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
vii
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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
Freq. Det.
0/20
0/21
8/21
17/21
6/21
ป
2/21
0/20
15/21
Range
ug/1
<1-13.2
<2-16
<4-14
<8-40
<15-63
James
Freq. Det
24/25 '
0/26
0/28
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
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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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19 !! ! Ill
1
AB Cd Cr Cu B> Nt Zn
HSusquehanrm H James H Potomac
""
''
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
V
30
-
l-r. III III llm l.i l.i
1
M*m O-OH B-Oil t-Oll DM*- BOT Nm
H Susquehanna James i
I
I
I
I
ป~ P-.
I Potomac
I
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
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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
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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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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.
ซt
*
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2
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40i
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10=
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( '
'
TT..'...................T........... ............ ...........t, .... .
*
"^ ^ * ^^^Ht^
3/6 3/29 4/3 5/12
6/19 7/15
5 Sampling Date, Mar. 1992
Simazine
3> Diazinon -
Prometon
" Alachlor
~~^^^' " ~~^^^fc ' ^ 4Kซ IMM^
9/2 11/18 11/25 1/8
- Jan. 1993
** Atrazine
Avg. QL
e
s
o
C
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e
03
Susquehanna River, Organo-N/P Pest.
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
Malathion
Hexazinone
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.
e
OS
s
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
Aldrin
a-<
Oxychlord.
g-Chlord.
Avg. QL
Susquehanna River, Organochlorines (d)
O\
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
-------
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
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Susquehanna River, Organochlorines (p)
1U=
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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
-------
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
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^o
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2
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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
-------
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*
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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
-------
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
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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
-------
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
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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
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1
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c
4>
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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
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*
+*
e
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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
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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
-------
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
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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
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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
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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
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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
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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
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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
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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
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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
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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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o
Cr
Cr
equip.
blank
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Feb Apr Jun Aug Oct
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Dec
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Water Quality Dam Results
73
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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
_l
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c
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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)
C
o
c
0
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c
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o
4 -
Pb
o Pb equip, blank
2 - o
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Feb Apr Jun Aug Oct
1992-93
quant nation
level
i i i r i
Dec Feb Apr
2.5-
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x
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Pb
o Pb equip, blank
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Jun
Aug Oct
1992-93
Dec Feb
A.
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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as
~ 30-
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1992-93
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1992-93
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quantitation
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Dec Feb Apr
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
u>
c
o
u
c
o
u
20-j
15-
10-
Cr
o Equip, blank
quantitation
level
Feb Apr Jun Aug Oct
1992-93
Dec
Feb
Apr
(b) Dissolved Cr
. Cr |
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x x
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Feb
X
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Apr
Jun
Aug Ocl
1992-93
Dec
Feb
quantitation
level
Apr
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 |
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Q v. ^ X XX
guanMalion
Feb Apr Jun Aug Oct Dec Feb Apr
1992-93
Water Quality Data Results
82
-------
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~
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8-
e ^
o 6-
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Feb Apr Jun Aug Oct Dec Feb Apr
1992-93
Water Quality Data Results
83
-------
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
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1992-93
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Apr- Jun Aug Oct Dec Feb
1992-93
AF
quantitation
level
Water Qualm- Data Results
84
-------
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
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0.29
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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
-------
CN
ON
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,q
a
a
S
T3
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r- TT C rs O
cc rr Tl"
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r- NC ^ c -vt o
rr TJ- 0 0
oc r- ND r- ON
ON rr O rr rr
r- NC ^ r-4 NC O
oc C O
oc r^ NO r^ r* ON
ON rr ON w rr
1- sC ^ - 0
oc 0 C
OC V. OO OO Tf V~,
rr o . . r-- oc TJ
fN r-. Q rr oo O
oc ir oc O ฃ3 v-,
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r-i r- o rs O
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f , oo oo v~, O
^ NC _ r- ON vc
r- r- ^ ^ oc c
r-" r*" TJ r^J O
r*" oC CC v, \C
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r--, r*- rr i C: C
r^i u-, o O
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oc f. \c O
rt v O O
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f-^ n O1 cc ON
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cc r^ ON rr i^-
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= g ฃ S o
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oo
fT \O CM ป"- CM
i/~, CM r^ NO rr
^ 0 r- * v,
O (N ON CM
f- . \C rM r~- r~i
c rM r- NO ฐ
0 r- 25
CM ON
oc r^i CM in
CM O O rr v-,
""' CM V-, 00 VI
C *"< r*". rr ปn
V, CM CM C-J
ir, C c rr in
^ rj v-, oo in
O rr r^, rr CM
ฃ ^
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t r r =5 H
3 U U ^ *-^
a ^ .* u u
4> .^ .y e e
S 2 2 N N
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V",
-------
Ov
ซ
x ^
U
z z
oo
o
SO
Tt
O
S
ง
o
S
*
Ov
es o ฃ !T-
oc O oc
Z Z
g S S
2 z z
S z z
o? 2 ;
-^ (N
ฃ 2 *
oo r- r-
CM rj
oo r- r-
\c TT i/-, c: oc
CM sc c-
^ rj ~ rg
v .
;> 0-
c> c:
~ ac -T oc
^ s
vC O
Csl rt ON OO
O CM sO ^
w-) r*- n-, o
rr, rM
-------
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
ฃ 1t>U -
O
. k.
^
B C
3 Q
3 Pt
2 Zr
1
n-ri
r'
j
3
1
1
ซr-rJ>! BS . M B->T-
/
/
X
/
V
S9>
1
^
^
*~lr-
7
/
\
/t
f
,
.
m ^
^
>
*
*
y
r
f
t
i
S
f
f
f /
' /
""U\i
f m> / B L,
j i>^ IP
p
y
fTi
>
y
VTLl 1 P
7
/
/
X
/
^
Apr May Jun Jul Aug Sep Oct Nov Dec Jan Feb Mar
1992 - 1993
(b) Dissolved Metal Loads
c
o
E
V)
E
n
-------
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
-------
O\
00
as
T3
C
OJ
D.
OJ .
x.
CJ
(N
4) J=
ฃ
VD C O
~
< ฃ
r*i oo oo
-
oo
o
-------
ij
ฃ
re
Tt OC
ฃ r- r^
O O O O oo
S
*
O oc O
rsi C oc cy.
OC C: CM OC
C; O C C O O^ C f O O O P" P-*
r- w. oc v, oc C: CM oc p-o^
0-. <-c I"*-. ปc oc u~, CM oc r-~ r~~
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
c ^D
o
L.
Q) p /"\
Q.
m
ฃ
ฃ 15 -
W O)
o o
^5 J
5 10 -
in
o
c
ซ c -
in ฐ
3
o
**
r- 0 -
US
7
X
/
J
/
^
/
/
I"!
_Li
IT
r;
^
/
/
1
z
7;
/
/
/
\
/
. B Cr
D Cu
S Pb
0 Zn
^
i ;
'
ง ;
H-V-H B-^_M H-J^ J& B~P'
pn
/
'
1
f
; I
' I
; if;
: If-;
B f-':
"n
?
2
^
/
^
^
/
1
B
/
/
/
/
/
/
/
/
^
/
Mar Apr May Jun Jul Aug Sep Ocl Nov Dec Jan Feb
(b) Dissolved Metal Loads
c
o
E
0)
a
in
E
re
o o
ซ .
o .*
tn
T3
C
re
I 1" ' "T
Mar Apr May Jun Jul Aug Sep Oct Nov Dec Jan Feb
Load KesuLts
101
-------
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
-------
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
-------
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
-------
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
E
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
-------
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
-------
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
-------
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
ง roooo
QJ
.0)
OO
>^
~E 5OOO
I
1
1
1
1
llgsg^
I
1
i
gg
i
i
1
1
i
i
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
-------
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
-------
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
-------
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
! ***./'"
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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 - ซป ..... 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-
c
c
o
i 1 o - t
^
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o
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it x*T/ '! '
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80000
60000
4000Q
20000
n
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tfl
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B>
^
(Q
e
3
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w"
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
D) | !
'.= 8 - ' ;
ง . ' ' I \
= ฐ - i \
re ' ' \
' i \
| ป - : j ^
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W . A \
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ei/e- !/ '. ^
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-
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:
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100000
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80000. 5-
?
(Q
60000 *
3
40000 ~
20000
n
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
0
1
c
0>
o
0
levt
40 -
'
20 - f
titation ^ซ
"/ - / *^. . 4 \7"nA^~ W A. '^w " ' ' 1 * . ^ j
1-4, - ~Jฑ*ฃ \- ' A JF^^'^^ป ^-^ *-^ * '- - - * ***^ A "!
(Q
Mar Jun Sep Dec Mar Jun Sep Dec Mar Jun Sep Dec Mar
1990-93
12
(b) Dissolved Pb
120000
1 n -
Discharge
- 100000
c 8 - ' -j 80000
._ . H
1
C
o ~
73 -
^
o
u
2 - i
: -j 60000
r " ^
/I -
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o/a auantitalion ^1 1 _ 'l .-ป..-'-. j.
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;
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aeiv auantnalior, ป. ' ^-A ^~^C/ - - ^ **
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=*ซ , w "ป ' ' ' U
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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 :
c
c 60 - *
o
2
I 40 - ,'
o
c -w
O
ฐ 20 - ^
!;/
^
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AT "|
- 100000
H 80000 8
- 60000 *ง
i 40000 o
20000
0
Mar Jun Sep Dec Mar Jun Sep Dec Mar Jun Sep Dec Mar
1990-93
(b) Dissolved Zn
30 -
25
20
Discharge
C oia Quaniilstior,
O level KiOi
O
- 100000
-i 80000 ฃ
1 B>
H -*
1 "
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-1 40000
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 monthsMarch 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
-------
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 concentrationssuch 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 monthssmall 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 causesa
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 stormsApril. 1992. and March,
1993had 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 monthexcept for March, 1992, and the December,
1992. to March. 1993. perioddue 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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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 DataVirginia.- 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
-------
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
-------
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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6 October Base How 9 920
19 December Slorm 2 740
26 January Base Ha '9 82 5
22 March Base How 1 1 320
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SAMPl_E
VOLUM 1
SAMPLE Liters
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nol analyzcc
c
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1
1
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CCCCCCCCCC 1
cceccecccc
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CCCCCCCCCC !
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