USEPA National Watershed Protection Program NY/NJ Harbor Estuary Program USEPA Region 2 New York, New York. USEPA Contract EP-C

Transcription

1 USEPA National Watershed Protection Program NY/NJ Harbor Estuary Program USEPA Region 2, EVALUATION OF AMMONIA TOXICITY IN THE NY/NJ HARBOR WITHIN THE CONTEXT OF NITROGEN AND CARBON TMDL PLANNING FOR ATTAINMENT OF DISSOLVED OXYGEN STANDARDS USEPA Contract EP-C Prepared by HydroQual, Inc MacArthur Blvd. Mahwah, NJ Under sub-contract agreement with RTI International RTI International Subcontract September 20, 2010 RTIN B

2 TABLE OF CONTENTS Section Page EXECUTIVE SUMMARY INTRODUCTION Unionized Ammonia Standard Unionized Ammonia Standard DATA COMPILATION PRELIMINARY SCREENING LEVEL OF ANALYSIS NY AND NJ SE1, SE2, AND SE3 WATERS... 3 REFINED SCREENING LEVEL OF ANALYSIS ALL WATERS... 3 DETAILED LEVEL OF ANALYSIS ALL WATERS... 4 ph SENSITIVITY ANALYSIS... 5 CONCLUSIONS... 6 APPENDIX A PROBABILITY DISTRIBUTIONS RAW DATA BY STATION i

3 LIST OF FIGURES Figure Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Figure 12 Figure 13 Figure 14 Figure 15 Figure 16 Figure 17 Figure 18 Figure 19 Figure 20 Figure 21 Figure 22 Figure 23 Calculation Based on Data Only Standard Calculation Based on Data Only Standard Preliminary Calculation Using Total Ammonia Daily Maximum Compared to the Standard Planned Improvements Preliminary Calculation Using Total Ammonia Daily Average Compared to the Standard Planned Improvements Preliminary Calculation Using Total Ammonia Four Day Average Compared to the Standard Planned Improvements Preliminary Calculation Using Total Ammonia Thirty Day Average Compared to the Standard Planned Improvements Preliminary Calculation Using Total Ammonia Daily Maximum Compared to the Standard Plan Run Preliminary Calculation Using Total Ammonia Daily Average Compared to the Standard Plan Run Preliminary Calculation Using Total Ammonia Four Day Average Compared to the Standard Plan Run Preliminary Calculation Using Total Ammonia Thirty Day Average Compared to the Standard Plan Run Period of Record for All NYC Harbor Survey and NJHDG Stations Refined Calculation Using the HEP-Core Wide Maximum ph = 10.2 Daily Maximum Compared to the Standard Planned Improvements Refined Calculation Using the HEP-Core Wide Maximum ph = 10.2 Daily Average Compared to the Standard Planned Improvements Refined Calculation Using the HEP-Core Wide Maximum ph = 10.2 Four Day Average Compared to the Standard Planned Improvements Refined Calculation Using the HEP-Core Wide Maximum ph = 10.2 Thirty Day Average Compared to the Standard Planned Improvements Refined Calculation Using the HEP-Core Wide Maximum ph = 10.2 Daily Maximum Compared to the Standard Plan Run Refined Calculation Using the HEP-Core Wide Maximum ph = 10.2 Daily Average Compared to the Standard Plan Run Refined Calculation Using the HEP-Core Wide Maximum ph = 10.2 Four Day Average Compared to the Standard Plan Run Refined Calculation Using the HEP-Core Wide Maximum ph = 10.2 Thirty Day Average Compared to the Standard Plan Run Refined Calculation Using the HEP-Core Wide Average ph = 7.6 Daily Maximum Compared to the Standard Planned Improvements Refined Calculation Using the HEP-Core Wide Average ph = 7.6 Daily Average Compared to the Standard Planned Improvements Refined Calculation Using the HEP-Core Wide Average ph = 7.6 Four Day Average Compared to the Standard Planned Improvements Refined Calculation Using the HEP-Core Wide Average ph = 7.6 Thirty Day Average Compared to the Standard Planned Improvements ii

4 LIST OF FIGURES (Continued) Figure Figure 24 Figure 25 Figure 26 Figure 27 Figure 28 Figure 29 Figure 30 Figure 31 Figure 32 Figure 33 Figure 34 Figure 35 Figure 36 Figure 37 Figure 38 Figure 39 Figure 40 Figure 41 Figure 42 Figure 43 Figure 44 Refined Calculation Using the HEP-Core Wide Average ph = 7.6 Daily Maximum Compared to the Standard Plan Run Refined Calculation Using the HEP-Core Wide Average ph = 7.6 Daily Average Compared to the Standard Plan Run Refined Calculation Using the HEP-Core Wide Average ph = 7.6 Four Day Average Compared to the Standard Plan Run Refined Calculation Using the HEP-Core Wide Average ph = 7.6 Thirty Day Average Compared to the Standard Plan Run Ammonia Fraction Un-Ionized for a Range of HEP Waters ph, Temperature and Salinity Values Detailed Calculation Using Monthly Maximum ph Daily Maximum Compared to the Standard Planned Improvements Detailed Calculation Using Monthly Maximum ph Daily Average Compared to the Standard Planned Improvements Detailed Calculation Using Monthly Maximum ph Four Day Average Compared to the Standard Planned Improvements Detailed Calculation Using Monthly Maximum ph Thirty Day Average Compared to the Standard Planned Improvements Detailed Calculation Using Monthly Maximum ph Daily Maximum Compared to the Standard Plan Run Detailed Calculation Using Monthly Maximum ph Daily Average Compared to the Standard Plan Run Detailed Calculation Using Monthly Maximum ph Four Day Average Compared to the Standard Plan Run Detailed Calculation Using Monthly Maximum ph Thirty Day Average Compared to the Standard Plan Run Detailed Calculation Using Monthly Average ph Daily Maximum Compared to the Standard Planned Improvements Detailed Calculation Using Monthly Average ph Daily Average Compared to the Standard Planned Improvements Detailed Calculation Using Monthly Average ph Four Day Average Compared to the Standard Planned Improvements Detailed Calculation Using Monthly Average ph Thirty Day Average Compared to the Standard Planned Improvements Detailed Calculation Using Monthly Average ph Daily Maximum Compared to the Standard Plan Run Detailed Calculation Using Monthly Average ph Daily Average Compared to the Standard Plan Run Detailed Calculation Using Monthly Average ph Four Day Average Compared to the Standard Plan Run Detailed Calculation Using Monthly Average ph Thirty Day Average Compared to the Standard Plan Run iii

5 LIST OF TABLES Table Table 1 Table 2 Summary of Unionized Ammonia Standards Attainment Results for Planned Improvements Nitrogen Conditions at Several ph Conditions Summary of Unionized Ammonia Standards Attainment Results for Preliminary TMDL Plan Nitrogen Conditions at Several ph Conditions iv

6 EXECUTIVE SUMMARY Calculations have been performed using SWEM outputs and measured ph that project full compliance with States standards for un-ionized ammonia toxicity under the expected nitrogen concentrations associated with preliminary sub-regional TMDL plans currently under development by EPA and the States. It is expected that the promulgation of Harbor TMDLs for nitrogen and carbon for dissolved oxygen standards attainment will also result in attainment with unionized ammonia standards in HEP waters for average observed ph conditions. Calculations were performed in a tiered approach considering various assumptions related to prediction of unionized ammonia along a continuum of 100% unionized (absolute worst case) to a realistic prediction of the unionized fraction based on spatially and temporally varying salinity, temperature, and ph. The nature of the approach allowed for an understanding of the effect of ph on unionized ammonia standards attainment. Based on calculations with both field data and model results, under average observed ph conditions, all Harbor waters should achieve both acute and chronic unionized ammonia standards for the preliminary TMDL plan reduced nitrogen conditions; however, there are some areas of the Harbor having the potential for violating standards under observed elevated ph conditions. 1.0 INTRODUCTION Both the States of and promulgate numeric water quality standards for unionized ammonia. The numeric unionized ammonia standards include ph, temperature, and salinity dependences. The numeric unionized ammonia standards are applicable to the waters of the NY/NJ Harbor. A violation of the unionized ammonia standards should trigger a Section 303(d) listing. For both States, the most recent Section 303(d) lists were reviewed. The (d) list which was approved by EPA on June 29, 2010 does not include a listing of the waters of the NY/NJ Harbor for unionized ammonia. The (d) list included unionized ammonia violations in the Lower Passaic River and several of its tributaries (i.e., Saddle River and Second River) and in the Hackensack River and several of its tributaries (i.e., Overpeck Creek and Berry s Creek). The (d) list is anticipated to be ready later in September On this basis, there is a regulatory context for considering ammonia toxicity in at least portions of the NY/NJ Harbor during ongoing TMDL planning for nutrient reductions and dissolved oxygen standards attainment. The calculation of unionized ammonia concentration is a function of ph, temperature, salinity, ammonia and ammonium concentrations. The fraction unionized has been described by Hampson, 1977 based on the equation: Fraction Unionized = [1 + 10^(X + 324(298-T) + 415(P/T) ph)] -1 Where: P = 1 atmosphere 1

7 T = Temperature ( K) X = pka = I I = S ( S) -1 S = salinity (ppt) It is necessary to calculate the fraction unionized in order to translate SWEM outputs for ammonia to unionized ammonia for comparison to the and standards which are specified as unionized ammonia rather than as ammonia. 1.1 Unionized Ammonia Standard The waters in the NY/NJ Harbor are classified as SA, SB, SC, I, and SD. For all of these classifications, the numeric standard for ammonia (NH3) and ammonium (NH4+) nitrogen is 230 ug/l of unionized ammonia as ammonia. The standard is aquatic, acute based. In addition, for all but the SD waters (i.e., applies to SA, SB, SC, and I), there is an aquatic, chronic based standard of 35 ug/l of unionized ammonia as ammonia. 1.2 Unionized Ammonia Standard The waters in the NY/NJ Harbor are classified as FW2-NT, FW2-NT/SE2, SE1, SE2, and SE3. The applicable standards for unionized ammonia are derived in accordance with the formulas set forth in Table 1. standards are expressed as three hour averages and chronic standards are expressed as 30-day averages. Essentially, no violations of the standards shall be permitted, with the exception of very low flow conditions. In summary, the majority of the Harbor is SE1, SE2, and SE3 waters and needs to meet un-ionized ammonia below mg/l acute and 30 mg/l chronic. FW2-NT applies in the uppermost reaches of the Lower Passaic and Raritan Rivers and variable standards for FW2-NT waters need to be calculated based on ph and temperature. In the uppermost reaches of the Lower Passaic River, the more stringent of FW2-NT and SE2 criteria must be met. 2.0 DATA COMPILATION SWEM calculates time varying concentrations of temperature, salinity, and ammonia nitrogen, but does not calculate unionized ammonia or ph. SWEM ammonia outputs were converted to unionized ammonia using the equation of Hampson, 1977 presented above with SWEM calculations of temperature and salinity. These calculations can be performed with temporal and spatial variation. Unfortunately, SWEM does not calculate ph. For purposes of unionized ammonia concentration prediction, ph data from the NYCDEP Harbor Survey and the NJHDG routine monitoring data collection program were assembled. These data were used to determine the ph values for use in the refined and detailed analyses below. The NYCDEP CTD ph data were not included in this analysis due to some anomalous values. Where the necessary data were available, attainment of the acute and chronic standards for the measured conditions were determined strictly based on the data. Maps of compliance with both the acute and chronic standards are presented in Figures 1 and 2 respectively. 2

8 While non-attainment of the acute standard in Figure 1 may represent an actual violation of the standard, the comparison of individual grab samples (instantaneous) with the chronic standard (30 day average) presented in Figure 2 only indicates the potential for a problem and not a violation of the standard. In addition to the maps, Appendix A presents probability plots of the raw data used in the analysis on a station by station basis. Data displayed on Figure 1 show minimal acute standard non-attainment, less than 2% of the data collected at three discrete locations in the Hackensack River, Kill van Kull, and Raritan Bay are in non-compliance with the acute unionized ammonia standard. Data displayed on Figure 2 show limited potential violations of the chronic standard in less than 6% of the data collected at discrete locations in the Hackensack River, Newark Bay, the Kills, the Raritan River, Raritan Bay, and the Harlem River. Displays on the maps are accumulated over all depths sampled at a location. Figures 1 and 2 also indicate that sampling locations do not fully cover all Harbor waters. It is therefore desirable to make use of the greater spatial coverage afforded by SWEM outputs for un-ionized ammonia toxicity evaluations. Further, because the measurement-based results in Figures 1 and 2 are indicative of some level of non-compliance under current conditions, it is also desirable to assess compliance under a potential future with a nitrogen TMDL condition. 3.0 PRELIMINARY SCREENING LEVEL OF ANALYSIS NY AND NJ SE1, SE2, AND SE3 WATERS For the preliminary screening level calculations, total ammonia concentrations were compared to un-ionized ammonia standards. In other words, for a first level screen, ph, temperature, and salinity were ignored, and a worst case assumption of fraction unionized ammonia of 100% was made. SWEM outputs were saved at a daily interval, and the daily maxima and average were compared to the acute standards. Both 4 day and 30 day moving averages were determined from the daily averages for comparison to the chronic standards. The applicable standards were applied for each reach of HEP waters, applying the more conservative standard in shared waters. Using this extremely conservative approach did not eliminate any individual model grid cells within the HEP jurisdiction waters from consideration for further analysis under either of the Planned Improvements or Preliminary Sub-Regional TMDL Plans reduced nitrogen conditions evaluated. Figures 3 through 6 display maps of percent non-attainment for the acute standard applied to the daily maxima and averages, and the chronic standard applied to the 4 day and 30 day average concentrations, respectively, for the Planned Improvements reduced nitrogen conditions. Figures 7 through 10 display the same type of maps for the preliminary sub-regional TMDL Plans reduced nitrogen conditions. REFINED SCREENING LEVEL OF ANALYSIS ALL WATERS Since the preliminary screening level analysis, which included a worst case assumption, failed to identify Harbor regions for which unionized ammonia toxicity concerns could be comfortably dismissed, it was necessary to refine the screening calculations. In the refined screening level analysis, the maximum measured ph for the Harbor was used in the un- 3

9 ionized ammonia calculations. The maximum ph was used for the fraction un-ionized calculation as well as in the calculation of the fresh water, ph dependant standards for the Upper Passaic and Raritan River reaches. The temperature, salinity, and ammonia for the standard and un-ionized ammonia fraction calculations came from SWEM outputs. The maximum ph reported in the data sets from NYC DEP Harbor Survey and the NJHDG routine monitoring data collection program was used. Figure 11 shows the probability distributions for all of the ph data reported for all stations for the period of record (NYCDEP , NJHDG ). The maximum measured ph value was This value was then used for all standard and un-ionized ammonia fraction calculations along with SWEM calculations of temperature, salinity and ammonia to determine attainment of standards. For the chronic standard calculations in the NJ fresh water reaches, the standard varies over time as the ph and temperature change. In this case, the standard was calculated for each day. To determine attainment of the chronic standard on a 4 day average basis, the 4 day moving average of the un-ionized ammonia was compared to the 4 day moving average of the standard. Attainment of the chronic standard on a 30 day average basis was determined in the same manner. This somewhat refined screening approach only fully eliminated the fresh water section of the Raritan River from consideration for further analysis under Preliminary Sub-Regional TMDL Plans reduced nitrogen conditions, and partially under Planned Improvements conditions. All other reaches within the Harbor require further refinement to determine unionized ammonia standards attainment. Figures 12 through 19 repeat the maps from Figures 3 through 10 for the results using the maximum measured ph. Using the same approach and substituting the average ph of 7.6 into the calculations would result in all reaches attaining standards with the exception of the Hackensack River SE1 and SE2 reaches under Planned Improvements nitrogen conditions, and nearly (i.e., ignoring a few grid cells in Jamaica Bay) full attainment under Preliminary Sub-Regional TMDL Plans reduced nitrogen conditions. Figures 20 through 27 repeat the maps from Figures 3 through 10 for the results using the average measured ph. The differences in attainment, when using the maximum and average ph values, is not surprising given the range of the fraction un-ionized calculation between the average ph and maximum ph values. Figure 28 shows the fraction un-ionized calculated for the range of ph, temperature and salinity values measured throughout the Harbor. For the same temperature and salinity conditions, there is a factor of 20 to 185 times greater between the fraction un-ionized at a ph of 7.6 and DETAILED LEVEL OF ANALYSIS ALL WATERS For required comprehensive calculations, ph data were distributed across the SWEM computational grid using the closest station to represent the ph for each grid cell. The 4

10 maximum and mean for each month/station was calculated for the period of record to capture the seasonal variability in ph. Calculations using the maximum ph were performed first. Each model grid cell was assigned the monthly maximum ph value for the nearest station, varying on a monthly basis. fresh water standards were calculated based on the monthly maximum ph and model daily average temperature where applicable and un-ionized ammonia was calculated based on monthly maximum ph and model daily average temperature and salinity. Figures 29 through 36 repeat the maps from Figures 3 through 10 for the results using the monthly maximum ph from the nearest station. Using the detailed maximum ph data, there is considerable improvement in predicted standards attainment over using one Harbor-wide maximum ph value. Under preliminary TMDL plan reduced nitrogen conditions, the fresh water Raritan River reach fully attains both the acute and chronic standard and many of the other reaches approach full attainment. For the detailed analysis using the average ph, each model grid cell was assigned the monthly average ph value for the nearest station, varying on a monthly basis. fresh water standards were calculated based on the monthly average ph and model daily average temperature, where applicable. Un-ionized ammonia was calculated based on monthly average ph and model daily average temperature and salinity. Figures 37 through 44 repeat the results maps from Figures 3 through 10 instead using the monthly average ph from the nearest station. Using the detailed average ph data there is nearly full attainment of standards for Planned Improvements nitrogen conditions with the exception of the Hackensack River SE1 and SE2 waters. Under Preliminary TMDL Plan reduced nitrogen conditions, using the detailed monthly average ph, all HEP waters meet both acute and chronic standards. ph SENSITIVITY ANALYSIS Since the unionized ammonia calculation is so dependent upon ph, a ph sensitivity analysis was performed. ph was varied until each Harbor reach obtained full attainment of the unionized ammonia standards. The ph required for each reach to obtain full unionized ammonia standards attainment was estimated in increments of 0.5 for both the Planned Improvements nitrogen conditions and the Preliminary TMDL Plan nitrogen conditions. Once the ph required for full attainment in each Harbor reach was determined, the rank of that ph value within the distribution of ph values for the nearest station was calculated. These values are tabulated in Tables 1 and 2, along with the maximum percent nonattainment for each reach and ph/fraction unionized ammonia examined in the analysis. Table 1 has the results for Planned Improvements nitrogen conditions and Table 2 has the results for the preliminary TMDL plan nitrogen conditions. An example of the sensitivity analysis presented in Tables 1 and 2 is described here for the Passaic River SE3 reach under Planned Improvements (Table 1) nitrogen conditions. For the preliminary level of analysis, worst case 100% fraction unionized ammonia, the Passaic River SE3 reach would have 100% non-attainment. Under a refined level of analysis, using the Harbor-wide maximum ph of 10.2, the percent non-attainment would decrease to 99.98%. Under a further refined level of analysis, using the Harbor-wide average ph of 7.6, 5

11 the Passaic River SE3 reach would fully attain the standards. Under a detailed level of analysis, using the monthly maximum ph from the nearest station, the percent nonattainment would be 3.81%. Under the final detailed level of analysis, using the average ph from the nearest station, the reach would again fully attain the standards. These results suggest that the reach would attain standards between the local average and some ph value between local maximum and local average, approximately 8, in this case. Based on the ph data from the closest station, the Passaic River SE3 reach would obtain standards for 92.8% of the measured ph values. CONCLUSIONS For NY/NJ Harbor it appears that the attainment of unionized ammonia standards may be more dependent on ph than on the total nitrogen concentration. Based on both field data and model results, there are some areas of the Harbor having the potential for violating standards under elevated ph conditions, but under average ph conditions all Harbor waters achieve both acute and chronic standards for the preliminary TMDL plan reduced nitrogen conditions. The areas of the Harbor with the greatest potential for violating standards, based both on the data analysis and the model results, are: Hackensack River, Newark Bay, and northern Arthur Kill reaches waters near the confluence of Raritan River, Arthur Kill and Raritan Bay North River across from Manhattan The ongoing NYCDEP and NJHDG monitoring programs which simultaneously measure ph, temperature, salinity, and ammonia will be important to the States for making 303(d) listing decisions for unionized ammonia in the future if/when nitrogen and carbon TMDLs are implemented for attainment of dissolved oxygen standards. 6

12 FIGURES

13 Calculation Based on Data Only 1.40 Non-Attainment Standard

14 Calculation Based on Data Only 0 Non-Attainment Standard

15 Preliminary Calculation Using Total Ammonia 10 9 Non-Attainment Daily Maximum Compared to the Standard Planned Improvements

16 Preliminary Calculation Using Total Ammonia 10 9 Non-Attainment Daily Average Compared to the Standard Planned Improvements

17 Preliminary Calculation Using Total Ammonia 10 9 Non-Attainment Four Day Average Compared to the Standard Planned Improvements

18 Preliminary Calculation Using Total Ammonia 10 9 Non-Attainment Thirty Day Average Compared to the Standard Planned Improvements

19 Preliminary Calculation Using Total Ammonia 10 9 Non-Attainment Daily Maximum Compared to the Standard Plan Run

20 Preliminary Calculation Using Total Ammonia 10 9 Non-Attainment Daily Average Compared to the Standard Plan Run

21 Preliminary Calculation Using Total Ammonia 10 9 Non-Attainment Four Day Average Compared to the Standard Plan Run

22 Preliminary Calculation Using Total Ammonia 10 9 Non-Attainment Thirty Day Average Compared to the Standard Plan Run

23 Including all data Maximum Measured ph =10.2 Average Measured ph =7.6 Minimum Measured ph =3.5 Excluding data with Qualifiers Maximum Measured ph =10.2 Average Measured ph =7.5 Minimum Measured ph = Period of Record for All NYC Harbor Survey and NJHDG Stations 8.5 ph (standard units) Qualifier Surface No Yes Mid-Depth

24 Refined Calculation Using the HEP-Core Wide Maximum ph = Non-Attainment Daily Maximum Compared to the Standard Planned Improvements

25 Refined Calculation Using the HEP-Core Wide Maximum ph = Non-Attainment Daily Average Compared to the Standard Planned Improvements

26 Refined Calculation Using the HEP-Core Wide Maximum ph = Non-Attainment Four Day Average Compared to the Standard Planned Improvements

27 Refined Calculation Using the HEP-Core Wide Maximum ph = Non-Attainment Thirty Day Average Compared to the Standard Planned Improvements

28 Refined Calculation Using the HEP-Core Wide Maximum ph = Non-Attainment Daily Maximum Compared to the Standard Plan Run

29 Refined Calculation Using the HEP-Core Wide Maximum ph = Non-Attainment Daily Average Compared to the Standard Plan Run

30 Refined Calculation Using the HEP-Core Wide Maximum ph = Non-Attainment Four Day Average Compared to the Standard Plan Run

31 Refined Calculation Using the HEP-Core Wide Maximum ph = Non-Attainment Thirty Day Average Compared to the Standard Plan Run

32 Refined Calculation Using the HEP-Core Wide Average ph = Non-Attainment Daily Maximum Compared to the Standard Planned Improvements

33 Refined Calculation Using the HEP-Core Wide Average ph = 7.6 Non-Attainment Daily Average Compared to the Standard Planned Improvements

34 Refined Calculation Using the HEP-Core Wide Average ph = Non-Attainment Four Day Average Compared to the Standard Planned Improvements

35 Refined Calculation Using the HEP-Core Wide Average ph = Non-Attainment Thirty Day Average Compared to the Standard Planned Improvements

36 Refined Calculation Using the HEP-Core Wide Average ph = 7.6 Non-Attainment Daily Maximum Compared to the Standard Plan Run

37 Refined Calculation Using the HEP-Core Wide Average ph = 7.6 Non-Attainment Daily Average Compared to the Standard Plan Run

38 Refined Calculation Using the HEP-Core Wide Average ph = 7.6 Non-Attainment Four Day Average Compared to the Standard Plan Run

39 Refined Calculation Using the HEP-Core Wide Average ph = 7.6 Non-Attainment Thirty Day Average Compared to the Standard Plan Run

40 Ammonia Fraction Un-Ionized for a Range of HEP Waters ph, Temperature and Salinity Values Ammonia Fraction Un-Ionized Average ph = 7.6 Maximum ph = 10.2 Temp=35, Salt=0 Temp=35, Salt=35 Temp=20, Salt=0 Temp=20, Salt=35 Temp=10, Salt=0 Temp=10, Salt=35 Temp=0, Salt=0 Temp=0, Salt= ph (Standard Units)

41 Detailed Calculation Using Monthly Maximum ph 30 Non-Attainment Daily Maximum Compared to the Standard Planned Improvements

42 Detailed Calculation Using Monthly Maximum ph 30 Non-Attainment Daily Average Compared to the Standard Planned Improvements

43 Detailed Calculation Using Monthly Maximum ph 10 9 Non-Attainment Four Day Average Compared to the Standard Planned Improvements

44 Detailed Calculation Using Monthly Maximum ph 10 9 Non-Attainment Thirty Day Average Compared to the Standard Planned Improvements

45 Detailed Calculation Using Monthly Maximum ph Non-Attainment Daily Maximum Compared to the Standard Plan Run

46 Detailed Calculation Using Monthly Maximum ph 3.50 Non-Attainment Daily Average Compared to the Standard Plan Run

47 Detailed Calculation Using Monthly Maximum ph Non-Attainment Four Day Average Compared to the Standard Plan Run

48 Detailed Calculation Using Monthly Maximum ph 3 Non-Attainment Thirty Day Average Compared to the Standard Plan Run

49 Detailed Calculation Using Monthly Average ph 0 Non-Attainment Daily Maximum Compared to the Standard Planned Improvements

50 Detailed Calculation Using Monthly Average ph 0 Non-Attainment Daily Average Compared to the Standard Planned Improvements

51 Detailed Calculation Using Monthly Average ph 30 Non-Attainment Four Day Average Compared to the Standard Planned Improvements

52 Detailed Calculation Using Monthly Average ph 4 Non-Attainment Thirty Day Average Compared to the Standard Planned Improvements

53 Detailed Calculation Using Monthly Average ph Non-Attainment Daily Maximum Compared to the Standard Plan Run

54 Detailed Calculation Using Monthly Average ph Non-Attainment Daily Average Compared to the Standard Plan Run

55 Detailed Calculation Using Monthly Average ph Non-Attainment Four Day Average Compared to the Standard Plan Run

56 Detailed Calculation Using Monthly Average ph Non-Attainment Thirty Day Average Compared to the Standard Plan Run

57 TABLES

58 HEP Region Standard Preliminary Table 1. Planned Improvements Volume Weighted Non-Attainment (Maximum of and Values) Refined Detailed Maximum ph = 10.2 Average ph = 7.6 Monthly Maximum ph Monthly Average ph Maximum ph for 0% Non-Attainment Approximate ph ile Hackensack River NJ-SE % Hackensack River NJ-SE % Hackensack River NJ-SE % Passaic River NJ-FW2-NT/SE % Passaic River NJ-SE % Newark Bay NJ-SE % Raritan River NJ-FW2-NT N/A % Raritan River NJ-SE % Kill van Kull NJ-SE % Kill van Kull NJ-SE % Arthur Kill NJ-SE % Arthur Kill NJ-SE % Raritan Bay NJ-SE % Raritan Bay NJ-SE % Raritan Bay NJ-SC % Raritan Bay NY-I % Raritan Bay NY-SA % Raritan Bay NY-SB % Hudson TZ-Battery NJ-SE % Hudson TZ-Battery NJ-SE % Hudson TZ-Battery NY-SB % Hudson TZ-Battery NY-I % Upper Bay NJ-SE % Upper Bay NY-I % Lower Bay NY-I % Lower Bay NY-SB % Lower Bay NJ-SC % SummaryTable.xls ReachVWAvg 8/5/2010 1:06 PM

59 HEP Region Standard Preliminary Table 2. Plan Run (Step 5, 2/15/2010 memo) Volume Weighted Non-Attainment (Maximum of and Values) Refined Detailed Maximum ph = 10.2 Average ph = 7.6 Monthly Maximum ph Monthly Average ph Maximum ph for 0% Non-Attainment Approximate ph ile Hackensack River NJ-SE % Hackensack River NJ-SE % Hackensack River NJ-SE % Passaic River NJ-FW2-NT/SE % Passaic River NJ-SE % Newark Bay NJ-SE % Raritan River NJ-FW2-NT N/A % Raritan River NJ-SE % Kill van Kull NJ-SE % Kill van Kull NJ-SE % Arthur Kill NJ-SE % Arthur Kill NJ-SE % Raritan Bay NJ-SE % Raritan Bay NJ-SE % Raritan Bay NJ-SC % Raritan Bay NY-I % Raritan Bay NY-SA % Raritan Bay NY-SB % Hudson TZ-Battery NJ-SE % Hudson TZ-Battery NJ-SE % Hudson TZ-Battery NY-SB % Hudson TZ-Battery NY-I % Upper Bay NJ-SE % Upper Bay NY-I % Lower Bay NY-I % Lower Bay NY-SB % Lower Bay NJ-SC % SummaryTable.xls ReachVWAvg 8/5/2010 1:06 PM

60 APPENDIX A PROBABILITY DISTRIBUTIONS RAW DATA BY STATION

61 ph (standard units) Un-ionized ( 7.69 ) 5.56 ( 5.63 ) ( ) 1.85 ( 2.82 ) NJHDG, Hackensack River, Station #14 Upper Hackensack River (Cell 8,54)

62 3 3 ph (standard units) Un-ionized ( ) 0.93 ( 2.04 ) ( ) ( ) NJHDG, Hackensack River, Station #15 Upper Hackensack 2 (Cell 8,49)

63 3 3 ph (standard units) Un-ionized ( ) 0.90 ( ) ( ) ( ) NJHDG, Hackensack River, Station #16 Upper Hackensack 1 (Cell 8,47)

64 ph (standard units) Un-ionized ( ) ( ) NJHDG, Passaic River, Station #5 Dundee Dam (Cell 6,64)

65 ph (standard units) Un-ionized ( 6 ) ( ) NJHDG, Passaic River, Station #7 Union Avenue (Cell 6,60)

66 3 0 ph (standard units) Un-ionized ( ) ( ) NJHDG, Passaic River, Station #8 Rutgers Street (Cell 6,56)

67 3 1 ph (standard units) Un-ionized ( ) ( ) NJHDG, Passaic River, Station #10 Clay Street (Cell 6,54)

68 ph (standard units) Un-ionized ( ) ( ) NJHDG, Passaic River, Station #11 Jackson Street (Cell 6,52)

69 3 3 ph (standard units) Un-ionized ( ) ( ) ( ) ( ) NJHDG, Passaic River, Station #12 Upper Kearny Point (Cell 6,47)

70 3 3 ph (standard units) Un-ionized ( 2.33 ) ( ) ( ) ( ) NJHDG, Newark Bay, Station #17 Upper Newark Bay 2 (Cell 8,44)

71 3 3 ph (standard units) Un-ionized ( 4.55 ) 0.94 ( 2.38 ) ( ) ( ) NJHDG, Newark Bay, Station #18 Upper Newark Bay 1 (Cell 8,41)

72 3 3 ph (standard units) Un-ionized ( ) ( ) ( ) NYCHS, Kill Van Kull, HARBOR-K02 (Cell 8,40)

73 3 3 ph (standard units) Un-ionized ( ) ( ) ( ) ( ) NYCHS, Kill Van Kull, HARBOR-K01 (Cell 16,40)

74 3 3 ph (standard units) Un-ionized ( 2.50 ) ( ) 1.08 ( 2.50 ) ( ) 1.08 NJHDG, Confluence of Newark Bay and Arthur Kill, Station #19 Upper Arthur Kill (Cell 7,39) ( 2.50 ) ( )

75 3 3 ph (standard units) Un-ionized ( ) ( ) ( ) ( ) NJHDG, Confluence of Elizabeth and Arthur Kill, Station #21 Upper Arthur Kill (Cell 5,39) ( ) ( )

76 3 3 ph (standard units) Un-ionized ( ) ( ) ( ) NYCHS, Arthur Kill, HARBOR-K03 (Cell 4,39)

77 3 3 ph (standard units) Un-ionized ( ) ( ) ( ) ( ) NJHDG, Confluence of Rahway and Arthur Kill, Station #23 Upper Arthur Kill (Cell 4,34) ( ) ( )

78 3 3 ph (standard units) Un-ionized ( ) ( ) ( ) NYCHS, Arthur Kill, HARBOR-K04 (Cell 4,32)

79 3 3 ph (standard units) Un-ionized ( ) ( ) ( ) ( ) NJHDG, Arthur Kill, Station #24 Upper Arthur Kill (Cell 4,30) ( ) ( )

80 3 3 ph (standard units) Un-ionized ( ) ( ) ( ) ( ) NYCHS, Arthur Kill, HARBOR-K05 (Cell 4,26)

81 ph (standard units) Un-ionized ( 2.22 ) ( ) NJHDG, Raritan Head of Tide, Station #25 Raritan River (Cell 2,61)

82 3 1 ph (standard units) Un-ionized ( ) 3.03 ( ) ( ) 1.01 ( ) NJHDG, Raritan River, Station #26 Upper Raritan River (Cell 2,47)

83 3 3 ph (standard units) Un-ionized ( ) 1.02 ( ) ( ) ( ) NJHDG, Raritan River, Station #27 Upper Raritan River (Cell 2,35)

84 3 3 ph (standard units) Un-ionized ( ) 0.99 ( ) ( ) ( ) NJHDG, Confluence of Raritan River, Raritan Bay and Arthur Kill, Station #28 Upper Raritan Bay (Cell 5,24)

85 3 3 ph (standard units) Un-ionized ( ) ( ) ( ) ( ) NYCHS, Raritan Bay, HARBOR-K05A (Cell 6,25)

86 3 3 ph (standard units) Un-ionized ( ) 1.19 ( ) 1.20 ( ) 1.19 ( ) NJHDG, Raritan Bay, Station #29 Upper Raritan Bay (Cell 8,26)

87 3 3 ph (standard units) Un-ionized NJHDG, Raritan Bay, Station #30 Upper Raritan Bay (Cell 10,30) ( ) ( ) ( ) ( )

88 3 3 ph (standard units) Un-ionized ( ) ( ) ( ) ( ) NYCHS, Raritan Bay, HARBOR-K06 (Cell 12,28)

89 ph (standard units) Un-ionized NYCHS, North River, HARBOR-N01 (Cell 20,70) ( ) ( )

90 ph (standard units) Un-ionized NYCHS, North River, HARBOR-N02 (Cell 20,66)

91 3 3 ph (standard units) Un-ionized ( ) ( ) ( ) ( ) NJHDG, Hudson River, Station #31 Upper Hudson River (Cell 19,62) ( ) ( ) ( ) ( )

92 ph (standard units) Un-ionized NYCHS, North River, HARBOR-N03 (Cell 20,61)

93 3 3 ph (standard units) Un-ionized ( ) ( ) ( ) ( ) NYCHS, North River, HARBOR-N03B (Cell 19,59)

94 3 3 ph (standard units) Un-ionized NYCHS, North River, HARBOR-N03A (Cell 19,56)

95 3 3 ph (standard units) Un-ionized ( ) ( ) ( ) ( ) NJHDG, Hudson River, Station #32 Upper Hudson River (Cell 18,54)

96 ph (standard units) Un-ionized ( ) ( ) ( ) ( ) NYCHS, North River, HARBOR-N04 (Cell 19,54)

97 3 3 ph (standard units) Un-ionized ( ) ( ) ( ) ( ) NJHDG, Hudson River, Station #33 Upper Hudson River (Cell 18,49)

98 3 3 ph (standard units) Un-ionized NYCHS, North River, HARBOR-N05 (Cell 20,48) ( ) ( )

99 3 3 ph (standard units) Un-ionized NYCHS, Upper Bay, HARBOR-G01 (Cell 23,43)

100 3 4 ph (standard units) Un-ionized ( ) ( ) ( ) ( ) NYCHS, Upper Bay, HARBOR-N06 (Cell 19,42)

101 3 100 ph (standard units) Un-ionized NYCHS, Upper Bay, HARBOR-N07 (Cell 19,39) ( ) ( )

102 3 3 ph (standard units) Un-ionized NYCHS, Upper Bay, HARBOR-N08 (Cell 20,35) ( ) ( )

103 ph (standard units) Un-ionized NYCHS, Lower Bay, HARBOR-N08A (Cell 16,32)

104 ph (standard units) Un-ionized NYCHS, Lower Bay, HARBOR-N09 (Cell 23,29) ( ) ( )

105 3 3 ph (standard units) Un-ionized NYCHS, Lower Bay, HARBOR-N09A (Cell 24,28)

106 3 4 ph (standard units) Un-ionized NYCHS, Lower Bay, HARBOR-N16 (Cell 23,26) ( ) ( )

107 3 3 ph (standard units) Un-ionized NYCHS, Upper East River, HARBOR-E10 (Cell 41,57) ( ) ( )

108 ph (standard units) Un-ionized NYCHS, Upper East River, HARBOR-E09 (Cell 40,58)

109 ph (standard units) Un-ionized NYCHS, Upper East River, HARBOR-E11 (Cell 38,54) ( ) ( )

110 3 3 ph (standard units) Un-ionized NYCHS, Upper East River, HARBOR-E12 (Cell 39,63)

111 ph (standard units) Un-ionized NYCHS, Upper East River, HARBOR-E12A (Cell 37,60)

112 ph (standard units) Un-ionized NYCHS, Upper East River, HARBOR-E08 (Cell 37,56) ( ) ( )

113 ph (standard units) Un-ionized NYCHS, Upper East River, HARBOR-E07 (Cell 34,58) ( ) ( )

114 ph (standard units) Un-ionized NYCHS, Upper East River, HARBOR-E13 (Cell 32,59)

115 3 3 ph (standard units) Un-ionized NYCHS, Upper East River, HARBOR-E15 (Cell 32,52) ( ) ( )

116 3 3 ph (standard units) Un-ionized NYCHS, Upper East River, HARBOR-E06 (Cell 30,54) ( ) ( )

117 ph (standard units) Un-ionized NYCHS, Upper East River, HARBOR-E14 (Cell 30,58) ( ) ( )

118 ph (standard units) Un-ionized NYCHS, Upper East River, HARBOR-E05 (Cell 29,57)

119 3 3 ph (standard units) Un-ionized NYCHS, East River, HARBOR-E04 (Cell 25,57) ( ) ( )

120 3 3 ph (standard units) Un-ionized NYCHS, Lower East River, HARBOR-E03 (Cell 22,53)

121 3 3 ph (standard units) Un-ionized NYCHS, Lower East River, HARBOR-E02A (Cell 24,52)

122 3 3 ph (standard units) Un-ionized NYCHS, Lower East River, HARBOR-E02 (Cell 22,52) ( ) ( )

123 3 3 ph (standard units) Un-ionized NYCHS, Lower East River, HARBOR-E01 (Cell 23,48)

124 ph (standard units) Un-ionized NYCHS, Harlem River, HARBOR-H01 (Cell 21,67)

125 3 3 ph (standard units) Un-ionized NYCHS, Harlem River, HARBOR-H02 (Cell 23,66)

126 3 3 ph (standard units) Un-ionized NYCHS, Harlem River, HARBOR-H03 (Cell 23,63) ( ) ( )

127 3 3 ph (standard units) Un-ionized NYCHS, Harlem River, HARBOR-H04 (Cell 23,60)

128 3 3 ph (standard units) Un-ionized NYCHS, Harlem River, HARBOR-H05 (Cell 23,58)

129 3 3 ph (standard units) Un-ionized NYCHS, Jamaica Bay, HARBOR-J12 (Cell 35,32) ( ) ( )

130 3 3 ph (standard units) Un-ionized NYCHS, Jamaica Bay, HARBOR-J07 (Cell 34,34) ( ) ( )

131 3 3 ph (standard units) Un-ionized NYCHS, Jamaica Bay, HARBOR-J05 (Cell 32,28) ( ) ( )

132 3 100 ph (standard units) Un-ionized NYCHS, Jamaica Bay, HARBOR-J08 (Cell 31,34) ( ) ( )

133 3 3 ph (standard units) Un-ionized NYCHS, Jamaica Bay, HARBOR-J09 (Cell 30,34)

134 3 3 ph (standard units) Un-ionized NYCHS, Jamaica Bay, HARBOR-J09A (Cell 30,34) ( ) ( )

135 3 3 ph (standard units) Un-ionized NYCHS, Jamaica Bay, HARBOR-J03 (Cell 29,34) ( ) ( )

136 3 3 ph (standard units) Un-ionized NYCHS, Jamaica Bay, HARBOR-J10 (Cell 28,34)

137 3 3 ph (standard units) v Un-ionized NYCHS, Jamaica Bay, HARBOR-J02 (Cell 28,32) ( ) ( )

138 3 4 ph (standard units) Un-ionized NYCHS, Jamaica Bay, HARBOR-J01 (Cell 27,28) ( ) ( )