LOXAHATCHEE RIVER WATER QUALITY AND BIOLOGICAL MONITORING        TASK 4: FINAL REPORT  ASSESSMENT OF 2009‐2010 LOXAHATCHEE RIVER WATER QUALITY    In Partial Fulfillment of Agreement No. 4600001907    For the Period    October 2009 through September 2010          Respectfully Submitted by    Bud Howard, Lorene Bachman, Susan Noel, David Porter, Jerry Metz,   Helen Johnson, Abbey Wilkison, Albrey Arrington, Ph.D.    Loxahatchee River District        December 2010 

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Contents  Executive Summary ....................................................................................................................................... 3  Introduction .................................................................................................................................................. 4  Study Area ..................................................................................................................................................... 5  Materials and Methods ................................................................................................................................. 6  Results & Discussion ................................................................................................................................... 11  Appendix A ‐ Stoplight Decision Rules & Data. ........................................................................................... 29  Appendix B – Box & Whisker Plots. ............................................................................................................. 32  Appendix C – Spatial Plots. .......................................................................................................................... 42  Appendix D – Analysis Methods & Calibration Criteria .............................................................................. 47  Appendix E – Parameter & Station Listing .................................................................................................. 48  Appendix F – Quality Control Summary ...................................................................................................... 49 

List of Figures  Figure 1.  Loxahatchee River watershed and associated features. ............................................................... 6  Figure 2.  Loxahatchee River District’s water quality monitoring stations in the Loxahatchee River and  associated waters, color coded by river segment/analysis group. ............................................................... 9  Figure 3. Plot of daily flow at Lainhart Dam and daily rainfall at LRD for the period of January 2008  through October 2010. ............................................................................................................................... 13  Figure 4.  Synthesis of 2010 water quality stoplight scoring by sampling site for total phosphorus (TP),  total nitrogen (TN), chlorophyll a (CLA), dissolved oxygen (DO), and fecal coliform (FC), Loxahatchee  River, Florida.. ............................................................................................................................................. 25 

  List of Tables  Table 1. RiverKeeper sampling sites. .......................................................................................................... 10  Table 2. Summary of annual rainfall and river flows measured at Lainhart Dam.  Lainhart flow data from  SFWMD‐DBHYDRO. ..................................................................................................................................... 12  Table 3. A ‘stoplight’ assessment of water quality for Total Nitrogen, Total Phosphorus, and Chlorophyll  a among the seven reaches of the Loxahatchee River for each period October through September  relative to the target levels of 1998‐2002.  See Appendix A for decision rules and data. ......................... 15  Table 4. Summary of annual geometric mean for total nitrogen by sample station, color coded by  numeric nutrient criteria for Florida streams, or 1998‐2002 target values, Loxahatchee River, Florida. .. 20  Table 5. Summary of annual geometric mean for total phosphorus by sample station, color coded by  numeric nutrient criteria for Florida streams, or 1998‐2002 target values, Loxahatchee River, Florida. .. 21  Table 6. Summary of annual geometric mean for chlorophyll a by sample station, color coded by 1998‐ 2002 target values, Loxahatchee River, Florida. ......................................................................................... 22  Table 7. Summary of annual geometric mean for dissolved oxygen by sample station, color coded by  1998‐2002 target values, Loxahatchee River, Florida. ................................................................................ 23  Table 8. Summary of annual geometric mean for fecal coliform bacteria by sample station, color coded  by 1998‐2002 target values, Loxahatchee River, Florida. ........................................................................... 24 

 

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Executive Summary  This report presents water quality data collected under the Loxahatchee River District’s  (LRD)  RiverKeeper  water  quality  monitoring  program.    This  monitoring  program  evaluates  29  water quality parameters at 39 sites throughout the Loxahatchee River watershed and estuary.  Fifteen sites are sampled every month, and the remaining sites are sampled bi‐monthly (every  other month).  The purpose of this program is to identify long‐term trends, assess compliance  with  established  water  quality  targets,  and  establish  baseline  conditions  prior  to  the  modifications of freshwater inflows resulting from the Comprehensive Everglades Restoration  Project (CERP) and the Northwest Fork Restoration Plan.  This  report  provides  a  simplified  characterization  and  overview  of  water  quality  conditions in the Loxahatchee River for the reporting period October 2009 through September  2010, with historical comparisons.  A stoplight analysis (green/good, yellow/caution, red/poor)  evaluating several key parameters to compare the 2010 water quality data to the established  Target Period of 1998‐2002 indicated generally good water quality throughout the watershed.  These  findings  are  encouraging  because  flows  into  the  river  were  higher  than  previous  years,  particularly  during  the  dry  season.  While  increased  base  flows  into  the  river  are  beneficial,  protecting freshwater dependent species in downstream segments of the river from saltwater  intrusion,  increased  flows  may  lead  to  increased  nutrient  loading  to  the  system.  The  results  presented here suggest that increased flows in 2010 did not increase nitrogen and phosphorus  concentrations to detrimental levels, e.g., observed concentrations did not exceed EPA’s newly  published numeric nutrient criteria.  On a less encouraging note, the sampling sites throughout  the watershed continue to exhibit elevated chlorophyll and low dissolved oxygen values relative  to the targets and FDEP criteria.  While two river segments scored a “yellow/caution” level, our  assessment  of  all  sampling  sites  indicates  elevated  chlorophyll  throughout  the  watershed.   Further investigation into the causes and potential consequences of these findings is needed.   Lastly, several sites in the watershed have consistently scored poorly for more than three key  parameters. Targeted projects should be developed and implemented to improve water quality  at these sites. 

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Introduction  Since 1971 the Loxahatchee River District (LRD) has been fulfilling its mission to preserve  and  protect  the  Loxahatchee  River  through  an  innovative  wastewater  treatment  and  reuse  program  and  an  active  water  quality  monitoring  program.    LRD  staff  have  monitored  water  quality in the surface waters of the Loxahatchee River and associated waters (see Figure 1) in  an  effort  to  document  the  condition  and  ecological  health  of  the  river  and  to  determine  the  location  and  extent  of  water  quality  issues  that  need  to  be  addressed.    Over  these  past  35  years, the Loxahatchee River District has contributed significantly to the understanding of the  ecology  of  this  river  (see  http://www.loxahatcheeriver.org/reports.php).  While  numerous  reports  have  been  written  regarding  the  Loxahatchee  River,  perhaps  none  are  as  comprehensive  as  the  Restoration  Plan  for  the  Northwest  Fork  of  the  Loxahatchee  River  (SFWMD  2006).  This  document  characterizes  the  watershed,  discusses  various  restoration  alternatives, and identifies the preferred restoration flow scenario.  In particular, Table 10‐1 of  the  restoration  plan  includes  the  water  quality  targets  for  the  marine  (salinity  >30  ppt),  polyhaline (salinity 18 – 30 ppt), meso/oligohaline (salinity 5 – 18 / 0.5 ‐ 5 ppt), wild and scenic  (salinity  0.09 (75% of NNC Limit) and 0.12 (NNC Limit)

Color Coded By Loxahatchee River District Targets from 1998 ‐ 2002 River Analysis Zone Site 1998‐2002 2003 2004 2005 Marine

Brackish Trib

Meso/Oligohaline

Polyhaline

10 0.017 0.012 0.012 0.043 20 0.013 0.008 0.010 0.034 25 0.019 0.014 0.012 0.022 30 0.030 0.022 0.027 0.031 32 0.029 40 0.022 0.015 0.013 0.031 * Color Code ‐ Yellow (>0.033 and 0.043 35 0.034 0.029 0.029 0.032 55 0.042 0.037 0.049 0.042 71 0.048 0.041 0.052 0.044 73 0.055 0.049 0.066 0.052 75 107 0.208 0.179 0.232 0.115 * Color Code ‐ Yellow (>0.080 and 0.150 62 0.049 0.045 0.062 0.050 63 0.054 0.055 0.062 0.059 64 0.053 0.062 0.065 0.057 65 0.056 0.064 0.066 0.055 * Color Code ‐ Yellow (>0.066 and 0.081 42 0.031 0.028 51 0.027 0.020 0.026 0.030 60 0.037 0.030 0.035 0.038 72 0.041 0.032 0.042 0.043 * Color Code ‐ Yellow (>0.044 and 0.070

2006

2007

2008 0.051 0.060 0.046 0.043 0.026 0.027 0.038 0.350 0.058 0.086 0.063 0.080 0.039 0.074 0.051 0.107 0.035 0.036 0.050

2008

2009 0.061 0.051 0.053 0.041 0.024 0.040 0.028 0.587 0.058 0.085 0.089 0.223 0.040 0.069 0.078 0.108 0.055 0.102 0.067

2009

2010 0.056 0.044 0.047 0.038 0.027 0.027 0.034 0.492 0.065 0.069 0.068 0.076 0.040 0.057 0.068 0.144 0.064 0.055 0.040

2010

0.013 0.010 0.022 0.033 0.029 0.023

0.009 0.004 0.013 0.024 0.019 0.008

0.016 0.008 0.015 0.021 0.020 0.019

0.014 0.011 0.013 0.022 0.022 0.013

0.014 0.008 0.012 0.027 0.023 0.015

0.030 0.045 0.047 0.049 0.091

0.022 0.043 0.031 0.040 0.067 0.107

0.026 0.039 0.046 0.065 0.079 0.101

0.024 0.040 0.034 0.048 0.074 0.110

0.023 0.040 0.044 0.047 0.088 0.118

0.051 0.059 0.065 0.068

0.056 0.062 0.064 0.072

0.057 0.064 0.064 0.063

0.048 0.058 0.062 0.061

0.052 0.069 0.066 0.066

0.025 0.028 0.041 0.037

0.021 0.016 0.056 0.031

0.024 0.023 0.038 0.038

0.018 0.023 0.031 0.030

0.026 0.024 0.037 0.035

 

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Table 6. Summary of annual geometric mean for chlorophyll a by sample station, color coded by 1998‐ 2002 target values, Loxahatchee River, Florida. 

FW Canal

Brackish Trib

FW Tributaries

Wild &  Scenic

Meso/Oligo haline

Polyhaline

Marine

Clorophyll a Color Coded By Loxahatchee River District Targets from 1998 ‐ 2002 Zone Site 1998‐2002 2003 2004 2005

10 1.9 2.3 2.3 3.3 20 1.5 1.8 1.9 2.9 25 2.8 4.0 3.4 4.7 30 4.4 6.0 8.9 6.3 32 4.7 40 2.6 3.5 2.7 4.1 * Color Code ‐ Yellow (>4.2 and 6.9 42 4.5 7.2 51 3.7 5.6 10.3 7.7 60 4.2 6.8 4.0 10.6 72 9.9 15.7 13.4 17.0 * Color Code ‐ Yellow (>9.3 and 14.5 62 4.1 6.9 6.2 7.6 63 4.2 8.8 4.6 7.6 4.0 10.3 3.8 7.6 64 65 3.7 7.5 4.5 5.3 * Color Code ‐ Yellow (>5.8 and 8.3 66 3.5 3.8 3.6 4.6 67 2.2 1.2 1.3 4.0 68 1.8 1.3 1.1 3.2 69 2.6 3.7 2.8 5.2 * Color Code ‐ Yellow (>4.4 and 8.3 81 5.0 10.5 3.8 6.4 86 87 88 100 2.8 3.2 2.3 3.7 106 4.4 6.7 9.9 4.0 108 * Color Code ‐ Yellow (>8.0 and 12.8 35 3.4 3.8 7.5 8.0 55 5.6 8.4 4.6 13.8 9.9 16.2 71 7.3 9.6 73 8.4 16.9 14.2 22.0 75 107 3.6 5.4 4.4 14.4 * Color Code ‐ Yellow (>8.9 and 13.7 59 6.3 13.3 2.5 6.0 92 4.5 10.1 3.6 8.4 95 3.1 4.5 3.8 6.4 101 10.6 27.3 10.8 13.5 104 11.3 11.7 9.7 21.1 105 3.5 3.6 2.4 4.5 111 19.1 9.0 7.1 112 16.2 12.3 6.6 * Color Code ‐ Yellow (>11.0 and 26.5

2006

2007

2008

2009

2010

0.9 0.9 2.5 4.6 4.3 2.0

1.0 0.5 1.7 5.4 4.9 2.2

2.4 3.4 3.7 8.4 7.3 3.9

1.6 1.2 1.8 5.6 5.5 2.4

2.0 1.1 2.2 7.9 5.7 2.6

3.0 3.2 5.8 6.5

5.6 4.2 4.9 13.3

6.8 6.0 7.4 12.8

4.4 5.0 8.4 11.7

7.1 5.4 7.3 14.8

6.9 5.3 4.0 3.1

5.6 5.6 3.2 4.7

8.8 8.9 8.1 5.6

9.4 8.7 7.0 8.5

8.1 7.9 8.5 5.6

3.0 1.6 1.5 2.1

4.1 3.7 2.8 5.7

1.9 3.5 4.1 7.1

5.4 3.8 3.2 9.6

3.2 2.3 3.0 8.6

2.4

12.5

1.4 5.2 5.2

4.0 4.0 3.3

6.9 10.0 11.2 49.5 2.7 10.4 7.5

7.0 12.4 10.3 48.2 3.1 7.3 4.6

9.0 12.2 12.6 19.5 2.9 5.5 3.5

4.5 5.0 6.2 5.8

5.5 11.2 10.5 11.1

5.7

5.0

8.5 5.3 12.3 17.8 16.0 4.0

6.0 10.1 11.3 12.6 11.6 4.0

7.9 8.7 12.6 15.2 20.1 7.0

15.7 3.4 2.0 8.3 7.7 2.3 5.2 8.5

6.8 9.1 10.0 13.9 3.4 1.2 9.4 7.0

10.1 7.3 8.4 7.1 17.3 2.7 7.3 9.8

14.5 10.9 11.0 9.8 20.0 4.0 12.1 7.0

11.9 11.0 7.8 21.6 12.8 4.4 9.6 5.5

 

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Table  7.  Summary  of  annual  geometric  mean  for  dissolved  oxygen  by  sample  station,  color  coded  by  FDEP’s criteria for surface waters of the State of Florida, Loxahatchee River, Florida. 

FW Canal

Brackish Trib

FW Tributaries

Wild &  Scenic

Meso/Oligo Polyhaline haline

Marine

Dissolved Oxygen (mg/l) Color Coded By FDEP Criteria for Class III Florida Waters Zone Site 1998‐2002 2003 2004 10 6.49 6.33 6.13 20 6.66 6.63 6.41 25 6.62 6.33 6.07 30 6.00 5.96 5.80 32 40 6.65 6.53 6.36 42 6.50 51 6.25 5.91 5.80 60 6.20 5.86 6.27 72 6.16 5.31 5.48 62 5.40 5.12 4.86 63 5.14 4.73 3.56 64 5.22 4.75 3.21 65 4.99 3.81 2.91 66 5.63 5.46 4.88 67 5.67 5.40 4.55 68 5.75 5.64 6.67 69 4.41 4.08 5.00 81 6.73 6.42 6.00 86 87 88 100 6.17 6.24 5.91 106 3.68 3.53 4.66 108 35 5.61 5.50 5.81 55 4.94 3.51 3.67 71 5.28 4.64 4.18 73 4.86 4.30 3.75 75 107 4.40 2.90 5.07 59 0.50 0.53 0.49 92 5.26 4.55 5.16 95 5.30 4.73 4.29 101 0.74 0.58 1.77 104 6.33 4.77 6.72 105 4.69 3.12 5.68 111 2.18 1.86 112 0.81 1.32 * Color Code ‐ Yellow (> 3.0 and /= 0.995 90 - 110 80 - 120 [0 - 10] [85-115] 28 days SM4500-NH3 C every10 samples bracket one prior LCS in dup everyevery 10 samples every 10 samples w /H2SO4 Titrimetric less than LOQ samples to sample analysis10 samples + end or matrix set or matrix set TKN 1 pre- + 0.2 6 to >/= 0.995 90 - 110 90 - 110 [0 - 20] 90 - 110 28 days EPA 351.2 every 10 samples bracket one prior LCS in dup everyevery 10 samples every 10 samples w /H2SO4 Block, FIA less than LOQ samples to sample analysis10 samples + end or matrix set or matrix set Nitrate+Nitrate-N low 1 pre- + 0.005 6 to >/= 0.995 90 - 110 90 -110 [0 - 20] 90 -110 48 hours EPA 353.2 every 10 samples bracket one prior LCS in dup everyevery 10 samples every 10 samples no acid Cd Reduc, FIA less than LOQ samples to sample analysis10 samples + end or matrix set or matrix set filter Nitrate+Nitrate-N high 1 pre- + 0.02 6 to >/= 0.995 90 - 110 90 -110 [0 - 14] 90 -110 28 days EPA 353.2 every 10 samples bracket one prior LCS in dup everyevery 10 samples every 10 samples w /H2SO4 Cd Reduc, FIA less than LOQ samples to sample analysis10 samples + end or matrix set or matrix set filter Ortho-Phosphate 1 pre- + 0.003 6 to >/= 0.995 90 - 110 80 -120 [0 - 20] [90 - 110] 48 hours SM4500-P F every 10 samples bracket 98 -102 one prior LCS in dup everyevery 10 samples every 10 samples no acid or matrix set filter FIA less than LOQ samples published o sample analysis10 samples + end or matrix set Ortho-Phosphate 1 pre- + 0.003 6 to >/= 0.995 90 - 110 80 -120 [0 - 20] [90 - 110] 48 hours SM4500-P E every 10 samples bracket 98 -102 one prior LCS in dup everyevery 10 samples every 10 samples no acid Color, Ascorbic less than LOQ samples published o sample analysis10 samples + end or matrix set or matrix set filter Total Phosphorus low 1 pre- + 0.002 6 to >/= 0.995 90 - 110 80 -120 [0 - 10] [85 - 115] 28 days SM4500-P E every 10 samples bracket 98 -102 one prior LCS in dup everyevery 10 samples every 10 samples w /H2SO4 Color, Ascorbic less than LOQ samples published o sample analysis10 samples + end or matrix set or matrix set Total Phosphorus high 1 pre- + 0.005 6 to >/= 0.995 90 - 110 80 -120 [0 - 20] [85 - 115] 28 days SM4500-P E every 10 samples bracket 98 -102 one prior LCS in dup everyevery 10 samples every 10 samples w /H2SO4 Color, Ascorbic less than LOQ samples published o sample analysis10 samples + end or matrix set or matrix set BOD 1 dil. H202.0 2 GGA 75 - 125 75 - 125 75 - 125 [0 - 30] [70 - 130] 48 hours SM5210B 1 seed Bk published one prior every 10 samplesevery 10 samples every 10 samples on ice 5 day, 20 C every 10 samples to sample analysis or at end or matrix set or matrix set NOTE: Must meet 2.0 mg/L minimum DO depletion (initial minus final) and 1.0 mg/L residual (final) DO for each test bottle. CBOD 1 dil. H202.0 2 GGA 75 - 125 75 - 125 75 - 125 [0 - 30] [70 - 130] 48 hours SM5210B 1 seed Bk published published one prior every 10 samplesevery 10 samples every 10 samples on ice 5 day, 20 C every 10 samples in method o sample analysis or at end or matrix set or matrix set NOTE: Must meet 2.0 mg/L minimum DO depletion (initial minus final) and 1.0 mg/L residual (final) DO for each test bottle. Alkalinity 1 pre- + 1 min of 2 >/= 0.995 90 - 110 80 -120 [0 - 5] [85 - 115] 14 days SM2320B every 10 samples bracket one prior every 10 samplesevery 10 samples every 10 samples on ice Titrimetric, pH 4.5 less than LOQ samples to sample analysis or at end or matrix set or matrix set Chloride 1 pre- + 2 min of 2 >/= 0.995 90 - 110 80 -120 [0 - 4] [80 - 120] 28 days SM4500Cl- B every 10 samples bracket one prior every 10 samplesevery 10 samples every 10 samples on ice Argentometric less than LOQ samples to sample analysis or at end or matrix set or matrix set Conductivity 1 pre- + 2 min of 2 95-105 95-105 95-105 [0 - 2] N/A 28 days EPA 120.1 every 10 sampl umhos/cm to bracket one prior every 10 samplesevery 10 samples on ice Lab Meter less than LOQ samples to sample analysis or at end or matrix set TDS 1 pre- + 10 1 [93 - 103] [93 - 103] N/A [0 - 6] N/A 7 days SM2540C every 10 samples every 10 samples on ice Gravimetric, 180 C less than LOQ or matrix set NOTE: Dried to constant w eight-- w hen w eight change is less than 0.005 gm. NOTE: Choose sample size to yield less than 200 mg residue. TSS 1 pre- + 1 1 [80 - 120] [80 - 120] N/A [0 - 45] N/A 7 days SM2540D every 10 samples every 10 samples on ice Gravimetric, 104 C less than LOQ or matrix set NOTE: Dried to constant w eight-- w hen w eight change is less than 0.005 gm. NOTE: Choose sample size to yield betw een 2.5 & 200 mg residue and complete filtration time w ithin 10 min. Sulfate 1 pre- + 5 12 >/= 0.995 90 - 110 90 -110 [0 - 20] 90 -110 28 days EPA 375.2 every 10 samples to bracket one prior LCS in dup everyevery 10 samples every 10 samples on ice Color, MTB, FIA less than LOQ samples to sample analys10 samples or end or matrix set or matrix set Turbidity 1 DI H2O 0.1 NTU 4 formazin 95 - 105 95 - 105 95 - 105 [0 - 5] N/A 48 hours EPA 180.1 every 20 samples quarterly 2 gelex stds to 1 gelex every 10every 10 samples on ice Turbidimeter less than LOQ bracket analysis samples or at end or matrix set pH N/A N/A 2 or 3 to 95 - 105 +/- 0.2 units +/- 0.2 units 0-5 N/A analyze EPA 150.1 bracket % efficiency immediately Lab Meters samples of electrode DO 1 initial +/- 0.5 mg/L 95 - 105 analyze EPA 360.1 N/A N/A Water With chart N/A 1 end Water N/A N/A immediately Field & Lab meters Sat air Sat air Chlorophyll a 1 pre 1 1 N/A none N/A 0 - 30 N/A 21 days filter/freeze Color 1 pre 5 1 N/A none N/A 0-5 N/A 48 hours filter/on ice PARAMETER/ METHOD

BLANK (mg/L)

LOQ (mg/L)

# OF INITIAL STDS N/A

INITIAL CALIB CORR COEF OR % R N/A

2ND STD %R N/A

CONTINUING CALIB (LCS) %R N/A

 

48

    Appendix E – Parameter & Station Listing   Parameters

TOC Station

Date Time Sample Depth Tide Stage Alkalinity Ammonia Chlorophyll-a corrected Chlorophyll-a uncorrected Color Dissolved Oxygen Dissolved Oxygen % Saturation Fecal Coliforms Light % at 1 meter Light % at 2 meter Light Attenuation Nitrate+Nitrite Organic Nitrogen Orthophosphate pH Salinity Secchi Disk Depth Specific Conductance Temperature Total Kjeldahl Nitrogen Total Nitrogen Total Organic Carbon Total Phosphorus Total Suspended Solids Turbidity

10 * 20 * 25 * 30 * 32 * 40 * 51 * 60 * 62 * 63 * 64 * 65 * 67 * 68 * 69 * 72 * 74 75 81 * 86 * 87 * 88 usually dry 92 95 100 101 104 105 107 108 111 112

* * * * * * *

Ammonia Historical * *

Current

*

* *

* *

* * *

* *

* * * * * *

* * * *

* * * * * * * * * * *

* * * *

Notes: All the parameters listed are analyzed on all the samples except for TOC and Ammonia. In 2009 several ammonia stations were discontinued at the marine stations because occurance is rare; facilitated additional freshwater stations.

49

            Appendix F – Quality Control Summary  Note: ‘I’, ‘P’ and ‘U’ qualifier codes not included

Site # 10 10 62 62 65 65 67 67 69 69 72 72 92 92 92 92 95 95 100 101 106 106 108 108 111 112 10 20 25 30 32 35 40 42 51 55 71 72 73 74 74 75 67 95 107 95 10 20 25 30 32 35 40 42 51 55 59 71 72 72 73 73 74 74 75 75 75 101 101 101 106 108 111 111

Date 10/21/2009 10/21/2009 10/21/2009 10/21/2009 10/21/2009 10/21/2009 10/21/2009 10/21/2009 10/21/2009 10/21/2009 10/21/2009 10/21/2009 10/21/2009 10/21/2009 10/21/2009 10/21/2009 10/21/2009 10/21/2009 10/21/2009 11/9/2009 11/9/2009 11/9/2009 11/9/2009 11/9/2009 11/9/2009 11/9/2009 11/16/2009 11/16/2009 11/16/2009 11/16/2009 11/16/2009 11/16/2009 11/16/2009 11/17/2009 11/17/2009 11/17/2009 11/17/2009 11/17/2009 11/17/2009 11/17/2009 11/17/2009 11/17/2009 11/24/2009 11/24/2009 11/24/2009 12/16/2009 1/19/2010 1/19/2010 1/19/2010 1/19/2010 1/19/2010 1/19/2010 1/19/2010 1/20/2010 1/20/2010 1/20/2010 1/20/2010 1/20/2010 1/20/2010 1/20/2010 1/20/2010 1/20/2010 1/20/2010 1/20/2010 1/20/2010 1/20/2010 1/20/2010 1/20/2010 1/20/2010 1/20/2010 1/20/2010 1/20/2010 1/20/2010 1/20/2010

Time 1259 1259 1153 1153 1111 1111 1021 1021 915 915 1227 1227 930 930 930 930 1030 1030 1030 849 813 813 837 837 903 930 1025 1010 940 1118 1105 1135 1045 1007 950 931 1040 1020 1031 1140 1140 1128 1000 1113 909 1107 1030 1000 937 1137 1120 1150 1053 1000 1045 1025 1103 928 949 949 938 938 1136 1136 913 913 913 1023 1023 1023 937 958 1038 1038

Analyte TKN TKN TKN TKN TKN TKN TKN TKN TKN TKN TKN TKN NH3 ortho P TKN TKN TKN TKN TKN CHL A CHL A ortho P CHL A ortho P CHL A CHL A CHL A CHL A CHL A CHL A CHL A CHL A CHL A CHL A CHL A CHL A CHL A CHL A CHL A CHL A TKN CHL A TKN NH3 Total P Fecal Alk Alk Alk Alk Alk Alk Alk Alk Alk Alk Alk Alk Alk NH3 Alk NH3 Alk NH3 Alk CHL A NH3 Alk TSS Turb Alk Alk Alk NH3

Appendix F - Quality Control Summary Method Code Data Qualifier Issue EPA351.2 J.3A+ Spike recovery above acceptable QC limits EPA351.2 V Analyte detected in the field blank EPA351.2 J.3A+ Spike recovery above acceptable QC limits EPA351.2 V Analyte detected in the field blank EPA351.2 J.3A+ Spike recovery above acceptable QC limits EPA351.2 V Analyte detected in the field blank EPA351.2 J.3A+ Spike recovery above acceptable QC limits EPA351.2 V Analyte detected in the field blank EPA351.2 J.3ASpike recovery below acceptable QC limits EPA351.2 V Analyte detected in the field blank EPA351.2 J.3ASpike recovery below acceptable QC limits EPA351.2 V Analyte detected in the field blank SM4500NH3C 18th ed J.3P % RPD of duplicates outside acceptable QC limits EPA365.2 J.3P % RPD is outside acceptable QC limits EPA351.2 J.3ASpike recovery below acceptable QC limits EPA351.2 V Analyte detected in the field blank EPA351.2 J.3ASpike recovery below acceptable QC limits EPA351.2 V Analyte detected in the field blank EPA351.2 V Analyte detected in the field blank SM10200-H Q Analyzed beyond acceptable hold time SM10200-H Q Analyzed beyond acceptable hold time EPA365.2 J.1+ % Recovery of standard is higher than acceptable QC limits SM10200-H Q Analyzed beyond acceptable hold time EPA365.2 J.1+ % Recovery of standard is higher than acceptable QC limits SM10200-H Q Analyzed beyond acceptable hold time SM10200-H Q Analyzed beyond acceptable hold time SM10200-H Q Analyzed beyond acceptable hold time SM10200-H Q Analyzed beyond acceptable hold time SM10200-H Q Analyzed beyond acceptable hold time SM10200-H Q Analyzed beyond acceptable hold time SM10200-H Q Analyzed beyond acceptable hold time SM10200-H Q Analyzed beyond acceptable hold time SM10200-H Q Analyzed beyond acceptable hold time SM10200-H Q Analyzed beyond acceptable hold time SM10200-H Q Analyzed beyond acceptable hold time SM10200-H Q Analyzed beyond acceptable hold time SM10200-H Q Analyzed beyond acceptable hold time SM10200-H Q Analyzed beyond acceptable hold time SM10200-H Q Analyzed beyond acceptable hold time SM10200-H Q Analyzed beyond acceptable hold time EPA351.2 J.3ASpike recovery below acceptable QC limits SM10200-H Q Analyzed beyond acceptable hold time EPA351.2 J.3A+ Spike recovery above acceptable QC limits SM4500NH3C 18th ed J.3ASpike recovery below acceptable QC limits EPA365.2 J.3A+ RPD of duplicates higher than acceptable QC limits SM9222D B Colony count higher than acceptable range SM2320B Q Samples analyzed beyond acceptable hold time SM2320B Q Samples analyzed beyond acceptable hold time SM2320B Q Samples analyzed beyond acceptable hold time SM2320B Q Samples analyzed beyond acceptable hold time SM2320B Q Samples analyzed beyond acceptable hold time SM2320B Q Samples analyzed beyond acceptable hold time SM2320B Q Samples analyzed beyond acceptable hold time SM2320B Q Samples analyzed beyond acceptable hold time SM2320B Q Samples analyzed beyond acceptable hold time SM2320B Q Samples analyzed beyond acceptable hold time SM2320B Q Samples analyzed beyond acceptable hold time SM2320B Q Samples analyzed beyond acceptable hold time SM2320B Q Samples analyzed beyond acceptable hold time SM4500NH3C 18th ed V Analyte detected in the method blank SM2320B Q Samples analyzed beyond acceptable hold time SM4500NH3C 18th ed V Analyte detected in the method blank SM2320B Q Samples analyzed beyond acceptable hold time SM4500NH3C 18th ed V Analyte detected in the method blank SM2320B Q Samples analyzed beyond acceptable hold time SM10200-H J.3P RPD of duplicate outside acceptable QC limits SM4500NH3C 18th ed V Analyte detected in the method blank SM2320B Q Samples analyzed beyond acceptable hold time SM2540D Q Sample analyzed beyond acceptable hold time EPA180.1 Q Sample analyzed beyond acceptable hold time SM2320B Q Samples analyzed beyond acceptable hold time SM2320B Q Samples analyzed beyond acceptable hold time SM2320B Q Samples analyzed beyond acceptable hold time SM4500NH3C 18th ed V Analyte detected in the method blank Page 1 of 4

Site # 112 112 60 62 65 67 68 69 69 81 81 86 86 87 87 92 92 95 95 100 104 105 105 107 107 69 92 95 95 35 42 60 62 63 64 65 66 67 67 69 100 59 59 101 106 108 111 112 62 62 62 81 100 100 101 101 111 112 40 73 75 75 60 62 65 67 69 72 92 95 100 10 20 25

Date 1/20/2010 1/20/2010 1/27/2010 1/27/2010 1/27/2010 1/27/2010 1/27/2010 1/27/2010 1/27/2010 1/27/2010 1/27/2010 1/27/2010 1/27/2010 1/27/2010 1/27/2010 1/27/2010 1/27/2010 1/27/2010 1/27/2010 1/27/2010 1/27/2010 1/27/2010 1/27/2010 1/27/2010 1/27/2010 2/16/2010 2/16/2010 2/16/2010 2/16/2010 3/17/2010 3/18/2010 3/22/2010 3/22/2010 3/22/2010 3/22/2010 3/22/2010 3/22/2010 3/22/2010 3/22/2010 3/22/2010 3/22/2010 3/23/2010 3/23/2010 3/23/2010 3/23/2010 3/23/2010 3/23/2010 3/23/2010 4/15/2010 4/15/2010 4/15/2010 5/12/2010 5/12/2010 5/12/2010 5/13/2010 5/13/2010 5/13/2010 5/13/2010 5/18/2010 5/19/2010 5/19/2010 5/19/2010 6/29/2010 6/29/2010 6/29/2010 6/29/2010 6/29/2010 6/29/2010 6/29/2010 6/29/2010 6/29/2010 7/7/2010 7/7/2010 7/7/2010

Time 1053 1103 1258 1239 1147 1053 947 1003 1003 1338 1338 1322 1322 1315 1315 1202 1202 1214 1214 1105 1128 1038 1038 925 925 934 1011 1055 1055 1109 1031 1248 1228 1212 1159 1132 1109 1042 1042 1010 1054 905 905 825 741 803 840 855 1145 1145 1145 1220 1019 1019 920 920 945 1020 1104 1003 907 907 1310 1133 1038 950 910 1323 936 1028 1000 1030 1015 943

Analyte Alk NH3 NH3 NH3 NH3 NH3 TKN NH3 TKN NH3 TKN NH3 TKN NH3 TKN NH3 TKN NH3 TKN NH3 TKN NH3 TKN NH3 TKN TKN TKN CHL A TKN TKN CHL A TKN TKN TKN TKN TKN TKN NH3 TKN NO2+NO3 TKN CHL A TKN TKN TKN TKN TKN TKN NH3 NH3 TKN TKN NH3 ortho P NO2+NO3 ortho P NH3 NH3 TP ortho P NH3 ortho P TKN TKN TKN TKN TKN TKN TKN TKN TKN Total P Total P Total P

Appendix F - Quality Control Summary Method Code Data Qualifier Issue SM2320B Q Samples analyzed beyond acceptable hold time SM4500NH3C 18th ed V Analyte detected in the method blank SM4500NH3C 18th ed V Analyte detected in the method blank SM4500NH3C 18th ed V Analyte detected in the method blank SM4500NH3C 18th ed V Analyte detected in the method blank SM4500NH3C 18th ed V Analyte detected in the method blank EPA351.2 J.3P RPD of duplicate outside acceptable QC limits SM4500NH3C 18th ed V Analyte detected in the method blank EPA351.2 J.3P RPD of duplicate outside acceptable QC limits SM4500NH3C 18th ed V Analyte detected in the method blank EPA351.2 J.3P RPD of duplicate outside acceptable QC limits SM4500NH3C 18th ed V Analyte detected in the method blank EPA351.2 J.3P RPD of duplicate outside acceptable QC limits SM4500NH3C 18th ed V Analyte detected in the method blank EPA351.2 J.3P RPD of duplicate outside acceptable QC limits SM4500NH3C 18th ed V Analyte detected in the method blank EPA351.2 J.3P RPD of duplicate outside acceptable QC limits SM4500NH3C 18th ed V Analyte detected in the method blank EPA351.2 J.3P RPD of duplicate outside acceptable QC limits SM4500NH3C 18th ed V Analyte detected in the method blank EPA351.2 J.3P RPD of duplicate outside acceptable QC limits SM4500NH3C 18th ed V Analyte detected in the method blank EPA351.2 J.3P RPD of duplicate outside acceptable QC limits SM4500NH3C 18th ed V Analyte detected in the method blank EPA351.2 J.3P RPD of duplicate outside acceptable QC limits EPA351.2 J.3A+ Spike recovery is higher than acceptable QC limits EPA351.2 J.3A+ Spike recovery is higher than acceptable QC limits SM10200-H J.3P RPD of duplicate outside acceptable QC limits EPA351.2 J.3A+ Spike recovery is higher than acceptable QC limits EPA351.2 J.3A+ Spike recovery is higher than acceptable QC limits SM10200-H J.3P RPD of duplicate outside acceptable QC limits EPA351.2 J.3ASpike recovery is lower than acceptable QC limits EPA351.2 J.3ASpike recovery is lower than acceptable QC limits EPA351.2 J.3ASpike recovery is lower than acceptable QC limits EPA351.2 J.3ASpike recovery is lower than acceptable QC limits EPA351.2 J.3ASpike recovery is lower than acceptable QC limits EPA351.2 J.3ASpike recovery is lower than acceptable QC limits SM4500NH3C 18th ed J.3P RPD of duplicate outside acceptable QC limits EPA351.2 J.3ASpike recovery is lower than acceptable QC limits EPA353.2 J.3A+ Spike recovery is higher than acceptable QC limits EPA351.2 J.3ASpike recovery is lower than acceptable QC limits SM10200-H J.3P RPD of duplicate outside acceptable QC limits EPA351.2 J.3A+ Spike recovery is higher than acceptable QC limits EPA351.2 J.3A+ Spike recovery is higher than acceptable QC limits EPA351.2 J.3A+ Spike recovery is higher than acceptable QC limits EPA351.2 J.3A+ Spike recovery is higher than acceptable QC limits EPA351.2 J.3A+ Spike recovery is higher than acceptable QC limits EPA351.2 J.3A+ Spike recovery is higher than acceptable QC limits SM4500NH3C 18th ed J.3P RPD of duplicate outside acceptable QC limits SM4500NH3C 18th ed J.3A+ Spike recovery is higher than acceptable QC limits EPA351.2 J.3ASpike recovery is lower than acceptable QC limits EPA351.2 J.3A+ Spike recovery is higher than acceptable QC limits SM4500NH3C 18th ed J.3P RPD of duplicate outside acceptable QC limits SM4500-P E J.3P RPD of duplicate outside acceptable QC limits EPA353.2 J.3ASpike recovery is lower than acceptable QC limits SM4500-P E J.3P RPD of duplicate outside acceptable QC limits SM4500NH3C 18th ed J.1+ Standard higher than acceptable QC limits SM4500NH3C 18th ed J.1+ Standard higher than acceptable QC limits SM4500-P E J.3P RPD of duplicate outside acceptable QC limits SM4500-P E J.1+ Standard higher than acceptable QC limits SM4500NH3C 18th ed J.1+ Standard higher than acceptable QC limits SM4500-P E J.1+ Standard higher than acceptable QC limits EPA351.2 J.3ASpike recovery is lower than acceptable QC limits EPA351.2 J.3ASpike recovery is lower than acceptable QC limits EPA351.2 J.3ASpike recovery is lower than acceptable QC limits EPA351.2 J.3ASpike recovery is lower than acceptable QC limits EPA351.2 J.3ASpike recovery is lower than acceptable QC limits EPA351.2 J.3ASpike recovery is lower than acceptable QC limits EPA351.2 J.3ASpike recovery is lower than acceptable QC limits EPA351.2 J.3ASpike recovery is lower than acceptable QC limits EPA351.2 J.3ASpike recovery is lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time SM4500-P E Q Sample analyzed beyond acceptable hold time SM4500-P E Q Sample analyzed beyond acceptable hold time Page 2 of 4

Site # 30 32 35 40 42 51 55 71 72 73 74 75 60 60 62 62 63 63 64 64 65 65 66 66 67 67 68 68 69 69 81 81 86 86 87 87 88 88 92 92 95 95 100 100 104 104 105 105 107 107 101 101 101 101 106 106 106 106 108 108 108 108 111 111 111 112 112 112 112 72 60 62 63 64

Date 7/7/2010 7/7/2010 7/7/2010 7/7/2010 7/8/2010 7/8/2010 7/8/2010 7/8/2010 7/8/2010 7/8/2010 7/8/2010 7/8/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/12/2010 7/20/2010 7/20/2010 7/20/2010 7/20/2010 7/20/2010 7/20/2010 7/20/2010 7/20/2010 7/20/2010 7/20/2010 7/20/2010 7/20/2010 7/20/2010 7/20/2010 7/20/2010 7/20/2010 7/20/2010 7/20/2010 7/20/2010 8/25/2010 9/8/2010 9/8/2010 9/8/2010 9/8/2010

Time 1125 1110 1140 1052 1129 1056 1030 1239 1151 1205 1323 1224 1221 1221 1205 1205 1147 1147 1134 1134 1113 1113 1055 1055 1030 1030 1004 1004 1023 1023 1309 1309 1219 1219 1211 1211 1258 1258 1127 1127 1139 1139 1040 1040 1103 1103 1035 1035 942 942 954 954 954 954 920 920 920 920 933 933 933 933 1006 1006 1006 1019 1019 1019 1019 1210 1131 1115 1059 1046

Analyte Total P Total P Total P Total P Total P Total P Total P Total P Total P Total P Total P Total P TKN Total P TKN Total P TKN Total P TKN Total P TKN Total P TKN Total P TKN Total P TKN Total P TKN Total P TKN Total P TKN Total P TKN Total P TKN Total P TKN Total P TKN Total P TKN Total P TKN Total P TKN Total P TKN Total P TKN NO2+NO3 Total P ortho P TKN NO2+NO3 Total P ortho P TKN NO2+NO3 Total P ortho P TKN Total P ortho P TKN NO2+NO3 Total P ortho P TKN TKN TKN TKN TKN

Appendix F - Quality Control Summary Method Code Data Qualifier Issue SM4500-P E Q Sample analyzed beyond acceptable hold time SM4500-P E Q Sample analyzed beyond acceptable hold time SM4500-P E Q Sample analyzed beyond acceptable hold time SM4500-P E Q Sample analyzed beyond acceptable hold time SM4500-P E Q Sample analyzed beyond acceptable hold time SM4500-P E Q Sample analyzed beyond acceptable hold time SM4500-P E Q Sample analyzed beyond acceptable hold time SM4500-P E Q Sample analyzed beyond acceptable hold time SM4500-P E Q Sample analyzed beyond acceptable hold time SM4500-P E Q Sample analyzed beyond acceptable hold time SM4500-P E Q Sample analyzed beyond acceptable hold time SM4500-P E Q Sample analyzed beyond acceptable hold time EPA351.2 J.3ASpike recovery is lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time EPA351.2 J.3ASpike recovery is lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time EPA351.2 J.3ASpike recovery is lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time EPA351.2 J.3ASpike recovery is lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time EPA351.2 J.3ASpike recovery is lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time EPA351.2 J.3ASpike recovery is lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time EPA351.2 J.3ASpike recovery is lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time EPA351.2 J.3ASpike recovery is lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time EPA351.2 J.3ASpike recovery is lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time EPA351.2 J.3ASpike recovery is lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time EPA351.2 J.3ASpike recovery is lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time EPA351.2 J.3ASpike recovery is lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time EPA351.2 J.3ASpike recovery is lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time EPA351.2 J.3ASpike recovery is lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time EPA351.2 J.3ASpike recovery is lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time EPA351.2 J.3ASpike recovery is lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time EPA351.2 J.3ASpike recovery is lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time EPA351.2 J.3ASpike recovery is lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time EPA351.2 J.3ASpike recovery is lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time EPA351.2 J.3ASpike recovery is lower than acceptable QC limits EPA353.2 J.1% Recovery of end standard lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time SM4500-P F V Analyte detected in the method blank EPA351.2 J.3A+ Spike recovery is higher than acceptable QC limits EPA353.2 J.1% Recovery of end standard lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time SM4500-P F V Analyte detected in the method blank EPA351.2 J.3ASpike recovery is lower than acceptable QC limits EPA353.2 J.1% Recovery of end standard lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time SM4500-P F V Analyte detected in the method blank EPA351.2 J.3ASpike recovery is lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time SM4500-P F V Analyte detected in the method blank EPA351.2 J.3ASpike recovery is lower than acceptable QC limits EPA353.2 J.1% Recovery of end standard lower than acceptable QC limits SM4500-P E Q Sample analyzed beyond acceptable hold time SM4500-P F V Analyte detected in the method blank EPA351.2 J.3A+ Spike recovery is higher than acceptable QC limits EPA351.2 J.3PA+ Matrix duplicate & spike recoveries higher than acceptable QC limits EPA351.2 J.3PA+ Matrix duplicate & spike recoveries higher than acceptable QC limits EPA351.2 J.3PA+ Matrix duplicate & spike recoveries higher than acceptable QC limits EPA351.2 J.3PA+ Matrix duplicate & spike recoveries higher than acceptable QC limits Page 3 of 4

Site # 65 66 67 100 108 72

Date 9/8/2010 9/8/2010 9/8/2010 9/8/2010 9/22/2010 9/23/2010

Time 1031 1009 946 957 914 1026

Analyte TKN TKN TKN TKN Total P TKN

Appendix F - Quality Control Summary Method Code Data Qualifier Issue EPA351.2 J.3PA+ Matrix duplicate & spike recoveries higher than acceptable QC limits EPA351.2 J.3PA+ Matrix duplicate & spike recoveries higher than acceptable QC limits EPA351.2 J.3PA+ Matrix duplicate & spike recoveries higher than acceptable QC limits EPA351.2 J.3PA+ Matrix duplicate & spike recoveries higher than acceptable QC limits SM4500-P E J.3P % RPD of matrix duplicate outside acceptable QC limits EPA351.2 J.3A% Recovery of matrix spike is lower than acceptable QC limits

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