CBP/TRS 115/94 August 1994 903R94050 Trends in Phosphorus, Nitrogen, Secchi Depth, and Dissolved Oxygen in Chesapeake Bay, 1984 to 1992 TD 225 .C54 T74 1994 Chesapeake Bay Program Printed on Recycled Paper ------- Regional Center for Environmental Information US EPA Region III 1650 Arch St. Philadelphia, PA 19103 ------- Online Library System (OLS) Libraries | US EPA Page 1 of 3 http://cave.epa.gov/cgi/nph-bwcgis/BASIS/ncat/lib/ncat/DDW?W%3D+%28TITLE+PH+WORD+% g+in+mtrogen+in+the+chesapeake+9627%29+ ~ OLS : Record Display Q Search —. Synnaru »™ 4 [ Serial Record 5 [ Display Records as Bibliography ] [ Item Status RECORD NUMBER: 1 OF 2 Main Title CORP Author Publisher Year Published Report Number Stock Number OCLC Number Subjects Subject Added Ent Collation Holdings Trends in phosphorus, nitrogen, Secchi depth, and dissolved oxygen in Chesapeake Bay, 1984 to 1992. Environmental Protection Agency, Annapolis, MD. Chesapeake Bay Program. Chesapeake Bay Program, 1994 CBP/TRS 115/94 PB95-136230 32995308 Nitrogen; Phosphorus; Environmental impacts; Water pollution abatement; Chesapeake Bay; Reductions; Nutrients; Dissolved oxygen; Monitoring; Water quality; Trends; Runoff; Seasonal variations; Chemical analysis; Mathematical models; Improvement; Point sources; Nonpoint sources; Tables(Data); Graphs(Charts); Organic loading; Maryland; Pennsylvania; District of Columbia; Virginia Water —Chesapeake Bay (Md. and Va.)— Phosphorus content— Statistics ; Water—Nitrogen content— Chesapeake Bay (Md. and Va.)~ Statistics ; Water- -Dissolved oxygen— Chesapeake Bay (Md. and Va.)~Statistics ; Chesapeake Bay (Md. and Va.) x, 63 p. : maps, charts ; 28 cm. LIBRARY CALL NUMBER LOCATION EJAM TD225.C54T74 1994 Region 3 http://cave.epa.gov/cgi/nph-bwcgis/BASIS/ncat/lib/ncat/DDW?W%3D+%28TITLE+PH+... 8/31/2006 ------- Online Library System (OLS) | Libraries | US EPA Page 2 of 3 Abstract Notes Corp Au Added Ent Place Published PUB Date Free Form NTIS Prices Holdings Modified Bib Level Library/Philadelphia, PA EJDD CB 00644 OASQA Library/Fort Meade,MD NTIS PB95-136230 Most EPA NTIS libraries have a fiche copy filed under the call number shown. Check with individual libraries about paper copy. The Chesapeake Bay Program (CBP) is a Federal-State partnership working to restore Chesapeake Bay. One of its main goals is to improve water quality conditions for living resources. The CBP started ambient water quality monitoring programs for Chesapeake Bay in 1984 to characterize current water quality, to assess trends in water quality over time, and to increase understanding of linkages between water quality and living resources. Nutrient enrichment is a major water quality problem in Chesapeake Bay. Spring and summer phytoplankton blooms, fueled by high nutrient levels, cause low dissolved oxygen (DO) levels in the summer when the plankton die and decompose. Low concentrations of DO can be lethal to Chesapeake Bay's aquatic animals. Both point source and nonpoint source reductions of nitrogen and phosphorus loads to Chesapeake Bay have been achieved since 1985. "CBP/TRS 115/94". Cooperative agreement no. TCRD-93-o8-oi-ooo". Includes bibliographical references (p. 49). United States. Environmental Protection Agency. Chesapeake Bay Program. {Annapolis, Md.} : 1994- PCA04/MFA01 LIBRARY Date Modified EJA 19970815 EJD 19950818 m http://cave.epa.gov/cgi/nph-bwcgis/BASIS/ncat/lib/ncat/DDW?W%3D+%28TITLE+PH+... 8/31/2006 ------- Online Library System (OLS) Libraries US EPA Page 3 of 3 OCLCTime Stamp Cataloging Source Language OCLC/NTIS Type OCLC Rec Leader 19970814135229 OCLC/T ENG OCLC MERGE oi046nam 2200253X3 45020 J3 HS4 jjsip,_j5 [ Display Records as Bibliography Item Status URLs Provided for your Reference i. http://cave.epa.gov/cgi/nph-bwcgis/BASIS/ncat/lib/ncat/SF 2. http://cave.epa.gov/ cgi/nph-bwcgis/BASIS/ncat/lib/ncat/SDW?W%3D+% 28TITLE+PH+WORD+%27trends+in+nitrogen+in+the+chesapeake+%27% 29+ORDER+BY+YR/Descend%26M%3Di%26R%sDY 3. http://cave.epa.gov/cgi/nph-bwcgis/BASIS/ncat/lib/ncat/DDW?W%3D+% 28TITLE+PH+WORD+%27trends+in+nitrogen+in+the+chesapeake+%27% 29+ORDER+BY+YR/Descend%26M%3D2%26K%3Di82828%26R%3DY%26U%3Di 4. http://cave.epa.gov/cgi/nph-bwcgis/BASIS/ncat/lib/ncat/SBC 5 . http : / /www. epa . gov/natlibr a/ olshelp .htm http://cave.epa.gov/cgi/nph-bwcgis/BASIS/ncat/lib/ncat/DDW?W%3D+%28TITLE+PH+... 8/31/2006 ------- Trends in Phosphorus, Nitrogen, Secchi Depth, and Dissolved Oxygen in Chesapeake Bay, 1984 to 1992 Cooperative Agreement No. TCRD-93-08-01-000 CBP/TRS 115/94 August 1994 Printed by the U.S. Environmental Protection Agency for the Chesapeake Bay Program ------- . ENDORSEMENT The Chesapeake Bay Monitoring Subcommittee has reviewed the assumptions and methods of data analysis used in this report and finds them appropriate for the analysis conducted. The findings of this report are consistent with and supported by the analytical techniques employed. Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 iii ------- iv Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- ABSTRACT The Chesapeake Bay Program (CBP) is a Federal-State partnership working to re- store Chesapeake Bay. One of its primary goals is to improve water quality and habitat conditions for living resources. The CBP began monitoring water and habitat quality in 1984 and continues to sample the main stem and tributaries for their physical and chemi- cal makeup. Nutrient enrichment is a major water quality problem in Chesapeake Bay. Nutrients fuel phytoplankton growth, which has an adverse (reduction) effect on dissolved oxygen (DO) levels. Low DO levels threaten the existence of Chesapeake Bay's aquatic animals. DO levels should increase if nutrient levels are reduced. A computer model pre- dicted that a 40-percent reduction in nitrogen and phosphorus would reduce nutrient levels and cause an increase in DO levels in the main stem to Chesapeake Bay. Nitrogen and phosphorus control programs have been initiated. Trend analyses, involving various criteria, were performed over an 8-year period (from October 1984 through September 1992) to see how these programs affected water and habitat quality conditions in Chesa- peake, Bay. Results of seasonal Kendall test analysis indicate that phosphorus levels decreased significantly baywide, especially in one upper Chesapeake Bay segment and two lower Chesapeake Bay segments. There were also marginally significant improvements in phos- phorus levels in two upper Chesapeake Bay segments and in one lower Chesapeake Bay segment. Nitrogen levels were somewhat increased (marginally significant) in one seg- ment of Chesapeake Bay. Secchi depths showed no significant trends baywide; however, there were marginally significant trends (improvements) in upper Chesapeake Bay. DO trends were not statistically significant baywide; however, segments at the mouth of Ches- apeake Bay showed marginally significant degradation. Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- CONTENTS Page Endorsement iii Abstract v Acknowledgments ix Abbreviations ix Executive Summary 1 Introduction 5 Methods 5 Parameters Analyzed and Data Preparation 5 Trend Analysis Methods 6 Adjustments for Changing Detection Limits 10 Susquehanna River Flow 10 Phosphorus 11 Nitrogen 11 Secchi Depth 12 Dissolved Oxygen 12 Results and Discussion 13 Susquehanna River Flow 13 Phosphorus 16 Total Phosphorus 16 Dissolved Inorganic Phosphorus (Orthophosphate) 17 Nitrogen 26 Total Nitrogen 26 Dissolved Inorganic Nitrogen 27 Secchi Depth 31 Dissolved Oxygen 39 Plans for Future Trend Analyses 46 Interpolating Above and Below Pycnocline Layers and Surface and Bottom Layers Separately 46 Accounting for Interannual Changes in Flow 47 Adding Parametric Trend Tests 47 Adding Trend Tests on Interpolated Tributary Data 47 Summary 47 References 49 Appendix—Frequencies of Below Detection Limit Values for Dissolved Inorganic Phosphorus and Dissolved Inorganic Nitrogen 51 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 vii ------- FIGURES 1. CBP main stem monitoring stations and segments 7 2. Total annual Susquehanna River flow (bars) and number of months above median flow line (water years 1985 to 1992) 14 3. Total phosphorus trends in Chesapeake Bay main stem segments (October 1984 through September 1992) 18 4. Average monthly concentrations of total phosphorus and dissolved inorganic phosphorus (1934 to 1992) 19 5. Dissolved inorganic phosphorus trends in Chesapeake Bay main stem segments (October 1984 through September 1992) 22 6. Average monthly concentrations of dissolved inorganic phosphorus (1984 to 1992) 23 7. Total nitrogen trends in Chesapeake Bay main stem segments (October 1984 through September 1992) 28 8. Average monthly concentrations of total nitrogen and dissolved inorganic nitrogen (1984 to 1992) 29 9. Dissolved inorganic nitrogen trends in Chesapeake Bay main stem segments (October 1984 through September 1992) 33 10. Average monthly concentrations of dissolved inorganic nitrogen (1984 to 1992) 34 11. Secchi depth trends in Chesapeake Bay main stem segments (October 1984 through September 1992) 36 12. Average monthly Secchi depths (1984 to 1992) 37 13. Dissolved oxygen delta and dissolved oxygen deficit trends in Chesapeake Bay main stem segments (October 1984 through September 1992) 40 14. Average monthly concentrations of dissolved oxygen and dissolved oxygen delta (1984 to 1992) 42 15. Total volumes of water with dissolved oxygen concentrations below 0.2, 1, 3, and 5 mg/L (June through September, 1985 to 1992) 44 TABLES Executive Summary Table. Summary of trend results (October 1984 through September 1992) 3 1. Correlations between log mean monthly Susquehanna River flow and mean monthly concentrations of water quality parameters (with P Values in parentheses) 14 2. Trend results for interpolated monthly mean total phosphorus by segment (12 months) 17 3. Trend results for interpolated monthly mean levels of dissolved inorganic phosphorus by segment, using four different method detection limit treatments 21 viii Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- 4. Trend results for interpolated monthly mean dissolved inorganic phosphorus by segment (12 months) 25 5. Trend results for interpolated monthly mean dissolved inorganic phosphorus by segment (7 months, April through October) 26 6. Trend results for interpolated monthly mean total nitrogen by segment 27 7. Trend results for interpolated monthly mean levels of dissolved inorganic nitrogen by segment using four different method detection limit treatments 32 8. Trend results for interpolated monthly mean Secchi depth by segment (7 months, April through October) 39 9. Trend results for interpolated monthly mean dissolved oxygen delta by segment (4 warm weather months, June through September) 41 10. Trend results for interpolated monthly mean dissolved oxygen deficit by segment (4 warm weather months, June through September) 46 11. Summary of trend results (October 1984 through September 1992) 48 A.I. Percent of observations with below detection limit values for dissolved inorganic phosphorus by segment, laboratory, and water year 52 A.2. Percent of observations with below detection limit values for dissolved inorganic nitrogen by segment, laboratory, constituent parameter, and water year 55 A CKNO WLEDGMENTS The Monitoring Subcommittee would especially like to express its gratitude to Peter Bergstrom and Marcia Olson for writing this report. The Monitoring Subcommittee would also like to express their gratitude to the field and lab crews that carefully and ex- pertly collected and analyzed the water quality samples discussed in the report. A great many other people provided both information insights and support that contributed to the preparation of this report, and to all of them our heartfelt thanks. ABBREVIATIONS BDL Below detection limit(s) CBL Chesapeake Biological Laboratory CBP Chesapeake Bay Program CRL (The U.S. Environmental Protection Agency's) Central Regional Laboratory (in Annapolis, Md.) DIN Dissolved inorganic nitrogen DIP Dissolved inorganic phosphorus DO Dissolved oxygen KD Light attenuation MDE Maryland Department of the Environment MDL Method detection limit(s) Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ix ------- ODU Old Dominion University P Probability that an observed trend, correlation, or difference was due to chance SAV Submerged aquatic vegetation TN Total nitrogen TP Total phosphorus VIMS Virginia Institute of Marine Science WY Water year(s) Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- EXECUTIVE SUMMARY The Chesapeake Bay Program (CBP) is a Federal-State partnership working to re- store Chesapeake Bay. One of its main goals is to improve water quality conditions for living resources. The CBP started ambient water quality monitoring programs for Chesa- peake Bay in 1984 to characterize current water quality, to assess trends in water quality over time, and to increase understanding of linkages between waster quality and living resources. Currently, over 150 stations in the tidal tributaries and main stem to Chesa- peake Bay are sampled once or twice a month and analyzed for more than 20 physical and chemical parameters. The main stem to Chesapeake Bay is divided into 10 segments based on similar salinity circulation and geomorphology. Nutrient enrichment is a major water quality problem in Chesapeake Bay. Spring and summer phytoplankton blooms, fueled by high nutrient levels, cause low dissolved oxygen (DO) levels in the summer when the plankton die and decompose. Low con- centrations of DO can be lethal to Chesapeake Bay's aquatic animals. Thus, summer DO levels should improve if nutrient levels are reduced. A computer model of Chesapeake Bay water quality predicted that 40 percent nitro- gen and phosphorus load reductions would reduce ambient nutrient levels sufficiently to cause' an increase in DO levels in the deeper areas of the main stem to Chesapeake Bay. The 1987 Chesapeake Bay Agreement and its 1992 amendments committed Pennsylva- nia, Maryland, Virginia, and the District of Columbia to achieve a 40-percent reduction of the 1985 nitrogen and phosphorus loads entering the main stem to Chesapeake Bay by the year 2000. Both point source and nonpoint source reductions of nitrogen and phosphorus loads to Chesapeake Bay have been achieved since 1985. Trend analyses of ambient levels of nitrogen, phosphorus, DO, and related water quality parameters were performed to deter- mine how these source reductions are affecting water quality conditions in Chesapeake Bay. Trends in Chesapeake Bay main stem levels of total phosphorus (TP), dissolved in- organic phosphorus (DIP), total nitrogen (TN), dissolved inorganic nitrogen (DIN), Secchi depth, and DO were analyzed over 8 years (October 1984 through September 1992). Phosphorus trends were analyzed with the nonparametric seasonal Kendall test* and were classified as marginally sufficient improvements (P<0.05) or significant im- provements (P<0.01). Data from 49 main stem monitoring stations were spatially averaged over 10 main stem segments using a three-dimensional interpolator. There were no adjustments for river flow, although correlations of Secchi depth with flow and trends in flow were examined. Monthly median values were analyzed because sampling fre- quency varied seasonally. Method detection limits declined over time for some parameters, but any trends that could have been caused by declining detection limits were eliminated. Parameters important to submerged aquatic vegetation (SAV) growth were analyzed for trends over the whole year and also over the 7-month SAV growing season (April through October). DO trends were only analyzed for the four warm weather months (June through September) when most low DO conditions occur. Percent change estimates were *The Kendall slope is a measurement of trend expressed as mg/L/yr. Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- based on the mean concentration for the first water year (October 1984 through Septem- ber 1985) and a projection for the last water year based on the seasonal Kendall slope. Interannual changes in Susquehanna River flow could produce the appearance of trends in water quality if there was a trend in flow, and water quality was correlated with flow; however, there were no significant trends in mean monthly Susquehanna River flow over any time period. In contrast, there were significant positive and negative cor- relations between the log mean monthly Susquehanna River flow and upper Chesapeake Bay water quality, but they did not follow a simple pattern. TP concentrations showed a statistically significant downward trend (P<0.01) bay- wide, especially in one upper Chesapeake Bay segment and two lower Chesapeake Bay segments. There were also marginally significant improvements (/><0.05) in two upper Chesapeake Bay segments and in one lower Chesapeake Bay segment. The median bay- wide percent change (decline) in TP over 8 years (1984 to 1992) was 16 percent, plus or minus 8 percent (90 percent confidence interval). DIP showed significant downward trends over 12 months at the mouth of Chesapeake Bay and over 7 months (April through October) in central Chesapeake Bay, but the trend was not significant baywide. TN concentrations showed a marginally significant increasing trend (degradation, P=0.027) in Mobjack Bay, including the mouth of the York River; however, there was no significant trend baywide or in an. other segments. The possible increase in TN in Mob- jack Bay was probably related to similar upward trends in TN in the York River. DIN showed no significant trends in any segments, although high detection limits made it im- possible to assess trends in nitrogen concentrations in several lower Chesapeake Bay segments. Secchi depths showed no significant trends baywide over a period of 7 or 12 months or for any segment over 12 months. There were marginally significant upward trends (improvements) in upper Chesapeake Bay over the 7-month SAV growing season (April through October). These trends may be related to statistically significant inverse correla- tions between the April-through-September Secchi depth and the mean monthly Susquehanna River flow, although there were no significant trends in flow. Secchi depth is not measured in the Susquehanna River, so it is not known whether there were trends in Secchi depth there. DO concentration trends as well as trends in several metrics calculated from the concentration were examined. These trends included oxygen delta (the difference be- tween DO at saturation and the actual DO concentration) and DO deficit (converting the delta concentration to the mass of DO that would have to be added to bring all the water in that segment to saturation). The volumes of water in each segment that were below four benchmark DO concentrations (5, 3, 1, and 0.2 mg/L) were also analyzed for trends. DO concentration and the four metrics for volumes below specific concentrations had no statistically significant trends (P>0.05) in any segments in the June-to-September period. The mouth of Chesapeake Bay showed marginally significant degradation in both DO delta and DO deficit. However, DO concentrations are generally high in the mouth of Chesapeake Bay and DO delta is quite low, so these trends are unlikely to have any nega- tive impact on aquatic animals living near the mouth of Chesapeake Bay. Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- Executive Summary Table. Summary of trend results (October 1984 through September 1992). Main Stem CBP Segments Parameter No. of Months All CB1 CB2 CB3 CB4 CBS CB6 CB7 CB8 WE4 EE3 TP DIP DIP TN DIN DIN Secchi Depth Secchi Depth DO Concentration DO Delta DO Deficit DO<0.2 DO<1.0 DO<3.0 DO<5.0 12 I IM I IM - - I IM I - 12-------- | -- 7 ____ | ______ 12 --------- DM - 12------ + + - + + 7 _-_-__ + + _ + + 12 ----------- 7 -IMIM -------- 4 ___________ 4 ________ DM -- 4 ________ DM -- 4 _. _________ 4 ___________ 4 ___________ 4 ___________ Legend and note: I—Significant improvement (P<0.01). IM—Marginally significant improvement (P<0.05). DM—Marginally significant degradation. Dash—No significant trend (P>0.05). +—DIN trends could not be assessed in these segments because detection limits did not stop declin- ing until July 1990. 7 months—April through October only, same as SAV growing season in lower salinity zones; 4 months—June through September only, used as period of anoxia in three-dimensional model analy- ses. DO data were not analyzed in EE3. See text for explanation of DO delta, DO deficit, and DO volumes below the four concentrations. Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- INTRODUCTION The Chesapeake Bay Program (CBP) is a Federal-State partnership working to re- store Chesapeake Bay. One of the main goals of the CBP is to improve water quality conditions for Chesapeake Bay living resources. CBP's water quality monitoring pro- grams were started in 1984 to characterize current water quality and to assess trends in water quality over time. Presently, over 150 stations are sampled once or twice a month and analyzed for more than 20 physical and chemical parameters. A major water quality threat in Chesapeake Bay is low summertime concentrations of DO, a condition which is potentially lethal to Chesapeake Bay aquatic animals. Spring and summer phytoplankton blooms, fueled by high nutrient levels, cause low DO levels during the summer when the plankton die and decompose. Thus, summertime DO levels should improve if nutrient levels are reduced. A computer model of Chesapeake Bay water quality predicted that 40 percent nitro- gen and phosphorus load reductions would reduce ambient nutrient levels sufficiently to cause an increase in DO levels in the deeper areas of the main stem of Chesapeake Bay. The 1987 Chesapeake Bay Agreement and its 1992 amendments committed Pennsylva- nia, Maryland, Virginia, and the District of Columbia to achieve a 40-percent reduction of the 1985 nitrogen and phosphorus loads entering the main stem of Chesapeake Bay by the year 2000. Both point and nonpoint source reductions of nitrogen and phosphorus loads to Chesapeake Bay have been achieved since 1985.' Trend analyses of ambient levels of nitrogen, phosphorus, DO, and related water quality parameters were performed to deter- mine how these source reductions are affecting water quality conditions in Chesapeake Bay. Trends in Chesapeake Bay main stem levels of total phosphorus (TP), total nitrogen (TN), and DO were analyzed over 6 years.2'4 This report updates the previous trend anal- yses using 8 years of main stem monitoring data, spanning October 1984 through September 1992. TP levels declined significantly between 1984 and 19903; however, TN and DO lev- els showed little or no change over the same period.2'4 This update, with 2 additional years of data, was conducted to see if these trends continued. This update also added sta- tistical analyses of trends in DO and trend analyses of three additional parameters: dissolved inorganic phosphorus (DIP), dissolved inorganic nitrogen (DIN), and Secchi depth (a measure of water clarity). These three parameters were added because their lev- els affect submerged aquatic vegetation (SAV) growth5 and are also closely related to phytoplankton growth. METHODS PARAMETERS ANALYZED AND DATA PREPARATION The CBP monitoring program and details of sample collection and analytical chem- istry methods used are described in three previous reports.2"4 The following water quality parameters were analyzed in this report: • TP concentration Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- • DIP concentration • TN concentration • DIN concentration • Secchi depth • DO concentration. The following calculated metrics derived from the water quality parameters were also analyzed in this report: • DO delta: the difference between DO saturation concentration and observed DO concentration • DO deficit: the difference between DO mass at saturation and the observed mass of DO • Volume of water with DO concentrations below 5, 3, 1, and 0.2 mg/L. A three-dimensional interpolator6 was used to estimate baywide main stem mean concentrations and mean concentrations in each CBP main stem segment (CB1 to CBS, EE3, and WE4). (See Figure 1.) Data from all sampling depths were used, except for Secchi depth, which has only one measurement per station. The annual periods used were water years (WY), from October through September (which include a complete hydro- logical cycle). The monitoring data from October 1984 through September 1992 were used; the previous reports included data through September 1990. The possible outliers that were removed from nitrogen and phosphorus data in the two previous reports3-4 were checked by the data submitters and were either verified or corrected. The Maryland monitoring data used in this report were resubmitted in 1992, incorporating numerous data corrections; there were also corrections made to Virginia monitoring data in 1992. Because the data had been verified or corrected, the analyses in this report used data as currently stored in the CBP data base without deleting any possible outliers. Data were not adjusted for river flow. In the Chesapeake Bay monitoring program, flow is only measured at the fall line stations, and only the Susquehanna River fall line station at Conowingo, Md. is close enough to the main stem to have a direct impact on it.7 Trend tests were performed on mean monthly Susquehanna River flow, and correla- tions between log mean monthly flow and all parameters were calculated to estimate the degree of association. However, a simple flow adjustment in the main stem of Chesa- peake Bay is not possible because it would assume that flow has either an immediate effect on concentrations or an effect after a fixed time lag. The effects of Susquehanna River flow on main stem water quality must be highly variable because "Chesapeake Bay's response to a freshet is a function of Chesapeake Bay's recent history and cannot be linearized or easily predicted."8 TREND ANALYSIS METHODS Trend analyses of nitrogen, phosphorus, and DO were performed on monthly mean concentrations, spatially interpolated in three dimensions. Trend analyses of Secchi depth were performed on monthly mean depths interpolated in two dimensions. Flow data used were monthly means of daily Susquehanna River flows measured at Conowingo, Md. Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- Relative Volumes of Main Stem Segments CB8 WE4 CB7 CB6 CB2 WE4 Figure 1. CBP main stem monitoring stations and segments. Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- Nutrient and Secchi monthly means for segment EE3 were estimated without using data from the Maryland tributary monitoring stations in this segment because the tributary data were not available for the whole time period. DO data were not estimated for seg- ment EE3 because it has higher spatial variability than the other parameters. Some of the metrics used for DO were slightly different from those used before. Trend analyses were performed only on interpolator output, not on concentrations observed at individual sta- tions (except for flow). Trend analyses were performed on DO, which was not done previously.2 Trend analyses for some parameters were performed on data from either April through October or June through September to correspond with the period of maxi- mum effects on living resources. A nonparametric trend test was substituted for the parametric test used in the previous analyses.3'4 The trend test used was the seasonal Kendall nonparametric test, which tests for monotonic trends. Monotonic trends need not be linear, but they are assumed to have a slope that is consistently positive or negative.9 Trends that change from positive to nega- tive slope (or vice versa) may not be detected. The previous nitrogen and phosphorus reports used linear, quadratic, and cubic parametric regression to assess both monotonic and nonmonotonic trends.3'4 The seasonal Kendall test was performed with a custom SAS program10 using the method described by Gilbert.9 The seasonal Kendall test assumes the successive monthly values are independent or have no serial correlation. This is not often true of Chesapeake Bay water quality data3-4; serial correlation tends to inflate the significance of the test.9 There are modifica- tions to the seasonal Kendall test that account for serial correlation9; however, they assume that the correlation has a fixed structure, while the actual correlations are quite variable.3'4 Thus, the test was used without correcting for serial correlation. To account for the possible inflation of significance levels that results from serial correlation, P val- ues falling between 0.05 and 0.01 were termed "marginally significant" because their actual P value might be more than 0.05. P values less than 0.01 were termed "significant" because their actual P value was probably less than 0.05. A similar approach to determin- ing significant trends with the seasonal Kendall test was > jd and reported as part of the 1991 re-evaluation of the Chesapeake Bay nutrient reduction strategy,* except that mar- ginally significant trends were not identified. The tables of seasonal Kendall test results list the sample size in months, the median trend slope in mg/L per year, and the Z** score for significant trend. A large Z score indi- cates a statistically significant monotonic trend: Z between 1.96 and 2.58 was considered "marginally significant," with P between 0.05 and 0.01; Z>2.58 was considered "signifi- cant," with P<0.01. The %2 value for seasonality tests whether the trend is homogeneous over different months. A small x2 value and a large P value (>0.05) indicates there were no significant seasonal differences in the trend. (Trends were not upward in some seasons and downward in others.) Almost all parameters in which significant trends were found had homogeneous trends over different months. The results were corrected for ties or concentrations from the same month that are the same in 2 or more successive years. The results were also checked to see if ties affected more than 50 percent of the results for any ""Water Quality Characterization Report for the 1991 Re-Evaluation of the Chesapeake Bay Nutrient Re- duction Strategy," (draft), CBP, Annapolis, Md. (1991). **Test statistic used to determine P value. Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- month. There were no cases when ties made up more than 50 percent of the observations for any month. Percent change over 8 years (1984 to 1992) is shown for parameters and segments with statistically significant and marginally significant trends. This was calculated using the 1985 WY mean value (October 1984 through September 1985) and the median slope from the seasonal Kendall test: t _. Slope (Per Year) X 8 Years Percent Change = — ino_ ..... . . x 100 . 1985 WY Mean Multiplying the slope by the number of years gives the total estimated change over that period. The previous phosphorus and nitrogen trend reports3'4 used percent change values calculated using the means of the first and last years of data (1985 and 1990 WY). The advantage of using the seasonal Kendall slope to estimate the overall percent change is that it uses all the data. Percent change calculated with the median slope will not be affected as much if the last year of data had unusually high or low results. However, it will still be affected if the first year of data was unusually high or low. Using the seasonal Kendall slope also makes it possible to put confidence limits on the percent change esti- mate9; 90 percent confidence limits were used for the one parameter with a significant bay wide change (for TP). The trend line shown in the graphs of the data also came from the mean of the first year and the seasonal Kendall slope: The start point of the line was the 1985 WY mean, and the end point was calculated from the following equation: End Point = 1985 WY Mean + [Slope (Per Year) x 8 Years] . Thus, the trend line represents the same data as the percent change estimate. The same percent change estimate could be calculated from the following equation: Percent Change = End Point-Start Point m r Start Point Trend lines and percent change estimates are only shown for parameters and seg- ments with statistically significant or marginally significant trends. Statistically significant and marginally significant trends were called either "im- provement" or "degradation." Declining levels are improvements for nutrients, DO delta, DO deficit, and DO volumes below specific concentrations. Increasing levels are im- provements for Secchi depth and DO concentration. What improvement and degradation mean in terms of the CBP efforts to preserve and restore Chesapeake Bay can be evaluated using the habitat requirements and CBP goals set for Chesapeake Bay's living resources. These have been established for SAV and for species sensitive to low DO levels. If there is an improving trend in an area that does not currently meet one of the SAV habitat requirements or DO goals, that trend will aid in living resource restoration efforts. SAV habitat requirements have been established for three of the parameters ana- lyzed: DIP, DIN, and Secchi depth.5 The habitat requirements represent the maximum concentrations or the minimum Secchi depth that will permit SAV growth. They are based on growing season median values; the SAV growing season is April through Octo- Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- her in most of Chesapeake Bay.5 For this reason, trends in these three parameters were evaluated over the whole year (12 months) and also over the April through October peri- od (7 months). There are also SAV habitat requirements for two parameters that were not analyzed in this report5: total suspended solids and'chlorophyll a. The benchmarks for improvements in DO are based on four target concentrations: 0.2, 1, 3, and 5 mg/L. The 0.2 mg/L benchmark is based on the anticipated effect of the 40 percent nutrient reduction strategy1: a reduction in the volume of anoxic waters (de- fined here as water with DO concentrations less than 0.2 mg/L). The last three benchmarks (1,3, and 5 mg/L) were established by the Habitat Restoration Goal for DO.11 ADJUSTMENTS FOR CHANGING-DETECTION LIMITS CBP monitoring data have method detection limits (MDL), which represent the lowest detectable concentration of that parameter. Analytical results that are less than the MDL are censored by setting them to the MDL and are identified with a separate vari- able. Parameters with observations censored at the MDL pose two problems for trend analysis: They may bias the slope, since the detection limit values are greater than the true values, and they may produce a statistically significant trend when none existed if the MDL changed consistent!} er time. The first problem is avoided by the use of me- dians in the seasonal Kendall tt . Censored data have no effect on the slope as long as the censored values make up less than half of the observations.9 Resolving the second problem is more complex. Several of the parameters analyzed had reductions in MDL, and the seasonal Kendall test results were apparently affected by these reductions. Reductions in MDL occurred in all four of the nitrogen and phosphorus parameters, but detection limits did not change for DO or Secchi depth. For nitrogen and phosphorus parameters, below detection limit (BDL) values were set to one-half the MDL before in- terpolation, as in the previous analyses. For one parameter (TN) the MDL reductions were small enough to be negligible.4 The effects of moderate reductions in MDL, which occurred in TP data, were checked by raising any lower values to the highest MDL dur- ing the time period. When the detection limits went down substantially over time, as they did for DIN and DIP, the possible effects were checked with four separate analyses, using two MDL adjustments and two time periods. These included setting BDL values to zero and analyzing only data collected after October 1988, after the largest reductions in detection limits had occurred. The appendix provides a listing of the frequencies of BDL values for DIP and DIN. SUSQUEHANNA RIVER FLOW Correlations between upper Chesapeake Bay water quality and Susquehanna River flow were analyzed to examine the strength of any relationships. The flow data used were log-transformed monthly means of the daily flow at Conowingo, Md. Log transforma- tions of flow data made their distribution closer to a normal distribution. Because flow data and water quality data tend to show serial correlation, the P values listed are approx- imate. The Pearson (parametric) correlation was performed with the correlation procedure in SAS.10 10 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- PHOSPHORUS. The two phosphorus parameters analyzed were TP and DIP, which is the same as orthophosphate (PO4 filtered). TP was chosen because it shows total enrichment for phosphorus, while DIP is the form most readily utilized by phytoplankton. The three main stem laboratories changed methods for TP several times,3 but their methods were consistent after October 1988. TP had moderate reductions in MDL levels. Although DIP had no method changes, it had large reductions in MDL, which can complicate trend analysis.3 Since BDL values are censored at the MDL in the CBP data base, this could produce a significant down trend that was caused by the lower MDL. To eliminate trends that were due to MDL changes, different approaches were used for TP and DIP. TP, with moderate MDL reductions, was interpolated two ways: with BDL values set to one-half the MDL and also with all values below the highest MDL raised to that value (0.01 mg/L). The results of the analyses were very similar, so the MDL changes did not appear to affect the TP trends. DIP had larger MDL reductions, so four different analyses were performed: trends over all 8 years and over 4 years, starting in October 1988, when most detection limits had been lowered; and with BDL values set to either one-half the MDL or set to zero to assess the effects of BDL data on trends. Thus, the four BDL treatments for DIP con- sisted of the following: 1. Eight years of data (1984 to 1992), with BDL data set to one-half the MDL; 2. Four years of data (1988 to 1992), with BDL data set to one-half the MDL; 3. Eight years of data (1984 to 1992), with BDL data set to zero; 4. Four years of data (1988 to 1992), with BDL data set to zero. Because DIP is one of the SAV habitat requirements, it was analyzed over 7 months (April through October) as well as over 12 months, so there were eight sets of analyses for DIP. The results of these four BDL treatments were compared to eliminate any signif- icant trends that were caused by MDL changes. Statistically significant trends were eliminated if they met one or more of the following criteria: • If there was a significant reduction with MDL set to one-half and no trend or a significant increase with MDL set to zero, the reduction was probably caused by declining MDL. • If a trend was significant over 4 years but not over 8 years, there may be a nonmonotonic trend that is unrelated to MDL changes. • If there was a significant increase with BDL set to zero over 8 years but not over 4 years, the increasing trend may be caused by lowering the early BDL values to zero. This approach to identifying real trends was conservative because any trends that appeared to be caused b\ declining MDL were eliminated. However, it is still possibl that some of the DIP trends identified were affected by MDL changes. e NITROGEN The two nitrogen parameters analyzed were TN and DIN. TN was chosen because it shows total enrichment for nitrogen, while DIN includes the forms most readily taken by Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- phytoplankton. TN is calculated from total Kjeldahl nitrogen whole plus nitrite/nitrate (NOis) in early main stem data and from total dissolved nitrogen plus paniculate nitro- gen in later data. DIN is calculated from nitrite/nitrate plus ammonium (NH4). As with phosphorus, the total parameter had method changes, although it had minimal MDL re- ductions, and the dissolved inorganic parameter had no method changes and large reductions in MDL.12 The changes in TN MDL were small enough to have no effect on trends.12 The de- clining MDL for DIN were dealt with using the same four treatments used for DIP, except that trends could not be estimated for segments sampled by the Virginia Institute of Marine Science (VIMS). This affected the four segments with a majority of VIMS sta- tions: Tangier Sound (EE3), Mobjack Bay (WE4), and lower Chesapeake Bay segments CB6 and CB7. VIMS detection limits for DIN had a series of large reductions that con- tinued until July 1990, which left only 2 years of data after the reductions stopped. (See Table A.2 in the appendix.) This was not enough time to evaluate whether any trends were affected by declining MDL. SECCHI DEPTH Although Secchi depth has a lower MDL (0.1 meter), it did not change and it was almost never encountered. Thus, there were no MDL problems for Secchi depth. There were more ties in Secchi depth than in other parameters, but they still did not exceed 50 percent for any month. DISSOLVED OXYGEN Eight DO metrics were calculated and interpolated, and seven were analyzed statis- tically for trend over the whole main stem and for each of nine main stem segments. DO saturation trends were not analyzed, and data from EE3 were not analyzed for DO trends. All DO metrics were analyzed for trend over the 4 warm weather months (June through September) when low DO is most frequent. This time period is also used in the assess- ment of low DO levels in CBP time-variable model output. Other months were excluded because they would tend to obscure any trends that occurred during the warm weather months. DO has no detection limits, since values of zero can occur. The following eight metrics were calculated: 1. Monthly mean DO concentration: An upward trend shows improvement. 2. Monthly mean DO saturation concentration: This is calculated from water temperature and salinity12 and expresses the potential DO concentration at that temperature and salinity if the water was saturated with DO. Trends are neither improvements nor degradation but represent changes in the amount of oxygen that can be held in solution due to changes in water temperature and/or salinity. For this reason, trends were not calculated for saturation; it was used as an intermediate step in calculating the next two parameters. 3. Monthly mean DO delta concentration: This is calculated from DO satura- tion minus DO concentration. To eliminate the effects of any supersaturated conditions, DO delta was set to zero if less than zero. A downward trend shows improvement. (The DO concentration is getting closer to saturation.) Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- 4. Monthly mean DO deficit: This is calculated from DO delta, converting it from a concentration to the mass of DO that would need to be added to that segment to bring all areas up to DO saturation. DO deficit is the mass of oxygen at saturation minus mass of oxygen present, omitting any supersatu- ration. A downward trend shows improvement. (Less DO mass would need to be added to achieve saturation.) 5 to 8. Monthly mean volume of water below four DO concentrations: 5, 3, 1, and 0.2 mg/L. These were calculated using DO data from all depths, but since water in the surface layers rarely has low DO, almost all the volume with low DO was from below the pycnocline. A downward trend shows im- provement. (A smaller volume of water was below the cutoff concentration.) RESULTS AND DISCUSSION SUSQUEHANNA RIVER FLOW Susquehanna River flow data were analyzed because some water quality parameters may have positive or negative correlations with flow. If trends in flow were similar in magnitude and direction to the trends in one of the parameters analyzed and levels of that parameter were correlated with flow, that would indicate that interannual changes in flow might be responsible for the apparent trend in the water quality parameter. Total annual Susquehanna River flow and the number of months with mean flow above the 1950 to 1992 median for that month are shown in Figure 2. In an average year there should be 6 months with flow above the median and 6 months with flow below the median. Annual Susquehanna River flow was relatively high in 1986, 1989, 1990, and 1991 and relatively low in 1985, 1988, and 1992 (see Figure 2). The WY with the highest total flow (1991) had relatively few months (5) with mean flows above the 1950 to 1992 median. This apparent discrepancy resulted from high flows in the first 5 months of that WY (October 1990 through February 1991), which produced the high total flow, fol- lowed by 7 months of below average flows. Although there was a bimodal pattern in total flows (see Figure 2), there were no statistically significant trends (F>0.05) in either mean or total monthly Susquehanna Riv- er flows over either 12 or 7 months, over 8 years, or the first and last 4 years, using the seasonal Kendall tests. This means that interannual changes in flow were probably not responsible for any of the significant water quality trends observed. The levels of some of the water quality parameters probably were related to interannual changes in flow, but not in a simple fashion. The complexity of the relationships between Susquehanna River flow and upper Chesapeake Bay water quality is shown by the correlations in Table 1. If there was a sim- ple relationship between nutrients and flow, nutrients would show positive correlations with flow, with the strongest correlations in segment CB1 (Susquehanna Flats), especially in surface samples. Correlations should generally be stronger for nitrogen than for phos- phorus because nitrogen, especially nitrate, is more soluble in water than phosphorus, and the lagged correlations should be stronger in segments farther from the fall line because it takes water from the fall line longer to reach these segments. Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- \ \ I I 1 1 I 1985 1986 1987 1988 1989 1990 1991 1992 Total Flow Year # Months > median Figure 2. Total annual Susquehanna River flow (bars) and number of months above median flow line (water years 1985 to 1992). Table 1. Correlations between log mean monthly Susquehanna River flow and mean monthly con- centrations of water quality parameters (with P values in parentheses). Parameter Months With CB1 CB2 CBS CB4 CBS TP TP DIP DIP DIP DIP TN TN DIN 12 12 12 12 7 7 12 12 12 Flow Lag Flow Lag Flow Lag Flow Lag Flow NS NS NS NS NS NS 0.394 (0.0001) 0.285 (0.0051) 0.432 (0.0001) NS NS -0.290 (0.0042) -0.310 (0.0022) NS -0.277 (0.0404) 0.651 (0.0001) 0.545 (0.0001) 0.660 (0.0001) -0.294 (0.0037) -0.260 (0.0109) -0.361 (0.0003) -0.484 (0.0001) -0.372 (0.0048) -0.463 (0.0004) 0.737 (0.0001) 0.672 (0.0001) 0.775 (0.0001) -0.426 (0.0001) -0.314 (0.0019) -0.485 (0.0001) -0.359 (0.0004) -0.468 (0.0003) NS 0.618 (0.0001) 0.715 (0.0001) 0.737 (0.0001) -0.538 (0.0001) -0.394 (0.0001) -0.554 (0.0001) . -0.360 (0.0003) -0.540 (0.0001) NS 0.547 (0.0001) 0.673 (0.0001) 0.678 (0.0001) 14 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- Table 1. Correlations between log mean monthly Susquehanna River flow and mean monthly con- centrations of water quality parameters (with P values in parentheses) (Continued). Parameter Months With CB1 CB2 CBS CB4 CBS DIN DIN DIN Secchi Depth Secchi Depth Secchi Depth Secchi Depth DO DO DO Delta DO Delta DO Deficit DO Deficit 12 7 7 12 12 7 7 4 4 4 4 4 4 Lag Flow Lag Flow Lag Flow Lag Flow Lag Flow Lag Flow Lag 0.310 (0.0022) 0.568 (0.0001) 0.333 (0.0130) -0.418 (0.0001) -0.315 (0.0019) -0.736 (0.0001) -0.274 (0.0426) 0.398 (0.0242) 0.361 (0.0461) NS 0.368 (0.0418) NS 0.368 (0.0418) 0.561 (0.0001) 0.791 (0.0001) 0.476 (0.0002) -0.382 (0.0001) -0.404 (0.0001) -0.578 (0.0001) -0.340 (0.0112) 0.448 (0.0102) NS NS NS NS NS 0.663 (0.0001) 0.813 (0.0001) 0.360 (0.0070) -0.222 (0.0300) -0.319 (0.0017) -0.334 (0.0119) NS NS NS NS NS NS NS 0.753 (0.0001) 0.772 (0.0001) 0.386 (0.0036) NS NS NS NS NS NS NS -0.361 (0.0461) NS -0.361 (0.0461) 0.690 (0.0001) 0.697 (0.0001) 0.384 (0.0038) NS NS NS NS NS NS NS NS NS NS Legend and note: NS—Not statistically significant (R>0.05). Months: Number of months data used: 12—all year (No. of months—96); 7—April through October (No. of months—56); 4—June through September (No. of months—32). With: Flow—Log mean monthly flow (log of mean of daily flows); Lag—Log mean monthly flow of previous month. The results (see Table 1) do show stronger positive correlations for nitrogen than for phosphorus, but the nitrogen correlations with flow were always strongest in CB3 (un- lagged) or CB4 (lagged) and weakest in CB1. Both forms of phosphorus had negative correlations with flow in all of the segments with significant correlations, even though a positive correlation is expected for TP. Paniculate phosphorus, part of TP, is often at- tached to sediment, and higher flow usually increases sediment loads. Thus, reasons for these negative correlations of phosphorus with flow are not clear. Only Secchi depth showed the expected pattern of the strongest correlations in CB1 (or CB2 for lagged flow). This may be because Secchi depth has only one measurement per station, while the values for the other water quality parameters were averaged over results from two or four depths. The correlations of flow with Secchi depth were nega- Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 15 ------- live, presumably because higher flow brings more sediment, which reduces water clarity. Correlations with unlagged flow were stronger during April through October than during the whole year. Some of the DO metrics showed positive correlations with flow or lagged flow in CB1 and CB2, but the conflicting nature of the correlations means they were probably not meaningful. The correlations suggest that higher flow is associated both with higher DO concentrations in the current and following months (improvement), possibly due to increased aeration, but also with higher DO delta and deficit a month later (degradation). PHOSPHORUS Total Phosphorus Results show a statistically significant downward trend (improvement, P<0.01) bay- wide, in upper Chesapeake Bay segment CB2, and in lower Chesapeake Bay segments CB6 and CBS (see Table 2 and Figure 3). There were also marginally significant im- provements (P<0.05) in upper Chesapeake Bay segments CB1 and CB3 and lower Chesapeake Bay segment CB7 (see Table 2 and Figure 3). One segment with a significant trend (CB2) had a barely significant seasonal heterogeneity: the %2 value was 20.6, slight- ly more than the critical value of 19.7. However, since only 3 months had increasing trends (November, January, and T ruary), the overall decline in CB2 appeared to be val- id. Changes in TP detection limits had little effect on the trend results. An interpolator run with any values below 0.01 mg/L raised to that value had significant trends in the same segments, with very similar slopes. Figure 4 shows average monthly TP and DIP concentrations for each segment. DIP (thin line) is shown for comparison to TP levels; it was also graphed separately. Segments with statistically significant or marginally significant TP trends have a trend line connect- ing the 1984 to 1985 mean and the 1991 to 1992 projection based on the seasonal Kendall slope. The median bay wide percent change in TP over 8 years (1984 to 1992), based on the seasonal Kendall slope, was 16 percent plus or minus 8 percent (90 percent confi- dence interval). This is slightly less than the previous baywide percent change estimate for TP, which was 19 percent.3 One reason for the lower percent change is that March 1985 TP data, which were included in the previous analysis, were subsequently deleted from the data base due to quality assurance problems and were not used in this analysis. Percent change values for individual segments are listed in Table 2. The declines (improvements) in TP in upper Chesapeake Bay segments CB1, CB2, and CB3 were probably related to declines in Susquehanna River fall line concentrations. There were statistically significant (P<0.1) declines in flow-adjusted TP concentrations at the Susquehanna River fall line between 1984 and 1990, using both parametric regres- sions and seasonal Kendall trend tests.* *B. Dobler. Maryland Department of the Environment (MDE), unpublished analyses. 16 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- Table 2. Trend results for interpolated monthly mean total phosphorus by segment (12 months). Segment (CBP) All CB1 CB2 CBS CB4 CBS CB6 CB7 CBS WE4 EE3 Slope mg/L/yr -0.00067 -0.001 -0.002 -0.001 - - -0.00092 -0.0008 -0.0024 - - Z Trend -2.72 -2.15 -2.87 -2.48 - - -3.33 -2.53 -4.86 - - P 0.0066 0.032 0.0042 0.013 NS NS <0.001 0.011 <0.0001 NS NS X2 Seasonal 3.28 15.64 20.63 13.59 - - 8.67 8.5 7.88 - - P >0.95 >0.1 <0.05 >0.2 - - >0.5 >0.5 >0.7 - - % Change 16 16 29 17 - - 21 19 36 - - Legend and note: The total number of months (A/) for all segments was 96 (October 1984 through September 1992); all depths; results shown for segments with significant (P<0.01, underlined) trends and marginally significant (P<0.05) trends only. A negative (down) trend shows improvement (less phosphorus); NS—Not signifi- cant (P>0.05). X2 seasonal and its P value (last two columns) are a test for ho- mogerieity of the trend over different months. A P value of more than 0.05 indi- cates the trends were homogeneous; the trend in CB2 appeared to be valid even though P<0.05. Possible causes of the declines (improvements) in lower Chesapeake Bay segments CB6, CB7, and CBS are less clear. None of the tributaries draining into these main stem segments (Rappahannock, York, and James Rivers) had declining trends in TP over the period 1984 to 1991.13 In fact, all three rivers had some .segments and seasons with sig- nificant increases (degradation) in TP, including the segment at the mouths of the Rappahannock and James Rivers.13 The mouth of Chesapeake Bay (segment CBS) had both the highest concentrations (see Figure 4) and the largest percent change (see Table 2) of these three segments, suggesting that the TP declines in that segment might be re- lated to changes in oceanic concentrations. The downward trends in TP concentrations are consistent with TP load reductions over the whole watershed. Point source loads of TP were reduced by 40 percent between 1985 and 1990, while controllable nonpoint source loads fell 8 percent between 1985 and 1991, based on watershed model load estimates.1 Point sources of phosphorus comprise 34 percent of the watershed total loads and 42 percent of the controllable loads (exclud- ing atmospheric deposition). Nonpoint sources of phosphorus comprise 60 percent of the watershed total loads and 58 percent of the controllable loads.1 Dissolved Inorganic Phosphorus (Orthophosphate) Reductions in MDL appeared to have a major impact on trend results for DIP. For this reason, DIP trends were analyzed with four different MDL treatments to eliminate Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- Upper Chesapeake Bay Lower Chesapeake Bay CB7 -CBS no significant change marginally significant improvement significant improvement Trend over all main stem segments marginally significant degradation significant degradation CSC.MN1D.793 Figure 3. Total phosphorus trends in Chesapeake Bay main stem segments (October 1984 through September 1992). 18 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- 0.12- j °'1~ £ 0.08- QL Q 6 CL 0.04- 0.02- —^—^ TP DIP Note: Segments with trend lines had significant trends. Total Bay TP DIP Oct84 Oct85 OcU" Oct87 Oct88 Oct89 OctSO Ocl91 Oct92 CB1 CB2 Oct84 Oc!85 Oct66 Oct67 OcIB8 Oc!89 Ocl 90 OctSl Ocl 92 Oct84 Oct85 OCI66 Oct87 Ocl 88 Oct69 0«90 CW91 Ocl 92 CB3 CB4 OC164 0:185 0:'65 Ocl 87 Ocl 88 Oct89 Ocl 93 0:191 0:192 Oct84 OC185 OC186 Ocl 87 Ocl 86 Ocl 69 Ocl 90 OctSl Ocl 92 Figure 4. Average monthly concentrations of total phosphorus and dissolved inorganic phosphorus (1984 to 1992). Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 19 ------- __ IP DIP Note: Segments with trend lines had significant trends. 0<4-r- 012- _ 01- - J 1. 008- g. O 006- 004- 002- CB5 TP DIP OC184 Oc165 Oct86 Oc! 87 Ocl88 Oct 89 Oct 93 Ocl91 Oct92 CB6 OCI84 del 85 Oct86 0087 Oc'66 Oct89 Oct9C Oct91 OC192 CB7 014- 012- 01- 008- g_ Q 00<-- DIP OC184 Oct85 Oct86 Oct67 Oct 88 OC189 Oct 90 OCI91 Oct92 CB8 OC184 OC185 OC186 Oct 87 Oct 88 Oct 89 Od90 Oct 91 Oct 92 EE3 014- WE4 Oc1 E9 Oct 90 Oct91 OCI92 Oct84 ones oaee octs? oase octsg Oct9o octgi Oct92 Figure 4. Average monthly concentrations of total phosphorus and dissolved inorganic phosphorus (1984 to 1992) (continued). 20 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- trends that were caused by MDL changes. Table 3 lists the results of these treatments over 12 months and over the 7-month SAV growing season, for a total of eight sets of anuhses Two trends that appeared to be real occurred o\er 12 months in CBS and 7 months in CB4 (both improvements) and are shown in Figure 5. Baywide, the trend was not significant (see inset, Figure 5). Table 3. Trend results for interpolated monthly mean levels of dissolved inorganic phosphorus by seg- ment, using four different method detection limit treatments. Table 3a. BDL data set to one-half. Main Stem CBP Segments No. of No. of Months Years All CB1 CB2 CBS CB4 CBS CB6 CB7 CBS WE4 EE3 12 12 7 7 8 I - - - 4 8 I 4 - - IM I I I I _ _ _ I* IM I _ _ _ I I* I* I IM IM I DM - _ I - I _ Table 3b. BDL data set to zero. Main Stem CBP Segments No. of Months 12 12 7 7 No. of Years All CB1 8 4 - - 8 4 CB2 - - - IM CBS CB4 - - - - IM* ' I CBS DM - - - CB6 CB7 CBS IM* - - I* _ - - IM WE4 D - D - EE3 D DM D - Legend and note: I—Significant improvement (P<0.01). IM—Marginally significant improvement (P<0.05). D—Significant degradation (P<0.01). DM—Marginally significant degradation (P<0.05). Dash—No significant trend (P>0.05). *Trends that appear to be real, i.e., not caused by declining detection limits. 7 months—April through October only, SAV growing season in lower salinity zones. Figure 6 shows average monthly DIP concentrations for each segment, with BDL value^ set to one-half the MDL (thick line) and to zero (thin line). Segments with statisti- cally significant trends have two trend lines connecting the 1984 to 1985 mean and the 1991 to 1992 projection based on the seasonal Kendall slope, one for BDL set to one-half (thick line) and one for BDL set to zero (thin line). In one segment these lines overlap (CB4). Details of the trend results from Table 3 that appeared to be real are summarized in Tables 4 and 5. Percent change was near 30 percent in both CB4 and CBS. Results over 4 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 21 ------- Mouth of Chesapeake L:/(CE~ -12 months Middle Chesapeake Bay (CB4)-7 months no significant change marginally significant improvement significant improvement Trend over all main stem segments marginally significant degradation significant degradation CSC.MN1D7/93 Figure 5. Dissolved inorganic phosphorus trends in Chesapeake Bay main stem segments (October 1984 through September 1992). Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- 0.03- D) i, 0.02- Q. Q 0.01- Censored data set to half of detection limit. Censored data set to zero. Note: Segments with trend lines had significant trends. Total Bay Oct84 Oct85 Oct86 Oct87 Oct88 Oct89 Oct90 Oct91 Oct92 CB1 004 CB2 Oc'86 Oc!87 Oc!88 OCI89 Oct90 OC191 Oct92 OMB< Oct85 Oct86 Oct87 Oct88 Oct89 OctM Oct91 Oc1S2 CBS CB4 Oc- 6; Oc: 85 or Oc'.86 Oct 89 Oc!90 Oct91 Oct92 OctBI Oct85 OctSS Oct87 OctSS Ocl89 CW90 Oct91 Oct92 Figure 6. Average monthly concentrations of dissolved inorganic phosphorus (1984 to 1992). Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 23 ------- Censored data set to half of detection limit. Censored data set to zero. Note: Segments with trend lines had significant trends. CB5 CB6 Od84 OC185 0086 Oc!87 Oc! 88 Oc! 69 Ocl90 CM 91 Oct92 Oct84 Ocl85 Oct86 Oct87 OctSB Oct89 OctSO Ocl91 Oct92 CB7 D) E. 002- CB8 OctBS Ofl86 Oct87 Oct88 Oct69 0«90 Oct91 Oct92 Oct84 Oct85 Oct86 Oct87 Oct88 Oct89 Oct90 Ocl91 Ocl92 EE3 0-* Oc!84 Ocl85 Ocl86 Ocl87 Oct88 CW89 Oc!90 Oct91 Ocl92 WE4 CW84 OcI85 Oct86 Ocl87 Oct88 Ocl89 Oct90 OCI91 Oct92 Figure 6. Average monthly concentrations of dissolved inorganic phosphorus (1984 to 1992) (continued). 24 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- years are not shown since those analyses were only performed to assess the effects of changing detection limits. Table 4. Trend results for interpolated monthly mean dissolved inorganic phosphorus by segment (12 months). Segment (CBP) All CB1 CB2 CBS CB4 CBS CB6 CB7 CBS CB8 WE4 EE3 BDL Slope Treatment mg/L/yr - - - - - - - - 1/2 -0.00069 0 -0.00059 - - X2 Z Trend P Seasonal - NS - - NS - NS NS NS NS NS NS -3.75 0.00018 7.62 -2.36 0.018 11.77 NS NS % P Change - - - - - - - - - >0.7 31 >0.3 29 - - - Legend and note: The total number of months (N) for all segments was 96 (October 1984 through September 1992); all depths; results shown for segments with significant (P<0.01, underlined) trends and marginally significant (P<0.05) trends only. A negative (down) trend shows improvement (less phosphorus); NS—Not significant (P>0.05). x2 seasonal and its P value (last two col- umns) are a test for homogeneity of the trend over different months. A P value of more than 0.05 indicates the trends were homogeneous. Where there are two slopes for the same seg- ment, they "bracket" the true slope. Possible reasons for the declines (improvements) in DIP in middle Chesapeake Bay (segment CB4) and the mouth of Chesapeake Bay (segment CBS) are not clear. DIP trends have not been analyzed in tributary segments, mainly due to high MDL. The trend in the mouth of Chesapeake Bay (segment CBS) may be related to changes in oceanic concentrations; as was found for TP, CBS had higher concentrations than nearby seg- ments CB6 and CB7 (see Figure 6). The ecological significance of these trends in terms of SAV restoration appears to be be minimal because both of the segments that had significant down trends had already achieved the SAV habitat requirement for DIP (0.01 rng/L in me-sohaline regions and 0.02 mg/L in other salinity regimes5). The areas where DIP levels need to be reduced to per- mit SAV growth are in tributary segments.* *"\\ater Quality Restoration Priorities for Living Resources Report." (draft), CBP. Annapolis, Md (1993 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 25 ------- Table 5. Trend results for interpolated monthly mean dissolved inorganic phosphorus by segment (7 months, April through October). Segment (GBP) All CB1 CB2 CB3 CB4 CB4 CBS CB6 CB7 CB8 WE4 EE3 BDL Slope Treatment mg/L/yr Z Trend - - _ _ _ 1/2 -0.0003 -2.81 0 -0.000267 -2.21 _ _ - - - - - - _ - - P NS NS NS NS 0.005 0.027 NS NS NS NS NS NS I2 % Seasonal P Change _ _ _ - - - - - - - 1.37 >0.95 31 2.33 >0.8 28 - - - - - - - - - - _ _ _ _ Legend and note: The total number of months (N) for all segments was 56 (April 1985 through September 1992); all depths; results shown for segments with significant (P<0.01, underlined) trends and marginally significant (P<0.05) trends only. A negative (down) trend shows improvement (less phosphorus); NS—Not significant (P>0.05). x2 seasonal and its P value (last two col- umns) are a test for homogeneity of the trend over different months. A P value of more than 0.05 indicates the trends were homogeneous. Where there are two slopes for the same seg- ment, they "bracket" the true slope. NITROGEN Tola! Nitrogen There was no significant trend baywide for TN (see Table 6 and inset, Figure 7). There was a marginally significant increase (degradation, P=0.027) in segment WE4, which includes the mouth of the York River (see Figure 7). Figure 8 shows average monthly TN and DIN concentrations for each segment. DIN (thin line) is shown for comparison to TN levels, it was also graphed separately. Seg- ments with marginally significant or statistically significant TN trends have a trend line connecting the 1984 to 1985 mean and the 1991 to 1992 projection based on the seasonal Kendall slope. The lack of any TN trend in upper Chesapeake Bay is consistent with the flow-ad- justed TN loads at the Susquehanna River fall line. Data from this station showed no significant changes in loads (P>0.1) between 1984 and 1990.* L'i \iDL. unpuhli'.nco anai\- Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- Table 6. Trend results for interpolated monthly mean total nitrogen by segment. Segment (CBP) All CB1 CB2 CBS CB4 CBS CB6 CB7 CBS WE4 EE3 Slope mg/L/yr Z Trend P NS NS NS - NS - NS NS NS - NS NS 0.006 2.21 0.027 - NS X2 % Seasonal P Change _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 5.74 >0.8 10 _ Legend and note: The total number of months (A/) for all segments was 96 (October 1984 through September 1992); all depths; results shown for marginally significant (P<0.05) trends only. A negative (down) trend shows improvement (less nitrogen); NS—Not significant (P>0.05). x2 seasonal and its P value (last two columns) are a test for homogeneity of the trend over different months. A P value of more than 0.05 indicates the trends were homogeneous. The increase (degradation) in Mobjack Bay (segment WE4) is probably related to increases in nearby tributary segments. York River tributary segments LE4, RET4, and TF4 also showed significant TN increases (degradation).* Trend analyses by the Virginia Department of Environmental Quality found increasing trends in both TN and chloro- phyll a in all of the tidal sections of the York River.13 The general lack of significant trends in TN concentrations is consistent with TN point source load reductions over the whole watershed, which have been smaller than point source load reductions for TP. Point source loads of TN were reduced by only 6 to 7 percent between 1985 and 1990, while controllable nonpoint source nitrogen loads fell 12 percent between 1985 and 1991, based on watershed model load estimates.1 Point sources of nitrogen comprise 23 percent of the watershed total loads and 46 percent of the controllable loads (excluding atmospheric deposition). Nonpoint sources of nitrogen comprise 68 percent of the watershed total loads and 54 percent of the controllable loads.1 Dissolved Inorganic Niirogen As was found for DIP, reductions in MDL appeared to have a major impact on trend results for DIN. For this reason, DIN trends were also analyzed four different ways: 1. Over all 8 years; ""Water Quality Characterization Report for the 1991 Re-Evaluation of the Chesapeake Bay Nutrient Re- duction Strategy" (draft). CBP. Annapolis. Md (1991) Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 27 ------- Mobjack Bay (WE-4) Trend overall main stem segments no significant change marginally significant improvement significant improvement marginally significant degradation significant degradation Figure 7. Total nitrogen trends in Chesapeake Bay main stem segments (October 1984 through September 1992). Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- ——— IN DIN Note: Segments with trend lines had significant trends. Total Bay Oct84 Oct85 Oct86 Oct87 Oct88 Oct89 Ocl90 Oct91 Oct92 CB1 CB2 25-r OC184 Oct 85 CW86 Oct67 Oct 68 Oct89 Oct90 Oct91 Oct 92 Oct64 OC185 Oct86 OC187 OC188 Oct89 Oct90 Oct91 Oct92 CBS CB4 25-q Oc'Si Oc!E5 Oct86 Oct 87 0:'65 Oc! 89 Oct9D OctSl Oct92 Oct85 Oct86 Ocl87 Oct88 Ocl89 Oct90 Oct91 Oct Figure 8. Average monthly concentrations of total nitrogen and dissolved inorganic nitrogen (1984 to 1992). Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 29 ------- ^—^—— IN DIN Note: Segments with trend lines had significant trends. CB5 CB6 Oct 84 Oct85 Oc;B6 Oct87 Ocl 88 Oct89 Oc! 90 0:191 Ocl 92 Oc:65 Oct86 0:187 Oc!88 Oct 89 0:190 Oe 91 Oc! 92 CB7 CBS 0=164 0:185 0:166 Ocl 67 Oct 88 Oct 69 Ocl 90 Ocl 91 Oct 92 0:184 Ocl 85 0:186 Oc! 87 Oct88 OCI89 Ocl 90 Oct 91 Oct92 EE3 WE4 Oc-,84 OciBS Ocl 86 Oct 87 Oct 88 Oct 89 Oct 90 0:191 0:192 Oct 84 Oct 85 Oct 86 Oct 87 Od«8 Oct 89 Oct 90 Oct 91 0:192 Figure 8. Average monthly concentrations of total nitrogen and dissolved inorganic nitrogen (1984 to 1992) (continued). 30 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- 2. Over the last 4 years; 3. Starting in October 1988, when most detection limits were lowered; 4. With BDL set to either one-half the MDL or set to zero to assess the effects of BDL data on trends. There was no significant trend bay wide over the 8-year period (see Table 7 and in- set, Figure 9). None of the significant trend results in Table 7 appeared to be real; the significant trends in lower Chesapeake Bay segments CB6, CB7, WE4, and EE3 could be caused by declining detection limits. The significant improvements in total (baywide) and other segments only appeared over 4 years (see Table 7), so they were eliminated as probable results of nonmonotonic trends. Figure 10 shows average monthly DIN concentrations for each segment, with BDL values set to one-half the MDL (thick line) and to zero (thin line). These lines usually overlap, and the thin line is only visible in a few segments. There is a pattern of increas- ing concentrations followed by decreasing concentrations in the three upper Chesapeake Bay segments (CB1, CB2, and CB3) that are closest to the Susquehanna River and, thus, most affected by its flow. This pattern was not apparent in any other segments. SECCHI DEPTH Results show no significant trend baywide (see inset, Figure 11) or for any segment over 12 months (see Figure 11). There were marginally significant upward trends (im- provements) in upper Chesapeake Bay segments CB1 and CB2 over the 7-month SAV growing season (April through October) (see Table 8 and Figure 11). CB2 includes the turbidity maximum in Chesapeake Bay. Figure 12 shows average monthly Secchi depths for each segment. Segments with significant or marginally significant trends have a trend line connecting the 1984 to 1985 mean and the 1991 to 1992 projection based on the seasonal Kendall slope. The SAV habitat requirement for light attenuation (KD), which is related to Secchi depth, was often not met in segment CB2. The requirement was usually met in years with low flow and not met in years with high flow. The KD requirement for this area (2.0 m"1), is equivalent to a Secchi depth of 0.73 m (using Secchi=1.45/KD5). In CB2, the KD/Secchi requirement was met in 3 of the last 8 years (38 percent attainment). It was met in 1988 and 1992, both low flow years, also in 1991, a year with high total flow but a below aver- age number of months (5) above median flow (see Figure 2). The KD/Secchi requirement was not met in 5 years (1985 through 1987 and 1989 and 1990). Four of these years had high Susquehanna River flow, but 1985 had relatively low flow (see Figure 2). Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 31 ------- Table 7. Trend results for interpolated monthly mean levels of dissolved inorganic nitrogen by segment using four different method detection limit treatments. Table 7a. Below detection limit data set to one-half. Main Stem CBP Segments No. of No. of Months Years All CB1 CB2 CBS CB4 CBS CB6 CB7 CBS WE4 EE3 12 12 7 7 8 4 8 4 _ IM IM I _ I IM I - - - I I IM - - - I I IM I+ IM+ IM IM l+ IM+ I I IM l+ IM+ IM+ IM - - IM Table 7b. Below detection limit data set to zero. Main Stem CBP Segments No. of No. of Months Years All CB1 CB2 CB3 CB4 CBS CB6 CB7 CBS WE4 EE3 12 12 7 7 8 4 8 4 - IM - I I I I - - IM I ! - - I IM - I IM l+ IM+ - IM l+ IM+ - I _ IM+ IM+ - - IM Legend and note: I—Significant improvement (P<0.01). IM—Marginally s'^:':~a-it improvement (P<0.05). Dash—No significant trend (P>0.05). +These trends were not identified as real because detection limits in these segments continued to de- cline until July 1990; therefore, the marginally significant 4-year trends could be caused by declining detection limits. 7 months—April through October only, SAV growing season in lower salinity zones. The annual pattern of attainment of the KD requirement suggests an inverse correla- tion between Susquehanna River flow and Secchi depth in these segments, which was found (>ec lable 1). However, the lack of a significant monotonic trend in flow over this period means that the marginally significant trends in Secchi depth in upper Chesapeake Bay were IT~>' a simple consequence of a trend in flow. 32 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- no significant change marginally significant improvement significant improvement Trend over all main stem segments marginally significant degradation significant degradation CSC.MN1D.7/93 Figure 9. Dissolved inorganic nitrogen trends in Chesapeake Bay main stem segments (October 1984 through September 1992). Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 33 ------- 2.5 -q Censored data set to half of detection limit. Censored data set to zero. Note: Segments with trend lines had significant trends. Total Bay 0 Oct84 Oct85 0 -i Oct87 Oct88 Oct89 Oct90 Oct91 Oct92 CB1 CB2 Oct64 Oc!65 OC186 Oc'.87 Oc',88 Ocl 89 Ocl 90 OcI91 Ocl S Oct84 OC185 Ocl 86 Oct87 Ocl 88 Ocl 69 OctSO Ocl 91 Ocl 92 CBS "64 Oc;65 Oc. £5 Oc' £7 Oc188 Ocl 89 0:1 K Ocl 91 Ocl 92 25-q 1.5- 05H CB4 0:184 Ocl 85 OC186 Ocl 87 Oct88 Oct89 Oct90 Oct91 Ocl 92 Figure 10. Average monthly concentrations of dissolved inorganic nitrogen (1984 to 1992). Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- Censored data set to half of detection limit. Censored data set to zero. Note: Segments with trend lines had significant trends. CB5 CB6 Oct 84 Octes Oct ee Ocie? Octes Octeg 0=190 Oci9t 00192 Oct84 Octss Octee Octe? Octee oass 0090 Oct9i Oct92 CB7 CBS 25 Oct64 Oci65 Oct86 Oc: 87 Oc!S6 OC189 Oc! 90 Oct 91 Oc! 92 OCI84 Oct 85 0:186 Oct 67 Oct 68 Oct 69 Oct 90 Oct 91 Oct 92 EE3 Oct 62 Oc'85 Oc;85 0:'87 Oc! 88 Oct 69 Oc: 90 C::S' 0:192 WE4 "i: 04-j 03H I 02- Oct6< Oct 65 Oct 86 Oct 67 Oa88 Oct 89 Oct 90 Oct 91 Oct 92 Figure 10. Average monthly concentrations of dissolved inorganic nitrogen (1984 to 1992) (continued). Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 35 ------- CB1 Northern and Upper Chesapeake Bay -7 C02 months no significant change marginally significant improvement significant improvement Trend over all main stem segments marginally significant degradation ' significant degradation CSC.MN1D.7/93 Figure 11. Secchi depth trends in Chesapeake Bay main stem segments (October 1984 through September 1992). 36 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- Secchi depth Note: Segments with trend lines had significant trends. Total Bay i i i r Oct84 Oct85 Oct86 Oct87 Oct88 Oct89 Oct90 Oct91 Oct 92 E 3- CB1 0:!64 Oct85 OclBS Oct 67 Oct 85 Oct 89 Oct 90 Oct 91 Oct 92 CB2 Oct 84 Oct 85 OC186 Oct 87 Oct 88 Oct 89 Oct 90 Oct91 Oct 92 CB3 CB4 Ocl6< OctES Oc!66 Oct 67 Oct 88 Oct 69 Oc'. K 0:'. 91 0::S2 Oct 84 Oct 85 Oct 86 Oct 87 Oct 88 Oct 89 Oct 90 Oct 91 Oct 92 Figure 12. Average monthly Secchi depths (1984 to 1992). Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 37 ------- Secchi depth Note: Segments with trend lines had significant trends. CB5 CB6 e 3- §25^ 05- 0:!64 OCI85 Oct 65 OC187 Oct 88 Oct 63 Oct 90 Oc!91 0:; 52 -1 1- Oct64 Oct 85 Oct 66 Oct 87 Oct 88 Oct 89 Oct 90 OctS1 Oct 92 CB7 CBS Oc',87 Oct 68 OS 89 Oct 90 Oct 91 Oc: 92 Oct 84 Oct 85 0086 Oct 87 Oct 68 Oct 89 Oc! 90 Oct 91 Oct 92 EE3 WE4 45- 4- •g ^ ,S 15- Oct64 Oc!85 Oct 86 Oct 67 Oc! 68 Oct 89 Oct 90 Oct 3: Oc! 92 Oct 84 Oct 85 Oct 86 Oct 87 Oct 88 Oct 89 Oc!90 Oct 91 Oct 92 Figure 12. Average monthly Secchi depths (1984 to 1992) (continued). Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- Table 8. Trend results for interpolated monthly mean Secchi depth by segment (7 months, April through October). Segment (CBP) All CB1 CB2 CBS CB4 CB5 CB6 CB7 CBS WE4 EE3 Slope m/yr - 0.017 0.025 - - - - - - - - Z Trend P NS 1.97 <0.05 2.38 <0.017 NS NS NS NS NS NS NS NS X2 Seasonal - 4.92 8.46 - - - - - - - - % P Change - - <0.7 18 >0.2 34 - - - - - - - - - - - - Legend and note: The total number of months (A/) for all segments was 56 (April 1985 through September 1992); all depths; results shown for marginally significant (P<0.05) trends only. No segments had significant trends over 12 months. A positive (up) trend shows improvement (clearer water); NS—Not significant (P>0.05). X2 seasonal and its P value (last two columns) are a test for homogeneity of the trend over different months. A P value of more than 0.05 indicates the trends were homogeneous. Secchi depth is not measured in the Susquehanna Rixer, so it is not known whether there were trends in Secchi depth there. Total suspended solids and turbidity data col- lected at the Susquehanna River fall line station (CB1.0) showed no significant trends overthe 1984-to-1991 period (P>0.1*). DISSOLVED OXYGEN Trend results for the two DO metrics that had significant trends are shown in Tables 9 and 10. Table 9 shows results for DO delta, and Table 10 shows results for DO deficit, both over the warm weather period (June through September). Trend results for DO con- centration and the four metrics for volumes below specific concentrations are not shown because no trends were statistically significant for those parameters. Segment CBS showed marginally significant degradation in both DO delta and DO deficit (see Figure 13). *B Dobler. MDE. unpublished analyses Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 39 ------- Mouth of Chesapeake Bay (CB8)-4 months, both parameters DO delta is DO at saturation minus DO. DO deficit is mass at saturation minus mass present. no significant change marginally significant improvement significant improvement Trend over all main stem segments marginally significant degradation significant degradation CSC.MN1D.5TO Figure 13. Dissolved oxygen delta and dissolved oxygen deficit trends in Chesapeake Bay main stem segments (October 1984 through September 1992). 40 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- Table 9. Trend results for interpolated monthly mean dissolved oxygen delta by segment (4 warm weather months, June through September). Segment (CBP) All CB1 CB2 CBS CB4 CBS CB6 CB7 CBS WE4 Slope mg/L/yr - - - - - - - - 0.038 - Z Trend P NS NS NS NS NS NS NS NS 2.50 0.012 NS X2 % Seasonal P Change _ _ - _ _ _ _ - - - - - - - 0.57 0.9 77 _ _ Legend and note: The total number of months (N) for all segments was 32 (June 1985 through September 1992); all depths; results shown for marginally significant (P<0.05) trends only. A positive (up) trend shows less desirable conditions (degrada- tion); NS—Not significant (P>0.05). x2 seasonal and its P value (last two col- umns) are a test for homogeneity of the trend over different months. A P value of more than 0.05 indicates the trends were homogeneous. DO data were not analyzed in EE3. Figure 14 shows average monthly DO and DO delta concentrations for each seg- ment. .V DO (upper line) goes down in the summer, DO delta (lower line) goes up. especially in segment CB4. Segments with marginally significant trends (DO delta in CBS) have a trend line connecting-the 1984 to 1985 mean and the 1991 to 1992 projec- tion based on the seasonal Kendall slope. Although some segments appear to have declining trends in DO concentration, e.g., total segments and segment CBS, these were not statistically significant when tested over the warm weather period only (June through September). Figure 15 shows the total volumes of water in each segment with DO below four concentrations: 0.2, 1, 3, and 5 mg/L, summed over all 4 months of the warm weather period (June through September). Hypoxia/anoxia is a problem during late spring and summer in the deeper waters of middle Chesapeake Bay (primarily segments CB4 and CBS). Reducing the volume of anoxic water in Chesapeake Bay is a major goal of nutri- ent reduction strategies. The trend results for anoxic volume and the volumes of water at the other target concentrations were not significant in any segment; in segments CB4 and CBS (segments with relatively large total volumes), the volumes at the higher concentra- tion categories were fairly consistent from year to year, with some shifting between the less than 0.2 and 0.2-to-l mg/L categories. Lower Chesapeake Bay segments CB6 and CB7, also relatively large segments, had almost no anoxic water and had more variability in the volumes of water in the other categories. A low flow year, 1988 (see Figure 2), Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 41 ------- DO concentration DO delta Note: Segments with trend lines had significant trends. Total Bay CONC. DELTA Oct84 Oct85 Oct86 Oc!87 Oc!88 Oct89 Oct90 Oct91 Oct92 CB1 CB2 - I _\_- I--1—J \_l \—l \—I—I—I—I 1—I CONC DELTA Oci84 oaes Octee Octe: Ocies oct89 Oct9o Oct84 OCI85 Oct86 Oc!87 OctBB Oct89 Oct90 OcS1 Oct92 CBS CB4 CONC DELTA CONC DELTA Ocl84 OC185 Oc'87 Oc!88 Ocl89 Oc!90 Oct91 Oct92 Ocl84 OCI85 OCI86 0«87 OcISS Oct89 Oct90 OCI91 Oct92 Figure 14. Average monthly concentrations of dissolved oxygen and dissolved oxygen delta (1984 to 1992). Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- DO concentration DO delta Note: Segments with trend lines had significant trends. ^ 9- 2 6- 8 34 o D CBS CONC DELTA CBS CONC DELTA OC184 OC185 Oc!86 Oc!87 Oc!88 Oc!B9 OctSD Oct9; Oct92 Oc!84 Oct85 Oct86 OC187 Oct88 OctBS CW90 0«91 Oct92 15- CB7 ^ \—/-\- CONC DELTA CBS CONC DELTA OCI84 Ocl35 OC186 OctB? OC186 Oc!89 Oct93 Oct91 Oc!92 Oct84 Oct85 Ocl86 Oc187 CW88 Oct89 Oct90 Oct91 0«92 WE4 CONC DELTA OC184 Oct85 OC186 OC187 Oct88 CW89 Ocl90 CW91 Oct92 Figure 14. Average monthly concentrations of dissolved oxygen and dissolved oxygen delta (1984 to 1992) (continued). Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 43 ------- 140- « Fso- DO Concentration Range 3.0-5.0 n 0.2-1.0 1.0-3.0 0.0-0.2 140^ Total Bay 1985 1986 1987 1988 1989 1990 1991 1992 CB1 CB2 140 -i •5 |3CH 19S5 1986 1987 1988 1989 1990 1991 1992 CBS 1985 1986 1987 1988 1989 1990 1991 1992 CB4 Ian 10-j B S H B B 1965 19S6 1967 1988 1989 1990 1991 1992 1985 1986 1987 1988 1989 1990 1991 1992 Figure 15. Total volumes of water with dissolved oxygen concentrations below 0.2, 1, 3, and 5 mg/L (June through September, 1985 to 1992). 44 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- DO Concentration Range 3.0-5.0 n 0.2-1.0 1.0-3.0 0.0-0.2 CBS it rso-i •5 : S«H !« CB6 pnP PPPDP 1985 1986 1987 1988 1969 1990 1991 1992 1985 1986 1987 1988 1989 1990 1991 1992 140 30- 10-i CB7 n 1985 1986 19E7 1988 1989 1990 1991 1992 01 50- |20i | 10- CBS r , — , 1985 1986 1987 1988 1989 1990 1991 1992 WE4 _ ?e I" 50- ^20^ 1985 1986 1987 1988 1989 1990 1991 1992 Figure 15. Total volumes of water with dissolved oxygen concentrations below 0.2,1, 3, and 5 mg/L (June through September, 1985 to 1992) (continued). Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 45 ------- usually had the lowest total volume of water below 5 mg/L. This is probably due to re- duced stratification in low flow years. Table 10. Trend results for interpolated monthly mean dissolved oxygen deficit by segment (4 warm weather months, June through September). Segment (CBP) All CB1 CB2 CBS CB4 CBS CB6 CB7 CBS WE4 Slope kg/yr* - - - - - - - - 143.4 - ZTrend P NS NS NS NS NS NS NS NS 2.04 0.041 NS X2 % Seasonal P Change _ _ _ _ _ _ _ - - - _ _ - - - 0.17 0.98 88 _ _ • 'Units are kgx 1011. Legend and note: Dissolved oxygen deficit is dissolved oxygen delta converted to a mass of oxy- gen. The total number of months (N) for all segments was 32 (June 1985 through September 1992); all depths; results shown for marginally significant (P<0.05) trends only. A positive (up) trend shows a movement toward less de- sirable conditions (degradation); NS—Not significant (P>0.05). x2 seasonal and its P value (last two columns) are a test for homogeneity of the trend over different months. A P value of more than 0.05 indicates the trends were homo- geneous. DO data were not analyzed in EE3. The marginally significant trends in two DO metrics at the mouth of Chesapeake Bay (segment CBS) have no obvious potential causes. DO concentrations are generally high in CBS (see Figure 14) and DO delta is quite low, so these trends are unlikely to ha\e any negative impact on living resources in CBS. The high percent change values (77 and 88 percent) appear to be partly due to abnormally low values in the 1985 WY. PLANS FOR FUTURE TREND ANALYSES INTERPOLATING ABOVE AND BELOW PYCNOCLINE LAYERS AND SURFACE AND BOTTOM LAYERS SEPARATELY Several enhancements to the trend analysis methods are planned for the next trend analysis update. The enhancements that may be implemented include interpolating above and below pycnocline layers and surface and bottom layers separately. This will make it possible to perform trend analyses of water quality in separate water layers. Trend analy- ses of DO concentrations will focus on the bottom layer and the region below the pycnocline, where almost all of the low DO concentrations occur. Trends in nutrient pa- 46 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- rameters affecting SAV growth, DIN, and DIP will focus on the surface mixed layer, since SAV habitat requirements are defined only for surface concentrations. ACCOUNTING FOR INTERANNUAL CHANGES IN FLOW The seasonal Kendall test accounts for seasonal changes in flow within years, but not for changes in flow between years. Interannual flow differences could be estimated from fall line flow data; however, this is difficult in the main stem, where the fall line may be quite far from the segment and flow from more than one river affects some seg- ments. Flow effects will probably be estimated indirectly from the degree of stratification within each main stem segment, especially for DO. ADDING PARAMETRIC TREND TESTS Software is currently being developed to streamline the autoregressive parametric trend tests that were used in two of the previous trend reports.3'4 The advantages of these tests are that they account for serial correlation in the data; therefore, the significance lev- els are more accurate and they can account for changes in detection limits. ADDING TREND TESTS ON INTERPOLATED TRIBUTARY DATA The volumetric interpolate! >es not currently operate in the tributaries, but there are plans to develop this capability This would permit the analysis of tributary water quality trends using the same methods and time periods used to analyze main stem trends. SUMMARY The trend results for phosphorus, nitrogen, Secchi depth, and DO are summarized in Table 11. Because eutrophication is "one of the main causes of low DO in Chesapeake Bay. there should be improvements in DO where there are improvements (declines) in nutrient levels. Improving trends in DO would increase the amount of living resource habitat in Chesapeake Bay. Table 11 shows that there were statistically significant de- clines (improvements) in TP and DIP in some segments but no corresponding improvements in any of the DO metrics. This lack of improving trends in DO could be due to two factors: 1. The nutrient declines, although statistically significant, may not have been large enough to improve DO conditions or they may not have affected enough of Chesapeake Bay. Also, nitrogen has not shown significant im- provements in any segments. Summer hypoxia and anoxia may be more affected by the freshet and its nitrogen supply than by phosphorus levels. 2. There has not been enough time for DO responses. There may be a time lag between nutrient reductions and DO improvements. Nutrients stored in sed- iments from previous years may promote DO depletion,8 although some authors have argued that the timing and extent of summer anoxia are gov- erned mainly by climatic conditions in that year.14 Upbay and downbay transfer of nutrients, organic matter, and DO also complicate any responses of DO levels to nutrient reductions. Improving trends in dissolved inorganic nutrients and Secchi depths can also lead to attainment of SAV habitat requirements if the requirements are not currently met. This Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 47 ------- should promote SAV restoration. Both of the segments that had improving trends in DIP are already in attainment for those requirements, so these trends should have little impact on SAV restoration. However, the improving trend in Secchi depth in one upper Chesa- peake Bay segment (CB2) may lead to an increased frequency of attainment of the Secchi depth requirement in that segment in the future. Table 11. Summary of trend results (October 1984 through September 1992). Main Stem CBP Segments Parameter No. oi Months All CB1 CB2 CBS CB4 CBS CB6 CB7 CBS WE4 EE3 TP DIP DIP TN DIN DIN Secchi Depth Secchi Depth DO Concentration DO Delta DO Deficit DO<0.2 DO<1.0 DO<3.0 DO<5.0 12 12 7 12 12 7 12 7 4 4 4 4 4 4 4 I IM I IM - - I IM I - - ________ | __ ____ | ______ _________ DM ------ + + - + + ------ + + - + + ___________ -IMIM -------- ----------- ________ DM -- __._ _ _ _ _ _ DM - ----------- ----------- ___________ ----------- Legend and note: I—Significant improvement (P<0.01). IM—Marginally significant improvement (P<0.05). DM—Marginally significant degradation. Dash—No significant trend (P>0.05). H—DIN trends could not be assessed in these segments because detection limits did not stop declin- ing untilJuly 1990. 7 months—April through October only, same as SAV growing season in lower salinity zones; 4 months—June through September only, used as period of anoxia in three-dimensional model analy- ses. DO data were not analyzed in EE3. See text for explanation of DO delta, DO deficit, and DO volumes below the four concentrations. 48 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- REFERENCES 1. "Progress Report of the Baywide Nutrient Reduction Reevaluation: 1991 Reeval- uation Report No. 5," CBP/TRS 92/93, CBP, Annapolis, Md. (1993). 2. "Dissolved Oxygen Trends in the Chesapeake Bay (1984-1990)," CBP/TRS 66/91, CBP, Annapolis, Md. (1991). 3. "Trends in Phosphorus in the Chesapeake Bay (1994-1990)," CBP/TRS 67/91, CBP, Annapolis, Md. (1991). 4. "Trends in Nitrogen in the Chesapeake Bay (1984-1990)," CBP/TRS 68/92, CBP, Annapolis, Md. (1992). 5. Batiuk, R.A., R.J. Orth, K. Moore, W.C. Dennison, J.C. Stevenson, V. Carter, N. Rybicki, R. Hickman, S. Kollar, S. Bieber, and P. Heasly, "Chesapeake Bay Sub- merged Aquatic Vegetation Habitat Requirements and Restoration Targets: A Technical Synthesis," CBP/TRS 83/92, CBP, Annapolis, Md. (1992). 6. Reynolds, R., and L. Bahner, "A Three-Dimensional Interpolator for Estimating Water Quality Conditions in the Chesapeake Bay: Description and Preliminary Application to Dissolved Oxygen," Computer Sciences Corp., Annapolis, Md. (1989). 7. Schubel, J., and D. Pritchard, "Responses of Upper Chesapeake Bay to Varia- tions in Discharge of the Susquehanna River," Estuaries, 9:236-249 (1986). 8. Taft, J., E. Hartwig, and R. Loftus, "Seasonal Oxygen Depletion in Chesapeake Bay," Estuaries, 3:242-247 (1980). 9. Gilbert. R., Statistical Methods for Environmental Pollution Monitoring, Van Nostrand Remhold Co., New York (1987). 10. SAS Procedures Guide, Version 6, Third Edition, SAS Institute, Inc. Gary, N.C. (1990). 11. Jordan, S., C. Stenger, M. Olson, R. Batiuk, and K. Mountford, "Chesapeake Bay Dissolved Oxygen Goal for Restoration of Living Resource Habitats: A Synthe- sis of Living Resource Habitat Requirements With Guidelines for Their Use in Evaluating Model Results and Monitoring Information," CBP/TRS 88/93, Mary- land Department of Natural Resources, CBP, Annapolis, Md. (1993). 12. "Guide To Using Chesapeake Bay Program Water Quality Monitoring Data," CBP/TRS 78/92, CBP, Annapolis, Md. (1992). 13. "Discussion Paper: Reducing Nutrients in Virginia's Tidal Tributaries," Virginia Department of Environmental Quality, Richmond, Va. (1993). 14. Boicourt, W., "Influences of Circulation Processes on Dissolved Oxygen in the Chesapeake Bay," in: Oxygen Dynamics in the Chesapeake Bay: A Synthesis of Recent Research, D. Smith, M. Leffler, and G. Mackiernan, Eds., pp. 7-59, Maryland Sea Grant College, College Park, Md. (1992). Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 49 ------- 50 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- APPENDIX FREQUENCIES OF BELOW DETECTION LIMIT VALUES FOR DISSOLVED INORGANIC PHOSPHORUS AND DISSOLVED INORGANIC NITROGEN Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 51 ------- Table A.1. Percent of observations with below detection limit values for dissolved inorganic phosphorus by segment, laboratory, and water year. Segment Laboratory Year % BDL Mean MDL CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB2 CB2 CB2 CB2 CB2 CB2 CB2 CB2 CB3 CBS CBS CBS CBS CB3 CBS CBS CB4 CB4 CB4 CB4 CB4 CB4 CB4 CB4 CBS CBS CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL7CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL L/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL 85 86 87 88 89 90 91 92 85 86 87 88 89 90 91 92 85 86 87 88 89 90 91 92 85 86 87 88 89 90 91 92 85 86 19.4 0 7.9 0 0 0 0 0 3.8 0 0 0 0 0 0 0 8.6 1.3 2.5 0 0 0 0 0 22.2 6.8 11.4 0.1 0 0 0.6 0 30.7 21.5 0.0055 - 0.0016 - - - - - 0.007 - - - - - - - 0.007 0.0016 0.0016 - - - - - 0.006 0.0016 0.0016 0.0006 - - 0.0006 - 0.0061 0.0016 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- Segment Laboratory Year % BDL Mean MDL CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 EE3 EE3 EE3 EE3 EE3 EE3 CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS v'IMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS 87 88 89 90 91 92 85 86 87 88 89 90 91 92 85 86 87 88 89 90 91 92 85 86 87 88 89 90 91 92 85 86 87 88 89 90 15.2 0.9 0.6 0 0 0.3 81.8 89.4 75.6 37.6 27.4 62 18.1 7.8 85.1 85.4 70.8 37.8 30.5 62.5 18.1 10.5 83.5 83.8 75.8 34.2 25 55.6 19.5 10.6 100 100 94.9 36.1 47.4 69.4 0.0016 0.0006 0.0006 - - 0.0006 0.01 0.0105 0.0101 0.0016 0.002 0.0028 0.0006 0.0006 0.01 0.0105 0.0104 0.0016 0.002 0.0027 0.0006 0.0006 0.01 0.0105 0.01 0.0016 0.0022 0.0028 0.0006 0.0006 ' 0.01 0.0105 0.0094 0.0019 0.0016 0.0024 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 53 ------- Segment Laboratory Year % BDL Mean MDL EE3 EE3 WE4 WE4 WE4 WE4 WE4 WE4 WE4 WE4 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CBS CBS CBS CBS CBS CBS CBS CBS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU 91 92 85 86 87 88 89 90 91 92 85 86 87 88 89 90 91 92 85 86 87 88 89 90 91 92 85 86 87 88 89 90 91 92 27.8 5.6 90.7 84.9 71.7 40.3 28.3 58.3 11.9 2.8 36.2 63.3 50 47.2 25.7 36.1 44.4 58.3 32.3 52.7 46.7 32.7 17.8 23.1 23.6 44.4 16.1 39.9 29.2 26.1 9 7.2 15 35.8 0.0006 0.0006 0.0099 0.0105 0.0109 0.0016 0.0022 0.0028 0.0006 0.0006 0.01 0.01 0.0053 0.005 0.005 0.005 0.005 0.005 0.01 0.01 0.0052 0.005 0.005 0.005 0.005 0.005 0.01 0.01 0.0051 0.005 0.005 0.005 0.005 0.005 54 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- Table A.2. Percent of observations with below detection limit values for dissolved inorganic nitrogen by segment, laboratory, constituent parameter, and water year. Segment Laboratory Parameter Year % BDL Mean MDL % of DIN CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB1 CB2 CB2 CB2 CB2 CB2 CB2 CB2 CB2 CB2 CB2 CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRUCBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL Both NH4 N023 Both NH4 NC-23 Both NH4 N023 Both NH4 NO23 Both NH4 NC-23 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 NO23 Both NH4 N023 Both 85 85 85 86 86 86 87 87 87 88 88 88 89 89 89 90 90 90 91 91 91 92 92 92 85 85 85 86 86 86 87 87 87 88 0 - - 13.9 0.0166 1.3 0 0 - - 2.8 0.003 0.3 0 0 - - 0 - - 0 - - 0 - - 5.3 0.003 0.5 0 0 10.5 0.003 0.2 0 0 - - 5 0.003 0.3 0 0 - - 15.4 0.003 0.3 0 - - 0 - - 2.5 0.003 0.3 0 0 0 0 0 0.9 0.003 1.4 0 - - 0 0 - - 0 - - o - • - Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 55 ------- Segment Laboratory Parameter Year % BDL Mean MDL % of DIN CB2 CB2 CB2 CB2 CB2 CB2 CB2 CB2 CB2 CB2 CB2 CB2 CB2 CB2 CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL NH4 NO23 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 NO23 Both NH4 N023 Both 88 88 89 89 89 90 90 90 91 91 91 92 92 92 85 85 85 86 86 86 87 87 87 88 88 88 89 89 89 90 90 90 91 91 91 92 0.9 0.005 0 0 0.9 0.003 0 0 5 0.003 0 0 3.3 0.003 0 0 1.7 0.003 0 0 2.9 0.0257 0 0 0 0 0 0 0 0 0 0 0 3.9 0.003 0 0 4.4 0.003 0 0 4.3 0.003 0 0 0.7 - - 0.2 - - 0.3 - - 0.9 - - 0.3 - - 6.7 - - - - - - - - - - - 0.5 - - 0.7 - - 7.6 ' 56 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- Segment Laboratory Parameter Year % BDL Mean MDL % of DIN CBS CBS CB4 CB4 CB4 CB4 CB4 CB4 CB4 CB4 CB4 CB4 CB4 CB4 CB4 CB4 CB4 CB4 CB4 CB4 CB4 CB4 CB4 CB4 CB4 CB4 CB5 CBS CBS CBS CBS CBS CBS CBS CBS CBS CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL - CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL NH4 N023 Both NH4 N023 Both NH4 NC-23 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both 92 92 85 85 85 86 86 86 87 87 87 88 88 88 89 89 89 90 90 90 91 91 91 92 92 92 85 85 85 86 86 86 87 87 87 88 2.5 0 0 7.5 3.8 0 0.7 0.1 0 0 0.1 0 5.7 0 0 7.8 0 0 10.3 6 0 13.9 0 0 11 0 3.8 10 14.1 0 0.6 0 0 0 0 0 0.0097 1.7 - - 0.0293 19.2 0.04 22 - 0.003 0.6 0.0009 0.3 - - - 0.0009 0.3 - 0.0046 25.9 - - - 0.003 2.3 - - - 0.003 4.8 - - 0.003 13.1 - - 0.003 13.4 - 0.06 0.0242 30 0.04 34 - 0.003 0.9 - - - - - Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 57 ------- Segment Laboratory Parameter Year % BDL Mean MDL % of DIN CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CBS CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL CRL/CBL VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 3th NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 NO23 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both 88 88 89 89 89 90 90 90 91 91 91 92 92 92 85 85 85 86 86 86 87 87 87 88 88 88 89 89 89 90 90 90 91 91 91 92 14.7 0 0 15.9 0 0 13.8 0 0 20.6 0 0 14.7 0 22.3 25.9 33.1 18.1 35.7 16.6 8.1 12.1 31.8 4.2 12.2 9.5 6.5 28.8 1.6 5.6 36.3 6.1 7.9 9.6 14.7 5 0.0043 - - 0.003 - - 0.003 - - 0.003 - - 0.003 - 0.0397 0.0198 0.0199 0.0418 0.0215 0.0198 0.0254 0.0155 0.0104 0.0161 0.0133 0.0033 0.0121 0.012 0.0021 0.0075 0.0094 0.0024 0.0045 0.0038 0.0024 0.0046 22 - - 5.2 - - 11.2 - - 20.7 - - 22.8 - - 19.1 22.8 - 13 26.7 - 14.7 21.2 - 53.5 9.6 - 23 7.2 - 23.5 19.9 - 8 24.5 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- Segment Laboratory Parameter Year % BDL Mean MDL % of DIN CBS CBS CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 NO23 DOth NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both 92 92 85 85 85 86 86 86 87 87 87 88 88 88 89 89 89 90 90 90 91 91 91 92 92 92 85 85 85 86 86 86 87 87 87 88 16.7 6.7 28.9 24.5 29.6 16.8 33.5 19.2 8.8 11.3 36.8 6.3 10 14.3 9 28.1 2 19.6 28.4 3.5 8.7 11.1 11.8 7 25.5 8 28.4 23.3 31.5 16.3 32.9 20.8 10.8 9.2 39.6 6.8 0.0039 0.0023 0.04 0.0193 0.0199 0.042 0.0215 0.0198 0.0212 0.0119 0.0112 0.0162 0.0124 0.0047 0.0121 0.0121 0.0021 0.0102 0.0096 0.0024 0.005 0.0038 0.0024 0.0046 0.0039 0.0023 0.0398 0.0197 0.02 0.0415 '0.0215 0.0199 0.0202 0.0147 0.0106 0.0183 31.2 31.2 - 25 29 - 14.9 26.6 - 12.8 24.5 - 56.1 16 - 26.2 8.1 - 36.2 22 - 9.6 28.7 - 43.6 34.6 - 27.4 25.2 - 18.5 30 - 25.5 21.5 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 59 ------- Segment Laboratory Parameter Year % BDL Mean MDL % of DIN CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 EE3 EE3 EE3 EE3 EE3 EE3 EE3 EE3 EE3 EE3 EE3 EE3 EE3 EE3 EE3 EE3 EE3 EE3 EE3 EE3 EE3 EE3 VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 NO23 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both 88 88 89 89 89 90 90 90 91 91 91 92 92 92 85 85 85 86 86 86 87 87 87 88 88 88 89 89 89 90 90 90 91 91 91 92 10.5 16.4 7.2 31.4 0.9 14.4 28.2 4.2 9.3 7.4 9.3 7.4 25.9 8.3 37.1 5.7 25.7 21.1 44.7 2.6 7.7 2.6 43.6 2.8 13.9 19.4 13.5 27 0 19.4 36.1 5.6 11.1 11.1 25 13.9 0.0129 0.0068 0.0122 0.0121 0.0021 0.0103 0.0092 0.0023 0.0053 0.0036 0.0024 0.0045 0.0039 0.0023 0.0398 0.02 0.02 0.0407 0.0214 0.021 0.02 0.021 0.0099 0.023 0.013 0.0054 0.0126 0.0121 - 0.0105 0.0095 0.0024 0.0049 0.004 0.0024 0.0045 67.9 20.4 - 37.3 8.1 - 45 12.9 - 9.1 27.6 - 48.2 40.5 - 30.8 28 - 23.1 28 - 21.2 26.6 - 77.2 18.9 - 50.4 - - 50.3 22.1 - 5 28.5 60 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- Segment Laboratory Parameter Year % BDL Mean MDL % of DIN EE3 EE3 WE4 WE4 WE4 WE4 WE4 WE4 WE4 WE4 WE4 WE4 WE4 WE4 WE4 WE4 WE4 WE4 WE4 WE4 WE4 WE4 WE4 WE4 WE4 WE4 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 ViMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS VIMS ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU NH4 N023 Both NH4 N023 Both NH4 '^23 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 NO23 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both 92 92 85 85 85 86 86 86 87 87 87 88 88 88 89 89 89 90 90 90 91 91 91 92 92 92 85 85 85 86 86 86 87 87 87 88 11.1 11.1 59.7 8.1 19.5 29.5 32.5 15.1 18.9 5 44 12.1 2.8 21.5 10.8 31.8 4.7 33.3 16.7 14.6 16.7 7.6 20.1 5.6 22.9 12.5 20.8 14.6 47.9 10 3.3 18.3 33.8 5.6 19.7 22.9 0.004 0.0024 0.0397 0.02 0.02 0.0412 0.022 0.0198 0.0236 0.0124 0.01 0.0226 3.0129 0.0073 0.0124 0.0124 0.0021 0.0113 0.01 0.0023 0.0052 0.004 0.0024 0.0045 0.0039 0.0022 0.0174 0.01 0.01 0.0106 0.0056 0.0064 0.0106 0.0056 0.005 0.0101 62.6 40.5 - 39.1 31.1 - 30 29.3 - 27.7 24.3 - 79.6 21 - 48.4 12.1 - 62.3 16.2 - 14.2 24.3 - 60.1 29.3 - 24.6 28.1 - 6 24.7 - 36.8 17.2 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 61 ------- Segment Laboratory Parameter Year % BDL Mean MDL % of DIN CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB6 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 CB7 ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU NH4 NO23 Both NH4 N023 Both NH4 NO23 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both NH4 N023 Both 88 88 89 89 89 90 90 90 91 91 91 92 92 92 85 85 85 86 86 86 87 87 87 88 88 88 89 89 89 90 90 90 91 91 91 92 7.1 22.9 8 10.7 6.7 20.8 22.2 4.2 6.9 22.2 0 34.4 21.9 4.7 35.4 10.8 36.9 20.4 4.1 30.6 45.4 4.6 23.7 29.1 4.1 37.2 18.4 10.5 18.4 31.3 23.6 14.6 16.7 22.2 6.3 44.4 0.0056 0.0039 0.0081 0.0056 0.0025 0.0081 0.0056 0.0025 0.0081 0.0056 - 0.0081 0.0056 0.0025 0.0172 0.01 0.01 0.0118 0.0056 0.0062 0.0106 0.0056 0.005 0.01 0.0056 0.004 0.0081 0.0056 0.0025 0.0081 0.0056 0.0025 0.0081 0.0056 0.0025 0.0081 48.1 23.3 - 28.6 19.8 - 38.1 26.8 - 17.1 - - 38.3 17 - 26.6 33.3 - 6.9 28.1 - 33 24.8 - 56.1 21.8 - 46.1 15.3 - 48.6 17.1 - 26.4 19.7 62 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 ------- Segment Laboratory Parameter Year % BDL Mean MDL % of DIN CB7 CB7 CB8 CBS CBQ CBQ CBQ CBQ CBQ CBQ CB8 CBQ CBQ CBQ CB8 CBQ CBQ CBQ CBQ CB8 CBQ CBQ CBQ CBQ CBQ CBQ ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU ODU NH4 N023 Both NH4 N023 Both NH4 NO23 Both NH4 N023 Both NH4 NO23 Both NH4 N023 Both NH4 N023 Both NH4 NT023 Both NH4 N023 92 92 85 85 85 86 86 86 87 87 87 88 86 88 89 89 89 90 90 90 91 91 91 92 92 92 22.9 9 29.7 4.2 35.8 11.3 4 28.8 29.8 3.7 28.8 25.9 3.2 33 13.8 4.2 12.2 19.1 19.1 9.6 13.3 16.7 6.1 39.9 12.9 5.6 0.0056 0.0025 0.018 0.0094 0.01 0.0113 0.0056 0.0059 0.0106 0.0056 0.005 0.0103 0.0056 0.0042 0.0081 0.0056 0.0025 0.0081 0.0056 0.0025 0.0081 0.0056 0.0025 0.0081 0.0056 0.0025 55.3 19.6 - 33.6 37.9 - 13.8 23 - 38.5 28.3 - 56.1 25.5 - 40.4 15.7 - 50 19 - 32.9 17.2 - 53 18.6 Trends in Phosphorus, Nitrogen, and Dissolved Oxygen, 1984 to 1992 63 ------- ------- |