CBP/TRS121/94
                         903R92018
     Chesapeake Bay Fall Line
    Toxics Monitoring Program
         1992 Final Report
TD
225
.C54
C549
1992
       Chesapeake Bay Program
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     Chesapeake Bay Fall Line
    Toxics Monitoring Program
         1992 Final Report
                  us
Printed by the U.S. Environmental Protection Agency for the Chesapeake Bay Program

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 Chesapeake Bay Fall Line Monitoring Program:  1992 Final Report
ACKNOWLEDGEMENTS


      This, report was a cooperative effort among several agencies who are working to understand, restore, and
preserve the water quality of the Chesapeake Bay and its tributaries. The following agencies and institutions
have contributed significantly to the success of this project:

      Maryland Department of the Environment

      United States Geological Survey

      George Mason University, Department of Chemistry

      Occoquan Watershed Management Laboratory

      Metropolitan Washington Council of Governments

      US Environmental Protection Agency, Chesapeake Bay Program Office

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Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report

TABLE OF CONTENTS
PROGRAM OVERVIEW	   1
      Metal and Organic Contaminants Introduction	   1
      Sampling Station Descriptions	   2

SAMPLING PROGRAM	   6
      Metal and Organic Contaminant Sampling Program - Susquehanna River  	   6
      Metal and Organic Contaminant Sampling Program - James River  	   9
      Metal and Organic Contaminant Sampling Program - Potomac River	  13

QUALITY ASSURANCE PROGRAM	  16
      Metals Quality Assurance Program - Susquehanna River  	  16
      Metals Quality Assurance Program - James River	  17
      Metals Quality Assurance Program - Potomac	  17
      Organic  Contaminant Quality Assurance Program - Susquehanna, James and
            Potomac Rivers	  17

LABORATORY ANALYSIS METHODS 	  21
      Metals Laboratory Analysis Methods - Susquehanna and James Rivers  	  21
      Metals Laboratory Analysis Methods - Potomac River	  21
      Organics Laboratory Analysis Methods - Susquehanna,  James and  Potomac
            Rivers  	  24

LOAD ESTIMATION METHOD 	  31

HYDROLOGIC CONDITIONS	  33
      Susquehanna River  	  33
      James River	  33
      Potomac River  	  33

QUALITY ASSURANCE RESULTS	  37
      Metals Quality Assurance Results - Susquehanna River	  37
      Metals Quality Assurance Results - James River	  40
      Metals Quality Assurance Results - Potomac  	  44
      Organics Quality Assurance Results - Susquehanna, James and Potomac Rivers .  .  45

WATER QUALITY DATA RESULTS  	  69
      Metals Water Quality Data - Susquehanna River	  69
      Metals Water Quality Data - James River	  77
      Metals Water Quality Data - Potomac River	  85
      Organics Water Quality Data - Susquehanna, James and Potomac Rivers	  89
      Metal Loads - Susquehanna River . .	  94
      Metal Loads - James River	  98
      Metal Loads - Potomac River	102
      Organics Loads - Susquehanna, James and Potomac Rivers 	112

                                                                             ii

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Chesapeake Bay.Fall Line Toxics Monitoring Program:  1992 Final Report

WATER QUALITY DATA DISCUSSION	.122
      Water Quality Metal Data - Susquehanna River  	y	122
      Water Quality Metal Data - James River  	128
   ••'  Water Quality Metal Data - Potomac River  	134
      Water Quality Organic Data - Susquehanna, James and Potomac Rivers  	135

METAL AND ORGANIC LOADS DISCUSSION	138
      Metal Loads Discussion - Susquehanna River	138
      Metal Loads Discussion - James River	141
      Metal Loads Discussion - Potomac River	144
      Organic Loads Discussion - Susquehanna, James  and Potomac Rivers	t.  146

RECOMMENDATIONS	148
      Metals Program	148
      Organics Program	149

REFERENCES	151

APPENDICES	154
                                                                            111

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 Chesapeake Bay.-Fall Line Toxics Monitoring Program: 1992 Final Report

 LIST OF FIGURES

 Figure 1.  Location of the Chesapeake Bay fall line toxics monitoring stations	, .    3
 Figure 2. Hydrograph showing mean monthly and long-term mean monthly discharge for
       the Susquehanna River fall line at Conowingo, Maryland	   34
 Figure 3. Hydrograph showing mean monthly and long-term mean monthly discharge for
       the James River fall line at Cartersville, Virginia.  . ._	   35
 Figure 4. Hydrograph showing mean monthly and, long-term mean monthly discharge for
       the Potomac River fall line at Chain Bridge, District of Columbia	   36
 Figure 5.  Field blank concentrations of the organonitrogen and organophosphorus
       pesticides in the dissolved phase for samples processed at the Susquehanna River
       fall line	   46
 Figure 6. Field blank concentrations of the organochlorines in the dissolved phase for the
       samples processed at Susquehanna River fall line	   47
 Figure 7. Field blank concentrations of the organochlorines in GF/D and GF/F filters for
       samples processed at the Susquehanna River fall line	   48
 Figure 8.  Field  blank concentrations of the polynuclear aromatic hydrocarbons in the
       dissolved phase for the samples processed at Susquehanna River fall line	49
 Figure 9. Field blank concentrations of the polynuclear aromatic hydrocarbons in GF/D
       and GF/F filters for samples processed at the Susquehanna River fall line	50
 Figure 10.   Field  blank concentrations of the organonitrogen and organophosphorus
       pesticides in the  dissolved phase for samples processed at the James  River fall
      'line	   51
 Figure 11. Field blank concentrations of the organochlorines in the dissolved phase for     s
       the samples processed  at James River fall line	   52
 Figure 12.  Field blank concentrations  of the organochlorines in GF/D and GF/F filters
       for samples processed at the James River fall line	   53
 Figure 13.  Field blank concentrations  of the polynuclear aromatic hydrocarbons in the
       dissolved phase for the samples processed at James River fall line	   54
Figure 14. Field  blank concentrations of the polynuclear aromatic hydrocarbons in GF/D
       and GF/F filters for samples processed at the James River fall line	   55
Figure 15. Laboratory blank concentrations of the organonitrogen and organophosphorus
      .pesticides in the dissolved phase	   56
Figure 16. Laboratory blank concentrations of the organochlorines in the dissolved phase.
        	   57
Figure 17.  Laboratory  blank  concentrations of the organochlorines in GF/D  and GF/F
       filters	   58
 Figure 18. Laboratory blank concentrations of the polynuclear aromatic hydrocarbons in
       the dissolved phase	   59
Figure 19. Laboratory blank concentrations of the polynuclear aromatic hydrocarbons in
       GF/D and GF/F filters	   60
Figure 20. Concentrations of (a) total recoverable and (b) dissolved chromium for 1992
       for the Susquehanna River fall line at Conowingo, Maryland.  Included on the
       graphs are analyses of equipment (total) and filter (dissolved) blanks	   73
Figure 21. Concentrations of (a) total recoverable and (b) dissolved copper for 1992 for
       the Susquehanna River fall line at Conowingo, Maryland.  Included on the graphs
       are analyses of equipment (total) and filter (dissolved) blanks	  74

                                                                                     iv

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 Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

 Figure 22.  Concentrations of (a) total recoverable and (b) dissolved lead for 1992 for the
       Susquehanna River fall line at Conowingo, Maryland	,	  75
 Figure 23.  Concentrations of (a) total recoverable and (b) dissolved zinc for 1992 for the
    :   Susquehanna River fall line at Conowingo, Maryland.  Included on the graphs are
       analyses of equipment (total) and filter (dissolved) blanks	  76
 Figure 24.  Concentrations of (a) total recoverable and (b) dissolved chromium for 1992
       for the James River fall line at Cartersville, Virginia. Included on the graphs are
       analyses of equipment (total) and filter (dissolved) blanks. ;	  81
 Figure 25.  Concentrations of (a) total recoverable and (b) dissolved copper for 1992 for
       the  James River fall  line at Cartersville, Virginia.  Included on the  graphs are
       analyses of equipment (total) and filter (dissolved) blanks.	  82
 Figure 26.  Concentrations of (a) total recoverable and (b) dissolved lead for 1992 for the
       James River fall line at Cartersville, Virginia. Included on the graphs are analyses
       of equipment (total) and filter (dissolved) blanks	  83
 Figure 27.  Concentrations of (a) total recoverable and (b) dissolved zinc for 1992 for the
       James River fall line at Cartersville, Virginia. Included on the graphs are analyses
       of equipment (total) and filter (dissolved) blanks	  84
 Figure 28.  Total Monthly Flows at Chain Bridge on the Potomac River: March, 1992,
       to March, 1993	  88
 Figure 29.   Monthly  loading estimates (upper limit) of (a) total recoverable and (b)
       dissolved chromium, copper, lead, and zinc for the Susquehanna River fall line at
       Conowingo Dam, Maryland, for the period March 1992 through March 1993.  ...  97
 Figure 30.   Monthly  loading estimates (upper limit) of (a) total recoverable and (b)
       dissolved chromium,  copper,  lead, and zinc for  the James River fall  line at
       Cartersville, Virginia, for the period March  1992 through March  1993	101
 Figure 31.  Arsenic Loads at Chain Bridge on the Potomac River: March 1992 to March
       1993. ...:•.	103
 Figure 32.   Cadmium Loads  at Chain Bridge on the  Potomac River:  March  1992 to
       March  1993	104
 Figure 33.  Chromium Loads at  Chain Bridge on the Potomac River:   March 1992 to
       March  1993	105
 Figure 34.  Copper Loads at Chain Bridge on the Potomac River: March 1992 to March
       1993	106
 Figure 35.  Nickel Loads at Chain Bridge on the Potomac River: March 1992 to March
       1993	107
 Figure 36.  Lead Loads at Chain Bridge on the Potomac River: March  1992 to March
       1993	.*	108
 Figure 37.   Selenium Loads at Chain Bridge on the  Potomac River:  March  1992 to
       March  1993	109
 Figure 38.  Zinc Loads at Chain Bridge on the Potomac River:  March, 1992, to March,
       1993  	110
Figure 39.  Load Estimates for the Period of April, 1992, to March, 1993, for the Metal
       Species Monitored at  Chain Bridge on the Potomac River 	Ill
 Figure 40.  Boxplots showing (a) total recoverable and (b) dissolved chromium,  copper,
       lead, and zinc concentrations during 1990-1992 at the Susquehanna River fall line
       station	123
Figure 41.   Concentration of (a) total recoverable and  (b) dissolved  chromium and

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Chesapeake Bay.-Fall Line Toxics Monitoring Program:  1992 Final Report

       instantaneous discharge for the Susquehanna River fall line station for the 1990-
       1992 sampling period	„••	 124
Figure 42.   Concentration of  (a) total  recoverable and (b) dissolved copper  and
       instantaneous discharge for the Susquehanna River fall line station for the 1990-
       1992 sampling period	 . 125
Figure 43. Concentration of (a) total recoverable and (b) dissolved lead and instantaneous
       discharge for the Susquehanna River fall line station for the 1990-1992 sampling
       period	,	126
Figure 44. Concentration of (a) total recoverable and (b) dissolved zinc and instantaneous
       discharge for the Susquehanna River fall line station for the 1990-1992 sampling
       period	127
Figure 45.  Boxplots showing (a) total recoverable and (b) dissolved chromium, copper,
       lead, and zinc concentrations during 1990-1992 at the James River fall  line
       station	129
Figure 46.  Concentration of (a)  total recoverable and (b) dissolved chromium  and
       instantaneous discharge for the James River fall line station for the 1990-1992
       sampling period	130
Figure 47.   Concentration of  (a) total  recoverable and (b) dissolved copper  and
       instantaneous discharge for the James River fall line station for the 1990-1992
       sampling period	131
Figure 48. Concentration of (a) total recoverable and (b) dissolved lead and instantaneous
       discharge for  the  James River fall  line station for the  1990-1992 sampling
       period	132
Figure 49. Concentration of (a) total recoverable and (b) dissolved zinc and instantaneous
       discharge for  the  James River fall  line station for the  1990-1992 sampling
       period	133
Figure 50. Annual loading estimates of (a) total recoverable and (b) dissolved chromium,
       copper,  lead,  and  zinc during  1990-1992 at the  Susquehanna River fall  line
       station	140
Figure 51. Annual loading estimates of (a) total recoverable and (b) dissolved chromium,
       copper, lead, and zinc during 1990-1992 at the James River fall line station	143
                                                                                      VI

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 Chesapeake Bay. Fall Line Toxics Monitoring Program: -1992 Final Report

 LIST OF TABLES

 Table. 1. James River sample bottles and preservation techniques	  10
 Table 2. Monitored metals and scheduled methods of analysis at the Susquehanna and
       James River stations	  22
 Table 3.  Monitored organic contaminants  and scheduled methods of analysis.  The
       fluvial phase analyzed, dissolved and paniculate, is indicated along  with the
       method of analysis and quantitation levels ,(QLs)	  25
 Table 4.   Quality assurance  data  collected  at the  Susquehanna  River  fall line  at
       Conowingo, Maryland, to compare old and new sample collection techniques for
       total-recoverable and dissolved trace metals	'.	  38
 Table 5.  Results  of field equipment blank and filter blank samples collected at the
       Susquehanna River at Conowingo, Maryland, for trace metals using ultraclean
       techniques.	  39
 Table 6.  Quality assurance data collected at the James River fall line at  Cartersville,
       Virginia, to  compare old and  new  sample  collection  techniques for  total-
       recoverable metals	  41
 Table 7. Results of field equipment blank and filter blank samples collected  at James
       River at Cartersville, Virginia, for trace metals using ultraclean techniques	  42
 Table 8. Summary of matrix spike recoveries using Carbopack B sorbent cartridges for
       Susquehanna and James River fall line samples."	  63
 Table 9.  Summary of matrix spike recoveries using C18  sorbent cartridges for the
       Potomac River fall line samples.8 	  64
 Table 10.  Summary of spike recoveries  of monitored organic contaminants from filtered
       particulates	  65
 Table 11.  Enrichment factors for the monitored organic contaminants in filtered surface
       water samples for both sorbents  used in this  study	„  67
 Table 12.  Indeterminate errors  associated  with the  concentrations of  the monitored
       organic contaminants in the fall line samples	  68
 Table 13.  Metal water-quality data  for the Susquehanna  River fall line at  Conowingo,
       Maryland, for the period March  1992 through March  1993	  70
 Table 14.  Metal water-quality data for the James River fall line at Cartersville,  Virginia,
       for the period March 1992 through March 1993	  79
 Table 15.   Summary of metals data gathered at Chain Bridge on the Potomac River,
       March, 1992-March, 1993	  86
Table 16.   Monthly flows at Chain Bridge on  the Potomac River:  March,  1992,  to
       March, 1993	  88
Table 17.   Summary of organic  contaminant concentrations in surface  water samples
       collected from the Susquehanna  River fall line	 .  91
Table 18.   Summary of organic  contaminant concentrations in surface  water samples
       collected from the James River fall line	  92
Table 19.   Summary of organic  contaminant concentrations in surface  water samples
       collected from the Potomac River fall line	  93
Table 20.   Monthly load  estimates in kg  for the  Susquehanna  River  fall line  at
       Conowingo, Maryland, for the period March 1992 through March 1993	  95
Table 21.   Monthly  load estimates  in kg for the James River fall line at  Cartersville,
       Virginia, for the period March 1992 through March 1993	  99

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 Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

 Table 22.  Estimated monthly arsenic loads at Chain Bridge on the  Potomac River:
       March, 1992, to March, 1993	 103
 Table 23.  Estimated monthly cadmium loads at Chain Bridge on the Potomac River:
   ..-   March 1992 to March 1993	104
 Table 24.  Estimated monthly chromium loads  at Chain Bridge on the Potomac River:
       March 1992 to March 1993	105
 Table 25.  Estimated monthly copper loads at Chain Bridge on the  Potomac River:
       March 1992 to March 1993	•:..'.	106
 Table 26.  Estimated monthly nickel loads at Chain1 Bridge on the Potomac River: March
       1992-to March 1993	107
 Table 27.  Estimated monthly lead loads at Chain Bridge on the Potomac River: March
       1992 to March 1993	108
 Table 28.  Estimated monthly selenium loads at Chain Bridge on the Potomac River:
       March 1992 to March 1993	109
Table 29.  Estimated monthly zinc loads at Cham Bridge on the Potomac River: March
       1992 to March 1993	110
Table 30.  Range of load estimates for monitored metals for the period of April 1992 to
       March 1993 at Chain Bridge on the Potomac River	Ill
Table 31.  Fluvial loads for the organonitrogen and organophosphorus pesticides at the
       Susquehanna River fall line during the period  of March 1992 to February  1993. .  . 113
Table 32.  Combined fluvial loads (sum of dissolved and paniculate phase contributions)
       for the organochlorines at the Susquehanna River fall line during the period of
       March 1992 to February 1993	114
Table 33.  Combined fluvial  loads (sum  of dissolved and particulate phase) for the
       polynuclear aromatic hydrocarbons at the Susquehanna River fall line during the
       period of March 1992 to February  1993	 115
Table 34.  FluviaMoads for the organonitrogen and organophosphorus pesticides at the
       Potomac River fall line during the period from March 1992 to February 1993. ... 116
Table 35.  Combined fluvial loads (sum of dissolved and particulate phase contributions)
       for the organochlorines at the Potomac River fall line during the period of March
       1992 to February 1993	117
Table 36.  Combined fluvial loads (sum of dissolved and particulate phase contributions)
       for the polynuclear aromatic  hydrocarbons at the Potomac River fall line during
       the period of March 1992 to  February 1993	118
Table 37.  Fluvial loads for the organonitrogen and organophosphorus pesticides at the
       James River fall line during the period of March 1992 to February 1993	119
Table 38.  Combined fluvial loads (sum of dissolved and particulate phase contributions)
       for the organochlorines at the James River fall line during the period of March
       1992 to February 1993	120
Table 39.  Combined fluvial loads (sum of dissolved and particulate phase contributions)
       for the polynuclear aromatic hydrocarbons at the James River fall line during the
       period of March 1992 to February 1993	121
Table 40.  Range in Susquehanna River fall line load estimates for 1990 to  1992. Units
       are in thousands of kilograms per year. The modeling technique used to calculate
       each set of estimates is indicated	139
                                                                                  via

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Chesapeake Bay fall Line Toxics Monitoring Program:  1992 Final Report

Table 41.  Range in James River fall line load estimates for 1990 to 1992. Units are in
       thousands of kilograms per year. The modeling technique used to calculate each
       set of estimates is indicated	142
                                                                                    IX

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 Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

 EXECUTIVE SUMMARY
Introduction

       A critical step in understanding the effects of toxic substances on the Chesapeake
Bay's ecosystems is knowing the types and quantities of substances being delivered to the
estuary. The Chesapeake Bay Fall Line Toxics Monitoring Program was established in April,
1990 as a pilot study to define the magnitude and timing of toxic substances entering the
Chesapeake Bay from the area above the fall line of the Susquehanna and James rivers.
Sampling for metals for the Potomac River was incorporated into the Fall Line Toxics
Monitoring Program in May, 1991.  In March, 1992, the program was expanded to include
organic constituents.  The Fall Line Toxics Monitoring Program can now provide preliminary
information on toxic substances originating from  combined point and nonpoint sources above
the fall line.
Objectives

       This report focused on samples collected between March 1992 and March 1993.  The
purpose of this study was to:

(1)    determine the ambient concentrations, nature, and transport of selected metals and
       organic contaminants over a range of hydrologic conditions in three major tributaries
       to the Chesapeake Bay;

(2)    improve monthly and annual load estimates of metals and organic contaminants
       entering the estuary at three major tributaries to the Chesapeake Bay by employing
       ultra clean sampling techniques and lowering analytical quantitation levels; and

(3)    upgrade the quality assurance program by increasing the number of quality-control
       samples in order to ensure the adequacy of sampling procedures and sample analysis.
Sampling Stations

       Samples were collected from the fall lines of three major tributaries to the Chesapeake
Bay.  These stations are the Susquehanna River at Conowingo Dam, the James River near
Cartersville and the Potomac River at Chain Bridge. The Susquehanna River is the largest
tributary to the Chesapeake, draining approximately 27,100 square miles.  The James River
has a drainage area of 6,257 square miles and the Potomac River drains 11,560 square miles.
Collectively, these  three rivers provide approximately 79% of the total freshwater flow to the
estuary (Table ES-I).
Executive Summary                                                               ES-1

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Chesapeake Bay.Fall Line Toxics Monitoring Program:  1992 Final Report

Table ES-I. Drainage Characteristics of the Susquehanna, Potomac, and James Rivers.
Location
Susquehanna @ Conowingo
Potomac @ Chain Bridge
James @ Cartersville
Average Daily Flow
(cfs)
36,370
10,340
7,416
Pet. of
Tot. Flow
51%
16%
12%
Drainage Area
(sq. miles)
27,100
11,570
6,257
Pet. of
Tot. DA
42%
18%
10%
Yield
(cfs/sq.
miles)
1.34
0.89
1.19
Results

       Results suggest that some constituents appear to be discharge dependent.  Total-
recoverable zinc and dissolved zinc concentrations showed similar patterns as river discharge
at the James River station.  At the Susquehanna River, dissolved copper appeared related to
discharge, whereas at the Potomac River, total-recoverable chromium and zinc varied
similarly with discharge.  Paniculate PAHs also appeared to be discharge dependent.  These
observations are based on visual inspection of the data.  A longer record with more frequent
sampling would be needed to establish a statistical relationship between discharge and
concentration.

       Temporal patterns may also exist for some constituents.  Organonitrogen herbicides,
primarily atrazine, peaked in May, for James River and June for  Susquehanna and Potomac
rivers. Organophosphorus compounds were rarely detected.  Organochlorine pesticides, while
detected often, did not show the same degree of temporal variability as organonitrogen
pesticides.

       A summary of metals concentrations at the three rivers for the period March 1992
through March  1993 is presented in Table ES-II. Organonitrogen and organophosphorus
pesticides are presented in Table ES-IJJ, Table ES-TV and organochlorine constituents are
presented in Table ES-IV.

       One of the program's objectives was to determine if  the use of ultra clean sampling
techniques and  lowered constituent quantitation levels improved the quality of data.  Ultra
clean techniques were employed at the Susquehanna and James rivers.  In general, the number
of occurrences of detectable concentrations of metals was increased by employing these
methods.  At the Susquehanna, the new techniques improved results   for total-recoverable
copper, lead, and zinc and for dissolved copper, lead and zinc. The James River had
Executive Summary
ES-2

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Chesapeake Bay fall Line Toxics Monitoring Program: 1992 Final Report


  Table ES-II. Summary of Metals Concentrations, Frequency of Detection and Range,
  for the period March 1992 through March 1993.                        :'
Metal
Aluminum, D
Arsenic, TR
Arsenic, D
Cadmium, TR
Cadmium, D
Chromium.TR
Chromium J>
Copper, TR
Copper, D
Iron, TR
Iron, D
Lead, TR
Lead, D
Lithium, TR
Manganese,TR
Mercury, TR
Mercury, D
Nickel.TR
Nickel, D
Selenium, TR
Silver, TR
Strontium, TR
Zinc, TR
Zinc, D
Potomac
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15/21

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Freq. Det
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0/26

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19/28
0/5
26/28
5/5

25/25
15/28
2/5




5/6
2/8
0/2


1/28
0/5
Range
ug/1
10-660




<1-20

<1-13

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^
PCBs(112
Congeners)
                                                                                                                                a
                                                                                                                                S
                                                                                                                                5
                                                                                                                               I

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 Chesapeake Bay..Fall Line Toxics Monitoring Program: 1992 Final Report

 improved results for total-recoverable arsenic, copper and zinc and for dissolved arsenic,
 copper, lead and zinc.  The higher quantitation levels employed for Potomac-samples was
 adequate for total-recoverable copper and zinc.

       Contamination was of concern for certain constituents. At the Susquehanna River,
 contamination was a problem with total-recoverable chromium and dissolved chromium and
 mercury.  At the James River, dissolved chromium and lead exhibited contamination
 problems.

 Loading Estimates

       Monthly and annual loads were prepared for the sampled constituents for each of the
 three tributaries. The loadings presented in this report represent the principal investigators'
best estimates of monthly and annual loads based on a very limited data set.  The loads
provided in this report represent a range of potential loads.  Minimum loads were calculated
by assigning constituent concentration a value of zero when the concentration was below
quantitation level.  Maximum loads were calculated by  assigning sample concentrations that
were below the quantitation level to the quantitation level. It should be noted that there exists
 a high degree of uncertainty in the loading estimates for substances that had a large number
 of observations below quantitation level. These loads should be used only for "order of
magnitude" comparisons between fluvial sources and other sources (atmospheric, point
sources) of toxic substances entering Chesapeake Bay.

       Figure ES-1 compares annual loading estimates of selected total-recoverable metals
using maximum loading estimates for each river.  In general, water discharge had a
significant effect on load estimates of metals. For the Susquehanna and James rivers, the
lowered quantitation  levels in 1992-1993 significantly improved the load estimates for certain
metals when compared with loads estimated during 1990-1991.  At the Susquehanna River,
load estimates were improved in 1992-1993 for total-recoverable copper, lead and zinc, and
dissolved arsenic, cadmium, copper, lead and zinc. Load estimates  for the James River were
improved in 1992-1993 for total-recoverable arsenic, copper and zinc and  for dissolved
arsenic, chromium, copper, lead and zinc. At the Potomac river, the best  load estimate was
for total-recoverable copper, which  had only two observations below quantitation level.

       Figure ES-2 and Figure ES-3 present maximum  annual load estimates for
organonitrogen and organophosphorus pesticides, dissolved and paniculate phases combined.
Maximum annual  load estimates for organochlorine compounds  are presented in Figure ES-4.
In general, annual load estimates of pesticides were highest for the Susquehanna River,
followed by the Potomac and James rivers.  However, loads were not always in direct
proportion to river discharge.  Organonitrogen and organophosphorus loads were
disproportionately higher in the Potomac in comparison with the Susquehanna.  Chlordane
was  disproportionately  higher in the James  River.
Executive Summary                                                                ES-6

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Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report
       Figure ES-1.  Maximum annual loads of selected metals for Susquehanna,
       James, and Potomac rivers.                                     /
1100
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Executive Summary
ES-1

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Chesapeake Bay.Fall Line Toxics Monitoring Program:  1992 Final Report
         Figure ES-2. Maximum annual loads of organonitrogen and
         organophosphorus compounds for the Susquehanna, James and Ppfomac
         rivers.

                   130 -
                   100 -
                         ISusquehanna
IJames
3Potomac
         Figure ES-3. Maximum annual loads of organonitrogen and
         organophosphorus pesticides for the Susquehanna, James and Potomac
         rivers.
                 U>

                 (0
                           I Susquehanna
 James
 3otomac
Executive Summary
                                   ES-8

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Chesapeake Bay.-Fall Line Toxics Monitoring Program: 1992 Final Report
      Figure ES-4. Maximum annual loads of organochlorine compounds for the
      Susquehanna, James and Potomac rivers.

200
g 150
43
— 100
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Executive Summary
ES-9

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 Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

 PROGRAM OVERVIEW

 Chesapeake Bay  is a collection of delicate ecosystems, many of which have been greatly
 perturbed, both by mismanagement of the resources within the Bay, as well as by continued and
 excessive pollution from the surrounding watershed. Only within the last ten to fifteen years
 have state and local governments recognized the imminent  danger of pollutants to this rich
 natural and economic resource.  Since the early 1980's there has been a growing commitment
 by all the states in the watershed of Chesapeake Bay, with backing from federal environmental
 agencies, to study this problem and begin clean-up measures.  The emphasis in clean-up efforts
 has been directed toward the reduction of nutrient inputs to the Bay, particularly nitrogen and
 phosphorus.There is  a now a need to identify and quantify the  toxic  substances, such as
 insecticides, herbicides, and certain metals, which are also entering the Bay.

 This report focuses on  a  project conducted to  quantify the magnitude and timing of toxic
 substance loadings from several of the major tributary sources of Chesapeake Bay. As such, the
 study assesses the combined input  of toxics from point and non-point sources  within the
 watershed from fluvial sources, but does not address other issues, such as atmospheric deposition
 to the Bay proper, groundwater inputs, or the fate of toxic substances  once they enter the estuary.

 The present study will (1) quantify the concentrations and fluxes of toxic substances entering the
 Bay from the watershed, (2) provide a baseline for future comparisons, an  important aspect for
 assessment of clean-up efforts and toxic reduction strategies, (3) allow determinations of surface
 water quality to be made, and (4) provide essential information for calibration of the Chesapeake
 Bay mass-balance models presently  being developed.

 Metal and Organic Contaminants Introduction

 In 1990  and 1991, a pilot study was conducted by the U.S.  Geological Survey  (USGS) in
 cooperation with the  Maryland Department  of  the Environment  (MDE) and the   U.S.
 Environmental  Protection  Agency,  Chesapeake Bay Program  Office (EPA),  to enhance the
 understanding  of the nature and transport of toxic substances entering Chesapeake Bay from its
 major tributaries.  The purpose of the 1990-91 Chesapeake Bay Fall Line Toxics Monitoring
 Program  was to identify and quantify toxic substances entering the Chesapeake Bay from above
 the fall lines of two major tributaries, the Susquehanna and James Rivers. Combined, these rivers
 represent 65 percent of the total freshwater flow to the Chesapeake Bay from fluvial sources.
 The study was continued through 1992, incorporating refinements from the pilot study.

 The specific objectives of the  1990-91  pilot study were:  (1) to identify types and quantities of
 toxic substances in fluvial  transport;  (2) to characterize constituent concentration with respect
to seasonality, water  discharge, and time;  and (3) to estimate monthly and annual  constituent
loads from two major tributaries to  the Chesapeake Bay, the Susquehanna and James rivers.
Results of the study are documented in the report Chesapeake Bay Fall Line Toxics Monitoring
Program: 1990-91 Loadings, (1993)  on file in the EPA Chesapeake  Bay  Program Office,
Annapolis, Maryland.

During this two-year period,  many  of the metals  and organic contaminants analyzed  were
detected  in fluvial transport. However, due to a limited occurrence of storm events during the

Program Overview                                                                   1

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 Chesapeake Bay. Fall Line Toxics Monitoring Program:  1992 Final Report

 1990-91 sampling period, sample collection was restricted primarily to baseflow conditions and
many constituent measurements were below analytical  quantitation levels.'' In addition,  the
analytical quantitation levels were not commensurate with the levels being used in other research
efforts, such as the atmospheric deposition study, within the Chesapeake Bay Program.  The
decision, therefore,  was made to revise the project during 1992-93 to include (1) ultra clean
sampling techniques for the collection of water samples; (2) lowered analytical quantitation levels
for metal and organic contaminant  analyses; and (3) continued monitoring during baseflow and
stormflow conditions to better represent toxic substances in transport.  During this period,  the
Potomac River was  added to the fall line toxics monitoring network.

In 1992, samples were collected throughout the year to estimate loads of toxic substances from
the Susquehanna River at Conowingo, Maryland, the James River at Cartersville, Virginia, and
the Potomac River at Chain Bridge, Washington, D.C., during periods of varying flow .  Figure 1
shows the drainage area of Chesapeake Bay, and the locations of the sampling sites.

The specific objectives of the 1992  Chesapeake Bay Fall Line Toxics Monitoring Program were:

(1)   Determine the ambient concentrations, nature, and transport of selected metals and
      organic contaminants over a range hi flow conditions at the major tributaries to
      the Chesapeake Bay. These  data will be used for comparison  to water quality
      standards and in calculating load estimates.

(2)   Improve the monthly and  annual calculations of total-recoverable  metal and  organic
      contaminant  load estimates  entering the Chesapeake Bay at the major tributaries to  the
      Bay.  Load estimates were to  be improved by:  a) adopting ultra clean sampling methods
      b)  lowering the analytical  quantitation level,  thereby increasing the number of values
      above the reporting limits; and c) obtaining additional high flow samples  over a longer
      period of record.

(3)   Upgrade  the  quality-assurance  program  by  increasing  the  number  of
      quality-control samples hi order to ensure the  adequacy of sampling procedures
      and sample analysis.
Sampling Station Descriptions

Each sampling location has unique physical characteristics, sampling methodologies and sampling
histories.  The following sections describe the characteristics of each sampling location.
Susquehanna River at Conowingo Dam, Maryland

The Susquehanna River was selected for the Fall Line Toxics Monitoring Program because it is
the Chesapeake Bay's largest tributary, draining approximately 27,100 square miles above the
fall line, and contributing an average of 51 percent of the freshwater flow to the Chesapeake Bay
annually.  The monitoring station, located at  Conowingo, Maryland, is the  southern-most
downstream site of three dams on the Susquehanna River, which include Safe Harbor, Holtwood,
and Conowingo Dams.  The Conowingo Dam is a  hydroelectric powerplant and is located ten
miles up the tidally-influenced portion of the Susquehanna River known as Susquehanna Flats.

Program Overview                                                                    2

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Chesapeake Bay. Fall Line Toxics Monitoring Program: 1992 Final Report


Figure 1.  Location of the Chesapeake Bay fall line toxics monitoring stations.
               Watershed
               OFall Line Toxics
               Monitoring Stations
Program Overview

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 Chesapeake Bay. Fall Line Toxics Monitoring Program: 1992 Final Report

 Baseflow and stormflow nutrient and suspended sediment data have been collected as part of the
 Chesapeake Bay River Input Monitoring Program since late 1984. Data have also been collected
 for the same set of parameters through the U.S. Geological Survey's National  Stream Quality
 Accounting Network (NASQAN)  since 1979, and from a USGS water quality study conducted
 during 1978-1981 for selected metals and pesticides. The specific location of the monitoring site
 is latitude 39ฐ39'31", longitude 76ฐ10'28", in Harford County, Maryland; the hydrologic unit is
 02050306.

 James River at Cartersville, Virginia

 The James River at Cartersville,  Virginia, with a drainage area of 6,257 square miles, was
 selected  for  the  Fall Line Toxics Monitoring Program  as another major tributary to the
 Chesapeake Bay.   It contributes an  average  of  12 percent of the freshwater flow to the
 Chesapeake Bay. The James River is less affected by dams and other manmade structures than
 the Susquehanna River, and so may be more representative of a natural river system. Historical
 data at this station include nutrients and suspended solids  collected  during  base  flow and
 stormflow events as part of the Fall Line River Input Project  begun in late 1988. Also, as part
 of the U.S. Geological Survey National Stream Quality Accounting Network (NASQAN) since
 1979,  samples  have been collected for a number of water quality constituents, so that an
 extensive water chemistry data base exists.  The specific location of this monitoring site  is
 latitude 37ฐ40'15", longitude  78ฐ05'10", located on  State  Highway 45  in Goochland County,
 Virginia; the hydrologic unit is 02080205.

 The sample-collection methods at the Susquehanna and James Rivers for both the 1990-91 period
 and the 1992 period were designed to ensure that samples were representative of river conditions.
 The methods were adapted from procedures that are documented in two USGS published reports:
 Field Methods for Measurement of Fluvial Sediment (Edwards and Glysson, 1988) and Methods
for Collection and Processing of Surface-Water and Bed-Material Samples for Physical and
 Chemical Analyses (Ward and Harr, 1990).

 Samples  for the entire sampling period (1990-92) were analyzed for concentrations of selected
 dissolved and total-recoverable metals. For 1992, specific parameters were selected based on the
 results of  the  1990-91  study and included all  metals on  the Chesapeake Bay Program's
 Chesapeake Bay Toxics of Concern List (Chesapeake Bay  Program, 1991).

 Because concentrations of total-recoverable metals are usually related to the amount and nature
 of suspended sediment, a sand-fine suspended-sediment analysis was also performed during the
 entire  sampling period of 1990-92.  This analysis provides the  breakdown of the particle size
 distribution of suspended sediments transported in river flow (sands, greater  than 0.062 um in
 diameter; silts, less than 0.062 um). The relationship between the particle size and concentrations
 of total-recoverable metals may be key in the development of load  estimations  for  metals.

 Potomac River at Chain Bridge, Washington, D.C.

 The Occoquan Watershed Monitoring Laboratory (OWML)  established a Potomac Fall Line
 Pollutant Input Monitoring Station in the early spring of 1983 for the Washington Metropolitan
 Area Coordinated Potomac River Monitoring Program. Since the original installation, the station
                                                                      ซ

 Program Overview                                                                    4

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 Chesapeake Bay, Fall Line Toxics Monitoring Program:  1992 Final Report

 has been included in the  Fall Line River Input Monitoring Program established as a part of
 Maryland's Chesapeake Bay Water Quality Monitoring Program. The station.-operations cost is
 currently  shared by  funding  from the Metropolitan Washington Council  of Governments
 (MWCOG) and the Maryland Department of the Environment.  Under normal operations, the
 station is  used to collect data on conventional pollutants (nutrients, etc.).  During the period
 March 1992 to March 1993, the station was also used to collect baseflow and stormflow samples
 for selected metals and organiccontaminants.

 The Potomac River fall line is located upstream of the northwestern border of Washington, D.C.
 The fall line water quality monitoring operations conducted by MWCOG/OWML are located at
 two separate points on the river just downstream of the fall line.

 The Little Falls Dam is located on the Potomac River just below the fall line near Washington,
 D.C.  The river drains 11,560 square miles at the dam location. The dam, which creates a pool
 for the major  raw water intake for the Washington Aqueduct Authority, is located at a natural
 bifurcation in  the stream, and provides control section for the maintenance of a stage-discharge
 relationship (Prugn et al, 1986). A USGS stream gage has maintained a continuous hydrologic
 record at the site since 1930.  From a sampling standpoint, a well-mixed cross section is key to
 the successful characterization of river flow with a point sample.  The wide cross section
 (approximately 1700 ft.), and the natural bifurcation created by a mid-stream island ensure that
 the river cross section is poorly mixed at the Little Falls  Dam, and therefore unsuitable for the
 extraction of a point  sample representative of the entire flow of the River.

 One and a half miles  downstream of the Little Falls Dam, the Potomac River passes through a
 very narrow (approximately 200  feet)  constriction in the vicinity of the Virginia  Route 123
 crossing at Chain Bridge, latitude 38ฐ55'46" and longitude 77ฐ07'02".  This location, because of
 its well-mixed cross section, was 'found to be suitable for the withdrawal of both baseflow and
 storm runoff samples.  However,  because the location is subject to backwater influences from
 tidal cycles in the upper estuary, it was found to be unsuitable for the  establishment of a stage-
 discharge relationship that could be used to pace automatic sampling equipment.

 Because the deficiencies at each location disqualified both for the joint role of gaging and
 sampling station, each site was instrumented to accomplish the function for which it was best
 suited, and to rely upon telecommunications hardware and software to coordinate station
 operation.  The Little Falls station, therefore, was instrumented for flow measurement, and the
 Chain Bridge station was equipped for automatic sample retrieval. Because there is only a minor
 increase in total drainage area between the two locations(two minor first-order tributaries), it was
 determined that the two stations could be operated as a single gaging and sampling system. The
 link was accomplished via telephone with an OWML-designed and constructed computerized
gaging system placed at the two locations.  The operation of this station is described later in this
report.
Program Overview

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Chesapeake Bay-Fall Line Toxics Monitoring Program: 1992 Final Report

SAMPLING PROGRAM

Metal and Organic Contaminant Sampling Program - Susquehanna River

Water quality samples were collected at the Susquehanna River at Conowingo Dam using an
equal-discharge increment method, meaning that the samples were collected along the river cross
section at the midpoint of equal increments of discharge. Samples were collected during periods
of baseflow and stormflow.  Storms on the Susquehanna River, for the purpose of this study,
were operationally defined as occurring when water passed over the spillway. This represents
a discharge exceeding 80,000 cubic feet  per  second  (ft3/s), which is the maximum turbine
capacity.

Sample  collection methods and  equipment used during the 1990-91 and  the 1992 study are
presented in the following text.  Equipment and methods used in 1992 reflect the adoption of
ultra clean sampling techniques.

Sample collection methods for the 1990-91 period

The field-collection  equipment used at this site included a Nalgene (metals) or glass  (organic
contaminants) collection bottle, an epoxy-coated weighted bottle holder, and a polyethylene churn
splitter.  For separation of the "dissolved" fraction of a sample, an aliquot of water collected with
this equipment was processed through a 0.45 um cellulose membrane filter, that was mounted
in a 142 millimeter plastic filter stand. The collection bottle, churn splitter, and filter stand were
cleaned  with a  10% hydrochloric acid  solution and rinsed with deionized  water prior to each
sampling event. All equipment was  rinsed with sample water prior to collection.

Water quality samples for metal  analysis were collected at several sections along the upper and
lower catwalks of the dam, located directly over the turbine outflow. At each section, the sample
bottle, placed in the weighted sampler, was lowered into the river and allowed to fill, but not
overflow.  The water quality sample was then poured into the churn splitter. A churn splitter is
a sample consolidation  device  that is designed to produce homogeneous  samples  that are
representative of the entire river cross section. Once water had been collected from all  sections,
the composite sample was mixed in the churn splitter.

Subsamples were then poured from the churn splitter into precleaned sample bottles.  At each
section,  a suspended-sediment sample was also collected in a precleaned glass bottle placed  in
the weighted sampler.  Samples  for  organic analysis were collected directly into sample  bottles
at the midpoint of the river cross section.

Samples for total-recoverable metal  analyses were preserved with nitric acid (1 mL per 250 mL
of sample).  Samples for dissolved  metals analysis were filtered on-site, placed in pre-cleaned
bottles, and preserved with nitric acid.  Total-recoverable and dissolved mercury (Hg) samples
were preserved with 10  mL  K2Cr2O7.  No preservative was added to  the  samples for organic
contaminant or suspended sediment analysis.

All of the sample bottles were labeled with the station number, date, time, and analysis to  be
Sampling Program

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 Chesapeake Bay, Fall Line Toxics Monitoring Program:  1992 Final Report

 conducted.  Information was also recorded on field sheets.  Metal and organic contaminant
 samples  were  packed  in  ice-filled coolers  and sent to  the  NWQL fqr analysis.   The
 suspendedsediment samples were analyzed at the USGS Sediment  Laboratory in Harrisburg,
 Pennsylvania.

 Sample collection methods for the 1992 period

 Standard operating procedures for collection and processing of water quality samples are given
 in the 1992  project Quality Assurance Project Plan (QAPP).   Some of the techniques are
 presented or expanded on in the following text.

 Water quality samples were collected according to ultra clean sampling protocol developed by
 Dr. Howard Taylor of the National Research Program of the U.S. Geological Survey, Boulder,
 Colorado, for metals,  and  Dr. Gregory D.  Foster, George Mason  University,  for organic
• contaminants. These methods include  the use of sample collection  and processing equipment
 which are non-contaminating and analyte-inert.

 Specifically, the term "ultra clean" indicates:

        1.     Stringent precleaning of  all containers, sampling equipment,
              filtration equipment, and filters;
        2.     Use of very high-quality water and acids for preparatory
              washing, blanks, preservation, and analysis;
        3.     Avoidance of contact between sample water and either metal or
              plastic surfaces, depending on the class of analyte;
        4.     Special precaution in the field handling of samples, including:
                 *  a.  Avoidance of  all metal or plastic surfaces,
                     b. Use of non-contaminating gloves and forceps,
                     c.  Avoidance of  car exhaust and atmospheric deposition; and
        5.     Use of a class 100 clean hood for laboratory processing  and
              analyses of metals samples.

 Project-dedicated  sampling equipment  included: a Teflon-coated stainless steel churn splitter,
 Teflon dosing bottles and bags for storing and transporting equipment; a  double-check-ball 2 liter
 Teflon bailer, normally used for groundwater sample collection; and a 100 foot length of 7/32
 inch diameter nylon or polyester rope wound on a plastic "Cordwheel" to lower and raise the
 bailer to and from the  point  of  sample collection.   Project-dedicated  laboratory equipment
 included  a Teflon filter apparatus, Teflon-coated tweezers, and Teflon bags for storage  of
 equipment.

 The equipment, including the bailer and nozzle, filter apparatus, Teflon bags, bins, and chum
 splitter were washed with a soapy water wash, thoroughly rinsed with  tap water, rinsed with a
 flush of lab-grade methanol, two flushes with high-quality organic-free  water, a flush with 10%
 nitric acid solution, and two flushes of high-quality inorganic-free water, before and after each
 sampling trip. The bailer was then stored in clean Teflon bags which slipped into a 3 inch PVC
 tube.  Other equipment was stored in clean Teflon bags in clean high-density-polyethylene bins.
 Sampling Program

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 Chesapeake Bay. Fall Line Toxics Monitoring Program:  1992 Final Report

 All equipment coming into contact with the sample was thoroughly rinsed initially with river
 water.  This rinsing included collecting two bailer volumes (approximately one gallon) and
 pouring each through the nozzle of the bailer into the churn splitter.  The churn splitter was
 thoroughly washed with river water, ensuring that all surfaces came into contact with the water.
 The river-water rinse was discarded and the rinse step repeated.

 Samples for metal analysis  were collected hi  bottles  provided  by the USGS NWQL;  the
prescribed 250 mL polyethylene, acid-rinsed bottles were prepared for the ultra clean program
by two initial rinses of high-quality inorganic-free water, a 24-hour soak in  10% Ultrex nitric
 acid,  and two 24  hour soaks with high-quality  inorganic-free water.   The bottles were then
refilled 1/2 to 3/4 full with fresh high-quality inorganic-free water and stored for use as needed.

 Samples for organic contaminant analysis were collected in 37.5L stainless steel milk cans or 4L
amber glass bottles with Teflon-lined lids.  Water samples collected in the Teflon bailer were
placed directly in the milk cans.  The lids to the milk cans remained tightly fitted except during
sample transfer from the bailer to prevent contamination.

Water quality samples were collected at  five sections  of equal  discharge along the turbine
outflow.   At each  section,  the sample was poured directly into the churn splitter via a Teflon
nozzle inserted into the bailer just before the moment of sample transfer.  In order to minimize
potential contamination, the collection process involved a minimum of two people, a designated
 "clean" person and a  designated "duty" person.  The  clean person, with a change  of surgical
gloves at each sample collection point along the cross-section was responsible for handling the
sample-collection device only and avoiding contact with metal objects or anything else that could
contaminate the sample.   The duty person, also with a clean pair of gloves at each section,
handled all other^quipment involved in the sample collection  process.  This process was
continued at each of the five sampling points along the cross section.

Field  measurements were performed for water and air temperature, pH, specific conductance,
dissolved oxygen, alkalinity, and barometric pressure. All field information was recorded on both
the laboratory analytical services request form and on the field sheet.

Processing of the samples was conducted in a designated van set up specifically for ultra clean
water quality sample processing. Inside the van, the composited sample was churned and poured
from the churn-splitter into the designated sample and holding bottles.

Water quality samples designated for total-recoverable analysis were preserved on  site with
Ultrex nitric acid (1 mL per 250 mL of sample),  dispensed from a Teflon dosing-bottle outside
the van,  and transported back to the office lab  to be processed  for shipment to the NWQL
laboratory, Denver, Colorado.   Samples for  dissolved  analysis were transported in  500  mL
Teflon-holding bottles to the office lab and filtered using a non-contaminating and analyte-inert
 filter apparatus and 0.4 um polycarbonate-membrane-filters that were initially rinsed with 0.1%
 Ultrex nitric  acid and then rinsed with high-quality  inorganic-free water.   Filtration was
 conducted in a Class 100 laminar flow hood.  A  filter blank was performed with each filtration
 using high-quality inorganic-free water. All metals samples were preserved with Ultrex nitric
 acid dispensed from a 300 mL Teflon-dosing bottle delivering a 1 mL dose.  A list of sample
 bottles used and the  preservation methods are  given in Table  1.  Specific sample process


 Sampling Program                                                                     8

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 Chesapeake Bay.Fall Line Toxics Monitoring Program:  1992 Final Report

 procedures are given in detail in the project QAPP.

 Samples for organic analysis were processed on-site immediately after collection or were shipped
 on ice to George Mason University. Because travel times were relatively short (<2 hours), no
 preservatives were added to the samples for organic contaminant analysis.

 Metal and Organic Contaminant Sampling Program -James River

 Water quality samples at the James River at Cartersville, Virginia, were also collected using an
 equal-discharge increment method, meaning that samples were collected along the river cross
 section at the midpoint of equal increments of discharge. Water-quality samples were collected
 using a depth-integrated sampler. As at the Susquehanna, samples were collected during periods
 of both baseflow and stormflow. For the purpose of this study, at the James River samples were
 considered stormflow samples if the maximum discharge after a precipitation event was greater
 than 12,000 cubic feet per second (cfs).

 Sample collection  methods and equipment used during the 1990-91 and the 1992 study are
 presented in the following text. Equipment and methods used in 1992 reflect the adoption of
 ultra clean sampling techniques. Although there is some overlap with the procedures used on the
 Susquehanna River, mere are a number of differences also. Therefore, the entire procedure is
 given.

 Sample collection methods for  1990-1991 period

 The field-collection equipment used at this site  differed depending on the flow conditions. At
 those times when the mean cross-sectional velocity at the James River was greater than 1.5. feet
 per second (ft/s), corresponding to a discharge of approximately 4,200 cfs, a  depth-integrating
 sampler was used.  At a velocity less than 1.5 ft/s, the depth-integrating sampler is ineffective
 so a point sampler was used.

 The  equipment used at this site included an epoxy-coated weighted-bottle sampler or an
 epoxy-coated depth-integrating sampler, depending on the flow velocity. Within each sampler was
 a glass collection bottle, from which the sample was poured into a polyethylene churn splitter.
 An aliquot of water collected with this  equipment was processed through a 0.45  urn cellulose
 membrane filter, which was mounted on a 142  millimeter plastic filter stand,  for separation of
 the "total" and "dissolved" fractions of a sample. All equipment was rinsed with sample water
 prior to sample collection.  Samples for the determination of suspended sediment were collected
 directly into a glass bottle placed in the depth-integrating sampler.  These bottles had been
 pre-cleaned at the USGS Sediment Laboratory in Harrisburg, Pennsylvania.

Water quality samples for the analysis of metals and organic contaminants were collected at the
midpoint of five sections of equal discharge. At each section, the sample bottle  was placed either
 in the weighted-bottle sampler or the depth integrating sampler, then was lowered into the river
 and allowed to fill, but not overflow. The water-quality sample was then poured into the churn
splitter. Once water had been collected from all five sections, the composite sample was mixed
in the churn.  Subsamples were then poured into precleaned sample bottles. At each section, a
 suspended-sediment sample was collected using a glass bottle placed in either the

 Sampling Program                                                                    9

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Chesapeake Bay.Fall Line Toxics Monitoring Program:  1992 Final Report
Table 1. James River sample bottles and preservation techniques.
 TOTAL RECOVERABLE METALS - NATIONAL WATER QUALITY LABORATORY
 Bottle Designation               Bottle Size and Prep.    Preservation
 RAH
 RA
 FA
 RAM
 FU
 RU
 TOC
8 oz. acid-rinsed
8 oz. acid-rinsed
8 oz. acid-rinsed
8 oz. glass
8 oz. regular
8 oz. regular
4 oz. amber glass
Add 1 ml ultrex nitric acid.
Add 1 ml ultrex nitric acid.
Add 1 ml ultrex nitric acid.
Add 5 ml KCr2.
None.
None.
Ice sample.
 DISSOLVED METALS - NATIONAL RESEARCH PROGRAM
 Bottle Designation               Bottle Size and Prep.    Preservation
 MERCURY HOLDING-BOTTLE
 METALS HOLDING-BOTTLE
 FA/FU HOLDING-BOTTLE
 pH CHECK BOTTLE
 FA BLANK
 FA RINSE
 FA
 FA BLANK FILTER
 FA FILTER
 FAM BLANK
 FAM RINSE
 FAM
500 ml Teflon
500 ml Teflon
500 ml Teflon
8 oz. regular
8 oz. acid-rinsed
8 oz. acid-rinsed
8 oz. acid-rinsed
50 mm petri-dish
50 mm petri-dish
4 oz. glass
4 oz. glass
4 oz. glass
Ice sample.
None.
None.
None.
Add 1 ml ultrex nitric acid.
None.
Add 1 ml ultrex nitric acid.
None.
None.
Add 5 ml K2CrO4. Chill.
None.
Add 5 ml K2CrO4. Chill.
 ORGANIC COMPOUNDS - GEORGE MASON UNIVERSITY
 Bottle Designation               Bottle Size and Prep.    Preservation
 ORGANICS SAMPLE
 EQUIPMENT BLANK
4-liter amber glass      Chill.
4-liter amber glass      Chill.
Sampling Program
                                           10

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Chesapeake Bay. Fall Line Toxics Monitoring Program:  1992 Final Report

depth-integrating sampler or the weighted-bottle sampler. Samples for total-recoverable metal
analyses were preserved with nitric acid (1 mL per 250 mL of sample).  Samples for dissolved
metals analysis were filtered on-site, placed in precleaned bottles, and preserved with nitric acid.
Total-recoverable  and dissolved Hg  samples  were preserved  with  10  mL  of a nitric
acid/potassium dichromate solution.  No preservation was needed for the suspended-sediment
samples.  The bottle type, volume, and preservation for each sample are listed in the 1990-91
QAPP on file at the EPA Chesapeake Bay Program Office.

All of the sample bottles were labeled  with the station number, date, tune, and analysis to be
conducted. . Information was also recorded on  field  sheets.  Metal samples were packed in
ice-filled coolers and sent to the NWQL  for analysis. The suspended-sediment samples were sent
to the USGS Sediment Laboratory in Harrisburg, Pennsylvania.

Sample collection methods for 1992 period

Standard operating procedures for collection and processing of water quality  samples are given
in the 1992  project QAPP.  Some  of the techniques are presented or expanded on in the
following text.

Water quality samples  collected in 1992 were collected  according to the ultra clean sampling
protocol developed by Dr. Howard Taylor of the National  Research Program of the U.S.
Geological Survey, Boulder, Colorado.  These methods include the use of sample collection and
processing equipment which are non-contaminating and analyte-inert.

       Specifically, the term ultra clean indicates:

              1.     Stringent  precleaning of all  containers,  sampling equipment, filtration
                    equipment, and filters;
              2.     Use of very high-quality water, organic solvents, and acids for preparatory
                    washing, blanks, preservation, and analysis;
              3.     Avoidance of contact between sample water and metal or plastic surfaces;
              4.     Special  precaution in the field handling of samples, including:
                    a. avoidance of all metal and/or plastic surfaces,
                    b. use of non-contaminating gloves and forceps,
                    c. avoidance of car exhaust and atmospheric deposition; and
              5. Use of a plexiglass glove box for laboratory processing and  analysis of metals
       samples.

At the James River at Cartersville,  special  equipment was utilized to collect and process a
contaminant-free representative sample. Project-dedicated field equipment included: a 3 liter
Teflon sampling bottle fitted with Teflon cap, nozzles, and bottle-to-cap adapter, a Teflon-coated
stainless steel  churn splitter, Teflon dosing bottles  and bags for storing  and transporting
equipment.  A modified D-77 depth-integrating sampler  fitted with the Teflon sampling bottle
was used for sample collection. The weight of the D-77  sampler requires that  a 4-wheel boom
fitted with an electric motor and a B-reel be used to lower and raise the  sampler at the point of
sample collection.   Project-dedicated laboratory equipment included a Teflon filter apparatus*
Teflon-coated tweezers and Teflon bags for storage of equipment.
                                                                       i

Sampling Program                                                                    11

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 Chesapeake Bay, Fall Line Toxics Monitoring Program: 1992 Final Report

 The equipment, including the Teflon bottle, cap, and nozzle, filter apparatus, Teflon bags, bins,
 and chum-splitter, was washed with a liquinox soapy water wash, thoroughly rinsed with tap
 water, rinsed with a flush of lab-grade methanol, two flushes with high-quality inorganic-free
 wafer, a flush with 10% nitric acid solution, and two flushes of high-quality inorganic-free water
 after each sampling trip.  The Teflon bottle, nozzles and other equipment were stored in clean
 Teflon bags in clean high-density-polyethylene bins.

 All equipment coming in contact with sample water was thoroughly rinsed  with river water
 before sampling began.  This rinsing included  collecting one sampler volume (approximately
 three liters each time), thoroughly rinsing the sampler bottle, then pouring the water into the
 churn  splitter.  The  churn-splitter was thoroughly washed with river water,  ensuring that all
 surfaces came  in contact with the water.  The  river  water rinse was discarded and the step
 repeated.

 Samples were  collected in  bottles  provided by the USGS NWQL; the  prescribed 250 mL
 polyethylene, acid-rinsed bottles were prepared for the ultra clean program by  2 initial rinses of
 high-quality inorganic-free water, a 24-hour soak in 10% nitric acid (made with Ultrex nitric acid
 and high-quality inorganic-free water), and two 24-hour soaks with high-quality inorganic-free
 water. The bottles were then refilled 1/2 to 3/4 full with fresh high-quality inorganic- free water
 (to be used as a filter rinse) and stored for use as needed.

 Samples were collected at the midpoint of five sections of equal discharge along the bridge. At
 each section, the sample  was poured directly into  the churn splitter.  The  sampling process
 involved a minimum of two people, a designated "clean hands" person and a  designated "dirty
 hands" person.  The clean  hands person,  with a  change of  surgical gloves at each sample
 collection point along the cross-section, was responsible for handling the sample bottle and nozzle
 only. The dirty hands person handled all other equipment, particularly any equipment with metal
 surfaces. This process was continued at each of the five sampling points along the cross-section.

 Samples for organic contaminant  analysis were  collected in 37.5 L stainless steel milk cans or
4-L amber glass bottles with Teflon lined caps. Precleaned milk cans were prepared for the
 fluvial samples by rinsing the can twice with  2 L of surface water. The rinses were discarded
prior to the placement of the surface water samples in the containers. Amber glass bottles were
prepared using  a similar technique, but were further heated to 350 ฐC twelve hours and prerinsed
with methanol.

Measurements  of water and air temperature, pH, specific conductance, dissolved  oxygen, and
 barometric pressure were conducted in the field.  All field information was recorded on both the
 laboratory analytical  services request form and on the  field sheet.

Initial  processing of the samples was  conducted in a designated van, set up specifically for
water-quality sample processing.   Inside the van, the sample composite was churned and
transferred from the chum-splitter into the designated sample bottles and holding bottles.

 Sample water designated for total-recoverable metals analysis was preserved on site with Ultrex
nitric acid (1 mL  per 250 mL of sample), dispensed from a Teflon  dosing bottle,  then was
transported back to the office lab to be processed for shipment to the NWQL.  Dissolved metals


 Sampling Program                                                                    12

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 Chesapeake Bay,-Fall Line Toxics Monitoring Program:  1992 Final Report

 samples were transported in 500 mL Teflon holding bottles to the office lab and filtered using
 a Teflon filter apparatus and 0.4 urn polycarbonate membrane filters that were initially rinsed
 with 0.1% Ultrex nitric acid wash and then rinsed with high-quality inorganic-free water. A filter
 blank was processed with each filtered sample using high-quality inorganic-free water.

 All metals samples were preserved with Ultrex nitric acid dispensed from a Teflon dosing bottle
 delivering a 1  mL dose.  Filtration was conducted in a plexiglass glovebox lined with Teflon.
 A list of sample bottles used and the preservation methods are given in Table 1.  Specific sample
 processing procedures are given in  detail in the QAPP.

 Samples for organic contaminant analysis were processed on-site immediately after collection or
 were shipped on ice to George Mason University. Because travel times were relatively  short
 (e.g., <2 hrs), no preservatives were added to samples for organic contaminant analysis.

 Metal and Organic Contaminant Sampling Program  - Potomac River

 As mentioned earlier in this report,  the OWML-operated monitoring station at Chain Bridge on
 the Potomac River is paced from the USGS gage at Little Falls, where the flow measurement is
 performed.

 The flow measuring equipment located at the Little Falls Dam station includes a microcomputer
 with an internal modem, an analog-to-digital (A/D) converter, and a contact pressure transducer
 submerged in the river. The transducer is oriented in the river flow in such a way as to assure
 that only static head is sensed. The pressure transducer creates an output voltage corresponding
 to river stage which is sent to the A/D converter, which then transforms the signal to a computer-
 readable digital form. The microcomputer is equipped with a program  which reads the signal
 from the A/D converter, calculates water surface height  above  the datum,  and determines
 discharge from a rating curve file stored in random access memory (RAM).  The rating curve
 for the Little Falls  Dam was developed, and is currently  maintained, by  the USGS.

When the pressure transducer senses an increase in stage, the computer program enters a storm
computation subroutine,  and begins calculating the total river flow volume passing the gage.
During a storm, at pre-set increments  of flow volume, the computer contacts the Chain Bridge
station via telephone, and instructs the equipment to withdraw a sample.

The microcomputer located at the Little Falls station stores flow data in RAM files. Stage, flow,
 and  sample  collection data may be retrieved over the telephone link using a third computer
 located at OWML.  Data are stored hourly during baseflow conditions  and every 15 minutes
 during storms.

The major consideration in siting the sample intake for the station was the requirement to extract
a truly representative sample of the river flow at a variety  of stages, ranging from baseflow to
extreme storm peaks. In order to accomplish this objective at Little Falls, the site of the gage,
it would have been necessary to install multiple sample intakes across the river cross section in
order to adequately represent the  various bifurcations and velocities observed.  Indeed, the river
cross section at Little Falls was deemed to be so poorly mixed that it was impractical to obtain
representative samples of the river flow at that point.

Sampling Program                                                                   13

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Chesapeake Bay, Fall Line Toxics Monitoring Program: 1992 Final Report

As noted previously, however, at Chain Bridge the river has been observed to be well-mixed.
The flow is constricted into a single channel near the Virginia shore, making the retrieval of
samples convenient.   A  room is located inside the bridge abutment on the Virginia side,
providing a convenient location to house sampling equipment. This location was also previously
used by the USGS to house a continuous monitor prior to 1983. Significant modifications to the
abutment room were undertaken, however, following the resurfacing of the Chain Bridge deck.

Because of the high suction lift from the water surface to the sampling room,  it was necessary
to install a submersible pump at the sample intake point.  The pump was attached to a flexible
intake line which was fixed to the downstream side of the bridge abutment.  In  the sampling
room, the pump discharge was routed to a constant head tank designed to allow complete mixing
of the  discharge flow, minimize  sedimentation, and allow rapid sample turnover.  With the
submersible pump operating at 10 gpm, the constant head tank was designed to allow a turnover
time of less than one minute.  The sampler is a Sigmamotor Refrigerated Automatic Sampler
(Sigmamotor, Inc.). A peristaltic pump is employed to transport samples from the constant head
tank into the sample containers. Because the constant head tank maintains a fixed  water surface
elevation,  the pump maintains a constant intake velocity, which  is greater than 3 ft/s, thereby
avoiding loss .of sediment in the sample stream. The unit may be programmed to collect discrete
or composite samples. Samples are kept at 4ฐC in the refrigerated compartment located in the
sampler base.

Samples for organic contaminant analysis were acquired from the head tank and placed in 37.5
L stainless steel milk cans.  The milk cans were then sealed and transported to George Mason
University for immediate processing.

Activation of the automatic sampling equipment at the Chain Bridge station is accomplished by
a microcomputer paced by the equipment located at the Little Falls gaging station.  When the
microcomputer receives a call from the Little Falls station, it activates the submersible pump
through an electrical relay. After allowing the constant head tank to fill, the computer triggers
the sampler to withdraw an aliquot from the tank.

Because of the large drainage area of the Potomac River at Chain Bridge, storm events may
continue over a number of days. For this reason, during storm events samples are retrieved daily
in order to avoid exceeding established holding times in the field. All installed  equipment is
housed in  the sampling room enclosed in the  bridge abutment. A site log of the  performance,
calibration, and maintenance of all instrumentation is kept as a  part of the permanent station
record.

The automated sampling system described above allows flow-weighted composite  samples to be
collected automatically through the duration of a storm event. This method eliminates most of
the common problems associated with attempting to occupy sampling sites with personnel during
a storm in order to collect grab samples.  Further, the method allows multiple samples to be
collected at equally spaced flow volume increments throughout a storm which may last several
days.  During baseflow periods manual grab samples were collected.

The only on-site measurements conducted as a part of the fall line monitoring program were
dissolved oxygen, pH, temperature, alkalinity, and conductivity.  All the foregoing analyses are
                                                                     *

Sampling Program                                                                  14

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Chesapeake Bay, Fall Line Toxics Monitoring Program:  1992 Final Report

conducted in accordance with accepted practice as detailed in Methods for Chemical Analyses
of Water and Wastes  (EPA,  1979),  the  applicable edition  of Standard ;'Methods for  the
Examination of Water and Wastewater (APHA,  1992),  and  manufacturer's literature, as
appropriate.  In the strictest sense, the measurement of time and stage at the Little Falls Gage
may also be considered to be on-site analyses. These are conducted as described above, and are
recorded on-site upon collection of baseflow samples.

The  station at Chain Bridge  is operated in such a way as to establish a well-defined estimate of
both base- and stormflow loads of conventional pollutants entering the estuary. To this end, the
station operates automatically, and attempts to sample all storm events occurring throughout the
year. The addition of toxics monitoring to the station analytical schedule did not significantly
alter the operating protocol.
Sampling Program                                                                    15

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 Chesapeake Bay fall Line Toxics Monitoring Program:  1992 Final Report

 QUALITY ASSURANCE PROGRAM

 A Quality Assurance Project Plan (QAPP) for  the Maryland  and Virginia Fall Line Toxics
 Monitoring Program was prepared by the USGS and MDE for the 1990-91 period.  This original
 QAPP was revised in 1992 to reflect changes to the program including an updated list of the
 constituents sampled, lowered  analytical quantitation levels,  and  ultra  clean  water  quality
 sampling techniques.  The  1990-91  and  1992 QAPP are  available for  review at  the EPA
 Chesapeake Bay Program Office, Annapolis, Maryland.  Some of the material included in the
 1992 QAPP is  presented or expanded on  in this Teport.

For the Susquehanna and  James Rivers,  the  transition  to  ultra clean sampling  and analysis
techniques was designed to minimize possible contamination of water quality samples and to
ensure that samples could be collected and analyzed for metals at lower quantitation levels.
Quality assurance was emphasized at the beginning of the sampling period in order to assess as
quickly as possible the new, ultra clean  methods in use.

Metals Quality Assurance Program  -  Susquehanna  River

The following quality-control samples were collected for metals at the Susquehanna River station:
(1)    Five sets of samples were collected to  compare the 1990-91  sample collection and
       analysis methods (known as "old" methods) to the 1992 sample  collection and analysis
       methods (known as "new" or ultra clean methods) for both total-recoverable and dissolved
       metals.
                *
(2)    Six equipment-blank samples were collected  using 1992  ultra clean methods for both
       total-recoverable and dissolved metal analyses, in order to  identify any potential sources
       of contamination  to the water quality  sample  from sample collection  and/or field
       processing techniques. An equipment-blank sample was collected by passing high-quality,
       inorganic-free water through all sample collection apparatus as well as filter apparatus,
       using 1992  analytical methods.

(3)    Nine filter-blank samples were collected using 1992 ultra clean methods for the dissolved
       metals analyses, in order to identify any potential sources  of contamination to the water
       quality sample from the filter apparatus.  A filter-blank sample  is collected by passing
       high-quality, inorganic-free water through the filter step  only, and analyzed  using the
       1992 methods.

(4)    Two sets of replicate water quality samples were collected using 1992 ultra clean methods
       for both total-recoverable and dissolved metal analyses, in order to assess  the precision
       of the laboratory methods.
The laboratories providing water analyses and data for this program  were the USGS National
Water  Quality Laboratory for  total-recoverable  metal analyses,  the USGS National Research
Program Laboratory for  dissolved metal analyses,  and the USGS Sediment  Laboratory for
suspended sediment analyses.
Quality Assurance Program                                                           16

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 Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report

 Metals Quality Assurance Program - James River

 The following quality-control samples were collected for metals at the James River station:

 (1)    Five sets of samples were collected to compare  the 1990-91 sample collection and
       analysis methods (known as "old" methods) with the 1992 sample collection and analysis
       methods  (known as "new"  or  ultra clean methods) for both  total-recoverable and
       dissolved metals.

 (2)   , Four equipment-blank samples were collected using  the 1992 ultra clean methods for
       total-recoverable  metal analyses,  in order  to  identify  any  potential  sources of
       contamination to  the water quality sample from  sample collection techniques.   An
       equipment- blank sample  was collected by passing  high-quality inorganic-free water
       through all sample collection apparatus then analyzed using the 1992 analytical methods.

 (3)    Sixteen filter-blank samples were collected using ultra clean methods for the dissolved
       metals analyses, in order to identify any potential sources of contamination to the water
       quality sample from the filter apparatus.  A filter-blank sample is collected by passing
       high-quality,  inorganic-free water through the filter step only, and analyzed using the
       1992 analytical methods.

 (4)    Two sets of replicate water quality samples were collected using 1992 ultra clean methods
       for total-recoverable metals, and one for dissolved metal analyses, in order to assess the
       precision of the laboratory methods.

 The laboratories providing water analyses and data for this program were the same as for the
 Susquehanna River.

 Metals Quality  Assurance Program - Potomac

 The quality assurance program  for  the Potomac River was limited to only the laboratory
 component.  Therefore, no equipment blanks were collected.  Because analysis was performed
 for total recoverable metals only, a filter blank was not necessary.  The laboratory  quality
 assurance program consisted of blanks,  duplicates  and spiked samples  that were part of the
 normal operating procedures.  Samples to be tested as duplicates, or those  to be spiked  for a
 recovery analysis,  were chosen from the entire sample set that  was to be analyzed at any
 particular time.

 Organic Contaminant Quality Assurance Program - Susquehanna, James and
Potomac Rivers

The reliability of analytical data was determined through quality assurance procedures conducted
 throughout this field study.   The following quality assurance  samples were collected and
processed for the Chesapeake Bay Fall Line Toxics Monitoring Program:

 (1)    Field  Blanks.  Dissolved  phase  and filter blanks  were acquired by rinsing all water
Quality Assurance Program                                                           \"j

-------
 Chesapeake Bay fall Line Toxics Monitoring Program:  1992 Final Report

       sampling equipment with contaminant-free distilled water (double distilled water with
       further removal of trace organic impurities by extraction using a 10-g Cf 18 bonded phase
       silica cartridges) on-site prior to sample collection.  The distilled  water rinse was
    ':   collected in  a  stainless steel milk  can for  further processing.   Blank water was
       subsequently  filtered through a stacked  arrangement  of  15.0-cm (diameter) Whatman
       GF/D and GF/F filters housed in the Millipore filtration apparatus. The filtered water was
       extracted as a sample in  the usual fashion. The filter was removed from the filter holder,
       wrapped in aluminum foil, and stored in an ice chest until its  return to the analytical
       laboratory.  The filter was then put in long term storage at -20 ฐC until analysis.  Field
       blanks indicated the presence of contamination in the analysis introduced during sample
       collection in the field. Precautions, described above for ultraclean sampling, were adopted
       to minimize sample contamination.   Suspected "analytes"  detected in the field blanks
       were  used  to screen sample concentrations.  Field blank  concentrations which were
       detected and  quantified  at levels >0.5 times the dissolved phase or paniculate  phase
       sample concentrations were used to flag sample concentrations in the fall line data base.
       Flagged concentrations are those which have questionable quality.  Field blank results also
       provided feedback on the effort being placed into cleaning field equipment, etc., and
       corrective measures were undertaken when possible if this occurred. Ten dissolved phase
       and filter phase field blanks were analyzed in the Susquehanna River fall line study, and
       twelve dissolved phase and filter phase field blanks were analyzed in the James River fall
       line study.

(2)    Laboratory Blanks.  Seven laboratory blanks were processed between March  1992 and
       February 1993, and were performed periodically throughout the entire Chesapeake Bay
       Fall Line Toxics Monitoring Program.  Laboratory blanks consisted of two components:
       a dissolved j>hase component and filter  phase  component.   Contaminant-free distilled
       water was filtered in the laboratory and the filtrate was extracted in the normal fashion.
       Suspected analytes in the laboratory blanks were used as  a means of  correcting sample
       concentrations.  Average suspected analyte concentrations from the  seven laboratory
       blanks (for both  dissolved and filter  phases) were averaged and subtracted (i.e., as a
       background subtraction) from individual sample concentrations to provide net sample
       concentrations for each analyte.

(3)    Matrix Spikes.  Nine matrix spikes  were performed for Susquehanna, Potomac, and
       James river fall line samples. Matrix spikes were used to determine the magnitude of
       determinant and indeterminant errors present in the analysis. A total of five matrix spike
       experiments were carried out with Carbopack B sorbents (including three Susquehanna
       River sub-samples and two James River sub-samples) between March and July 1992, and
       a total of four matrix spike evaluations were performed on Potomac River sub-samples
       using C-18 bonded  phase silicas.  Matrix spikes provided information regarding the
       accuracy and  precision of the reported results, and matrix spikes accounted for 10% of
       all samples processed.  A percent mass recovery  (%Rec) value and'its uncertainty
       (%RSD) were computed for the matrix spikes according to the equations below:
Quality Assurance Program                                                           18

-------
 Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report
                                %R6C =
                                         MaSS.piked
                          %RSD =           Deviation,,,                            (2)
                                        Mean %Rec
(4)    Extraction Mass Balance.  Approximately, 30% of the number of extractions initially
       included both front and back sorbent cartridges (in the stacked configuration) to determine
       analyte breakthrough occuring  during the extraction  of dissolved phase  analytes.
       Breakthrough was evaluated according to the calculation of collection efficiency (CE)
       shown below (%B is the percent of analyte measured on the back sorbent cartridge, and
       %F is the percent of analyte measured on the front sorbent cartridge):

                                  C, - (1 - **) X 100

              A solvent rinse of milk cans or glass bottles was performed during the collection
              of fall line samples to determine detectable levels of analysis of associated with
              container surfaces.

(5)    Duplicate Analysis.  Method precision was further evaluated through the analysis of the
       organonitrogen and organophosphorus pesticides in duplicate samples.  Several of the fall
       line samples were  analyzed in duplicate for these pesticides.  Duplicate analyses were
       conducted for thirteen river fall line samples including all three tributaries.

(6)    Enrichment Factors.  The  LSE sorbent cartridges  employed in this  study act  to
       preconcentrate the  target analytes from  water  on solid  sorbents.   The degree  of
       preconentration used  in this study was necessary to  achieve  the  desired QL values.
       Preconcentration is defined in this study by the enrichment factor (Ef), which is calculated
       from the sample volume (ca. 10 L in this study), the final volume of the sample extract
       subjected to GC/MS or GC-ECD analysis (ca. 0.2  mL), and the efficiency of extraction
       from the sample, determined from the percent mass recovery (%Rec) values of the matrix
       spike data. The  enrichment factor was calculated by using the relation:
                                =    Volume.^.    x                               (4)
                                   volume..^. Mtrmct    TTJTT


(7)     Error  Evaluation.   Determinate errors in the  reported fluvial sample concentrations
       provided in this report can be derived from the %Rec values determined from the matrix
       spike experiments.  Dividing the reported fluvial  sample concentrations by %Rec/100
       would, theoretically, provide the actual  ambient  analyte  concentration  in  the  fluvial
       sample at the time of collection.  Although this correction procedure was not adopted in
       this study,  is  does give  a perspective on  the accuracy  of the reported  fluvial
       concentrations and insight on the level of potential biases in the data.

              Indeterminate (random) errors associated  with GC/MS and GC-ECD analyses are
              derived from a  consideration of errors arising from the following sources: (a)
                                                                        4

Quality Assurance Program                                                            19

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Chesapeake Bay fall Line Toxics Monitoring Program:  1992 Final Report

              measurement of the amount of internal standard added to eacli sample extract in
              the analysis  (%(*,), (b) variations in relative response factors computed from
              instrument calibration data from the analysis of at least 10 calibrations C&o,), and
              (c) the measurement of each fluvial sample volume via a 2.0 L graduated cylinder
              — or the measurement of particulates collected on GF/F filters by using analytical
              balances  — C&otj).  Each of the  random error  terms in  internal  standard
              quantitation relation can be expressed in terms of percent  relative error (%cc)
              according to the equation
                                             .,
                                              (ฑ*Ot2)
             which is the  same  equation described  above for  internal standard
             quantitation but in this case errors are factored into it.  The RF term in
             equation 5 is the response factor (area of analyte peak divided by area of
             internal  standard  peak  in   GC analysis)  which  has  no  assigned
             indeterminate error. Because RF is a ratio of GC peak areas, it is assumed
             that the indeterminate errpr terms cancel.  Therefore, the error associated
             with  any single reported concentration (%oc4)  can  be expressed as
             propagated random error by the relation:

                               %
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 Chesapeake Bay. Fall Line Toxics Monitoring Program:  1992 Final Report

 LABORATORY ANALYSIS METHODS

 Metals Laboratory Analysis Methods - Susquehanna and James Rivers

 The USGS National Water Quality Laboratory (NWQL) in Denver, Colorado performed analyses
 of all constituents during the 1990-91 period, and performed analyses for total-recoverable metals
 during the 1992 period. The analytical procedures used by the laboratory are standard procedures
 used in water quality studies, and are documented in  the publication entitled, Methods for
 Determination of Inorganic Substances in Water and Fluvial Sediments (Fishman and Friedman,
 1985).  The NWQL quality assurance program provides an ongoing measure of the quality of
 data reported, and documentation is available on request. The USGS National Research Program
 (NRP) in Boulder,  Colorado, performed all analyses of dissolved metals collected during 1992.
 In order to achieve the lower quantitation levels necessary for the program, new techniques were
 developed for the analysis of dissolved metals that did not follow EPA analytical guidelines.

 Metals monitored for the ultra clean study, and their analytical methods and quantitation levels
 are summarized hi  Table 2.

 Metals Laboratory Analysis Methods - Potomac  River

 Water samples that have been collected and preserved for analysis are often digested or extracted
 to solubilize trace elements associated with particulates in the sample. There are several types
 of digestion procedures.  These vary primarily in  the type and concentration of acid used, and
 the temperature at which the digestion is performed.  The decision to use a particular digestion
 method is dependant upon the extent of sediment  breakdown desired.  For geological purposes
 a strong digestion^referred to as a "total digestion", is often needed to break down particulates
 into their elemental components.  For  environmental purposes a "total  recoverable" digestion is
 generally preferred to extract elements sorbed onto  the particulates. A total recoverable digestion
 is often chosen for  environmental work because the interest is in trace metals  that are labile and
 may become available to an ecosystem.  OWML  uses a total-recoverable digestion method as
 described hi the 18th Edition of Standard Methods for the Examination of Water and Wastewater
 (APHA, 1992).  It is listed in section 3030 and titled Preliminary Treatment for Acid-Extractable
 Metals.  The extraction is done with 6N hydrochloric acid with  the sample heated until the
 boiling point is reached (approximately an hour).

 OWML purchased  new instrumentation for metals analysis in the spring of 1992 (Perkin-Elmer
 5100 system from Perkin-Elmer Corporation). Samples collected at the Chain Bridge station on
the Potomac River  were analyzed using the new instrumentation.  The new instrumentation has
the capability of measuring metals by either flame or furnace atomization  followed by light
absorption spectrophotometry.  All metals were analyzed using furnace  analyses, except for zinc,
which was analyzed using flame atomic absorption. The analyses were performed in accordance
with the manufacturer's guidelines and using a stabilized platform furnace atomization method.
This method of furnace atomization is recommended in EPA Method Number 200.9 (EPA, 1991).
The EPA method was written for drinking water analysis but is also applicable for
Laboratory Analysis Methods                                                        21

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Chesapeake Bay.Fall Line Toxics Monitoring Program: 1992 Final Report

Table 2. Monitored metals and scheduled methods of analysis at the Susquehanna and James
River stations.                                                      :'
Constituent
Analytical Technique
Quantitation Level(ug/L)
Al (aluminum, Dis)
As (arsenic, TR)
As (arsenic, Dis)
Ba (barium, TR)
Cd (cadmium, TR)
Cd (cadmium, Dis)
Cr (chromium, TR)
Cr (chromium, Dis)
Cu (copper, TR)
Cu (copper, Dis)
Fe (iron, TR)
Fe (iron, Dis)
Pb (lead, TR)
Pb (lead, Dis)
Li (lithium, TR)
Mn (manganese, TR)
Hg (mercury, TR)
Hg (mercury, Dis]^
Ni (nickel, TR)
Ni (nickel, Dis)
Se (selenium, TR)
Ag (silver, TR)
Sr (strontium, TR)
Zn (zinc, TR)
Zn (zinc, Dis)
   AA, DCP
   AA, gaseous hydride
   ICP-MS
   AA, direct aspiration
   AA, graphite furnace
   ICP-MS
   AA, DCP
   ICP-MS
   AA, graphite furnace
   ICP-MS
   AA, direct aspiration
   AA, direct
   AA, graphite furnace
   ICP-MS
   AA, direct aspiration
   AA, direct aspiration
   AA, cold vapor
   Cold vapor fluorescence
   AA, graphite furnace
   AA, graphite furnace
   AA, gaseous hydride
   AA, graphite furnace
   AA, direct aspiration
   AA, direct aspiration
   ICP-MS
             10
             1.0
             0.6
             100
             1.0
             0.1
             1.0
             0.2
             1.0
             0.02
             10
             10
             1.0
             0.06
             10
             10
             0.1
             0.003
             1.0
             1.0
             1.0
             1.0
             1.0
             10
             0.08
ug/L = micrograms per liter; AA = Atomic Absorption; ICP-MS = Inductively coupled plasma,
mass spectrometer; DCP = Direct current plasma; Dis = dissolved; TR = total-recoverable
Laboratory Analysis Methods
                                                           22

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 Chesapeake Bay:Fall Line Toxics Monitoring Program:  1992 Final Report

 non-potable freshwater samples.

Detection and Quantitation Levels for Metals

 As part of the procedure of bringing the new instrumentation on-line, OWML performed a
 detection limit study.  Method detection (MDL) and quantitation levels(QL) were determined
 for each of the two atomization techniques — flame and furnace.

Metals Analyzed by Flame Atomic Absorption Spectrophotometry. A commonly-used method for
 determining detection limits in the environmental field is outlined in the Federal Register (Vol.
49, No. 209, Appendix B to Part 136, October 26, 1984).  A similar method for the calculation
 of the detection limit is listed in Standard Methods for the Examination of Water and Wastewater
 (APHA, 1992).  That document also provides methods  for calculation of quantitation levels.
 Quantitation levels are determined by multiplying the detection limit by a factor to represent
 concentrations that can be consistently measured as reliable. A key factor in the determination
of detection and  subsequent  quantitation levels is the concentration chosen to be analyzed.
 Guidelines refer to trying to estimate the detection limit and using a concentration for analysis
 that is 1-10 times the estimated detection limit.
                                ,                  *

Rather than using a single concentration, it  has been suggested that it may be more  valid to
 measure a range of concentrations. Taylor (1987) is a proponent of the concept of using multiple
concentrations. Taylor also states that the uncertainty of a value close to the determined method
detection limit can be as much as 100%.  Quantitation levels may be as high as 5-10 times the
method  detection  limit and are valuable when increased validity of results is desired.

OWML chose to determine a quantitation level that could provide a 20-30% mean absolute
difference in precision when measuring  seven replicates of a standard.  The percent mean
absolute difference is defined as:

                                                   L I (Ccb.~cซtซl)l
                                                                                   (7)
             Percent Mean Absolute Difference = _ x 100
A few of the elements that were analyzed had quantitation levels that provided a mean absolute
difference in precision of less than 20%;  these elements, therefore, will be measured with less
error. A 20-30% difference was considered optimal:  less than 20% may be overly conservative
while greater than 30% may not be considered conservative enough. The common method of
computing detection limits was employed.  This involved analyzing seven replicates of a single
concentration.  However, in accordance with Taylor's recommendation for using multiple
concentrations, six concentrations  were chosen.   This  resulted in a total of 42 analyses, as
opposed to 7, for  computing the detection limit.  The six chosen concentrations ranged  from
below the estimated detection limit to above  ten times the estimated detection limit, depending
upon the element.  In most  cases, a factor of 1.0-2.7 provided a mean absolute difference in
precision of 20-30%, and this was used to determine the quantitation levels.  Lead and nickel
were difficult to measure at trace concentrations and only two of the six concentrations chosen
were found to be  in the detectable range.
Laboratory Analysis Methods                                                          23

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Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

Metals Analyzed by Furnace Atomic Absorption Spectrophotometry

The number of samples analyzed  using a furnace atomic  absorption spectrophotometer is of
concern because these  analyses require a long analysis time and higher expense per sample
analyzed.   When determining furnace detection limits the number of samples analyzed was
decreased to seven replicates of a single carefully selected concentration for each element.  The
quantitation levels were conservatively estimated by either  multiplying the detection limit by a
factor of two or by choosing the standard concentration used  in the detection limit study.  The
simplified approach of multiplication by a factor is fairly standard in reference texts and articles
on quantitation limits (APHA, 1992; Federal Register, 1984; Keith, et al., 1983; Taylor, 1987).
The use of the standard concentration as the quantitation level was  chosen  when the standard
deviation was so low that the resulting detection and quantitation levels were also calculated to
be very low.  Although extremely low detection limits are  a positive attribute in laboratory
analysis, OWML is also concerned with reporting limits that  are achievable and not simply an
artifact of statistics. Because of this, hi the case of cadmium and chromium, the lowest standard
measurable was considered a more valid measure than the MDL calculation.

OWML is reporting QLs  for the case of all metals.  Also, because of the  analysis procedure
employed (specifically, analysis by flame AA, and, if the concentration were below the QL for
flame AA, then analysis by furnace AA), the effective QLs for all values reported are those for
furnace AA. The QL for Zinc is for the flame AA method. This is because this element could
not be resolved at a lower QL using furnace AA.

Organics Laboratory Analysis  Methods - Susquehanna, James  and Potomac
Rivers

The fluvial samples collected from the fall line study were analyzed for the presence of nine
organonitrogen   and  organophosphorus  pesticides,  eight  organochlorine  pesticides,  112
polychlorinated biphenyl (PCB) congeners, and four polycyclic aromatic hydrocarbons (PAH).
The names of the analytes, the fluvial phase analyzed, and quantitation levels for each analyte
are listed in Table 3.

Filtration of Suspended Particulate Matter

Suspended paniculate matter >0.7 um in nominal diameter was isolated from water in all of the
fall line samples  via filtration through pre-cleaned glass fiber  filters.  River water placed in the
milk cans from collection was pumped via a positive displacement pump at a rate of ca. 1 L/min.
(Model QB-1, Fluid Metering Inc., Oyster Bay, NY) through a stacked configuration of a 15-cm
Whatman GF/D glass fiber filter (25 um nominal pore diameter) overlaying a  15-cm Whatman
GF/F glass fiber  filter (0.7 um nominal pore size) housed in a Millipore stainless steel filtration
apparatus.  (The  filter holder had been customized by the addition of a PTFE  Teflon O-ring hi
place of the original Viton O-ring to minimize sample contamination and analyte reaction.) The
filtered water was collected in another precleaned 37.5-L stainless steel milk can for subsequent
extraction.  Convoluted  TFE Teflon tubing was used for sample transfer lines, the  only type of
surface apart from the metering pump that was allowed to come in contact with the water during
sample filtration.
Laboratory Analysis Methods                                                         24

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 Chesapeake Bay.Fall Line Toxics Monitoring Program:  1992 Final Report

 Table 3. Monitored organic contaminants and scheduled methods of analysis. The fluvial phase
 analyzed, dissolved and  particulate, is indicated  along  with the method.* of analysis and
 quantitation levels (QLs).
Analyte                           method              QL, diss.            QL, part.
	      ng/L	ng/g	

(organonitrogen & organophosphorus group)
simazine                          gc/ms              2.0                  na
prometon                         gc/ms              1.6                  na
atrazine                           gc/ms              1.3                  na
diazinon                          gc/ms              2.5                  na
alachlor                           gc/ms              2.5                  na
malathion                         gc/ms              2.3                  na
metolachlor                       gc/ms              0.7                  na
cyanazine                         gc/ms              2.4                  na
hexazinone                        gc/ms              0.8                  na

(organochlorine group)
aldrin                             gc-ecd             0.2                   2.2
oxychlordane                      gc-ecd             0.1                   1.8
gamma-chlordane                  gc-ecd             0.1                   1.7
alpha-chlordane                   gc-ecd             0.1                   1.7
dieldrin                           gc-ecd             0.2                   2.1
4,4'-DDT                         gc-ecd             0.5                   6.0
cis- & trans (c/t)-permethrin        gc-ecd             1.7                  21.6
cis- & trans(c/t)-fenvalerate         gc-ecd             0.6                   7.3
SPCBs (112 congeners)            gc-ecd             0.5                   6.0

(polycyclic aromatic hydrocarbon group)
naphthalene                       gc/ms              0.1                   1.0
fluoranthene                       gc/ms              0.3                   1.0
benz(a)anthracene                  gc/ms              1.0                   1.4
benzo(a)pyrene                    gc/ms              2.0                   2.7

gc/ms=gas chromatography/mass spectrometry;  gc-ecd=gas chromatography-electron capture
detection.
Laboratory Analysis Methods                                                          25

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 Chesapeake Bay.Fall Line Toxics Monitoring Program: 1992 Final Report

 GF/D and GF/F filters were folded into quarters together and placed in precleaned aluminum foil
 envelopes as soon as filtration was completed. The envelopes were sealed, labeled, added to Zip-
 lock plastic bags, and placed in an ice chest until they were returned to the GMU analytical
 laboratory. The filters were stored in a freezer at -20 ฐC until chemical analysis was performed.

Analyte Isolation and Preconcentration from Water

 The monitored organic contaminants (Table 3) were extracted from the filtered fall line samples
by using liquid-solid extraction (LSE) according to procedures previously described by Foreman
 and Foster (1991).  Eight to twelve liters of filtered surface water was passed through LSE
 sorbent cartridges configured in a stacked front and back arrangement.  For the extraction of
 Susquehanna and James River filtered water, the front sorbent cartridge contained 4 g of
 Carbopack B graphitized carbon (120/400 mesh; Supelco, Inc., Bellefonte, PA) and the back
 cartridge contained 2 g of the same sorbent.  For the extraction of filtered Potomac River water,
cartridges containing 10-g of octadecylsilyl-bonded silica (CIS) (Varian Assoc., Inc., Harbor City,
CA) were used similarly in a stacked front and back arrangement.

Filtered water was  pumped  through the LSE cartridges  using a Model QRHB-1CKC  (Fluid
Metering) pump at a flow rate of 50-75 mL/min.  Upon completion of the extraction step the
 sorbent cartridges were rinsed with 10 mL of distilled water, and the cartridges were wrapped
in aluminum foil, labeled, placed in Zip-lock plastic bags, and immediately placed in an ice chest.
Upon return to the GMU laboratory, the LSE cartridges were placed in storage at 3 ฐC and they
were subsequently eluted within 24 hours  of returning to the laboratory.

On-site LSE was performed at the Susquehanna River and James River stations during base flow
 sampling for as many samplings as scheduling would allow. Extractions were preformed in a
USGS  Chevrolet van at the Susquehanna River site, and in a volunteer firehouse in Cartersville,
VA, located within one mile of the James River sampling location. Potomac River samples were
extracted at the GMU analytical laboratory immediately upon arrival.  All of the storm samples
from each of the three fall line sites were  extracted in the GMU analytical laboratory by using
exactly the same approach described above for the 4-L surface water samples.

Field and Laboratory Blanks

Field blanks were performed on-site during each Susquehanna and James River base flow
sampling event. Field blanks consisted of a distilled water (Burdick and Jackson, Muskegon, MI)
rinse of all of the surface water sampling equipment (contacting all of the surfaces a normal
sample would contact during sampling, filtration, and LSE) which was collected in a precleaned
stainless steel milk  can.  The blank was  subsequently filtered and extracted as was a normal
sample. Four to eight liters of distilled water rinse was typically used as the field blank.   A
single blank was processed prior to the filtration and extraction of surface water samples. During
storm sampling, all of the surface water sampling equipment was rinsed with distilled water on-
site in the normal manner, but in this case the blanks were shipped on ice to the GMU analytical
laboratory and processed according to the usual procedure.

Laboratory blanks  were  performed  intermittently  to  check  for  equipment  and  reagent
contamination. Laboratory blanks were performed in exactly the same fashion as  described for


Laboratory Analysis Methods                                                         26

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 Chesapeake Bay-Fall Line Toxics Monitoring Program:  1992 Final Report

 field blanks except they were conducted without the distilled water rinse of the surface water
 sampling equipment.

 Matrix Spikes

 A matrix spike as defined in this study was the addition of each target analyte to eight to twelve
 liters of a filtered sub-sample of the composited surface water sample collected at each of the
 river fall lines. In this procedure, the filtered sub-sample was transferred to a precleaned 37.5-L
 milk can and the target analytes were added to the water as a methanol solution (5 mL) to give
 a final concentration of ca. 100 ng/L for each component (for PCBs, the amount corresponded
 to 300 ng/L of total PCBs).  The amended water was mixed thoroughly by agitation, and  was
 subsequently extracted in the normal manner.  Results  from the matrix spikes were used to
 calculate the mass percentages of the amended target analytes recovered from the surface water
 samples.

 Sample Container Rinse

 Hydrophobia organic compounds dissolved in water are known to undergo sorption reactions with
 the walls of sample  containers.  The  degree  of  sorption depends  on the  physicochemical
 properties and reactivity of the analytes and the surface composition of the container. Sorption
 from water to the  surface would reduce the dissolved phase concentrations  of the organic
 contaminants underbiasing the data. Milk cans and glass bottles which came in contact with the
 sample were solvent rinsed with 50 mL of cyclohexanerisopropanol  (7:3) after filtration  and
 extraction had been completed.   The solvent rinses were analyzed by  using  the procedures
 described below.

Equipment and Glassware Cleaning and Preparation

All non-volumetric glassware was scrupulously cleaned with Alconox detergent in hot tap water,
rinsed  with distilled water, and baked hi a muffle furnace  at 450 ฐC for 15  hours.  Baked
glassware was stored wrapped in aluminum foil (all aluminum foil used for wrapping and storage
hi this study was fired at  450 ฐC prior to use),  and was repeatedly rinsed with n-hexane  and
methanol before use.  Volumetric  glassware was initially soaked in 15% aqueous nitric acid,
washed in Alconox  detergent, rinsed with distilled water, and hexane rinsed repeatedly prior to
use. Volumetric (i.e., precisely calibrated) glassware was also stored wrapped in aluminum foil.

Stainless steel  milk cans were washed hi the same manner as glassware but \vere not baked. The
cans were repeatedly rinsed with methanol prior to use and were stored with their lids securely
fastened to prevent  the entry of organics into clean cans from ambient air.

Positive displacement pumps and associated Teflon tubing were thoroughly washed with methanol
and distilled water between extractions.  This was often accomplished in the field as well as the
laboratory depending on the sampling schedule.  All exposed ends of Teflon tubing were kept
wrapped with aluminum foil when not in use to prevent contamination.
Laboratory Analysis Methods                                                          27

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 Chesapeake Bay fall Line Toxics Monitoring Program:  1992 Final Report

 LSE Cartridge Elation

 LSE cartridges were eluted according to the procedures described by Foreman and Foster (1991).
 The/LSE cartridges were initially dewatered by purging with nitrogen for 30 minutes followed
 by vacuum aspiration for an additional 5 minutes. Each cartridge was subsequently eluted with
 60 mL of cyclohexane:isopropanol (7:3, v/v) solvent (both Carbopack B and CIS sorbents) into
 a 250 mL boiling flask with the aid of nitrogen gas head pressure: 20 mL of solvent was quickly
 purged through the cartridge to wet the  sorbent with the elution  solvent and then 40 mL of
 solvent was allowed to saturate the sorbent for 15 minutes in static mode; the remaining solvent
 was purged through the cartridge in dynamic mode at a rate of 2 drops/sec (ca.  15 mL/min) until
 the sorbent bed was dry.

 When a visible water layer was present in the eluent, approximately 5 mL of isopropanol was
 added to the boiling flask, then the eluent volume was reduced to approximately 10 mL by using
 rotary-flash evaporation. As the solvent volume was reduced to ca. 10 mL, 5 mL of cyclohexane
 was added to the flask to check for the presence of water, which, if present,  would produce a
 cloudy emulsion.  When needed, subsequent 5 mL additions of the  cyclohexane-isopropanol
 mixture were added  and  solvent  volume reduction continued until the eluent was  clear when
 mixed with cyclohexane.  The eluent was further reduced to approximately 5 mL and .transferred
 to centrifuge tube by  a  pasteur pipet, rinsing  the sides of the  flask twice with 2 mL of
 cyclohexane:isopropanol solvent.  The volume was further reduced to 0.2 mL by using nitrogen
 gas evaporation, occasionally rinsing the  centrifuge tube with  solvent to release any analytes
 adhering to the sides of the tube. The concentrated eluents were centrifuged for 15 minutes at
 3000 rpm, and then the samples were transferred to sample vials by using a 500 uL syringe.

 Glass Fiber Filter Extraction

 Filters were thawed  to room temperature, placed in glass  Soxhlet extraction thimbles, and
 extracted for 24 hours in  a Soxhlet extractors with cyclohexane:isopropanol (7:3).  Both GF/D
 and GF/F filters were combined for each sample hi the Soxhlet apparatus during the extraction
 (i.e., no attempt was made to measure particle size differences in sorption and fluvial transport).

Alumina/Silica Fractionation

 The organochlorine  compounds  (PCBs,  aldrin,  oxychlordane, alpha-  & gamma-chlordane,
 dieldrin, 4,4'-DDT, cis- & trans-permethrin, and cis- & trans-fenvalerate) were analyzed by using
 a gas chromatograph  equipped with an electron capture detector (i.e., GC-ECD).  Because of the
 limited  selectivity  of the instrument  for the target analytes  and the number of interfering
 organochlorine compounds that may also be present in the samples, extracts from the LSE
 cartridges and filters needed to be fractionated  via column  chromatography prior to GC-ECD
 analysis to isolate the PCBs (plus aldrin) and the remaining organochlorines in separate fractions.
 Fractionation columns consisted of 25 mL medical grade polyproplyene syringe barrels that were
 fitted  with  25 mm  ANOTOP filters (0.2 urn pore size; Alltech  Associates, Inc.), which in turn
 were fitted with PTFE (Teflon) flow valves to regulate solvent flow through the cartridge.  The
 cartridges were packed, in order of filling from bottom to top,  with 2 g of granular anhydrous
 sodium sulfate (J.T. Baker Chemical Co.), 3 g of fully activated silica gel (60/200 mesh, Fisher
 Chemical  Co.;  previously activated at 135 ฐC), 6 g of 2%  (wt/wt) water deactivated neutral

 Laboratory Analysis  Methods                                                         28

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 Chesapeake Bay.-Fall Line Toxics Monitoring Program:  1992 Final Report

 alumina  (80/200  mesh, Fisher  Chemical Co.;  previously activated at 500 ฐC),  and 4 g  of
 anhydrous sodium sulfate. The sorbent cartridges were connected through polypropylene adapters
 to 25 mL polypropylene reservoirs, and the tops of the reservoirs were connected to a nitrogen
 evaporator manifold through 1/8 in. (od) Teflon tubing.

 The fractionation columns were first washed with 50 mL of n-hexane, which was discarded, and
 the extracts  were  loaded into the sorbent cartridges and were eluted with 45 mL of  ri-hexane
 (PCBs plus  aldrin)  followed by 45  mL of dichloromethane (chlordanes,  dieldrin, DDT,
 permethrins, and fenvalerates). Details of the eluent compositions in this fractionation  sequence
 are described by  Shan (1991).   Each  eluent was  collected separately and both  eluents  are
 concentrated to a final volume of 0.2 mL by using rotary flash evaporation and nitrogen gas
 blowdown and analyzed by using GC-ECD.

 PAHs associated with fluvial particulates eluted in the DCM fraction in column chromatography.
 The DCM fraction was further analyzed by using GC/MS for PAHs.

 Instrument Parameters

 The fall line target analytes have instrument analysis designations along with then- quantitation
 levels (QLs) as shown in Table 3. QL values for  each analyte were calculated according to
 analytical procedures previously described by Foster et al. (1993). A Hewlett-Packard (HP) 5890
 Series n gas chromatograph (GC) equipped with an electron capture detector (ECD) was used
 to measure all of the  organochlorine compounds.  The GC-ECD output was transferred from an
 HP 3396A recording integrator to an HP Vectra QS/20 microcomputer through HP 3396A file
 server software (ver.  1.2).  Hard copies of each chromatogram obtained from GC-ECD analysis
 were labeled and stored, according to sample name, in a filing cabinet. The report files  uploaded
 to the Vectra computer were imported into Quattro Pro (ver. 2) spreadsheet software  (Borland
 Associates, Scotts Valley, CA),  evaluated as needed, and stored both on floppy disks and  the
 Vectra QS/20 hard drive. Periodically, data on the Vectra QS/20 hard drive was backed up  on
 40 megabyte streamer tapes for long term storage.

The GC/MS  analyses were performed on a HP 5890A GC coupled to a Finnigan INCOS 50 mass
 spectrometer.  The system is controlled and operated through INCOS 50 software. The mass
 spectrometer was  tuned and calibrated daily with perfluorotributyl  amine.  Data files produced
 by the INCOS 50  system were archived and converted to PCDS (ver. 3.0; Finnigan) format for
auto-quantitation.  Archived data files on the INCOS 50 GC/MS were electronically transmitted
via ethernet to the HP Vectra QS/20 microcomputer for processing and storage. The GC/MS data
 files, quantitation  files, and calibration files were stored on floppy  disks and on the hard drive
of the Vectra computer.   Streamer tape backup  copies  were made periodically.  Specific
instrument operational parameters used  for both GC-ECD and GC/MS have been described in
the fall line  survey QA document (Foster 1992).

Instrument Calibration and Quantitation

All instruments were calibrated daily  prior to  the  analysis of the fluvial samples.  Primary
standards were prepared either from neat compounds (Chem Service Inc., West Chester, PA) or
were obtained as preprepared solutions  with known analyte concentrations and accompanying
                                                                       •ป

Laboratory Analysis Methods                                                         29

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Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report

QA/QC information (Chem Service).  Secondary calibration standards were prepared from the
primary standards using the appropriate mixtures and dilutions.  The PCB calibration standard
was prepared from a 1:1:1 (wt/wt/wt) mixture of Arochlors 1242:1254:1260, and the relative
abundance  of each congener was determined by using the composition data of Schulz et al.
(1989) for the same  Arochlor mixtures.   One-hundred and  twelve PCB  congeners were
quantitated in each dissolved phase and suspended particle sample extract. A single calibration
standard for GC-ECD and GC/MS was used to calculate relative response factors (RRF's) by
manipulating the fundamental internal standard quantitation formula shown below:
                                          RRF x
                                                '-ltd
During  calibration,  the  analyte and  internal  standard concentrations were  known to four
significant figures and all integrated GC peak areas (instrument analog to digital count output)
were obtained from the GC. Peak identifications were made by using relative retention time data
(retention time of analyte/retention time of internal standard).  Relative response factors were
calculated from calibration procedures and the internal standard quantitation  equation above.
Calibration nf data was recorded and  a hard  copy was saved on file daily to query instrument
variability and drift through time. Quantitation levels were calculated from a signal-to-noise ratio
of three in instrumental analysis.

In GC/MS analysis, confirmation of the monitored organic contaminants was determined by the
presence of 2 characteristic electron impact-ionization mass peaks that were present at the correct
retention time and had the correct relative abudance relative to the primary quantiation ion. At
least one of the  confirmatory ions  needed  to be present for the detection of an organic
contaminant.

Organic contaminants detected and quantitated by using GC-ECD were confired when possible
by combining several sample extracts and reducing  the extract volumes  to  <100 uL.  The
combined and volume-reduced extracts were analyzed by GC/MS to confirm the  presence of
organochlorine compounds detected via GC-ECD.
Laboratory Analysis Methods                                                         30

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 Chesapeake Bay^Fall Line Toxics Monitoring Program:  1992 Final Report

 LOAD ESTIMATION  METHOD

 Load. estimates  were calculated  for the 1990-91  period using one  of two  load  estimation
 techniques: a log linear regression model termed the "Adjusted Maximum Likelihood Estimator"
 (AMLE) (Cohn, 1988), or the Interpolation-Integration model (E).  A discussion of the AMLE
 technique and resulting load estimates is provided in the report Chesapeake Bay Fall Line Toxics
 Program:  1990-1991 Loadings (1993).  Annual estimates for this period are presented in the
 following text for comparative purposes.        ,.'

 Annual load estimates for 1992  were calculated using the AMLE model, when applicable.
 Otherwise, the load estimates were made with the Interpolation-Integration model (II), which is
 a consistent method between all members of the Chesapeake Bay Fall Line Toxics Program.
 Monthly load estimates using the Interpolation-Integration method are also provided for the  1992
 sampling period.

 Load estimates calculated using the Interpolation-Integration model were made by first calculating
 daily loads and then summing these values over each monthly  period.   Daily loads  were
 calculated using the following formula:

                                                                                   (9)
                                 Loadt A  = Qt x Ct ฃ x K
Load, j = calculated load for constituent i on day t in pounds per day
Q     = mean daily discharge for day t, in cubic feet per second
Cti     = concentration of constituent i for  day t in micrograms per liter
K     = conversion factor (2.4485 sees x L x kg/ft3 x ug x days)

Mean discharge was calculated daily using  flow values electronically  measured every   15
minutes.  Metal and organic contaminant  concentrations were measured less frequently and,
therefore, daily values were interpolated from the existing data set. Interpolated data points were
assigned the value of the nearest measured concentration.

The load estimates were calculated twice to determine a range in values. Censored data were
assigned a value of zero for the calculation of a lower boundary, or "minimum" load, and were
assigned the values of the quantitation level for each constituent in order to calculate an upper
boundary, or "maximum" load.

The AMLE  model  is still  considered  the loading estimate method of  choice because  it
incorporates long-term trends, has improved handling of censored data (values  below quantation
level), and provides an estimate of model and prediction error. A range in  load estimates was
calculated using the AMLE based on statistical variance observed in the data  as determined by
the model.

Samples for  the Potomac River  were integrated  over  storm events; therefore the following
adjustments to the n Model were made. To compute baseflow loads, the first step was to divide
the time interval between each pair of successive baseflow samples at the midway point. The

Load Estimation Method                                                              31

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Chesapeake Bay-Fall Line Toxics Monitoring Program: 1992 Final Report

first half of this interval was then associated with the concentrations of trace metals in the first
sample of the pair, while the second half was associated with the concentration of the second
sample of the pair.  The time before the  very first baseflow sample (i.e., at the start of the
sampling period) was associated with the  very first baseflow sample, and, similarly, the time
interval after the last baseflow sample was associated with that sample. Daily baseflow values
were obtained from MWCOG. These daily flow values were multiplied by the concentration
associated for that day and the time for which the flow and concentration were valid. Normally,
the time would be one day (86,400 seconds), unless the beginning or end of a storm event or the
dividing point of the interval between two  successive baseflow samples occurred that day. All
the daily baseflow loads and all the stormflow loads for each month were then summed to obtain
the total load for the month.

For the organic constituents, baseflow loads were estimated separately from storm flow loads.
Loads estimated from storm flow were assumed to be contributed entirely from runoff.  No
attempt was made to estimate baseflow loads separately during storm events.
Load Estimation Method                                                             32

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 Chesapeake Bay.Fall Line Toxics Monitoring Program:  1992 Final Report

 HYDROLOGIC CONDITIONS

 Susquehanna River

 The USGS stream-gaging data values for daily water discharge were used in calculating toxic
 substances loadings at the Susquehanna River fall line monitoring stations.  The calendar year
 long-term average water discharge for  the Susquehanna River at Conowingo Dam is 40,956
 cubic feet per second (ftVs).  The average water'discharge in 1990, 1991, and 1992  at  this
 station was 48,535,29,748, and 35,495 frVs, respectively.  Calendar year 1990 was the only year
 that flow exceeded the long-term mean.  Water discharge for the three-year period is illustrated
 in Figure 2.

 James River

 USGS stream-gaging data values for daily water discharge were  used in calculating toxic
 substance loadings at the James River fall line monitoring station. Figure 3 shows the long-term
 monthly discharge at the James River station, overlain by the 1990-92 calendar year hydrograph.
 The calendar year long-term average water discharge for the James River at Cartersville is 7,113
 cfs. Average water discharge in calendar years 1990, 1991, and 1992 at the James River  was
 8,397, 6,930, and 7,173 cfs, respectively. For these periods, water discharge in 1990 exceeded
 the long-term average, 1991 was below average, and 1992 was close to the long term average.

 Potomac River

The flows in the Potomac River at Little Falls during the period of this  study (March,  1992, to
March, 1993) were either below or at  the 60-year average reported by the USGS (1991) for all
months except  June and July of 1992, and March of 1993. Flows in September, 1992, were near
the average,  and those in January, 1993, were slightly above average. Flows in October, 1992,
and February, 1993, were approximately one-half the average, whereas those in November, 1992,
were less than one-half the average.  March, 1993, had  flows that were more than twice the
average.  The  annual flow for the 12 month period of April 1992,  to March 1993, was 10%
higher than the 60-year average.  Figure 4 shows the 1990 to 1993 hydrograph and long-term
mean monthly  discharge for the Potomac River.
Hydrologic Conditions                                                               33

-------
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-------
 Chesapeake Bay .Fall Line Toxics Monitoring Program: 1992 Final Report

 QUALITY ASSURANCE RESULTS

Metals Quality Assurance Results - Susquehanna River

The quality-assurance program included collection of quality-control samples to meet the QA
objectives of the project.  Results of these analyses for metals are listed in Table 4 and Table 5.
Five sets of samples were collected to compare the "old" 1990-91 sample collection and analysis
methods to the "new" 1992 ultra clean sample collection and analysis methods (Table 4). Results
indicate that for total-recoverable  concentrations of As, Cd, and Zn there was no difference in
values between the two collection techniques. Concentrations  of total-recoverable Cr, Cu, Hg,
and Pb were lower in samples collected using the ultra clean techniques. Results of the dissolved
analyses indicate  that generally concentrations of Pb and Zn were lower using the ultra clean
techniques, while concentrations of Cr and Cu were higher.

Equipment blanks were performed prior to sample collection at the midpoint of the sample-
collection cross section using high-quality inorganic-free water provided by the USGS Ocala,
Florida laboratory. Blank samples were collected to monitor the efficiency of the new ultra clean
techniques. Results for the equipment and filter blanks initially indicated that clean samples were
being  collected. After the  first two months, however, a ubiquitous contamination problem
developed for most of the dissolved  metal constituents. The source of the contamination is still
under investigation. The two sampling periods are discussed separately.

In order to provide a preliminary assessment of new sampling procedures, four equipment blank
samples  were  collected using ultra clean methods  during  March  and April 1992  for both
total-recoverable and dissolved metal analyses (Table 5, Figure 20-Figure 23).  Specifically, we
wished to identify any potential sources of contamination to  the water-quality sample from the
ultra clean sample collection and/or field processing techniques. Results indicate that equipment
blank samples did not contain detectable concentrations of total-recoverable As, Cd, Cu, or Zn.
One occurrence each of total-recoverable Cr (1 ug/L) and total-recoverable Pb (2 ug/L) was
detected, and total-recoverable Hg was present in all but one equipment-blank sample at a range
of 0.2 ug/L or less during this initial two-month period.  Results of the equipment blank samples
collected during  this period for the dissolved  metal analysis  indicate that no detectable
concentrations of  dissolved As, Cd, and Pb were present. One  occurrence each of dissolved Cr
(0.9 ug/L) and dissolved Cu (0.2 ug/L) was detected, two occurrences of dissolved Zn (0.4 and
1.2 ug/L) were detected, and  dissolved Hg was consistently  present in all equipment-blank
samples at 0.032 ug/L or less during this initial two-month period.

In addition to the equipment-blank samples, which identify potential sources of contamination
to the water quality sample from the entire sample collection procedure, four filter-blank samples
were collected during March and  April, 1992 to identify potential sources of contamination to
the sample from the filter step only  (Table 5).  Results from the first two months of sampling
indicate that dissolved As, Cd, Cr, and Pb were not present in  detectable concentrations.  Only
one occurrence each of dissolved Cu (0.1  ng/L) and  dissolved Zn  (0.9 ug/L) was  reported.
Dissolved Hg was present in all  of the blanks at about 0.035 ug/L or  less during  the initial
two-month period.
Quality Assurance Results                                                            37

-------
Chesapeake Bay-Fatt Line Toxics Monitoring Program:  1992 Final Report
Table 4. Quality assurance data collected at the Susquehanna River fall line at Conowingo,
Maryland, to compare old and new sample collection techniques for total-recoverable and
dissolved trace metals.


Date
03-30-92
04-03-92
04-22-92
05-12-92
07-15-92


Discharge
(ff/s)
169,000
88,500
87,700
66,300
12,300
Total Recoverable Metals
Arsenic
Suspended
Sediment Sediment old new
(% finer) •'' (mg/1) (ug/1) (ug/1)
100 49 <1 <1
99 22 <1 <1
98 15 <1 <1
100 13 <1 <1
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-------
 Chesapeake Bay. Fall Line Toxics Monitoring Program:  1992 Final Report

 During the period from May to September 1992, two equipment-blank samples were collected
 for the analysis of both total-recoverable and dissolved metals, and five filter-blank samples were
 collected for the analysis of the dissolved metals.  Results of equipment-blank samples for total-
 recoverable analyses for this period indicate that no detectable concentrations of total-recoverable
 As, Cd, Cu, Hg, Pb, or Zn were present.   Total-recoverable Cr, however, was present in both
 equipment-blank samples at 8 ug/L or less. These results are consistent with the March to April
 1992 period with the exceptions of total-recoverable Pb and total-recoverable Hg, which were
 detected during the March to April 1992 period but not during the May to September 1992
 period.

 Results of equipment-blank  samples for dissolved analyses for the May to  September period
 indicate that all  dissolved constituents were  detected with the exception  of dissolved  As.
 Dissolved Cd was detected once at 1.10 ug/L, dissolved Cr at 4.27 and 6.32 ug/L, dissolved Cu
 at 0.35 and 0.51  ug/L, dissolved Pb once at 0.37 ug/L, and dissolved Zn once  at 2.63 ug/L.
These results are inconsistent with the earlier March to April 1992 period for dissolved Cd and
Pb, when they were not detected.  Moreover, the concentrations of dissolved Cr, Cu, and Zn were
much higher during the May to September 1992 period than during the March to April 1992
period. Data for dissolved Hg are pending.

 Results of the filter blanks  paralleled the results of the equipment blanks in that they were
 consistently higher during the latter part of the sampling period. In the March-April sampling
 period, environmental concentrations were two to five times higher than blank concentrations for
 the four constituents. This indicates sufficient sensitivity in our methods for  detection of these
 elements above ambient background contamination.  From March to September, 1992, elevated
concentrations of total-recoverable Cr, and dissolved Cr, Cu, Pb, and Zn occurred in the blank
 samples.   Dissolved Cu was the  only constituent that continued to show significantly higher
 values for river water samples. Quality-control checks were continued after the September period
 to determine the source of contamination occurring in the blank samples.

Two sets of replicate samples were collected  to assess the precision of the laboratory methods.
Estimates of precision were made by dividing the range in replicates by the average of the
replicate values.  Precision was poor, primarily because concentration values occurred at or near
the quantitation levels, and only two sets of replicates were used in the calculation.

Metals Quality Assurance Results - James River

The  quality-assurance program for  the  James  River  also  consisted of  the  collection of
 quality-control samples to meet the quality assurance objectives of the project.  Results of these
 analyses for metals are listed in Table 7 and Table 7.

 As at the Susquehanna, equipment blank samples were collected prior to sample collection and
 analyzed to 1) compare the old and new sampling techniques, and 2)  to identify any potential
 sources of  contamination from the  ultra clean sampling protocols  and/or field  techniques
 (Table 7).  Results indicate that the equipment blank  samples for both old and new techniques
 did not contain detectable quantities of total-recoverable As or Cd.  Random occurrences of
 total-recoverable Cr, Cu, Pb, and Zn were, however, reported in two of the four blank samples.
With one exception (Cr on 9/3/92), the concentrations of all constituents found in the blanks that

 Quality Assurance Results                                                             40

-------
 Chesapeake Bay^Fall Line Toxics Monitoring Program:  1992 Final Report
Table 6. Quality assurance data collected at the James River fall line at Cartersville, Virginia,
to compare




Date
04-10-92
04-24-92
04-28-92
05-20-92
06-24-92
old and new sample collection techniques for total-recoverable metals.
Total Recoverable Metals
Arsenic Cadmium
Suspended
Discharge Sediment Sediment old new old new
(fWs) (% finer) (mg/1) (ug/1) (ug/1) (ug/1) (ug/1)
4750 89 4 <1 <1 <1 <1
80100 73 454 <1 <1 <1 <1
14700 69 62 <1 <1 <1 <1
10900 88 31 <1 <1 <1 <1
5600 88 6 <1 <1 <1 <1



Date
04-10-92
04-24-92
04-28-92
05-20-92
06-24-92
Chromium Copper Lead Zinc
old new old new old new old new
(ug/1) (ug/1) (ug/1) (ug/1) (ug/1) (ug/1) (ug/1) (ug/1)
2 <1 8 1 <1 <1 20 <10
6 4 10 6 15 10 60 60
3 1 2 2 2 2 10 <10
<1 <1 3 <1 2 1 <10 <10
"** 2 10 2 2 <1 <1 <10 <10
Dissolved Metals


Date
04-10-92
04-24-92
04-28-92
05-20-92
06-24-92
Chromium Copper Lead Zinc
old new old new old new old new
(ug/1) (ug/1) (ug/1) (ug/1) (ug/1) (ug/1) (ug/1) (ug/1)
<1 0.6 <1 1.17 <1 0.09 <10 2.42
<1 <0.2 3 3.10 <1 2.83 <10 11.65
<1 <0.2 2 1.20 2 0.55 <10 3.72
<1 1.12 3 0.99 1 0.40 <10 1.50
<1 11.60 2 1.77 <1 0.20 <10 2.08

Quality Assurance Results
41

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 Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

 were collected  using the new technique were consistently lower  than those using the old
 technique.

 In addition to the equipment blanks, which assess potential sources of contamination to the water
 quality sample from the entire sample collection procedure, filter blank samples were collected
 with each dissolved metal analysis sent to the USGS National Research Program.  Results from
 the filter blank samples indicate that,  with the  exception  of dissolved As, all  dissolved
 constituents were detected in the blank samples to varying degrees.  Dissolved Cd was detected
 only within a period between June and September 1992. Within that same time interval Cr, Cu,
 Pb and Zn were detected consistently in the sample blanks.  From September 1992 through
 March 1993 Cr, Cu, Pb  and Zn continued to be detected periodically, but generally at lower
 levels than for the June-September period. Low levels of Hg contamination were present in all
 of the  blanks  at about 0.03 ug/L or less during the sampling period (Terry Brinton, personal
 commun, 1993).

 Five sets of environmental samples were collected  during 1992  to compare the "old" 1990-91
 sample collection and analysis methods with the  "new" ultra  clean collection  and analysis
 methods used  in 1992 (Table 7).  Results indicate  that for total-recoverable As and Cd, there
 were no differences in the concentrations between the two collection techniques, with both
 methods resulting  in non- detectable values for those  constituents.   Concentrations of
 total-recoverable Cr, Cu, Pb, and Zn using the new  technique were lower than or  equal to
 concentrations generated using the old technique with one exception; a sample  collected on
 6/24/92 had a greater Cr value using the ultra clean  technique than the old technique.  For
 dissolved As  and Cd, again there was no difference  between results from  the old and new
 technique, with both methods resulting in non-detectable concentrations of these constituents.
 For Cr, Cu, Pb and Zn, most samples resulted in concentrations that, for the new technique, were
 lower than or  effectively equal to concentrations resulting from the old technique.  A set of
 samples .collected on 6/24/92, however, displayed differences in concentrations between the two
 techniques, with the sample from the new technique resulting in greater values.

Two sets of replicate samples  were collected to evaluate laboratory precision.  Estimates of
precision for each constituent  were made by dividing the range in  duplicates by the average
between  the duplicate values. Precision was generally  good for total-recoverable metals.  Only
one set of duplicates  was available for dissolved metals (9/3/92); the precision for dissolved
metals was poorer than for total-recoverable metals, possibly because the concentration levels
were lower and therefore subject to greater variability.

Metals  Quality Assurance Results - Potomac

As mentioned  earlier, there was no special field quality assurance program for the Potomac River
metals monitoring, and laboratory quality assurance was performed in conjunction with other
 samples  from  other projects.  Therefore, there are  no  results that are specific to the Potomac.
Instead,  all  data that have been reported  are  those  that have passed all laboratory quality
assurance and quality control procedures. These include, but are not limited to, blanks, duplicates
 and spiked samples.
Quality Assurance Results                                                             44

-------
 Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

 Organics Quality Assurance  Results -  Susquehanna, James  and Potomac
 Rivers

 Field Blanks

 Concentrations of the organic contaminants detected in the field blanks are shown in Figure 5-
 Figure 19 for each of the three fall line sampling programs.  The average QL for each compound
 class of contaminants is shown by the dotted line in all of the figures.

 Organonitrogen and Qrganophosphorus Pesticides.  Field blank concentrations were used for two
 purposes: (1) as a check of the quality of the low detection limit method; and (2) to flag fall line
 sample concentrations when field blank concentrations were >0.5 times the magnitude of the fall
 line sample concentrations.   Flagged  sample  concentrations  denote  that  the particular
 concentration value is suspected of having a sizable, but unknown, determinate error associated
 with it. The field blank that was used to compare with a particular fall line sample was the one
 that was performed  the same day as the fall line  sample analysis.  If a  field blank was not
 performed the same day as the fall sample analysis, then the preceding field blank was used for
 comparison purposes.

 The concentrations of the organonitrogen and phosphorus pesticides in the Susquehanna River
 field blanks were below QL concentrations for most of the samples. Exceptions included atrazine
 on the 7/15/92 sampling date, alachlor on 3/6/92 and 9/2/92,  prometon on 9/2/92,  hexazinone
 on 3/6/92 and 7/15/92, cyanazine on 9/2/92, and malathion in all blanks  after 4/3/92. With the
 exception of malathion, the occurrence of these pesticides in the field blanks were random and
 dropped below QL concentrations at the next sampling period.  In addition, the field  blank
 concentrations of these pesticides were low, often much lower than measured concentrations in
 the fall line samples. It is of interest to note that this elevated blank concentration of malathion
 coincides with  the commencement of malathion application in residential  areas for mosquito
 control, but the exact reason  for this phenomenon is not clear.  The only flagged sample
 concentrations  for this group of pesticide for the Susquehanna  River  database include only
 metolachlor in the 25 November and  30 November storm samples.

 The organonitrogen and phosphorus pesticide field blanks for the James River fall line samples
 show a pattern  similar to that seen for the Susquehanna River: most field blank concentrations
 were 
-------
Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report
Figure 5. Field blank concentrations of the organonitrogen and organophosphorus pesticides in
the dissolved phase for samples processed at the Susquehanna River fall line:
  o
           Susquehanna River, Organo-N/P Pest.
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Sampling Date, Mar. 1992 - Jan. 1993
                   Malathion
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                           Metolachlor
                           Avg. QL
                                Cyanazine
 Quality Assurance Results
                                                                46

-------
Chesapeake Bay.Fall Line Toxics Monitoring Program: 1992 Final Report


Figure 6.  Field blank concentrations of the organochlorines in the dissolved phase for the
samples processed at Susquehanna River fall line.
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         Susquehanna River, Organochlorines (d)
3/6   3/29   4/3    5/12  6/19   7/15   9/2   11/18  11/25  1/8

             Sampling Date, Mar. 1992 - Jan. 1993
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                    Susquehanna River, Organochlorines (d)
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lllll
    ซ  51
    b  ,
    u

    O
   U
   •*  0
           3/6   3/29   4/3    5/12  6/19   7/15   9/2   11/18  11/25   1/8

                        Sampling Date, Mar. 1992 - Jan. 1993
                DDT
Permethrins

Avg.
                                             Fenvalerates.
Quality Assurance Results
                                                              47

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Chesapeake Bay. Fall Line Toxics Monitoring Program:  1992 Final Report


Figure 7.  Field blank concentrations of the organochlorines in GF/D  and GF/F filters for

samples processed at the Susquehanna River fall line.
  ec
  2
  I
  .*
  c
  es
           Susquehanna River, Organochlorines (p)
3/6     3/29
4/3     5/12    6/19    7/15    9/2   11/18   11/25    1/8

Sampling Date, Mar. 1992 - Jan. 1993
— Aldrin —
_. /^il 1 ซ J
8=3 a-Chlord.
•• — Oxychlord. — *
•_ป ~r\: .1 .]..:_ ....
** — Dieldnn
— g-Chlord.
.... A -. f\l
Avg. Ql
  00
  c
  2
  ซJ
  c
  4)
  u
  c
  o
  c
  C8
           Susquehanna River, Organochlorines (p)
1U=
9 =
=
=
=
=
=
=
3=
=
2^
=
11
=



CO
y/\
/ \v
/ ^V
/ jar-—— — **\ _ 	



3/6     3/29    4/3    5/12   6/19    7/15     9/2    11/18   11/25

              Sampling Date, Mar. 1992 - Jan. 1993
                                                   1/8
— DDT
" rCBs
— • — Permethrins — *
........ A _. f\t
Avg. Ql
•ซ— Fenvalerates

Quality Assurance Results

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Chesapeake Bay. Fall Line Toxics Monitoring Program: 1992 Final Report



Figure 8. Field blank concentrations of the polynuclear aromatic hydrocarbons in the dissolved

phase for the samples processed at Susquehanna River fall line.
00


ฃ
^o
ซj

2
ซj
s
                           Susquehanna River, PAH (d)
           3/6
              3/29    4/3    5/12   6/19   7/15   9/2   11/18 11/25   1/8

                      Sampling Date, Mar. 1992 - Jan. 1993
                        Naphth.


                        BAP
                                    Fluoran.


                                    Avg. QL
BAA
Quality Assurance Results
                                                                        49

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Chesapeake Bay;Fall Line Toxics Monitoring Program: 1992 Final Report

Figure 9.  Field blank concentrations of the polynuclear aromatic hydrocarbons in GF/D and
GF/F'filters for samples processed at the Susquehanna River fall line.
                           Susquehanna River, PAH (p)
V*
o
*rf
2
4_ป
c
V
o
c
o
u
JgJ
c
03
1U=
9=
=
=
=
65
=
=
4=
=
25
=
=








-=-?^ซ—
^f ^^^ ^S^ ^^

3/6 3/29 4/3 5/12 6/19 7/15 9/2 11/18 11/25 1/8
                         Sampling Date, Mar. 1992 - Jan. 1993
Naphth.

BAP
                                    • — Fluoran.
                                        Avg. Ql
BAA
Quality Assurance Results
                                                    50

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Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report	


Figure 10.  Field blank concentrations of the organonitrogen and organophosphorus pesticides
in the dissolved phase for samples processed at the James River fall line.
  ec
  —
                         James River, Organo-N/P Pest.
  g  40=]
  g   "  3/13   4/10   4/23   5/20   6/24   7/22    9/3   10/28  11/23  12/11   1/28   2/23

 5                      Sampling Date, Mar. 1992 - Feb. 1993
• Simazine —
10 Diazinon j
* — Prometon — *

*— Atrazine
Avg. yL,
ec

 •>!
C
                           James River, Organo-N/P Pest.
 ^
  I   "  3/13  4/10   4/23   5/20   6/24   7/22    9/3   10/28  11/23  12/11   1/28   2/23

 5                      Sampling Date, Mar. 1992 - Feb. 1993
Malathion

Hexazinone
                                       Metolachl.

                                       Avg. QL
                                                         Cyanazine
Quality Assurance Results
                                                                            51

-------
Chesapeake BayFall Line Toxics Monitoring Program:  1992 Final Report
Figure 11.  Field blank concentrations of the organochlorines in the dissolved phase for the
samples processed at James River fall line.
                         James River, Organochlorines (d)
  ^2
  ซri

  I
  "e
  0>

  S
  o
 s
ป
     81
     7=
     61
     51
     41
     3=
     21
     ll
     0
          3/13  4/10  4/23  5/20   6/24   7/22   9/3  10/28 11/23 12/11   1/28  2/23

                         Sampling Date, Mar. 1992 - Feb. 1993
                   Aldrin

                   a-Chlord.
                                      Oxychlord.
g-Chlord.

Avg. QL
  oc
  c
  .o
  tZ!
  2
 c
 o
U
.*
 ^H
 5
S
                       James River, Organochlorines (d)
         3/13  4/10  4/23  5/20   6/24   7/22   9/3  10/28 11/23  12/11   1/28  2/23

                         Sampling Date, Mar. 1992 - Feb. 1993
                 DDT

                 PCBs
                              —•-— Permethrins

                              	Avg. QL
 Fenvalerates.
Quality Assurance Results
                                                                          52

-------
Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report	



Figure 12.  Field blank concentrations of the organochlorines in GF/D and GF/F filters for

samples processed at the James River fall line.
oc
s

c
o
  u
  s
  IS
                         James River, Organochlorines (p)
       9=

       81

       71
     51

     41

     31

     21
        3/13   4/10   4/23   5/20   6/24   7/22   9/3   10/28  11/23  12/11   1/28   2/23


                       Sampling Date, Mar. 1992 - Feb. 1993
• Aldrin —
(Tpi ,. fl.!^,...! 	 1
1=3 a-Chlord. '
* — Oxychlord — *
M Uieklnii
*— g-Chlord.
Avg. yi
  oe
  =
  2
  o
  U

  .ฃ
  s
  03
                       James River, Organochlorines (p)
        3/13   4/10   4/23   5/20   6/24   7/22   9/3   10/28  11/23  12/11   1/28   2/23


                       Sampling Date, Mar. 1992 - Feb. 1993
^— DDT
c- 1 . T>f~'T>..
a rl^Us
— • — Permethrins — *
	 Avg. l^L,
•*— Fenvalerates

Qualify Assurance Results
                                                                            53

-------
Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report '


Figure 13. Field blank concentrations of the polynuclear aromatic hydrocarbons in the dissolved
phase for the samples processed at James River fall line.
  ec

   Vl
  S
  JO
  •taJ

  2
  •4^
  e
  V
  u
  e
  o
  c
  S3
                      James River, PAH (d)

3/13  ^1/10   4/23  5/20  6(24  7/22   9/3  10/28  11/23  12/11  1/28  2/23

                Sampling Date, Mar. 1992 - Feb. 1993
                         Naphth.

                         BAP
                               Fluoran.

                               Avg. QL
BAA
Quality Assurance Results
                                                                    54

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Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report

Figure 14.  Field blank concentrations of the polynuclear aromatic hydrocarbons in GF/D and
GF/F filters for samples processed at the James River fall  line.
1
ฃ>
o
•M
2

c

n
u

e
S

1U=
9=
=
8=
=
7s
2
6=
=
5S
_ =
4s
=
3=
=
2i
=
1—
=

James River, PAH (p)







y/^".. ./p"xl
....2ป.._.....rt!i!SU........... iil.._.™,.^rtv....... ..............p^J^M.........................
/ -*5ซ^ rpe ^^"^><^^ฃi^J.J^^*^ -ซ5ปs^
3/13 4/10 4/23 5/20 6/24 7/22 9/3 10/28 11/23 12/11 1/28 2/23
                         Sampling Date, Mar. 1992 - Feb. 1993
                         Naphth.

                         BAP
Fluoran.

Avg. QL
BAA
Quality Assurance Results
                                     55

-------
Chesapeake Bay. Fall Line Toxics Monitoring Program: 1992 Final Report
Figure 15.  Laboratory blank concentrations of the organonitrogen and organophosphorus
pesticides in the dissolved phase.
^ ••
-c
c
at
2
c
e

.X
G
08

rn=
^n=
40 E
30E
=
0 —
3

Laboratory Blanks, Organo-N/P Pest.


, •
-


1234567
                                     Blank Number
*• Simazine — •-
"" Diazinon —+*
- Prometon — **-
- Aiachlor 	
- Atrazine
• Avg. QL
  00
  c
 ^o
 1
 •*•)
  c
  4>
  o
  C
  o
 O
60:
so:
40 i
30:
20:
101
 0-
                 Laboratory Blanks, Organo-N/P Pest.
                                 345
                                     Blank Number
                    Malathion
                    Hexazinone
                                 Metolachl.
                                 Avg. QL
Cyanazine
Quality Assurance Results
                                                                       56

-------
Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report


Figure 16.  Laboratory blank concentrations of the organochlorines in the dissolved phase.
  ec
  c
   *i
  c
  o
 *••
 +*
  e
  o
 c
5
                   Laboratory Blanks, Organochlorines (d)
                                   Blank Number
— ~— Aldrin —
i— i *"M '1 n ..J
01 a-Chlord.
" — Oxychlord. — *
A T\! ..!.!_:.. ....
*^ JLJielarin
~— g-Chlord.
.... A _. f\f
Avg. QL
OJJ

  o
 U
 .ฃ
                    Laboratory Blanks, Organochlorines (d)
     91
     81
     71
     61
     5=
     4i
     31
     21
                                345

                                   Blank Number
                   DDT

                   PCBs
                                    Permethrin

                                    Avg. QL
Fenvalerate
Quality Assurance Results
                                                                        51

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Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report


Figure 17. Laboratory blank concentrations of the organochlorines in GF/D and GF/F filters.
  ec
                   Laboratory Blanks, Organochlorines (p)
                                345

                                    Blank Number
— — Aldrin —
in .1 *""•!• IJL^J! .1
10 a-ClilorU. '
* — Oxychlord — *
•* Uieldrin
— g-Chlord.
Avg. QL
^

 c
  C
  o
  e

  5
                     Laboratory Blanks, Organochlorines (p)
9=
=
=
=
=
5=
=
=
=
2=
=
1 =
=
n=







^^Jป 	 ~J1I~ ~B=I\i>^ ^ 	 ^
....]H^^ct^rr..._....................r^w^...............................J>^rฃf^:.....~rri.......
=r^ -V^' ^^JR^^—
                     23456

                                  Blank Number
— - DDT
rcB0
— ••— - Permethrins — *
........ A ..~ f\"W
Avg. QL
•*— Fenvalerates

Quality Assurance Results
                                                                         58

-------
 Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report

 Figure 18. Laboratory blank concentrations of the polynuclear aromatic hydrocarbons in the
 dissolved phase.
fiฃ
 oc

.2
1
   o
  O
  .a
   c
                            Laboratory Blanks, PAH (d)
                                345
                                   Blank Number
Naphth.

BAP
                                       Fluoran.

                                       Avg. QL
                                                         BAA
Quality Assurance Results
                                                                          59

-------
Chesapeake Bay, Fall Line Toxics Monitoring Program:  1992 Final Report

Figure 19.  Laboratory blank concentrations of the polynuclear aromatic hydrocarbons in GF/D
and GF/F filters.                                                    .
  oc
  2
  u
 .1
Laboratory Blanks, PAH (p)
1U=
9=
5
8=
=
72
=
6=
,1
5=
4s
=
3=
=
2=
=
1=
=
(P














..... . •••*••
	 ป^ —
1













......... [[[ ...... ....^tf^C**"

234567
Blank Number
•• Naphth. — • — Fluoran. "* BAA
r- . 1> A 1> ........ A . f\f
03 JDAr 	 Avg. yL

-------
 Chesapeake Bay .Fall Line Toxics Monitoring Program:  1992 Final Report

 concentrations of the organonitrogen and organophosphorus pesticides in the Potomac River
 database.

 Organochlorine Compounds. Field blank concentrations of the organochlorine compounds in both
 the dissolved and paniculate phases exceeded  QL values more often that any other group of
 contaminants.  This is due primarily to lack of specificity in the GC-ECD analysis compared with
 GC/MS, and the further lack of spectrometric data (i.e., confirmatory ions) in GC-ECD analysis.
 However, excluding the PCBs, the concentrations of the monitored contaminants detected in the
 field blanks were relatively small and oscillated around the QL values. There was no apparent
 relation in field blank concentration and type of fluvial sample (i.e., baseflow or storm flow).

 Susquehanna River field  blanks showed that PCBs were  often detected at concentrations >QL
 values in both phases.  However, the PCB blanks were not actually as high as related to the  fall
 line samples, with the exception of the 11 November 1992 field blank.  The PCBs are presented
 in the figures  as total PCBs and represent the summed  quantity  of 112 individual  congeners
 (ZPCB). The  corrections that were made to the fluvial sample PCB concentrations were done
 by subtracting out individual congener concentrations, and it was found that many of the PCB
 congeners detected in the  blanks were not present in the samples. The blank concentrations were
 a smear of very low  levels of interfering substances at extremely low concentrations  that when
 summed over 112 peaks often gave rise to >QL concentrations, and in some cases substantially
 above because of the unusual occurrence of uncommon PCB  congeners. It must be emphasized
 that the sample PCB  congener profiles reflected the dominant  congeners in the  secondary
 Arochlor 1:1:1 standard and not the congener profiles present in the blanks.  The net effect of
 this would be to substantially lower the PCB blank concentrations If the blanks were normalized
 for those congeners present in the samples.  However, the 3/6/92 Susquehanna River dissolved
 phase PCB blank was contaminated to such an extent that quantitation of natural levels was  not
 possible.  There are nine  flagged concentrations  of the organochlorine  compounds in  the
 dissolved phase and eight in the paniculate phase database.

 Organochlorine concentrations in the James River field blanks were typically  at or below the  QL
 concentrations.  The  exception,  as noted above  for the Susquehanna River field blanks, is with
 the PCBs, which showed  relatively high concentrations in several summer and autumn periods,
 although the PCB congeners  in the blanks did show the same patterns as observed in the fall line
 samples.

 Concentrations of the organochlorine compounds in the laboratory blanks were normally below
 QL concentrations, with  a few  exceptions notably alpha- and gamma- chlordane in dissolved
 phase  and PCBs  in paniculate  phase.   As  was  observed with  the  organonitrogen  and
 organophosphorus pesticides, the organochlorine compound concentrations were frequently lower
in the laboratory blanks relative to the field  blanks.   This demonstrates that collection of large
volumes of surface water in the  field  does  increase contamination.   Whether this increased
contamination  during sampling in the field is  due to inadequate  cleaning and preparation of
 sampling equipment or is  inherent in the sampling process, such as the sorption of atmospheric-
 derived vapors to container surfaces, has not been determined.

Polynuclear Aromatic Hydrocarbons. PAH concentrations in the field blanks were generally low
in each of the fall line samples with the exception of naphthalene, especially in the dissolved


 Quality Assurance Results                                                            61

-------
Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

phase. In the Susquehanna River field blanks, naphthalene was detected at concentrations >QL
values for the 5/12/92 and 1/8/93 field blanks, and fluoranthene in the 5/12/92,and 11/25/92 field
blanks for dissolved phase analysis. In the paniculate phase, only fluoranthene was substantially
above the QL value for the 4/3/92 field blank. Three dissolved phase and three paniculate phase
PAH concentrations were flagged in the Susquehanna River database.

Naphthalene was detected at high concentrations in the dissolved phase field blanks conducted
at the James River fall line. The source of this interference has not been determined.  The only
other PAH detected in the James River dissolved field blanks was benz(a)anthracene at 1/28/93.
Naphthalene was detected in three of the particulate phase James River field blanks above QL
concentrations, showing that the particulate phase field blanks were relatively free of interfering
PAH.  As a result, seven dissolved phase sample concentrations  and three  particulate phase
sample concentrations were flagged in the James River database.

Laboratory blanks were free of PAH interferences with two exceptions where naphthalene and
fluoranthene were detected in dissolved phase blanks substantially above QL values.

Matrix Spikes

Distilled water and matrix spike  recoveries fall line dissolved phase and particulate phase sub-
samples are summarized in Table 8, Table 9, and Table  10.  Recoveries for Carbopack B and
CIS sorbents have been reported separately because the measured recoveries for the two sorbents
were different, with generally higher recoveries being observed using C18 for the Potomac River
fall line samples.

There were no apparent differences between recoveries using Carbopack B sorbent cartridges for
the Susquehanna and James River fall line samples, therefore, the %rec  values were combined
for extractions performed on these two fluvial sources. A total of five matrix spike experiments
were carried out with Carbopack B (including three Susquehanna  River sub-samples and two
James River sub-samples) between March  1992 and February 1993, and a total of four matrix
spike evaluations were  performed on Potomac River sub-samples.

Extraction Mass Balance

The mass distribution of analytes between front and back LSE traps is  shown  in Table 8 and
Table 9.  Collection efficiency values indicate that analyte breakthrough from the front cartridges
during LSE was  not a major problem in this study.  Typically, greater than 90% of the analytes
were collected on the front traps for both Carbopack B and CIS sorbents.  As a result of these
findings, LSE performed on all baseflow samples now incorporates  only front traps. However,
filtered fall line  samples from  storm  sample  collection are  extracted  with the tandem trap
configuration because of the high turbidity observed in these samples. Some breakthrough has
been observed for native analytes during the processing of storm samples.
Quality Assurance Results                                                             62

-------
 Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

 Table 8.  Summary of matrix spike  recoveries using Carbopack B sorbent cartridges for
 Susquehanna and James River fall line  samples.8
                   Distilled Water            Surface Water
                   Front                    Front
                   Cartridge               Cartridge
Analyte            %Rec(RSD)  Q      %Rec(RSD)
Organonitrogen & Organophosphorus Pesticides

Simazine            53 (5)      99%         61 (33)      96%
Prometon            83(16)      99%         57(21)      94%
Atrazine            104 (12)      98%         65 (39)      95%
Diazinon           109 (15)      96%         93 (35)      98%
Alachlor             98(17)      98%         80(56)      97%
Malathion           91 (8)      99%        79 (n=2)      98%
Metolachlor        109(26)      97%         92(38)      95%
Cyanazine           98(42)      99%         57(33)      96%
Hexazinone         102(7)      96%        137(50)      86%

Organochlorines

Aldrin              58(7)      94%         46(8)      96%
Oxychlordane        46(22)      98%         40(23)      92%
gamma-Chlordane    59(14)      87%         46(23)      92%
alEha-Chlordane      61 (13)      92%         48 (24)      94%
Dieldrin             71 (3)       97%         65 (22)      93%
4,4'-DDT            na          -           105 (24)      99%
c/t-Permethrin        62(5)      82%         56(78)      74%
c/t-Fenvalerate       33 ( 6)      77%         34 (50)      85%
ZPCBs              na          -           65 (n=l)

Polycyclic Aromatic Hydrocarbons
Naphthalene
Fluoranthene
Benz(a)anthracene
Benzo(a)pyrene
na
na
na
na
na
na
na
na
na
na
na
na
na
na
na
na
Three distilled water and five surface water replicates were performed unless otherwise specified
by the number in parenthesis;  CE = collection efficiency; na = not available.
Quality Assurance Results                                                         63

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Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report

Table 9.  Summary of matrix spike recoveries using CIS sorbent cartridges for the Potomac
River fall line samples.8                                              , •
Analyte
Distilled Water"

Front
Cartridge
%Rec(RSD)  CE
Surface Water

.Front
Cartridge
%Rec(RSD)  CE
Organonitrogen & Organophosphorus Pesticides
Simazine
Prometon
Atrazine
Diazinon
Alachlor
Malathion
Metolachlor
Cyanazine
Hexazinone
Organochlorines
Aldrin
Oxychlordane
gamma-Chlordane
alpha-Chlordane
Dieldrin
4,4' -DDT
c/t-Pennethrin
c/t-Fenvalerate
ZPCBs
Polycyclic Aromatic
Naphthalene
Fluoranthene
Benz(a)anthracene
Benzo(a)pyrene
92(3)
78 (12)
93(3)
95(1)
95(3)
102 ( 1)
93(4)
86(3)
na

48 (n=2)
56 (n=2)
70 (n=2)
75 (n=2)
92 (n=2)
91 (n=2)
90 (n=2)
79 (n=2)
64 (n=2)
Hydrocarbons
na
na
na
na
100%
100%
100%
98%
100%
100%
99%
97%
-

98%
99%
98%
97%
98%
97%
83%
86%
96%

-
-
-
—
.44(7)
56 (10)
87 (24)
119(24)
109 (21)
114(n=l)
109 (28)
105 (33)
151 (56)

40 (24)
65(5)
74(6)
80(8)
105 ( 8)
93 (22)
85 (13)
91 (19)
57 (12)

35 (n=l)
105 (n=l)
110(n=l)
80 (n=l)
96%
94%
94%
99%
96% -
97%
95%
97%
85%

99%
92%
92%
93%
93%
99%
84%
86%
84%

na
na
na
na
"Three distilled water and five surface water replicates were performed unless otherwise specified
by the number in parenthesis;  bData from Foreman and Foster (1991) and this study; CE =
collection efficiency; na = not available.
Quality Assurance Results
                                                               64

-------
Chesapeake Bay.-Fall Line Toxics Monitoring Program:  1992 Final Report

Table 10.  Summary of spike recoveries  of monitored organic contaminants  from filtered
particulates.
Analyte                          %Rec(RSD)a
Organochlorines

Aldrin                           105 ( 3)
Oxychlordane        .             84 (22)
gamma-Chlordane                 68 (18)
alpha-Chlordane                  64 (27)
Dieldrin                          106(11)
4,4'-DDT                        45 (20)
c/t-Permethrin                     na
c/t-Fenvalerate                    na
SPCBs                           86 ( 5)

Polycyclic Aromatic Hydrocarbons

Naphthalene                      83(11)
Fluoranthene                     98 (4)
Benz(a)anthracene                 101 (3)
Benzo(a)pyrene                   98 (16)
"Spike concentration at 20 fig/kg; na = not available.
Quality Assurance Results                                                           65

-------
Chesapeake Bay, Fall Line Toxics Monitoring Program:  1992 Final Report

Results from the analysis of solvent rinses of both milk can containers and glass bottles.used
during the collection of fluvial samples has revealed no detectable levels of the target analytes
associated with container surfaces. Only the containers from the first three months of sampling
have been analyzed, but it is assumed that since the same sampling protocol is used for every
fluvial sampling that the results can be applied universally.

Enrichment Factors

The enrichment factors for each of the fall line target analytes, for the fluvial samples only, are
listed in Table 11.  The matrix spike %Rec values used to calculate enrichment factors were
those listed in Table 8 and Table 9 for river water.

Error Evaluation

The magnitudes of the percent relative uncertainty terms calculated for each analyte are listed in
Table 12, where it can be  seen that the major source of indeterminate error in the analysis is in
gc/ms  and gc-ecd analysis, given the  variations in relative response factors from  instrument
calibration data (RF,
Quality Assurance Results

-------
 Chesapeake Bay .-Fall Line Toxics Monitoring Program:  1992 Final Report

 Table 11.  Enrichment factors for the monitored organic contaminants in filtered surface water
 samples for both sorbents used in this study.
Analyte
EfCarbopack B
ErC18
Organonitrogen & Organophosphorus Pesticides
Simazine
Prometon
atrazine
Diazinon
Alachlor
Malathion
Metolachlor
Cyanazine
Hexazinone
Organochlorines
Aldrin
Oxychlordane
gamma-Chlordane
alpha-Chlordane
Dieldrin
4,4'-DDT
c/t-Permethrin
c/t-Fenvalerate
EPCBs
Polycyclic Aromatic Hydrocarbons
Naphthalene
Fluoranthene
Benz(a)anthracene
Benzo(a)pyrene
30500 .
28500
32500
46500
40000
39500
46000
28500
68500

23000
20000
23000
24000
32500
52500
28000
17000
na

na
na
na
na
22000
28000
43500
59500
54500
57000
54500
52500
75500

20000
32500
37000
40000
52500
46500
42500
45500
28500

25000
52500
55000
40000
Ef = enrichment factor; na = not available.
Quality Assurance Results
                                                  67

-------
Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

Table 12.  Indeterminate errors  associated with the concentrations of the monitored organic
contaminants in the fall line samples.                                    ,•
                                 IS           RRF         Vol                Cone
Analyte                          %(Xi         %o^         %a^                %oc4
Organonitrogen & Organophosphorus Pesticides
Simazine
Prometon
Atrazine
Diazinon
Alachlor
Malathion
Metolachlor
Cyanazine
Hexazinone
Organochlorines
Aldrin
Oxychlordane
gamma-Chlordane
alpha-Chlordane
Dieldrin
4,4'-DDT
c/t-Permethrin
c/t-Fenvalerate
ZPCBs
Polycyclic Aromatic Hydrocarbons
Naphthalene
Fluoranthene
Benz(a)anthracene
Benzo(a)pyrene
2
2
.2
2
2
2
2
2
2

2
2
2
2
2
2
2
2
2

2
2
2
2
11
26
10
21
19
27
22
41
38

8
18
10
8
8
31
13
27
10

12
28
27
32
1
1
1
1
1
1
1
1
1

1
1
1
1
1
1
1
1
• 1

1
1
1
1
11
26
10
21
19
27
22
41
38

8
18
10
8
8
31
13
27
10

12
28
27
32
IS = error propagated  from addition of  internal  standard;  RRF =  error propagaged from
instrument response factors in quantitation; Vol = error propagaged from measuring the sample
volume; Cone = propagated error associated measured concentrations of the monitored organic
contaminants hi the samples.
na=not available.
                                                                        ซ

Quality Assurance Results                                                            68

-------
Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report

WATER QUALITY DATA JRESULTS

Metals Water Quality Data - Susquehanna River

Following are the results of water  quality data  collected  for metals and suspended sediment
during the 1992 ultra clean study for the Susquehanna River.  Results of the 1990-91  study may
be found in  a report written for EPA Chesapeake Bay Program Office entitled Chesapeake Bay
Toxics Monitoring Program:  1990-1991 Loading Results available in the Annapolis, Maryland
office.  A listing of instantaneous discharge and concentration data collected during the entire
1990-92 sampling period for the Susquehanna River are presented in Appendix A.

Samples were collected  in 1992  under baseflow conditions during March,  May, June, July,
September, and November. Two storm events were sampled, one each during March  and April.
Discrete samples were collected daily  throughout the storm events.

An assessment of 1992 data quality was made based on results of the quality-assurance program.
Through a comparative analyses of quality-control (QC) equipment-blank sample concentrations
and concurrently collected environmental concentrations, constituent data were given  a grade of
excellent, good,  fair,  poor, or invalid.  Data quality for a constituent  collected  in  1992 was
considered excellent if no detectable concentrations of the  constituent were found in the blank
samples; good, if detectable  concentrations of the constituent were found in the blank samples
yet none of them exceeded environmental concentrations; fair, if detectable concentrations of the
constituent were found in the  blank samples and less than half of them exceeded environmental
concentrations; poor,  if detectable concentrations of the constituent were found in  the blank
samples  and more than half  of them  exceeded environmental concentrations; and  invalid, if
detectable concentrations  of  the constituent were found  in  the  blank  samples,  all  of which
exceeded environmental concentrations.  Based upon this criteria, excellent data were collected
for total-recoverable  As,  Cd, Cu, Zn.  and dissolved As.  Good data were collected  for total-
recoverable Pb and dissolved Cu. Fair data were collected for total-recoverable Hg and dissolved
Cd. Cr. Pb.  and  Zn. and  poor data, considered suspect, were collected for total-recoverable Cr
and dissolved Hg. Dissolved Cr values, although considered of fair quality, are suspect due to
the significant increase observed in concentration data during 1992.  This criteria is more rigorous
than  the previous data quality assessment conducted for the Chesapeake Ba\ Fall Line  Toxics
Monitoring Program 1992 Interim Report, as it will be used to determine the effect  that ultra
clean sampling techniques and lowered reporting limits had on load estimates.

Instantaneous discharge  and concentration data  collected in  1992 for the Susquehanna River
station are listed in Table 13 and are discussed in this text.  Analysis for total-recoverable trace
metals and suspended- sediment is complete.  However, dissolved metal analysis for samples
collected after June. 1992 are pending. Concentration data associated with a less-than (<) sign
indicates that the  constituent concentration  is less  than the  quantitation limit.  A   dash (--) •
indicates that the constituent was not analyzed. Asterisks (**) denote pending data. Figure 20-
Figure 23 show  the concentrations for selected  dissolved and total-recoverable metals for  the
1992 data collection period  with  the concentrations for blanks  collected during  the  sampling
period.
Water Quality Data Results                                                            59

-------
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-------
Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

Figure 20.  Concentrations of (a) total recoverable and (b) dissolved chromium for 1992 for the
Susquehanna River fall line at Conowingo, Maryland. Included on the graphs are analyses of
equipment (total) and filter (dissolved) blanks.
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Cr
equip.
blank
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                                                                 level
Feb     Apr      Jun     Aug      Oct

                          1992-93
                                                              Dec
                                                    Feb
Apr
                                         (b)  Dissolved  Cr
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Water Quality Dam Results
                                                               73

-------
Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

Figure 21.  Concentrations of (a) total recoverable and (b)-dissolved copper for 1992 for the
Susquehanna River fall line at Conowingo, Maryland.  Included on the graphs are analyses of
equipment (total) and filter (dissolved) blanks.
                                    (a)   Total-Recoverable   Cu

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^^

-------
Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report



Figure 22.   Concentrations of (a) ,total recoverable1 and (b) dissolved  lead for 1992 for the

Susquehanna River fall line at Conowingo, Maryland.
                                    (a)   Total-Recoverable  Pb
           D)
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                                               1992-93
                                                                quant nation

                                                                  level
                                             i    i     i    r   i

                                            Dec     Feb      Apr
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                          Aug      Oct


                            1992-93
Dec      Feb
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                                                                                  quantitation

                                                                                    level
Apr
\\aier Quality Data Results
                                                                75

-------
Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Repon

Figure 23.  Concentrations of (a) total recoverable and (b) dissolved zinc for  1992 for the"-
Susquehanna River fall line at Conowingo, Maryland.  Included on the graphs are analyses of
equipment (total) and filter (dissolved) blanks.
                                          Total-Recoverable   Zn
4U-
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Water Quality Data Results
76

-------


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                                   77

-------
Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report

limits had on load estimates.

Instantaneous discharge and concentration data collected during 1992 for the James River are
presented in Table 14.  Concentration data associated with a "less than" sign (<) indicate that the
constituent concentration is less  than  the quantitation level.   A dash (--) indicates  that the
constituent was not analyzed.  Asterisks (**) denote pending data. Figure 24-Figure 27 show the
concentrations for selected  dissolved and total-recoverable metals for  the 1992 data collection
period with the concentrations for blanks collected during that same period.

Most metals monitored during the report  period. March  1992 through February  1993' were
detected in fluvial transport (Table 14, Figure 24-Figure 27  ).  Metals detected include dissolved
Al, As, Cr, Cu, Fe, Pb, and Zn, and total-recoverable Cd, Cr, Cu, Pb,  Zn, and Hg.  Cadmium,
Cr, Cu, and Pb, all of which are regarded as 'Toxics of Concern"  in the USEPA Chesapeake Bay
Program, were  evident in transport.  Metals  that were not detected above quantitation  levels
throughout the 1992 monitoring period included dissolved As, and total-recoverable As and Cd.
Water Quality Data Results      .                                                      78

-------
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Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report



Figure 24. Concentrations of (a) total recoverable and (b) dissolved chromium for 1992 for the

James River fall line at Cartersville, Virginia.  Included on the graphs are analyses of equipment

(total) and filter (dissolved) blanks.
                                    (a)  Total-Recoverable   Cr
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                           1992-93
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                                  Feb
         Apr
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                                                level
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Water Quaiiry Data Results
                                              81

-------
Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report
Figure 25. Concentrations of (a) total recoverable and (b) dissolved copper for 1992 for the
James River fall line at Cartersville, Virginia. Included on the graphs are analyses of equipment
(total) and filter (dissolved) blanks.
(a) Total-Recoverable Cu
: ' '• • i : i ! i : i i . i
• Cu • .
6 -1 • ... o Equip, blank •
O> ' • •
c
— 4 -, - o •
c
o
'•53- • •
g 2- • • • 0 ••
ง
0.. 	 	 ,.,.,
_
_ quantitation
level
i : i 1 1 i i i
Feb Apr Jun Aug Oct Dec Feb Apr
1992-93
(b) Dissolved Cu
4 * . . • i , ! ' • i |
• Cu
=d 35~ x Filter blank
en ^^^^^^^ '
3- •
c . .
•c 2'5~ •
o •
ซ 2- x *
• c f •
S 1.5- 0 •
o x
O 1 -f • xx
0.5- ...
x^ x x x
Q v. ^ X XX
guanMalion
Feb Apr Jun Aug Oct Dec Feb Apr
1992-93
Water Quality Data Results
82

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Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

Figure 26. Concentrations of (a) total recoverable and (b) dissolved lead for 1992 for the James
River fall line at Cartersville, Virginia.  Included on the graphs are analyses of equipment (total)
and filter (dissolved) blanks.
                                    (a)  Total-Recoverable   Pb
1 1-
d 10~
"?
8-
e ^
o 6-
4^
(0
c 4 -
8
J 2-
0-
Fซ
•

0 •
•
•

?b Apr Jun Aug Oct
1992-93
• Pb
0 Equip. Wank
•

•
•

u
•^

i
quantitation
ievei
it'll
Dec Feb Apr

                                          (b)   Dissolved   Pb
           en
           c
           o
                  4-1
                                                                •   Pb
                                                                x   Filter blank
Concen
5 -ป r
i
-
:
• $
• x •
• •
• ซr * • • ฃ v ? *
quantitalion
u , i , , i i i i l avel
Feb Apr Jun Aug Oct Dec Feb Apr
1992-93
Water Quality Data Results
83

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Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report

Figure 27. Concentrations of (a) total recoverable and (b) dissolved zinc for 1992 for the James
River fall line at Cartersville, Virginia. Included on the graphs are analyses of equipment (total)
and filter (dissolved) blanks.
                                    (a)   Total-Recoverable  Zn

_J
O)
c
*^
c
_o
75
"c
0)
u
c
o
u

. • • Zn.
— o Equip, blank
50- ' •

40-


30- • • •

20- o •



n- ... , .— . .. .. -'... . , . ...

-
-

-


-

-


quantitation
level
                    Feb      Apr     Jun     Aug     Oct      Dec     Feb      Apr

                                              1992-93

                 1 0 -
                                         (b)  Dissolved  Zn
! D .- 	 '
•
1 4-
• Zn
x Filter blank
Concen
c „
4 -
i
2 -
n •
Feb
•
.: ; . S "x"
. • . x x x . •
• • x
„ x ~ x xv
i i i ;
Apr- Jun Aug Oct Dec Feb
1992-93

AF
                                                                                  quantitation
                                                                                    level
Water Qualm- Data Results
84

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Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

Metals Water Quality Data • Potomac River

During the thirteen month monitoring period of March, 1992, to March, 1993, twelve baseflow
and nine stormflow samples were collected.  Baseflow samples were collected once each month.
OWML attempted to collect a sample for every storm event.  There were few storms of sufficient
flow and duration thaf resulted in adequate sample volume  collected to enable analysis for the
constituents of concern. One storm in March, 1992, at the beginning of the sampling period was
missed.  The earliest sample (a baseflow sample) was collected on March 17,  1992. and the last
sample (a  stormflow sample) was composited  for March 27-April 1, 1993.   The last  two
stormflow'samples (LabID numbers 24158 and 24180) for the period of March 21-March 27 and
March 27-April 1, 1993, were collected while the river was entirely in stormflow.  Due to
holding-time limitations, two  samples had to be collected for this long event.  Also  due to the
fact that the storm lasted until the end of the month, the last baseflow  sample, scheduled to be
collected then,  could not be  collected.  Baseflow loads for March,  1993. were, therefore,
estimated based on the baseflow concentrations of February, 1993.

A  summary of the concentration data is  given in  Table 15.   The samples  are arranged
chronologically.  Stormflow samples have a beginning and  ending date/time combination (i.e.,
Datel/Time 1 and Date2/Time2).  These samples also have a total  flow value reported.  In those
cases, the flow reported in the 'Flow' .column is the average flow during the storm (i.e., total
flow divided by the duration of the storm). The stage and flows are as measured at Little Falls.
As noted earlier, however, there is very little added flow between  Little Falls and Chain Bridge.
pH  values are  not  given  for stormflow samples, because  these were  composite samples.
Figure 28  is a plot of the total monthly flows at Chain Bridge; the data are given in  Table  16.
\\atcr Qiialiry Data Results

-------
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-------
Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

Figure 28.  Total Monthly Flows at Chain Bridge on the Potomac River:   March, 1992.- to
March, 1993
             5.O
             4..
                      Ma*  Apr May Jun  Jul Auo Sep Oct Nov Dec Jan Feb Mar
                     1992                                1993
Table 16. Monthly flows at Chain Bridge on the Potomac River: March, 1992, to March, 1993
Month
March. 1992
April
May
June
July
August
• September
October
November
December
January. 1991
February
March
Total
Flow, xlO ' m3
1.44
1.25
0.96
0.66
042
0.27
0.29
0.19-
' 0 60
1.57
1.31
0.59
4.83
12.95
water Qualm Data Results

-------
 Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

• Organics Water Quality Data - Susquehanna, James and Potomac Rivers

 The concentrations of all of the monitored organic contaminants are listed in Appendix C for
 each of the three rivers. The lists in Appendix C include concentrations measured during both
 baseflow and storm flow hydrologic conditions, the numbers of which type  of sample can be
 obtained from the database. Flagged concentrations in the database are indicated by a measured
 concentration value bound by parenthesis.

 Organonitrogen and  Organophosphorus Pesticides

 The organonitrogen and Organophosphorus pesticides were analyzed in the filtered river fall line
 samples  only.  The fractional composition of organic compounds in the suspended paniculate
 phase in aquatic systems  is governed  by  several variables, including the  magnitude  of
 particle/water partition  coefficients,  the amount of organic carbon associated with the particle
 phase, and the concentration of suspended particulates. Because  the partition coefficients of the
 organonitrogen and  organophosphorous pesticides are near or less than  1,000, the fractional
 composition of these pesticides in the particle phase is predicted to be less than 5% even for total
 suspeneded particulate  concentrations  as large as  1,000  mg/1 (Samiullah  1990).  The particle
 phase is not important  in the fluvial transport of the organonitrogen and  orgahnophosphorous
 pesticides  analyzed   in this  study.   Summaries of the maximum,  minimum,  and  average
 concentrations of the  organonitrogen and Organophosphorus pesticides are provided in Table 17
 through Table 19.

 Peak concentrations of the organonitrogen and Organophosphorus pesticides occurred during the
 months of agricultural  field  application, from approximately April  1992 through June 1992.
 These pesticides  are highly mobile and are readily washed from soils during preciptiation, and
 are transported from field sites in surface runoff.  However,''only 1-2% of the total amount of the
 applied pesticides in  this category, e.g., atrazine, are typically accounted for in surface runoff
 from the results of  field  studies of  this type.   Concentrations  of the organonitrogen  and
 organophosphourus pesticides in the river fall line samples dropped dramatically after June 1992
 to  below quantitation  levels during  the  winter  months.   During  the  winter  months,  the
 concentrations of these pesticides were slighlty elevated in storm flow  relative to baseflow
 samples
                         %
 The trend in pesticide occurrence was similar for each of the  three river fal] lines.  Atrazine was
 the most frequently detected pesticide and was present at the  highest concentration, followed by
 metolachlor, simazine, and cyanazme.  The organophosphate pesticides were not often detected
 in the river  fall line samples, and were present at concentrations <20 ng/L.

 Organochlorine Compounds

 The  concentrations  of the organochlorine  compounds  in  the river  fall line  samples  are
 summarized in Table  17 through Table  19.  Concentrations of the organochlorines in the fall line
 samples  were much  lower relative  to  the organonitrogen pesticides,  as  is expected  because
 organochlorine pesticides have been  banned from widespread agrichemical use since the early
 1970's or have had restricted use over  the past 20 years (e.g., chlordane).
 Water Quality Data Results                                                            39

-------
Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

The most frequently detected organochlorines were the chlordanes (alpha- and gamma-), dieldrm,
and PCBs.  The  organochlorines were also often detected in both dissolved and paniculate
phases. Paniculate phase concentrations were dependent on river discharge, especially during
summer  and  autumn  when baseflow  suspended  sediment concentrations  are low.   The
concentrations of hydrophobic organic compounds in the paniculate phase depends on dissolved
phase  concentrations, sediment-water distribution constants  (i.e., Kj), and  paniculate  phase
concentrations (i.e., TSP in this study),  and  fractional composition of organic carbon in the
paniculate phase.  During low flow when paniculate concentrations are low, paniculate phase
organochlorine concentrations are also Very low becuase there is very little sediment in fluvial
transport.    Storms. which  occur during JQW flow dramatically .increase paniculate  phase
concentrations, and, thereby, enhance paniculate associated organic contaminant concentrations.

The organochlorines have the greatest number of flagged concentrations relative to any of the
other classes of organic contaminants monitored in this study. This can be partly explained by
the way the  analysis is performed for organochlorine analysis: the GC-ECD is not as selective
as GC/MS.  There exists  a greater likelihood of achieving a false positive identification in GC-
ECD relative to GC/MS beeuase in GC-ECD analysis only chromatographic peaks are identified
without chemical or spectral information provided.  GC-ECD  chromatograms contain many
background  peaks, many of which are near the analyte retention times. GC-ECD analysis is
followed by GC/MS confirmation,  but the concentrations of the organochlorines are below
detection limits when even several sample extracts are combined for a single GC/MS analysis.

Unlike the organonitrogen  and organophosphorus pesticides  which differed in concentration
between the three river fall line samples, the organochlorine concentrations were much similar
in magnitude.

Polynuclear Aromatic Hydrocarbons

Concentrations of the four polynuclear aromatic hydrocarbons in the river fall line samples are
summarized in Table  17  through   Figure 28  (Appendix C contains all  of  the  database
concentrations).  Napthalene  concentrations were  higher in the dissolved phase  relative to the
paniculate phase, which  is. dependent on the; limited partitioning  of napthalene  to suspended
particulate's in  transport.  Converesly, nearly all of the benzo(a)pyrene  detected was associated
with paniculate material, reflecting its low water solubility and large sediment-water distribution
constant (>log 5).   PAH  concentrations differed  between the river fall line samples, with the
highest concentrations detected in the James River suspended  particulates.

Naphthalene was the only PAH that  has  a substantial number of flagged concentrations in the
database.
Water Quality Data Results        • .                                                    90

-------
 Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

 Table 17.  Summary of organic contaminant concentrations in surface water samples collected
 from the Susquehanna River fall line.
Susquehanna River, March 1992 - February 1993
Concentration units are in ng/L

Constituent
Simazine
Prometon
Atrazine
Diazmon
Alachlor
Maiathion
Metolachlor
Cynazme
Hexazmone
"Aldnn
Oxvchlordanc
gamma-Chlordane
alpha-Chlordane
Dieldnn
4 4'. DDT
t/i-Permethnn1.
c/l-Fenvalerales
ZPCBs
Naphthalene
Fluoranthene
Ben/laianthraceni-
Ben/o(a)pyrer,c
Dissolved Phase
Max
91.3
189
2937
' 177
23 1
77
1396
1080
163
1 6
11 1
95
170
5 5
01
7 !
3 8
96
39 5
7 ->
3 y
00
Mm
2.3
24
77
58
2 5
43
1 4
4 1
1 0
02
0?
02
0 1
02
01
7 1
2 3
Oi
1 0
0 5
1 i
00
Avg
24.2
8.8
56.3
11.8
11.8
56
313
357
49
08
27
2 3
33
1 6
03
7 1
30
4 4
66
2 3
26
00
Freq
11
8
17
T
7
3
17
9
8
10
fi
-7
9
5
i
1
->
1 1
i:
s
•>
0
Paniculate Phase
Max
na
..na
na
na
na
na
na
na
na
0 1
1 2
02
03
19
1 4
28
00
127
38
189
21 9
55 1
Mm
na
na
na
na
na
na
na
na
na
0 1
02
0 1
02
0 1
03
2 8
00
04
05
2 S
07
96
Avg
na
na
na
na
na
na
na
na
na
0 1
05
0 I
02
08
07
28
00
44
1 6
100
80
306
Freq
0
0
0
0
0
0
0
0
0
1
4
5
2
7
3
]
0
1 1
8
10
4
3

Combined Dissolved + Paniculate Phases
Max
91 3
189
2937
177
23 1
f
77
1396
108.0
163
30
11 1
456
17.0
21 4
1 4
477
405
160
120
249
21 9
55 1
Mm
2.3
24
77
5.8
. 2 5
4.3
1 4
4.)
1.0
0 1
0.3
O.I
0 1-
0 1
03
28
1 1 -
04
05 •
04
07
47
Avg
24.2
88
56.3
11.8
11 8
56
31.3
357
49
08
2 1
6 1
29
4 1
06
186
152
6 1
3.2
9 1
90
242
Fre'q
11
8
17
2
7
3
19
9_!
8
10
7
II
11
9
4
4
3
13
13
12
9
4
Total
19
19
19
19
19
19
19
19
19
15
15
15
15
15
15
15
15
15
15
15
15
15
MaA - maximum measured concentration. Mm = minimum mea
ol detection. Total = total number of samples analyzed, na = not
sured concentration. Avg = average measured concentration. Frecj = frequency
 analvzcd
water (Jualiry Data Results
                                                   91

-------
Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

Table 18.  Summary of organic contaminant concentrations in surface water samples collected
from the James River fall line.
James River, March 1992 - Febniary 1993
Concentration units are in ng/L

Constituent
Simazine
Prometon
Atrazine
Diazmon
Alachlor
MaJathion
Metolachlor
Cynazine
Hexazmone
Aldnn
Oxychlordane
jramrna-Chlordane
alpha-Chlordane
Dieldnn
4.4--DDT
c/t-Permethnns
c/i-Fenvalerates
XPCEU
Naphlhaleni-
Fluoramhene
Benz(a)an(hracent
Benzo(a)pyrene
Dissolved Phase
Max
369.6
18.1
476.3
11.6
20.2
11 6
210.3
249
16.8
1.6
12 1
85
17.2
24
00
00
40
•67
14 -8
29
8 8
9 1
Mm
2.6
I 7
39
2.8
4.2
3.1
I 4
24
1.3
0.2
0 1
.0.2
01
02
00
00
40
04
02
03
1 7
9 1
Avg
501
55
607
6.8
9.9
7.3
31.3
11 6
80
06
44
29
39''
07
00
00
4 0
1 8
7?
I.I
5 7
9 1
Freq
12
6
15
6
7
T
12
9
10
6
7
10
15
9
0
0
1
16
16
9
4
1
Paniculate "Phase
Max
na
na
na
na
na
na
na
na
na
- 24
1 4
1 8
1.2
0 1
1 4
00
26
136
14 8
1968
272
137.2
Mm
na
na
na
na
na
na
na
na
na
24
0.3
0.2
0 1
0 1
04
00
26
04
0 1
02
2 1
94
Avg
na
na
na
na
na
na
na
na
na
24
09
0.5
04
O.I
09
00
26
53
32
35.6
132
39 1
Freq
0
0
0
0
0
0
0
0
0
!
4
6
5
3
2
0
1
ii
8
15
13
9
Combined Dissolved + Paniculate Phases
Max
369.6
18.1
476.3
11.6
20.2
11.6
210.3
24.9
16.8
2.7
129
8.5
17.2
2.4
1 4
00
4.0
18.3
34.8
198.7
294
137.2
Min
2.6
1.7
3.9
2.8
4.2
3.1
2.1
2.4
1.3
0.2
03
0.2
0 1
0.1
04
00
2.6
04
02
0.5
1 7
9.4
Avg
501
5.5
60.7
6.8
9.9
7.3
34.1
11.6
7.5
1.0
5.1
2.7
5.1
06
09
00
3.3
5.5
8 1
32.0
129
40.1
Freq
12
6
15
6
7
2
11
9
9
6
6
11
II
10
2
0
o
15
13
17 •
15
9
Total
24
24
24
24
24
24
24
24
24
20
20
20
20
20
20
20
20
20
20
20
20
20
Max = maximum measured concentration. Mm = minimum measured concentration, Avg = average measured concentration; Freq = frequency
of detection. Total = total number of samples analyzed, na = not analyzed
Water Quality- Data Results
92

-------
 Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

 Table 19.  Summary of organic contaminant concentrations in surface water samples collected
 from the Potomac River fall line.
1
Potomac River, March 1992 - February 1993 ,
Concentration units are ng/L
'
Constituent
Simazine
Prometon
Atrazine
Diazmon
AJachlor
Malalhion
Metolachlor
Cynazme
'Hexazmone
Aldnn
Oxychiordane
gamma-Chlordane
aJpha-Chiordane
Dieldnn
4,4 -DDT
c/t-Permethrms
I c/f-Fenvalerates
SPCBv
iNaphthalenc:
Fluoranthcnc:
Hcn/i a janthracenf
Hen/oijjpvrent.1
Dissolved Phase
Max
1428
170
5790
100
209
11 5
3580
2124
197
05
31 8
3 5
5 3
4 1 '
I 7
00
00
3 6
19 X
1 4
3 S
00
Mm
57
8.2
96
100
90
11 5
9 1
98
1 8
03
31 8
02
08
04
1 7
00
00
05
3 7
1 4
3 5
00
Avjg
625
135
1585
100
123
11 5
957
1144
86
05
31 8
I 5
3 5
1 5
1 7
00
00
T •>
94
1 4
3 5
00
Freq
12
9
14
I
5
1
13
6
3
3
i
4
3
6
1
0
0
^
X
1
1
0
Paniculate Phase
Max
na
na
na
na
na
na'
na
na
na
2 3
36
04
32
36
1 2
15 /
3 s
390
S 1
(05
12 4
11 4
Mm
na
na
na
na
na
na
na
na
na
2.3
1.8
0.2
03
02
I 1
15 /
3 5
1 1
0 "
06
~> *7
7 5
Avg
na
na
na
na
na
na
na
na
na
2 3
27
03
1.5
1 7
1 1
15 1
3 5
144
28
4 8
9 3
75
Freq
0
0
0
0
0
0
0
0
0
1
2
3
4
5
T
1
1
3
5
8
3
0
Combined Dissolved + Paniculate Phases
Max
142.8
17.0
579.0
10.0
209
11.5
358.0
2/24
19.7
2.3
31 8
3.5
8.5
6 1
28
15 1
35
426
25 1
105
124
II 4
Mm
5.7
8.2
96
10.0
9.0
11.5
9.1
9.8
1.8
0.3
1 8
0.2
0.3
0.2
1 1
15 1
3 5
1 1
44
06
3 5
3.5
Avf
62.5
13.5
158.5
100
12.3
11.5
95.7
1144
.8.6
0.9
124
14
2.7
o •>
2.0
15 1
3.5
108
11 1
44
79
7.5
Freq
12
9
J4
1
5
1
13
6
3
4
3
5
6
8
2
•1
1
5
8
9
4
2
TOTAL
. 15
15 •
15
15
15
15
15
15
15
10
10
10
10
10
10
10
10
10
10
10
10
10
Max = maximum measured concentration. Mm = minimum measured concentration. Avp = average measured concentration, Freq = frequency
of detection. Total = total number of samples analyred. na = not analyzed
\\aier (Duality Data Kesutts
93

-------
Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report

LOAD RESULTS

Metal Loads • Susquehanna River

Susquehanna River load estimates for the 1992 sampling period are given in Table 20. Bar graph
summaries of the maximum monthly load estimates for April, 1992 through March, 1993 are
presented  in Figure 29 for total-recoverable and dissolved Cf,  Cu,  Pb, and Zn.   The loads
presented  have been calculated with the II model.

The accuracy, of load estimates is, to  a  large extent,, determined by the quality of data used to
calculate them.  Based on the 1992 data quality assessment, discussed previously in this-report,
load estimates for total-recoverable As,  Cd, Cu, Pb, Hg, Zn and dissolved As, Cd, Cu, Pb, and
Zn are considered fair to excellent in terms of data quality.  Loads calculated for dissolved and
total-recoverable Cr and dissolved Hg are  considered suspect in terms of data quality.

Figure 29  provides a graphical  representation of  1992  monthly loads  calculated using the
Interpolation Integration method.  The Susquehanna River produces the highest loads in metals
during the spring freshets, when discharges are greatest. Loading estimates are therefore highly
correlated  to discharge. Suspended sediments are also increased during periods of high flow and
it is likely that much of the toxic metal loads  are carried on suspended particles.  Constituent
loadings of suspended-sediment averaged over 2.5 billion kilograms(2,559,248,986) in 1992. Of
the metals monitored, dissolved Fe  had the greatest load, followed by dissolved  Al and total-
recoverable Zn.
Load'Results                                                              • .         94

-------
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-------
Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Repon

Figure 29.  Monthly loading estimates (upper limit) of (a) total recoverable and (b) dissolved
chromium, copper, lead, and zinc for the Susquehanna River fall line at Conowingo Dam,
Maryland, for the period March 1992 through March  1993.
                             (a)   Total-Recoverable  Metal  Loads
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-------
Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

•Metal Loads - James River

Monthly load estimates for the 1992 sampling period are given in Table 21. Bar graphs of the
maximum monthly load estimates for 1992 are presented in Figure 30 for total-recoverable and
dissolved Cr, Cu, Pb, and Zn.

The quality of load estimates is determined by the quality of the data used to calculate them.
Based on the data quality assessment discussed previously in this report, load estimates'for total-
recoverable As, Cd, Cu, Cr, Pb, and Zn and dissolved As, Cu, Pb, and Zn are considered fair to
excellent in terms of data quality. Loads calculated for dissolved Cr and Cd are considered
suspect  in terms of data quality.                                                     .  ..
Load Results                                                                         93

-------
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               r-"                                         •
-------
 Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report


 Figure 30.  Monthly loading estimates (upper limit) of (a)-iotal recoverable and (b) dissolved

 chromium, copper, lead, and zinc for the James River fall  line at Cartersville, Virginia, for the

 period March 1992 through March  1993.
                              (a)  Total-Recoverable  Metal  Loads
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Load KesuLts
                                                                               101

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 Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

'Metal Loads - Potomac River

 Figure 31-Figure 38 are plots of the computed monthly loads for the metals and Table  22-
 Table 29 are the data tables associated with these plots. As discussed earlier, load estimates were
 performed using two different substitutions for censored data.  A minimum estimate was obtained
 by replacing all values below  the  QL by  zero, and a  maximum estimate was obtained by
 replacing all values below  the  QL  by the QL.  In  this  manner, two loading estimates were
 obtained, for each month.  If all data for that  month was above the QL, then both estimates
 resulted in the same load value.  The heavily-shaded region of the plot, thus, represents the range
 between the two estimates.                 .    .

 Figure 39 and Table 30 give the total loads for the eight metals during the April, 1992, to March,
 1993, period.  (The month of March, 1992, was not included in order to obtain a load for one
 year.) The minimum and maximum load estimates are the sums of the monthly load estimates
 for each individual metal.
Load Kesuits
                                                                                  102

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 Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report


 Figure 31.  Arsenic Loads at Chain Bridge on the Potomac River:  March 1992 to March 1993.
           2OOOO

           1 8OOO


           1600O


           1 4OOO


           1 2OOO


           1 OOOO


            8OOO

            6OOO
            2000
                          %
%i
%
                      Mar Apr May Jun  Jul  Aua Sep Oct Nov Dec  Jan Feb Mar
                     1992                                 1 993
Table 22.  Estimated monthly arsenic loads at Chain Bridge on the Potomac River:  March,
1992. to March. 1993
Estimated Monthly Arsenic Loads, kilograms
Month
March. 1992
April
Ma\
June
July
August
September
October
November
December
January. 1993
Februarx
March
Total
Minimum
0
0
0
0
0
0
0
0
0
0
0
0.
0
0
Maximum
7211
6258
4791
3318
2085
1357
1468
943
3010
7875
5267
2342
19322
65247
Load Kesults
                                                                                 103

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Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report	

Figure 32. Cadmium Loads at Chain Bridge pn the Potomac River: March 1992 to March 1993.
           5OOO
                     Mar Apr May Jun  Jul  Aug Sซp Oct Nov Dec Jan Feb Mar
                     1992                               1993
Table 23.  Estimated monthly cadmium loads at Chain Bridge on the Potomac River:  March
1992 to March 1993.
Estimated Monthly Cadmium Loads, kilograms
Month
March. 1992
April
Mav
June
July
August
September
October
November
December
January, 1993
February
March
Total
Minimum
0
0
0
0
0
0
0
0
0
0
0
0
0
o
Maximum
2885
2503
1916
1327
834
- 543
587
377
1204
2697
1310
586
4830
21600
Load Results
                                                                                104

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Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

Figure 33. Chromium Loads at Chain Bridge on the Potomac River:  March 1992 to March
1993.
          25OOO
          20000
        _g
        15
          J 5 O O 0
 o

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 o
_G
f->
          1 oooo
        =~  5OOO
        o
                      Mar Apr  May Jun Jul Aug Sep  Oct Nov Dec Jan  Feb Mar
                     1992                                1993
Table 24.  Estimated monthly chromium loads at Chain Bridge on the Potomac River:  March
1992 to March 1993.
Estimated Monthly Chromium Loads, kilograms
Month
March. 1992
April
May
June
July
August
September
October
November
December
January. 199?
February
March
Total
Minimum
0
10017
106
0
0
0
0
0
1631
920
362
0
17570
30606
Maximum
3606
11234
2428
1659
1043
678
734
472
2457
3258
1492
586
24204
53849
Load Results
                                                                                105

-------
Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report


Figure 34. Copper Loads at Chain Bridge on the Potomac River:  March 1992 to March 1993.
          3OOOO
          25OOO
        -5 2OOOO

        cn
        o
        3 15OOO
        Q_

        cS' 1 OOOO
           5OOO



                      Mar Apr May  Jun Jul Aug Sep Oct Nov Dec  Jan Fab Mar
                     1992                                 1993
Table 25.  Estimated monthly copper loads a: Chain Bridge on the Potomac River:  March 1992
to March 1993.
Estimated Monthly Copper Loads, kilograms
Month
March. 1992
April
Ma\
June
Juh '
August
September
October
November
December
January 1993
February
March
Total
Minimum
0
13713
2551
3069
952
86
867
404
3370 '
2854
2355
0
13310
43534
Maximum
7211
14251
2551
3069
1363
577
867
404
3487
4362
3013
1171
25101
67429
Load Results
                                                                                 106

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Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report	


•Figure 35.  Nickel Loads at Chain Bridge on the Potomac River:  March 1992 to March 1993.
          6OOOO
                     Mar Apr May Jun  Jul Aua Sep Oct Nov Dec  Jan Fob Mar
                     1992                                1993
Table 26.' Estimated monthly nickel loads at Chain Bridge on the Potomac River: March 1992
to March 1993.
Estimated Monthly Nickel Loads, kilograms
Month
March. 1992
April
May
June
July
August
September
October
November
December
January, 1993
February
March
Total
Minimum
0
30586
0
0
0
0
0
0
0
0
0
0
29283
59868
Maximum
17308
36428
11498
. • 7963
5005
3256
3523
2263
7224
17089
10484
4684
57278
184002
Load Results
                                                                                107

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Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report


Figure 36. Lead Loads at Chain Bridge on the Potomac River:  March 1992 to March 1993.
          35OOO
                      Mar Apr  May Jun Jul Aua Sep  Oct Nov Dec Jan  Feb
                     1992                                1993
Table 27.  Estimated monthly lead loads at Chain Bridge on the Potomac River:  March  1992
to March 1993.
Estimated Monthly Lead Loads, kilograms
Month
March. 1992
April
Ma>
June
July
August
September
October
November
December
Januars. 1993
Februan.
March
Total
Minimum
0
8029
5320
2156
2240
2672
0
0
2093
0
0
0
18635
41144
Maximum
5769
9976
5928
3377
3086
2777
1174
754
3414
6300
5242
2342
32632
82772
Load Results
                                                                                 108

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Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report


Figure 37. Selenium Loads at Chain Bridge on the Potomac River: March 1992 to March 1993.
          25OOO
        ง 20000
        -x


        -g  1 5 O O 0

        o
        _—i



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        QJ
        .0)
        OO

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1




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1
i
gg

i
i
1
1
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                      Mor Apr May  Jun  Jul  Aua Sep Oct Nov Dec Jan Feb Mar
                     1992                                 1993
Table 28. Estimated monthly selenium loads at Chain Bridge on the Potomac River:  March

1992 to March 1993.
Estimated Monthly Selenium Loads, kilograms
Month
March. 1992
April
Mav
June
July
August
September
October
November
December
January 1993
February
March
Total
Minimum
0
0
0
0
0
0
0
0
o'
0
0
0
0
0
Maximum
10096
8761
6707
4645
2919
1899
2055
1320
4214
10119
6552
2928
24152
86368
Load Results
                                                                                 109

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Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report



.Figure 38.  Zinc Loads at Chain Bridge on the Potomac River:  March, 1992, to March, 1993
          14.00001



          120000
          100000
       „,- 80OOO -
       -o
       o
       o


       o 6OOOO
       IS" 4.OOOO
          20OOO
                      Mar  Apr May Jun  Jul Aua Sep Oct Nov Dec Jon  Feb Mar

                     1992                                1993
Table 29,  Estimated monthly zinc loads at Chain Bridge on the Potomac River: March 1992

to March 1993.
Estimated Monthly Zinc Loads, kilograms
Month
March. 1992
April
Ma\
June
July
August
September
October
November
December
January. 1993
February
March
Total
Minimum
27404
50217
15902
11496
0
655
6793
3093
9787
15684
25981
9368
92466
268847
Maximum
27404
55906
17743
-16077
6256
4332
6793
3345
14739
26994
25981
9368
139279
354216
Load Results
110

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Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

Figure 39. Load Estimates for the Period of April, 1992, to March, 1993, for the Metal Species
Monitored at Chain Bridge on the Potomac River
         35000O
                        As    Cd    Cr '   Cu
Table 30. Range of load estimates for monitored metals for the period of April 1992 to March
1993 at Chain Bridge on the Potomac River.
Constituent
Arsenic (As)
Cadmium (Cd)
Chromium (Cr)
Copper (Cu)
Nickel (Ni)
Lead (Pb)
Selenium (Se)
Zinc (Zn)
Range of Load Estimates (kilograms)
with Values Below the Quantitation Limit
(QL) Set to
Zero the QL
0
0
30606
43534
59868
41 144
0
.241443
58035
18715
50243
60218
166694
77003
76272
326812
Locta Results
                                                                                 111

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Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report

Organics Loads  - Susquehanna, James and Potomac Rivers

Estimates of monthly pesticide and PCB loads for each tributary in the fall line study are listed
in Table 31-Table 39.   The monthly loads were estimated  separately for the dissolved and
paniculate phases. Estimated loads in these tables were calculated from both the maximum and
minimum daily fluxes summed for each month providing maximum and minimum load estimates.
Zero loads represent minimum values that were calculated assuming that there was no existing
level (i.e.,  0 ng/L)  of contaminant in-"the fluvial sample when the measured value was 
-------
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    -------
     Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report
    
     WATER QUALITY DATA  DISCUSSION
    
     Water Quality Metal Data - Susquehanna River
    
     The 1992 study resulted in the development of ultra clean  sampling procedures, adoption of
     lowered quantitation levels, an extensive quality-assurance program, identification of metals in
     fluvial transport, and estimates of toxic loadings.entering  the Chesapeake Bay.  Additionally,
     results  from the 1992  quality assurance program  were 'used to assess the  quality of  1992
     concentration data .and load estimates, and 10 make inferences as to the validity of 1990-91 fall
    .line"results when ultra clean techniques  were not used.
    
     Concentration data collected throughout the period  1990-93 for the Susquehanna station, are
     presented in Appendix A.  Results are reported for dissolved and total-recoverable metals.
     Ranges in constituent concentration provide year to year comparisons for river samples.  Boxplots
     of concentration data collected over the  three year period are shown in Figure 40.
    
     Figure 41-Figure 44 show the  concentrations of total-recoverable and dissolved Cr, Cu, Pb, and
     Zn for the entire three-year sampling period. The old quantitation levels for  1990-91 and new
     levels for 1992 are indicated on each graph for the dissolved species. The quantitation levels did
     not change over the sampling period for total-recoverable metals. Where duplicate measurements
     were made, the average of the two data  points  was used for the time series.
    
     The ultra  clean  sampling  procedures  as well as  the lowered  quantitation  levels  for  1992
     significantly  improved  concentration data for some  constituents.   Concentration data  for  a
     particular constituent were considered improved in 1992 if one or more of the following criteria
     were met: (1) if more ambient concentration data were detected; (2) if the range in concentration
     data decreased in 1992 or the precision increased; and (3) if concentration data exhibited a better
     relation with discharge.
    
     Based  on these criteria, water quality data were improved in  1992 for total-recoverable Cu, Pb,
     Zn,  and dissolved Cu, Pb, and Zn.  Although dissolved Cr and Hg met one or more of the
     criteria, they were not considered improved in  1992 due to their suspect  data quality.
    
     Generally, results indicate that there was a greater percentage of detections in 1992 compared to
     the  1990-91 period for dissolved Cr, Pb, Hg, and Zn, a result of lowered quantitation levels in
     1992.    Total-recoverable  Cu,  Pb,  and  Zn  were  detected  less  frequently  and  at lower
     concentrations in 1992, which may be attributed  to the cleaner sample-collection  methods used
     during that period.  Precision in concentration data increased in 1992 for dissolved Cr and Cu,
     while concentration data exhibited  a better relation with discharge in 1992 for total-recoverable
     Cu,  Pb, and dissolved Cr, Cu,  Pb, and Zn. High censoring  (values below quantitation  levels) in
     1990-91 masked the concentration/discharge  relation that  later became evident  with lower
     quantitation levels.
    
     Because data were  improved for a number of constituents in 1992, the validity  of previously
     collected data for the fall line program  was assessed.  A general assessment of the validity of
     1990-91 concentration data was made from observing the range in  1990-93 concentration  data
     Water Quality Data Discussion                                                        122
    

    -------
    Chesapeake Bay Fall Line Toxics Monitoring Program:' 1992 Final Repon
    
    Figure 40.  Boxpiots showing (a) total recoverable and (bydissolved chromium, copper, leac.
    and z:nc concentrations during 1990-1992 at the Susquehanna River fall line station.
                              (a)   Total-Recoverable   Metals
                        Cr
    Cu
    Pb
    Zn
                                   (b)  Dissolved  Metals
                                                                    /.n
    \\aier Uuaury Daia Discussion
                                                123
    

    -------
    Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report
    
    Figure 41. Concentration of (a) total recoverable and (b) dissolved chromium and instantaneous
    discharge for the Susquehanna River fall line station for the 1990-1992 sampling period.
                               (a)  Total-Recoverable   Cr
                                                                  '
                                                                       - 400000 <
    
                                                                       - 350000
                                                                       '
                                                                      •- 300000''  -
                                                                                  
                                                                       ; '         o
                                                                       -" 250000  S
                                                                                 ce
                                                                      -  200000
                ~  *
                     ;-  Sec Dec  Mar JUH  Sec  Dec  Mar Jun Sec  Dec Mar
                                        1990-92
                                    (b)  Dissolved  Cr
                                                                     . -  1 50000   o_
                                                                       -           wT
                                                                      -;  100000  '•
                                                                     i ' -  50000
    
                                                                    -^  0
    ^ *
    ' ป ~
    , I
    
    
    - ^
    - ^ t
    •! ***./'•"
    -^ ; •-.- ' "V *Nj
    4.UUUUU
    350000
    300000
    250000
    
    200000
    150000
    100000
    50000
    n
    
    n
    s;
    <0
    5'
    o
    uT
    
    
               Mar _ur  Sec Tec  Ma' ^un  Sec  De<:  Mar  Jun Sec  Dec Mar
                                ••      1 9 9 0 -1 9 9.3
    \\arer Qualify Dam Discussion   •.
                                                                                  124
    

    -------
    Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report
    
    
    
    Figure 42.  Concentration of (a) total recoverable and (b) dissolved copper and- instantaneous
    
    discharse for the Susauehanna River fall line station for the 1990-1992 samolinE period.
                                (a)   Total-Recoverable   Cu
                                          •Qj
    
    
                                          • Discnarae
                     •ป ••
                                                                          ^00000
     -|  25GOOC '
    
    
    
     -_  3COOCC  'E
    
    
    
     -  25000C  5
    
    
    
     -  20000C  ฐ •
    
    
    
     -_  15000C  2.
    
    
    
     -j .100000
    
    
    
    '-  5000C
                                                    '•ป t ป *
                      r.  Se^ Tec  Mar  our Sec  Dec Mar  Jun Sec  Dec Mar
    
                                         1 990-32
                                     (b)   Dissolved  Cu
                                           •  -  Ciscnarge
                          ป ป  *-ป
     '0** z^arntancr
                                                                          .100000
                                                                       -  250000
                                                                       -  300000  3T
                                                                       •;          o
    
    
                                                                       -  250000  -
                                                                                  (C
                                                                                  (0
    
                                                                       -:  200000  -
    ป-  150000  2.
    1  I          <"
    
    
    ;-  100000
                         Sec Zee Mar  our. Sec  Dec Mar  Jun Sec  Dec Mar
    
                                       1  990-1 993
         (Juaur\ uam Discussion
                                                                                 125
    

    -------
    Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report
    
    
    
    Figure 43.  Concentration  of (a)  total recoverable and (b) dissolved lead and  instantaneous
    
    discharge for the  Susquehanna River fall line station for the 1990-1992 sampling period.
    
    
    
                                 (a)  Total-Recoverab.le  Pb
         O)
    
    
    -------
    Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Repon
    
    
    Figure 44.  Concentration  of (a)  total recoverable  and  fb) dissolved zinc and instantaneous
    
    discharge for the Susquehanna River fall line station for the 1990-1992 sampling period.
                                  (a)   Total-Recoverable   Zn
    
               so - : - : - : -iobooo
    
    
                                             '                           - 35000C
               5C -              ซ•ป      ..... Discharge      .               :
    
                                 ;                                       - 300000  5
                                 !                                        "          ^
    
               4"                '               *                        - 250000  a"
    I
                                                                        - 2000CO
       0                        '                      j               ,,  i- 150000  o
    
               ^~                                     *      *       .  * "          ^
    
       6                        ;                                     \ -   looooc
                                                                        - 50000
                        r Sec  Dec  Mar Jun  Sec  Dec  Mar  Jun Sec  Dec  Mar
    
                                          1  990-93
                                      (b)  Dissolved  Zn
                                      	 400000
                                                      •                 - 350000
                                           _ i s c n a : a e
                                                                        :          D
                                                                        - 300000  
    -------
    Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report
    
    (Figure 41-Figure 44).   If the range in concentration data for a given  constituent remained
    approximately the same throughout the three-year period and the 1992 data for that constituent
    was considered valid, data collected during 1990-91 was also considered valid.  Additionally, if
    data collected during the  1990-91 period were all at or below quantitation levels, the data was
    considered valid. If, however, the range in concentration data for a given constituent exhibited
    a significant decrease in 1992, when ultra clean techniques were implemented, and the J992 data
    for that constituent was considered valid, the quality of data collected in 1990-91 was considered
    suspect.  Applying this criteria to constituents monitored throughout the 1990-9 J period at the
    Susquehanna River station, valid.concentration data was collected during 1990-9'J  for total-
    recoverable As, Cd.'Cr. Pb. Hg. and dissolved As. Cd. Cr. Cu. Pb, Hg. and Zn are valid.. Water
    quality data collected for  total-recoverable Cu and Zn during the 1990-9] period is considered
    suspect.
    
    Colloids and  dissolved organic matter are expected to strongly influence metal concentration in
    the fluvial environment.  Ratios of dissolved to total-recoverable metal concentration were higher
    than expected for many of the constituents monitored at the Susquehanna River station, including
    Cr. Cu. Pb. and Zn.  Significance of the dissolved fraction may be related to the chemical or
    biotic- conditions thai exist within the reservoir (pH. EH. dissolved oxygen, bacterial action).
    Reducing conditions, which exist at  the bottom of the reservoir, where water is drawn by the
    turbines, affects sediment-bound metals by  increasing their solubility in the water  column.
    Limitations on the separation of colioidally-sized particles, which are inherent  to the filtration
    procedure, may also be a  factor.
    
    Water Quality  Metal Data - James River
    
    Concentration data collected throughout the period 1990-92 are presented in Appendix B for the
    James River.  Ranges of constituent concentration shown provide year to year comparisons for
    river samples.   Figure 45 shows  boxplots  of selected  constituent  concentrations  over the
    three-year period.
    
    Figure  46-Figurc 49 shou  the concentrations of selected metals in environmental samples over
    the three-year data collection period.  The quantitation levels for 1990-91 and the new levels for
    1992 are'indicated  on  each graph  for  the  dissolved species.   The quantitation  levels for
    total-recoverable- metals did not change  over the sampling period.   The  ultra  clean sampling
    procedures and the lowered quantitation levels for 1992 significantly improved concentration data
    lor some constituents Concentration data were  considered improved in  1992  if one or more of
    the following criteria were met: (11 if there were a greater number of detections of ambient
    concentration data. (2) if the range in concentration data decreased in 1992 or the precision was
    increased; and (3)  if concentration data exhibited a better relation with discharge.
    
    Based on these criteria, water quality data were improved in 1992 for total-recoverable As and
    and dissolved As.  Cu. Pb. and  Zn.  Although dissolved  Cr and Cd met one or more  of these
    criteria, the)  were  not considered improved in 1992 due  to the suspect data  quality.  Also,
    although total-recoverable Pb and Zn did not meet the specific criteria above, plots of the data
    clearly  shou- that for these  constituents, improved  quality  of the  data is  shown by fewer
    detections of ambient concentration data  as compared to previous data.
    \\alcr Quulit\ Data Discussion                       •                        •          J28
    

    -------
    Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Repon
    
    
    Figure 45.  Boxplots showing (a) total recoverable and (b) dissolved chromium, copper, lead.
    
    and zinc concentrations during 1990-1992 at the James River fall line station.
        O)
        c
        o
    CD
    u
    c
    o
    o
        O)
        c
        o
        o
        c
        o
       o
                            (a)   Total-Recoverable   Metals
            100
                       Cr
                                 Cu
    o   Pb
    Zn
                                                            o
             80 -
             60 -
       r-    40 -
                                                   o
            20-3
                                                           PCCTj
                                 (b)  Dissolved  Metals
     35 -
    
    
    
     30 -
    
    
    
     25 -
    
    
    
     20 -
    
    
    
    ' 1 5 ~
    
    
    
     1 0 -
                      Cr
                                 Cu
        Pb
    Zn
                                                   O
    
                                                   f~\
                                                   X
                                                     -    o
                                                             o
    
                                                             O
                  90  91   92   90  91  . 92   90  91   92   90  91   92
                  90  91   92   90  91   92   90  91   92  90   91   92
    water (Juaun Data Discussion
                                                                             129
    

    -------
    Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report
    
    Figure 46. Concentration of (a) tptal recoverable and (b) dissolved chromium and instantaneous
    discharge for the James River fall line station for the 1990-1992 sampling period.
                                  (a)  Total-Recoverable   Cr
    zu 	 — 	
    -ซ~Cr
    _j
    •"ro •*
    nii o^^
    LMSCi
    -.15-
    
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    n
    
    
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                                                           I  i r  I I  I I  1 I  T
    
                  Mar  Jun  Sep Dec  Mar Jun  Sep Dec  Mar  Jun Sep  Dec Mar
                                           1990-93
                                       (b)  Dissolved  Cr
    — •— Cr t
    1Q _ - Discharge ;' j\
    • •ซ- : 1 1
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    '.= 8 -• ' ;
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    40000 ~
    
    20000
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                  Mar  Jun  Sep Dec  Mar  Jun  Sep  Dec Mar  Jun Sep  Dec Mar
                                           1990-93
    U ater Uuant\ Data Discussion
    130
    

    -------
    Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Repon
    
    
    Figure 47.  Concentration of (a) total recoverable and (b) dissolved copper and instantaneous
    
    discharge for the James River fall line station for the 1990-1992 sampling period.
           100
                       Cu
       O)
       c
       o
           .80 -
            60 -
       CD
       i:    40
       c
       0)
       U
       c
            20 -
                   ti
        auaninaucr,^
         ,eve< ซ'i
                               (a)  Total  Recoverable  Cu
        120000
     -  100000
    
     ;           o
    
     -  80000   %
     '           3"
    
    
     -  60000  *ง
    
    
    
     -  40000   ฃ
    
    
    
     ^  20000
    
    
    
    ==  o
               Mar Jun  Sep Dec  Mar Jun  Sep Dec  Mar Jun  Sep Dec  Mar
    
                                        1990-93
                                    (b)  Dissolved  Cu
       o>
       c
       o'
       c
       0)
       o
    
       O
       U
     o/cr Quanjitatron
     new Quantitat/on
    
      >6ve< ' <0 OC
                                                                          120000
               Mar  Jun  Sep  Dec  Mar  Jun Sep  Dec  Mar Jun  Sep Dec  Mar
    
                                        1990-93
    \\aier ()uaur\ Data Discussion
                                                                                     131
    

    -------
    Chesapeake Bay Fall Line Toxics Monitoring Program:  -1992 Final Report
    
    Figure 48.  Concentration of (a) total recoverable  and  (b) dissolved lead and  instantaneous
    discharge for the James River fall line station for the 1990-1992 sampling period.
          100
           80  -;
           60  -
                              (a)   Total-Recoverable. Pb
                                    •— Pb
                                    ••- Discharge
                                                                 120000
                                                             -   100000
                                                                     -j  80000'  %
    c
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                                                                                (Q
              Mar Jun  Sep Dec Mar  Jun  Sep Dec  Mar Jun  Sep Dec  Mar
                                      1990-93
    12
                                  (b)  Dissolved  Pb
                                                                        120000
           1 n  -
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                                                             -  100000
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              Mar Jun  Sep Dec Mar  Jun  Sep Dec  Mar Jun  Sep  Dec Mar
                                      1990-93
    water (Juatir\ Dam Discussion
                                                                                  132
    

    -------
        Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report
    
       ' Figure 49.   Concentration  of (a) total recoverable and (b) dissolved zinc and instantaneous
        discharge for the James River fall line station for the 1990-1992 sampling period.
    01
                                 (a)  Total-Recoverable   Zn
             100
              80
                                      120000
                                              Discharge :
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                                      20000
                                                                           0
                 Mar Jun  Sep Dec Mar  Jun Sep  Dec Mar  Jun  Sep  Dec  Mar
                                          1990-93
                                      (b)  Dissolved  Zn
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    C  oia Quaniilstior,
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                                                                        1  20000
                 Mar Jun  Sep  Dec Mar  Jun  Sep  Dec  Mar  Jun  Sep Dec  Mar
                                         1990-93
        \\aier Uuaiity Uaia Discussion
                                                 133
    

    -------
     Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report
    
    •Generally, there was an increased percentage of detections in  1992 compared to the 1990-91
     period for dissolved Cd, Cr, Cu. Pb, and Zn, due to the lowered quantitation levels in  1992.
     Total-recoverable Ar, Cu. Pb and Zn, were detected less frequently and at lower concentrations
     in  1992, which may be attributed to the cleaner sample-collection methods used during that
     period. Precision in concentration data increased in  1992 for  dissolved As.  Cr  and Cu, and
     concentration data showed an improved relation with discharge in 1992 for dissolved Pb and Zn.
    
     Because data were improved for a number of constituents in 1992. the validity of previously
     collected data for the Fall Line program was also assessed. A general assessment of the validity
     of 1990-91 data can be made by observing the changes in 1990-92 concentration data (Figure 46-
     Figure 49).  If the range in concentration data for a given constituent remained approximately
     the same throughout the three-year period, and the 1992 data for that constituent are considered
     valid, it can be  assumed that the data collected during  1990-91  is  also valid. Additionally, ifdata
     collected during the 1990-91 period were all at or  below quantitation levels, the data can be
     considered valid.  If. however, the range in concentration data for a given constituent exhibits
     a significant decrease in 1992. and the 1992  data for that constituent are considered  valid, the
     quality of the data collected in 1990-91  may  be considered suspect. Applying these  criteria  to
     constituents monitored throughout the 1990-91 period  at the James River station, it appears that
     concentration data collected during 1990-91 for total-recoverable As. Cd, Cr, Cu. and Zn, and
     dissolved As. Cd.  Cu. Pb. and Zn are valid   Water quality data collected for total-recoverable
     Pb  and dissolved Cr during 1991 are considered suspect.
    
     Water Quality  Metal Data - Potomac River
    
     While  some  preliminary conclusions can be drawn from  the data, it should be recognized that
     these are based on a fairK  limited dataset.  Over the thirteen month sampling period, a total of
     twelve baseflow and nine stormflov. samples were collected. Observations based on the data will
     therefore be sub|ect to the caveat that the data may be  extended in reaching certain conclusions,
     and that these ma\  he  invalidated after more data have been gathered.
    
     Relationships Between Discharge and Suspended Sediments and the Constituent Concentration
    
     As  can be  seen in  Figure 28.  the total flov.  in March 1993. \vas  more than three times the total
     flow for the next  highest months—March and December  1992.  The Potomac River was  in
     stormflpv.  tor 18 days during that month  The concentrations of most metals and total suspended
     solids  rose substantial!} during stormflou (see Table  15).  Although  there  was no general
     correlation between the magnitude oi the stormflow and  the  concentration of the  measured
     constituent. Cr  and Zn concentrations rose during storms. The  iwo storms of March 1993, March
     5-1 1 and March 21-April 1, had average  flows that were  more than double the average flow of
     the April 21-29. 1992 storm.  However, metal concentrations Were higher for the April 21-29,
     1992, storm than they  were for the March 1993 storms.
    
     It is also  interesting to note that the storm of Ma\  17-18. 1992,  which had an average storm
     discharge  of 314.0  m'/s, had similar concentrations  of  metals as  had  the  baseflow samples
     collected when the baseflow was in the same range (baseflow samples of March 17, May 19, and
     June 16.  all in 1992)   This  can  be most  clearly  seen in  the  case  of 'zinc..  The average
     concentration of Zn during the storm of Ma\  1992 was 20 ug/L, whereas that  for the baseflow
    
     \\'atc*r Quality  Data Discussion                                                •        J34
    

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    Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report
    
    sample of March 17, 3992  (flow of 444.9 mVs) was  19 |ag/L. and for the baseflow sample of
    May 19, 1992. (flow of 502.4 m3/s) was 19 ug/L.  Such trends are also discernible  when the
    storm of December  18-22, 1992  (average flow of 598.0 m3/s) is  compared to the  baseflow
    samples which were taken when the flow was in the same range (baseflow samples of May 19,
    1992, and January 5, 1993).   The storm of November 23-28, 1992  had significantly higher
    concentrations of Cr, Cu and Zn, even though the flow  was in the same range (573.0 mVs).
    Also, lower  flows can result in higher concentrations—such as the Zn concentration of 25 ug/L
    observed for the baseflow sample of September 9, 1992, when the flow was 184.7 mYs. Similar
    aspects are seen with respect to the other metals. It would, therefore, be premature to  draw any
    conclusion regarding any relationship between the- discharge and the constituent concentration.
    A statement  can be made that it appears that the expected rise in constituent concentrations with
    a rise in flow is seen if the average flow during storms is significantly higher than the prevailing
    baseflow.  With the limited data at hand, the basis for such a statement  is quite tenuous. The
    relationship  between  higher flows  and higher TSS values  appears to be better supported.
    
    Water Quality Organic Data - Susquehanna, James and Potomac Rivers
    
    Organomtrogen and Organophosphorus Pesticides
    
    All  three  rivers  showed  similar  temporal  patterns in the  relative  concentrations  of the
    organomtrogen and organophosphorus pesticides measured during the March 1992 to  February
    1993 sampling period.  The dominant pesticide in  this group in fluvial transport was atrazine,
    followed.b\. in roughly descending abundance, metolachlor. cyanazine, simazme. prometon.
    alachlor. diazmon. and  malathion.  The magnitude of the fluvial sample concentrations varied
    with the source of water.  Peak concentrations of atrazine,  for example, varied from 255 ng/L in
    the  Susquehanna  River  to  540  ng/L in  the Potomac River  to 58  ng/L in the James  River
    (Appendix C).
    
    Concentrations peaked in Ma\ (James River) or June  (Susquehanna  and  Potomac Rivers), and
    the largest measured concentrations of the organomtrogen herbicides directly coincided with their
    period of field application which has been reported to occur from April to July (Pait et al. 1992).
    It.appears that these pesticides arc subject to maximal runoff during the spring flush from heavy
    rainfall  • In  addition, the peak concentrations of the organomtrogen herbicides in  the fall line
    stud)  correspond  to  a similar temporal  trend observed for the fluvial transport of related
    herbicides in- the'Cedar. River basin. Iowa, where peak concentrations  were observed during June
    and earl)  Juh (Squillace and  Thurman   1992)  The tnazine herbicides,  especially  atrazine,
    simazme. and  cyanazine. and  chloracetanihde herbicides, especially metolachlor and  alachlor,
    were the most common!) detected pesticides m this group.
    
    The organophosphorus pesticides were rarely detected, and when present in the  fluvial samples
    their concentrations were near the QL values.  Organophosphorus pesticides typically have short -
    half-lives  m  aquatic  systems  (Tinsle) 1979. Lyman  et  al.  1990)  are not expected to  have
    extreme!)  elevated concentrations  m non-point  source runoff especially  if sampling occurs  at
    locations remote from the area of field application
    
    Percent deviation values (calculated from  replicate measurements as (rep,  - rep7[(rep, + rep,)/2]
    X 100) from duplicate measurements of the organonitrogen and organophosphorus pesticides in
    
    \\citctr Qualm- Daia Discussion                                               .
    

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     Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report
    
     the same water source were quite high when measured concentrations were near the QLs (e.g.. -
     200% for alachlor in the Potomac River), but were much lower when concentrations were above
     ca. 20 ng/L. Reproducibility appeared to be much better at the largest measured concentrations,
     especially  when the measured concentrations were one to two orders of magnitude larger than
     the QL  values.   In fact,  at concentrations  above  ca. 20 ng/L the %deviation values for  the
     duplicate samples  compared  quite favorably with the indeterminate  error values shown  in
     Table 12.
    
     The organonitrogen and organophosphorus pesticides were not analyzed in the paniculate phase
     of the fluvial samples.  The  fractional composition of organic compounds in the  suspended
     paniculate phase in aquatic systems is governed by several variables, including the  magnitude
     of particle/water partition coefficients, the amount of organic carbon associated with the particle
     phase, and the concentration of suspended particulates.  Because the partition coefficients of the
     organomtrogen and organophosphorus pesticides are near or less than  1.000.  the fractional
     composition of these pesticides in the particle phase is predicted to  be less than 5%  even  for
     TSPs as  large as 1.000 mg/L (Samiullah 1990). The particle  phase in not important in the fluvial
     transport of monitored organomtrogen and organophosphorus pesticides.
    
     Organochlorine Compounds
    
     The organochlorine pesticide and PCB concentrations in both dissolved and paniculate phase
     fluvial samples are shown for each river in Appendix C.  Two storms  were sampled in the
     Susquehanna River during the sampling period, and one each in the James and Potomac Rivers
     (although more storms occurred at the Potomac River).  The concentrations of the organochlorine
     compounds were  much lower than were the organonitrogen and organophosphorus pesticides in
     the same samples.  Typical organochlorine concentrations in  the fluvial  samples, including
     dissohed and paniculate phases,  were in the 1-20 ng/L range.  The  organochlorine pesticides
     detected  most often included aldrin, the chlordane isomers.  and dieldrin.
    
     The organochlorine pesticides did not appear to show the degree of temporal  variability  that was
     e\ident with the  organonitrogen pesticides (e.g.. atrazine).  A determination  of concentration
     dependence on river discharge lor these  analytes has  not been made but correlations  between
    'flou  and concentration are in  progress  The concentrations of the organochlorine pesticides in
     the fluvial  samples seemed to van in a rather random way and no obvious pattern was evident,
     with  the exception that  for  the  James  and Potomac  Rivers  the  organochlorine  pesticide
     concentrations were slightly larger in storm  samples relative to baseflow samples. Most of the
     measured  concentrations  were within  2  to 10  times  the  respective  QL  values.   More
     comprehensive determinations of the organochlonne pesticides in the fluvial samples will likely
     require the development of a  method with QL's  in the range of 0.01 ng/L, a full  order of
     magnitude lower than  those inherent in the present method.
    
     Closer evaluation of the-chlordane isomers. alpha- and gamma- isomers, showed  that, generally,
     the alpha isomer tended to be the predominant form in the. dissolved phase of the fluvial  samples.
     There uas no apparent trend oi this kind in  the  particulate  phase  samples, although the
     concentrations of the two  isomers appeared  to be more similar in magnitude.  The permethrins
     and  fenvalerates  were only  detected  in  one sample, which  was  fenvalerate  in the  20 May
     paniculate phase  for the James River (2.6 ng/Li.
    
     \\'aicr Qualm Daiu Discussion       .                                                 136
    

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     Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report
    
    •The PCS concentrations for both dissolved and paniculate phases are also listed for the three
     rivers in  dissolved  and  paniculate  phases  in  Appendix  C.    (The  individual   congener
     concentrations can be obtained from G.D. Foster at the Chemistry Department at George Mason
     University upon request.)  Total PCB concentrations (ZPCBs) typically ranged from  1-20 ng/L
     in both dissolved and paniculate phases, but higher levels were observed throughout the sampling
     period in the Susquehanna River  fluvial samples. The PCBs  were observed commonly in both
     the dissolved and paniculate phases, with larger concentrations appearing often in the paniculate
     phase.   This  large fraction of the  PCBs in the paniculate  phase  reflects the large partition
     coefficients these contaminants have in freshwater  systems.
    
     Polynuclear Aromatic Hydrocarbons
    
     The PAH concentrations in the fluvial samples  are listed in Appendix C.  The dissolved phase
     PAH concentrations  showed  no definite  trend in  concentrations  throughout the  March to
     September period, a pattern similar to the OC compounds.  However, the paniculate phase PAH
     concentrations were dramatically elevated  during  storm events for the three rivers.  One
     explanation for this observation is  that substantially more sediment was'collected on filters during
     storm flow, thereby allowing lower quantnation levels in this  matrix.
    
     Naphthalene  was the most prominent PAH detected in the  dissolved phase  -samples, which
     correlates with the fact  this compound  has the highest water solubility  of  the PAH group.
     Furthermore, the  prominence of all  four PAH in the dissolved phase indirectly correlated with
     water solubilities: for example, benzol ajpyrene  was rarely detected in the  dissolved phase  and
     it  has the lowest  water  solubihu.   In contrast,  fluoranthene and  benz(a)anthracene were
     frequently detected  in the paniculate phase  of the fluvial  samples.  These two PAH have large
     enough octanol-water partition  coefficients  to thermodynamically favor partition into sediment
     materials with appreciable  organic matter content.   Interestingly, the highest concentrations of
     PAH detected in all of the collected  fluvial samples occurred in James  River March storm
     samples
    \\ciier Qualit\ Data Discussion                                                        J37
    

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    Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report
    
    METAL AND ORGANIC  LOADS DISCUSSION
    
    Metal Loads Discussion - Susquehanna River
    
    Water  discharge has a  significant effect on resulting load estimates for metals.  Although the
    concentration of metals carried by suspended sediment may theoretically decrease during period
    of high discharge due to dilation by larger grain size sediments, the transport, or load, of metals
    will significantly increase. This is'due to the large increase in water volume that  occurs during
    storm events, which, is capable of carrying  a greater mass of sediment.
    
    Susquehanna River load estimates for the 1990-92 sampling period are given in Table 40. Bar
    graph summaries of the maximum annual load estimates for 1990-92 are presented in Figure 50
    for total-recoverable and dissolved Cr, Cu,  Pb. and Zn.
    
    The  adoption  of  ultra  clean sampling  procedures and  lowered quantitation  levels in  1992
    significantly improved load estimates for some constituents.  Two criteria used to determine if
    load  estimates for a particular constituent were improved included:  (1) if concentration data for
    the constituent was improved in 1992 as a result of the ultra clean study; and/or (2) if the upper-
    bound  load estimate for the constituent was minimized due to lower quantitation level in 1992.
    Based on these criteria, load estimates were improved in  1992 for total-recoverable Cu, Pb, Zn
    and dissolved As, Cd. Cu, Pb. and Zn.  Load estimates were improved for total-recoverable Cu,
    Pb. and Zn. and dissolved Cu, Pb, and Zn based on improved data quality. Loads were improved
    for dissolved As. Cd, Pb. and Zn based  on lower quantitation levels used  in 1992.  Although
    dissolved Cr and Hg met the above criteria, they were not considered improved in 1992 due to
    their suspect data quality.
    
    Generally, the improvements in 1992 either lowered the quantitation  level, thereby increasing the
    number of detections, and/or improved the  analytical accuracy for  a specific metal. Therefore,
    for these  constituents, the ranges on the  load estimates for 1992  are generally smaller and the
    estimates  are presumed to  be closer to  the  true values, than for  the  1990-91 period.   For
    example,  loads for dissolved Zn in the 1990-91 period were based primarily on values determined
    as equal  to or less than the quantitation'  level  (
    -------
     Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report
    Table 40. Range in Susquehanna River fall line load estimates for 1990 to 1992. Units are in
    thousands of kilograms per year. The modeling technique used to calculate each set of estimates
    is indicated.
    Constituent
    Aluminum (DIS)
    Arsenic (DIS)
    Arsenic (TR)
    Cadmium (DIS)
    Cadmium (TR)
    Chromium (DIS)
    Chromium (TR)
    Copper (DIS)
    Copper (TR)
    Iron (DIS)
    Iron (TR)
    -Lead (DIS)
    Lead (TRi
    Mercurv (DIS)
    Mercur\ (TR)
    Nickel (DISi
    Nukd iTRi
    /.IIK iDISi
    /IFK iTR>
    Sus Sedmieni
    1990
    Minimum Maximum
    1 .245 1 .434
    0 42.93
    0 42 93
    0.193 4293
    0 42 93
    5.994 44.25
    86 14 91 35
    101 7. 1 199
    1847* 2242*
    1.291 1.291
    18.844 38.706
    1076 4379
    127.3 1676
    0 4 293 -
    0215 4.293
    | IT-! ] 11 1
    -i-l-;-; -l-T g
    98 3 4151
    580 1 ". "75 9*
    K03.644 900.626
    1991
    Minimum
    673.2
    0
    0
    1896
    0
    4589
    73.37
    45.27
    85.24*
    1.156
    12.247
    1096
    6481
    1 238
    2061
    90 53
    1390
    102"
    345 3"
    144.07"*
    Maximum
    792.5
    26.51
    26.51
    26.51
    26.51
    26.51
    82.63
    54.38
    105.4*
    1.167
    1.8.886
    26.95
    8679
    3 270
    4039
    90 53
    t7()6
    273 7
    473 2*
    453.861
    1992
    Minimum
    827.8
    5.206
    0
    . • 1.610
    0
    43.41*
    63.55*
    43.07
    60.3 I
    7.541*
    17.100
    7037
    41.66
    0843
    0.315
    216.3
    1467
    106.7
    3486'
    418.390
    Maximum
    993.8
    21 09
    31.81
    4.661
    31.81
    50.39*
    74.43*
    49.94
    71.35
    7.553*
    28.919
    14.22
    52.90
    0.843
    •3.397
    2 1 6.3
    1904
    169.8
    452.9
    476.767
    Model
    , AMLE
    II
    II
    11
    II
    II
    II
    AMLE
    AMLE
    II
    AMLE
    II
    AMLE
    II
    II
    II
    AMLE
    II
    AMLE
    AMLE
    Notes  DIS - dissohed load
           TR = total recoverable load
           II  = Interpolation - Integration model
           * = loads are suspect, based on quaht\  assurance results
    Metal ana Organic Loads Discussion
    139
    

    -------
             
             0.
    
             1/5
             ฃ
             cc
    
    
    
           Si
           (U •*•
           o
             •o
             c
             en
             01
             3
             O
                  800
                  700
    600  -
    500 -
    400 -
                 300  -
    200 -
                 100 -
                               (a)   Total-Recoverable  Metal  Loads
                             1990
                                              1991
                                                                1992
                 500
                                   (b)  Dissolved  Metal  Loads
                            1 990
                                             1991
                                                              1992
    Metal 'and Organic Loads Discussion
                                                                            140
    

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     Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report
    
     Greatest loads over the three-year period were observed in  1990, corresponding to the year of
     greatest  discharge.  Dissolved Cr, Ni, and  Fe were the only exceptions, with  their greatest
     transport occurring in  1992.  Load estimates calculated for dissolved Cr  and Fe  werenot
     considered valid, however, due to the suspect water quality data that was  used to estimate them.
    
     There are several limitations associated with estimating toxic constituent loads.  First, calculating
     loads for metals is always difficult due to high censoring and multiple reporting limits within the
     data base. Second, due to high censoring, modeling of these  constituents  in terms  of hydrologic
     variables such as  discharge,  or seasonalm. is often impossible.  Third, it is difficult to collect
     representative river samples for metals with concentrations in the parts per trillion range.  As a
     result  of the ultra clean  study  in  1992. error associated  with these  limitations has  been
     significantly  reduced, and load estimates have been improved.
    
     Metal Loads Discussion • James River
    
     Load estimates for the James River for the 1990-92 sampling period are given in Table 41. Bar
     graph summaries of the maximum annual load estimates for  1990-92 sre presented in Figure 51
     for total-recoverable and dissolved Cr. Cu. Pb. and Zn.
    
     The adoption of  ultra  clean sampling procedures and  lowered quantitation  levels in  1992
     improved load estimates for some constituents.  Two criteria used to determine  if load estimates
     for a particular constituent were  improved included: (1) whether  concentration  data for the
     constituent were improved in 1992  as  a result of the  ultra clean study: and/or (2) if the
     upper-bound  load estimate for the constituent  was minimized due to lower quantitation levels in
     1992.  Based on these criteria, load estimates  were  improved in  1992  for total-recoverable As,
     Cu. Pb and Zn. and dissolved As, Cd. Cr, Cu. Pb, and Zn.  Although the quality of dissolved Cr
     and Cd data is considered suspect, based on the lower ranges of concentration values in  1992,
     the loads for  these constituents were also improved.
    
     Generalh, the program changes in 1992 served to either  lower the level  of quantitation and/or
     improve  the analytical accuracy for a  specific constituent. Therefore, for these constituents, the
     ranges oi load  estimates for  1992 are general!)  smaller and the  estimates are  presumed  to be
     closer to  the true values than those for the 1990-91 period.
    
     Because  the .load estimates were improved for a number of constituents in 1992. the validity of
     the 1990-91 load estimates must be determined  The validity  of 1990-91 load estimates is based
     on an assessment of the 1990-91  water quality data  discussed previously.  Results suggest that
     1990-91 load  estimates are considered \alid tor total-recoverable As, Cd, Cu, Cr, Pb and Zn, and
     dissolved As,  Cu.  Pb. and  Zn. Load estimates which may be considered suspect due  to data
     quality include dissolved Cr and Cd  Load estimates tor these constituents should be considered
     upvvardh biased estimates of the true  load
    Menu and Organic Loads Discussion
    

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    Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report
    Table 41. Range in James River fall line load estimates for 1990 to
    thousands of kilograms per year. The modeling technique used to calculate
    is indicated.
    1990
    Constituent
    Aluminum (DIS)
    Arsenic (DIS)
    Arsenic (TR)
    Cadmium (DIS)
    Cadmium (TR)
    Chromium (DIS)
    Chromium (TR)-
    Copper (DIS)
    Copper (TR )
    Iron (DIS >
    Lead (DIS)
    Lead (TR)
    Mercur\
    Nickel (DIS)
    Nickel (TR)
    ZIIK iDISi
    ZIIK iTR.
    Sus Sediment
    Minimum
    392
    NM
    0
    NM
    0
    209
    22.3
    11.8 •
    44.8
    683
    3 77
    536
    008
    6.98
    21 0
    663
    245
    576.0()fi
    Maximum
    530
    NM
    622
    NM
    749
    3 72
    342
    154
    64.4
    1 290
    8 66
    81.0
    74si
    111 '
    289
    469
    461
    700.000
    1991
    Minimum
    378
    NM
    0
    NM
    0
    3.98
    12.6
    12.5
    38.9
    868
    544
    489
    .006
    570
    187
    609
    150
    465.00(1
    Maximum
    424
    NM
    7.49
    • ' NM
    6.22
    5.74
    16.5
    15.2
    49.1
    1340
    8.25
    67.2
    .622
    737
    230
    577
    193
    554.000
    1992. Units arc- in
    each set of estimates
    1992
    Minimum
    729
    0
    .- o
    .519
    0
    .84
    30.7
    11.8
    22.4
    1490
    11.8
    24.5
    .024
    4.80
    25.0
    30.7
    93.4
    669.000
    Maximum
    949
    3.85
    6.43
    1.13
    6.43
    3.04
    44.2
    19.6
    28.2
    .1940
    5.45
    34.5
    .643
    6.87
    •' 37.5
    30.7
    118
    892,000
    Mpdel
    AMLE
    II
    II
    11
    II
    AMLE
    AMLE
    AMLE
    AMLE
    AMLE
    II
    AMLE
    II
    AMLE
    AMLE
    II
    AMLE
    AMLE
    Notes   DIS = dissoUed load
           TR = total recoverable load
          • II = Interpolation - Integration model
    Me ml and Organic Loads Discussion
    142
    

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    Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report
    
    
    Figure 51.   Annual loading estimates of (a) total recoverable and (b) dissolved chromium,
    
    copper, lead, and zinc during 1990-1992 at the James River fall line station.
                               (a)  Total-Recoverable  Metal   Loads
            0)
            a.
            E
            CO
          re
          o
            in
            TJ
            C
            CO
            V)
            3
            o
            -C
                 500
                 400
                 300 -
                 200 -
    100 -
                              1990
                                    1991
    1992
            CO
            0)
            0>
            Q.
            C
            O
          CO
          o
            c
            CO
            3
            O
                                    (b)  Dissolved  Metal  Loads
                              1990
                                    1991
    1992
    Meiai ana Organic Loads Discussion
                                                                     143
    

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     Chesapeake Bay Fall Line Toxics Monitoring Program:  J992 Final Report
    
     Metal Loads Discussion - Potomac River
    
     A general statement can be made  about the metals loads and censored data.  The greater the
     number of observations below the QL value for any metal, the larger the range of possible loads.
     However, the fact that in some cases there is only one value for the load does not imply that that
     value is a highly accurate estimate of the load.   One should keep in mind that, although  the
     loadings during storms can be estimated fairly accurately  from the average flow-weighted storm
     concentration and the total stormflow (as has been done for this report), the loadings for baseflow
     are based on one baseflow sample analysis per month.  The collection of fewer samples leads to
     a higher  level  of uncertainty associated  with load computations!   These limitations  can be
     overcome by more frequent baseflow sampling, and/or a longer-term sampling effort wherein the
     average loadings over a period of  years may give a better approximation of the true baseflow
     loadings.
    
     Arsenic: As can be seen in Figure  31 and Table 22. the range of loads estimated for Arsenic is
     large. This is due to -the fact that As was never detected above the QL in any of the samples (see
     Table 15). The uncertainty associated with the  value of the constituent concentration, therefore,
     leads to larger ranges of possible loads.  The low loading estimates are all zero, because to obtain
     these all values below the  QL  were  set to zero.   The high As  loads expected varied between
     about 950 and  19300 kilograms (Kg) during the monitoring period.  The total estimated load for
     As during the  thirteen month period of the study ranged between 0 and 65200 Kg, with the
     lowest load occurring in October. 1992. Because  As was  never detected above the QL. the high
     loads reflect the flows for the months—small flows resulted in smaller loads, and the  largest flow
     of March.  1993. resulted in the largest load
    
     Cadmium:  Cadmium monthly loads (see Figure 32 and Table  23) have characteristics similar to
     those for As. because Cd, too. was  not found above the QL in any sample. Because the  QL for
     Cd is lower than that for As (initially 2 ug/L and later 1 ug/L, as opposed to 5 ug/L and 4 ug/LJ,
     the computed estimated loads were  similarly lower  The lowest estimated high load occurred in
     October. 1992.  and was 3   Kg, while the highest  load ol 4830 Kg was obtained in March. 1993.
     The total estimated load ior the duration ot the study ranged between 0 and 21600  Kg.
    
     Chromium  Foi the most  pan.  chromium  estimated monthh loads ranged between  0 and  3600
     Kg. except tor the month of-April. 1992. and March. 1993. where the estimated loads were 11234
     and 24204 Kg.  respective!)  (see Figure 33 and Table 24)  Although the range bars appear shorter
    'tor Cr than the\ do tor AN and Cd. this is  actualh not the case and is due to the scale of the y-
     axes hems: different   In  realit\.  the  ranges  (between  the  low and  the  high  estimate) are
     comparable  The high April. 1992. load is due to a Cr concentration of 13.1 ug/L observed  for
     an  eight-da\  storm (April 21-29. 1992). The  high March.  1993, load is due to  two causes—a
     concentration of 13.2 ug/L tor the storm of March  5-11, 1993, combined with high flows for both
     that storm and  the one from March 21-April  1. 1993.  The latter storm, even though it had Cr
     concentrations  in the range of 1-3 ug/L. contributed a large load because of the total stormflow
     ol 2 4x10  m   The month with the  lowest load was. again. October. 1992. The months of April,
     1992. and  March.  1993. accounted  for 66<7r of  the total estimated  high load. The total Cr load
     was m the range of 30600  to 53800 Kg
    
     Copper  The estimated load values for copper show the resuh of having most'values  above the
    
     Mtual and Organic Loads Discussion         .                                     .   144
    

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    Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report
    
    QL (see Figure 34 and Table 25). The estimated ranges show very small deviations between the
    low and high estimates, except for both the months of March.  The high loads range from 400
    to 7200 Kg, except for April,  1992, and March, 1993, when the  loads were about 14300 and
    25100 Kg, respectively. These loads accounted for 58% of the total load. The total copper load
    was in the range of 43500 to 67400 Kg.                                    .  •
    
    Nickel:  The estimated loads observed for nickel ranged from 0 to  17300 Kg (see-Figure 35 and
    Table 26).  Again,  the  months with-high  flows  due to  storms—April.  1992.  and March,
    1993—had much higher loads at 36400 and 57300 Kg, respectively.  It should be noted that all
    observed values for Ni were below the QL.  except for the value  associated with the storm in
    April, 1992. which was 40jag/L. and that for the storm of March 5-11, 1993, which was 22 ug/L.
    This was in spite of the fact that the QL for Ni was lowered from 12 to 8 ug/L in January,  1993.
    The April,  1992, estimated load was about  2.1 times higher than the highest estimated load for
    any other month, and the March. 1993, load  was, similarly, about 3.3 times higher.  It is clear'
    that, just as for the other constituents, the April.  1992, and  March, 1993, storms were responsible
    for a large part of the 'Ni loading to the Potomac during the course of the study.  In fact, these
    two months accounted for 519r of the total load.  The total estimated Ni loads ranged from 59900
    to 184000 Kg.
    
    Lead.   Similar to the results seen, with copper, the estimated loads for lead (Figure 36 and
    Table  27)  had  a narrower range for each month—except  for March, 1992, and the December,
    1992.  to March.  1993. period—due  to the  greater number  of values above the  QL.   The
    variability  is greater than that for copper because there were more values below the QL than for
    copper.  Again, the  loads for April.  1992  (ranging between 8000  and  10000 Kg),  and March,
    199?  (ranging  between  18600  and  32600 Kg), were greater than those for the  other months.
    These loads constitute 51% of the total load. The estimated loads for September, 1992, are lower
    than those for August,  1992, although the  average September flow was twice that of August.
    October.  1992. was  again the month with the lowest load.  The total estimated  loads for lead
    ranged between 41 100 and 82800 Kg.
    
    Selenium.   Selenium was not  detected  above the QL. and this is reflected in  the  low load
    estimates ot zero for each month (see Figure 37 and Table  28)  In fact, apart from the numerical
    \alue'of the load estimates, the characteristics of the monthly loadings are  similar to those for
    As and Cd. which were also  not detected  above the QL.  The total loads ranged between 0 and
    86400.Kg
    
    Zinc  Along with copper and  lead,  zinc was detected most frequently (Table 15).  For most
    months, with the exception of April. 1992 and March, 1993, the estimated loads ranged between
    0 and  27400 Kg (see Figure  38 and Table 29).  April. 1992, estimated  loads were in  the range
    of 55900 Kg. and  March. 1993. loads were in the range of 139300 Kg.  The total loads for Zn
    were from 268900 to 354200 Kg.  The months of April, 1992, and March. 1993, contributed 55%
    of the  total  load during  the period   A  large  portion  of this  was due to the storm average
    concentrations  ot 63 ug/L (April 21-2C^. 1W2) and 56 ug/L (March 5-11. 1993).
    Meuil and Organic Loads Discussion                                        •       '  145
    

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    Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report
    
    •Total Load Estimates
    
    Figure 39 and Table 30 present the total load estimates for the metals monitored.  These load
    estimates are for the 12-month period of April, 1992, to March, 1993.  It can be seen that the
    load for Zn  was the highest, followed by that of Ni.  The loading values for most of the other
    metals were relatively close to each other in the 50000 to 75000 Kg range.  Cd had the lowest
    estimated load of 19000 Kg, and this was due to the fact that it was never detected, even when
    the QL was lowered from 2.0 to  1.0-u.g/L.  Although .the load for  Ni was quite'high, the
    uncertainty  associated  with the estimates  was  also the highest, inasmuch as  all  observed
    concentrations,  except two. were below the QL.  The uncertainty in the estimate for Zri was
    somewhat less.   The best estimate was obtained  for copper,  because only  four measured
    concentrations,  all baseflou. were below the'QL (see Table 15).' In most cases, except when all
    measured concentrations were below the QL (i.e., for As. Cd and Se), the storms of April 21-29,
    1992. and those of March 5-11 and March 21-April  1. 1993, contributed a large fraction of the
    total load for the metal.  This  fraction ranged from 51  to 66%.  This may perhaps indicate that,
    although it  is important to perform more  frequent  baseflow  sampling, the greater degree of
    accuracy obtained in estimating the loads may not have much effect on the total  loads because
    of the overwhelming nature of the loads thai occur during large storms.
    
    Organic Loads Discussion - Susquehanna,  James and Potomac Rivers
    
    Estimates of monthly pesticide. PCB and PAH loads for each tributary  in the fall line study are
    listed in Table 31-Table 39. The monthly loads were estimated separately for the dissolved and
    paniculate phases.  Estimated  loads in these tables were calculated from both the maximum and
    minimum daily  fluxes summed for each montn providing maximum and minimum load estimates.
    Zero loads represent  minimum values that \\ere calculated assuming that there was  no existing
    level (i.e..  0 ng/L) of contaminant m the  fluvial sample'when the measured value was 
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     •Chesapeake Bay Fall Line Toxics Monitoring Program: ,1992 Final Report
    
     ' same compounds occurred in April for the James River.  James River loads appeared to be more
      discharge dominated than the other rivers, possibly because lesser amounts of these pesticides
      are used in the basin relative to the other river basins.  The concentrations of these pesticides
      were the lowest in  the James River fluvial samples.   The maximum monthly loads for the
      Susquehanna and Potomac Rivers occurred  during the period of heaviest pesticide application.
    
      The organochlorine compound loads had a different temporal profile than the organonitrogen and
      organophosphorus compounds in some instances.  In the Susquehanna River, the greatest loads
      occurred in April for both the dissolved and paniculate phases showing dominance to flow and
      are  contrasted  to  the organonitrogen  and  organophosphorus  loads  in this'  river.   The
    .  organochlorine compounds are  not  intentionally applied  in  basin  and  loads  appeared -to  be
      discharge dominated. However, in contrast to this trend the PCB loads were the greatest during
      June. July, and August.  In the Potomac River, the organochlorine loads were the greatest du'ring
      June, similar to  the pattern  shown  for the organonitrogen and organophosphorus pesticides.
      Discharge in the Potomac River was as high in June as it was during the spring months of March
      and  April.   In the James River,  the organochlorine and organonitrogen loads were both at the
      highest levels during April-due to the coincidence of the highest discharge in the river.
    
      Loadings of the organochlorine pesticides  were seldom  greater than 1  kg/month,  with the
      exception May and June loadings. Both the paniculate and  dissolved phases are  important in the
      fluvial transport of the organochlorine pesticides.  The permethrins, fenvalerates, and 4,4'-DDT
      were not detected in any of the fluvial samples from the fall line study, and consequently there
      was no estimated loading  for each.  Zero  monthly  loads  were much more common for the
      organochlorine compounds than  for the organonitrogen and phosphorus pesticides
    
      PCB  loadings in the Potomac River were higher in the  spring  and  early summer than in late
      summer Unlike the organonitrogen and organochlorine pesticides, PCB  loadings were the largest
      in March, especially in the paniculate phase of the fluvial  samples.
    
      PAH loadings were the highest during the spring months  and during storm events.  Naphthalene
      uas  the predominant PAH in  the dissolved phase load while fluoranthene and benz( a (anthracene
      were the predominant PAHs  m the paniculate phase load for all of the fall line locations.
      Metal anil Organit  Loads Discussion                                               •   547
    

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    Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report
    
    RECOMMENDATIONS
    
    Metals Program
    
    Several pieces of information must still be obtained to further understand the nature and transport
    of toxic substances entering the Chesapeake Bay from its major tributaries. Future fall line toxics
    monitoring programs must include:  (1) improved Susquehanna River Potomac and James load
    estimates, given their potential impact on Bay water quality; (2) determination of the impact that
    "total", "total- recoverable" and "dissolved" concentration has on load estimates; (3) determination'
    of the concentration of toxic  chemicals in Susquehanna River bed sediments, behind Conowingo
    Dam, that will be transported during major.storm  events, and;.(4) determination of the toxic
    loadings from  Bay watersheds with different land uses.
    
    Load estimates calculated for the Susquehanna River must continue to be improved given their
    potential impact  on Bay water quality. The Susquehanna River contributes  an average of  50
    percent  of the  freshwater inflow to the Chesapeake Bay annually. A long-term record of water
    quality data is  needed to continue to refine the load estimates.  The information may  also prove
    useful in the future for calibration of the Chesapeake Bay Watershed Model  and,  hence, for
    prediction of the future environment of the Bay.
    
    An initial comparison of total versus total-recoverable metal concentration was made in 1992 at
    the Susquehanna River station.  "Total" refers to the complete dissolution of metals  associated
    with  sediment in a water sample. "Total-recoverable" concentration refers to the acid-extractable
    fraction of metals associated with sediment in a water sample.  This initial study revealed that
    constituents previously undetected using total-recoverable analysis can be detected in ambient
    concentration using total analysis. These results suggest that monitoring of the total concentration
    of metals would provide a means of estimating loads for previously undetected toxic constituents
    and  that load  estimates could  be comparec  to  varying sources  (atmospheric, point source).
    However,  the value of assessing non-labile fractions may be questionable. As well as assessing
    the impact that total versus  total-recoverable  concentration  has on load  estimates, the  impact
    dissolved concentration  has  on  load estimates must also  be assessed. . The dissolved fraction
    represents n large portion- of the  total  meta!  m  a water sample for  many constituents at the
    Susquehanna River station.  Because the  dissolved fraction is"readily available to the biota, it
    poses great concern with regard to loading estimates.
    
    Continued monitoring of the  Susquehanna River should include analysis of metals from  bottom
    sediment.  Bottom sediments  can act as a reservoir for many metals and must, therefore, be given
    serious consideration. High flow conditions during large storm events (>400,000 cubic feet per
    second) at  the Susquehanna  River  station cause  scour behind  Conowingo  Dam,  thereby
    transporting toxic-laden sediments to the Bay.   As well  as providing an  historical record  of
    chemical conditions,  the concentration of me:als  in the bottom sediments can provide essential
    mtormation on the transport  of suspended sediment  during major storm events.
    
    The  Potomac  River  at Chain  Bridge offers some  unique characteristics (well-mixed,  narrow
    channel) that allow for effective automated  sampling of the flow in a cost-efficient manner.
    Recommendations     .           •                                                     J48
    

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    Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report
    
    The initial phase of monitoring at Chain Bridge on the Potomac has been beneficial in allowing
    for the estimation of  loadings.  However, the question of annual loadings,  complicated by
    variabilities from year to year, cannot yet be answered satisfactorily.  It is recommended that
    baseflow  monitoring continue, perhaps on a more-frequent basis (say, twice to four times per
    month), for another one to two years (for a total of two to three years).  Following that, the
    baseflow  can be monitored less frequently.  However, an effort should be made to monitor all
    storm events, especially the larger ones, because a disproportionate fraction of the total  load in
    any  time  period is due to large  storms.  It is felt that this recommendation will  make more
    prudent use of limited  funds.
    
    The  1990-1992 study has provided information needed to refine the network design for future
    fall line toxic monitoring studies, including adoption  of ultra clean sample-collection techniques
    and development of the toxics-loading model. Results  suggest that a minimum  of two years of
    water quality monitoring  (60 water quality samples) throughout a range of flow conditions is
    necessary to characterize constituent concentration and to estimate  toxic constituent loads. This
    implies that fall line toxics monitoring  can be extended to other Bay tributaries, with varying
    landuse, for a two-year period.  Upon completion of the monitoring period, characterization of
    constituent concentration  and  calculation of toxic loadings to  the  Bay  can be provided.
    Additionally, if future needs  include the assessment  of trends that may  have developed in
    response to toxic-reduction strategies established within the Bay basin, a second term of two-year
    monitoring can be conducted to subsequently assess  trends.
    
    A  tributary that would  provide valuable information  regarding toxic inputs from Bay basins of
    varying" land use would be the Patuxent River.   Land  use in the Patuxent River is rapidly
    becoming urbanized.  Additionally, the basin is contained entirely within Maryland so the  impact
    of controls imposed by the state can  be  directly assessed.  The Patuxent River has an extensive
    historical  data  base  which includes  water  quality data- for nutrients,  dissolved  metals, and
    suspended sediment.
    
    Oryani.cs  Program
    
    Annual  loadings of selected organic  contaminants from the .fall  lines of ma|or tributaries  of
    Chesapeake Ba\ ha\e been  determined, and comparisons can be make among the pathways of
    contaminant fluxes in Chesapeake Ba\   However, the present loading  estimates  from  fluvial
    transport arc burdened  by sizable uncertainties. Individual  recommendations are listed below:
    
    (1 )    Include all tributaries of the Bay (approximately nine) in the fall line toxics monitoring
    program    Although  fluxes have been  determined for three  of the Bay's largest tributaries,
    differences in land use  could substantially  impact  flux  estimates (in  kg/yr/km2), providing
    systematic errors in  the  determination of annual budgets.   All  of  the tributaries could be
    incorporated through a  rotational basis, focusing on one or two tributaries per year.  The present.
    synoptic  approach, which  includes  all the tributaries,  does not use  the same load estimation
    techniques, therefore systematic  variations m  the estimation  of annual loads will be inherent.
    
    (2) Streamline sampling  and analysis.  To help lower the cost of conducting low detection limit
    analyses, fewer samples will need to be collected for organics analysis.  Detection limits continue
    to  decrease, and the  feasibility of collecting  60 samples per-year for analysis  is'diminishing.
    
    Recommendations                                                                     J49
    

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    Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report
    
    Streamlining can be accomplished in several ways:
           (a)  continuous sampling devices should be tested such as the automated sampler at Chain
           Bridge on the Potomac River,
           (b)  semipermeable membrane devices which are deployable in situ to sample dissolved
           phase constituents, and
           (c)  continuous samples could provide time integrated composite  samples, minimizing
           short-term variability in constitiuent concentrations.
    
    (3)  Determine temporal variability in constituent concentrations.  Sampling is conducted twice
    per month, and temporal variability has never been defined.  Temporal variability  could  be
    factored into loading computations to provide more accurate load estimates.
    
    (4)  Invest  efforts to determine linear free energy relationships that exist between dissolved and
    particulate  phase constituent  concentrations. This predictive tool could be  used to minimize the
    number of  phases that need to be  subjected to analysis, because, for example, particulate phase
    concentrations could be estimated given dissolved phase concentrations. This would be extremely
    valuable in conjunction with number 2(b) above.
    Recommendations                                                                    150
    

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    Chesapeake Bay Fall Line Toxics Monitoring'Program:  1992 Final Report
    
    REFERENCES
    
    American Public Health Association. 1992. Standard Methods for the Examination of Water and
    Wastewater, 18th Edition.  Washington, D.C.
    
    Conn, T.A.  1988.  Adjusted Maximum Likelihood Estimation of the Moments of Lognormal
    Populations from Type 1 Censored Samples: U.S. Geological Survey Open-File Report 88-350.
    p. 34..
    
    Cohn, T.A.,. W. G. Baier and E. J. Gilroy.   1992.  Estimating.Fluvial Transport  of Trace
    Constituents Using a Regression Model with Data Subject to Censoring: Proceedings. American
    Statistical Association, p. 9.
    
    Cohn, T.A., Caulder, D.L., Gilroy, E.J., Zynjuk. L.D.. and R.M. Summers.  1991. The Validity
    of 2. Simple Log-linear Model for Estimating Fluvial  Constituent Loads: An Empirical  Study
    Involving Nutrient Loads Entering Chesapeake Bay. Water Resources Research, v. 28.  no. 9. pp.
    2353-2363.
    
    Edwards, T.K., and D.G. Glysson. 1988. Field Methods for Measurement of Fluvial Sediment:
    U.S. Geological Survey Open-File Report 86-531. p. 118
    
    Federal  Register.   October  26.  1984.   Appendix B  to  Part  136.   Volume  49,  No. 209.
    Washington, D.C.
    
    Federal Register.  1984.  Volume 54, No. 97.  Washington.  D.C.
    
    Fishman, M.J., and  L.C. Friedman, Editors.  1989.   Methods for Determination of Inorganic
    Substances  in  Water  and   Fluvial  Sediments.   U.S.  Geological  Survey  Techniques  of
    Water-Resources Investigations Book 5, Chapter A.
    
    Foreman, W.T. and G.D. Foster.  1991.  Isolation of Multiple Classes of Pesticides from Large-
    volume Water Samples Using Solid Phase Extraction Cartridges:  U.S. Geological Survey Open
    File Report 91-4034. pp. 530-533.
    
    Foster.- G.D.  1992.  Chesapeake Bay Fall  Line Loadings Survey: Quality Assurance Plan for
    Organic Contaminants.  Report submitted to the Chesapeake Bay and Special Projects  Program.
    
    Foster,  G.D.,  P.M.  Gates.   W.T  Foreman.  S.W.  McKenzie.  and  F.A. Rinella.    1993.
    Determination of Dissolved-phase Pesticides  in Surface Water  from the  Yakima River Basin,
    Washington.  Using the Goulden  Large-sample  Extractor  and Gas Chromatography/Mass
    Spectrometry.  Environ. Sci.  Technol. (in press. Sept. issue).
    
    Gibbus,  R.   1967.  Amazon  Rjver: Environmental Factors that Control  its  Dissolved and
    Suspended Load.  Science, v. 156, pp.  1734-1737.
    
    Horowitz, A.J.  1985.  A Primer on Trace Metal-sediment Chemistry, U.S.Geological Survey
    Water-supply Paper  84-2277. p. 67.
    
    References         •                                                       '151
    

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    Chesapeake Bay Fall Line Toxics Monitoring Program: 1992 Final Report
    
    Jenne, E.  1968.  Controls of Mn, Fe, Co, Ni,-Cu, and Zn Concentrations in Soils and Water: The
    Significance of Hydrous Mn and Fe Oxides: Advances in  Chemistry Series, v. 73, pp. 337-387.
    Jones, B., and C. Bowser.  1978.  The Mineralogy and Related Chemistry of Lake Sediments.
    In Lerman, A., Editor.  Lakes: Chemistry. Geology. Phvsics.  New York, Springer-Verlag, pp.
    179-235.
    
    Keith, Lawrence H., el al.  1983.  Principles of Environmental  Analysis,  Analytical Chemistry.
    Vol. 55, No, 14.
    
    Krauskopf, K.  1956.  Factors Controlling the Concentration of Thirteen Rare Metals in Sea
    Water: Geochimica et  Cosmochimica Acta. v.  9, pp. 1-32.
    
    Lyman, W.J., W.F. Reehl. and D.H. Rosenblatt,  editors.   Handbook of Chemical  Property
    Estimation Methods:  Environmental Behavior of Organic Compounds.  American  Chemical
    Society, Washington, DC.
    
    Maryland  Department  of the Environment.  1989.  Pesticides Considered from Inclusion in a
    Maryland Surface Water  Monitoring -Program.  Maryland Department of the Environment. Water
    Management Administration, Technical Report No. 111.
    
    Occoquan Watershed Monitoring Laboratory.  May 1990.  Quality Assurance  Project Plan for
    the Potomac River Fall Line Toxic Monitoring Program.  Report submitted to the Chesapeake
    Bay and Special Projects Program.
    
    Pait. A.S., A.E. De Souza and D.R.G. Farrow.   1992. Agricultural Pesticide Use in Costal Areas:
    A National  Summary.   U.S.  Department of Commerce. National Oceanic and  Atmospheric
    Administration.
    
    Prugh. B.J., Easton. F.J..  and D.D. Lynch.  1986. Water Resources Data—Virginia.- Water Year
    1985. Water-Data Report VA-85-1.   U.S. Geological  Survey Resources Division, Richmond,
    Virginia, p. 75
    
    Samiullah, Y.   1990. Prediction oi' the Environmental Fate of Chemicals. Elsevier
    Applied Science Publishers. London, p. 285
    
    Schulz. D.E., G. Petrick.  and J.C. Duinker. 1989. Complete Characterization of Polychlorinated
    Biphenyl Congeners m Commercial Arochlor and Clophen Mixtures By Multidimensional Gas
    Chromatography-electron Capture Detection   Environ. Sci. Technol. 23,  pp. 852-859.
    
    Shan. T.   1992.  Multiresidue Analysis of Organohalogen Contaminants in Tissues of
    Aquatic Organisms. M.S. Thesis. George Mason University.
    
    Skoog, D.A. and J.J. Leary.  1992. Principles of Instrumental Analysis, 4th ed., Saunders College
    Publishing, Fort Worth, TX. p. 700.
    References
    

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     Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report
    
     Squillace,  P.  and  E.M.  Thurman.   1992.   Herbicide  Transport  in  Rivers:  Importance • of
     Hydrology and Geochemistry in Nonpoint-source Contamination.  Environ. Sci. Technol. 26, pp.
     538-545.
    
     Taylor, John K.  1987.  Quality  Assurance  of Chemical Measurements. 3rd Edition.  Lewis
     Publishers, Chelsea,'MI.
    
     Tinsley, I.J.  1979.  Chemical Concepts in Pollutant Behavior. John Wiley & Sons, New York,
     NY, p. 265.      .                  '                 .                        •
    
     U.S. Environmental Protection Agency.  1979.  Methods for Chemical Analysis of Water and
     Wastes.  Cincinnati, Ohio.
    
     U.S. Environmental Protection Agency.   1991.  Methods for the Determination  of Metals  in
     Environmental Samples. EPA/600/4-91/010.  Washington. D.C.
    
     U.S. Environmental Protection Agency.  1994.  Chesapeake Bay Fall  Line Toxics Monitoring
     Program 1992  Interim Report.   Chesapeake Bay  Program Office,  Anapolis. MD,  pending
     publication.
    
     United States Geological  Survey.   1991.  Water Resources Data. Virginia,  Water Year 1991.
     Volume  1. Surface Water  and Surface-Water-Quality  Records.   USGS Water-Data Report
     VA-91-1.
    
     Ward. J.R., and Albert Harr.  1990.  Methods for Collection and Processing of Surface-water and
     Bed-material Samples for Physical and Chemical Analyses:  U.S.  Geological Survey Open-File
     Report 90-140.
    References                     •                                                   153
    

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    Chesapeake Bay Fall Line Toxics Monitoring Program:  1992 Final Report
    
    APPENDICES
    
    
    Appendix A:  Susquehanna River water quality data: January 1990-March 1993
    
    Appendix B:  James River water quality data: January 1990-December 1993
    
    Appendix C:  Susquehanna, James, and Potomac Rivers concentration data for monitored organic
               .  contaminants
    Appendices                                                                     J54
    

    -------
                                                     APPENDIX  A
                                           SUSQUESANNA R AT CONOWINGO, MD
    
    
                          WATER QUALITY  DATA,  CALENDAR YEAR JANUARY 1990 TO DECEMBER 1990
          DATE
    APR
       20. .
     * 20. .
    MAY
        03.
        18.
        19.
        20.
        21.
        23.
      JUN
        13.
        27.
      JUL
        18.
        25.
      AUG
        16.
        29
      SEP
        06
        26
      * 26
      OC7
        - q
        16
        • -I
    
        26.
      NOV
        15
      DEC
        06.
        07
        i 2
        26"
        27
         DATE
     APR
       20
       20
     MAY
       03
       18
       • Q
       23.
     JUN
     AUG
       16
       29
     SEP
       06
       2o
       26
     OC7
       15
       16
    
       26
     NOV
       15.
     DEC
       06.
       07
       12.
       2b.
    
    
    TIME
    
    1200
    1205
    1330
    1330
    1230
    1530
    1230
    1200
    1230
    1125
    1135
    1200
    1130
    1200
    1100
    0945
    0950
    1300
    ::oo
    1103
    1130
    1210
    1135
    1140
    1130
    1200
    120C
    po
    WATER
    WHOLE
    LAB
    (STAND-
    ARD
    UNITS)
    7 9
    --
    ~ i
    " 7
    ^ *
    7 2
    7 o
    7 3
    "• 9
    7 6
    - ' 7
    3
    7 3
    D
    - 3
    "ฐ
    
    ' =
    3
    " 3
    -
    7 3
    - 7
    7 0
    7 7
    7 7
    3 0
    DIS-
    CHARGE,
    INST.
    CUBIC
    FEET
    PER
    SECOND
    62200
    62200
    6110.0
    133000
    39600
    89000
    87900
    88600
    52600
    48300
    79000
    52800
    6400
    53000
    41000
    23000
    26000
    174000
    125000
    78300
    257000
    97600
    164000
    131000
    79400
    147000
    143000
    ALKA-
    LINITY
    WAT WH
    TOT FET
    FIELD
    MG/L .AS
    CAC23
    30
    30
    „ 7
    36
    3 1
    —
    27
    31
    50
    51
    40
    34
    •* o
    4 t*
    „ 5
    -5
    ., 5
    --
    28
    35
    2 1
    37
    47
    33
    35
    38
    32
    TEMPER-
    ATURE
    WATER
    TEMPER-
    ATURE
    
    (DEC C)
    12.0
    12.0
    17.
    18.
    24.
    20.
    17.
    18.
    23.
    25.
    24.
    27.
    •^ T
    2*
    26
    8
    8.
    2
    B'.
    3 .
    3
    j
    7
    6 .
    6 .
    6 .
    5
    ALKA-
    LINITY
    WAT DIS
    TOT IT
    "I ELD
    MG/L .AS
    CAC03
    	
    --
    47
    —
    —
    —
    —
    —
    -_
    --
    --
    --
    --
    
    --
    —
    --
    --
    —
    —
    29
    —
    —
    —
    —
    —
    --
    
    
    0
    0
    0
    5
    0
    5
    0
    0
    0
    0
    s
    0
    3
    G
    0
    0
    3
    0
    0
    0
    0
    0
    0
    0
    0
    
    
    
    
    
    
    AIR
    (DEG
    17.
    17.
    14
    24
    24
    22
    19
    20
    25
    28
    28
    28
    28
    28
    28
    ' Q
    19
    23
    19
    1 Q
    12
    7
    17
    14
    18
    13
    2
    
    .ALKA-
    LINITY
    ' LAB
    (MG/L
    AS
    
    C)
    0
    0
    .0
    .0
    .0
    .0
    .0
    .0
    0
    .0
    .0
    .0
    0
    0
    0
    0
    0
    0
    .0
    0
    .0
    .0
    0
    .0
    .0
    .0
    .0
    
    
    
    
    
    
    CAC03)
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    29
    --
    42
    35
    32
    30
    27
    29
    50
    49 •
    38
    32
    47
    51
    43
    -5
    —
    30
    28
    36
    28
    34
    44
    30
    31
    33
    30
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    BARO-
    METRIC
    PRES-
    SURE TUR-
    (MM
    OF
    EG)
    775
    775
    —
    759
    —
    —
    760
    —
    769
    764
    770
    768
    --
    758
    764
    760
    760
    _-
    771
    772
    760
    773
    765
    768
    768
    778
    786
    
    
    SEDI-
    MENT,
    SUS-
    PENDED
    (MG/L)
    ^5
    —
    13
    ^ c
    18
    37
    23
    15
    10
    
    12
    10
    3
    3
    5
    20
    --
    <.7
    39
    23
    76
    34
    33
    39
    12
    40
    30
    3ID-
    ITY
    (NTU)
    _L
    --
    8.1
    	
    	
    	
    	
    	
    __
    7.2
    -_
    —
    -_
    —
    2.2
    
    --
    __
    —
    —
    38
    --
    __
    —
    —
    —
    
    SEDI-
    MENT,
    DIS-
    CHARGE.
    SUS-
    PENDED
    (T/DAY)
    2520
    --
    2150
    5370
    4360
    8890
    5460
    3590
    1420
    1430
    2560
    1430
    138
    1140
    553
    1510
    
    22100
    13100
    -860
    52700
    8960
    14600
    13700
    2570
    15900
    11600
    SPE-
    CIFIC
    CON-
    DUCT-
    ANCE
    (US/CM)
    173
    173
    —
    185
    ••169
    —
    157
    170
    237
    265
    250
    186
    270
    283
    267
    283
    283
    153
    162
    185
    136
    175
    220
    155
    175
    163
    148
    SED.
    SUSP.
    SIEVE
    DIAM.
    I FINER
    THAN
    .062 MM
    	
    --
    79
    98
    87
    100
    —
    98
    100
    97
    100
    92
    92
    9t>
    98
    86
    --
    99
    99
    98
    99
    98
    97
    99
    98
    98
    98
    SPE-
    CIFIC
    CON-
    DUCT-
    ANCE
    LAB
    (US/CM)
    160
    
    220
    179
    156
    149
    152
    168
    232
    265
    246
    189
    268
    262
    250
    277
    
    168
    154
    136
    128
    164
    208
    156
    163
    156
    146
    
    ALUM-
    INUM,
    DIS-
    SOLVED
    (UG/L
    AS AL)
    30
    40
    40
    50
    20
    40
    30
    20
    60
    30
    30
    30
    40
    30
    20
    30
    20
    50
    30
    20
    50
    50
    50
    3-0
    30
    70
    60
    OXYGEN ,
    DIS-
    SOLVED
    (MG/L)
    11.2
    11.2
    7.9
    9.2
    6.5
    
    9.3
    9.b
    7 7
    6.7
    7.3
    6 . 6
    b 7
    7 6
    0 D
    3 Z
    5 . 2
    ._
    S.a
    9 3
    ii.:
    13 5
    14.0
    13 t>
    13.2
    12.9
    13 3
    
    
    ARSENIC
    DIS-
    SOLVED
    (UG/L
    AS AS)
    	
    —
    <1
    —
    —
    —
    —
    —
    __
    —
    __
    --
    __
    --
    <1
    —
    --
    __
    —
    —
    1
    —
    -_
    —
    —
    —
    —
    PH
    WATER
    WHOLE
    FIELD
    (STAND-
    ARD
    UNITS)
    7 2
    7.2
    7.3
    7 0
    8.1
    6 . i
    6.8
    
    6 7
    / &.
    6 9
    7.0
    7 -
    t> 9
    7 0
    
    7 1
    __
    o.ง
    0
    o 5
    6 ?
    6.3
    6.7
    6 3
    6 . 7
    7 2
    
    
    
    ARSENIC
    TOTAL
    (UG/L
    AS AS)
    <1
    <1
    -_
    ^
    <1
    <1
    <1
    <1
    <1
    <1
    <1
    <1
    <1
    <1
    <1
    <1
    <1
    <1
    <1
    <1
    
    <1
    <1
    <1
    <1
    <1
    <1
        Duplicate samples collected for quality-assurance  purposes.
    

    -------
                                             APPENDIX  A. . .Continued
                                         SUSQUEHANNA R AT CONOWINGO, MD
    
    
                         WATER QUALITY DATA.  CALENDAR YEAR JANUARY 1990 TO DECEMBER  1990
         DATE
    APR
       20.
    •   20.
    MAY
       03.
       18.
    '   19.
       20.
       21.
       23.
    JUN
       13,
       27
    JUL
       18.
       25.
    AUG
       16.
       29.
    SEP
       06.
       26
       26.
    OCT
       15.
      26.
    NOV
    
    DEC
      06
      07
      12.
      26
      27
    CHRO-
    CADMIUM CHRO- MIUM.
    CADMIUM TOTAL MIUM, TOTAL
    DIS- RECOV- DIS- RECOV-
    SOLVED ERABLE SOLVED ERABLE
    (UG/L (UG/L (UG/L (UG/L
    AS CD) AS CD) . AS CR) AS CR)
    <1 <1 2
    <1 <1 2
    
    -------
                                                 APPENDIX  A...Continued
    
    
    
    
    
    
                                             SUSQUZHANNA R AT CONOWINGO, MD
    
    
    
    
                             WATER QUALITY DATA,' CALENDAR YEAk JAMUARY 1991 TO DECEMBER  1991
    
    
    DATE
    
    JAN
    02. .
    03. .
    15. . .
    MAR
    06. ..
    07 . .
    21
    APR
    24. ..
    MAY
    08. ..
    22. .
    JUN
    05. .
    19. ..
    * 19. ..
    JUL
    10. ..
    AU5,
    SEP"
    
    * ii
    OC7
    09
    30.
    NOV
    ' 3
    
    
    
    
    
    DATE
    
    JAN
    02
    3 3
    1 c
    MAR
    36
    37
    2, '
    APR
    24
    MAY
    08
    ~ n
    JUN
    05
    19
    19
    JUL
    •• Q
    AUG
    2 ^
    SEP
    1 1 .
    "" ^
    OCT
    09
    30
    NOV
    
    
    TIME
    
    
    1230
    1110
    1100
    
    1200
    1130
    1100
    
    1030
    
    1000
    .1120
    
    1010
    1015
    1020
    
    1025
    1035
    
    1030
    1035
    
    1030
    1030
    
    1035
    ALKA-
    LINITY
    WAT rlV.
    TCT ~ET
    "TT ฃ
    MG/L~AS
    CAC03
    
    5 ^
    Z 5
    „ 7
    
    -5
    —
    - 4
    
    -9
    
    —
    -2
    
    5 -
    4 q
    49
    
    5 1
    
    60
    
    ^ Q
    59
    
    63
    i-7
    
    DIS-
    CHARGE,
    INST.
    CUBIC
    FEET
    
    SECOND
    
    169000
    181000
    55300
    
    233000
    201000
    72500
    
    73500
    
    66300
    9700
    
    OQQO
    5400
    5400
    
    6200
    6500
    
    4400 .
    -400
    
    4300
    10600
    
    -700
    ALKA-
    LINITY
    WAI DIS
    
    "T"T 3
    MG/L **AS
    CACC3
    
    
    
    - 7
    
    
    
    -3
    
    —
    
    —
    
    
    --
    --
    —
    
    34
    
    
    
    51
    —
    
    —
    o 7
    
    TEMPER-
    ATURE
    WATEK
    (DEG C
    
    A .
    t,
    3.
    
    8.
    8.
    3.
    
    12 .
    
    18.
    23
    
    28.
    27.
    27
    
    29.
    28.
    
    2 7
    27.
    
    20.
    ID
    
    11.
    
    ALKA-
    LINITY
    LAB
    (MG/L
    AS
    CACQ3
    
    3 3
    27
    - o
    
    39
    Zb
    39
    
    -4
    
    38
    .. ^
    
    - ~
    - D
    - 0
    
    49
    
    60
    
    59
    —
    
    62
    60
    
    
    )
    
    0
    0
    0
    
    0
    0
    0
    
    n
    
    0
    3
    
    0
    0
    0
    
    0
    0
    
    0
    0
    
    0
    3
    
    0
    
    
    
    
    
    
    )
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    TEMPER-
    -ATURE
    AIR
    (DEG C)
    
    10.0
    12.0
    12.0
    
    18 0
    15 3
    15 3
    
    15.0
    
    23.0
    25.3
    
    28.0
    22.0
    22.0
    
    28.0
    26.0
    
    27.0
    27 3
    
    5 0
    7 3
    
    6 3
    
    
    SEDI-
    MENT ,
    SUS-
    PENDED
    (MG/L)
    
    i 7
    37
    3
    
    3 3
    5 o
    13
    
    24
    
    ^ A
    6
    
    3
    7
    5
    
    A
    
    6
    
    6
    —
    
    9
    5
    
    BARO-
    METRIC
    PRES-
    SURE
    (MM
    OF
    HG)
    
    773
    774
    771
    ,
    756
    7 c 2
    766
    
    758
    
    773
    768
    
    765
    766
    766
    
    762
    763
    
    763
    763
    
    774
    '771
    
    766
    SEDI-
    MENT.
    DIS-
    CHARGE,
    SUS-
    PENDED
    (T/DAY)
    
    16900
    13100
    1190
    
    20800
    30400
    2540
    
    4760
    
    2510
    157
    
    0 "* A
    102
    73
    
    67
    
    105
    
    71
    —
    
    104
    1-.3
    
    TUR-
    BID-
    ITY
    (NTU)
    
    	
    	
    3.6
    
    —
    —
    3.0
    
    —
    
    3.2
    
    
    —
    —
    SPE-
    SPE- CIFIC
    CIFIC CON-
    CON- DUCT- OXYGEN
    DUCT- ANCE DIS-
    ANCE LAB SOLVE
    (US/CM) (US/CM) (MG/L
    
    192 178 14
    161- 153 14
    PH PH
    WATER WATER
    WHOLE WHOLE
    FIELD LAB
    (STAND- ( STAND -
    D ARD ARD
    ) UNITS) UNITS)
    
    3 "" - 8 ^
    Z 'o . 5 7 -
    260 247 14.0 69 33
    
    215 201 12.
    150 141 12.
    
    Z 7.1 81
    
    205 • 205 12.3 6.7 75
    
    234 219 12.
    
    
    5 7.2 77
    
    194 187 12.0 -- - o
    210 210 9:
    
    254 249 4.
    260 -- 3
    3 72' 74
    
    7.5 76
    
    260 274 3.4 7.3 7 5
    
    2.0
    
    332 334 7.
    ,
    : 6.9 75
    395 -18 5.5 74 75
    
    0.60
    
    390 389 5
    
    3 72 75
    390 -- 5.0 7 -
    
    —
    3. 1
    
    "
    SED
    SUSP
    SIEVE
    DIAM
    : FINER
    THAN
    .062 MM
    
    05
    Q ^
    90
    
    100
    0 q
    99
    
    78
    
    08
    98
    
    qo
    83
    92
    
    93
    
    92
    
    90
    —
    
    04
    94
    
    
    400 402 a.
    410 419 ?
    
    420 -- 9
    
    ALUM-
    INUM. ARSENIC
    
    7s 76
    3 73 73
    
    5 73
    
    'BARIUM,
    TOTAL CADMIUM
    DIS- DIS- ARSENIC SECOV- DIS-
    SOLVED SOLVED TOTAL
    (UG/L (UG/L (UG/L
    ERABLE SOLVED
    (UG/L (UG/L
    AS AL) AS AS) AS AS) AS 3A) AS CD )
    
    20 -- <
    4Q -- <
    20 -- <
    
    40 -- <
    4-0 ~ ~" ^
    20 <1
    
    30 -- <
    
    70 <1 <
    	 	 <
    
    20 -- <
    < 10 — <
    < 10 — <
    
    < 10 — <
    
    20 -- <1
    
    < 10 < 1 <
    < 10 — <
    
    20 -- <
    10
    
    
    — —
    — —
    — —
    
    — —
    — —
    1.0
    
    <100
    
    <100 <1 0
    <100
    
    <100
    100
    <100
    
    <100
    
    100
    
    100 
    -------
                                                 APPENDIX  A. . .Continued
                                             SUSQUEHANNA R AT CONOWINGO, MD
    
    
                             WATER QUALITY DATA,  CALENDAR YEAR JANUARY 1991 TO DECEMBER  1991
        DATE
    JAN
      02.
      03.
      15.
    MAR
      06.
      07
      21.
    APR
      24.
    MAY
      08.
      22.
    JUN
      05.
      19.
      19.
    JUL
      10.
    AUG
      21.
    SEP
    CCT
      09
      30.
    NOV
      13
     JAN
       02
       03
       ' s
     MAR"
       06.
       07.
       21.
     APR
       24.
     MAY
       08
       22
     JUN
    .   05
     SEP
     OCT
       09. .
       30  .
     NOV
    CADMIUM
    TOTAL
    RECOV-
    ERABLE
    (UG/L
    AS CD)
    <1
    <1
    <1
    <1
    <1
    <1
    <1
    <1
    <1
    <1
    <1
    <1
    <1
    <1
    < i
    <1
    <1
    MERCURY
    DIS-
    SOLVED
    t'JG/L
    AS HG)
    --
    <0 1
    --
    3 2
    --
    --
    --
    
    -------
                                                 APPENDIX   A...Continued
                                             SUSOUEHANNA R  AT CONOWINGO.  MD
    
    
                             WATER QUALITY DATA, CALENDAR YEAR JANUARY 1992 TO DECEMBER 1992
        DATE
    MAR
       14.
       15.
       16.
       29
       30.
       31.
    APR
       03.
       22.
       2*
    MAY '
       12.
       19.
    JUN
       19.
    JUL
       15.
    *  15.
    SEP
       02.
    *  02.
    NOV
        DATE
    MAR
      30
      31.
    APR
      33
      22.
      24.
    MAY
      12
      19
    JUN
      ' 9
    JUL
    SEP
      02
    NOV
      25
      30
    
    
    
    
    TIME
    
    1400
    1315
    1300
    1700
    1330
    1400
    1145
    1230
    1100
    1130
    1000
    1345
    1300
    1305
    1030
    1035
    1100
    1330
    1400
    ALKA-
    LINITY
    ^AT WK
    TCT ~~""*
    'FIELD"
    MG/L AS
    CAC03
    1 1
    22
    26
    —
    —
    --
    --
    —
    --
    --
    --
    -1
    —
    --
    --
    --
    --
    —
    --
    DIS-
    CHARGE,
    INST.
    CUBIC
    FEET
    PER
    SECOND
    87900
    77900
    80100
    166000
    169000
    120000
    88500
    87700
    88700
    66300
    9160
    22800
    12300
    12300
    36400
    36400
    54700
    70400
    70400
    ALKA-
    LINITY
    WAT 2IS
    TOT IT
    ~*r* 3
    MG/L AS
    CACC3 '
    	
    	
    	
    1 *5
    23'
    30
    23
    27
    34
    46
    --
    --
    = 9
    59
    53
    t 1
    43
    "0
    "" "}
    
    
    TEMPER-
    ATURE
    WATER
    (DEC C)
    6.0
    6.0
    5.0
    7.0
    8.0
    7 0
    7 0
    13.0
    13.0
    16.0
    19.5
    26 0
    28.0
    28. -0
    26.0
    26.0
    6 0
    10 0
    8.0
    
    ALKA-
    LINITY
    LAB
    !MG/L
    AS
    CAC03 )
    30
    32
    28
    T 1
    30
    26
    28
    33
    31
    43
    --
    --
    s 7
    --
    54
    --
    1 -J
    43
    33
    
    
    TEMPER-
    ATURE
    AIR
    (DEG C)
    8.0
    8.0
    4.0
    17.0
    17 0
    16.0
    8.0
    22.0
    21.0
    20.0
    17.0
    23.0
    33 0
    33.0
    21.0
    21.0
    8 0
    1- 3
    7 5
    
    
    SEDI-
    MENT,
    sus-
    OPNDED
    (MG/L)
    28
    24
    ^ 7
    90
    49
    75
    •ป 1
    15
    23
    13
    10
    5
    2
    --
    8
    --
    10
    38
    • 13
    BARO-
    METRIC
    PRES-
    SURE
    (KM
    OF
    HG)
    762
    764
    771
    764
    762
    759
    758
    .764
    ' 759
    768
    --
    —
    758
    758
    770
    770
    "76
    764
    759
    SEDI-
    Mf *J~
    ' DIS1
    CHARGE,
    SUS-
    PENDED
    (T/DAY!
    6650
    5050
    3680
    40200
    22400
    24300
    5260
    3550
    5510
    2330
    247
    308
    66
    --
    786
    --
    1480
    7220
    2470
    
    
    TUR-
    BID-
    ITY
    (NTU)
    	
    	
    	
    	
    	
    	
    --
    	
    --
    * .2
    --
    --
    __
    —
    3 0
    
    ** 1
    —
    "
    SED
    SUSP.
    SIEVE
    DIAM.
    : FINER
    THAN
    062 MM
    97
    "9
    91
    99
    100
    100
    99
    98
    98
    100
    99
    98
    --
    --
    98
    --
    =>9
    100
    97
    SPE- .
    CIFIC
    CON-
    DUCT-
    ANCE
    (US/CMT
    188
    173
    172
    223
    208
    174
    176
    188
    178
    • 218
    208
    205
    310
    310
    272
    272
    197
    181
    148
    
    ALUM-
    INUM.
    DIS-
    SOLVED
    (UG/L
    AS AL)
    30
    20
    30
    70
    50
    30
    20
    110
    230
    20
    80
    70
    20
    50
    40
    ป0
    <10
    <10
    <10
    SPE-
    CIFIC
    CON-
    DUCT-
    ANCE
    LAB
    (US/CM)
    169
    186
    162
    179
    174
    155
    169
    187
    163
    200
    205
    195
    289
    286
    257
    258
    '71
    187
    158
    
    
    ARSENIC
    DIS-
    SOLVED
    (UG/L
    AS AS)
    	
    —
    —
    <0.60
    <0.60
    <0.oO
    <0.60
    <0.60
    <0.60
    <0 .60
    <0 60
    <0 60
    <0.60
    l.ol
    1.15
    <0 . 60
    <0.60
    <0 . 60
    <0.60
    
    
    OXYGEN ,
    DIS-
    SOLVED
    (MG/L)
    12.3
    13.3
    13.2
    12.5
    12.8
    12.7
    12.3
    10.8
    10 3
    10.1
    —
    5.9
    5.2
    C ")
    6 6
    b . 0
    15 1
    " T
    11.3
    
    
    
    ARSENIC
    TOTAL
    (UG/L
    AS AS)
    <1
    <1
    <^
    <1
    <1
    <1
    <1
    <1 .
    <1
    <
    <
    <
    <
    <
    <
    <
    <
    <
    <
    PH
    WATER
    WHOLE
    FIELD
    (STAND-
    ARD
    UNITS)
    6.9
    7 2.
    7 "
    f ' 2
    •j <;
    ?. 1
    •" C
    7 _ i
    7 7
    t e;
    7^3
    7 4
    7 4
    7.4
    7 3
    7 7
    7 ^
    - T
    7 3
    
    BARIUM,
    TOTAL
    RECOV-
    ERABLE
    ;UG/L
    AS BA)
    <100
    <100
    <100
    —
    —
    --
    ._
    —
    --
    „
    --
    --
    __
    --
    --
    --
    -_
    —
    --
    PH
    WATER
    WHOLE
    LAB
    (STAND-
    ARD
    UNITS)
    - 3
    
    7 7
    7 5
    7 ?
    7 ^
    7 9
    7.3
    7 . 3
    3.1
    7 9
    7.5
    7 5
    7 5
    .3
    . 9
    C
    0
    9
    
    
    CADMIUM
    DIS-
    SOLVED
    (UG/L
    AS CD)
    „
    —
    —
    <0.1
    <0. 1
    <0. 1
    <0.1
    <0. 1 .
    <0.1
    <0.1
    1.24
    <0.1
    <0.1
    <0.1
    <0.1
    <0.1
    <0 1
    <0.1
    <0.1
       DupLicaLe samples  collect.ed  for  quality-assurance purposes
    

    -------
                                           APPENDIX  A...Continued
                                        SUSQUEHANNA R AT CONOWINGO, MD
    
    
                             WATER QUALITY DATA, CALENDAR YEAR JANUARY  1992 TO  DECEMBER 1992
        DATE
    MAR
      14.
      15.
      16.
      29.
      30.
    
    APR"'
      03.
      22.
      2*..
    MAY
      12.
      19
    JUN
      19.
    JUL
      15.
      1 C,
    SE?"
      02
      02.
    MOV
      13
      1 t
      20
        DATE
    APR
      J3
    MAY
    
      " g
    JUN"
    NOV
    
    
    
    CADMIUM CHRO-
    TOTA^ MIUM,
    RECOV- DIS-
    ERABLE SOLVED
    (UG/L (UG/L
    AS CD) AS
    <:
    <
    <
    <1.
    <1.
    <1.
    
    —
    --
    
    
    
    COPPER,
    DIS-
    SOLVED
    (UG/L
    AS
    2
    2
    2
    i
    3
    1
    2
    
    2
    
    1
    1
    1.
    1
    0
    ^
    
    
    -
    
    NIC
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    >
    
    CU)
    00
    00
    00
    50
    10
    63
    00
    90
    20
    45
    18
    19
    12
    07
    97
    ?5
    15
    5 ^
    * /
    
    
    AL'
    RECOV-
    ERABLE
    ( U
    AS
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    G
    
    
    
    
    -
    -
    -
    -
    -
    -
    -
    -
    -
    -
    -
    -
    -
    -
    -
    -
    i '
    NI)
    6
    ^
    7
    -
    -
    -
    -
    -
    -
    -
    -
    -
    -
    -
    -
    -
    -
    -
    -
    
    COPPER.
    TOTAL IRON ,
    RECOV- DIS-
    ERABLE SOLVED
    (UG/L (UG/L
    AS CU) AS FE)
    3
    <1
    < 1 —
    3 . 430
    2 55
    2 310
    1 410
    2 290
    2 430
    i 42
    2 300
    1 120
    1 4
    1 91
    cl 6
    5 18
    2 ~"
    3 540
    2 <3
    
    SILVER,
    SELE- TOTAL
    NIUM RECOV-
    TCTAL ERABLE
    (UG/L (UG/L
    AS SE) AS AG)
    <1 <1
    c i < i
    c 1 < i
    — —
    — —
    --
    --
    — —
    --
    --
    --
    --
    --
    --
    --
    --
    --
    — —
    --
    
    IRON,
    TOTAL
    RECOV-
    ERABLE
    (UG/L
    AS FE)
    '1100
    900
    640
    
    —
    --
    __
    —
    —
    __
    —
    --
    —
    —
    _-
    --
    _-
    —
    
    STRON-
    TIUM.
    TOTAL
    RECOV-
    ERABLE
    (UG/L
    'AS SR)
    110
    70
    50
    —
    —
    --
    --
    —
    -.-
    --
    --
    --
    --
    --
    __
    --
    --
    —
    --
    
    LEAD,
    
    
    DIS-
    SOLVED
    (UG/L
    AS FB
    
    -------
                        APPENDIX  A...Continued
                    SUSQUEHANNA R AT CONOWINGO, MD
    
    
    
    
    WATER QUALITY DATA, CALENDAR YEAR JANUARY  1993 'TO MARCH  1993
    
    
    
    
    DATE
    
    JAN
    05. ..
    08. .
    MAR
    11. .
    25
    27. .
    28..
    30.
    31. . .
    31. . .
    
    
    
    
    
    DATE
    
    JAN
    05
    08. ..
    MAR
    
    25 '
    27
    28. ..
    30
    31. .
    31 .
    
    
    
    
    DATE
    
    JAN
    05.
    08.
    MAR
    11. .
    25.
    27.
    28. ..
    30. ..
    31.
    31.
    
    
    
    
    TIME
    
    
    1430
    1300
    
    1AOO
    1130
    12*5
    1330
    1645
    : 0145
    1400
    
    ALKA-
    LINITY
    LAB
    (MG/L
    AS
    CAC03 )
    
    —
    28
    
    46
    
    39
    40
    27
    *> C
    23
    
    COPPER
    TOTAL
    RECOV-
    ERABLE
    (UG/L
    AS CU)
    
    -)
    5
    
    2
    <1
    2
    
    a
    it
    T
    DIS-
    CHARGE,
    INST.
    CUBIC
    FEET
    PER
    SECOND
    
    95900
    114000
    
    70900
    145000
    162000
    184000
    314000
    321000
    415000
    
    
    SEDI-
    MENT,
    SUS-
    PENDED
    (MG/L)
    
    25
    18
    
    14
    21
    32
    28
    79
    67
    97
    
    IRON.
    DIS-
    SOLVED
    (UG/L
    AS FE)
    
    12
    1*.
    
    13
    * -1
    11
    12
    
    22
    --
    
    
    TEMPER-
    ATURE
    WATER
    CDEG C)
    
    5.0
    6.0
    
    4.0
    5.0
    6.0
    7.0
    7.0
    7.0
    8.0
    SEDI-
    MENT,
    DIE-
    CHARGE,
    SUS-
    PENDED
    (T/DAY)
    
    0470
    5540
    
    2680
    8220
    14000
    13900
    67000
    58100
    109000
    
    IRON.
    TOTAL
    RECOV-
    ERABLE
    .'UG/L
    AS FE)
    
    —
    —
    
    —
    650
    800
    830
    2400
    3000
    3000
    
    
    TEMPER-
    ATURE
    AIR
    (DEG C)
    
    18.0
    9.0
    
    10.0
    9.0
    11.0
    15.0
    16.0
    8.0
    15.0
    SED.
    SUSP.
    SIEVE
    DIAM.
    : FINER
    THAN
    062 MM
    
    99
    96
    
    99
    96
    96
    98
    90
    9ซ
    98
    
    LEAD,
    DIS-
    SOLVED
    ;UG/L
    AS ?S)
    
    0.92
    <0.06
    
    —
    0
    0.65
    <0 60
    
    MERCURY
    TOTAL
    RECOV-
    ERABLE
    (UG/L
    AS HG)
    
    <0. 10
    <0.10
    
    <0. 10
    <0 10
    <0. 10
    <0. 10
    <0.10
    <0. 10
    <0 10
    SPE-
    CIFIC
    CON-
    DUCT-
    ANCE
    (US/CM)
    
    138
    163
    
    290
    270
    225
    220
    160
    165
    146
    
    
    
    ARSENIC
    TOTAL
    (UG/L
    AS AS)
    
    <1
    <1
    
    <1
    <1
    <1
    <1
    <1
    1
    <1
    
    NICKEL,
    DIS-
    SOLVED
    (UG/L
    AS NI)
    
    —
    —
    
    4-
    4
    2
    2
    3
    3
    • 3
    SPE-
    CIFIC
    CON-
    DUCT-
    ANCE
    LAB
    (US/CM)
    
    155
    154
    
    255
    258
    207
    202
    154
    149
    132
    
    
    CADMIUM
    DIS-
    SOLVED
    (UG/L
    AS CD)
    
    0 16
    <0.10
    
    —
    <0.10
    <0 10
    <0.10
    <0. 10
    <0.10
    <0.10
    
    NICKEL,
    TOTAL
    RECOV-
    ERABLE
    (UG/L
    . AS NI)
    
    	
    	
    
    5
    5
    5
    5
    9
    12
    12
    
    
    OXYGEN ,
    DIS-
    SOLVED
    (MG/L)
    
    13.0
    12.9
    
    12.5
    13.0
    13.2
    12. 7
    —
    12.5
    12.3
    
    CADMIUM
    TOTAL
    RECOV-
    ERABLE
    (UG/L
    AS CD)
    
    •^1
    <1
    
    <1
    <1
    <1
    <1
    <1
    <1
    <1
    STRON-
    TIUM,
    TOTAL
    RECOV-
    ERABLE
    (UG/L
    AS SR)
    
    	
    	
    
    130
    100
    100
    80
    70
    60
    60
    PH
    WATER
    WHOLE
    FIELD
    (STAND-
    ARD
    UNITS)
    
    —
    7.9
    
    7 3
    7.3
    j c.
    7'3
    7 3
    7 ' 2
    7 .2
    
    CHRO-
    MIUM.
    DIS-
    SOLVED
    (UG/L
    AS CR)
    
    1. 90
    0 63
    
    —
    <0.20
    0.36
    0.59
    <0 20
    <0.20
    <0.20
    
    ZINC,
    DIS-
    SOLVED
    (UG/L
    AS ZN)
    
    9. 83
    4.ซ5
    
    	
    2.59
    15.06
    8. 06
    4 00
    1. 72
    1.55
    PH
    WATER
    WHOLE
    LAB
    (STAND-
    ARD
    UNITS)
    
    7 ฃ
    7^3
    
    7.6
    T -T
    7 ' 4
    7 u
    7 0
    7.0
    1 '
    CHRO-
    MIUM. .
    TOTAL
    RECOV-
    ERABLE
    (UG/L
    AS CR)
    
    5
    --
    
    <1
    < i
    ^
    1
    3
    <1
    5
    
    ZINC,
    TOTAf.
    RECOV-
    ERABLE
    (UG/L
    AS ZN)
    
    30
    30
    
    10
    <10
    <10
    10
    20
    30
    30
    ALKA-
    LINITY
    WAT DIS
    TOT IT
    FIELD
    MG/L .AS
    CAC03
    
    26
    28
    
    . —
    45
    25
    . 31
    17
    25
    20
    
    
    COPPER,
    DIS-
    SOLVED
    (UG/L
    AS C'J)
    
    1 47
    0 69
    
    —
    0 74
    u 9
    5. 70
    1 24.
    0.36
    0.39
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    
    

    -------
    

    -------
                                                    APPENDIX B
                                            JAMES  RIVER AT CARTERSVILLE, VA
    
                            WATER-QUALITY DATA, CALENDAR YEAR JANUARY 1990 TO DECEMBER 1990
        DATE
    APR
      25. . .
    MAY
      11. ..
      12. ..
      13...
      24. ..
      25. . .
      27. ..
      28..'.
      29...
      30...
      31.. .
    JUN
      01.. .
      01. ..
      02.. .
      03. ..
      27 ...
    JUL
      25.. .
    AUG
      29. ..
    SEP
      26. . .
    OCT
      23...
      24. ..
      25
      26..,
    NOV
      29...
    DEC
      21. ..
      31. ..
                  DIS-
                CHARGE,
                  INST.
                  CUBIC
                  FEET
                  PER
     6390
    
    27800
    16100
    11400
    17800
    13800
    22700
    15300
    37100
    44700
    39700
    
    24100
    24100
    18800
    15600
     3620
    
     3430
    
     2600
    
     1560
    
    42900
    66500
    35800
    19400
    
     5760
    
     4950
    26100
    
    
    
    APER-
    TURE
    UTER '
    EG C)
    19.0
    18.0
    17.5
    17.0
    18.5
    18.0
    19.0
    18.0
    16.5
    17.0
    17.0
    17.5
    17.5
    18.5
    19.5
    26.0
    28.0
    29.0
    .18.5
    15.5
    16.5
    15.5
    14.0
    11.0
    7.5
    9.0
    
    
    
    TEMPER-
    ATURE
    AIR
    (DEG C)
    21.5
    18.5
    9.0
    22.0
    22.5
    21.0
    . 20.0
    18.0
    18.0
    23.0
    19.0
    20.5
    20.5
    20.0
    20.5
    30.0
    26.5
    33.0
    18.5
    24.0
    19.0
    16.0
    13.0
    11.5
    9.0
    15.0
    BARO-
    METRIC
    PRES-
    SURE TUR-
    (MM BID-
    OF ITY
    HG) ' (NTU)
    752 2.7
    755
    758
    745
    750
    765
    752
    760
    746
    747
    757
    757
    757
    757
    752
    760' 2.8
    752
    744 1.4
    745
    750
    749
    752
    753
    753 3.4
    765
    .-
    
    SPE-
    CIFIC
    CON-
    DUCT-
    ANCE
    (US/CM)
    129
    65
    120
    110
    165
    220
    98
    97
    86
    105
    127
    123
    123
    108
    115
    162
    153
    260
    275
    80
    80
    105
    88
    220
    143
    92
    SPE.-
    CIFIC
    CON-
    DUCT- OXYGEN,
    ANCE DIS-
    LAB SOLVED
    (US/CM) (MG/L)
    135 8.7
    7.9
    8.6
    8.9
    8.4
    7.0
    9.3
    9.3
    9.6
    9.2
    9.1
    9.4
    9.4
    9.5
    8.9
    156 7.9
    7.4
    260 7.2
    8.9
    9.0
    8.5
    9.0
    9.8
    220 10.6
    11.7
    11.8
    PH ALKA-
    WATER LINITY .
    WHOLE WAT DIS
    FIELD TOT IT
    (STAND- FIELD
    ARD MG,L AS
    UNITS) CAC03
    7.7 47
    7.0
    7.0
    7.4
    7.5
    7.6
    T -7 	
    7.4
    7.4
    7.0
    7.2
    6.8
    6.8
    7.0
    6.9
    8.2 50
    7.5
    8.3 73
    8.3
    7.3
    ' 6.3
    7.5
    7.4
    7.6 71
    7.7
    6.5
    
    
    SEDI-
    MENT,
    SUS-
    PENDED
    (MG/L)
    11
    472
    . 159
    56
    146
    89
    '748
    142
    246
    182
    197
    --
    133
    83
    87
    7
    7
    5
    1
    --
    230
    272
    115
    6
    6
    89
    

    -------
                          APPENDIX B...Contirtued
                     JAMES RIVER AT CARTERSVILLE, VA
    WATER-QUALITY DATA, CALENDAR YEAR JANUARY 1990 TO DECEMBER 1990
    
    
    
    
    
    DATE
    
    APR
    25...
    MAY
    11.. .
    12...
    13.. .
    24. ..
    25...
    27...
    28. ..
    29. ..
    30.. .
    31. ..
    JUN
    01...
    01. ..
    02...
    03...
    27...
    JUL
    25...
    AUG
    29. ..
    SEP
    26...
    OCT '
    23. . .
    24. . .
    25. ..
    26...
    NOV
    29. . .
    DEC
    21...
    31...
    SED.
    SUSP.
    SIEVE
    DIAM.
    % FINER
    THAN •
    .062 MM
    
    97
    
    87
    94
    97
    92
    98
    90
    94
    97
    99
    85
    
    --
    92
    83
    • 77
    96
    
    96
    
    91
    
    83
    
    --
    97
    92
    91
    
    98
    
    95
    52
    
    ALUM- • CADMIUM CHRO-
    INUM, . ARSENIC BARIUM, CADMIUM TOTAL MIUM,
    DIS- DIS- ARSENIC DIS- - DIS- RECOV- DIS-
    SOLVED SOLVED TOTAL SOLVED SOLVED ERABLE SOLVED
    (UG/L (UG/L (UG/L (UG/L (UG/L (UG/L (UG/L
    AS AL) AS AS) AS AS) AS BA) AS CD) AS CD) AS CR)
    
    30 <1 <1 25 <1.0 <1 <1
    
    120 -- <1 -- -- <1 <1
    60 -r <1 -- — <1 <1
    40 -- <1 — -- <1 <1
    40 -- <1 -- — <1 <1
    70 -- <1 -- -- <1 <[
    190 -- <1 -- — <1 1
    70 -- <1 — -- <\ <[
    170 -- <1 — -- <1 <1
    190 -- <1 — — <1 <1
    70 -- <1 — — <\ <1
    
    40 -- <1 -- -- " <1 <1
    50 -- <1 -- -- <\ <1
    40 -- <1 -- — <1 <1
    50 -- <1 -- — 
    -------
                                             APPENDIX 8...Continued
    
                                        JAMES RIVER AT CARTERSVILLE,  VA
    
                      WATER-QUALITY  DATA,  CALENDAR YEAR JANUARY 1990 TO DECEMBER 1990
                COPPER,                      LEAD,
                 TOTAL     IRON,     LEAD,     TOTAL    MERCURY
                 RECOV-   . DIS-      DIS-     RECOV-     DIS-
                 ERABLE    SOLVED    SOLVED    ERABLE    SOLVED
        DATE     (UG/L     (UG/L     (UG/L     (UG/L     (UG/L
                 AS CU)    AS  FE)    AS  PB)'    AS  PB)    AS  HG)
    
    APR
      25...           4       99       <1        1     <0.1
    MAY
      11...          16     —          1       22.
      12...           3     --         <1        6
      13...           3     --         <1        3
      24...           5     —          1        9
      25...           3     —         <1        3
      27...          24     —   .       1       27
      28...           8     —         <1       12
      29...          12     --         <1       21
      30...          10     --         10       96
      31...          13     --          2       28
    JUN
      01...           4     —          1        4     —
      01...           4     —          2        5     —
      02...           4     —          1        5     —
      03...           3     —         <1        3
      27...           5     —         <1        2
    JUL
      25...           3                 1        1     --
    AUG
      29...           4       50       <1        3     <0.1
    SEP
      26...           3     —          1        2     --
    OCT
      23... '         11  .   —          1       1'8
      24...          14     --          1       22
      25...           9     —          1       17
      26...           7     —         <1        7
    NOV
      29...           3       70        1        1     <0.1
    DEC
      21...           3     —  .        1        1     "
      31...           3     —          1        6     --
    •NICKEL,
    IICKEL, TOTAL SELE-
    DIS- -RECOV- NIUM,
    SOLVED ERABLE TOTAL
    (UG/L (UG/L (UG/L
    AS NI) AS NI) AS SE)
    <1 ' <1
    <1 6 <1
    1 4 <1
    <1 1 <1
    <1 3 <1
    <1 2 <1
    5 18 . <2
    1 6 <1
    1 7 <1
    1 4 <1
    1 5 <1
    1 4 <1
    <1 4 <1
    - <1 4 <1
    <1 3 <1
    < 1 ^ < I
    2 1 <1
    1 1 <1
    2 3 <1
    2 9 <1
    2 7 <1
    1 10 <1
    1 4 <1
    1 2 <1
    1 1 <1
    < 1 "> <\
    ZINC,
    ZINC, TOTAL
    DIS- RECOV-
    SOLVED ERABLE
    (UG/L (UG/L
    AS ZN) AS ZN)
    <3 <10
    <10 60
    <10 30
    <10 10
    <10 20
    <10 20
    <10 90
    <10 40
    <10 80
    <10 40
    <10 40
    <10 30
    <10 30
    <10 30
    <10 20
    6 <10
    ' <10 <10
    <3 <10
    <10 20
    <10 50
    <10 40
    30 40
    ' <10 30
    <3 20
    <10 <10
    10 <10
    

    -------
                          APPENDIX B...Continued
                      JAMES RIVER AT CARTERSVILLE, VA
    WATER-QUALITY DATA, 'CALENDAR YEAR JANUARY  1991 TO DECEMBER  1991
    • DATE
    JAN
    02.. .
    03...
    14. . .
    29...
    FEB
    28.. .
    MAR
    ' 04...
    05...
    07...
    08. ..
    10. ..
    26. ..
    APR
    01...
    03...
    05...
    25...
    MAY
    30. . .
    JUN
    19.. .
    24. ..
    25. ..
    27. ..
    JUL'
    30. . .
    AUG
    22. ..
    SEP
    26. ..
    OCT
    30. . .
    30...
    NOV
    26...
    DEC
    04. . .
    06...
    30. ..
    31...
    DIS-
    CHARGE.
    INST.
    CUBIC
    FEET
    PER
    SECOND
    
    25100 '
    19500
    39500
    7280
    
    7750
    
    15600
    51100
    25000
    21200
    12600
    20700
    
    33500
    19700
    13800
    8170
    
    4110
    
    2280
    •5970
    5840
    3780
    
    15900
    
    2080
    
    2340
    
    1500
    1500
    
    2000
    
    15000
    11500
    13900
    10700
    TEMPER- TEMPER-
    ATURE ATURE
    WATER AIR
    (DEG C) (DEG C)
    
    7
    8
    6
    5
    
    6
    
    12
    11
    15
    9
    8
    11
    
    11
    10
    12
    14
    
    29
    
    26
    25
    25
    25
    
    23
    
    26
    
    21
    
    15
    --
    
    •J
    
    10
    8
    5
    5
    
    .0
    .0
    .0
    .0
    
    .0
    
    .5
    . 5
    .0
    .5
    .0
    .5
    
    .5
    .0
    . 5
    .0
    
    .0
    
    .0
    .0
    .0
    .5
    
    .0
    
    . 5
    
    .0
    
    .5
    .
    
    .0
    
    .5
    .0
    .0
    .5
    
    10
    9
    11
    13
    
    13
    
    11
    18
    12
    9
    10
    13
    
    12
    12
    19
    19
    
    28
    
    22
    23
    22
    24
    
    21
    
    24
    
    19
    
    18
    18
    
    4
    
    6
    5
    10
    1
    
    .0
    . 5
    .0
    .0
    
    .0
    
    .0
    .0
    .5
    .0
    .0
    .0
    
    . 5
    .0
    .0
    .0
    
    .5
    
    .0
    .0
    .0
    .0
    
    . 5 .
    
    .0
    
    .0
    
    .0
    .0
    
    .0
    
    .0
    .0
    .0
    .0
    BARO-
    METRIC
    PRES-
    SURE TUR-
    (MM B'D-
    OF ITY
    HG) (NTU) .
    
    762
    758
    757
    753 4.1
    
    755 4.3
    
    734
    746
    750
    750
    748
    755
    
    753
    763
    768
    752 4.5
    
    760
    
    764
    768
    769
    768 1.5
    
    749 •
    
    765 1.9
    
    749
    
    762
    762
    
    767 1.1
    
    751
    758
    758
    770
    SPE-
    SPE- CIRC
    CIRC CON-
    CON- DUCT- OXYGEN,
    DUCT- ANCE DIS-
    ANCE LAB SOLVED
    (US/CM) (US/CM) (MG/L)
    
    94
    95'
    88
    140 145
    
    121 127
    
    145
    150
    135
    118
    130
    119
    
    115
    109
    120
    159 135
    
    169
    
    171
    185
    170
    204 206
    
    131 — -
    
    205 204
    
    225
    
    305
    
    
    260 272
    
    168
    211
    120
    120
    
    14.4
    • 11.5
    10.4
    12.2
    
    12.6
    
    10.1
    9.8
    11.4
    11.0
    11.6
    10. 1
    
    —
    10.7
    10.9
    9.6
    
    7.2
    
    7.3
    7.2
    7.4
    7.8
    
    6.8
    
    7.7
    
    8.2
    
    9.9
    —
    
    13.2
    
    9.5
    11.6
    12.0
    12.0
    PH ALKA-
    WATER LINITY
    WHOLE WAT DIS SEDI-
    FIELO TOT IT MENT,
    (STAND- FIELD sus-
    ARD MG/L AS. PENDED
    UNITS) CAC03 (MG/L)
    
    7
    7
    7
    7
    
    7
    
    7
    6
    6
    6
    /
    7
    
    6
    7
    7
    7
    
    7
    
    7
    7
    8
    7
    
    7
    
    8
    
    7
    
    3
    --
    
    7
    
    7
    7
    7
    7
    
    .5
    .4
    .1
    .6
    
    .6
    
    .3
    .8
    .7
    .9
    .0
    .6
    
    .9
    .5
    .6
    .6
    
    .8
    
    .4
    .3
    .0
    .6
    
    .1
    
    .1
    
    .8
    
    .1
    
    
    .6
    
    .2
    .6
    .2
    .0
    
    -- ' _ 187
    76
    204
    53 6
    
    41 6
    
    53'
    439
    121
    82
    34
    90
    
    137
    31
    --
    46 9
    
    4
    
    5
    40
    28
    59 10
    
    167
    
    61 3
    
    7
    
    1
    ..
    
    70 2
    
    249
    --
    141
    66
    

    -------
                                        APPENDIX  B...Continued
    
                                   JAMES  RIVER  AT CARTERSVILLE,  VA
    
                  WATER-QUALITY DATA, CALENDAR  YEAR JANUARY  1991  TO  DECEMBER  1991
    DATE
      SED.                                                                   CHRO-
      SUSP.   ALUM-                                       CADMIUM   CHRO-    MIUM,
     SIEVE    INUM,   ARSENIC           BARIUM,  CADMIUM   TOTAL    MIUM,    TOTAL   COPPER,
      DIAM.    DIS--     DIS-   ARSENIC   DIS-      DIS-    RECOV-   OIS-     RECOV-   OIS-
    % FINER   SOLVED   SOLVED   TOTAL   SOLVED    SOLVED   ERABLE   SOLVED   ERABLE   SOLVED
      THAN    (UG/L    (UG/L    (UG/L    (UG/L    (UG/L    (UG/L    (UG/L    (UG/L    (UG/L
    .062'MM   AS AL)   AS AS)   AS AS)   AS BA)   AS CD)   AS CD)   AS CR)   AS CR)   AS CU)
    JAN
    02...
    03...
    14.. .
    29...
    FEB
    28...
    MAR
    04...
    05.. .
    07...
    08...
    10.. .
    26...
    APR
    01. ..
    03.. .
    05...
    25...
    MAY
    30.. .
    JUN
    19.. .
    24.. .
    . 25...
    21 ...
    JUL
    30.. .
    AUG
    22.. .
    SEP
    26...
    OCT
    30.. .
    30.. .
    NOV
    26.. .
    DEC
    04...
    06...
    30...
    31...
    
    84
    65
    89
    85
    
    94
    
    61
    71
    91
    70
    85
    93
    
    72.
    93
    --
    79
    
    91
    
    92
    97
    97
    97
    
    90
    
    95
    
    96
    
    91
    —
    
    100
    
    84
    --
    91
    87
    
    90 -- <1
    50 -- <1
    90 — <1
    30 — <\
    
    <10 <1 <1
    
    20 — <1
    170 — <1
    30 -- <1
    100 ~ <1
    20 -- <1
    30 -- <1
    
    50 -- 
    -------
                                        APPENDIX'S...Continued .
    
                                   JAMES RIVER AT CARTERSVIUE. VA
    
                  WATER-QUALITY DATA, CALENDAR YEAR JANUARY 1991 TO DECEMBER 1991
            COPPER,                     LEAD.                     NICKEL,                      ZINC,
             TOTAL   • IRON,    LEAD,    TOTAL   MERCURY  NICKEL,   TOTAL    SELE-    ZINC,     TOTAL
             RECOV-    DIS-     DIS-    RECOV-    DIS-    DIS-     RECOV-   NIUM,     DIS-     RECOV-
             ERABLE   SOLVED   SOLVED   ERABLE   SOLVED   SOLVED   'ERABLE   TOTAL    SOLVED    ERA8LE
    DATE     (UG/L    (UG/L    (UG/L    '(UG/L    (UG/L    (UG/L    (UG/L    (UG/L    (UG/L     I UG/L
             AS CU)   AS FE)   AS PB)   AS PB)   AS HG)   AS NI)   AS NI)   AS SE)   AS ZN)    AS  ZN)
    JAN
    02...
    03...
    14...
    29...
    FEB
    28. ..
    MAR
    04. ..
    05...
    07...
    08.. .
    10...
    26...
    APR
    01.,..
    03...
    05.. .
    25...
    MAY
    30...
    JUN
    19.. .
    24...
    25...
    27. ..
    JUL
    30...
    AUG
    "22...
    SEP
    26. ..
    OCT
    30...
    30...
    NOV
    26...
    DEC
    04...
    06 . . .•
    30...
    31...
    
    7
    7
    12
    4 -- .
    
    84 . 75
    
    3
    6
    4
    7
    5
    3
    
    5
    5 •
    8
    80
    
    4
    
    7
    9
    7
    •J 	
    
    19 -- •
    
    2 150
    
    3
    
    7
    4
    
    140
    
    ..
    „
    --
    <1
    
    2 11
    1 5
    <1 13
    <1 2
    
    1 13 <0.1
    
    <1 1
    <1 11
    1 ?
    <1 3
    1 3
    1 5
    
    :
    ; i
    3 -5
    1 - <0.1
    
    1 3
    
    1 4
    <1 ')
    i .:
    <1 2
    
    5 33
    
    <1 4 <0.1
    
    <1
    
    
    -------
                             APPENDIX  B...Continued   '
    
    
    
    
    
    
                        JAMES  RIVER AT  CARTERSVILLE,  VA
    
    
    
    
    
    
    .  WATER-QUALITY DATA, CALENDAR YEAR JANUARY  1992  TO DECEMBER  1992
    
    
    DATE
    
    JAN
    05..'.
    06...
    07...
    08...
    29...
    FEE
    18...
    • 19...
    26...
    27
    28...
    29...
    MAR
    02. ..
    04. ..
    APR
    10...
    10. . .
    22. ..
    24...
    24...
    26. ..
    ~)1
    28.. .
    28...
    30...
    MAY
    20.. .
    20...
    JUN
    24. ..
    24. ..
    DIS-
    CHARGE,
    INST.
    CUBIC
    FEET
    PER
    SECOND
    
    17600
    23100
    13900
    10500
    3760
    
    8640
    8050
    12900
    36200
    36200
    21300
    
    12600
    9140
    
    4750
    4750
    ll'lOOO
    80100
    80100
    21800
    17500
    14700
    14700
    9730
    
    11000
    10900
    
    5600
    5600
    TEMPER-
    ATURE
    WATER
    (DEG C)
    
    3.5
    8.0
    7.0
    7.0
    4.0
    
    5.5
    6.0
    8.0
    7.0
    7.0
    9.0
    
    9.0
    10.5
    
    15.0
    15.0
    16.0
    15.5
    15.5
    17.0
    14.0
    13.5
    13.5
    14.0
    
    19.0
    19.0
    
    22.0
    22.0
    TEMPER-
    ATURE
    AIR
    (DEG C)
    
    12.0
    11.0
    13.0
    11.0
    0.0
    
    4.0
    9.0
    6.0
    9.0
    15.0-
    8.0
    
    17.0
    7.0
    
    18.0
    18.0
    27.0
    19.0
    19.0
    17.0
    16.5
    14.5
    14.5
    . 19.0
    
    18.0
    18.0
    
    24.0
    24.0
    BARO-
    METRIC
    PRES-
    SURE
    (MM
    '' OF
    HG)
    
    751
    750
    755
    760
    763
    
    757
    752
    744
    751
    748
    752
    
    759
    763
    
    757
    757
    760
    753
    753
    750
    754
    755
    755
    752
    
    766
    766
    
    749
    749
    SPE-
    SPE- CIFIC
    CIFIC CON-
    TUR- CON- DUCT-
    BID- OUCT- ANCE
    ITY ANCE LAB
    (NTU) (US/CM) (US/CM)
    
    -- ' ' 'ioi
    165
    120
    110
    4.0 167 176
    
    . 237
    235
    28 117 110
    110
    102
    93
    
    115
    121
    
    162
    162 159
    138 144
    85
    85 92
    118 122
    155 131
    135 136
    135
    8.5 155 150
    
    135
    135 134
    
    178 172
    178
    OXYGEN,
    DIS-
    SOLVED
    (MG/L)
    
    10.9
    11.1
    11.2
    11.6
    13.0
    
    11.9
    11.3
    13.8
    12.0
    12.0
    10.8
    
    11.3
    10.6
    
    10.8
    10.8
    10.6
    8.5
    8.5
    8.7
    11.0
    9.8
    9.8
    9:9
    
    8.6
    8.6
    
    8.4
    8.4
    PH
    WATER
    WHOLE
    FIELD
    (STAND-
    ARD
    UNITS)
    
    ".1
    7.4
    7.2
    7.1
    7.4
    
    7 ^
    7.6
    7.1
    7.0
    ' 7.0
    7 ">
    ( • ^
    
    7.3
    7.4
    
    7.7
    / . /
    7.0
    7.0
    7.0
    7.3
    6.9
    6.9
    6.9
    7.5
    
    7.3
    7.3
    
    7.8
    7.8
    ALKA-
    LINITY
    WAT OIS
    TOT IT
    FIELD
    MG, L AS
    CAC03
    
    --
    --
    --
    --
    52
    
    --
    —
    31
    —
    --
    --
    
    --
    --
    
    —
    --
    --
    —
    --
    --
    —
    --
    --
    52
    
    --
    —
    
    --
    --
    

    -------
                          APPENDIX B...Continued
    
    
    
    
    
                     JAMES RIVER AT CARTERSVILLE. VA
    
    
    
    
    
    WATER-QUALITY DATA, CALENDAR YEAR JANUARY 1992 TO DECEMBER 1992
    
    
    
    
    
    DATE
    
    JAN
    05...
    06...
    07...
    08. ..
    29...
    FEE
    18...
    19...
    26...
    27. . .
    28...
    29...
    MAR
    . 02...
    04.. .
    APR
    10...
    10... •
    23...
    24.. .
    24. ..
    ' 26...
    27.. .
    "28...
    28...
    30. ..
    MAY
    20.. .
    20. ..
    JUN
    24...
    .24...
    
    
    SEDI-
    MENT,
    SUS-
    PENDED
    (MG/L)
    
    98
    133
    75
    39
    2
    
    49
    34
    114
    345
    381
    145
    
    36
    20
    
    --
    4
    888
    --
    454
    106
    74
    62
    --
    30
    
    --
    31
    
    --
    -;
    SED.
    SUSP.
    SIEVE
    DIAM.
    % FINER
    THAN
    .062 MM
    
    78
    77
    81
    87
    95
    
    81
    82
    78
    74
    88
    81
    
    85
    86
    
    --
    89
    90
    --
    73
    85
    80
    69
    --
    '85
    
    ' --
    88
    
    --
    -
    
    ALUM- CADMIUM
    INUM, BARIUM, TOTAL
    DIS- ARSENIC DIS- RECOV-
    SOLVED TOTAL SOLVED' ERABLE
    (UG/L. (UG/L (UG/L (UG/L '
    AS AL) AS AS) AS BA) AS CD)
    
    170 <1 — <1
    100 <1 -- <1
    90 <1 -- <1
    <1 -- <1
    <1 - 
    -------
                                    APPENDIX B...Continued
    
                               JAMES RIVER AT CARTERSVILLE, VA
    
              WATER-QUALITY DATA. CALENDAR YEAR JANUARY 1992 TO DECEMBER 1992
    DATE
    JAN
      05...
      06...
      07. ..
      08...
      29.. .
    FEB
      18.. .
      19. . .
      26...
      27...
      28...
      29. ..
    MAR
      02...
      04...
    APR
      10. . .
      10. . .
      23...
      24...
      24...
      26.. .
      27...
      28. ..
      28. ..
    .  30...
    MAY
      20.. .
      20...
    JUN
      24...
      24...
    COPPER.
    TOTAL
    RECOV-
    ERABLE
    (UG/L
    AS CU)
    12
    6
    9
    3
    4
    3
    2
    10
    4
    7
    13
    3
    8
    1
    1
    10
    6
    ->
    •-)
    -)
    2
    —
    3
    <1
    
    IRON,
    DIS-
    SOLVED
    (UG/L
    AS FE)
    __
    --
    --
    '--
    --
    
    200
    --
    --
    --
    --
    --
    —
    110
    200
    --
    140
    380
    310
    270
    —
    56
    --
    200
    
    LEAD,
    DIS-
    SOLVED
    (UG/L
    AS PB)
    1
    --
    2
    —
    --
    —
    --
    --
    --
    --
    --
    --
    <1
    —
    --
    <1
    --
    --
    --
    —
    2
    --
    1
    —
                                            LEAD,            f<
                                            TOTAL   NICKEL,   TOTAL
                                            RECOV-   DIS-
                                            ERABLE   SOLVED
                                            (UG/L    (UG/L    (UG/L
                                            AS P8)   AS NI)
                                             9
                                             9
                                            14
     6
    16
     8
    27
    37
                                            15
                                            10
                                             3
             <1
             
    -------
                          APPENDIX B...Continued
    
    
    
    
    
    
                      JAMES RIVER AT CARTERSVILLE, VA.
    
    
    
    
    
    
    WATER-QUALITY DATA, CALENDAR YEAR JANUARY 1992 TO DECEMBER 1992
    
    
    
    
    DATE
    
    JUL
    22...
    22. ..
    SEP
    03...
    03.. .
    03. ..
    OCT
    28...
    MOV
    23. ..
    23. . .
    25...
    DEC
    1 1 ....
    12. ..
    DIS-
    CHARGE,
    INST.
    CUBIC
    FEET
    PER
    SECOND
    
    1980
    1980
    
    1680
    1580
    —
    
    1750
    
    5340
    5450
    23000
    
    32800
    18200
    
    
    TEMPER-
    ATURE
    WATER
    (DEG C)
    
    29.0
    29.0
    
    25.0
    25.0
    25.0
    
    12.0
    
    11.0
    11.0
    12.0
    
    3.0
    4.0
    
    
    TEMPER-
    ATURE
    AIR
    (DEG C)
    
    25.5
    25.5
    
    24.5
    24.5
    24.5
    
    15.0
    
    20.0
    20.0
    15.5
    
    8.0
    7.0
    BARO-
    METRIC
    PRES-
    SURE
    (MM
    OF
    HG)
    
    760
    760
    
    758
    758
    758
    
    753
    
    750
    750
    760
    
    738
    751
    SPE-
    CIFIC
    TUR- CON-'
    BID- DUCT-
    ITY ANCE
    (NTU) (US/CM)
    
    205
    205
    
    1.0 295
    295
    295
    
    250
    
    165
    5.7 165
    145
    
    88
    95
    SPE-
    CIFIC
    CON-
    DUCT-
    ANCE
    LAB
    (US /CM)
    
    ' 218
    217
    
    291
    288
    291
    
    253
    
    170
    160
    141
    
    84
    89
    
    
    OXYGEN,
    DIS-
    SOLVED
    (MG/L)
    
    6.3
    6.3
    
    7.7
    7.7
    7-7
    
    10.4
    
    10.2
    10.2
    10.2
    
    12.7
    12.4
    PH ALKA-
    WATER LINITY
    WHOLE WAT DIS
    FIELD TOT IT
    (STAND- FIELD
    ARD MG/L AS
    UNITS) CAC03. •
    .
    6.5
    6.5
    
    8.3 77
    8.3
    8.3
    
    8.0
    
    7.8
    7.8 39
    7.4
    
    7.2
    7.2
    

    -------
                                     APPENDIX  B...Continued
    
                                JAMES RIVER  AT CARTERSVILJ.E,  VA
    
              WATER-QUALITY DATA,  CALENDAR  YEAR  JANUARY  1992 TO" DECEMBER 1992
    DATE
    
    
    SEDI-
    MENT,
    SUS-
    PENDED
    (MG/L)
    SED.
    SUSP.
    SIEVE
    DIAM.
    % FINER
    THAN
    .062 MM
    
    ALUM-
    INUM,
    DIS-
    SOLVED
    (UG/L
    AS AL)
    
    
    
    ARSENIC
    TOTAL
    •(UG/L.
    AS AS)
    
    
    BARIUM,
    DIS-
    SOLVED
    (UG/L
    AS BA)
    
    CADMIUM
    TOTAL
    . RECOV-
    ERABLE
    (UG/L
    AS CD)
    
    CHRO-
    MIUM,
    DIS-
    SOLVED
    (UG/L
    AS CR)
    CHRO-
    MIUM,
    TOTAL
    RECOV-
    ERABLE
    (UG/L
    AS CR)
    
    
    COPPER,
    DIS-
    SOLVEP
    (UG/L
    AS CU)
    JUL
    22...
    22...
    SEP
    03...
    03...
    03...
    OCT
    28...
    NOV
    23. . .
    23. . .
    25...
    DEC
    11...
    '12...
    
    3
    --
    
    2
    —
    --
    
    1
    
    14
    14
    165
    
    485
    167
    
    85
    --
    
    83
    —
    --
    
    84
    
    86
    86
    79
    
    73
    91
    
    50
    50
    
    40
    80
    60
    
    <10
    
    110
    20
    660
    
    390
    320
                                                     40
                                                     25
                                                                                 20
                                                                                  1
                                                                                 16
                                                                                 17
                                                                                  5
    

    -------
                           APPENDIX B...Continued
    
                      JAMES RIVER AT CARTERSVILLE, VA
    
     WATER-QUALITY DATA, CALENDAR YEAR JANUARY 1992 TO DECEMBER  1992
    DATE
    COPPER,
     TOTAL    IRON,
     RECOV-    DIS-
     ERABLE   SOLVED
     (UG/L    (UG/L
    LEAD,
     DIS-
    SOLVED
                               LEAD,
                               TCTAL   NICKEL,
                               RECOV-   DIS-
                               ERABLE   SOLVED
    (UG/L ..  (UG/L
    JUL
    22...
    22...
    SEP
    03...
    03. ..
    03. ..
    OCT
    28...
    NOV
    23...
    23...
    25.. .
    DEC
    11. ..
    12...
    
    ->
    3
    
    --
    T
    2
    
    T
    
    1
    --
    2
    
    6
    4
    
    120
    100
    
    43
    92
    88
    
    140
    
    - 380
    120
    890
    
    1100
    800
    
    <1
    • <1
    
    --
    <1
    <1
    
    <1
    
    <1
    --
    4
    
    3
    4
                                        (UG/L
    AS CU)   AS FE)   AS PB)   AS PB)   AS NI)
    IICKEL,
    TOTAL
    RECOV-
    ERABLE
    (UG/L
    AS NI)
    
    SELE-
    NIUM,
    TOTAL
    (UG/L
    AS SE)
    
    ZINC,
    DIS-
    SOLVED
    (UG,L
    AS ZN)
    ZINC,
    TOTAL
    RECOV-
    ERABLE
    (UG/L
    AS ZN)
                                                                                 30
                                                                                 50
                                                                                 30
    

    -------
    DATE
                                                  APPENDIX  B...Continued
    
                                             JAMES  RIVER AT CARTERSVILLE, VA
    
                           WATER-QUALITY DATA, CALENDAR YEAR JANUARY  1993 TO DECEMBER  1993
    DIS-
    CHARGE.
    INST.
    CUBIC
    FEET
    'PER
    SECOND
    
    
    TEMPER-
    ATURE
    WATER
    (DEG G)
    
    
    TEMPER-
    ATURE
    AIR
    (DEG C)
    BARO-
    METRIC
    PRES-
    SURE
    (MM
    OF
    HG)
    
    
    TUR-
    . BID-
    ITY
    (NTU)
    SPE-
    CIFIC
    CON-
    DUCT-
    ANCE
    (US /CM)
    SPE-
    CIFIC
    CON-
    DUCT-
    ANCE
    LAB
    (US /CM)
    
    
    OXYGEN,
    DIS-
    SOLVED
    (MG/L)
    PH
    WATER
    WHOLE
    FIELD
    (STAND-
    ARD
    UNITS)
    ALKA-
    LINITY
    WAT DIS
    TOT IT
    FIELD
    MG/L AS
    'CAC03 •
    
    SEDI-.
    MENT,
    SUS-
    PENDED
    (MG/L) •
    SED.
    SUSP.
    SIEVE
    DIAM.
    •; FINER
    THAN
    .062 MM
    JAN'
    28..
    FEB
    23..
    24. .
    25..
    25..
    
    . 9180
    
    . 20300
    . 25500
    . 20000
    . 20000
    
    3
    
    5
    . 4
    3
    3
    
    .5
    
    .0
    .0
    . 5
    .5
    
    2
    
    3.
    1.
    _ -)
    -2.
    
    .0
    
    .0
    .0
    .0
    .0
    
    757
    
    751
    759
    767
    767
                                                  16
                                                                      160
                                                                              13.4
                                                                                        6.8
    125
    140
    138
    138
    129
    155
    145
    147
    10.4
    12.6
    1Z.8 '
    12.8
    6.6
    6.6
    6.5
    6,5
                                                                                                   39
                                                                                              98
                                                                                             193
                                                                                             105
                                                                                             105
                                                                    92
    
                                                                    66
                                                                    53
                                                                    54
                                                                    54
        DATE
    ALUM-                     CADMIUM
    INUM,         '   BARIUM,    TOTAL
     DIS-   ARSENIC   DIS-     RECOV-
    SOLVED   TOTAL   SOLVED    ERABLE
    (UG/L    (UG/L    (UG,L    (UG/L
    CHRO-
    MIUM,
    TOTAL
    RECOV-
    ERABLE
    (UG/L
    COPPER,             LEAD,            NICKEL,   ZINC,
     TOTAL    IRON,     TOTAL   NICKEL,   TOTAL    TOTAL
     RECOV-     DIS-     RECOV-   DIS-     RECOV-   RECOV-
     ERABLE    SOLVED   ERABLE   SOLVED   ERABLE   ERABLE
     (UG/L    (UG/L     (UG/L    (UG/L    (UG/L    (UG/L
                 AS AL)   AS AS)   AS 8A)   AS CD)   AS CR)   AS CU)   AS FE)    AS PB)   AS NI)   AS NIJ
                                                                                              AS ZN)
    JAN
      28. ..
    FEB
      23. .  .
      24. ..
      25
      25. .  .
       100
    
       450
       380
        60
       260
                 <1
    <1
    
     3
     3
                                                <1
    320
    
    840
    450
    100
    400
    <1       <1
    
    
     3       <1
    
     2-       <1
                                                     13
                                                      3
                                                      10
                                                      30
    
                                                      20
    

    -------
    

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