01 0.004 0.14 0.048 0.19 0.095 0.095 0.095 0.048 0.048 0.76 0.19 0.14 0.048 0.048 0.14 0.24 0.095 0.19 0.48 0.048 0.095 0.19 0.095 0.57

24

Remark U U U U U U U U U U U U U U U U U U U UJ U U U U U U U U U UJ U U U U

Units mg/L ug/L ug/L ug/L ug/L ug/L mg N/L mg N/L mg P/L mg N/L mg P/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L

MDL 0.075 0.5 30 0.5 0.25 0.02 0.08 0.004 0.02 0.01 0.004 0.14 0.048 0.19 0.095 0.095 0.095 0.048 0.048 0.76 0.19 0.14 0.048 0.048 0.14 0.24 0.095 0.19 0.48 0.048 0.095 0.19 0.095 0.57

PQL 0.3 2 120 2 1 0.08 0.2 0.01 0.06 0.02 0.01 0.56 0.19 0.76 0.38 0.38 0.38 0.19 0.19 3 0.76 0.56 0.19 0.19 0.56 0.96 0.38 0.76 1.9 0.19 0.38 0.76 0.38 2.3

Appendix E. (continued) Date Sampled 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15

Field ID Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank

Analysis Pesticides Pesticides Pesticides Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants

Component Norflurazon Bromacil Chlorpyrifos Ethyl 2,4-Dinitrotoluene 4-Bromophenyl phenyl ether 4-Chloro-3-methylphenol 4-Nitrophenol Acenaphthene Indeno(1,2,3-cd)pyrene delta-BHC 2,4-Dimethylphenol Benzo(b)fluoranthene Bis(2-chloroethyl)ether Chrysene Endosulfan I Endosulfan II Heptachlor epoxide Pentachlorophenol Pyrene 2,6-Dinitrotoluene 4,4'-DDD Benzidine Butyl benzyl phthalate Dimethyl phthalate Phenanthrene 3,3'-Dichlorobenzidine Endrin aldehyde Fluoranthene Fluorene Phenol alpha-BHC 2-Chlorophenol 2-Nitrophenol Acenaphthylene

25

Result 0.14 0.19 0.048 0.95 0.95 0.95 14 0.95 0.95 1.4 9.5 0.95 0.95 0.95 3.8 3.8 1.4 2.9 0.95 0.95 1.4 95 4.8 9.5 0.95 38 3.8 0.95 0.95 0.95 1.4 0.95 0.95 0.95

Remark U U U U U U U U U U U U U U U UJ U UJ U U U U U UJ U U UJ U U U U U U U

Units ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L

MDL 0.14 0.19 0.048 0.95 0.95 0.95 14 0.95 0.95 1.4 9.5 0.95 0.95 0.95 3.8 3.8 1.4 2.9 0.95 0.95 1.4 95 4.8 9.5 0.95 38 3.8 0.95 0.95 0.95 1.4 0.95 0.95 0.95

PQL 0.56 0.76 0.19 3.8 3.8 3.8 57 3.8 3.8 5.7 38 3.8 3.8 3.8 15 15 5.7 11 3.8 3.8 5.7 380 19 38 3.8 150 15 3.8 3.8 3.8 5.7 3.8 3.8 3.8

Appendix E. (continued) Date Sampled 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15

Field ID Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank Blank

Analysis Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants

Component Anthracene Bis(2-chloroisopropyl)ether Dibenzo(a,h)anthracene Heptachlor Isophorone 2,4,6-Trichlorophenol 4,4'-DDE 4,4'-DDT 4-Chlorophenyl phenyl ether Aldrin Benzo(a)anthracene Benzo(g,h,i)perylene Di-n-octyl phthalate Diethyl phthalate Hexachlorocyclopentadiene Naphthalene beta-BHC 2,4-Dichlorophenol 2,4-Dinitrophenol 2-Chloronaphthalene 2-Methyl-4,6-dinitrophenol Benzo(k)fluoranthene Endosulfan sulfate Endrin Hexachlorobutadiene N-Nitrosodi-n-propylamine Nitrobenzene gamma-BHC 1,2,4-Trichlorobenzene Benzo(a)pyrene Bis(2-chloroethoxy)methane Bis(2-ethylhexyl)phthalate Di-n-butyl phthalate Dieldrin

26

Result 0.95 2.9 0.95 1.4 0.95 0.95 1.4 1.4 1.9 1.4 0.95 0.95 0.95 0.95 2.9 0.95 1.4 0.95 14 0.95 2.9 0.95 1.4 1.4 2.9 1.9 1.9 1.4 0.95 0.95 0.95 14 4.8 1.4

Remark U U U U U U U U U UJ U U U U U U U U U U U U U U U U U U U U U U U U

Units ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L ug/L

MDL 0.95 2.9 0.95 1.4 0.95 0.95 1.4 1.4 1.9 1.4 0.95 0.95 0.95 0.95 2.9 0.95 1.4 0.95 14 0.95 2.9 0.95 1.4 1.4 2.9 1.9 1.9 1.4 0.95 0.95 0.95 14 4.8 1.4

PQL 3.8 11 3.8 5.7 3.8 3.8 5.7 5.7 7.6 5.7 3.8 3.8 3.8 3.8 11 3.8 5.7 3.8 57 3.8 11 3.8 5.7 5.7 11 7.6 7.6 5.7 3.8 3.8 3.8 57 19 5.7

Appendix E. (continued) Date Sampled 7/28/2008 10:15 7/28/2008 10:15 7/28/2008 10:15

Field ID Blank Blank Blank

Analysis Priority Organic Pollutants Priority Organic Pollutants Priority Organic Pollutants

Component Hexachlorobenzene Hexachloroethane N-Nitrosodimethylamine

Result 0.95 2.9 1.9

27

Remark U U U

Units ug/L ug/L ug/L

MDL 0.95 2.9 1.9

PQL 3.8 11 7.6

Appendix F. Bioassay Instruments Test Dates: July 29 - 31, 2008 SRT Dates: July 8 - 12, 2008

Test ID: Crystals METER / DEVICE

SOP

Parameter

Method

√ used

90H018262

TA06_04

Dissolved Oxygen

SM 4500 O G



Accumet AR-10 pH Meter Mettler-Toledo SevenMulti Conductivity Meter

93312105 SN 1225117049 Probe H04257

TA06_23

Denver Model 225 ISE with ammonia probe

SN K01377

YSI Model 58 Dissolved Oxygen Meter

ID

+

SM 4500 H

TA06_25

pH Conductivity Salinity

SM 2510 B SM 2520 B

√ √ √

TA06_17

Ammonia

SM 4500 NH3 F



SM-2530B modified DEP SOPTemperature 001/01 FT1400 Total Residual EPA 330.5 Chlorine SM 4500 CL G

YSI 5750 SN 05J1720

TA06_05

05050C026378

TA06_22

Alkalinity (Hach Kit)

No SN

TA06_08

Alkalinity

SM 2320 B



Hardness (Hach Kit)

No SN

TA06_09

Hardness

SM 2340 C



1125481084

TA06_21 TA06_27

Weight

-



BIO-S-WEIGHTS-01

NA

Balance check

-



Thermometer (DO probe) Hach Pocket Colorimeter II

OHAUS Balance 250D S-Weights

SM-2530B modified to allow use electronic and non-mercury filled thermometers. Insert other device information in blank spaces(if used).

Test ID = Facility or SRTs (acute SRT--Chronic SRT)

Comments:

V 1.4 8/21/08 BA

28

√ √

The Bioassay of the Crystals effluent sampled on July 28, 2008. NPDES #FL0037389. Fill Out This Section For All Surface Water Discharger Inspections(CEI, CSI, CBI, PAI, XSI-RI Optional) Transaction Code

1 N

2

NPDES NUMBER

5

3 F L

0

0

3

7

3

YR/MO/DA

8

8 11 12

0

8

0

7

Insp Type

2

8

18 B

Inspector

19 S

Fac Type

20

2

Remarks 66

The Priority Pollutants Analysis of the Crystals effluent sampled on July 28, 2008. NPDES #FL0037389. Fill Out This Section For All Surface Water Discharger Inspections(CEI, CSI, CBI, PAI, XSI-RI Optional) Transaction Code

1 N

2

NPDES NUMBER

5

3 F L

0

0

3

7

3

YR/MO/DA

8

9 11 12

0

8

0

7

Insp Type

2

8

18 X

Inspector

19 S

Fac Type

20

2

Remarks 66

Biological Analyses of the Crystals effluent sampled on July 28, 2008. NPDES #FL0037389. Fill Out This Section For All Surface Water Discharger Inspections(CEI, CSI, CBI, PAI, XSI-RI Optional) Transaction Code

1 N

2

NPDES NUMBER

5

3 F L

0

0

3

7

3

YR/MO/DA

8

9 11 12

0

8

0

7

Insp Type

2

8

18 S

Inspector

19 S

Fac Type

20

2

Remarks 66

29