903R96002
CBP/TRS 144/
May 19
1
Chesapeake Bay Fall Line
Toxics Monitoring Program
1994 Final Report
CB 00738
• (
Chesapeake Bay Program
\ Printed on recycled paf
-------
Chesapeake Bay Fall Line
Toxics Monitoring Program
1994 Final Report
Printed by the U.S. Environmental Protection Agency for the Chesapeake Bay Program
-------
ACKNOWLEDGMENTS
This program has been 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 have contributed significantly to the success of this project:
Maryland Department of the Environment
2500 Broening Highway
Baltimore, Maryland 21224
U.S. Geological Survey
Water Resources Division
208 Carroll Building
8600 LaSalle Road
Towson, Maryland 21204
George Mason University
Chemistry Department
Fairfax, Virginia 22030
University of Delaware
College of Marine Studies
700 Pilottown Road
Lewes, Delaware 19958
-------
TABLE OF CONTENTS
LIST OF FIGURES iv
LIST OF TABLES vi
ABSTRACT viii
L INTRODUCTION 1
LI Background 1
L2 Objectives of the Program 2
H. METHODOLOGY 4
ILl Sample Collection 4
ILl.a Site Descriptions and Sampling Strategies 4
ILl.b Suspended Sediments 9
ILl.c Organic Constituents 10
D.l.d Trace Elements 10
n.2 Laboratory Analyses 12
n.2.a Suspended Sediments 12
H.2.b Organic Constituents 12
IL2.c Trace Elements 21
IL2.e Load Estimation Method 24
m. WATER-QUALITY DATA 25
nLl Susquehanna River 25
IILl.a Suspended Sediments 25
IILl.b Organic Constituents 27
m.l.c Trace Elements 46
m.l.d Discussion of Water-Quality Results, Susquehanna River 61
m.2 Tributary Synoptic Study Results 63
m.2.a Suspended Sediments 63
in.2.b Organic Constituents 66
m.2.c Trace Elements 75
m.2.d Discussion of Water-Quality Results, Synoptic Study 80
IV. LOAD ESTIMATES 81
IV.l Monthly and Annual Loads for the Susquehanna River 81
IV.l.a Suspended Sediments 81
IV.l.b Organic Constituents 82
IV.l.c Trace Elements 88
IV.l.d Discussion of Annual Loads for the Susquehanna River 91
11
-------
IV.2 Instantaneous Loads and Yields for the Spring and Fall Tributary Synoptic
Study 92
IV.2.a Suspended Sediments 92
IV.2.D Organic Constituents 93
IV.2.C Trace Elements 105
IV.2.d Discussion of Instantaneous Loads and Yields for the Spring and Fall
Tributary Synoptic Study 116
V. SUMMARY 118
VL SUGGESTIONS FOR FUTURE RESEARCH 120
VIL REFERENCES 123
APPENDIX A: 1994 Suspended Sediment Concentration Data
APPENDIX B: Susquehanna River Fall Line Concentration Data - Organic Constituents
APPENDIX C: 1994 Trace-element Concentration Data
APPENDIX D: Susquehanna River Fall Line Field Blanks - Organic Constituents
APPENDIX E: Tributary Synoptic Study Concentration Data - Organic Constituents
APPENDIX F: Tributary Synoptic Study Field Blanks - Organic Constituents
APPENDIX G: Susquehanna River Fall Line Loads - Organic Constituents
111
-------
LIST OF FIGURES
Figure 1. Map of the entire Chesapeake Bay watershed, showing location of drainage basins and
sampling sites 5
Figure 2. Time-series plot of suspended sediment concentration (mg/L) and streamflow (cfs) at
the Susquehanna River at Conowingo, Maryland, 1990 through 1995 26
Figure 3. Box plots of selected dissolved (dis) and participate (part) trace-element concentration
data collected at the Susquehanna River at Conowingo, Maryland, during the period
February 1994 through January 1995 54
Figure 4 . Time-series plots of mean daily discharge and dissolved and paniculate aluminum and
iron concentration data, collected during February 1994 through January 1995 at the
Susquehanna River at Conowingo, Maryland 56
Figure 5. Time-series plots of mean daily discharge and dissolved and particulate copper and
cadmium concentration data, collected during February 1994 through January 1995 at the
Susquehanna River at Conowingo, Maryland 57
Figure 6. Time-series plots of mean daily discharge and dissolved and particulate nickel and
chromium concentration data, collected during February 1994 through January 1995 at the
Susquehanna River at Conowingo, Maryland 58
Figure 7. Time-series plots of mean daily discharge and dissolved and particulate manganese and
arsenic concentration data, collected during February 1994 through January 1995 at the
Susquehanna River at Conowingo, Maryland 59
Figure 8. Time-series plots of mean daily discharge and dissolved and particulate zinc and lead
concentration data, collected during February 1994 through January 1995 at the
Susquehanna River at Conowingo, Maryland 60
Figure 9. Statistical plots of concentration data for selected dissolved (dis) and particulate (part)
trace elements collected during the Spring and Fall 1994 tributary synoptic studies. ... 77
Figure 10. Annual load estimates for PAH for the Susquehanna River at Conowingo, Maryland,
for the period February 1994 through January 1996 85
Figure 11. Annual load estimates for PCBs for the Susquehanna River at Conowingo, Maryland,
for the period February 1994 through January 1996 86
Figure 12. Annual load estimates for the organochlorines for the Susquehanna River at
Conowingo, Maryland, for the period February 1994 through January 1996 87
Figure 13 . Annual load estimates for total cadmium, chromium, copper, nickel, lead, and zinc for
the Susquehanna River at Conowingo, Maryland, for the period February 1994 through
January 1995 90
Figure 14. Bar graph showing yields (ug/s/km2) of simazine, prometon, and atrazine determined
from stream fall line samples collected during the 1994 spring and fall tributary synoptic
studies 95
Figure 15. Bar graph showing yields (ug/s/km2) of alachlor, metolachlor, and cyanazine
determined from stream fall line samples collected during the 1994 spring and fall tributary
synoptic studies 96
Figure 16. Bar graph showing yields (ug/s/km2) of hexazinone, and dissolved + particulate 2-
methylnaphthalene and 2,6-dimethylnaphthalene determined from stream fall line samples
collected during the 1994 spring and fall tributary synoptic studies 97
IV
-------
Figure 17. Bar graph showing yields (ug/s/km2) of dissolved + paniculate acenaphthylene,
acenaphthene, and fluorene determined from stream fall line samples collected during the
1994 spring and fall tributary synoptic studies 98
Figure 18. Bar graph showing yields (ug/s/km2) of dissolved + paniculate phenanthrene,
fluoranthene, and pyrene determined from stream fall line samples collected during the
1994 spring and fall tributary synoptic studies 99
Figure 19. Bar graph showing yields (ng/s/km2) of dissolved + paniculate chrysene,
benz(a)anthracene, and benzo(a)pyrene determined from stream fall line samples collected
during the 1994 spring and fall tributary synoptic studies 100
Figure 20. Bar graph showing yields (ug/s/km2) of dissolved + paniculate perylene, total-PCBs
(t-PCBs), and hexachlorobenzene (HCB) determined from stream fall line samples
collected during the 1994 spring and fall tributary synoptic studies 101
Figure 21. Bar graph showing yields (ng/s/km2) of dissolved + paniculate p,p'DDE, and alpha-
and fota-BHC determined from stream fall line samples collected during the 1994 spring
and fall tributary synoptic studies 102
Figure 22. Bar graph showing yields (ng/s/km2) of dissolved + paniculate gamma-BBC, and
gamma- and a//?/za-chlordane determined from stream fall line samples collected during
the 1994 spring and fall tributary synoptic studies 103
Figure 23. Bar graph showing yields (jig/s/km2) of dissolved + paniculate dieldrin, o,p'- and p,p-
DDD determined from stream fall line samples collected during the 1994 spring and fall
tributary synoptic studies 104
Figure 24 . Bar graph showing instantaneous total cadmium yields, in micrograms per second per
square kilometer, collected during the 1994 Spring and Fall tributary synoptic studies.
Ill
Figure 25. Bar graph showing instantaneous total chromium yields, in micrograms per second per
square kilometer, collected during the 1994 Spring and Fall tributary synoptic studies.
112
Figure 26. Bar graph showing instantaneous total copper yields, in micrograms per second per
square kilometer, collected during the 1994 Spring and Fall tributary synoptic studies
113
Figure 27. Bar graph showing instantaneous total lead yields, in micrograms per second per
square kilometer, collected during the 1994 Spring and Fall tributary synoptic studies.
114
Figure 28 . Bar graph showing instantaneous total zinc yields, in micrograms per second per
square kilometer, collected during the 1994 Spring and Fall tributary synoptic studies.
, 115
-------
LIST OF TABLES
Table 1. Land use and basin area for the non-tidal portions of the nine major river basins of the
Chesapeake Bay 4
Table 2. Organic constituents, analytical techniques and quantitation limits 14
Table 3. Instrument parameters for GC-ECD and GC/MS analysis 17
Table 4. Analytical techniques and detection limits for the trace elements analyzed for the 1994
Fall Line Toxics Program 22
Table 5. Summary results of standard reference material for trace elements 23
Table 6. Laboratory QA blank concentrations (ng/L) for water analysis 28
Table 7. Laboratory QA blank concentrations (ng/L) for filter analysis 29
Table 8. ClgBPE and GLSE QA spike recoveries for the organo-N/P pesticides and PAH. ... 30
Table 9. GLSE QA spike recoveries for PCBs and organochlorines 31
Table 10. Soxhlet QA spike recoveries for PAH, PCBs, and organochlorines 32
Table 11. Water matrix spike recoveries for the organo-N/P pesticides and PAH 34
Table 12. Water matrix spike recoveries for the PCBs and organochlorines 35
Table 13. Filter matrix spike recoveries for PAH and PCBs 36
Table 14. Filter matrix spike recoveries for the organochlorines 37
Table 15. QA analysis of standard reference sediment for PAH and organochlorines 38
Table 16. QA analysis of standard reference sediment for PCBs 39
Table 17. Sampling parameters for organics in Susquehanna River Fall Line Study 41
Table 18. Summary of organo-N/P pesticide and PAH dissolved phase concentrations measured
in the Susquehanna River at Conowingo, MD 42
Table 19. Summary of PCBs and organochlorine dissolved phase concentrations measured in the
Susquehanna River at Conowingo, MD 43
Table 20. Summary of PAH and PCB paniculate phase concentrations measured in the
Susquehanna River at Conowingo, MD 44
Table 21. Summary of organochlorine particulate phase concentrations measured in the
Susquehanna River at Conowingo, MD 45
Table 22. Quality-assurance criteria for the University of Delaware laboratory 47
Table 23. Dissolved trace-metal field-blank concentration data collected in 1994 at the
Susquehanna River at Conowingo, Maryland 48
Table 24. Dissolved trace-element replicate sample concentration collected in 1994 at the
Susquehanna River at Conowingo, Maryland 50
Table 25. Particulate trace-element replicate sample concentrations collected in 1994 at the
Susquehanna River at Conowingo, Maryland 51
Table 26. Data summaries of trace-element concentrations collected February 1994 through
January 1995 at the Susquehanna River at Conowingo, Maryland 53
Table 28. Data summaries of suspended-sediment concentrations (mg/L) collected at the fall line
river stations for the 1994 Spring and Fall tributary synoptic studies 64
Table 29. Results of the suspended-sediment cross-sectional variability study at each of the nine
fall line synoptic tributaries 65
Table 30. Data summaries of dissolved phase organo-N/P pesticide and PAH concentrations in
samples collected at the fall lines of eight tributaries for the 1994 Spring synoptic study.
67
VI
-------
Table 31. Data summaries of dissolved phase PCB and organochlorine concentrations in samples
collected at the fall lines of eight tributaries for the 1994 Spring synoptic study 68
Table 32. Data summaries ofparticulate phase PAH and PCB concentrations in samples
collected at the fall lines of eight tributaries for the 1994 Spring synoptic study. ...... 69
Table 33. Data summaries of particulate phase organochlorine concentrations in samples
collected at the fall lines of eight tributaries for the 1994 Spring synoptic study 70
Table 34. Data summaries of dissolved phase organo-N/P pesticide and PAH concentrations in
samples collected at the fall lines of eight tributaries for the 1994 Fall synoptic study.
71
Table 35. Data summaries of dissolved phase PCBs and organochlorines concentrations in
samples collected at the fall lines of eight tributaries for the 1994 Fall synoptic study.
72
Table 36. Data summaries of particulate phase PAH and PCBs concentrations in samples
collected at the fall lines of eight tributaries for the 1994 Fall synoptic study 73
Table 37. Data summaries of particulate phase organochlorines concentrations in samples
collected at the fall lines of eight tributaries for the 1994 Fall synoptic study 74
Table 38. Dissolved trace-element field-blank concentration data collected during the Fall 1994
tributary synoptic study 75
Table 39. Data summaries of trace-element concentrations collected at the fall line river stations
for the 1994 Spring tributary synoptic study 78
Table 40. Data summaries of trace-element concentrations collected at the fall line river stations
for the 1994 Fall tributary synoptic study „ 79
Table 41. Annual and monthly loads (February 1994 through January 1995) for suspended
sediment and river discharge for the Susquehanna River at Conowingo, Maryland 82
Table 42. Annual loads or load intervals (February 1994 through January 1995) of total organic
constituents (dissolved + particulate phases) for the fall line of the Susquehanna River.
84
Table 43. Annual and monthly loads (February 1994 through January 1995) of total trace
elements and river discharge for the Susquehanna River at Conowingo, Maryland. ... 89
Table 44. Instantaneous loads and basin yields for suspended sediment collected at the major
tributaries of the Chesapeake Bay, collected in spring (April-May) and fall (late
November) of 1994 92
Table 45. Instantaneous loads of total trace elements collected for the 1994 Spring tributary
synoptic study, and the mean and range of each constituent 106
Table 46. Instantaneous yields of total trace elements collected for the 1994 Spring tributary
synoptic study, and the mean and range of each constituent 107
Table 47. Instantaneous loads of total trace elements collected for the 1994 Fall tributary
synoptic study, and the mean and range for each constituent 109
Table 48. Instantaneous yields of total trace elements and river discharge collected for the 1994
.Fa//tributary synoptic study, and the mean and range of each constituent 110
Table 49. Summary of present status for load estimates on the major Chesapeake Bay tributaries.
120
Table 50. Comparison of fall line loads for Susquehanna River for selected organic constituents
for the March 1992 through February 1993 and February 1994 through January 1995
Chesapeake Bay Fall Line Toxics Monitoring Program load estimates 122
vn
-------
ABSTRACT
The Fall Line Toxics Program for 1994 is a continuation of a long term effort funded by the
USEPA Chesapeake Bay Program and the USGS cooperative program to make accurate load
estimates of contaminants entering the Chesapeake Bay from the non-tidal portion of the watershed.
This program has identified nine major tributaries on which to make fall line load estimates;
combined the non-tidal portions of these tributaries contribute greater than 80% of the freshwater
input to the Bay and hence, have the potential of transporting significant quantities of toxic
constituents to the estuary.
The 1994 Fall Line Toxics Program consisted of two components. First, the Susquehanna
River was sampled from February 1994 through January 1995 during baseflow and stormflow
conditions. Secondly, eight additional tributaries were sampled twice synoptically, once in Spring,
1994 and once in Fall, 1994. This report presents the results of both components.
Samples were analyzed for dissolved and paniculate fractions of trace elements and organic
constituents. Concentration data and extensive quality assurance results are presented. In addition,
monthly and annual loads of trace elements and organic constituents were estimated for the
Susquehanna River. Instantaneous loads and basin yields are presented for each tributary for the
Spring and Fall synoptic study. The report also makes recommendations for further study.
Vlll
-------
L INTRODUCTION
LI Background
The "fall line" of the Chesapeake Bay basin is the geographical boundary between two
physiographic provinces, the Piedmont and the Atlantic Coastal Plain (Thornbury, 1965). This break
in physiography is distinguished by numerous waterfalls and usually coincides with the break between
the tidal and non-tidal portions of the watershed, as well. The term fall line, in this report, will
indicate the landward boundary of tidal effects in tributaries of the Chesapeake Bay watershed,
including tributaries of the Delmarva peninsula. River discharge at the fall line captures loadings from
all point and non-point sources in the contributing portion of the watershed. When compared to
other major sources of toxic contaminants, such as atmospheric deposition and point sources in the
tidal portion of the Bay, fall line loadings have been identified by the 1989 Chesapeake Bay Program's
Toxic Loading Inventory (TLI) as the largest source of toxic contaminants to the Bay estuary. There
is therefore a need to accurately measure the fall line contaminant loads from the major tributaries and
to identify the spatial variability between fall line sites so that an estimate of the contaminant loads
can be made for the entire non-tidal portion of the watershed.
With funding support from the U. S. Environmental Protection Agency's Chesapeake Bay
Program (USEPA-CBP) and the U. S. Geological Survey's (USGS) Cooperative Program, the Fall
Line Toxics Program ran a pilot study in 1990-91 to determine the feasibility of making accurate load
estimates of organic compounds and trace elements for the Susquehanna and James Rivers.
Constituents were analyzed for dissolved and total-recoverable fractions at the USGS National Water
Quality Laboratory (NWQL). Results of the pilot study indicated that concentrations were on the
order of micrograms to nanograms per liter, and that new, improved methods, including ultra-clean
sample-collection and analytical techniques with lower detection limits, would be required to attain
the desired accuracy in load estimates. Since 1992, all samples have been collected using the ultra-
clean techniques developed by Dr. Howard Taylor of the USGS National Research Program (NRP).
Other changes to the program in 1992 included sample collection at the Potomac River fall line, with
total-recoverable trace-element analysis by the Occoquan Watershed Management Laboratory, and
organic compounds analyzed at George Mason University (GMU). Trace elements for the
Susquehanna and James rivers were analyzed by the USGS. In 1993, the primary objective of the Fall
Line Toxics Program was to estimate trace element loads transported by the Susquehanna River only.
Total-recoverable trace elements were still analyzed at the NWQL through 1993. Results for the
1992-93 fall line data are given in the Fall Line Toxics Program 1992 Final Report and 1993 Addenda
to that report.
As detailed in this report, several major revisions to the 1994 Fall Line Toxics Program
occurred. The principle investigating agencies for 1994 were the USGS charged with sample
collection and project management; the University of Delaware (UDE) for trace element analyses;
and GMU with for organic analyses. The Maryland Department of the Environment (MDE) provided
project oversight. All water samples collected for the 1994 program were analyzed for both
paniculate and dissolved concentrations, which when combined, provide an estimate of the total
concentration for each constituent. A total analysis provides a better load estimate for comparison
to other sources in the mass balance which is being prepared by the TLI. The breakdown of the
1
-------
measurements into paniculate and dissolved fractions also allows some interpretation of transport
processes and potential fates for the contaminant loads. In the past, trace elements have been
determined as the "total-recoverable" fraction of the sample, which is analytically defined and thus
difficult to interpret or verify. Organic compounds were analyzed for both the dissolved and
particulate phases, and included forty constituents for the 1994 study.
L2 Objectives of the Program
The objectives of the Fall Line Toxics Program fall within the broader objectives of the
Chesapeake Bay Program's 1989 Chesapeake Bay Basinwide Toxics Reduction Strategy (TRS) The
long-term goal of the basinwide strategy is
"...a Chesapeake Bay free of toxics by reducing or eliminating the input of chemical
contaminants from all controllable sources to levels that result in no toxic or
bioaccumulative impact on the living resources that inhabit the Bay or on human health."
As a starting point to attain this goal, the TRS must establish a current baseline of all
quantifiable sources of contaminant loads into the Bay, and with this information develop a mass
balance that can be used for future modeling efforts and management decisions. The mass balance,
called the Toxics Loading Inventory, will define the "nature, extent, and magnitude of toxic
contaminants within the Bay and its surrounding watershed". The charge from the Chesapeake Bay
Program to the Fall Line Toxics Program has been to estimate loads of suspended sediment and
selected trace elements and organic compounds to the Chesapeake Bay from the non-tidal riverine
sources of the area above the fall line. In 1994, the Fall Line Toxics Program collected daily
stormflow and monthly baseflow data at the Susquehanna River fall line at Conowingo, Maryland,
to determine total annual loads of these constituents. The Susquehanna River was chosen because
it is the largest tributary in the Chesapeake Bay watershed, draining an area of diverse land use. In
order to measure the spatial variability of fall line contaminant loads, eight additional Chesapeake Bay
tributaries were sampled synoptically in 1994; once in the spring and once again in the fall. Thi»
tributary synoptic studies allowed the calculation of instantaneous loads and basin yields for each of
the rivers.
The choice of constituents to measure in this study included the following Chesapeake Bay
Program Toxics of Concern: atrazine, cadmium, chromium, chlordane, copper, lead, the
polychlorinated biphenyls (PCB's), and some polynuclear aromatic hydrocarbons (PAH'S) (EPA
CBP, 1991). However, a total suite of 40 organic compounds and 10 trace elements, as well as
suspended sediment have been included for load estimates. All trace-element and organics samples
were analyzed for both the particulate and dissolved fractions; combined, these measurements provide
an estimate of the total concentration, which is used to estimate the total load for each constituent.
The objectives of the Chesapeake Bay Fall-Line Toxics Program (1994) may be summarized
as the following:
(1) Determine the ambient concentration of suspended sediment and selected trace elements
and organic constituents for baseflow and stormflow conditions at the Susquehanna River fall
-------
line through continued sampling at the Conowingo Dam site. These data were used to
calculate annual total load estimates for the area above the Susquehanna River fall line, and
are also available for comparison to water-quality criteria.
(2) Calculate the monthly and annual load estimates of total suspended sediment and
selected trace elements and organic constituents to the Chesapeake Bay from the
Susquehanna River fall line.
(3) Conduct an analysis of the paniculate phase for the trace elements and organic
compounds, which, when combined with the dissolved fraction, provided a total
concentration for each constituent, and therefore, a more accurate load estimate, which can
be used in a mass balance of the Chesapeake Bay.
(4) Continue to evaluate the quality of data collected by including standard reference
materials, blanks, and triplicate samples.
(5) Twice yearly, once in the spring and once in the fall, the same suite of constituents
measured for the Susquehanna River portion of the study was additionally measured at the
"fall lines" of the Potomac, Patuxent, James, Rappahannock, Pamunkey, Mattaponi,
Choptank, and Nanticoke Rivers. Instantaneous contaminant loads and basin yields were
calculated for each of these sites, providing some measure of the spatial variability of fall line
loads . Results of this synoptic study also identified regions that may require future
management and more intensive study.
-------
IL METHODOLOGY
H.1 Sample Collection
ILl.a Site Descriptions and Sampling Strategies
Figure 1 is a map of the Chesapeake Bay watershed. This watershed covers
approximately 166,000 square kilometers (64,000 square miles) and includes parts of the
states of Delaware, Maryland, New York, Pennsylvania, Virginia, and West Virginia. In 1994,
the Fall Line Program sampled nine separate river basins in the Bay watershed: the
Susquehanna, Potomac, James, Rappahannock, Pamunkey, Mattaponi, Patuxent, Choptank,
and Nanticoke Rivers. The entire watershed for each river, including tidal and non-tidal, and
the approximate location of the fall line, is delineated separately on the map in Figure 1.
Combined these tributaries contribute greater than eighty percent (USGS 1994A; USGS
1994B) of all the freshwater flow from the non-tidal portion of the watershed into the
Chesapeake Bay.
Table 1 presents the breakdown in landuse for each individual basin as delineated in
the EMAPS database (Langland, 1995).
Table 1. Land use and basin area for the non-tidal portions of the nine major river basins of
the Chesapeake Bay. The % Urban category includes cities as well as residential and
municipal properties such as golf courses and private lawns.
River, Sampling Site
Susquehanna River at
Conowingo, Maryland
Potomac River at Chain
Bridge at Washington, D.C.
James River at Cartersville,
Virginia
Rappahannock River near
Fredericksburg, Virginia
Pamunkey River near
Hanover, Virginia
Mattaponi River near
Beulahaville, Virginia
Patuxent River near Bowie,
Maryland
Choptank River near
Greensboro, Maryland
Nanticoke River near
Bridgeville, Delaware
Basin
Area
(km2)
70,160
29,950
16,200
4,132
2,799
1,556
901
293
195
%
Forest
62.3
55.9
71.6
50.3
59.2
68.7
18.9
42.4
NA
%
Agri-
culture
31.2
37.1
23.0
44.4
35.0
28.0
45.9
54.8
NA
%
Urban
4.8
6.1
4.8
4.9
3.4
2.7
35.1
2.6
NA
NA = not available
-------
80*
75'
45'
EXPLANATION
II SUSQUEHANNA
POTOMAC
PATUXENT
CHOPTANK
IAMES
NANTICOKE
RAPPAHANNOCK
MATTAPONI
PAMUNKEY
WATER QUALTTY MONTTORING STATION
PENNSYLVANIA
WEST
VIRGINIA
NEW YORK%
MARYLAND
0 26 50 MILES
0 2550 KILOMETERS
80e
75°
Figure 1. Map of the entire Chesapeake Bay watershed, showing location of drainage basins
and sampling sites. Approximate location of the fall line is indicated.
-------
While forest is the largest land-use category for most of the basins, with the highest
percentage occurring in the James River basin, agriculture can be seen to be a significant
percentage as well. The highest percentage of agriculture occurs in the Choptank River basin,
which is located on the Delmarva peninsula. With the exception of the Patuxent River basin,
which has experienced accelerated development over the last 20 or so years, all other basins
have a relatively low overall urban component. Although urban areas may make up a small
percentage of the landscape, they can have a significant impact on water quality.
Samples at the Susquehanna River were collected from February 1994 through
January 1995 during baseflow and stormflow conditions, in order to obtain accurate annual
and monthly load estimates of suspended sediment and selected trace elements and organic
compounds. Storm events were sampled during February, March, April, August, November,
and December 1994 and January 1995. Several samples were collected during each storm
event in order to characterize changes in constituent concentrations with respect to changes
in streamflow, including several samples collected during the peak discharge of the spring
1994 freshette (March 11 - April 22).
All nine tributaries were sampled twice synoptically, once in the spring and once again
in the fall, and estimates of instantaneous loads and yields for each constituent were made for
each individual river basin. Both synoptic studies were conducted under baseflow conditions.
The instantaneous load and yield estimates for these tributaries only represent two
instantaneous measurements in the annual cycle. Results from the 1990-91, the 1992 and this
1994 Fall Line Toxics Programs indicate that intra-annual load estimates for some tributaries
are highly variable.
The sampling strategy and justification for each basin in the Fall Line Toxics Program
is given below:
The Susquehanna River at Conowingo, Maryland was sampled during the 1994 Fall
Line Toxics Program. It has a drainage area of 70,160 square kilometers, and is the largest
single freshwater source to the Chesapeake Bay, contributing an average of fifty-one percent
of the freshwater flow to the Bay annually. Runoff to the river is from a wide range of
sources, including agriculture, coal mining, metal industries, and urban land use. The river
has been sampled for nutrients and suspended sediment since 1984. The specific location of
this station is latitude 39°39'31", longitude 76°10'28", located at the Conowingo Dam in
Harford County, Maryland; the hydrologic unit is 02050306.
There are two different ways that water can pass across the Conowingo Dam: through
the turbines on the lower portion of the dam, and across the upper flood gates, which only
occurs when flows exceed 80,000 cubic feet per second (cfs) - the maximum turbine capacity.
The number of turbines running or flood gates open at any one time depends on the amount
of river discharge as well as the daily variation in public needs for hydroelectric power.
Sampling for the Fall Line Toxics Program used a horizontal cross-integration sampling
-------
techniques to ensure a representative sample. Samples for trace-element and suspended-
sediment analyses were collected separately at four to five increments of equal discharge
across the dam. The samples for trace-element analysis were collected using a Teflon bailer
and composited using a USGS device called a churn splitter. The samples for suspended-
sediment analysis were composited at the laboratory. All samples for organic analysis were
collected directly from the river at the center of flow above the turbine outflows.
The Potomac River was sampled from Chain Bridge at Washington, D.C., Arlington
County, Virginia, latitude 38°55'46", longitude 77°07'02", hydrologic unit 02070010. This
fall line site was chosen because it drains a major metropolitan area with a contributing
watershed area of 29,950 km2. The river contributes approximately sixteen percent of the
total freshwater discharge into Chesapeake Bay. Discharge measurements are made one and
one half miles upstream at the Little Falls Dam USGS gaging station (01646500), latitude
38°56'58", longitude 77°07'40".
This river was sampled from Chain Bridge, which is approximately 70 feet above the
water surface. Samples for trace-element and suspended-sediment analyses were collected
separately at four to five increments of equal discharge across the river cross section. The
samples for trace-element and suspended-sediment analysis were collected and processed
using the same techniques as the Susquehanna River. Due to the extreme height of the
bridge, and length limitations on the sampling equipment, samples for organic analysis were
collected at the river's edge below the bridge.
The Patuxent River was sampled near Bowie, Maryland, downstream from bridge
on U.S. Highway 50, Anne Arundel County, latitude 38°57'21", longitude 76°41'36",
hydrologic unit 02060006. This site was chosen because it represents an area which is
quickly becoming urbanized. The Patuxent River fall line drains a total watershed area of 901
km2. The river contributes less than 1% of the freshwater input to the estuary.
This river site is approximately 50 feet wide with an average water depth of less than
10 feet. All samples were collected from Governor's Bridge using the same techniques as for
the Susquehanna River. Samples for trace-element and suspended-sediment analyses were
collected separately at four to five increments of equal discharge across the river. All samples
for organics analysis were pumped directly from the river at the center of flow.
The Choptank River was sampled near Greensboro, Maryland, Caroline County,
latitude 38°59'50", longitude 75°47'10", hydrologic unit 02060005. This site represents areas
that are strongly agricultural on the Delmarva peninsula. The Choptank River at the fall line
site drains a watershed area of 293 km2, and contributes less than 1% of the total freshwater
input to the estuary.
Sampling was conducted from a bridge that is approximately 15 feet above the water
surface. Samples for trace-element analyses were collected using a dedicated 1 liter
-------
polyethylene bottle fitted with a Teflon nozzle. The bottle was raised and lowered with a
fiberglass rod. Samples for trace-element and suspended-sediment analyses were collected
separately at four to five increments of equal discharge across the river cross section. All
samples for organic analysis were pumped directly from the river at the center of flow.
The Nanticoke River was sampled near Bridgeville, Delaware, Sussex County,
latitude 38°43'42", longitude 75°33'44", hydrologic unit 02060008. Because of poor
drainage, this watershed has less agriculture than other areas on the Delmarva peninsula. The
Nanticoke River at the fall line site drains a watershed area of 195 km2 that is largely wetlands
and the discharge contributes less than 1% of the total freshwater input to the estuary.
This site has a small bridge that is approximately 6 feet above the water surface.
Samples for trace-element and suspended-sediment analyses were collected separately at four
to five increments of equal discharge across the river cross section. Samples were collected
using the same techniques as for the Patuxent River.
The James River was sampled at Cartersville, Virginia, on State Highway 45,
Goochland County, latitude 3T4ffl5*, longitude 78°05'10", hydrologic unit 02080205. The
James River drains a large watershed (16,200 km2) contributing approximately 12% of the
freshwater to the Chesapeake Bay estuary. Approximately 75% of the drainage basin for this
river is forested or undeveloped wetlands.
This site is approximately 650 feet wide with an average water depth of 2 to 20 feet.
Sampling occurred from a bridge which is approximately 50 feet above the water surface.
Samples for trace-element and suspended-sediment analyses were collected separately at four
to five increments of equal discharge across the river cross section. All samples for organic
analysis were pumped directly from the river at the center of flow.
The Rappahannock River was sampled near Fredericksburg, Virginia, upstream
from the dam of Virginia Power, Spotsylvania County, latitude 38°19'20", longitude
77°31'05", hydrologic unit 02080104. Land use in the Rappahannock River basin is mostly
agriculture and forest. This river contributes approximately 3% of the freshwater input to the
estuary.
The only accessible passage across the Rappahannock River near the fall line is a
cableway, maintained by the USGS, that is suspended approximately 30 feet above the river
surface. For the spring sampling the cableway was used for collection of cross-sectionally
integrated samples for trace elements and suspended sediment. Extra precautions were taken
to avoid metal contamination from the cable car. Double bagging of the equipment as well
as plastic covers for the railings were used. Samples for organic analysis were collected by
wading into the river approximately 20 feet from the right bank and manually filling the
Containers. For the fall synoptic sampling, the cableway was not available for use, so all
samples were collected by wading into the river approximately 30 feet from the right bank and
-------
manually filling the containers.
The Pamunkey River was sampled near Hanover, Virginia, downstream from bridge
on State Highway 614, Hanover County, latitude 37°46'03", longitude 77°19'57", hydrologic
unit 02080106. The Pamunkey and the Mattaponi are the major tributaries to the York River.
Land use in the Pamunkey basin is largely agricultural, but has possible contamination from
old mining activities. This river contributes approximately 1% of the freshwater input into
the estuary.
This river station is approximately 200 feet wide. Samples were collected from a
bridge that is approximately 15 feet above the water level, using the same techniques
employed for the Susquehanna River station. Samples for trace-element and suspended-
sediment analyses were collected separately at four to five increments of equal discharge
across the river cross section. All samples for organic analysis were pumped directly from
the river at the center of flow.
The Mattaponi River was sampled near Beulahville, Virginia, upstream from bridge
on State Highway 628, King and Queen County, latitude 37°53'02", longitude 77°09'55",
hydrologic unit 02080105. Land use in this basin is mostly agriculture and forest, with much
wetland area. This river contributes less than 1% of the freshwater input into the estuary.
This river station is approximately 50 feet wide, and samples were collected from a
bridge that is 10 to 15 feet above the water surface, using the same techniques employed for
the Susquehanna River station. The water depth at the center of flow beneath the bridge was
approximately 10 feet. Samples for trace-element and suspended-sediment analyses were
collected separately at four to five increments of equal discharge across the river cross
section. All samples for organic analysis were pumped directly from the river at the center
of flow.
ELl.b Suspended Sediments
For the determination of suspended-sediment concentration, surface grab samples
were collected at five increments of equal discharge along the horizontal cross-section of each
river fall line station. Samples were collected directly into individual 400 mL glass sample
bottles at each point along the river cross section to be composited at the laboratory for
analysis of a single estimate of total suspended sediment and grain size analysis. Sample
bottles were lowered into the water column at each point in a weighted-bottle sampler,
allowed to fill but not overflow, and then capped for storage and shipment to the USGS
Sediment Laboratory in Lemoyne, PA.
-------
ILl.c Organic Constituents
For the Susquehanna River study, organics samples were collected from the river's I
center of flow into two 37.5 L stainless steel milk cans, using a Fultz pump with all metal and
Teflon fittings and tubing. Total sample volume was approximately 70 liters (i.e. two full
cans). All equipment was precleaned with a solution of Liquinox soap, rinsed with organic-
free water, then with 5% methanol, and then again with organic-free water. For blank
collection, 16 liters of organic-free blank water was placed into a separate milk can at the
center of flow at the sample collection site, both ends of the pump were placed in the milk can
and the blank water was cycled through the system until it had equaled the total volume of
an environmental sample, which was about 70 liters. Organic samples were immediately
placed on ice and sent to the laboratory at GMU.
For the synoptic study, organics samples were collected from the center of flow for
the eight tributaries using identical techniques. However, total water volume collected per
tributary was limited to 30-35 L.
H.l.d Trace Elements
Equipment for trace-element sample collection at each site included a dedicated
double-checkball 2 liter Teflon bailer (except at the Choptank River, where a 1 liter
polyethylene bottle fitted with a Teflon nozzle was used), a polyethylene churn-splitter, and
a Teflon tube called a "bottom-emptying device" for draining the bailer contents into the
chum splitter. A 100 foot length of7/32 inch diameter nylon or polyester rope wound on a
plastic cordwheel was used to lower and raise the bailer to and from the point of sample
collection. All sampling equipment was wrapped with two layers of acid-washed plastic bags
until used for sample collection.
All equipment coming in contact with the sample was thoroughly rinsed with river
water before sample collection to ensure that all surfaces equilibrated with the sample water.
The rinses with river water were made by collecting 2 bailer volumes (about three liters) that
were emptied through the bottom-emptying device of the bailer into the churn splitter. The
river-water rinse was discarded and the procedure was repeated before collecting the sample.
Water-quality samples were collected at four or five sections of equal discharge along
the cross section of the river. As the sample was collected at each section, it was poured
directly into the polyethylene churn splitter via a Teflon bottom-emptying device inserted into
the bailer just before the moment of sample transfer. This process involved a minimum of 2
people; a designated "clean" person and a designated "dirty" person. The clean person, using
clean vinyl gloves at each sample collection point along the cross section, handled the bailer
and bottom-emptying device only. The dirty person handled the cordwheel and uncovered
the various holding devices and churn splitter providing an entry port for the sample.
10
-------
Processing of all trace element samples was completed at the river site. The samples
in the churn-splitter were homogenized by churning and poured into the designated sample
and holding bottles. For the first three months of the project, paniculate trace elements were
filtered through a 47 mm Teflon plate filter fitted with pre-cleaned and pre-weighed (by the
UDE laboratory) 0.45 um Nuclepore filters. However, problems inherent in the filtration
procedure, such as significant clogging of the filters, even with a minimum amount of sample,
and static electricity on the filters, were resolved by changing to a 142 mm acrylic plate filter,
beginning May 1994 until the end of the study period. Using the larger filters also allowed
for more paniculate matter being collected and thus improving the detection limits. The
paniculate samples were filtered from a separate 1 liter Teflon bottle through the 142 mm
acrylic plate filter fitted with a 0.45 um Nuclepore filter. The entire plate filter apparatus had
been acid-cleaned and pre-loaded with the filter at the UDE laboratory prior to sampling.
After filtering the field sample, the plate filters were stored in a double layer of plastic bags
and transported without further handling to the UDE lab for analysis. All samples were
stored frozen until shipment to the UDE laboratory. On each bottle was noted the site
location, date, and type of sample. Samples were held frozen for up to eighteen months at
the UDE laboratory.
The dissolved trace elements were collected directly from a single point on the water
surface at the center of flow of the river for the first three months of the project. Beginning
May 1994 until the end of the study period, because of the limitations of the peristaltic pump
during low flow conditions, all samples for dissolved trace-element analysis were taken from
the homogenized sample in the chum splitter. Samples were collected from the churn splitter
using a peristaltic pump with dedicated, acid-washed, 1 cm diameter C-flex Tygon tubing.
A 0.45 um Gelman Sciences groundwater sampling capsule filter, which was pre-washed with
0.1% hydrochloric acid, followed by a distilled water rinse (DIW), was fitted in line with the
tubing, and allowed to flush with no more than 100 mL of river water to rinse the filter, thus
avoiding clogging by river particles. The sample was collected directly into a pre-acid-
washed 500 mL polyethylene sample bottle, after three rinses with the first 100 mL of river
water. Each sample was preserved on site with 2 mL of concentrated, double-distilled
hydrochloric acid prepared by UDE, which was stored in a Teflon dosing bottle.
After each sampling trip the equipment, including the bailer and bottom-emptying
device, filter apparatus, sample bottle, plastic bags, bins, and churn-splitter was washed with
a Liquinox water wash, thoroughly rinsed with tap-water, followed by a flush with 10% HC1
solution, and 2 flushes of DIW, so as to prevent adsorption of contaminants to the surfaces
of the equipment. The bailer was stored in an acid-washed 3-inch PVC tube. Other
equipment was stored in clean Teflon bags in clean high-density polyethylene bins. If more
than 3 days elapsed between sampling trips, the six-step rinse procedure was performed prior
to sample collection to ensure that storage-induced contamination was removed.
11
-------
IL2 Laboratory Analyses
n.2.a Suspended Sediments
During baseflow conditions, the suspended-sediment samples were routinely collected
at the Susquehanna River at Conowingo Dam from the catwalk area above the turbines of the
dam. When spillage from the flood gates occurred during stormflow conditions, samples for
suspended sediment were collected from the flood gates as well as from the turbine area in
equal increments of flow across the river. This additional method was used because of the
variability of the suspended-sediment concentrations collected from the upper catwalk, lower
catwalk, and the flood gates. On March 26,1994, these three points in the cross section were
sampled separately for suspended sediment to determine the variability. The results were 187,
171, and 71 mg/L of suspended sediment, respectively.
Suspended-sediment analysis was performed at the USGS sediment laboratory in
Lemoyne, PA. Samples were separated with a 0.062 mm sieve and both fractions analyzed
separately using a filtration and gravimetric method. All five bottles from a single field sample
were vacuum-filtered through two separate Gooch crucibles with perforated bottoms, fitted
with glass fiber filters, and determined gravimetrically. The sand (>0.062 mm) and fine
(O.062 mm) fractions were added together to give the total suspended sediment value. More
details on this method are provided in Guy (1969).
IL2.b Organic Constituents
All surface water samples collected for organic analysis through the Chesapeake Bay
Fall Line Toxics Monitoring Program were shipped immediately to the George Mason
University Environmental Chemistry Laboratory. Table 2 lists the organic constituents
measured in the surface water samples along with accompanying quantitation limits.
All sample handling was accomplished using ultra-clean techniques. All materials used
were compatible with trace organic analysis and equipment and glassware were scrupulously
cleaned prior to collection and analysis. Specific procedures are described below.
Suspended Particulate Matter Filtration. Processing of the surface water samples
was initiated upon filtration to isolate the suspended particulates from the bulk water phase.
The entire sample (70 L) was filtered through Whatman glass fiber filters. The sample water
was pumped via a positive displacement pump (Model QB-1, Fluid Metering Inc., Oyster
Bay, NY) through a stacked arrangement of Whatman GF/D (10 urn pore diameter)
overlaying Whatman GF/F (0.7 urn nominal pore size) 15 cm glass fiber filters housed in a
Millipore stainless steel filtration apparatus. The filter holder had been customized by the
addition of a Teflon O-ring in place of Viton to prevent sample contamination and analyte
12
-------
reaction. The filtered water was collected in a fresh 37.5-L stainless steel milk can.
Convoluted Teflon tubing was the only type of tubing that was allowed contact with the
sample during filtration.
Fresh filters were placed in the filter apparatus as needed. Particle-laden filters were
folded into quarters together (i.e., both the GF/D and GF/F filters) and placed in precleaned
aluminum foil envelopes. The envelopes are sealed, labeled, and added to zip-lock plastic
bags, and placed in a freezer at -20 °C until analysis.
LSE CIS Extraction. The organonitrogen and organophosphorus (organo-N/P)
pesticides (Table 2) were extracted from the filtered water samples collected for the
Susquehanna River study by using liquid-solid extraction (LSE). An eight to twelve liter
aliquot of the filtered water was transferred to a separate Pyrex container where a surrogate
standard mixture (terbuthylazine and fluoranthene-d10) was added and allowed to equilibrate
for 30 minutes. The sample was passed through a LSE sorbent cartridge containing lOg of
octadecylsilyl-bonded silica (C18) (Varian Assoc., Inc.) 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 this extraction step, the sorbent cartridges were rinsed with 10
mL of distilled water and the cartridges were dewatered and eluted.
LSE cartridges were eluted according to procedures previously developed by Foreman
and Foster (1991) and Foster and Lippa (1995). In brief, the LSE cartridges were initially
dewatered by nitrogen gas purging for 15 minutes followed by vacuum aspiration for 5
minutes. Each cartridge was eluted with 100 mL of cyclohexane:isopropanol (7:3, v/v)
solvent into a 250 mL boiling flask with the aid of nitrogen 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 10 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 sorbet bed was dry. The eluent was reduced in
volume to approximately 0.5 mL by using rotary film evaporation and nitrogen gas
evaporation and subjected to GC/MS analysis.
13
-------
Table 2. Organic constituents, analytical techniques and quantitation limits.
Constituent
Method
(ng/L)
QL^fng/g)
Acenaphthene
Acenaphthylene
Alachlor
Aldrin
Atrazine
aJeha-BHC
beta-BHC
gamma-BHC
Benz(a)anthracene
Benzo(a)pyrene
alpha-Chlordane
gamma-Chlordane
Chrysene
Cyanazine
o.p'-DDD
p,p'-DDD
Ej^-DDE
E^-DDT
Diazinon
Dieldrin
2,6-Dimethyhiaphthalene
Endrin
Fluoranthene
Fluorene
Hexachlorobenzene
Hexazinone
Malathion
Metolachlor
p.p'-Methoxychlor
2-Methylnaphthalene
trans-Nonachlor
Oxychlordane
PCB's (112 congeners)
Perylene
Phenanthrene
Prometon
Pyrene
Simazine
GC/MS (d,p)
GC/MS (d,p)
GC/MS (d)
GS/ECD (d,p)
GC/MS (d)
GC/ECD (d,p)
GC/ECD (d,p)
GC/ECD (d,p)
GC/MS (d,p)
GC/MS (d,p)
GC/ECD (d,p)
GC/ECD (d,p)
GC/MS (d,p)
GC/MS (d)
GC/ECD (d,p)
GC/ECD (d,p)
GC/ECD (d,p)
GC/ECD (d,p)
GC/MS (d)
GC/ECD (d,p)
GC/MS (d,p)
GC/ECD (d,p)
GC/MS (d,p)
GC/MS (d,p)
GC/ECD (d,p)
GC/MS (d)
GC/MS (d)
GC/MS (d)
GC/ECD (d,p)
GC/MS (d,p)
GC/ECD (d,p)
GC/ECD (d,p)
GC/ECD (d,p)
GC/MS (d,p)
GC/MS (d,p)
GC/MS (d)
GC/MS (d,p)
GC/MS (d)
0.02
0.01
0.9
0.01
1.4
0.02
0.03
0.02
0.01
0.01
0.009
0.009
0.06
0.9
0.02
0.01
0.01
0.02
1.3
0.02
0.02
0.04
0.01
0.01
0.005
2.9
2.9
0.8
0.09
0.02
0.01
0.009
1.3
0.01
0.01
1.7
0.01
1.6
1.0
0.5
na
0.8
na
0.2
0.5
0.2
0.4
0.7
0.08
0.08
0.6
na
0.5
0.1
0.1
1.7
na
0.2
0.2
0.3
0.2
0.1
0.1
na
na
na
0.2
2.0
0.1
0.1
0.9
0.1
0.1
na
0.1
na
d=dissolved p=particulate na=not analyzed in particulate phase
14
-------
Goulden Large-Sample Extraction. The organochloride (OC) pesticides, PCBs and
polycyclic aromatic hydrocarbons (PAH) (Table 2) were isolated in the filtered water which
remained after removing the aliquot for organo-N/P pesticide analysis (50-60 L) using the
Goulden large-sample extractor (GLSE). This approach was used for the Susquehanna River
study. In the synoptic study, all organic constituents were isolated from 30-35 L samples of
filtered surface water via the GLSE. GLSE theory and general operational parameters have
been previously reported by Foster and Rogerson (1990) and Foster etal. (1991 and 1993).
Dichloromethane (DCM) was used as the extraction solvent. Surrogate standards (delta-
hexachlorocyclohexane, 4,4'-dichlorobenzophenone, PCB-14, and PCB-166) were added to
DCM immediately prior to extraction of the filtered water samples. The sample was pumped
into the entrance side arm of the extractor using a fluid metering pump at a rate of 110
mL/min. A solvent recovery system was configured in line with the GLSE to recycle DCM
escaping in the waste stream, returning the recovered DCM back into the main chamber of
the extractor. Throughout the extraction, the level of DCM in the main extraction chamber
was checked and additional volumes are added to keep the solvent volume at approximately
300 mL.
After all of the filtered water sample was extracted, the DCM layer was passed
through a powder funnel containing precleaned anhydrous sodium sulfate, and the DCM was
reduced in volume to 0.5 mL, using rotary flash evaporation and nitrogen gas blowdown. n-
Octane (1 mL) was added as a keeper solvent prior to solvent volume reduction. The DCM
extract was subjected to GC/MS analysis to determine PAH concentrations in the GLSE
extracts.
Filter Extraction. Filters were thawed to room temperature, placed in a Soxhlet
extraction thimble, spiked with the surrogate standards for OC pesticide, PCB, and PAH
schedules (Table 3) and extracted for 24 hours in a Soxhlet extraction apparatus using
cyclohexane:isopropanol (7:3) as the solvent. Both GF/D and GF/F filters were combined
for each sample in the glass thimbles (no attempt was made to measure particle size
differences in sorption and riverine transport). The filter extracts were reduced in volume to
0.5 mL using rotary film evaporation and nitrogen gas blowdown. n-Octane was added to
the extracts prior to solvent volume reduction to serve as a keeper solvent.
The concentrated filter extracts were treated overnight in gas chromatography vials
with 0.5 g of precleaned, HCl-activated granular copper to remove sulfur and other
interferring substances. The filter extracts were subjected to GC/MS analysis after copper
treatment.
Alumina/Silica Fractionation. Following GC/MS analysis of the GLSE and filter
extracts for PAH constituents, organochlorine pesticides and PCBs 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
organohalogens that may also be present in the samples, extracts from the LSE cartridges and
15
-------
filters were fractionated via column chromatography prior to GC-ECD analysis to isolate
PCBs (plus aldrin and p,p'-DDE) and the remaining pesticides in separate fractions.
Fractionation columns were made of modified glass separatory funnels with a 11 cm long
column body (25 mL) separating the funnel (125 mL) and the ground glass stopcock. The
columns 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 folly activated silica gel (60/200 mesh,
Fisher Chemical Co.; previously activated at 135 °C), 6 g of 2% (wt/wt) water deactivated
neutral alumina (80/200 mesh, Fisher Chemical Co.; previously activated at 500 °C), and 4
g of anhydrous sodium sulfate.
The chromatography columns were initially rinsed with 50 mL of n-hexane, and the
extracts were loaded directly onto the top sodium sulfate layer of the sorbent bed via a
transfer pipet and were eluted with 45 mL of n-hexane (PCB, aldrin and p,p'-DDE) followed
by 45 mL of DCM (remaining OC pesticides). Each eluent was collected separately and both
eluents were concentrated by using a Savant speed vac (Savant Instruments, Inc.,
Farmingdale, NY) where 0.5 mL of a keeper solvent n-octane was added beforehand. The
samples were reduced to a final volume of 0.5 mL and analyzed using GC-ECD.
Instrument Parameters. A Hewlett-Packard (HP) 5890 Series n GC equipped with
an electron capture detector was used to measure all of the organochlorine compounds. The
GC operational conditions are listed in Table 3. The GC-ECD output occurs through an HP
3396A recording integrator, which transmits the final data report after each run to an HP
Vectra QS/20 microcomputer (386 microprocessor) through HP 3396A File Server ver. 1.2
software. Hard copies of each chromatogram obtained from GC analysis were stored labeled
in a filing cabinet. The report files uploaded to the Vectra computer were imported into
Quattro Pro (Borland) spreadsheets, evaluated as needed, and stored on both on floppy disks
and the Vectra QS/20 hard drive.
The GC/MS system consisted of an HP 5890A GC coupled to a Finnigan INCOS 50
mass spectrometer. The system was controlled and operated through INCOS 50 software
according to the conditions listed in Table 3. The mass spectrometer was tuned and
calibrated daily with perfluorotributyl amine. Data files provided by the INCOS 50 system
were archived and converted to PCDS (Finnigan software) 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. 4 GC/MS data files,
quantitation files, and calibration files were stored on floppy disks and on the hard drive of
the Vectra computer. All GC separations were carried out using high resolution capillary
columns to attain the highest degree of efficiency and resolution in the analysis.
16
-------
Table 3. Instrument parameters for GC-ECD and GC/MS analysis.
Parameter
Column
Carrier Gas
Detector Gas
Injection Mode/Vol.
Split: Septum Flows
Injector/Detector T
GC Program
MS Source T
MS EM Voltage
MS Acquis./Scan Rate
MS Mode
Internal Standards
Surrogate Standards
GC-ECD
HP-1, 30m X 0.25mm
Helium, 40cm/s (100°)
Ar/Methane, 60mL/min
Splitless, 2uL
30mL/min:3mL/min
250°/325°
85° (Imin); 85°-120° @
107min; 120° (Imin);
120°-285° @
3.5°/min;OCPs
1200-285°@1.5°/min;
PCBs
285° (6.0min); 60min run
NA
NA
NA
NA
Phenanthrene-dlO
Chrysene-dl2
Isodrin/Mirex
PCB 30 and PCB 204
Schedule
Organo-N/P Pesticides:
PAH:
PCBs:
OC Pesticides:
GC/MS
HP-5, 30m X 0.25mm
Helium, 40cm/s (100°)
NA
Splitless, 2uL
30mUmin:3mL/min
250°/290° TL
70° (Imin); 70M200 @
107min; 120° (Imin); 120°-
290° @ 57min; 290° (4.5
min); 45min run
200°
1350V
MID/1. Os per scan
El, 70eV
Phenanthrene-d 1 0
Chrysene-dl2
Standard
Terbuthylazine
Fluoranthene-dlO
PCB 16 and PCB 166
delta-BHC
Instrument Calibration and Quantitation. GC-ECD and GC/MS instruments were
calibrated daily prior to the analysis of surface water samples. Primary standards were
prepared either from neat compounds (Chem Service Inc., West Chester, PA) or were
17
-------
obtained as preprepared solutions with known analyte concentrations (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 Aroclors 1232:1248:1262. Approximately 112 PCB congeners
associated with 80 GC-ECD peaks were quantitated in each dissolved phase and suspended
particle sample. The retention times of the PCB congeners were assigned according to the
relative retention times reported by Eganhouse et al.(1989) and Shulz et al.(1989). PCB
nomenclature in this study conforms to that reported by Ballschmitter and Zell (1981). A
single calibration standard for GC-ECD was used in the PCBs analysis to calculate relative
response factors (RRFs) by manipulating the fundamental internal standard quantitation
formula shown below:
std
CONCENTRATIONanalyte CONCENTRATION.^^
Four point calibrations were performed in the analysis of organo-N/P pesticides (GC/MS),
OC pesticides (GC-ECD), and PAH (GC/MS) and linear regressions constants were
evaluated (in y = mx + b format) according to the equation:
AREA
AREAinternaJ std *"*"" internal std
Regression constants resulting from the evaluation of equation 2 were incorporated into
Quattro Pro spreadsheets for quantitation. During calibration, the analyte and internal
standard masses were known to four significant figures and all integrated GC peak areas
(instrument ADC output) were obtained from PCDS software (GC/MS) or an HP 3396A
integrating recorder (GC-ECD). GC peak identifications were made based upon retention
time data, or if retention times had shifted then retention times relative to the internal
standards were used to identify individual constituents. All quantitation was performed
automatically with the aid of the HP 3396 integrator for GC-ECD analysis and PCDS
software for GC/MS analysis Calibration RRF data was recorded and a hard copy was saved
on file daily to query instrument variability and drift through time. Estimated method
detection limits were determined for each analyte according to procedures previously
described (Foster etal. 1993).
Equipment and Glassware Cleaning and Preparation. All non-volumetric
glassware was scrupulously cleaned with Alconox detergent in hot tapwater, rinsed with
distilled water, and fired in a muffle furnace at 450 °C for 15 hours. Fired glassware was
stored wrapped in aluminum foil (all aluminum foil used for wrapping and storage in this
study is fired at 450 °C prior to use), and was repeatedly rinsed with solvent before use.
Volumetric glassware was initially soaked in 20% aqueous nitric acid, washed in Alconox
18
-------
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 in the same manner as glassware but were not
fired. The cans were repeatedly rinsed with methanol and n-hexane prior to use and were
stored with their lids securely fastened to prevent the entry of organics into the clean can from
ambient air.
The Goulden extractor was cleaned by boiling tapwater containing Alconox detergent
with immersion heaters for one hour. The extractor was drained and rinsed with tap water,
distilled water and methanol. It was then soaked in 20% aqueous nitric acid, rinsed with
distilled water, and repeatedly solvent rinsed prior to use.
Positive displacement pumps and associated Teflon tubing were thoroughly washed
with hot soapy tap water, distilled water and methanol between experiments. All tubing and
swagelock connections were sonicated in a hot soap water bath on a monthly basis. All
exposed ends of Teflon tubing were kept wrapped with aluminum foil when not in use to
prevent contamination.
Organic Constituent QC. Quality assurance practices in organic constituent analysis
included (a) laboratory and field blanks, (b) sample container solvent rinses, (c) duplicate and
triplicate replicates dissolved and paniculate phase measurements, (d) full suite matrix spikes,
(e) surrogate standards for each constituent schedule, and (f) National Institute of Standards
and Technology (NIST) standard reference materials (SRMs) for sediment analysis.
Field and Laboratory Blanks. Organic constituent field and laboratory blanks were
performed on-site during each of the Susquehanna River fall line base flow sampling events.
Field blanks consisted of a double distilled water (prepared at George Mason University -
GMU) rinse of all of the USGS sampling equipment (contacting all of the surfaces a normal
sample would contact during sampling, filtration, and LSE) which was placed in a stainless
steel milk can. The distilled water was recirculated via the Fultz pump as previously
described. The blank was filtered and extracted in the normal fashion. A total of eight liters
of distilled water rinse was used as the field blank. A single blank was processed as the first
sample prior to sample filtration and extraction. During storm sampling, all of the USGS field
equipment was rinsed with distilled water on-site in the normal manner, but in this case the
blank was shipped on ice to the GMU analytical laboratory and was processed according to
the usual procedure.
Laboratory blanks were performed on a monthly basis at the George Mason
University environmental chemistry laboratory to check for equipment and reagent
contamination. Lab blanks were performed in exactly the same fashion as described for field
blanks without the water collection rinse through the Fultz pump. These blanks provided an
average background subtraction for sample data.
19
-------
Matrix Spikes. A matrix spike as defined in this study represented the addition of
each target analyte to a replicate sample of filtered surface water. In this procedure, the
matrix spike sample was filtered as the first replicate. Both the dissolved and particulate
phases were spiked with the full suite of target analytes. For each of the three laboratory
extraction methods used, two low spikes and two high spikes were performed throughout the
sampling year. Matrix spike solutions for the dissolved phase samples were prepared as a
methanol solution (5 mL) to give a final concentration of 10 ng/L for low spiking and 100
ng/L for high spiking for each component (for PCBs, the amount corresponds to 300 ng/L
total PCBs). High level matrix spike solutions for particulate phase samples ranged from
1000 ng for PAHs to 25 ng for organochlorine pesticides. For low level spiking the range
was 100 ng for PAHs to 2.5 ng for organochlorine pesticides.
For the dissolved phase sample, approximately 10 liters of the sample was transferred
to a separate can for the LSE CIS extraction matrix spiking procedure. The remaining 50 to
60 liters of sample was used for GLSE matrix spiking. The spiked water was mixed
thoroughly by using agitation, and was subsequently extracted in the normal manner. Results
from the matrix spike were used to calculate the mass percentage of the target analytes
recovered from the spiked water.
Sample Container Rinse. Trace organic compounds dissolved in water are known
to undergo sorption to the walls of the 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 biasing the data. Milk cans that were in contact
with the matrix spiked samples were solvent rinsed with 50 mL of cyclohexane:isopropanol
(7.3) after filtration and extraction was completed. The solvent rinses are analyzed by using
the procedures described below.
Replicate Analysis. Replicate samples were collected and analyzed throughout this
study. Replicate analysis provided a measure of the repeatability in the determination of the
organic constituents.
Surrogate Standards. A suite a surrogate standards was added to each sample to
evaluate the performance of each sample analysis. The surrogates used in this study are listed
in Table 3. Corrections were made to normalize analyte concentrations relative to the
recoveries of the appropreate surrogate standards. Surrogate corrections greatly improved
the repeatability of measured analyte concentrations in the samples.
Standard Reference Materials. River sediment (SRM 194la) was analyzed to
provide a measure of the systematic errors resulting from the analysis of the filtered
particulates. A sample of 1.5 g of SRM 194 la was placed on a GF/F filter and was processed
as a normal filtered particle sample.
20
-------
H.2.C Trace Elements
In general, the concentrations of trace elements in the river samples are lower than the
detection limits of most standard practices. Therefore, a considerable amount of method
development has been done to obtain quality, finite measurements at such low levels of the
analytes. All trace-element analyses for samples collected during the 1994 Fall Line Toxics
Program were conducted by the DDE laboratory. Table 4 lists the trace element constituents
analyzed in this study as well as the analytical methods and detection limits for each
constituent. Analytical detection limits for the 1994 program were lower than the 1990-91,
1992, and 1993 Fall Line Toxics Programs for all dissolved trace elements except copper and
zinc.
All sample handling and analysis were accomplished using trace element clean
procedures, such as manipulation with polyethylene-gloved hands, multiple-bagged sample
storage, transfers under a laminar-flow clean bench, and analysis within a class-1000 clean
room.
Samples for dissolved trace elements were analyzed without further pretreatment.
Paniculate samples were unloaded from the filter cartridge and air dried in a laminar-flow
clean bench, then heated for at least 24 hours in a 50° C oven, and then cooled in a desiccator.
The filters were weighed to measure the mass of paniculate matter, then transferred to Teflon
microwave bombs for total digestion. The digestion procedure was modified from Robisch
and Clark, 1993. Briefly, the procedure consisted of successive heating with increasing
amounts of acid. The final digestate (approximate ratio of HNO3:HCL:HF 4:4:1) was
brought up to 25-30 mL with a saturated H3BO3 solution. All samples were run in batches
of eight to ten. The digestate for cadmium was analyzed by GFAAS; the remaining metals
were analyzed using a Jobin Yvon 70 Plus Inductively-Coupled Plasma-Atomic Emissions
Spectrometer (ICP-AES). Filter blank analyses were run on separate Nuclepore filters for
both field blanks (filters were processed with DIW water in the field, concurrently with
riverine samples) and laboratory blanks (unused filters). Additionally, the standard reference
material BCSS-1 (Marine Sediment Reference Material for Trace Elements, National
Research Council of Canada) was digested in parallel with the blanks and river samples to
determine the completeness of the digestion procedures (Table 5).
The dissolved samples were analyzed for the trace elements without further processing
using a Perkin Elmer 1100-B Atomic Absorption Spectrometer, equipped with a 700 HGA
graphite furnace (GFAAS). Dissolved arsenic was analyzed using hydride generation,
followed by cryogenic trapping and subsequent analysis by AASwhich was fitted with a
quartz burner with an air-hyrogen flame (Cutter et al., 1991).
21
-------
Table 4. Analytical techniques and detection limits for the trace elements analyzed for the
1994 Fall Line Toxics Program. Detection limits for particulate analyses are calculated
assuming 0.1 mg dry weight of particulate and dilution to 25 mLs; however, actual detection
limits vary with the mass of particulate (sediment) collected onto the filter. The dissolved
fraction is reported as micrograms per liter and the particulate fraction as micrograms per
gram.
Constituent
Technique
Detection Limit
Al (Aluminum), particulate
Al, dissolved
As, (Arsenic), dissolved
Cd (Cadmium), particulate
Cd, dissolved
Cr (Chromium), particulate
Cr, dissolved
Cu (Copper), particulate
Cu, dissolved
Fe (Iron), particulate
Fe, dissolved
Pb, (Lead), particulate
Pb, dissolved
Mn (Manganese), particulate
Mn, dissolved
Ni (Nickel), particulate
Ni, dissolved
Zn (Zinc), particulate
Zn, dissolved
ICPAES
GFAAS
Hydride,AAS
GFAAS
GFAAS
ICPAES
GFAAS
ICPAES
GFAAS
ICPAES
GFAAS
GFAAS
GFAAS
ICPAES
GFAAS
ICPAES
GFAAS
ICPAES
GFAAS
3.0 ug/g
0.12 ug/L
0.007 ug/L
0.10 ug/g
0.006 ug/L
3.0 ug/g
0.03 ng/L
3.0 ug/g
0.03 ug/L
2.0 ug/g
0.05 ug/L
3.0 ug/g
0.03 ug/L
3.0 ug/g
0.10 ug/L
3.0 ug/g
0.12 ug/L
3.0 ug/g
0.14 ug/L
GFAAS = Graphite Furnace; Atomic Absorption Spectroscopy
ICPAES = Inductively Coupled Plasma; Atomic Emission Spectroscopy
22
-------
For instrument calibration, secondary standards were diluted from commercially
available, certified stock solutions. Working standards were prepared daily and were diluted
individually rather than by the instrument. Standardization was accomplished with at least a
four-point calibration (one blank (zero) and three standards) that bracketed the expected
concentration of the samples.
Standard reference materials were used for verification of trace-element analytical
methods: SLRS-2 for dissolved trace elements, and BCSS-1 for paniculate trace elements.
All experimental values for SLRS-2 were within the acceptable range for all of the dissolved
trace elements, with the exception of nickel. The experimental BCSS-1 values for Al, Cr, Fe
and Ni are slightly below the limits of the 95% confidence range, but are within 80-90% of
the expected value. We, however, note the possibility of incomplete digestions for the
procedure. The results are presented in Table 5.
Table 5. Summary results of standard reference material for trace elements. Standard reference
materials were obtained from the National Research Council in Canada, Institute for Environmental
Chemistry, Measurement Science. The SLRS-2 is reported in micrograms per liter and the BCSS-1
is reported in micrograms per gram. The number of measurements made to determine the
experimental mean and standard deviation was 6 for SLRS-2 and 13 for BCSS-1.
SLRS-2
Exp.
Mean
Exp. SD
True
Mean
TrueSD
BCSS-1
Exp.
Mean
Exp. SD
True
Mean
TrueSD
Al
95.48
3.81
84.40
3.40
Al
57024
5400
62630
2200
As
0.765
0.019
0.77
0.09
As
NA
NA
NA
NA
Cd
0.031
0.002
0.028
0.004
Cd
0.219
0.044
0.25
0.04
Cr
0.45
0.016
0.45
0.07
Cr
93
19.6
123
14
Cu
2.713
0.033
2.76
0.17
Cu
17.1
3.3
18.5
2.7
Fe
128
4.676
129
7
Fe
27400
4470
32900
980
Mn
10.07
0.659
10.1
0.3
Mn
212
33
229
15
Ni
0.805
0.055
1.03
0.1
Ni
47.5
2.5
55.3
3.6
Pb
0.12
0.025
0.129
0.011
Pb
22.1
5.7
22.7
3.4
Zn
3.84
0.022
3.33
0.15
Zn
106
14.2
119
12
Exp. = experimental
NA = not analyzed
SD = standard deviation
SLRS-2 = Riverine Water Reference Material for Trace Metals; n = 6
BCSS-1 = Marine Sediment Reference for Trace Elements and Other Constituents; n = 13
23
-------
IL2.e Load Estimation Method
Numerous estimation techniques have been used to calculate contaminant loads into the
Chesapeake Bay and other estuaries. Some of these techniques are described and compared as
applied to selected organic compounds in a recent paper by Foster and Lippa (1994). The main
conclusion from Foster and Lippa was that there is a great deal of uniformity in load estimates
calculated by the different techniques. Results agreed within a factor of 2 to 3 for any given
constituent, a range that is more than adequate to make load estimates. For the first several years of
this project the multiple log-linear regression model developed by Cohn et al. (1989) was used to
estimate loads. However, Conn's model has large requirements for the data set (at least 50 water
quality samples and a minimum of three years of data), creating a large burden. Given the results of
Foster and Lippa, the Fall Line Program has changed to a simpler spreadsheet technique for load
estimation, which we have determined to be adequate, and which we have named the Interpolation
Integration method (n). Monthly load estimates are also calculated using this method.
Load estimates were made by first calculating daily loads within a spread-sheet program
(Microsoft Excel or Lotus) and then summing these values over each monthly or annual period. Daily
loads were calculated using the following formula:
QiXC.iXK (3)
g - calculated load for constituent i on day t in kilograms per day
Qt = mean daily discharge for day t, in cubic feet per second
Qj = concentration of constituent i for day t in mg/L for suspended sediment,
and ng/L for trace elements and organics
K! = conversion factor of 2.4485 (secxLxkg/ft3xmgxdays) when using suspended-sediment
concentrations in mg/L
Kj = conversion factor of 0.0024485 (secxLxkg/ft3x//gxdays) when using trace-element and organic
concentrations in ng/L
Mean discharge was calculated daily from river stage that was electronically measured every
fifteen minutes at the USGS gaging station at or near each sampling site. Suspended-sediment, trace-
element, and organic compound concentrations were analyzed less frequently and daily values were
interpolated within the spread-sheet program from the existing data set. Interpolated data points
were assigned the value of the nearer concentration. When reported concentrations were below the
detection limit (or quantitation limit), the load was estimated by two means to define a range: (1) the
minimum load was calculated by assigning a concentration of zero, and (2) the maximum load was
calculated using the value of the detection limit (or quantitation limit).
24
-------
WATER-QUALITY DATA
Results of the water-quality and quality-assurance data collected for the 1994 Fall Line Toxics
Program at the Susquehanna River during the period February 1994 through January 1995, and for
the Spring 1994 and Fall 1994 tributary synoptic studies are presented in this section. Water-quality
concentration data were used in conjunction with daily discharge data to estimate loadings of each
constituent. Load estimates are presented in a subsequent section.
nLl Susquehanna River
In 1994, the Fall Line Toxics Program collected samples at the Susquehanna River at
Conowingo, Maryland, for the analysis of suspended sediment and selected trace elements and
organic compounds. Monthly baseflow samples and daily stormflow samples were collected so that
all hydrologic conditions and seasons were represented, and in order to capture the major sources of
variation in constituent concentrations. Trace-element and organic constituent samples were analyzed
for both the dissolved and paniculate fractions to provide a better understanding of transport
mechanisms. Combined, these two fractions provide a measurement of the total concentration for
each constituent.
IILl.a Suspended Sediments
A time-series plot showing the relation of total suspended-sediment concentration and
instantaneous stream flow for the period covering 1990-1995 is presented in Figure 2. Suspended-
sediment concentration shows a positive correlation to discharge (R^O.79). Concentrations less than
50 mg/L generally occurred at flows less than about 100,000 cfs; concentrations greater than about
75 mg/L only occurred during stream flows exceeding about 150,000 cfs.
Suspended-sediment data, including concentrations, streamflow, and particle-size distribution,
collected at the Susquehanna River at Conowingo, Maryland, for the 1994 study are in Appendk A.
Stream flow during sample collection ranged from 389,000 to 5,100 cfs, and suspended-sediment
concentrations ranged from 148 to 7 mg/L, with an arithmetic mean concentration of 50 mg/L.
Quality assurance for suspended-sediment measurements was maintained by routinely
collecting field blanks. Results from field blanks, nine collected at the various tributaries during the
year, were all less than the quantitation limit, one mg/L, indicating that contamination during field
collection and processing probably did not occur for this constituent.
25
-------
Discharge in cfs
uoijBJjuaouoo
ts
-------
ULl.b Organic Constituents
All dissolved and paniculate organic constituent concentrations are listed in Appendix B for
the Susquehanna River fall line study for February 1994 to January 1995. Quality assurance results
are presented first in each section prior to the surface water concentrations.
Quality Assurance Results - Susquehanna River
The constituent concentrations listed in Appendix B were corrected for background
contributions to the measured concentrations. The laboratory blanks represented the background
contributions to the sample concentrations. Six laboratory blanks for the dissolved (C18BPS and
GLSE) and particulate (Soxhlet extraction) phases were performed throughout the study period from
February 1994 through January 1995 and the mean concentrations of each constituent measured in
the laboratory blanks are listed in Tables 6 and 7. The mean values listed in Tables 6 and 7 were used
as background corrections which were applied to all of the sample concentrations.
Constituent concentrations in the field blanks which were prepared for the Susquehanna River
fall line are listed in Appendix D. The concentrations measured in the field blanks in Appendix D are
listed in two formats. The first series of entries pertains to unscreened measured values determined
in the field blank samples, and the second series (below the first) lists field blank concentrations
screened for the quantitation limits for each constituent. Field blank concentrations were used to flag
the measured constituent concentrations reported in Appendix D if the measured field blank
concentrations were greater than or equal to 0.5 times the sample concentrations. Flagged
concentrations are noted in Appendix B.
Constituent concentrations in the field blanks were frequently below quantitation limit values.
Quantifyable concentrations in the field blanks were relatively infrequent, were random in distribution
throughout the year, and did not present a data quality conflict for the reported sample
concentrations. The most frequently detected constituents were for the GLSE extraction of water
in the PAH analysis, especially the alkyl-substituted naphthalenes and fluoranthene. When field blank
concentrations were quantifiable, the concentrations found were most frequently substantially below
the measured concentrations in the sample, including the PAHs listed above. Evaluation of the field
blanks clearly indicated the ultra-clean sampling techniques used in this study were compatible and
appropriate with the quantitation limits of the organic constituents listed in Table 2.
Quality assurance spikes (QA spikes) of the target analytes in distilled water and to clean glass
fiber filters were used to evaluate the performance of the extraction methods in the absence of matrix
effects and under optimal conditions. Results of the QA spikes are shown in Tables 8 -10 for the
entire suite of organic constituents.
27
-------
Table 6. Laboratory QA blank concentrations (ng/L) for water analysis.
Organo-N/P Pesticides
Mode:
No. of Blanks:
C18BPE
6
Mean
(ng/L>
Simazine
Prometon
Atrazine
Diazinon
Alachlor
Malathion
Metolachlor
Cyanazine
Hexazinone
0.042
1.32
QL
C,8BPE = C-18 Bonded phase extraction
GLSE = Goulden large sample extraction
% Rec = % recovery
Polychlorinated Biphenyls
Mode:
No. of Blanks:
Dichlorobiphenyls
Trichlorobiphenyls
Tetrachlorobiphenyls
Pentachlorobiphenyls
Hexachlorobiphenyls
Heptachlorobiphenyls
Octachlorobiphenyls
Nonachlorobiphenyls
2PCBs
Mean %Rec PCB 166 (SS)
Organochlorines
Mode:
No. of Blanks:
Hexachlorobenzene
p,p'-DDE
alpha-BHC
beta-BHC
gamma-BHC
Oxychlordane
gamma-Chlordane
alpha-Chlordane
trans-Nonachlor
Dieldrin
o,p'-DDD
Endrin
p,p'-DDD
p,p'-DDT
MethoxychJor
Mean %Rec delta-BHC
GLSE
6
Mean
(ng/L)
-------
Table 7. Laboratory QA blank concentrations (ng/L) for filter analysis.
Polynuclear Aromatic Hydrocarbons
Mode: Soxhlet
No. of Blanks: 6 ,
2-Methylnaphthalene
2,6-Dimethylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(a)pyrene
Perylene
Mean %Rec Fluor-d10 (SS)
Mean
(ng/U
0.388
0.003
QL
% Rec = % recovery
29
-------
Table 8. ClgBPE and GLSE QA spike recoveries for the organo-N/P pesticides and PAH.
Spike Level:
Sample Volume:
No. Replicates:
Extraction Mode:
Matrix:
Analyte
Organo-N/P Pesticides
Simazine
Prometon
Atrazine
Diazinon
Alachlor
Malathion
Metolachlor
Cyanazine
Hexazinone
Terbutylazine (SS)
PAH
2-Methylnaphthalene
2,6-Dimethylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(a)pyrene
Perylene
Fluoranthene-d10 (SS)
lOng/L
10L
3
CMBPE
DW
Mean
%Rec(%rsd)
89 (10)
100 (10)
103 4
94 2
88 13
113 1
125 3
116 5
149 (N=2)
89 6
18 9
81 7
95 12
85 10
93 7
109 16
118 2
118 2
91 4
93 2
64 13
66 13
102 7
lOOng/L
10L
lor 2
ClgBPE
DW
Mean
OX. ID rf> /* f QXi t*p t\ i
/Q^X.C^» /OI oU I
80 (N=l)
81 (N=l)
94 (N=l)
104 (N=l)
88 (N=l)
99 (N=l)
97 (N=l)
108 (N=l)
na
97 (N=l)
95 1
107 6
101 3
106 10
102 5
92 1
110 10
107 11
104 13
76 7
76 18
84 24
89 24
5ng/L
25 L
1
GLSE
DW
%Rec
na
na
na
na
na
na
na
na
na
na
27
42
40
46
58
73
80
75
63
81
79
114
104
20ng/L
25 L
1
GLSE
DW
%Rec
60
105
104
103
104
104
94
103
53
87
87
81
84
88
89
86
90
86
72
95
93
104
100
C18BPE = C-l 8 Bonded phase extraction.
GLSE = Goulden large-sample extraction.
DW = Double distilled water.
na = not analyzed
% Rec = % recovery
% dev = % standard deviation
% rsd = % relative standard deviation
N = number of observations
30
-------
Table 9. GLSE QA spike recoveries for PCBs and organochlorines.
Polychlorinated Biphenyls
Spike Level:
Sample Volume:
No. Replicates:
Matrix:
Analyte
Dichlorobiphenyls
Trichlorobiphenyls
Tetrachlorobiphenyls
Pentachlorobiphenyls
Hexachlorobiphenyls
Heptachlorobiphenyls
Octachlorobiphenyls
Nonachlorobiphenyls
SPCBs
Organochlorines
Spike Level:
Sample Volume:
No. Replicates:
Matrix:
Analyte
Hexachlorobenzene
Aldrin
p,p'-DDE
alpha-BHC
beta-BHC
gamma-BHC
Oxychlordane
gamma-Chlordane
alpha-Chlordane
trans-Nonachlor
Dieldrin
o,p'-DDD
Endrin
p,p'-DDD
p,p'-DDT
Methoxychlor
5ng/L
25 L
1
DW
%Rec
88
71
61
72
61
67
84
175
110
5ng/L
25 L
1
DW
%Rec
na
na
96
58
128
44
98
116
143
60
159
153
56
108
105
80
20ng/L
25 L
1
DW
%Rec
13
88
98
79
65
75
74
56
79
20ng/L
25 L
1
DW
%Rec
71
73
98
80
68
77
50
45
49
46
44
76
na
82
101
105
40ng/L
25 L
1
DW
%Rec
na
na
na
na
92
98
95
83
94
50ng/L
25 L
1
DW
%Rec
80
85
112
63
98
77
65
63
78
67
77
108
na
125
95
70
GLSE = Goulden large-sample extraction
na = not analyzed
DW = Double distilled water.
% Rec = % recovery
31
-------
Table 10. Soxhlet QA spike recoveries for PAH, PCBs, and organochlorines.
Polynuclear Aromatic Hydrocarbons
No. Replicates: 4
Spike Level: 100 ng
%Rec
2-Methylnaphthalene
2,6-Dimethylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(a)pyrene
Perylene
Fluoranthene-d10 (SS)
Polychlorinated Biphenyls
No. Replicates:
Spike Level (SPCBs):
Dichlorobiphenyls
Trichlorobiphenyls
Tetrachlorobiphenyls
Pentachlorobiphenyls
Hexachlorobiphenyls
Heptachlorobiphenyls
Octachlorobiphenyls
Nonachlorobiphenyls
SPCBs
na
80 (13)
73 (11)
95 (12)
86 (6)
89 (12)
114(9)
116(7)
108 ( 8)
99 (6)
90(3)
96(4)
104 ( 6)
4
600 ng
%Rec (%rsd;>
61 (13)
100(11)
87(5)
98(3)
104(2)
90(1)
84(2)
93(1)
94(4)
Organochlorines
No. Replicates:
Spike Level:
Hexachlorobenzene
Aldrin
p,p'-DDE
alpha-BHC
beta-BHC
gamma-BHC
Oxychlordane
gamma-Chlordane
alpha-Chlordane
trans-Nonachlor
Dieldrin
o,p'-DDD
Endrin
p,p'-DDD
p,p'-DDT
MethoxycMor
delta-BHC (SS)
4
100 ng
%Rec (%rsd)
90 (1)
96 (4)
98 (3)
93 (6)
85 (7)
93 (2)
85 (9)
69 (6)
83 (10)
75 (9)
75(11)
97 (7)
na
116(25)
119(14)
115(2)
102 ( 4)
na = not analyzed.
% Rec = % recovery
% rsd = % relative standard deviation
32
-------
Matrix spikes were performed using the entire suite of organic constituents using Susquehanna River
water (natural surface water source) and suspended particulates isolated from Susquehanna River
water (natural sediment source). The matrix spike recoveries are presented in Tables 11 - 14, and
these tables provide the range of recoveries and recovery variabilities in these matrices which may be
indicative of the determinate and indeterminate errors inherent in the fall line organics study.
Comparisons of selected PAH, organochlorines, and PCB measured quantities in NIST SRM
194la versus the reported reference values are shown in Tables 15 and 16. Since SRMs are not
available for the dissolved phase analysis, only sediments were evaluated in this study. The SRM
results provide another measure of the level of determinate error related to the organics analysis in
this study.
Results from duplicate sample analyses are presented in Appendix B for the Susquehanna
River fall line. Percent deviations between duplicate sample measurements are provided in Appendix
B before the reported sample concentrations. Sample concentrations used for load estimations in
cases where duplicates were collected and analyzed were determined from the mean of the two
measured values (refer to Appendix B for details). Percent deviations calculated for duplicate results
varied widely for each collection data, analyte, and matrix. The trends apparent upon inspection of
the duplicate variability results are (a) when the sample concentrations were >10X the detection limit
values, precision in duplicate measurements was the highest, and (b) paniculate phase variabilities are
generally lower than dissolved phase measurement variabilities (because of the low detection limit
methods used for dissolved phase analysis).
33
-------
Table 11. Water matrix spike recoveries for the organo-N/P pesticides and PAH.
Spike Level (ONP):
Sample Volume:
No. Replicates:
Extraction Mode:
Matrix:
Analyte
Simazine
Prometon
Atrazine
Diazinon
Alachlor
Malathion
Metolachlor
Cyanazine
Hexazinone
Terbutylazine (SS)
Spike Level (PAH):
Sample Volume:
No. Replicates:
Extraction Mode:
Matrix:
Analyte
2-Methylnaphthalene
lOng/L
10 L
3
C18BPS
SRW
Mean
%Rec(%rsd>)
99
94
110
174
150
151
99
128
na
110
(18)
{29}
(7)
(8)
{10}
N=l
(20)
{38}
(13)
40ng/L
10L
2
C18BPS
SRW
Mean
lOOng/L
10L
3
CWBPS
%Rec(%dev>
103
135
74
95
97
124
110
144
135
96
20ng/L
2,6-Dimethylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(a)pyrene
Perylene
Fluoranthene-d,0 (SS)
SOL
1
GLSE
SRW
%Rec
71
76
86
77
80
64
84
88
71
90
71
129
82
(30)
(5)
(2)
(11)
(42)
(10)
(15)
(10)
N=l
(25)
SRW
Mean
%Rec(%rsd)
108
130
88
108
118
156
101
122
120
131
(50)
(11)
(14)
(13)
(7)
(18)
(19)
(15)
(11)
{16}
20ng/L
35 L
1
GLSE
SRW
%Rec
114
104
90
95
90
144
88
150
176
107
40ng/L
35 L
3
GLSE
SRW
Mean
%Rec
118
94
63
91
84
138
87
106
114
80
(%TSd)
{59}
(11)
(48)
(13)
(13)
(17)
(16)
(8)
{2}
(26)
40ng/L
SOL
3
GLSE
SRW
Mean
%Rec
59
65
71
66
76
89
91
95
88
96
88
78
71
(%rsd)
(25)
(26)
(13)
(10)
(2)
(19)
(9)
(10)
(7)
(13)
(8)
(15)
(39)
SRW = Susquehanna River water % Rec = % recovery
{} = percent deviation (%dev) calculated from two recoveries with triplicate extractions
na = not available % rsd = relative standard deviation
C18BPS = C-18 Bonded phase extraction GLSE = Goulden large-sample extraction
34
4
-------
Table 12. Water matrix spike recoveries for the PCBs and organochlorines.
Spike Level (SPCBs):
Sample Volume:
No. Replicates:
Extraction Mode:
Matrix:
Analyte
Dichlorobiphenyls
Trichlorobiphenyls
Tetrachlorobiphenyls
Pentachlorobiphenyls
Hexachlorobiphenyls
Heptachlorobiphenyls
Octachlorobiphenyls
Nonachlorobiphenyls
SPCBs
Spike Level (OCs):
Sample Volume:
No. Replicates:
Extraction Mode:
Matrix:
5ng/L
SOL
1
GLSE
SRW
%Rec
na
30
182
53
109
101
92
95
85
20ng/L
SOL
1
GLSE
SRW
15ng/L
SOL
3
GLSE
SRW
Mean
%Rec f%rad)
na
28 (36)
115(12)
59 (23)
104(11)
125 (18)
122 (26)
144 (16)
80 (17)
15ng/L
SOL
3
GLSE
SRW
SRW = Susquehanna River water
na = not available
GLSE = Goulden large-sample extraction
% Rec = % recovery
% rsd = % relative standard deviation
35
-------
Table 13. Filter matrix spike recoveries for PAH and PCBs.
Spike Level (PAH):
Sample Mass:
No. Replicates:
Extraction Mode:
Matrix:
Analyte
2-Methylnaphthalene
2,6-Dimethylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(a)pyrene
Perylene
Fluoranthene-dio (SS)
Spike Level (SPCBs):
Sample Mass:
No. Replicates:
Extraction Mode:
Matrix:
Analyte
Dichlorobiphenyls
Trichlorobiphenyls
Tetrachlorobiphenyls
Pentachlorobiphenyls
Hexachlorobiphenyls
Heptachlorobiphenyls
Octachlorobiphenyls
Nonachlorobiphenyls
SPCBs
5ng
-0.5 g
1
Soxhlet
SR Particles
%Rec
102
106
107
113
109
88
89
81
87
115
143
136
61
30 ng
-0.5 g
1
Soxhlet
SR Particles
%Rec
28
109
97
77
106
145
81
116
97
30 ng
-0.5 g
3
Soxhlet
SR Particles
Mean
%Rec (%rsd}
71 (53)
82 (26)
87 (35)
93 (33)
96 (20)
91 (11)
108 (40)
101 (42)
84 (11)
116 (14)
104 (19)
111 (20)
69 (17)
lOOng
-0.5 g
3
Soxhlet
SR Particles
Mean
%Rec (%rsd)
72 (43)
89 (12)
80 (22)
62 (29)
103 (23)
127 (32)
73 (68)
161 (25)
96 (6)
SR Particles = Susquehanna River particulates isolated on glass fiber filters.
% Rec = % recovery
% rsd = % relative standard deviation
36
-------
Table 14. Filter matrix spike recoveries for the organochlorines.
Spike Level (OCs):
Sample Mass:
No. Replicates:
Extraction Mode:
Matrix:
Analyte
Hexachlorobenzene
Aldrin
p,p'-DDE
alpha-BHC
beta-BHC
gamma-BHC
Oxychlordane
gamma-Chlordane
alpha-Chlordane
trans-Nonachlor
Dieldrin
o,p'-DDD
Endrin
p,p'-DDD
p,p'-DDT
Methoxychlor
delta-BHC (SS)
5ng
~0.5 g
1
Soxhlet
SR Particles
%Rec
100
91
53
103
114
101
123
89
69
68
58
72
46
124
102
65
109
30 ng
~0.5 g
2
Soxhlet
SR Particles
Mean
%Rec (%dev>
94 (15)
113(19)
71 (33)
118(8)
131 (12)
115(32)
88 (14)
54 (42)
76 (28)
72 (1)
32 (9)
45 (27)
na
92 (45)
70 (66)
91 (2)
104 ( 6)
SR Particles = Susquehanna River particulates isolated on glass fiber filters
na = not analyzed
37
-------
Table 15. QA analysis of standard reference sediment for PAH and organochlorines.
Sample Mass:
No. Replicates:
Extraction Mode:
Matrix:
Analyte
PAH
2-Methylnaphthalene
2,6-Dimethylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(a)pyrene
Perylene .
%Rec Fluoran-d10
0.612 g
1
Soxhlet
SRM 1941a
Measured
Value, ng
73.7
46.2
21.2
22.0
38.9
231
589
425
312
256
370
273
(102%)
Reference
Value, ng*
na
na
22.7
25.1
59.6
300
601
497
262
233
385
277
% Error"
-6.6%
-12.3%
-53.2%
-23.0%
-2.0%
-14.5%
19.1%
10.0%
-3.9%
-1.4%
Organochlorines
HCB
Aldrin
p,p'-DDE
alpha-Chlordane
trans-Nonachlor
Dieldrin
p,p'-DDD
p,p-DDT
33.7
6.90**
4.01
0.83
2.40**
1.01
3.35
0.60
42.9
2.94
4.04
1.43
0.77
0.77
3.10
0.77
-21.4%
135%
-0.7%
-42.0%
212%
31.2%
8.1%
-22.1%
•Reference values reported in NIST Certificate of Analysis calculated as ng/g(ref.) X 0.612 g
b %Error = (measured - reference)/reference X 100
**Analyte GC peak unresolved with background interference
na = not analyzed
SRM 1941 a = River sediment standard reference material
38
-------
Table 16. QA analysis of standard reference sediment for PCBs.
Sample Mass:
No. Replicates:
Extraction Mode:
Matrix:
Analyte
PCB Congener No.c
8/5
18
31/28
49
47
66/95
101/90
99
87
85
77/110
151
149/118
105
153/132
138
187/128
183
156
180
170/190
194
206
209
0.612 g
1
Soxhlet
SRM 1941a
Measured
Value, ng
0.483
1.28
7.92
4.69
3.88
4.21
6.53
3.60
3.97
4.20
4.64
1.35
10.5
2.42
11.0
5.70
4.77
1.03
0.86
5.82
2.25
1.59
2.52
5.07
Reference
Value, ng*
0.851
0.704
9.80
5.82
4.22
4.16
6.74
2.55
4.10
4.59
5.80
1.60
11.8
2.24
10.8
8.20
5.43
0.99
0.57
3.57
1.84
1.09
2.25
5.11
% Error*
-43.2%
81.8%
-19.2%
-19.4%
-8.1%
1.2%
-3.1%
41.2%
-3.2%
-1.5%
-20.0%
-15.6%
-11.0%
8.0%
1.9%
-30.5%
-12.2%
4.0%
50.9%
63.0%
22.3%
45.9%
12.0%
-1.0%
•Reference values reported in NIST Certificate of Analysis calculated as ng/g(ref.) X 0.612 g
b%Error = (measured - reference)/reference X 100
'Nomenclature of PCB congeners conforms to that of Ballschmitter and Zell
SRM 1941 a = River sediment standard reference material
39
-------
Water Quality Data Results - Susquehanna River
Tables 18-21 summarize the concentration data reported in Appendix B for both dissolved
and paniculate phase organic constituents (Table 17 lists sample parameters for the 1994-1995 fall
line study). The incorporation of the GLSE method greatly increased the frequency of detection for
the PAH, PCBs, and organochlorines in the dissolved phase relative to the 1992 Chesapeake Bay Fall
Line Toxics Monitoring Program. The very low concentrations shown in Tables 18-21 highlight the
need to apply ultra-trace analytical methods for measuring surface water concentrations of the organic
constituents.
The organo-N/P pesticides were only detected in the dissolved phase of the surface water
samples. During one winter storm event, atrazine was detected in the paniculate phase but it was
present at a concentration below quantitation limit value. PAH were detected primarily in the
paniculate phase. PCBs and the organochlorines were detected at approximately equal
concentrations in both the dissolved and paniculate phases.
Temporal behavior differs between compound classes, especially between the organo-N/P
pesticides and the other organics. Atrazine concentrations peaked in July and decreased exponentially
through the winter months. Maximal atrazine concentrations did not coincide with the greatest river
discharge. This is due to the fact that atrazine runoff correlates with field application, which occurs
between April to July. Atrazine, like most of the herbicides, is highly mobile and subject to rapid
runoff after field application. The other organic constituents showed more flow dependence with
concentrations; PCB and fluoranthene peak concentrations correlated with the greatest fall line river
discharges. This is especially true for the P AHs such as fluoranthene which are transported primarily
through fluvial sediments.
40
-------
Table 17. Sampling parameters for organics in Susquehanna River Fall Line Study.
Date
03/11/94
03/23/94
03/28/94
03/29/94
03/30/94
04/06/94
04/20/94
05/04/94
05/26/94
06/10/94
06/29/94
07/13/94
07/27/94
08/18/94
08/22/94
08/29/94
09/01/94
09/14/94
10/19/94
11/18/94
11/30/94
12/02/94
12/12/94
TSP
(mg/U
31
36
115
78
60
38
22
17
9
—
20
14
10
..
106
20
20
7
—
12
11
21
16
Sample
Volume. L
62.255
51.815
33.830
32.840
33.600
67.545
60.045
62.508
61.455
65.335
67.227
64.285
62.375
66.198
28.263
31.610
56.165
63.300
67.367
33.755
31.005
32.295
73.583
Fluvial Sediment
Mass, mg
1930
1865
3890
2562
2016
2567
1321
1063
553
—
1345
900
624
»
2996
632
1123
443
__
405
341
678
1177
TSP = total suspended particulate concentration
— = not available
41
-------
Table 18. Summary of organo-N/P pesticide and PAH dissolved phase concentrations measured in
the Susquehanna River at Conowingo, MD.
Analyte
Organo-N/P Pesticides
Simazine
Prometon
Atrazine
Diazinon
Alachlor
Malathion
Metolachlor
Cyanazine
Hexazinone
PAH
2-Methylnaphthalene
2,6-Dimethylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
Chrysene
Benz(a)anthracene
Benzo(a)pyrene
Perylene
Frequency
ofDetection
<%)
65
100
100
61
96
9
100
78
35
52
52
65
91
74
100
74
91
70
83
22
48
Maximum
Observed
Cone.. ng/L
132
77.4
241
16.7
187
32.0
195
185
61.8
9.0
2.6
1.2
1.7
1.8
2.3
17.2
15.0
2.1
2.1
1.5
3.3
Minimum
Observed
Cone.. ng/L
14.6
2.2
26.1
1.9
1.1
5.6
16.5
29.5
3.3
0.1
0.1
0.1
0.1
0.1
0.1
0.3
0.4
0.2
0.1
0.1
0.1
Mean Observed
Cone.. ng/L
69.1
29.9
81.5
5.5
19.4
18.8
61.2
84.2
22.0
2.3
1.0
0.3
0.4
0.7
1.1
3.4
3.0
0.6
0.4
0.8
0.9
42
-------
Table 19. Summary of PCBs and organochlorine dissolved phase concentrations measured in the
Susquehanna River at Conowingo, MD.
Analyte
PCBs
Dichlorobiphenyls
Trichlorobiphenyls
Tetrachlrorbipyenyls
Pentachlorobipyenyls
Hexachlorobiphenyls
Heptachlorobiphenyls
Octachlorobiphenyls
Nonachlorobiphenyls
SPCBs
Organochlorines
Hexachlorobenzene
Aldrin
p,p'-DDE
alpha-BHC
beta-BHC
gamma-BHC
Oxychlordane
gamma-Chlordane
alpha-Chlordane
trans-Nonachlor
Dieldrin
o,p'-DDD
Endrin
p,p'-DDD
p.p'-DDT
Methoxychlor
Frequency
of Detection
(%}
17
100
100
100
96
91
78
43
100
100
39
87
100
22
100
96
87
74
87
96
65
0
48
35
9
Maximum
Observed
Cone.. ng/L
0.125
0.621
1.913
1.543
1.118
0.607
0.232
0.129
5.312
0.284
0.155
0.817
0.297
0.180
0.617
0.430
0.655
0.260
0.669
0.523
0.625
0.688
0.813
1.210
Minimum
Observed
Cone.. ng/L
0.028
0.025
0.092
0.039
0.013
0.018
0.009
0.001
0.472
0.007
0.020
0.014
0.035
0.047
0.130
0.026
0.057
0.033
0.030
0.032
0.050
0.017
0.048
0.138
Mean Observed
Cone.. ng/L
0.069
0.252
0.520
0.415
0.343
0.161
0.062
0.046
1.734
0.042
0.081
0.153
0.149
0.098
0.342
0.152
0.208
0.102
0.169
0.215
0.200
0.152
0.233
0.674
43
-------
Table 20. Summary of PAH and PCB particulate phase concentrations measured in the
Susquehanna River at Conowingo, MD.
Analyte
PAH
2-Methylnaphthalene
2,6-Dimethylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
Chrysene
Benz(a)anthracene
Benzo(a)pyrene
Perylene
PCBs
Dichlorobiphenyls
Trichlorobiphenyls
Tetrachlorobiphenyls
Pentachlorobiphenyls
Hexachlorobiphenyls
Heptachlorobiphenyls
Octachlorobiphenyls
Nonachlorobiphyenyls
SPCBs
Frequency
ofDetection
(%\
91
100
100
100
100
100
96
96
100
100
100
100
13
100
83
96
96
96
96
96
100
Maximum
Observed
Cone.. ng/L
19.0
8.7
7.7
2.6
7.1
25.2
58.3
62.0
20.4
18.9
40.1
49.5
0.10
0.31
0.59
0.45
2.07
1.08
0.81
0.95
4.90
Minimum
Observed
Conc.r ng/L
0.4
0.2
0.2
0.1
0.6
2.5
5.1
4.4
1.3
1.9
1.5
1.8
0.04
0.01
0.02
0.04
0.19
0.12
0.08
0.00
0.02
Mean Observed
Conc.r ng/L
3.9"
2.5
1.1
0.7
2.0
8.2
23.5
21.6
6.8
7.4
9.1
11.1
0.06
0.08
0.19
0.15
0.50
0.35
0.27
0.18
1.61
44
-------
Table 21. Summary of organochlorine particulate phase concentrations measured in the
Susquehanna River at Conowingo, MD.
Analyte
M^MM^H^AK
Organochlorine
Hexachlorobenzene
Aldrin
p.p'-DDE
alpha-BHC
beta-BHC
gamma-BHC
Oxychlordane
gamma-Chlordane
alpha-Chlordane
trans-Nonachlor
Dieldrin
o,p'-DDD
Endrin
p,p'-DDD
p,p'-DDT
Methoxychlor
Frequency
ofDetection
(%)
^*"™»*
30
74
96
43
39
22
57
74
13
61
83
91
52
91
83
9
Maximum
Observed
Cone.. ne/L
•^Kn^hMMAO^^B^^^^
0.03
0.21
0.54
0.07
0.19
0.11
0.18
0.20
0.17
0.42
0.26
0.70
0.18
0.65
0.49
0.22
Minimum
Observed
Conc.r ng/L
0.01
0.02
0.06
0.02
0.04
0.03
0.02
0.02
0.11
0.02
0.02
0.02
0.03
0.03
0.02
0.10
Mean Observed
Cone., ng/L
0.01
0.08
0.22
0.05
0.12
0.06
0.08
0.08
0.14
0.16
0.09
0.24
0.11
0.22
0.16
0.16
45
-------
m.l.c Trace Elements
All dissolved, paniculate, and total trace-element concentration data collected at the
Susquehanna River at Conowingo, Maryland, for the period February 1994 through January 1995
are presented in Appendix C. Quality-assurance results will be presented first in each section, prior
to river data.
Quality Assurance Results - Susquehanna River
The quality-assurance program for the 1994 Fall Line Toxics Program included the collection
of the following quality-control samples: eight field blanks (six at the Susquehanna River, and one
each at the Pamunkey and Nanticoke Rivers) for dissolved analysis, three sets of triplicate river
samples for dissolved, and two sets of triplicate river samples for paniculate trace-element analysis.
Table 22 gives a summary of all the quality-assurance objectives for the University of Delaware
Laboratory and lists the quality-assurance criteria and procedures used for trace-element sample
collection and analysis.
Field-blank samples are collected in order to identify potential sources of contamination to
the water-quality sample during sample collection and/or field processing. Results of the field-blank
samples collected at the Pamunkey and Nanticoke Rivers are presented in the subsequent section
discussing the tributary synoptic study. Field-blank samples were collected for the analysis of the
paniculate phase as well, but because of significant blank concentrations, the average of the field
blank values for each trace element was subtracted from all environmental data.
Field-blanks were subjected to the same aspects of sample collection, field processing,
preservation, transportation, and laboratory handling as the sample. To this end, in order to best
represent collection of the sample, the field-blank samples for this project were collected and
processed on site at the river station, under field conditions, using the same equipment as is used to
collect the environmental sample. All blank water, sample bottles, and hydrochloric acid used to
collect the field blank sample was provided by the University of Delaware.
46
-------
Table 22. Quality-assurance criteria for the University of Delaware laboratory.
QA Criteria Sample
Type
Precision
Accuracy
Blanks
Complete-
ness
Instrument
Calibration
Field
Triplicate
field samples
Instrument:
replicate
analyses (at
separate
times)
certified
reference
standards
Field
Laboratory
Process
Analytical/
Instrumental
Field samples
Standard
curve
based on
f-factors
Minimum
Frequency
3 sets of
replicates
5%
5%
10%
10%
10%
Daily
—
per 15-25
samples
Acceptance
Criteria
rsd<10%
rsd<10%
within 95%
confidence
specified the
agency
15% of the
average mean
for samples
>MDL
90% of
planned
samples
Control
Action
re-analyze*
repeat
measurement
until criteria
met
re-analyze
&/or
re-calibrate
until
criteria met
analyze
equip, blanks
re-analyze*
j
____
re-optimize
instrument,
repeat
calibration
Reporting
Units
rsd
%
Mean,
Std Dev
Mass/Mass
Volume
Std Dev = standard deviation
rsd = relative standard deviation = Std Dev/Mean * 100
* = if sufficient sample volume is unavailable, data results will be flagged
47
-------
Results of the dissolved trace-element field-blank concentration data collected in 1994 at the
Susquehanna River are in Table 23.
We require our field-blanks to be less than 10-15% of the average sample concentration (on
a weight basis). In the case of undetectible concentrations, comparisons are made using the detection
limit. In general, the concentrations of the field blanks do not indicate any serious contamination
problems with the field collection Potential problems exist with Cd (field-blanks are approximately
18% of the average sample) and Cr and Pb (-35%). The sample concentrations of each of these
elements are often close to the detection limits. It is suggested that in future projects of this nature,
close attention should be paid to potential contamination of these elements.
Table 23. Dissolved trace-metal field-blank concentration data collected in 1994 at the Susquehanna
River at Conowingo, Maryland. All data are reported in micrograms per liter.
Date
940629
940901
940928
941019
941118
941212
Mean of
Blanks
Range of
Blanks
Mean of
River
Range
of River
Al
0.42
0.20
1.01
<0.12
0.24
0.36
0.39
<0.12
- 1.01
48.14
8.15-
154.35
As
<0.007
NA
<0.007
NA
NA
<0.007
<0.007
—
0.273
0.106
• 0.438
Cd
0.012
<0.006
<0.006
<0.006
0.020
0.013
0.010
<0.006
- 0.020
0.040
0.012
• 0.114
Cr
0.04
0.05
<0.03
0.03
<0.03
0.04
0.04
<0.03
-0.05
0.08
<0.03
-0.14
Cu
0.24
0.10
<0.03
<0.03
0.10
0.15
0.11
<0.03
-0.24
0.90
0.48
-2.03
Fe
0.32
0.62
0.75
<0.05
0.52
0.60
0.48
<0.05
-0.75
79.7
7.8-
301.5
Mn
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
<0.10
—
64.51
2.33
- 240.15
Ni
0.19
0.24
<0.12
<0.12
<0.12
0.24
0.17
<0.12
-0.24
2.07
1.02
-3.79
Pb
0.07
0.04
0.05
0.12
0.06
<0.03
0.06
<0.03
-0.12
0.12
<0.03
-0.28
Zn
<0.14
O.14
O.14
O.14
O.14
<0.14
<0.14
—
1.26
0.32
-3.14
NA = not analyzed
< = value is less than the analytical detection limit. All less-than values were given the value
of the analytical detection limit to calculate the mean.
48
-------
Additional blank samples were also collected throughout the year to verify sample collection
procedures, which include individual equipment blanks on the bailer, churn splitter, capsule filter,
hydrochloric acid, and sample-collection bottles. Results paralleled the results of the field-blank
samples.
Replicate river samples were collected in order to document and quantify the precision and
variability of both the field collection procedures and laboratory analytical techniques. During the
1994 study, three sets of replicate samples for dissolved trace elements, and two sets of replicate
samples for particulate trace elements were collected at the Susquehanna River at Conowingo,
Maryland. N = 3 for each replicate.
Replicate samples were collected in the following manner. A cross-sectional, depth-integrated
sample was collected, transferred to the churn splitter, and three subsamples were collected. While
keeping the river water in the churn splitter well mixed and homogenized, the three subsamples for
the dissolved phase were filtered, using three separate, pre-cleaned capsule filters, into 500 mL sample
bottles, and preserved with hydrochloric acid. Replicate samples for the particulate phase were
collected from the churn splitter as well. The sample for the particulate replicate was first collected
into 500 mL Teflon bottles, that were weighed before and after to determine the mass of sample. The
sample was then filtered through an acrylic plate filter which was preloaded at the University of
Delaware laboratory with an acid-washed 0.45 urn Nucleopore filter. This process was repeated for
the two other samples, using a total of three plate filters. The plate filters were triple bagged and
frozen until transported to the laboratory for analysis.
The mean, standard deviation, and relative standard deviation were calculated for each trace
element for each dissolved and particulate replicate sample, and the results are presented in Tables
24 and 25, respectively. The relative standard deviation (RSD) is used to evaluate the results of the
replicate samples. The RSD identifies and quantifies the precision of all the constituents analyzed.
For the purpose of this report, an RSD greater than thirty percent indicates low precision.
Results of the dissolved trace-element replicate samples on Table 24 show that cadmium,
chromium, lead, and zinc had RSD values greater than thirty percent for at least one replicate sample,
indicating low precision for these constituents. Replicate results for all remaining constituents listed
on Table 24 had RSD values less than thirty percent, indicating better precision for these constituents.
One reason for the low precision in some constituents may be instrument noise at these low detection
limits, especially for chromium and lead. The RSD for dissolved constituents ranges from 80 percent
for dissolved chromium in Replicate 2 to one percent for dissolved manganese in Replicate 1.
Results of the particulate trace-element replicate samples on Table 25 show that aluminum,
iron, and manganese have RSD values less than thirty percent, indicating reasonable precision for
these constituents. RSD values for cadmium, chromium, copper, nickel, lead, and zinc were greater
than thirty percent for at least one replicate sample, indicating lower precision for these constituents.
At least one sample for cadmium, chromium, lead, and zinc had RSD values greater than fifty percent,
indicating low precision. The RSD for particulate constituents ranges from 92 percent for particulate
cadmium in Replicate 1 to about seven percent for particulate iron in Replicate 1.
49
-------
to
1
«2
si
i§
Ci
^
•fii
•1
Q
05!
^
S
O
•
CA
i
^**
a
f
&
$
a
C«
^
•»•»
£
£
^^
a
&
o
^D
S
™
s
L
[Constituent
0
00
en
CS
O
ON
VO
cs
00
ON
cs
o
00
ON
en
O
«/">
s
^J1
CS
en
vo
ON
O
||Aluminum
00
cs
f-
o
d
vo
o
cs
d
vo
00
t-
en
O
o
trt
O
VO
O
f«-4
CS
o
o
§
o
o
•a
oo
cs
^J-
vr>
00
s
d
o
t-
o
o
00
J^
§
o
en
O
VO
CS
o
o
0
en
O
O
llCadmium
8
o
S
d
o
o
o
o
d
00
S
o
0
o
cs
cs
cs
cs
o
o
ON
o
0
llchromium
P
O
^•M
d
cs
00
o
•<*•
—
s
o
ON
en
_
o
o
^f
o
o
o
00
o
o.
a
0
0
cs
5
ON
00
~*
00
oo
ON
^
cs
en
^
cs
r-
w-i
ON
T
vo
ON
OO
1
cs
^_l
ON
VO
en
en
00
cs
en
vo
•"I"
en
cs
00
vo
00
en
p
00
CS
Z
o
^^
cs
IIManganese
o
«— i
vo
en
en
d
0
CS
o
en
•^
oo
o
0
~
m
00
o
en
00
O
o
o
VO
CS
%o
2
r-
d
t-
o
o
8
S
g
O
o
o
Tf
•Tt
VO
o
O
^
O
1
VO
ON
vo
CS
en
d
£
«-H
CS
r-
en
vo
o
en
O
O
^^
oo
O
cs
,_!
u
1
o
•fi
•a e
•a o
II II
Q ri
en R
-------
^
^^
Q
g
«N
J -
| *
*
^•^
e
w
%
X
Q
ro
tf
VM
1 .
^ ft
§ ri
as
T
|
e
0!
9i
S
•+*
U
.-§
*^
e
U
*-N
«r>
oo
00
CO
t-^
en
m
CS
?
oo
r-
o
00
r~'
in
ON
CS
o
?
g
1
<;
on
>— i
<
V)
HH
4f>
VI
*•*
^
en
cs
ON
i
o
vo
cs
o
o
1
•a
v
r>
ON
r~-
»n
O
i^-
C)
ON
VO
O
O
m
^
0
cs
o
t~-
Is-
*-H
mium
1
V
f*
vo
m
vo
CS
o
cs
t~~
o
m
0
cs
m
o
s
o
&
p
o.
o
u
VO
t*-
ON
t^
—
«/•>
CS
ON
«r>
en
t-
VO
ON
TT
CS
1-*
o
r-
en
O
NH
TT
«/•>
CS
00
•
g
Kft
1
^
VO
CS
TT
•^~
r-
cs
o
^
VO
o
TJ-
Tfr
r^
*r>
1— H
o
VO
oo
o
1
0
g
m
Tt
r~-
o
cs
o
00
cs
o
m
en
ro
i— <
VO
o
o
«Tl
T
O
•s
J
cs
cs
cs
cs
»r>
o
«r>
•^~
CS
t~»
VO
s
r-
ON
CS
cs
g
N
o
o
o
•o
1
T3
-------
Water-Quality Data Results - Susquehanna River
Samples for trace elements were collected monthly at the Susquehanna River for the period
from February 1994 through January 1995. Storm events were sampled during February, March,
April, August, November, and December 1994 and January 1995. Several samples were collected
during each storm event in order to characterize changes in constituent concentrations with respect
to changes in streamflow, including several samples collected during the peak discharge of the spring
1994 freshette (March 11 - April 22).
Appendix C presents all dissolved, paniculate, and total trace-element concentration data
collected during the period February 1994 through January 1995, and Table 26 presents data
summaries of dissolved, paniculate, and total trace-element concentration data. For the purposes of
comparison and for load estimation, paniculate concentrations have been converted from jig/g to
ug/L. This conversion was made using the suspended-sediment concentration for each observation:
[concentration of the trace element in the solid phase for each observation] x [concentration of
suspended sediment for each observation] /1000.
Due to lower analytical detection limits for most of the trace elements, the number of values
below the detection limit was reduced from previous years, and hence all the trace elements were
detected in fluvial transport at some point during the study period.
Mean concentrations of iron, manganese, and aluminum for both phases were greater than
those concentrations determined for the other elements listed in Table 26. For example, the mean
concentration of dissolved iron was about 80 ug/L, but the means for dissolved zinc and arsenic were
only 1.26 ug/L and 0.27 |ig/L, respectively. The mean concentrations for the toxics of concern were
all less than 1 ug/L for the dissolved phase, and all were less than 3 ng/L for the paniculate phase.
Of the toxics of concern, the mean dissolved concentration of copper was 0.90 ^ig/L, and the mean
paniculate chromium concentration was 2.97 ng/L; and the mean dissolved and paniculate cadmium
concentrations were 0.040 ^ig/L and 0.15 ^ig/L, respectively.
As a statistical summary of the elemental concentrations, box plots were constructed to show
the mean, quartiles and outliers of the data. Selected elements are shown in Figure 3. As seen in this
figure, the paniculate trace metals exhibit considerable variability throughout the year with Zn
showing the highest variation. In comparison, all dissolved trace elements seem to be fairly
homogenous throughout the year.
52
-------
§-•
«
^2
I
1
Particulate
1
^
1
aj
•a
15
S
•
c
i
e
1
S5
H
05
(e
1
«
^
M
M
•••
e
S
£
*•«
3
•*->
w
e
U
VO
cs
£.
o
1
ON
0
t"
00
ON
VO
CS
vo
CS
vb
ON
1—4
O
ON
00
1-M4
00
0
VO
cs
f>
5
1-H
00
1— H
00
"*
z
1
<
*
<
^f,l
X
<;
*z*
<
£-*
oo
o
1
VO
o
o
cs
o
u
1
cs
o
oo
oo
cs
o
o
s^
o
»0
cs
r-
F— 4
1
CS
0
o
m
1—4
o
1
cs
o
0
o
o
o
3
1
vo
cs
TT
O
'
rr
r-
o
«n
o
CO
vo
cs
o
0
1—4
ON
VO
O
5
cs
ro
O
O
d
V
00
o
o
1
i
V
vo
cs
o
'
o
«A
f^.
cs
f^.
cs
oo
o
1
«n
cs
o
00
m
o
i
oo
0
o
ON
O
fc
O.
o.
o
VO
VO
00
i
1
en
«n
^
VO
rr
f-
cs
ON
oo'
00
cs
00
o
s
m
*"*
rr>
o
m
i
oo
ON
|
VO
cs
rr
VO
O
•
ON
CO
f>
O
§
VO
CS
o
vb
o
cs
1
00
ON
o
00
VO
ro
*••"<
O
TJ-
cs
1
cs
-
^
VO
u
1
VO
cs
ON
ON
1
^^
en
«0
ON
CO
VO
cs
1—4
VO
f-'
00
cs
o
ON
m
ON
r-
rn
i
cs
0
r-
o
cs
|
VO
CS
CO
«n
_^^
0
o
ON
"""
VO
cs
VO
o
w-i
cs
• o
o
s
m
cs
o
1
o
cs
1— H
o
1
VO
cs
TT
ON
CS
00
00
00
o
vo
cs
00
m
00*
cs
~
vo
vo
ON
en
2
i
cs
C)
VO
cs
^
N
O
I
I
§
•a
u
f
-------
Box Plots of dissolved and particulate
trace element concentrations in 1994
dU -
si 25 -
O>
A
£ 20 -
c
o
^ 15 "
l_
*rf
c
o
o 10 -
c
o
0
5 -
0.
As
^ri^i^L
Cd
o
rv
I
Cr
*-\
o
T
T'T'tl
r,x|i]
III
i i
Cu
o
— r-
.0. ffijffi
I p^
Pb
rj.
, B
i
ZnT
efe
KS2
LXJCJ
pl^wt^
T i^ i'
aSjx
rrT5rri
f*^f^Y^i
kXJt!JtN
_L
i
dis
i i i i r i i
dis part dis part dis part dis part dis part
Figure 3. Box plots of selected dissolved (dis) and particulate (part) trace-element concentration
data collected at the Susquehanna River at Conowingo, Maryland, during the period February 1994
through January 1995. Each box encloses 50% of the data, with the median value shown by the line
inside the box. The lines extending from the top and bottom of the box mark the 95th and 5th
percentile, respectively.
54
-------
Figures 4 through 8 are time-series plots of concentration data for selected trace elements
collected from February 1994 through January 1995. Dissolved concentrations do not appear to be
related to flow or seasonality in any of the time-series plots. Concentrations for most of the
paniculate trace elements appear to be positively correlated with flow, although statistical correlations
between discharge and the concentrations are low.
The partitioning of metals into the dissolved or paniculate phases is largely dependent on the
individual chemistry of the element as well as the chemical conditions of the water. The paniculate
fraction of most of the elements makes up the majority of the total load. However, during the spring
to mid-summer at the Susquehanna River, Cu, Mn, Ni, and to some extent Cd, seem to partition into
the dissolved phase. This period is also characterized by higher biological activity which could be
repartitioning the metals from the suspended sediment.
55
-------
12000
Aluminum
Jan Mar
May Jul Sep
1994-1995
Jan
400000
350000
O
300000 o
Al (dis.)
Al (part.)
Discharge
Iron
5000
400000
350000
Fe (dis.)
Fe (part.)
Discharge
Jan Mar May Jul Sep
1994-1995
Nov
Jan
Figure 4. Time-series plots of mean daily discharge and dissolved and particulate aluminum and iron
concentration data, collected during February 1994 through January 1995 at the Susquehanna River
at Conowingo, Maryland.
56
-------
Copper
3
O
II
1 =
o
o
c
o
o
12
10 -
8 -
6 -
4 -
2 -
Jan
• Cu (dis.)
•Cu (part.)
• Discharge
Mar
i i i i i i i r
May
Jul Sep
1994-1995
Nov
Jan
- 400000
- 350000
- 300000 o
5T
- 250000 §•
B>
- 200000 «
- 150000
o
- 100000
- 50000
- 0
Cadmium
O
»-
o
5 2
«
~ £
o
o
o
o
b -
5 -
4 -
3 -
2 -
1 -
— o— Cd (dis.)
:': — •— Cd (part.)
Discharge
\ »•*
• *.' •,;• !
• ' '<*• I
•' * '• .'•
* « *• * .
liM \ j A
VjV V^ L__ A 5,/ai//
i i -"• r"i"i"i"i i r r~i f
' 400000
- 350000
O
' 300000 *
tt
- 250000 co
o
- 200000 3
- 150000 w
- 100000
~ 50000
- o
Jan Mar May Jul Sep Nov Jan
1994-1995
Figure 5. Time-series plots of mean daily discharge and dissolved and particulate copper and
cadmium concentration data, collected during February 1994 through January 1995 at the
Susquehanna River at Conowingo, Maryland.
57
-------
Nickel
o o>
33 3.
CO
e
o
c
o
O
8
7 -
6 -
5 -
4 -
3 -
2 -
1 -
0
-Ni (dis.)
•Ni (part.)
Discharge
I I I I I I I I I I
Jan Mar May Jul Sep Nov
1994-1995
Jan
- 400000
- 350000
O
- 300000 8
3-
- 250000 <2
o
- 200000 3"
- 150000 5?
- 100000
- 50000
- 0
Chromium
o
o »
»• "*•
CD
CD
O
C
o
o
10
8 H
6 J
4 -
2 -
•Cr (dis.)
•Cr (part.)
•Discharge
Jan Mar May Jul Sep
1994-1995
Nov
Jan
400000
350000
O
300000 o
3-
0>
250000 to
200000 5*
o
Figure 6. Time-series plots of mean daily discharge and dissolved and paniculate nickel and
chromium concentration data, collected during February 1994 through January 1995 at the
Susquehanna River at Conowingo, Maryland.
58
-------
Manganese
iiOU -
s 200 -
2E
"o
_J
Q O)
"^ -^
To
i: c
«" 100 ~
u
c
o
o
50 -
n
Js
5_
<
o 4 -
J 5
to 3 ~
i: e
** *W
0
g 2 -
o
U
1 -
n -
t
i
A ••"•.
'• \' '
f
"'"'
i i
in Mar
i i
{
:• ,.•;
' 1 "*
• '
.' •.'
'">•' £
'O—o^
— * — Mn (dis.)
• — • — Mn (part.)
; Discharge
i
'*"s '
"*• '
*•% 1
A A A
/ \ / A • / \ /
' \ xA / ;i/\ / \ / //
*•»* •*?•„'•„• '»• "•;'•... ".•".„_ •^f. •"''vVv*' v!^ ••''"•
i i i i i i i Iii
May Jul Sep Nov Ja
1994-1995
Arsenic
i i i i i i t i i i
— o — As (dis.)
....... Discharge
•
••.
'••'i?
/ * i • i
*j • \
;.
i * S ''
1 > .I * *' '
'i '**' '•• t\ -& "• •'• * .' . ' ' v . \ . i'
?o— -v~" v
»
>«
n
.
-
^
-
•
•~
-
-
„
-
-j
: :
', —
-
-------
Zinc
N
II
»• "*•
f c
o
o
o
u
30
Zn (dis.)
Zn (part.)
Discharge
Jan Mar May Jul Sep
1994-1995
Nov
Jan
400000
350000
300000 5T
o
250000 »
(Q
O
200000 _
a
150000 «
w
100000
50000
0
Lead
XI
Q.
o
o
Jan Mar May Jul Sep
1994-1995
Nov
Jan
400000
- 350000 D
5T
300000 §•
m
250000 *§
Pb (dis.)
Pb (part.)
Discharge
Figure 8. Time-series plots of mean daily discharge and dissolved and paniculate zinc and lead
concentration data, collected during February 1994 through January 1995 at the Susquehanna River
at Conowingo, Maryland.
60
-------
Table 27 lists the crustal abundances and enrichment factors for the paniculate phase of the
trace elements collected at the Susquehanna River during the report period. Cadmium, by a factor
of 110, suggests probable anthropogenic loadings of this element.
Table 27. Average crustal abundances, and enrichment factors for trace elements in suspended
paniculate material collected at the Susquehanna River at Conowingo, Maryland. An enrichment
factor greater than 1 is considered to be enriched over the crustal abundances, and therefore, may
suggest anthropogenic sources. Enrichment factors were calculated on the paniculate fraction only.
Trace
Element
Aluminum
Cadmium
Copper
Chromium
Iron
Lead
Manganese
Nickel
Zinc
Average Crustal
Abundances, ug/g
(Taylor and
McLennan, 1985)
84000
0.098
75
185
70600
8
1400
105
80
Mean
Particulate
Concentration, u.g/g
63970
8.11
70
114
34810
35
2610
52
280
Enrichment1
Factor
__
110
1.2
0.8
0.6
5.8
2.4
0.6
4.6
'Enrichment factor was calculated using the following equation:
, Metal >
AJ particulate
Metal
crust
m.l.d Discussion of Water-Quality Results, Susquehanna River
Procedures for the collection and analysis of samples at the Susquehanna River provided an
improved data set by (1) using sensitive analytical techniques to obtain low detection limits for most
of the trace-element constituents, and (2) the continued use of ultra-clean sampling methods. Data
reported as below the detection limit in the environmental samples was infrequent. The
concentrations in the field-blank samples for cadmium, chromium, and lead were in many cases about
the same as the environmental concentration data, which suggests needed improvements in sample
61
-------
collection and analysis for these three constituents. Additionally, the analytical precision for chromium
and lead was about ±50 percent.
Results of the replicate sample data suggests that the precision was low for dissolved
cadmium, chromium, lead, and zinc, and participate cadmium, chromium, copper, nickel, lead, and
zinc. One reason for the low precision for the paniculate trace elements may be due to re-occurring
problems in the paniculate filtration procedure. The plate filters have a tendency to leak during
filtration which possibly resulted in loss of sample and therefore different values for each subsample.
The mean concentrations for the toxics of concern were less than 1 ug/L for the dissolved
phase, and the mean for dissolved cadmium was 0.040 ug/L. The mean concentrations for the toxics
of concern were less than 3 ug/L for the paniculate phase, and the mean for paniculate cadmium was
0.15 ug/L.
Dissolved concentrations do not appear to be related to flow or seasonally. Concentrations
for most of the paniculate trace elements appear to be positively correlated with flow, although
statistical correlations between discharge and concentration are low. Also, there are other sources
of variation that have not yet been identified.
The paniculate trace elements exhibit considerable annual variability: the interquartile ranges
are greater for the paniculate phase than for the dissolved phase. The range for paniculate and
dissolved zinc is about 13 ug/L and 2 ug/L, respectively. However, the range for the remaining
dissolved phases generally was less than about 1 ug/L. The narrow range determined for the
dissolved trace element concentrations suggests that accurate estimates of dissolved trace elements
could be made with fewer samples.
The majority of the elements partition into the paniculate phase, although Cu, Mn, Ni, and
Cd are higher in dissolved concentration in the late spring-early summer. This period just after the
spring freshette is characterized by a decrease of some paniculate metals. One theory is that higher
biological activity during the summer months repartitions the metals from the suspended sediment.
This behavior could also be attributed to lower stream velocity and thus lower erosion of the
paniculate material.
As the enrichment factors indicate, only paniculate Cd seems to have a significant
anthropogenic proportion. The remainder of the particulate metals are predominantly from crustal
sources. Other anthropogenic contributions are most likely limited to the dissolved phase.
62
-------
m.2 Tributary Synoptic Study Results
The following sections present water-quality data from the two tributary synoptic studies
conducted by the Fall Line Toxics Program in 1994. The first synoptic study occurred in the spring,
from April 25 through May 6, 1994, collecting one or two sites per day. Hydrologic conditions
during this time were base flow, and no storms occurred during sampling, but discharges were above
average since it was the end of the spring rainy season. Pesticide applications for agriculture generally
begin in late March and early April, so there was a good potential to capture the effects of this source
of contaminant loading during the spring synoptic study.
Sampling for the second synoptic study occurred in the fall, from November 8 through 18,
1994. Hydrologic conditions were at or near base flow. Some mild rain storms occurred during the
Virginia portion of this synoptic study, but these did not appear to affect flow conditions in the
tributaries. The discharges during the fall synoptic study were lower than those during the spring for
all rivers except the Susquehanna.
m.2.a Suspended Sediments
All suspended-sediment concentration data collected during the spring and fall tributary
synoptic studies are presented in Appendix A. The mean, minimum, and maximum for suspended-
sediment concentrations for each of the fall line synoptic sites are presented in Table 28. Data from
other USGS studies (USGS 1994A, USGS 1994B) were included in the summary. For each
tributary, the suspended-sediment concentrations were higher in the spring than in the fall (Appendix
A); the mean suspended-sediment concentrations for the spring and fall were 12 mg/L and 5 mg/L,
respectively.
63
-------
Table 28. Data summaries of suspended-sediment concentrations (mg/L) collected at the fall line
river stations for the 1994 Spring and Fall tributary synoptic studies. Data from other USGS studies
(USGS 1994A, USGS 1994B) were included in the summary.
Susquehanna River at Conowingo,
MD
Potomac River at Chain Bridge
at Washington, B.C.
James River at Cartersvillc, VA
Rappahannock River nr
Fredericksburg, VA
Pamunkey River nr Hanover, VA
Mattaponi River nr Beulahville,
VA
Patuxent River nr Bowie, MB
Choptank River nr Greensboro,
MB
Nanticoke River nr Bridgeville,
BE
Mean
(mg/L)
48.5
22.7
9.9
24.2
18.0
9.0
58.3
17.8
3.5
Min-
Max
5-148
7-56
5-18
2-78
3-56
3-25
7-299
2-87
3-4
N
37
9
7
6
6
6
25
24
2
Min = minimum value
Max = maximum value
N = number of data points
During the spring tributary synoptic study, this program also conducted an experiment to
determine the cross-sectional variability at each river site. For each site, four to five discrete samples
were collected at equal increments of flow across the river. A replicate, with N=3, was also collected
at the center of flow for each river at the same time the cross-sectional sample was collected. The
results of this experiment as well as the mean and relative standard deviations for each group of
samples are presented in Table 29. The minimum and maximum relative standard deviations for the
replicate center-of-flow measurements were 2.78 and 36.36 percent, respectively. The minimum and
maximum relative standard deviations for the cross-section measurements were 2.22 and 35.00
percent, respectively. Results for the cross section and the center of flow for the Susquehanna River
showed apparent differences between the two methods. A student's t-test comparing the two
methods gives t-statistic of 1.85 with 10 df and 90% confidence. Results from the other tributaries
showed only small differences between the two methods. However, this experiment was conducted
during baseflow conditions, and it is recommended that it be repeated during stormflow conditions.
64
-------
Table 29. Results of the suspended-sediment cross-sectional variability study at each of the nine fall
line synoptic tributaries. All suspended-sediment concentration values are in mg/L. Values for the
cross section are discrete samples collected at increments of equal flow across each river, and are
listed here in sequential order from the left bank of each river. Values for center of flow are replicates
with N=3 and were collected at approximately the same time as the cross-section samples.
Susque.
Potom.
James
Rapp.
Pamun.
Mattap.
Patux.
Chop.
Nant.
Date
5/4/94
5/3/94
4/27/94
4/28/94
4/26/94
4/26/94
5/6/94
5/5/94
5/5/94
Cross Section
Concen-
tration
(mg/L)
18/1 5/10/
13/11
/10
35/3 6/377
36
10/6/5/5
75
3/3/4/3/4
9/8/8/9
9/9/10/8
11/13/13
6/7/8/6/7
3/3/5/6/4
Mean
Concen-
tration
12.8
36.0
6.2
3.4
8.5
9.0
12.3
6.8
4.2
S.D./
RSD%
3.2 /
25.00
0.8 /
2.22
2.177
35.00
0.5 /
14.70
0.6 /
7.06
0.8 /
8.89
1.2 /
9.76
0.8 /
11.76
1.3 /
30.95
Center of Flow
Concen-
tration
(mg/L)
10/11/10
37/36/35
5/6/5
4/2/4
8/8/9
10/11/10
13/12/13
8/7/8
3/5/5
Mean
Concen-
tration
10.3
36.0
5.3
3.3
8.3
10.3
12.7
7.7
4.3
S.D.7
RSD%
0.6 /
5.82
1.07
2.78
0.6 /
11.32
1.27
36.36
0.6 /
7.23
0.6 /
5.82
0.6 /
4.72
0.6 /
7.79
1.2 /
27.91
SD = standard deviation
RSD = relative standard deviation = S.D./Mean * 100 in percent
65
-------
m.2.b Organic Constituents
Dissolved and paniculate organic concentrations for the eight tributary synoptic study are |
presented in Appendix E.
Quality Assurance Results - Tributary Synoptic
The field blanks processed as part of the eight tributary synoptic study are summarized in
Appendix F and are not further elaborated here given the few number of blank determinations made.
Water Quality Data Results - Spring and Fall Eight Tributary Synoptic
Concentrations of the organic constituents are summarized in Tables 30 through 37 for the
eight tributaries. Raw data are presented in Appendix E. The concentrations of the organic
constituents at the tributary fall lines showed spatial variability, but a few general trends are evident.
First, during the spring sampling, the Choptank River consistently had the greatest concentrations of
the organo-N/P pesticides and low-end PAHs (<4 ring structures) in dissolved phase transport; and
the Potomac River had the greatest concentrations of PCBs and PAH in paniculate phase transport.
Secondly, the minimum observed concentrations for PAH and PCBs in both transport phases were
more frequently associated with the eastern shore tributaries, apart from the organo-N/P pesticides
in the Choptank River during the spring as mentioned above. Thirdly, with respect to paniculate
phase transport, the greater concentrations of PAH and PCB were found for the spring sampling,
when the river discharges were higher, relative to the fall.
66
-------
Table 30. Data summaries of dissolved phase organo-N/P pesticide and PAH concentrations in
samples collected at the fall lines of eight tributaries for the 1994 Spring synoptic study. Tributaries
with maximum and minimum concentrations are indicated.
Organo-N/P Pesticides
Simazine
Prometon
Atrazine
Diazinon
Alachlor
Malathion
Metolachlor
Cyanazine
Hexazinone
PAH
2-Methylnaphthalene
2,6-Dimethylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(a)pyrene
Perylene
Cone. Range
(ng/U
14-171
3-37
6-630
1-31
2-24
3-24
3-450
4-240
0.6 - 12
0.30-1.7
0.06 - 0.7
0.08 - 0.3
0.07 - 2.3
0.42 - 2.2
1.0-4.8
0.55-2.8
0.25 - 2.8
0.02 - 0.2
nd
nd
0.03 - 0.6
Maximum Cone.
Tributary
Choptank
Choptank
Choptank
Choptank
Choptank
Choptank
Choptank
Choptank
Pamunkey
Choptank
Choptank
Choptank
Choptank
Choptank
Choptank
Patuxent
Patuxent
James
Choptank
Minimum Cone.
Tributary
Rappahannock
James
James
Potomac
Pamunkey
Potomac
James
Mattaponi
Rappahannock
Potomac
Mattaponi
Rappahannock
Rappahannock
Mattaponi
Potomac
Rappahannock
Mattaponi
Potomac
Rappahannock/
Potomac
Detect.
Freq.
75%
88%
88%
50%
62%
50%
88%
75%
88%
88%
88%
88%
88%
88%
88%
88%
88%
88%
0%
0%
38%
nd = not detected
67
-------
Table 31. Data summaries of dissolved phase PCB and organochlorine concentrations in samples
collected at the fall lines of eight tributaries for the 1994 Spring synoptic study. Tributaries with
maximum and minimum concentrations are indicated.
PCBs
Dichlorobiphenyls
Trichlorobiphenyls
Tetrachlorobiphenyls
Pentachlorobiphenyls
Hexachlorobiphenyls
Heptachlorobiphenyls
Octachlorobiphenyls
Nonachlorobiphenyls
SPCBs
Organochlorines
Hexachlorobenzene
Aldrin
p,p'-DDE
alpha-BHC
beta-BHC
gamma-BHC
Oxychlordane
gamma-Chlordane
alpha-Chlordane
trans-Nonachlor
Dieldrin
o,p'-DDD
Endrin
p,p'-DDD
p,p'-DDT
Methoxychlor
Cone.
Range Cng/L')
nd
0.02 - 0.5
0.16-0.8
0.03 - 0.3
0.02 - 0.2
0.01 - 0.2
0.30
nd
0.01-1.4
0.01 - 0.07
02
0 02 - 0.3
0 02 - 0.2
0.1
0.1-0.8
nd
0.01 - 0.08
0.02 - 0.07
0.02 - 0.05
0.05 - 0.6
0.02 - 0.07
nd
0.02 - 0.08
0.07 - 0.09
nd
Maximum Cone.
Tributary
Potomac
James
Potomac
James
Pamunkey
Choptank
Potomac
Potomac
Choptank
Nanticoke
Choptank
Rappahannock
Nanticoke
Choptank/
Nanticoke
Nanticoke
Rappahannock
Choptank
Potomac
Choptank
Choptank
Minimum Cone.
Tributary
Pamunkey
Rappahannock
James
Rappahannock
Mattaponi
-
Mattaponi
Nanticoke
-
Rappahannock
Pamunkey
-
Pamunkey
Potomac
James
Potomac
Potomac
Pamunkey
Potomac
Nanticoke
Detect.
Freq.
88%
88%
88%
88%
75%
12%
100%
88%
12%
62%
88%
12%
88%
0%
75%
75%
75%
75%
38%
0%
50%
38%
0%
nd = not detected
68
-------
Table 32. Data summaries ofparticulate phase PAH and PCB concentrations in samples collected
at the fall lines of eight tributaries for the 1994 Spring synoptic study. Tributaries with maximum and
minimum concentrations are indicated.
PAH
2-Methylnaphthalene
2,6-Dimethylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(a)pyrene
Perylene
PCBs
Dichlorobiphenyls
Trichlorobiphenyls
Tetrachlorobiphenyls
Pentachlorobiphenyls
Hexachlorobiphenyls
Heptachlorobiphenyls
Octachlorobiphenyls
Nonachlorobiphenyls
SPCBs
Cone. Range
fag/L)
1.6
0.03 - 9.5
0.01 - 1.1
0.02 - 0.5
0.01 - 1.6
0.03 - 4.9
0.41 - 21
0.08 - 15
0.02 - 5.0
0.17-6.2
2.1-9.8
0.03 - 10
nd
0.02 - 0.03
0.06 - 0.5
0.05 - 0.3
0.02 - 0.6
0.01 - 0.4
0.0. - 0.2
0.03
0.10-2.0
Maximum Cone.
Tributary
Potomac
Potomac
Potomac
Potomac
Potomac
Potomac
Potomac
Potomac
Potomac
Potomac
Potomac
Mattaponi
Potomac
Potomac
Potomac
Potomac
Potomac
Potomac
Potomac
Potomac
Minimum Cone.
Tributary
Mattaponi
Pamunkey
Nanticoke
Mattaponi
Rappahannock
Pamunkey
Rappahannock
Mattaponi
Nanticoke
James
Nanticoke
James/
Choptank
Nanticoke
James
Choptank
Rappahannock
James/Patuxent
Nanticoke
Detect.
Freq.
12%
100%
75%
50%
75%
100%
100%
100%
100%
62%
50%
100%
38%
100%
50%
88%
50%
38%
12%
100%
nd = not detected
69
-------
Table 33. Data summaries of particulate phase organochlorine concentrations in samples collected
at the fall lines of eight tributaries for the 1994 Spring synoptic study.
Organochlorines
Hexachlorobenzene
Aldrin
p,p'-DDE
alpha-BHC
beta-BHC
gamma-BHC
Oxychlordane
gamma-Chlordane
alpha-Chlordane
trans-Nonachlor
Dieldrin
o,p'-DDD
Endrin
p,p'-DDD
p,p'-DDT
Methoxychlor
Cone. Range
(ng/U
0.03-0.1
0.06 - 0.2
0.02 - 0.3
0.02
0.03-0.1
0.23
nd
0.08 - 0.2
nd
0.1
0.03 - 0.2
0.01 - 0.5
nd
0.03 - 0.3
0.06 - 0.3
0.08
Maximum Cone.
Tributary
Potomac
Patuxent
Potomac
Minimum Cone.
Tributary
James
Choptank/
Mattaponi
Patuxent
Rappahannock/Choptank/Patuxent
James/Nanticoke
Potomac
Potomac
Patuxent
Patuxent
Patuxent
Potomac
Potomac
Potomac
James
Rappahannock
[Several]
Pamunkey/
Rappahannock
Mattaponi/
Rappahannock
Detect.
Freq.
25%
88%
75%
38%
100%
12%
0%
62%
12%
100%
100%
0%
75%
50%
12%
nd = not detected
70
-------
Table 34. Data summaries of dissolved phase organo-N/P pesticide and PAH concentrations in
samples collected at the fall lines of eight tributaries for the 1994 Fall synoptic study. Tributaries
with maximum and minimum concentrations are indicated.
Organo-N/P Pesticides
Simazine
Prometon
Atrazine
Diazinon
Alachlor
Malathion
Metolachlor
Cyanazine
Hexazinone
PAH
2-Methylnaphthalene
2,6-Dimethylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(a)pyrene
Perylene
Cone. Range
(ng/L)
12-66
6-20
3-65
0.6 - 23
2-47
1-8
1-49
89-118
2-17
2.3 - 5.4
6.6
0.4 - 2.2
0.07 - 0.6
0.3
0.5 - 2.7
0.5-2.0
nd
0.06 - 0.4
0.5 - 2.6
nd
2.4 - 8.6
Maximum Cone.
Tributary
Patuxent
Potomac
Patuxent
Patuxent
Nanticoke
Pamunkey
Nanticoke
James
Pamunkey
James/
Choptank
Choptank
Patuxent
Potomac
Choptank
Patuxent
Pamunkey
Patuxent
Patuxent
Mattaponi
Minimum Cone.
Tributary
James
Mattaponi
James
Nanticoke
Potomac
Rappahannock
James
Potomac
Potomac
Mattaponi
Rappahannock
Rappahannock
Rappahannock
Rappahannock
Mattaponi
Mattaponi
Potomac
Detect.
Freq.
100%
100%
100%
75%
50%
25%
100%
25%
88%
75%
12%
100%
62%
12%
88%
100%
62%
75%
100%
nd = not detected
71
-------
Table 35. Data summaries of dissolved phase PCBs and organochlorines concentrations in samples
collected at the fall lines of eight tributaries for the 1994 Fall synoptic study. Tributaries with
maximum and minimum concentrations are indicated.
PCBs
Dichlorobiphenyls
Trichlorobiphenyls
Tetrachlorobiphenyls
Pentachlorobiphenyls
Hexachlorobiphenyls
Heptachlorobiphenyls
Octachlorobiphenyls
Nonachlorobiphenyls
SPCBs
Organochlorines
Hexachlorobenzene
Aldrin
p,p'-DDE
alpha-BHC
beta-BHC
gamma-BHC
Oxychlordane
gamma-Chlordane
alpha-Chlordane
trans-Nonachlor
Dieldrin
o,p'-DDD
Endrin
p,p'-DDD
p,p'-DDT
Methoxychlor
Cone.
Range (ng/L)
nd
0.2 - 0.4
nd
0.03-0.1
0.03 - 0.3
0.01-0.2
0.01 - 0.3
nd
0.4 - 0.7
0.03 - 0.07
nd
0.2
0.06 - 0.4
0.03 - 0.4
0.05 - 2.0
0.01-0.1
0.03-0.1
0.03 - 0.04
0.02
0.03-0.1
0.02 - 0.07
nd
0.02-0.1
0.04
nd
Maximum Cone.
Tributary
Potomac
James
Pamunkey
Pamunkey
Pamunkey
James
Rappahannock
Choptank
Rappahannock
Rappahannock
Patuxent
James
Rappahannock
Nanticoke
Patuxent
James
Choptank
Patuxent
Patuxent
Minimum Cone.
Tributary
James
Mattaponi
Potomac
Choptank
Rappahannock
Choptank
Choptank
Choptank
Potomac
Choptank/
Nanticoke
Potomac
Choptank
James
Rappahannock
Patuxent
Pamunkey/
James
Detect.
Freq.
50%
0%
75%
62%
62%
62%
75%
50%
0%
12%
75%
62%
88%
62%
50%
25%
12%
50%
50%
0%
88%
12%
0%
nd = not detected
72
-------
Table 36. Data summaries of paniculate phase PAH and PCBs concentrations in samples collected
at the fall lines of eight tributaries for the 1994 Fall synoptic study. Tributaries with maximum and
minimum concentrations are indicated.
PAH
2-Methylnaphthalene
2,6-Dimethylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
Benz(a)anthracene
Chrysene
Benzo(a)pyrene
Perylene
PCBs
Dichlorobiphenyls
Trichlorobiphenyls
Tetrachlorobiphenyls
Pentachlorobiphenyls
Hexachlorobiphenyls
Heptachlorobiphenyls
Octachlorobiphenyls
Nonachlorobiphenyls
SPCBs
Cone.
Range (ng/L)
nd
0.0-1.6
0.01 - 0.2
nd
0.02-0.1
0.02- 1.5
0.09 - 4.6
0.02 - 5.0
0.07-1.4
0.10-2.1
1.3-2.0
0.01 - 1.8
nd
nd
0.06 - 0.2
0.03-0.1
0.04 - 0.4
0.02-1.2
0.02-1.9
0.2 - 0.3
0.03 - 3.8
Maximum Cone.
Tributary
Potomac
Potomac
Potomac
Patuxent
Potomac
Patuxent
Patuxent
Patuxent
Patuxent
Patuxent
Pamunkey
Patuxent
Rappahannock
Rappahannock
Rappahannock
Rappahannock
Rappahannock
Minimum Cone.
Tributary
Mattaponi
Pamunkey
Pamunkey
Rappannock
Mattaponi
Mattaponi
James
James
Potomac
Potomac
Potomac
Mattaponi
Potomac
Nanticoke
Potomac
James
Mattaponi
Detect.
Freq.
75%
50%
50%
75%
75%
75%
38%
38%
25%
25%
0%
0%
88%
50%
50%
62%
62%
25%
100%
nd - not detected
73
-------
Table 37. Data summaries ofparticulate phase organochlorines concentrations in samples collected
at the fall lines of eight tributaries for the 1994 Fall synoptic study. Tributaries with maximum and
minimum concentrations are indicated.
Organochlorines
Hexachlorobenzene
Aldrin
p,p'-DDE
alpha-BHC
beta-BHC
gamma-BHC
Oxychlordane
gamma-Chlordane
alpha-Chlordane
trans-Nonachlor
Dieldrin
o,p'-DDD
Endrin
p,p'-DDD
p,p'-DDT
Methoxychlor
Cone.
Range
nd
0.03
0.02-
nd
0.03-
nd
nd
0.05-
nd
0.08
0.03-
0.03-
nd
0.04-
0.06-
nd
(ng/U
0.1
0.3
0.2
0.2
0.2
0.2
0.08
Maximum Cone.
Tributary
Patuxent
Nanticoke
James
Potomac
Patuxent
Potomac
Potomac
Nanticoke
Patuxent
Minimum Cone.
Tributary
Potomac
Rappahannock
Nanticoke
Mattaponi/
Rappahannock
Mattaponi
Patuxent
Nanticoke
Detect.
Freq.
0%
12%
38%
0%
88%
0%
0%
38%
0%
12%
62%
62%
0%
38%
25%
0%
nd = not detected
74
-------
m.2.c Trace Elements
Dissolved, particulate, and total trace-element concentration data collected at each of the fall
line sites for the spring and fall synoptic studies are presented in Appendix C.
Quality-Assurance Results - Tributary Synoptic Study
Two field-blank samples for the analysis of dissolved trace elements were collected during the
Fall tributary synoptic study. Results shown in Table 38 indicate that, except for Cr and Cd do not
indicate potential field sampling problems.
Table 38. Dissolved trace-element field-blank concentration data collected during the Fall 1994
tributary synoptic study. The bottom row of the table provides the minimum and maximum
concentrations for all nine tributaries, for comparison. All data are listed in micrograms per liter.
Date
941108
941115
Min-Max
for
Rivers
Al
(H/L)
0.40
<0.12
8.38
- 50.87
As
(H/L)
<0.007
<0.007
0.078
-0.242
Cd
(H/L)
0.009
<0.006
0.036
- 0.165
Cr
itt/L)
0.05
0.07
0.03
-0.14
Cu
(H/L)
0.06
0.06
0.11
-1.00
Fe
(M/L)
<0.05
0.18
20.9
- 826.6
Mn
(ji/L)
<0.10
<0.10
2.33
- 93.90
Ni
(H/L)
0.16
0.14
0.13
-1.92
Pb
(U/L)
<0.03
<0.03
<0.03
-0.31
Zn
(M/L)
<0.14
<0.14
0.40
- 18.95
< = value is less than the analytical detection limit.
Water-Quality Data Results - Spring and Fall Tributary Synoptic Study
During the Spring and Fall 1994 tributary synoptic studies, samples were collected from the
nine tributaries listed in Table 1 and shown in Figure 1. The same suite of chemical constituents from
the Susquehanna River portion of the study was also measured at the fall line sites for the Potomac,
Patuxent, James, Rappahannock, Pamunkey, Mattaponi, Choptank, and Nanticoke Rivers.
Suspended-sediment, organic-compound, and trace-element data were collected at each of these river
stations, providing a measure of the spatial variability of fall line concentration data in the Chesapeake
Bay basin. Appendix C lists all trace-element concentration data collected for the spring and fall
tributary synoptic studies.
Statistical summaries of the trace-element concentration data collected during the spring and
fall 1994 tributary synoptic studies are presented in Tables 39 and 40, respectively. Figure 9 shows
statistical plots of concentration data for selected dissolved and particulate trace elements.
Trace-element sampling results for the spring tributary synoptic study for each of the nine
tributaries are in Appendix C and summarized in Table 39. During the spring tributary synoptic study,
75
-------
concentrations for both the dissolved and paniculate phases of selected trace elements were detected
in samples collected at the nine tributary sites (Table 39). Mean concentrations for aluminum, iron,
and manganese for both phases were greater than those means determined for the other elements
(Table 39). Mean concentrations of the toxics of concern exceeded 1 ug/L only for dissolved copper
(1.6S ug/L) and paniculate chromium (1.42 ug/L). Mean concentrations for dissolved cadmium were
about 0.06 ug/L.
Differences in the total concentrations between the nine sites were also observed. Results for
the spring synoptic (Appendix C) show that maxima concentrations for total iron (1700 ug/L),
manganese (173 ug/L), and lead (0.61 ng/L) were at the Choptank River and maxima for total
cadmium (0.27 ug/L), nickel (3.18 ug/L), and zinc (19.6 ug/L) occurred at the Nanticoke River. The
Patuxent River had the highest total aluminum concentration, the Susquehanna River the highest total
chromium concentration, and the Potomac River had the highest total copper concentration. The
Rappahannock River had the lowest total concentration for the majority of constituents: aluminum,
cadmium, manganese, nickel, and zinc. The lowest total concentration for chromium was at the
Pamunkey River; copper at the Mattaponi River; iron at the Susquehanna River; and lead at the James
River.
Trace-element sampling results for the fall tributary synoptic study for each of the nine
tributaries are in Appendix C and summarized in Table 40. During the fall tributary synoptic study,
concentrations for both the dissolved and paniculate phases of selected trace elements were detected
in samples collected at the nine tributary sites (Table 40). None of the mean concentrations for
dissolved and paniculate phases of the toxics of concern exceeded 0.60 ug/L, and means for both
phases of cadmium and lead were less than 0.2 ug/L.
Differences in the total concentrations between the nine sites were also observed. Results for
the fell synoptic (Appendix C) show that maxima concentrations for total iron (1067 ug/L) were at
the Mattaponi River and manganese (94 ng/L) at the Patuxent River. The maxima for total cadmium
(0.43 ug/L), chromium (2.12 ug/L), and lead (0.59 ug/L) were at the Susquehanna River. Maxima
for total zinc (19.4 ug/L) and nickel (2.20 ug/L), were at the Nanticoke River. The Susquehanna
River also had the highest total aluminum concentrations and the Pamunkey River had the highest
total copper concentration. The Choptank River had the lowest total concentrations of total
aluminum, chromium, and copper; the Rappahannock had the lowest total manganese and nickel
concentrations; the James River had the lowest total iron and zinc concentrations; and the Nanticoke
River had the lowest total lead concentrations.
76
-------
a) 1994 Spring Synoptic
iJU -
_J
^>
A 15 -
£
C
O
;= 10 -
«
c
•
o
o 5 -
0
As
Cd
i
Cr
o
sggi
1
Cu
^^T^P'^
I
Pb
i i
0 Zn
o
T
11 T
LiuiwiM f*w*Y*^
1
dis dis part dis part dis part dis part dis part
b) 1994 Fall Synoptic
o
o
£.\J
15 -
10 -
5 -
As
Cd
o o
Cr
0
p^g^
Cu
r-7r-> 0
Pb
!-! ft
o Zn
T
r-Tbr.
|| o
I££ ^@
dis
~ I I I I I I I ! I
dis part dis part dis part dis part dis part
Figure 9. Statistical plots of concentration data for selected dissolved (dis) and paniculate (part)
trace elements collected during the Spring and Fall 1994 tributary synoptic studies.
77
-------
8-
2
a
2
M
OS
B
§
B
S
1
z
^J
^J^
Particulat
M
08
1
B
S
*
2
i
a
1
H
08
i
s
OS
u
^
Constituent
ON
^
Tt- ,§
«i
~s
£
<
<
*
^
/c
[Suspended
Sediment
ON
cs
ON
vo
00
CS
00
cs
cs
ON
CS
00*
00
1
ON
O
m
oo'
2
ON
oo
oo
•<*•'
CS
ON
ON
in
|| Aluminum
55
<
*
^
*
$
1
ON
oo
O
i
oo
o
o
o
cs
o
Arsenic
ON
CO
f-
O
CS
cs
o
o
VO
0
ON
m
O
o
o
o
o
o
ON
ON
CS
o
1
cs
o
0
VO
0
o
»"• — ' -
Cadmium
ON
B
o
vo
*"-
ON
TT
00
0
CS
ON
oo
o
1
o
cs
o
I Chromium
ON
oo
cs'
0
00
o
vo
ON
1—1
ON
VO
O
VO
O
o
oo
cs
o
ON
CS
1
vo
o
00
VO
,_
1-1
&
&
o
u
ON
CS
•— t
o
r-
t
ON
m
00
vo
ON
in
vo
i
cs
oo'
ON
ON
ON
CS
I**
in
•n
1
•— i
ON
vo
O
en
00
vq
vo
cs
ON
06
en
O
cs
o
ON
ON
5
00
cs
"*
|| Manganese
ON
cs
cs
o
vo
"~<
ON
o
r-
o
s
o
o
o
ON
00
cs
o
V
m
^H
"o
ON
VO
O
CS
o
«n
o
ON
vo
en
O
cs
m
o
0
m
O
ON
ON
O
oo
O
o"
cs
o
•o
ON
ON
•n
cK
i
in
o
cs
o
t^
ON
>n
ON
O
i
oo
o
>n
cs
ON
VO
cs
ON
ON
CS
o
«n
Tf
rj-
N
g
•I,
I
o
V
•S ^ -o
H V
-------
o
1
1
S 2
z
i
&4
a
>2
|
M
OS
s
i
g
e
•>
*
Z
i
>3
Particulate
M
i
i
e
4;
2
z
a
>3
•«
,1
I
«
j?
i
s
a
£
*
Constituent
ON
N 5
"7 s
5
P
^
s
<
z
<
.
s<
~
4.
£<
1 Suspended
Sediment
ON
OO
ON
00
\
00
2
*r>
oo
ON
vo
ON
r-
i
ts
m
oo
vo
ON
00
O
i
00
oo'
ON
vb
I Aluminum
$
S
<
Z
Z
z
<
z
ON
ts
IS
o
1
00
o
o
(S
1— 1
o
|| Arsenic
00
m
en
TT
o
ON
s
o
VO
0
00
t-
ON
o
ts
0
o
o
ON
VO
o
>
VO
m
o
o
ON
O
O
\ Cadmium
ON
(N
CS
ts
O
m
0
ON
§
CS
O
r>
VO
O
ON
^
o
I
o
o
vo
o
o
II Chromium
ON
^
00
i
o
t-
d
ON
00
O
00
O
O
O
(S
o
ON
O
O
-~
>
^
O
s
o
o.
Q.
O
U
ON
vb
§
(
ON
ON
m
TT
ON
(S
i
ON
00
vo
O
~
ON
vo
vb
(S
00
1
ON
o
cs
CO
f>
VO
1
ON
o
«r
i
ts
ON
rn
vo
in
m
ON
O
O
d
o
1—1
ON
§N
ON
1
ts
VO
_i
ts
I Manganese
ON
o
ts
1
p-
d
m
ts
ON
0
O
o"
0
O
ON
ON
i
2
o
oo
o
1
ON
ON
d
1
s
d
ts
d
ON
d
1
ON
o
o
2
o
ON
~
o
o
v
oo
o
o
"O
J
ON
«r»
ON
J
(S
»n
d
^
^:
ON
00
(S
fi
1
00
o
vo
ON
d
ON
ON
00
i
O
0
£
f>
'I
ON
r-
-------
m.2.d Discussion of Water-Quality Results, Synoptic Study
During the spring and fall tributary synoptic studies, procedures for the sample collection and
analysis provided adequate data results by (1) using sensitive analytical techniques to obtain low
detection limits for most of the trace-element constituents, and (2) the continued use of ultra-clean
sampling methods. During the spring, below-detection data only occurred for dissolved nickel at the
Rappahannock and Pamunkey Rivers. Values below detection were more frequent for analytical
results during the fall than from samples collected during the spring. During the fall, below-detection
data occurred for dissolved lead at the James, Pamunkey, Choptank, and Nanticoke Rivers; for
paniculate lead from the Nanticoke River, and for particulate zinc at the James River.
Sample results collected from the Susquehanna River during the period February 1994
through January 1995 show minimal differences between all the samples for most dissolved
constituents. Results of the synoptic study support the same conclusion, but there were some
differences in dissolved concentration both between sites and between different synoptic periods.
Mean concentrations determined for the spring synoptic study were somewhat greater than those
determined for the fall synoptic study. For example, the mean dissolved zinc concentration was 4.45
ug/L in the spring and 3.77 ug/L during the fall; dissolved copper was 1.68 ug/L and 0.57 ug/L; and
dissolved chromium was 0.21 ng/L and 0.06 ug/L. Maxima concentrations for the same constituents
occurred for samples at the same site for each synoptic. For example, maximum concentrations of
dissolved zinc at the Nanticoke River were about 19 ug/L for both samplings, and dissolved copper
at the Pamunkey was 2.34 \igfL and 1.00 ng/L, for the spring and fall studies, respectively.
The Nanticoke River during both the spring and fall synoptic studies had relatively high
concentrations for total cadmium, nickel, and zinc. It is suggested that additional samples should be
collected at this site to determine if this observation is an anomaly or a chronic problem.
The particulate trace elements show significantly less variance between sites when compared
to the year of data at the Susquehanna River. The most likely explanation for this is that sampling
at the Susquehanna River included storms, while both synoptic studies were conducted during base
flow conditions.
The limitations of collecting only two samples per year at each site must be considered. The
concentration data only represent two instantaneous measurements in the annual cycle, which we have
determined from the 1990-91 and the 1992 Fall Line Toxics Programs to be highly variable. Since
both the spring and fall synoptic studies occurred during baseflow conditions, we were unable to
capture the full range of trace-element concentrations at the fall line of the major tributaries. The
concentration data, and load estimates calculated using this data, represent, at best, a snapshot in
time, and hence should be used with caution.
80
-------
IV. LOAD ESTIMATES
The transport of constituents through the river system is a function of the concentration of
the constituents and the volume of water that flowed in the river. In terms of load, transport is
calculated as the product of the concentration and the river discharge, which produces units of metric
tons per unit of time (see equation 3). Monthly and annual load estimates for suspended sediment,
organic compounds, and trace elements for the Susquehanna River, and instantaneous load and yield
estimates for the spring and fall tributary synoptic studies are presented in the following sections.
IV.l Monthly and Annual Loads for the Susquehanna River
FV.l.a Suspended Sediments
Annual and monthly loads for suspended sediment (in metric tons) along with annual and
monthly river discharge totals are presented in Table 41. As similarly observed in Figure 2, most of
the suspended-sediment load is delivered during months with higher discharge. For example, in
March, monthly loads of suspended sediment were about 760,000 metric tons and discharge was
about 40x1010 cfs. In contrast, the months with the lower discharge, for example September and
October, had the lowest suspended-sediment loads. About 75 percent of the annual suspended-
sediment load and about 60 percent of the river discharge occurred during the months of March,
April, and December 1994 and January 1995.
81
-------
Table 41. Annual and monthly loads (February 1994 through January 1995) for suspended sediment
and river discharge for the Susquehanna River at Conowingo, Maryland. Loads are summations of
daily load, calculated using equation 3.
Annual
Monthly
Feb
Mar
Apr
May
Jun
Jul
Aug
Sep
Oct
Nov
Dec
Jan
Discharge
(cubic feet'1016)
180.06
13.034
39.594
38.322
9.993
6.714
6.499
13.012
5 151
5798
12.717
14.903
14.322
%of
Annual
100.0
7.2
22.0
21.3
5.5
3.7
3.6
7.2
2.9
3.2
7.1
8.3
8.0
Loads for
Suspended Sediment % of
(metric tons) Annual
1,940,000
99,000
764,000
336,000
38,400
32,500
25,000
227,000
17,400
15,300
42,200
72,500
272,000
100.0
5.1
39.4
17.3
2.0
1.7
1.3
11.7
0.9
0.8
2.2
3.7
14.0
The potential sources of error in suspended-sediment load estimates are assumed to be from
the following: (1) streamflow measurements - about 5%; (2) sampling precision - about 1 to 10%;
(3) interpolation of concentration data for all days not sampled during the year - about 10 to 100%;
and (4) real variation in concentration within each 24 hour period - about 50% during a storm event
and 10 to 20% during baseflow. These sources of error suggest that the accuracy of load estimates
for suspended sediment is approximately 200%.
IV.l.b Organic Constituents
Monthly loads for the organic constituents above the fall line of the Susquehanna River for
February 1994 through January 1995 are listed separately for the dissolved and paniculate phases in
Appendix G. Temporal variability in monthly load was dependent on the compound class. For
example, the organo-N/P pesticide load maxima occurred during March 1994 when application rates
82
-------
of these pesticides and stream discharge were the greatest. The loads decreased after March but
increased again in June or July. This second load peak occurred because a surface water
concentration maxima existed in June and July, after which the loads decreased exponentially from
August to October 1994. Loads increased slightly again during November to January 1995 when
stream discharge increased from additional precipitation in the winter months.
The PAH loadings paralleled stream discharge. Several load maxima were observed: one
during February to April 1994; the second in August 1994; and the third during November 1994 to
January 1995. The majority of PAH are transported in the particulte phase, and sediments are
transported through a flow-release mechanism whereby stream velocity is directly related to
paniculate concentrations.
The PCBs loadings were also related to stream discharge, but there was a much more
pronounced spring loading maxima relative to the PAH. The PCB paniculate loadings paralled
identically that observed for PAH. The PCBs are more evenly distributed between the dissolved and
paniculate phases than were the PAHs.
The organochlorine pesticide loadings followed the same pattern observed for the PCBs, with
loading maxima occurring during the spring and winter months. There was, however, much more
variability among the monthly loadings than that observed for the other compound classes.
The combined (dissolved + paniculate phases) annual loads and load intervals are summarized
in Table 42. Load intervals are displayed when censoring provided estimated minimum and maximum
loads which differed by more than two kilograms. The loads listed in Table 42 should be considered
precise to two significant figures. The distribution of the annual loads are illustrated in Figures 10
to 12 for the PAH, PCBs, and organochlorines. The majority of the PAH were transported in the
paniculate phase; the SPCBs were transported relatively equally in both phases (but showed the
expected congener class disbributions with the tri- through pentachlorobiphenyls predominantly in
dissolved phase transport and the octa- and nonachlorobiphenyls primarily in paniculate phase
transport); and the organochlorines showed a wide range of variability in transport phases. The
organochlorine group has widely ranging physicochemical properties. The BHC compounds have
relatively large water solubilities for hydrophobic organics and were found predominantly in dissolved
phase transport. Chlordane appeared to be transported primarily in the dissolved phase. The DDT
derivatives were found predominantly in particulate phase transport, except for o,p'-DDD.
83
-------
Table 42. Annual loads or load intervals (February 1994 through January 1995) of total organic
constituents (dissolved + paniculate phases) for the fall line of the Susquehanna River. For
constituents with observations below the quantitation limit, the minimum and maximum load estimates
are given.
Organo-N/P Pesticides
Simazine
Prometon
Atrazine
Diazinon
Alachlor
Malathion
Metolachlor
Cyanazine
Hexazinone
Load, Kg
2010 - 2020
1030
2970
220 - 260
710
20-180
2450
3010
130 - 250
Polynuclear Aromatic Hydrocarbons
Load, Kg
2-Methylnaphthalene 220
2,6-Dimethylnaphthalene 140
Acenaphthylene 50
Acenaphthene 57
Fluorene 120
Phenanthrene 450
Fluoranthene 1130
Pyrene 1030
Benz(a)anthracene 380
Chrysene 330
Benzo(a)pyrene 440
Perylene 480
Polychlorinated Biphenyls
Load, Kg
Dichlorobiphenyls 1-20
Trichlorobiphenyls 18
Tetrachlorobiphenyls 36
Pentachlorobiphenyls 29
Hexachlorobiphenyls 39
Heptachlorobiphenyls 24
Octachlorobiphenyls 13
Nonachlorobiphenyls 8
SPCBs 160 - 190
Organochlorines
Load, Kg
Hexachlorobenzene 4
Aldrin 4
p,p'-DDE 16
alpha-BHC 11
beta-BHC 6
gamma-BHC 18
Oxychlordane 10
gamma-Chlordane 12
alpha-Chlordane 6
trans-Nonachlor 13
Dieldrin 12
o,p'-DDD 20
Endrin 4-11
p,p'-DDD 13
p,p'-DDT 12
Methoxychlor 1-8
84
-------
Susquehanna River Fall Line PAH Loads
OX)
o
1200
1100
1000 -:
900 --
800 -:-
700 --
ja
•a
«
o
MN DMN ACY ACE FLR PHN FLN PYR BNA CHY BAP PER
Polycylic Aromatic Hydrocarbons
Participate Load | | Dissolved Load
Figure 10. Annual load estimates for PAH for the Susquehanna River at Conowingo, Maryland, for
the period February 1994 through January 1996.
85
-------
Susquehanna River Fall Line PCB Loads
DiCB TriCB TetCB PenCB HexCB HepCB OctCB NonCB PCBs
Polychlorinated Biphenyls
Particulate Load | | Dissolved Load
Figure 11. Annual load estimates for PCBs for the Susquehanna River at Conowingo, Maryland, for
the period February 1994 through January 1996. 4
86
-------
Susquehanna River Fall Line OC Loads
0
HCB ALD DDE aBH bBH gBH OXY
Organochlorines
gCHL
0
aCHL tNON
DLD ODD' END DDD
Organochlorines
DDT MET
Particulate Load
Dissolved Load
Figure 12. Annual load estimates for the Organochlorines for the Susquehanna River at Conowingo,
Maryland, for the period February 1994 through January 1996.
87
-------
IV.l.c Trace Elements
Annual and monthly loads, in metric tons, of total aluminum, cadmium, chromium, copper,
iron, manganese, nickel, lead, and zinc for the Susquehanna River at Conowingo, Maryland, for the
period February 1994 through January 1995 are presented in Table 43, along with annual and monthly
river discharge totals. The total concentration (the sum of the dissolved and paniculate
concentrations) was used to calculate the load estimates for each trace element. The load estimates
for dissolved cadmium, chromium, copper, nickel, lead, and zinc should be considered upper, or
maximum, estimates, because selected concentration data were near the detection limits in both the
environmental samples and the field-blank samples, and background analytical noise was evident.
The Susquehanna River transported the highest loads for the majority of the trace elements
during the months when discharge was greatest: March, April, November, and December 1994, and
January 1995. Monthly loads were, in most part, elevated during the months with high discharge,
with the maxima for loads of aluminum, cadmium, chromium, copper, iron, nickel, lead, and zinc
occurring in January 1995 (Table 43). While the discharge for this month was not the highest of the
reporting period, the suspended-sediment load was indeed one of the highest during the period, and
many of these trace elements are carried on suspended particles. Another reason that the loads for
these trace elements were the highest in January 1995 is due to the interpolation of the concentration
data. There were only two samples collected during January 1995, one of which had elevated
concentrations of these trace elements. These high concentrations were interpolated over the entire
month, thereby giving an elevated load. The percentage of the annual load which was transported
during January ranged from about 80 for cadmium to about 25 for manganese. Elevated loadings of
most trace elements also occurred in March, April, and December, months of highest discharge.
Of all the trace elements collected during the February 1994 through January 1995 period,
aluminum had the greatest total annual load, followed by iron, then manganese. These results reflect
the crustal abundances of these trace elements. The lowest annual total load occurred for cadmium,
which also reflects the crustal abundance of this trace element although the loads for this trace
element appear to be significantly higher than expected from the crustal abundance. Refer to Table
27 for the crustal abundances of the trace elements collected for this project.
Figure 13 presents the annual dissolved and paniculate load estimates for total cadmium,
chromium, copper, nickel, lead, and zinc, in bar graph format. The dissolved portion of the annual
total load is indicated as the stippled portion of each bar in order to evaluate the relative contribution
of the dissolved and the paniculate load to the total load. The paniculate load, with the exception
of nickel, comprises more than 75 percent of the total annual load for these trace elements. For
example, the paniculate load for copper is about 150 metric tons, or 75 percent of the annual load.
In contrast, the paniculate load for nickel is about 50 metric tons, or 28 percent.
The accuracy and the potential sources of error of the load estimates is determined by a
number of factors, which include the following: (1) about 5% is due to streamflow measurements;
(2) about 10-80% is due to sampling precision; (3) about 10 to 300% is due to interpolation of
concentration data for all days not sampled during the year; (4) about 50% is due to real variation in
the concentration within each 24 hour period during a storm event and 10 to 20% during baseflow;
and (5) about 30 to 50%, when considering the blank data. These sources of error suggest that the
accuracy of load estimates for the trace elements is ±500%.
88
-------
I
«r>
•^=E
•a 5
"
.*"> i
N
ffff
*
*
B
§
«
P*4
s
U
U
S
^^
^
fail ^
Si * '
QQ *-*
rd V
u <*-•
M U
S|
00
i
i
e
o
o
1
•
55
00*
T5
a
s
(•^
VO
o
00
1^4
o
^ «a
1 "«
0
8
00
»n
Ov
00
S
p
f>
—
o
r-
00
O
o
0
f**>
~^
•8
u.
£
S
c»i
Ov
o
~"
O
CS
,«•
Ov
Ov
O
CS
•«*•
0
o
f>
CS"
vO
Ov
f*"i
i
o
o
cs
t--'
o
0
o
VO
00
fS
CS
o
s
^^
.-H"
<*"!
00
CO
a
is
00
i
r-
VO
Ov
O
O
r-
rf
00
in
m
0
(^
(N)
Ov
Ov
Ov
I
%
O
CS
o
s
p
Ov
00
r-
cs
00
CS
0
r-
o
o
oo
o
1— ^
t
r-
vd
1
3
VO
Ov
Ov
CS
Ov
i
cs
cs
o
1
CS
0
0
o
tf
^M
o
m
vO
•3
in
Ov
1™^
9
o
VO
in
vo
S
*— <
i
m
vo
^>
in
Ov
O
Ov
O
O
cn
S
es
ov
O
r-
CS
CS
g
^^
CS
in
m
^
^H
1
ON
oo
-------
• s
O
El E
c
< c
500
400 -
300 ~
200 -
100 -
Annual Loads of Selected Trace Elements
at the Susquehanna River, Conowingo MD
[J - Dissolved Load
• - Particulate Load
Cd
Cr
Cu
Ni
Pb
Zn
Figure 13 . Annual load estimates for total cadmium, chromium, copper, nickel, lead, and zinc for
the Susquehanna River at Conowingo, Maryland, for the period February 1994 through January 1995.
90
-------
IV.l.d Discussion of Annual Loads for the Susquehanna River
As indicated in Figure 13, cadmium, chromium, copper, lead, and zinc were transported in
the Susquehanna River primarily in the paniculate phase. Nickel was the only exception. Discharge
volume is directly proportional to the resulting load estimates for trace elements. Although the
concentration of the trace elements carried by suspended-sediment particles may theoretically
decrease during periods of high discharge due to dilution by larger grain size sediments, the load of
the trace elements will significantly increase. This is due in large part to the increase in water velocity
that occurs during storm events, which is capable of carrying a greater total mass of sediment.
During the February 1994 through January 1995 study period, load estimates for both the
trace elements and organic compounds were improved over previous years by: (a) more sensitive
analytical techniques and the continued use of ultra-clean sampling methods, thus permitting lower
analytical detection limits; and (b) obtaining additional samples over a wide range of seasonal and
hydrologjc conditions thereby improving load estimates. The use of ultra-clean sampling procedures
in conjunction with the high sensitivity of laboratory analysis resulted in the reduction of censored
concentration data and provided an enhanced data set for load estimation. Also, in addition to
monthly base flow samples, stormflow samples were collected over the storm hydrograph in March,
April, and August 1994 (during tropical storm Beryl) and in January 1995. Load estimates were
improved by having additional concentration data, thereby reducing the number of interpolated points.
However, load estimates for cadmium, chromium, copper, nickel, lead, and zinc should be considered
upper estimates of the loads because selected observations for concentration data were near the
detection limits in environmental samples and in field-blank samples, and the analytical precision for
chromium and lead was about ±50 percent.
The organo-N/P pesticides were found exclusively in dissolved phase transport because the
water solubilities of these organics do not favor sorption to particulates. These compounds were
detected ocassionally in storm flow particulates at extremely low concentrations, most often below
detection limits. The other classes of organic compounds, as illustrated in Figures 10 to 12 were
distributed between dissolved and paniculate transport depending on the physicochemical properties
of the individual compound. It needs to be emphasized that the illustrated distributions are only
approximate. The collected samples were returned to the laboratory for filtration and extraction.
Because filtration was conducted at a temperature different from that of the ambient temperature at
the time of collection, some redistribution between the phases may have occurred within the 24-48
hour period of collection to filtration. The effect of temperature on the distribution of organics
between the dissolved and paniculate phases in not fully understood and cannot be corrected through
calculation. However, the combined load estimates are accurate insomuch as loadings from both
phases are summed, and thus are not dependent on the constituent distribution profiles.
Introduction of the Goulden large-sample extractor provided a significant upgrade in the load
estimates for PAH, PCBs, and organochlorines in dissolved phase transport relative to the solid-phase
extraction methods used in the 1992 fall line study for the same constituents, as evidenced by the
much narrower load inervals estimated for the constituents for the 1995-1995 fall line monitoring
program.
91
-------
IV.2 Instantaneous Loads and Yields for the Spring and Fall Tributary Synoptic Study
Instantaneous load and yield estimates for suspended sediment, organic compounds, and trace
elements for the spring and fall 1994 tributary synoptic studies are presented in the following sections.
The spring synoptic was sampled from April 25 through May 6, and the fall synoptic was sampled
from November 8 through 18. One or two sites were sampled per day.
IV.2.a Suspended Sediments
Table 44 presents the instantaneous suspended-sediment loads and yields for the nine
tributaries sampled during the two synoptics. For comparison purposes, the rivers are listed in order
of decreasing drainage area.
<
92
-------
Table 44. Instantaneous loads and basin yields for suspended sediment collected at the major
tributaries of the Chesapeake Bay, collected in spring (April-May) and fall (late November) of 1994.
Susquehanna
Potomac
James
Rappahonnock
Pamunkey
Mattaponi
Patuxent
Choptank
Nanticoke
SPRING
Load
g/sec
29,400
23,800
1220
173
221
133
150
37.9
21.1
Basin Yield
(mg/sec/
km2)
FALL
Load
g/sec
419 25,800
794 484
75 291
42 20.6
79 20.8
86 16.8
166 28.4
129 3.23
108 2.89
Basin Yield
(mg/sec/
km2)
367
16
18
5
7
11
31
11
15
Results of the spring and fall tributary synoptic studies show that instantaneous suspended-
sediment loads and basin yields are very low during baseflow conditions (Table 44). The
instantaneous loads and basin yields vary considerably throughout the Chesapeake Bay basin, being
primarily influenced by the basin size. About 99% of the suspended-sediment load comes from the
three largest tributaries - the Susquehanna, Potomac, and James Rivers. During the spring and fall
tributary synoptic studies, the Susquehanna River was the predominant source of suspended sediment
to the Chesapeake Bay, both for total loads and yields on a per area basis. However, the Potomac
River in the spring sampling of 1994 delivered almost an equivalent load to that of the Susquehanna,
and the suspended-sediment yield from the Potomac for this time was considerably larger than for the
Susquehanna. The high suspended-sediment yields in the Potomac were not repeated for the fall
synoptic results.
The discharge for the smaller tributaries in the fall were approximately one-quarter of the
spring flow, and the larger rivers (Susquehanna and Potomac) the fall discharge was 10% less than
in the spring. Assuming a direct proportionality between discharge and load, one would expect to
observe up to 4 times higher loads in the spring. However, one observes large (up to 10 times)
differences of some trace elements both in the dissolved and in the particulate phases between the
spring and fall sampling. These differences cannot be completely explained be the increase in load
of suspended sediment. In addition, the concentration of Cd were higher in the fall as was the
concentration of particulate Pb.
93
-------
FV.l.b Organic Constituents
Basin yields, in units of micrograms per second per square km — ng/s/km2, of selected
organic constituents are illustrated in Figures 14 through 23. Basin yields are instantaneous loads
normalized to the total area of the stream basin above the fail lines. Instantaneous loads may be
determined by multiplying the basin yields given in Figures 14 through 23 by the basin areas listed in
Table 1. Basin yields provide a more clear comparison of individual basin dynamics in fluvial
transport because instantaneous loads were found to follow the order of decending stream discharges
above the fall lines, as can be inferred from equation 1. The basin yield figures are presented in
logarithm-base ten format because individual constituent fluxes varied over several orders of
magnitude. The estimated basin yields presented in Figures 14 through 23 were determined as the
maximum values, meaning that when a particular constituent was not detected or quantified in either
transport phase in a fall line sample the detection limit value (i.e., the censored value) was used in the
calculation. The organic constituents not included in Figures 14 through 23 included those which
were infrequently detected and for which >80% censoring would have existed. These organic
compounds omitted include diazinon and malathion (the organophosphorus pesticides) and several
of the organochlorine pesticides: p,p'-DDT, endrin, frons-nonachlor, and methoxychlor.
A great deal of spatial variability was found in basin yields among the nine tributaries
(including the Susquehanna River) for both spring and fall collections. The Susquehanna River basin,
by far the largest in the Chesapeake watershed, did not consistently show the greatest basin yields,
indicating that basin size and area were not directly related to measured fluxes. The was a great deal
of spatial variability in basin yields for the organics. The Choptank and Nanticoke Rivers showed
relatively large basin yields for small drainage basins, showing that organic fluxes cannot be accurately
averaged over the entire Chesapeake Basin and that different functional behaviors in fluvial transport
are apparent among the nine river systems. Functional behavior in fluvial transport arises from land
use (see Table 1), basin lithology, and climatic variables.
For those organic constituents whose transport occurred primarily in the particulate phase
(most PAH and some organochlorines such as 4,4'-DDE), basin yields were often dramatically lower
in fall relative to spring. Particulate transport is strongly dependent on river discharge as described
above, and substantial differences in temporal variability were observed. This was in contrast to some
of the organic constituents which undergo primarily dissolved phase transport such as simazine and
atrazine which showed less reduction in basin yields temporally. The exception was cyanazine which
is known to be rapidly hydrolyzed in soil pore water and showed a much reduced basin yield in fall,
well after field application had occurred.
Basin yield trends among the organic compound classes generally showed the order organo-
N/P pesticides > PAH > organchlorines and PCBs. The organo-N/P pesticides are heavily applied
throughout most of the nine streams basins during the spring and early summer months. The PAH
arise in fluvial transport from (1) the atmospheric fall out on land surfaces of products from fossil fuel
combustion with subsequent washout via precipitation, (2) storm drains discharging in streams
following precipitation events, and (3) industrial waste stream discharges. The organochlorines arise
from continual global geochemical cycling and dispersal mechanisms because these compounds are
very recalcitrant to degradation processes, and are washed off of land sufaces following precipitation
events.
94
-------
Simazine - Spring
Simazine ~ Fall
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
100 ,-
Prometon - Spring
10 T
2
"a!
o.oi
0.001
0.0001
IE-OS
100
10
1
0.1
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Atrazine — Spring
•I 0.01
0.001 -
0.0001
IE-OS
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
I °-01
a o.ooi
0.0001
IE-OS
100
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Prometon — Fall
100
Pam Mat Jam Rap Pot Cbo Nan Pat Sus
Tributary
Atrazine — Fall
IE-OS
•si o.oi
1=3 0.001
0.0001 -T-
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Figure 14. Bar graph showing yields (ng/s/km2) of simazine, prometon, and atrazine determined
from stream fall Une samples collected during the 1994 spring and fall tributary synoptic studies.
Note that only the upper limit yield values is shown.
95
-------
10
Alachlor — Spring
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Metolachlor ~ Spring
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Cyanazine — Spring
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
10
Alachlor - Fall
3 0.1 -
1 0.01 -
EQ
0.001
0.0001
rlii
U1L
10
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Metolachlor - Fall
0.0001
10
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Cyanazine — Fall
0.0001
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Figure 15. Bar graph showing yields (ug/s/km2) of alachlor, metolachlor, and cyanazine determined
from stream fall line samples collected during the 1994 spring and fall tributary synoptic studies.
Note that only the upper limit yield values is shown.
96
-------
Hexazinone - Spring
10
I I I I I
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
2-Methylnaphthalene — Spring
2 0.1
* 0.01 -J-
I 0.001 i-
0.0001 ,-
IE-OS
Illllll,
Pam Mat Jam Rap Pot Cho Nan' Pat Sus
Tributary
2,6-Dimethylnaphthalene - Spring
0.1
0.01
M 0.001
0.0001
IE-OS
11
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
10 7
Hexazinone - Fall
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
2-Methylnaphthalene - Fall
0.1 4
3 °-01t
I 0.001
0.0001 f
3
IE-OS
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
10
1
0.1
2,6-Dimethylnaphthalene — Fall
0.001 -
0.0001
IE-OS
lllllllll
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Figure 16. Bar graph showing yields (jig/s/km2) of hexazinone, and dissolved + paniculate 2-
methylnaphthalene and 2,6-dimethylnaphthalene determined from stream fall line samples collected
during the 1994 spring and fell tributary synoptic studies. Note that only the upper limit yield values
is shown.
97
-------
Acenaphthylene — Spring
Acenaphthylene - Fall
0.1
IE-OS
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Acenaphthene - Spring
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Fluorene — Spring
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
ea
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Acenaphthene — Fall
IE-OS
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Fluorene — Fall
IE-OS
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Figure 17. Bar graph showing yields (ug/s/km2) of dissolved + particulate acenaphthylene,
acenaphthene, and fluorene determined from stream fall line samples collected during the 1994 spring
and fall tributary synoptic studies. Note that only the upper limit yield values is shown.
98
-------
1
Phenanthrene - Spring
Phenanthrene - Fall
0.1 i-
5 o.oi 4-
N H
1 0.001 -
a
0.0001
IE-OS
Pam Mat jam Rap Pot Cho Nan Pat Sus
Tributary
Fluoranthene - Spring
0.1
•o
!5 0.01
0.001
oa
0.0001
1E-05
Pam Mat jam Rap Pot Cho Nan Pat Sus
Tributary
Pyrene - Spring
0.0001
IE-OS
Pam Mat jam Rap Pot Cho Nan Pat Sus
Tributary
Fluoranthene - Fall
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Pyrene — Fall
Pam Mat )am Rap Pot Cho Nan Pat Sus
Tributary
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Figure 18. Bar graph showing yields (ng/s/km2) of dissolved -f paniculate phenanthrene,
fiuoranthene, and pyrene determined from stream fall line samples collected during the 1994 spring
and fall tributary synoptic studies. Note that only the upper limit yield values is shown.
99
-------
Chrysene - Spring
Chrysene - Fall
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Ben(a)anthracene — Spring
1
0.1
2 0.01
!**
* 0.001
saO.OOOl
IE-OS
1E-06
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Benzo(a)pyrene — Spring
luliiu
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Ben(a)anthracene - Fall
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Benzo(a)pyrene — Fall
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Figure 19. Bar graph showing yields (ug/s/km2) of dissolved + paniculate chrysene,
benz(a)anthracene, and benzo(a)pyrene determined from stream fall line samples collected during the
1994 spring and fell tributary synoptic studies. Note that only the upper limit yield values is shown.
100
-------
Perylene — Spring
Perylene - Fall
Pam Mat Jam Rap' Pot Cho Nan Pat Sus
Tributary
t-PCBs — Spring
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
HCB - Spring
IE-OS
1E-06
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
t-PCBs — Fall
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
HCB - Fall
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Figure 20. Bar graph showing yields (ng/s/km2) of dissolved + paniculate perylene, total-PCBs (t-
PCBs), and hexachlorobenzene (HCB) determined from stream fall line samples collected during the
1994 spring and fell tributary synoptic studies. Note that only the upper limit yield values is shown.
101
-------
p,p'-DDE ~ Spring
p,p'-DDE - Fall
PamMatlamRap Pot ChoNanPat Sus
Tributary
alpha-BHC - Spring
PamMatJamRapPot ChoNanPat Sus
Tributary
beta-BHC - Spring
PamMatJamRapPot ChoNanPat Sus
Tributary
alpha-BHC -- Fall
PamMatJamRap Pot ChoNanPat Sus
Tributary
beta-BHC - Fall
PamMatJamRap Pot ChoNanPat Sus
Tributary
PamMatJamRap Pot ChoNanPat Sus
Tributary
Figure 21. Bar graph showing yields (ug/s/km2) of dissolved + particulate p,p'DDE, and alpha- and
teta-BHC determined from stream fell line samples collected during the 1994 spring and fall tributary
synoptic studies. Note that only the upper limit yield values is shown.
102
-------
0.1
0.01
2 0.001
.£
^0.0001
'a
« IE-OS
1E-06
1E-07
0.1
0.01
2 0.001
.—
^0.0001
« IE-OS
1E-06
1E-07
gamma-BHC - Spring
gamma-BBC - Fall
T
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
gamma-Chlordane — Spring
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
alpha-Chlordane ~ Spring
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
0.1
0.01
2 0.001
ma>
^0.0001
I IE-OS
1E-06
1E-07
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
gamma-Chlordane — Fall
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
alpha-Chlordane — Fall
i i
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Figure 22. Bar graph showing yields (ug/s/km2) of dissolved + paniculate gamma-BHC, and
gamma- and a//?/ia-chlordane determined from stream fall line samples collected during the 1994
spring and fall tributary synoptic studies. Note that only the upper limit yield values is shown.
103
-------
o.i
0.01
2 0.001
3
Dieldrin — Spring
Dieldrin - Fall
I IE-OS
1E-06
1E-07
Pam Mat Jam Rap Pot Clio Nan Pat Sus
Tributary
o,p'-DDD - Spring
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
p,p'-DDD - Spring
Pam Mat Jam Rap Pot Cbo Nan Pat Sus
Tributary
o,p'-DDD - Fall
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
p,p'-DDD - Fall
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Pam Mat Jam Rap Pot Cho Nan Pat Sus
Tributary
Figure 23. Bar graph showing yields (jig/s/km2) of dissolved + paniculate dieldrin, o,p'- and p,p-
DDD determined from stream fall line samples collected during the 1994 spring and fall tributary
synoptic studies. Note that only the upper limit yield values is shown.
104
-------
IV.2.C Trace Elements
Instantaneous total loads, in milligrams per second, and instantaneous total yields, in
micrograms per second per square kilometer, for total aluminum, cadmium, chromium, copper, iron,
manganese, nickel, lead, and zinc collected for the 1994 spring tributary synoptic study are presented
in Table 45 and Table 46, respectively. The total concentration was used to calculate the load
estimates for each trace element. All samples for the spring tributary synoptic study were collected
during baseflow conditions.
In the spring, some concentrations were less than the detection limits for nickel and lead, but
this data was included in the data set. Therefore, instantaneous loads and yields for these constituents
should be considered upper, or maximum, estimates.
Results of the spring tributary synoptic study show that for all trace elements, with the
exception of total iron, the highest instantaneous loads were at the Susquehanna River (Table 45).
However, loads at the Potomac and the James Rivers were greater than those at the other six
tributaries. For example, the iron load at the Potomac River was greater than all of the other eight
tributaries. These loads are, in large part, the result of higher stream flows measured at these three
river sites than those at the other six tributaries.
The instantaneous loads for aluminum, chromium, copper, manganese, and lead for the spring
tributary synoptic were less at the Nanticoke River than those loads estimated for the other eight
tributaries listed in Table 45. Minima instantaneous loads for nickel and zinc were at the
Rappahannock, and cadmium at the Choptank River.
Total instantaneous yields, in ug/sec/km2, for the trace elements analyzed during the spring
tributary synoptic study are shown in Table 46. The yields varied throughout the watershed: the
Nanticoke River had the highest cadmium, nickel, and zinc yields; the Susquehanna River had the
highest chromium and copper yields; while the Choptank River had the highest iron, manganese, and
lead yields. The Rappahannock River had the lowest cadmium, copper, and zinc yields, as well as
aluminum, manganese, and nickel. The James River had the lowest lead yields, and the Pamunkey
River had the lowest chromium yields.
105
-------
1
u
•o
U
O\
ON
o
«n
to
cs
o
8
SS
00
8
o
cs
••s-
CS
ro
CO
NO
CS
g
CO
in
00
0
CO
8
CO
CO
8
SO
ON
ON
CS
CN
Pot
8
8
S
o\
fS
ts
8
CS
CS
00
cs
in
cs
O
§
ON
r-
ON
ON
O
P;
ON
g
ON
VN
0
00
cs
CS
o
r*-
cs
VO
NO
00
00
in
VO
CS
NO
00
NO
CS
CS
CS
m
CS
ON
CS
CS
5
CS
ON
00
%
CS
CS
oo
o
>n
VO
NO
I
CO
cs
CS
00
ON
00
\e
CS
00
rs e
-------
***
b| « g
llll
«
93 -O 09 o
C « °
«=• - a>
S £.
1
£
u
S
o
00
VO
«n
m
oo
i
"
8
ve r-
•s oe
r-
eo
«M in
fS
to
as
^
Si
vo
i
&
i
r-
o
-------
Instantaneous total loads and total yields for total aluminum, cadmium, chromium, copper,
iron, manganese, nickel, lead, and zinc collected for the 1994 fall tributary synoptic study are
presented in Table 47 and Table 48, respectively. The total concentration was used to calculate the
load estimates for each trace element. All samples for the fall tributary synoptic study were collected
during baseflow conditions.
In the fall, some concentrations were less than the detection limits for lead and zinc, but these
data were included in the data set. Therefore, instantaneous loads and yields for these constituents
should be considered upper, or maximum, estimates.
Results of the fall tributary synoptic study show that for all trace elements the highest
instantaneous total loads were at the Susquehanna River (Table 47). All loads at the Potomac River
and most loads at the James River were greater than those at the other six tributaries. Loads for
aluminum, iron, manganese, and zinc at the Pamunkey River were only exceeded by those loads at
the Susquehanna and Potomac Rivers.
The loads for most constituents were less at the Choptank River than those loads estimated
for the other eight tributaries listed in Table 47. Minima instantaneous loads for iron and lead were
at the Nanticoke River.
Total instantaneous yields for the trace elements analyzed during the fall tributary synoptic
study are shown in Table 48. The yields varied throughout the watershed: the Susquehanna River
had the highest yields for all constituents with the exception of zinc. The Nanticbke River had the
highest zinc yield, and the second highest yields for cadmium, chromium, and nickel. The
Rappahannock River had the lowest cadmium, chromium, iron, manganese, and nickel yields. The
Choptank River had the lowest aluminum and copper yields, while the Nanticoke River had the
lowest lead yields.
108
-------
* 2 "°
§1 s
G "
<2|13
« *o .2
f S |
il|
ft> s
•^^ * -
e| S
ilft
^ s "5 §
"2 «» S 3
Sf If
f 1 3 =s
O « O u,
g! -O e O
&> C8 O K."
frill
1*11
«I1*
=3 € J fc
^||
•sr -o «t-" 3
(T\ *^ O C
2t/ j> o a
O\ !> U* 03
*-• 0 g <*H
*?*S
i_ 13 o • -I
<2 G 3 ta
<4H U «3 JS
wrt *i* CO f^
*n 3 ET 3
35 -g > O
tj to * "3
« e -o t>
13|l
«2 O 'S fa
!* S<2
8-2 8'i
1 § gj
8 w a S
2 S -2 -a
•^ «3 t5 g
•a a, v S
ill-8
llll
3 *2 *o c3
•*• *" en C
02 C *> »
3 "" P fl)
§§IS
3 «2 .0
S • a ft «
CG M V »4
1 ^-if
. € J «
^ « -S T3
^ 3 o> »
« -S 85) c
3 tn s 5i)
S s e'g
H O cd to
p^
[^
£
,—
c
s
£
5
i
•o
U
^
o-i
^»
V
o
•n
S
cs
O
en
cs
en
8
en
in
VO
|
cs
o
>n
i
ON
V* O
-H O
ON
i
ve o
W4
*4
yL
is
*S
^J
0 ON
»s
ON
i
se
"1
•H
I
'I
f
&
1
I
^^
•o
w
s.
1
O u
3 •§
§1
•aj
Q = discharge
- = unable to
-------
B /r? S «
§> S "S a.
fi-S h g-
sis*
sill
w S TJ 5
!!*
*» U «4 W
'& -2 °* O
&l| s
&Ml
tU £ ««
•° -s
-. a £ e
2 e 5 u-
£ « i c
- 2 « o
|1|8
fa; § t> £
*• S tt-o
£ 6-S-a
•It
-s «-: -S ^
" o> a* T3
a «-° i
42 i"8 «
O O 3 S
S ^ -5 *
•K M & <+*
«B D K* O
1 1 - s
S & 2 -a
^> * -i >•
s*H
13 § &.§>
^ w § S
•a «3 * "c
I sllr
g|S |
fi -s •§ :§
? § B §
2 w -
°.« "S 0
«•-« S *i
o 5 ^ b •
•ft S * T9
till*
s 1 8 1 i
^J *^ ^ ^ ^
1 1 - s 1
s " » ^ a
•9 1 3 1 "°
5 8>a -S &
S .2 JS -o
ll^l i
H S -5 o x>
S
JQ
ON
2
e
£
s
U
•o
U
*
o|
t
00
o
oo'
fHH
o
o\
s
00
rr
VO
^
§
o
00
o
o
J3
V)
%
o
•ft
VO
fS
3
s
o
c>
o\
ri
OH
1
o
oo
o
1
ON
O
1-H
ON
S
O\
fN
f)
VO
ts
o
o
s
8
i
1-H
m
d
00
ON
en
O
VO
O
ts
0
i
s
I
fS
s
1— t
t
0
00
cs
*
o
IS
00
llMattaponi
00
CN
0
Vt
o
ss
fS
Tf
m
p
rn
00
3
d
04
S
1 Patuxent
3
00
c>
o
d
£
VO.
O
51
d
£
o
fl
o
5i
00
m
11
|| Choptank
i
d
t
8
d
ON
o
^
00
JS
1-H
2
in
•".
(S
en
| Nanticoke
s
3
S
00
2303.24
5
3
oo
m
S
o
o
•M
V
s
25
•
Is
*
2 ^
^
£I
^^ ^^
i
O **
i
ve oo
f
^« •
^d PO
1
o
10 1
2 o
f*) ^?
vf
1
I
•o
b
&
15
J
^^
3-3
Q = discharge, in
~ = unable to calc
= I
-------
a) Instantaneous Cadmium Yields
for the Spring 1994 Tributary Synoptic
D Dissolved Yields
• Participate Yields
Sus Pot Jam Rap Pam Mat Pat Cho Nan
b) Instantaneous Cadmium Yields
for the Fall 1994 Tributary Synoptic
I I
D Dissolved Yields
• Paniculate Yields
NA
Sus Pot Jam Rap Pam Mat Pat Cho Nan
Figure 24. Bar graph showing instantaneous total cadmium yields, in micrograms per second per
square kilometer, collected during the 1994 Spring and Fall tributary synoptic studies. Note that only
the upper limit yield value was used.
-------
a) Instantaneous Chromium Yields
for the Spring 1994 Tributary Synoptic
140
D Dissolved Yields
• Participate Yields
Sus Pot Jam Rap Pam Mat Pat Cho Nan
b) Instantaneous Chromium Yields
for the Fall 1994 Tributary Synoptic
140
D Dissolved Yields
• Particulate Yields
Sus Pot Jam Rap Pam Mat Pat Cho Nan
Figure 25. Bar graph showing instantaneous total chromium yields, in micrograms per second per
square kilometer, collected during the 1994 Spring and Fall tributary synoptic studies. Note that only
the upper limit yield value was used.
112
-------
a) Instantaneous Copper Yields
for the Spring 1994 Tributary Synoptic
a st
CD r-
D Dissolved Yields
• Participate Yields
Sus Pot Jam Rap Pam Mat Pat Cho Nan
b) Instantaneous Copper Yields
for the Fall 1994 Tributary Synoptic
60
45
50 -
J 40 -
•^.
« 30 -
2 a.
60 £ 20 H
10 -
D Dissolved Yields
• Paniculate Yields
Sus Pot Jam Hap Pam Mat Pat Cho Nan
Figure 26. Bar graph showing instantaneous total copper yields, in micrograms per second per
square kilometer, collected during the 1994 Spring and Fall tributary synoptic studies. Note that only
the upper limit yield value was used.
113
-------
20
5 I
« 8
c £
m
15 -1
10 -
5 -
a) Instantaneous Lead Yields
for the Spring 1994 Tributary Synoptic
i i i i i i i i
D Dissolved Yields
• Participate Yields
Sus Pot Jam Rap Pam Mat Pat Cho Nan
b) Instantaneous Lead Yields
for the Fall 1994 Tributary Synoptic
20
j i i i
I I
G Dissolved Yields
• Participate Yields
2
9
«
a
CD
s
15 -
10 -
5 -
0
Sus Pot Jam Rap Pam Mat Pat Cho Nan
Figure 27. Bar graph showing instantaneous total lead yields, in micrograms per second per square
kilometer, collected during the 1994 Spring and Fall tributary synoptic studies. Note that only the
upper limit of the yield value was used.
114
-------
a) Instantaneous Zinc Yields
for the Spring 1994 Tributary Synoptic
D Dissolved Yields
• Participate Yields
Sus Pot Jam
Pam Mat Pat Cho Nan
600
500 -
« £ 400
300 -
m
200 -
100 -
b) Instantaneous Zinc Yields
for the Fall 1994 Tributary Synoptic
D Dissolved Yields
• Participate Yields
I i i i i ; r
Sus Pot Jam Rap Pam Mat Pat Cho Nan
Figure 28. Bar graph showing instantaneous total zinc yields, in micrograms per second per square
kilometer, collected during the 1994 Spring and Fall tributary synoptic studies. Note that only the
upper limit of the yield value was used.
115
-------
IV.l.d Discussion of Instantaneous Loads and Yields for the Spring and Fall Tributary
Synoptic Study
Instantaneous total loads and total yields, for aluminum, cadmium, chromium, copper, iron,
manganese, nickel, lead, and zinc were calculated for the 1994 spring and fall tributary synoptic
studies. The total concentration was used to calculate the load estimates for each trace element. All
samples for both the tributary synoptic studies were collected during base-flow conditions.
Results of these studies show that for all trace elements, except iron in the spring, the highest
instantaneous total loads were at the Susquehanna River. The iron load at the Potomac River in the
spring was greater than those at Susquehanna, James, Rappahannock, Pamunkey, Mattaponi,
Patuxent, Choptank, and Nanticoke Rivers. Generally, all loads at the Potomac River and most loads
at the James River were greater than those at the other six tributaries. During the fall synoptic study,
loads for aluminum, iron, manganese, and zinc at the Pamunkey River were only exceeded by those
loads at the Susquehanna and Potomac Rivers.
The instantaneous loads for aluminum, chromium, copper, manganese, and lead for the spring
tributary synoptic study were less at the Nanticoke River than those loads estimated for the other
eight tributaries; minima instantaneous loads for nickel and zinc were at the Rappahannock, and
cadmium at the Choptank River. Minima instantaneous loads for the fall for all constituents, except
iron and lead, were at the Choptank River; minima instantaneous loads for iron and lead occurred at
the Nanticoke River.
Loads for most constituents during both synoptic studies were highest at the Susquehanna,
Potomac, and James Rivers. These loads are in large part the result of higher stream flow measured
at these three tributaries than those at the other six tributaries.
Estimates for instantaneous dissolved and paniculate yields for both synoptic studies are
shown for cadmium, copper, chromium, lead, and zinc in Figures 24 through 28. Paniculate yield.'
were greater than dissolved yields for chromium except at the Pamunkey River during the spring
Dissolved yields were generally greater than paniculate yields for copper. Also, dissolved yields: >r
cadmium, lead, and zinc represent a considerable portion of the total yield.
The Susquehanna River had the highest chromium and copper yields during both synoptics;
during the fall synoptic, the highest yields for all constituents, except for zinc, were found at this site.
In the spring, the Nanticoke River had the highest cadmium and zinc yields. In the fall, cadmium and
zinc at the Nanticoke River were not as dramatically high as in the spring, but each of these
constituents had yields that were elevated relative to the other sites.
All instantaneous loads and yields should be considered upper, or maximum, estimates
because of the censored data for some constituents (nickel and lead in the spring, and lead and zinc
in the fall) and the field-blank data (particularly for chromium, and copper).
Earlier in this report, it was shown that the data collected for the Susquehanna River during
stormflow conditions resulted in higher loads than those collected at any of the synoptic sites.
Stormflow data collected at the other tributaries would probably produce similar results.
116
-------
The objective of the synoptic study was to provide a preliminary evaluation of the spatial and
temporal variability of contaminants in runoff entering Chesapeake Bay. The three major tributaries,
including the Susquehanna, Potomac, and James rivers have been studied previously by the
Chesapeake Bay Fall Line Toxics Monitoring Program. Extrapolations over the entire Chesapeake
drainage basin requires knowledge of the variability of contaminant fluxes across the watershed.
Although there was a great deal of variability in the basin yields estimated for the organic
constituents, a few trends were evident as described below.
1). The Choptank River has the greatest percentage of land use in the agricultural catagory (Table
1), and consistently showed the largest basin yields for many of the organic constituents, especially
for many of the the organo-N/P pesticides, during sping and fall. The fall basin yields in the Choptank
River were especially pronounced relative to the other streams. Land use and organo-N/P pesticide
fluxes correlated very well for this river basin.
2). The Potomac and Susquehanna Rivers showed the largest basin yields for PAH in the spring
study. These are the two largest river basins. PAH are found predominantely in the particulate phase
and this result is suggestive of flow-release type of functional behavior, wherein particulate transport
is directly correlated with stream discharge. This suggests that the large river basins collect deposited
PAH from combustion sources over large areas that are washed off land surfaces during precipitation
events via runoff, and represents classical non-point source behavior. Conversely, the Choptank
River had the largest basin yields of many of the more water soluble PAH (i.e., those primarily in
dissolved transport including 2-methylnaphthalene through fluoranthene in Figures 14 through 23),
and this pattern is suggestive of point-source behavior wherein stream concentrations increase with
decreasing flow and constant source input (decoupled from precipitation and runoff). Choptank
River total-PCBs also displayed this trend.
3). The Patuxent River basin has the greatest relative percentage of land use in the urban catagory
(Table 1), but this basin did not display enhanced PAH basin yields as would be expected in surface
runoff. This example shows that not all of the land use patterns correlate with contaminant fluxes and
that the airsheds for these basins are more widespread than the watersheds.
4). The PCBs and organochlorine pesticides showed the most uniform basin yields among the organic
constituents. Since PCBs and the organochlorine pesticides have little or no current inputs within the
river basins, most of the fall line loads arise for global distribution and cycling mechanisms. Given
this dispersal mechanism, it is expected that these contaminants are more evenly distributed among
the river basins where fluxes appeared to approach a near steady-state condition. As a general trend,
the PCB and organochlorine pesticide fluxes were a factor of 10 lower in fall relative to spring across
most river basins.
The implications arising from the synoptic study are that contaminant fluxes are dependent
upon a variety of variables which may be unique to each basin. Some compound classes are more
dependent on unique basin features than others. Extrapolation of fall line loads across the entire
Chesapeake watershed would introduce considerable uncertainties.
117
-------
V. SUMMARY
In 1994, the Fall Line Toxics Program collected samples for the analysis of total suspended
sediment; dissolved and paniculate trace elements, including those listed on the Chesapeake Bay
Program's Toxics of Concern; and dissolved and paniculate organic compounds, including most of 4
those listed on the Chesapeake Bay Program's Toxics of Concern.
For the trace elements, procedures for the collection and analysis of samples at the
Susquehanna River provided an improved data set by (1) using sensitive analytical techniques to
obtain low detection limits for most of the trace-element constituents, and (2) the continued use of
ultra-clean sampling methods. Values below the limit of detection in the environmental samples was
infrequent, and no detectable concentrations of dissolved arsenic, manganese, and zinc were found
in the field-blank samples. Field blanks with high enough concentrations to be compared to the
average sample concentrations indicate that field contamination is minimal, except for possibly Cd,
Cr and Pb.
Suspended sediment at the Susquehanna River at Conowingo, Maryland, shows a positive
correlation to river flow (R2 = 0.79). Dissolved concentrations of the trace elements at the
Susquehanna River at Conowingo, Maryland, do not appear to be related to flow or seasonally in
any of the time-series plots. This, along with the previous observation that there is only a small range
in dissolved concentrations for all the trace elements, emphasizes the point that the dissolved trace
elements can be sampled with less frequency.
Cadmium, chromium, copper, lead, and zinc are transported in the Susquehanna River
primarily in the paniculate phase. Nickel was the only exception. Concentrations for most of the
paniculate trace elements appear to be positively correlated with flow, with elevated concentrations (
of aluminum, iron, nickel, lead, and zinc occurring during various storm events throughout the year,
although statistical correlations between discharge and concentration are low. Also, there are other
sources of variation that have not yet been identified. Paniculate chromium and copper also show
elevated levels during storm events, but have what appears to be randomly distributed high
concentrations during base flow as well. This suggests a more complex geochemistry for these two
elements.
Water discharge has a significant effect on resulting load estimates for suspended sediment,
organic compounds, and trace elements. The Susquehanna River, which contributes 51% of the
freshwater flow to the Chesapeake Bay, contributes most of the suspended-sediment and trace-
element load to the Bay. However, about 99% of the total trace-dement load to the Chesapeake Bay
is explained when, in addition to the Susquehanna River, loads from the Potomac and James Rivers
(which contribute 16% and 12% of the fresh water flow, respectively) are considered. Although the
other tributaries may only contribute a small portion of the load to the Bay, the concentrations of
some of the trace elements cannot be overlooked, as these tributaries support many living resources
in the Bay and affect a significant portion of the tidal shoreline.
118
-------
Cadmium, copper, lead, manganese, and zinc in samples collected at the Susquehanna River
show an enrichment with respect to crustal abundance. Cadmium is enriched by a factor of 110,
suggesting probable anthropogenic loadings of these elements. This is just a general comparison to
average crustal abundances of these elements. More study of background abundances in local
sediment material would need to be done to verify these observations.
Dissolved phase transport was the primary mode for the fluxes of organo-N/P pesticides at
the Susquehanna River fall line. Paniculate phase was dominant for the PAH. Dissolved and
paniculate phase transport was more equally significant for the majority of the organochlorines.
Implications regarding impact of methodological changes made in the 1994-1995 fall line
study can be drawn from the data listed in Table 50. Only constituents common to both studies are
included in Table 50 (the 1994-1995 611 line program has an expanded organics list). Average stream
discharge at the Susquehanna River fall line was much larger in 1994 than in 1995 (Table 50), and
the loads for the organo-N/P pesticides and PAH reflect enhanced discharged with larger estimated
loads. However, the organochlorine loads are less than those estimated for the 1992-1993 fall line
program even though stream discharge was greater in 1994. This was not due to rapidly changing
organochlorine levels within the basin, but rather to the effect of censoring on load estimation. The
organochlorine constituent detection frequencies were much less in 1992-1993 than they were for the
present sampling year. Lower detecion limits coupled with greater detection frequency provided
more accurate load estimates for the 1994-1995 fall line study. Since the organo-N/P pesticide and
PAH loads were generally in agreement with the relative increase in discharge in the Susquehanna
River for the two sampling years, both annual estimates for these constituents were considered to be
relatively accurate.
119
-------
VL SUGGESTIONS FOR FUTURE RESEARCH
Based on the summary recently completed by the Chesapeake Bay Program's Toxics Loading
Inventory, fall line loads have been determined to be an important source of contaminants to
Chesapeake Bay. These results confirm earlier estimates made by Bieri et al. in 1982, who concluded
that the largest inputs for most contaminants came from major tributaries. It is therefore important
that these loads continue to be evaluated and updated as new data become available. At the present,
the Fall Line Toxics Program has accurate total annual load estimates only for some rivers. Table 49
diagrams our present status for contaminant load data.
Table 49. Summary of present status for load estimates on the major Chesapeake Bay tributaries.
Loads were determined by the Fall Line Toxics Program. The 1994 tributary synoptics were analyzed
for paniculate and dissolved fractions of trace elements and organics for all rivers.
Susquehanna
River
Potomac River
James River
Nine
Synoptic
Rivers
trace elements
organic
constituents
trace elements
organic
constituents
trace elements
organic
constituents
trace elements
and organic
constituents
1992
(dry year)
TR +
some dissolved
Paniculate +
Dissolved
(Total)
-
Particulate +
Dissolved
(Total)
TR +
some dissolved
Paniculate +
Dissolved
(Total)
-
1993
(wet year)
TR +
some dissolved
-
-
-
-
-
-
1994
(wet year)
Paniculate +
Dissolved
(Total)
Paniculate +
Dissolved
(Total)
2 synoptic
studies
2 synoptic
studies
2 synoptic
studies
2 synoptic
studies
2 synoptic
studies
To summarize this table, we now have good annual loads for the Susquehanna River over
several years with a range of hydrologic conditions. The James and Potomac Rivers trace element
loads were estimated for total-recoverable rather than for total, and we now know that we need to
do total loads for comparison to other sources. The other tributaries sampled in the two 1994
synoptics have instantaneous loads collected during baseflow conditions, and there appears to be a
large spread in the load estimates between these two points.
120
-------
Our first recommendation is that the tributary synoptic should be continued for at least a total
of five years. We believe that this will allow sampling to occur over a wide range of hydrologic and
seasonal conditions. At the end of this period, the Chesapeake Bay Program can examine the data
and decide if the sampling strategy has captured the sources of variability. The Bay Program may
also wish at this point to re-examine the Susquehanna river for a comparison to the 1994 load
estimates.
The tributary synoptic will be additionally useful for identification of other "hot spots" that
should be monitored and managed more carefully. For example, the spring and fall synoptic studies
identified elevated yields for most trace elements and some organic constituents in the Nanticoke
River. If future synoptic sampling were to confirm this observation, then the Nanticoke may be a
candidate for more intensive sampling. While this river contributes a small percentage of the overall
freshwater to the Bay, it contains a large portion of the eastern shoreline and significant habitat for
living resources.
Our second recommendation is that the Potomac River be selected for annual contaminant
load estimates in 1996. This river is not only the second largest tributary in the Chesapeake Bay, but
has some of the highest yield and will provide a good comparison to the Susquehanna River.
Additionally, we recommend a detailed study of a watershed to examine which processes
(geochemical, biochemical, geographical, etc.) contribute to differences in basin yields.
The Chesapeake Bay Fall Line Toxics Monitoring Program has provided load estimates for
various tributaries of Chesapeake Bay from 1990 through 1995. These best available load estimates
may be used to identify the magnitude of mass balance input sources (e.g., fluvial transport and
atmospheric deposition) in Chesapeake Bay at least within an order of magnitude of each other. To
this end the goals of the fall line program have been accomplished. However, the fall line program
has also shown substantial variability in fall line load estimates annually among all tributaries, implying
that the accuracy of input mass balance determinations is limited if only a few tributaries have been
well characterized within the watershed. Other tributaries than the Susquehanna should be intensively
studied with respect to concentration-discharge influences, which can only be accomplished with
intensive sampling.
Outlined below are the major subjects which need to be addressed in the fall line program to continue
to provide load estimates of organic constituents in response to water quality management actions.
1. Develop integrative sampling techniques such as semipermeable membrane devices which provide
concentration estimates of organic contaminants in fluvial transport with a much reduced sampling
effort. These in situ devices may be used to estimate surface water concentrations at approximately
monthly intervals for load estimates comparable to those available. These devices would save
considerable cost in monitoring efforts.
2. Develop models for fluvial transport which are predictive or provide mathematically filtered
values. The GMU laboratory is exploring the use of the Kalman filter method to provide annual loads
with a much reduced sampling effort (4 times per year) without the loss of accuracy in these
estimations. These models may provide accurate fluvial load estimates with a much reduced cost.
3. Identify important hydrodynamic and geochemical variables which correlate with organic
contaminant concentrations in fluvial transport. Predictive models require the input of variables
which correlate with contaminant behavior, such as stream discharge, water temperature, sulfate ion
concentrations, alkalinity, and other easily obtainable measurements. It is likely that other dissolved
121
-------
and paniculate phase species have similar functional behavior to organic contaminants.
4. Characterize the mode of transport of organic contaminants. Fluvial transport occurs in dissolved,
paniculate, and colloidal phases. Determining the mode of transport at the river fall lines is important
to understanding contaminant behavior in th transition zone between the stream system and the
mainstem Chesapeake Bay. The mass balance of organic constituents passing the river fall lines in
unknown. It is normally assumed that the fell line loads represent inputs to the mainstem Chesapeake
Bay. This assumption is incorrect as geochemical processes in die transition zone influence mass
balance in the estuary.
Table 50. Comparison of fall line loads for Susquehanna River for selected organic constituents for
the March 1992 through February 1993 and February 1994 through January 1995 Chesapeake Bay
Fall Line Toxics Monitoring Program load estimates.
Year:
Avg. Stream Discharge at Fall
Line (cfs):
Organo-N/P pesticides
Simazine
Prometon
Atrazine
Alachlor
Metolachlor
Cyanazine
Hexazinone
PAH
Fluoranthene
Benz(a)anthracene
Benzo(a)pyrene
Organochlorines
SPCBs
Aldrin
Oxychlordane
y-Chlordane
a-Chlordane
Dieldrin
Load
Interval (kg/y)
(L,)
1992-1993
35,495
580-610
110-160
1700
97-160
920
430-480
170-180
120-140
55-98
14-120
170-198
16-21
26-32
11-17
21-28
7-14
Load
Interval (kg/y)
-------
VH. REFERENCES
1. Ballschmher, K. and M. Zell. 1980. Analysis of polychlorinated biphenyls (PCB) by glass capillary
gas chromatography. FreseniusZ. Anal. Chem. 302: 19-31.
2. Bieri, R. O. Bricker, R. Byrne, R Diaz, GHelz, G. Hill, R. Huggett, R. Kerhin, M. Nichols, E.
Rdnharz, L. Schaffiier, D. Wilding, and C. Stroebel. 1982. "Toxic Substances" in Chesapeake Bay
Program Technical Studies: A Synthesis. E.G. Macalaster, D.A. Barker, and M Kasper (eds.)
USEPA-CBPO. pps. 263-355.
3. Conn, T.A., L.L. DeLong, EJ.Gilroy, RM. Hrsch, and D.K. Wells. 1989. "Estimating constituent
loads." Water Resources Research. 25(5):937-942
4. Cutter, L.S., Cutter, G.A., and San-Diego-McGlone, M.L.C., 1991. "Simultaneous determinations
of inorganic arsenic and antimony species in natural waters using selective hydride generation with
gas chromatography-photoionization detection. Analytical Chemistry, 63(1138-1148).
5. Eganhouse, RP., B.R Gould, D.M Olaguer, C.S. Phinney, and P.M. Sherblom. 1989. Congener-
specific determination of chlorobiphenyls in biological tissues using an Aroclor-based sedondary
calibration standard. Intern. J. Environ. Anal. Chem. 35:175-198.
6. Foreman, W.T.; Foster, G.D.; Gates, P.M. Isolation of Multiple Classes of Pesticides from
Water Samples Using Commercial 10-Gram C-18 Solid-Phase Extraction Cartridges. Preprint
Extended Abstract, Environmental Chemistry Division, American Chemical Society, Denver, CO,
March 1993, pp. 415-417.
7. Foster, G.D. and P.P. Rogerson. 1990. Enhanced preconcentration of pesticides from water
using the Goulden large-sample extractor. Intern. Environ. Anal. Chem. 41:105-117.
8. Foster, G.D., W.T. Foreman, and P.M. Gates. 1991. Performance of the Goulden large-
sample extractor in multidass pesticide isolation and preconcentration from stream water. /. Agric.
Food Chem. 39:1618-1622.
9. Foster, G.D.; Gates, P.M.; Foreman, W.T.; McKenzie, S.W.; 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 27:1911-1917. •
10. Foster, G.D. and K.A. Lippa. 1995. Fluvial loadings of selected organonitrogen and
organophosphorus pesticides in Chesapeake Bay. J. Agric. Food Chem. (in press).
11. Foster, G. and K. Lippa. 1995. "Estimated annual loads of selected organic contaminants to
Chesapeake Bay via a major tributary." Environmental Science and Technology. 29(8):2059-2064.
12. Guy, H.P. 1969. "Laboratory theory and methods for sediment analysis." in Techniques of Water
Resources Investigations of the USGS. Book 3 Applications of Hydraulics. Book 5 Laboratory
Analysis.
123
-------
13. Guy, H.P. and V.W. Norman. 1970. "Field Methods for measurement of fluvial sediment."
Chapter 2 in Techniques of Water Resources Investigations of the USGS. Book 3 Applications of
Hydraulics.
14. Langland, M.J. 1995. "A synthesis of nutrient and sediment data for the Chesapeake Bay drainage
basin." USGS-Water Resources Investigations Report, in press.
15. Maryland Department of the Environment Chesapeake Bay Water Quality Monitoring River Input
Monitoring Component: Level 1 Data Summary Report 1994.
16. Schulz, D.E., G. Petrick, and J.C. Duinker. 1989. Complete characterization of polychlorinated
biphenyl congeners in commercial Aroclor and Clophen mixtures by multidimensiosnal gas
chromatography-electron capture detection. Environ. Sci. Technol 23: 852-859.
17. Taylor, S.R and S.M McLennan. 1985. The Continental Crust: Its Composition and Evolution.
Blackwell Scientific Publishing. 312 pps.
18. Thombury, W.D. 1965. "Regional geomorphology of the United States." John Wiley and Sons,
Inc, New York. pps. 609.
19. Robisch, P. A. and Clark, R.C., 1993. "Sample preparation and analyses of trace metals by
atomic absorption spectroscopy". in Sampling and Analytical Methods of the National Status and
Trends Program, National Benthic Surveillance and Mussel Watch Projects 1984-1992. Vol. m,
Comprehensive Descriptions of Elemental Analytical Methods, Lauenstein, G.G. and Cantillo, A.Y.
(eds.).
20. U.S. Army Corps of Engineers. The Chesapeake Bay Future Conditions Report vol. 1 Summary.
U.S. Department of the Army, Baltimore District Corps of Engineers. 125 pps.
21. U.S. Environmental Protection Agency. 1991. "Chesapeake Bay Toxics of Concern List
Information Sheets".
22. U.S. Environmental Protection Agency Chesapeake Bay Program. 1991. Chesapeake Bay Fall
Line Toxics Monitoring Program: 1990-1991 Loadings. CBP/TRS 98/93.
23. U.S. Environmental Protection Agency Chesapeake Bay Program. 1992. Chesapeake Bay Fall
Line Toxics Monitoring Program 1992 Final Report. CBP/TRS 121/94.
24. U.S. Environmental Protection Agency Chesapeake Bay Program. 1993. Contaminant Trace
Element Loads at the Susquehanna River Fall Line during the Spring, 1993 High Flow Event.
Addendum to the Fall Line Toxics 1992 Final Report. CBP/TRS 129/94.
124
-------
25. U.S.G.S., 1994A. Water Resource Data, Maryland and Delaware, Water Year 1994: U.S.
Geological Survey Water-Data Report MD-DE-94-1. pps 421.
26. U.S.G.S., 1994B. Water Resource Data, Virginia, Water Year 1994: U.S. Geological Survey
Water-Data Report MD-DE-94-1. pps 421.
125
-------
APPENDIX A
1994 Suspended Sediment Concentration Data
-------
-------
APPENDIX A. 1994 SUSPENDED-SEDIMENT
CONCENTRATION DATA
Susquehanna River at Conawingo, Maryland
Date/Time
940224/1516
940311/1400
940323/1345
940325/1630
940326/1930
940327/1115
940327/2130
940328/1130
940328/1830
940329/0830
940329/1730
940330/1000
940406/1030
940420/1130
940504/1116
940526/1045
Q
(cfs)
133,000
120,000
164,000
295,000
389,000
369,000
372,000
364,000
331,000
348,000
310,000
290,000
259,000
132,000
61,000
28,700
Sed
(mg/L)
47
31
36
101
125
98
115
148
115
85
78
60
38
22
17
9
Percent finer than
.062 millimeters
100
98
NC
93
97
97
97
96
94
95
94
94
95
96
97
90
mg/L = milligrams per liter
Q = discharge, in cubic feet per second (cfs)
A-l
-------
APPENDIX A. 1994 SUSPENDED-SEDIMENT
CONCENTRATION DATA
Susquehanna River at Conomngo, Maryland
Date/Time
940629/1130
940727/1215
940820/1300
940822/1345
940829/1330
940901/1430
940914/1248
940928/1100
941019/1300
941118/1300
941130/1230
941201/1300
941212/1430
950118/1200
950122/1000
Q
(cfs)
59,400
53,800
243,000
154,000
67,700
68,400
26,000
45,700
5,100
5,100
84,000
82,900
82,500
82,700
172,000
Sed
(mg/L)
20
10
47
106
20
20
7
10
9
12
11
21
16
16
99
Percent finer than
.062 millimeters
100
100
98
100
99
99
94
98
97
96
97
98
98
99
99
mg/L = milligrams per liter
Q = discharge, in cubic feet per second (cfs)
A-2
-------
APPENDIX A. 1994 SUSPENDED-SEDIMENT
CONCENTRATION DATA
Tributary Synoptic - Spring
River/Date
Susquehanna/940504
Potomac/940503
James/940427
Rappahannock/940428
Pamunkey/940426
Mattaponi/940426
Patuxent/940506
Choptank/940505
Nanticoke/940505
Q
(cfs)
61,000
22,100
6,100
1,500
867
671
311
167
186
Sed
(mg/L)
17
38
7
4
9
7
17
8
4
Percent finer than
.062 millimeters
97
95
90
85
87
69
95
89
NC
Tributary Synoptic - Fall
River/Date
Susquehanna/94 1118
Potomac/941117
James/941110
Rappahannock/94 1 1 09
Pamunkey/941108
Mattaponi/941108
Patuxent/941116
Choptank/941115
Nanticoke/941115
Q
(cfs)
5,100
2,400
1,700
Sed
(mg/L)
12
7
6
364 2
245
198
143
38
3
3
7
3
34| 3
Percent finer than
.062 millimeters
96
95
NC
79
89
91
96
68
57
mg/L = milligrams per liter
NC = not collected
Q = discharge, in cubic feet per second (cfs)
A-3
-------
APPENDIX B
Susquehanna River Fall Line Concentration Data - Organic
Constituents
-------
Nomenclature
A. Chemical Abbreviations
Abbrev.
Appendix B. 1
Sim
Pro
Atr
Diaz
Ala
Mala
Metol
Cyan
Hexa
Appendix B.2
Mnp
Dmn
Acy
Acn
Flu
Phn
Fin
Pyr
Chr
Bnz
Bzp
Per
Complete Compound Name Abbrev. Complete Compound Name
Simazine
Prometon
Atrazine
Diazinon
Alachlor
Malathion
Metolachlor
Cyanazine
Hexazinone
2-Methylnaphthalene
2,6-Dimethylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
Chrysene
Benz(a)anthracene
Benzo(a)pyrene
Perylene
Appendix B.3
Aid
Non
DDE
DDT
PCB1
PCB2
PCB3
PCB4
PCB5
PCB6
PCB7
PCB8
PCB9
SPCBs
Appendix B.4
BHC1
BHC2
BHC3
Oxych
Chll
Chl2
Nona
Did
DDD1
Endr
DDD2
DDT
Methoxy
Aldrin
.trans-Nonachlor
4,4'-DDE
4,4'-DDT
Monochlorobiphenyls
Dichlorobiphenyls
Trichlorobiphenyls
Tetrachlorobiphenyls
Pentachlorobiphenyls
Hexachlorobiphenyls
Heptachlorobiphenyls
Octachlorobiphenyls
Nonachlorobiphenyls
total PCBs
alpha-HCH
beta-HCH
gamma-HCH
Oxychlordane
trans-chlordane
cis-chlordane
trans-Nonachlor
Dieldrin
2,4'-DDD
Endrin
4,4'-DDD
4,4'-DDT
Methoxychlor
B-l
-------
B. Concentration File Abbreviations
Term Definition
Date Date sample was collected
-------
o
•o
1
S
a
,-a-svd
o o
£
A
$
!
s
ro
I
CO
O
1
S
•o
£di
oa
x
§
I
-------
e
x
§
s
si
"S3
£
S
5
e
to
rv Fv
co QO
°>q
rs
en
-S«n,v:-5:o-^ON-2
CfN^C^C-HG
vo en oo »n oo o ON «n "* r^
,^ Tf CM _ t oo ON ^ oo cs ^\ oo oo
oo
en -o *o
en ~2 "S
iii
en ^H o t-; *-> q ts ON
^Ht^incsoo^SenrXICSJ
in CniniricsenS^IQSICS^
o o q q n-
_ _ r* en
en ^ en en
CN NO
t^eno
o\ •& -o -o
•^, t** r* -^. -^. ~z.
c en CN c c d
ON
'O
g
•8,'
VO gj CN ON \O
06 -H Tt «n vo
^H ON
cs ~*
•a vo
c in
ts
vo
ON
•Q -a i o cs »-j q -o
vo ON
en NO vo
VO
vo ON oo en ^
TJ/ *-4 cs| en '—i
cs —4 ^H
t- tN
•* en csi CN
ONVOJ*
^OoocS^csenfSO
nS2e^c^§?ie^'~:^e^
en
ON
^,, — ,, — ,0 en
"
en o in
en oo
oo
en
oo oo
Tfr VO
a-3
S23
p^ oo oo *—•• co ON QQ ^H
ONOO^^en^o,
**1 "^
oo 06 2
O ON oo oo
GJ -H
I .1
d^ ^ 5j S£ ^ ^
0<
ON
•* Tj-
ON ON
_ _..inr-oofsON25*ovoooC3
-------
0.
•8
o
V)
co
£
a,
ca
CO
CO
U-
«
'2
I
o
§
1
X
I
8-
ca
s
ca
U
c
E
9
E
g
c
Q
CO
1
ao «-H o\
•o-o-o
" -
o\
O
-------
8-
OQ
B
E
3
E
&
i
oo q
~H d
a
Oi CO ^^ ^N OQ
d d d "a d en
•a vo
o s o
•o -a -o -o
in en o —i cs *n cs en TJ-
oddoddodd
111
o cs o
en en en
odd
•o -o -o
•B--a~a
oo cs
«—i en
•O 73
$
a-o
£
•O T3 T3 13
O O O O
CS
d
q
d
^S1"
O V o
vo ON en m
en ON f» oo
d fi d cs'
OO O T}- ON
•i O CS —< CS -i
• • -^
o o d
1-1 en ON
-fr ^ vo
en ^j1 T|*
oo en cs
r-; q q
d -i
en in ON
vo in p-
vo
ON
o o o
en
CS CS CS *•* -i
00
ONONTtoNOOooomooi-i
1-1 en cS p1* Tf ^3 ^ ON CD .^j
cs'deni-ics'cs'cscs'cs'i-i
oo
en
oo
vo
in
_enT£ini*tcsoNONTi'oovo
2" O q cs r^ vo oo vo oei ON ^
*iicsdcsi-^-i^i-H-^dcs
— r*- ON
•rt vo m
1?
vo -i ON
t~> en ^i
O O O O -i O
en r> -H
odd
ON -O -O 8
d B "a d
m ON ON
O cs| -i
cs cs' cs'
vo ~ ON
•O en en «-•
"^-. • • •
B CS O CS
m en vp cs
Tf f^ O *O
oooNooTfcsin'^oo
cs-ivocsoor^ooqcsvo
-I'dddddd—- r^ ^ aaa
P-« « v v v
as
d d
cs
^ J J J _ J _
8 aaag ag
c> v v v o; v H
•§5:
ON t- O
P"- VO P*1
o
00
p-P*vooNP*-ONVoenen-iin
oo p*» p^« oo p*> oo p*» oo p^ vo P^
Tfinoop*rtvqON-iqvooooot-toovovo
CS 1-1 ON oo ON oo oo oo o ^ vo en ^d CS ^f vo
»nTfcscscsinTj-Ttinvom«ninvocscs
»-* en oo
ON ON
o ^
en S
ON ON ON ON ON
Svo O ON en
cs -i cs ^
ssssssssss
I*1* Q\ G\ OO OO r**
S^^ ^^ ^Z) ^^ C3
f'^ CO CO CO ^O
I I
Os^^5\ooor5cs
^I^^^^COO^
oo^^o<-«*-«^
-------
3
!
• •
%
"3,
g
J
£
t_
Si
CT1
CO
C^
1
£
£
_o
2
a
£
(S
cs
oa
x
I
m
S
m
u
Ou
4
c
Q
CO
$'&
vo o oo P~ o en cs O vq —; cs vq £; (
cs' •— — S°xcs'vdTj:O«ninoNvdC!"
vo ^j1 C7 NO o oo
*—> en 0s O ON ON
•vo
vo r- N^
en en ON P^ oo , * . —.
o o <* £* ^ "> ~- ^
O O -: r>j -• ,•• • _i
•—i i—« OO ^^ 00 P"» OO >_
cs ~ cs'
o ^ ^.
• — ^ cs" O ^t en vd •<*• Q —« P~ ON Cl* <—• vd oo' S en
in cs oo
\o" «n in
cs ON *•*
cs — cs
O en" rr ^ S T' ^ •*•' f' Q vd vd vd
enenr-^g
Sen
•^"^S
o «n vo
ON ON ON
~- «n en vo
• r-f OO" ON
ON
xP
i—i en --* £ O
O O oo o oo
en" en cs O in
00
en
mm^ cs cs o^ en vo in o^ p** ^D oo p^ cs
— _. ,, eni ooi « cs --t t-i vq r~ p».00 cs JJJ ON
i 5j- en" S m' ^ m" in O vo" m' in" O T" en ^ CJ^ --*
CS ^- 00 ON CS CS
cs
oo P* ON
•^ ^ cs
cs cs cs
CS vo
i2 ON vd cs J^ en" o en m' 2 dI o' O °^ ^ *°. ^
s^ »— cSCSsJ/enen^en ^x --* --* *-• v-^ ON ON ON
o cs
ON ^ vd <<* oo ON" ~ o o o" ?^ T- O .^-
S
S
,* en en en
g o O o
A) ^M ^) t^»
^^ ^D Vi ^^
3 o o o
"3,
en — oo
CS
oo
f- «n O
O VO OO
in
cs -H o
cs o p
en en en
cs
ON OO
\q in
oo oo
' P~ P~ P~ xp
en «n TT ^
ON ON ON" •"
' vo ON cs
O — —
cs
vo O •—' vp «n m m
cs cs cs «^ ^r cs en
• • • en • • •
o"
voocn^oooocs
' <—> 00 O ^ CS Tf 00
p>. ^» vq o in TT Tt
o" o" o' ^ o" o o o ^ o" o" o S o" o o
o
^
Is* en
oo
OOOd'OOOOO^OO
xP
cs oo <£
m m oo
• o' o" o O
s*~\
CS P*
ON ON ON
ON ON ON
•t •t
ON ON
ri cs
2^ — ^<^SSS
-------
J*»
Ps
f\
K]
ffl
1
0
J3
U
5^
p^
t^
JS
OH
J3
8
^
Q*
^J
i
Q
o.
-H
2
(8 CS
S «3
cS CO
.
Is
1
Q
cs
vb
cs
o
£
ON
vo
r-'
00
00
(-»
^^
00
o
,_H
CS
^.
t*"* I-*
ON
g CO
i5 co
(3 «n
8 °
y co
rs o
Q.
Is
• •
pp
3 cs
Pk •— '
^
So
CO
1
CO
o
oo in co ON IT vo
OOTtOOOOOOCO»-«COCSONVOVOcOTr
**: in xr o f". °°. <"! ~ ^ *°. ^ m. vb ON
ir^^^NVOr-HTr^covoTi-r-^Tr
cs o cs ~*
oocsoNOONoocsooNvocor^cs—*
°°. CO CS CS "">. °. <* °°. ^ ^ °. *"". °. O
oor*f«<-ivocscsvo>-*Trcs^roNrr
ri- o •— i co o
t-ONr-400COCOOON''rinO^»— 'CS
o ob vb 06 M °° ° ^ ° ^ ^ ^ ** S
rtr__^vom'«i;cscsi— lOOcofr^ON'^'Osincst^
csor--in'^iOinvOooONVovo»^t^
vb cs co' vb p^ •— cs • TT in cs co' o" cs'
csvo-'Co
o o in cs -! °°. °. ^ ^. °°. "*. ^ •* m'
^^cscscsoNvo^-cscsincoTrvo —
COOOOOTTmOOi— iVOCOCOVOONVOt^
^•COOCSVO^—'^vOtO'-iONCS
ooincsooococot^-r^O'—coO'— i
ooovocsininco^t'^'^tcocovoON
OOCSCSOOOOOOOOO —
CSO-H^CSt~cOt--CSOOVOcOONOO
•ncst'-int'^invoin^-oovoooooco
oor-csooooooooocs
OOvoONVoooinOini^'coO'i*cs
i— icsvo — r^-vor~-co-*r^ooTrooo
/-^*
co , O t^ «n
VOHJO^ONVO^t^OOinvoCS^ON
r^ O' o^«w^l'^t**ONco'^ONOvoQ
•—V ^> *-< cs cs o' <-«' o ^' o «-• co' ^
v^^^x^v^v^v^^^v^v^v^v^v^
inm^-coi— >t^oo^<— iincsvom^^
t>-voooONONt^voinoor~vovoinin
oooooovomommcocsco^rcsco
•^cocscot^ocS'—int^'Vcsvooo
•ncococovovovovovovovovovocs
II 1 1
Tf ^ ^ ^ ^ ^ Tf Tf ^ ^ "tf ^ if ^
OSONONONONONONONONONONONONON
COOOO^O"vO'O~^:VOOONCOt»-OOCS
f>jcscsco^cs^csr-«cs-^cs^js
co co co co ^ ^ in in vo vo t^- c^ oo oo
oooooooooooooo
o
o
cs
ON
CO
m
vo
CS
m
CS
CO
_
^^
ON
CS
_
^^
in
vo
s
cs
ON
OO
O
i_|
cs
^«
VO
cs
CO
CS
VO
^
00
rr
VO
i— <
CO
^
ON
i
00
ON
CO
••*
fx*
TT
oo
00
CO
•n
oo
cs
•*
vo
*f
ON
O
ON
ON
ON
ON
^
CO
00
o
oo
in
0
•n
m
i-<
oo
CO
cs
sp
^J.
m
CS
vo
m
1
1
1
•n
ON
CO
•n
r^
—
00
*^
VO
CS
—
CO
"*f
^^
t^
o
in
^
m
cs
cs
o
cs
o
rf
CO
o
£
o
o
ON
0
£
r-
m
CO
CO
vo
ON
1
ON
ON
00
vo
ON
""I"
00
cs
ON
CS
cs
o
oo
^^
I— 1
^
m'
o
o
CO
CS
ON
CO
O
ON
m
o
ON
cs
f— N
cs
ON
r-»
v£
fN,
in
^.
vo
1
1
ON
s.
^
CO
O
oo
r>
m
o
00
CO
00
m
ON
CS
o'
rr
in
S
cs
m
O
Tf
ON
0
vo
CS
^
^^
^-
^
ON
^
00
CO
CO
1
oo
ON
***'
^^
rr
t^
ON
CO
VO
CS
CO
m
f*»
ON
^
ON
ON
^
^
oo
o
o
in
0
CO
•— >
m
00
cs
0?
vo
m
O
1-*
CO
1
0
CO
vo
O
co'
r-
o
j^;
^*
VO
00
J^
VO
TT
00
_;
^^
cs
CO
f-H
•n
vo
f».
s
cs
£
o
VO
t^-
O
VO
O
CO
cs
^t
^
Q
vo
CO
cs
CO
ON
CS
1
CO
<— '
00*
flBI^
CO
ON
00
m
S
rr
00
in
oo
t*-
rf
ON
CS
m
in
CO
in
m
O
O
0
CO
»-*
oo
t*»
«-•
^
^^
•n
vo
CO
Sj
is
r5
§
c/)
e
i
Q.
*r*
5
S
M-l
J
*O4
i
^
«
•s
o
2
1*
8
1
2
HH
5
PH
2
c
o
'%
U3
•5
e
0
o
•a
»
u
I
1
<
u^
1
-------
o-
1
1
5
09
4)
CO
C
&
eo
I
1
£
I
i
CQ
CQ
1
Cu
en
CQ
x
••o
I
Gi
to
PQ
W
ON
8
Cu
oo
r-
8
CU
CQ
U
Cu
*• i
8
Tfr
8
cu
CQ
X
* 1
S
H
Q
Q
§
I
s
I
• ^^ • ™^^ ^^^ *^^ *"*-•» • • \ / \ / • • • \y • po
O C O i C C C i COO i V V o i O O v O >—<•
fs oo v> oo »—i «—i cs is r— m --i n "^ <^ o* o* ^
SSd*~*d"ad ddd*^dVd d^Vd
*~l'~l*~l"^55 .®.®S®.®.^e'>.®..S
d d d C. d d d d- d d d Ci d d o' 5G- o' d o' d t'
dddC-dddC-dddC-Vdo ' ddddC-
<4 ^^ t«^ ^O ^3 ^3 ^j *tj ^Q *O ^3 T3 ^3 T3 ^3 ^3 T3
O-O-OTS -o-o-o -o-o-o -OTJ-O TS-O-O-O
•* "a -a "a , "a ^ ^ ,c^~a , "a *a -a ,^73-5^
•o p -o -o -o -o
C C C i C C C i
^
o
^
o
•^^^(N^^OO 050 0000-05
go'o'o'&eo'o* i o c o' i d o o S- g e d o'
m
•S'O'O'O -O-O-O
8 "a "a "a , "a"a"a ,
a in jn -H -H
.. o "a d i "c d d i
, "a"a"a ,
•o -o -o
, "a "a "a .
-OtS-O-O
''-
• * • w^ \/ • • • \/ • • • *
00C
-------
01
en
a
w
ON
f3docdcodooooeov es v
oo SSRSSggq^So'SSq'SSq^'^-oS'oS
g d d d d d o' d d v d d o' d d o" d d v V "a d "a o"
04
~adddddd"addddddddddddddd
\o __. _.__ _ _
5 dd-Hd«^^dVc>dddddddddddddd
22 —^ON^^r^r^Crici>fSf'Sor4r^^"-Hor:ii-<<5cnO'=<-^
a
U dd-^d^ddddddddddddddddoo
«n
ffl
U ooooooooooooooooooooooo
fS
S 355
ON ^^ ^
! •
Q §"adddd"Sddddddddddddddd"cd
^ ^
^ccicdccicccicieicciccccic
D«
"112
CO
CO
P 39
ooooooooooooooooooooooo
—» CO ON
S3
ON ON ON ON ^ ON ON ON ^
ON
Tf Tj-
-------
£
•3
I
8
I
t
s
!
•c
o
en
«
I
l
D.
<
L>
flu
W
ON
OO
8
a.
VO
£
in
CQ
^
8
OH
fS
fe
Q
1
CQ
£
^ o -^ 2i"^ o -*
OO -H OO Tfr ON tN
«•» *••« tr\ >w w i""! vi r»» -^ v_^ >—' xrf w-» i^- »— -^^ ^k< vi HTJ «r «««---
.... a^^ ... ^^ ... ^^ .... ^J ... Wfr
,^»^H»^»^;.Z'^H^H^HiG.^»^«i^H2'Oooo>-!'OooS
tN^-itNtNOO—i—<-*
• • • • f%l • • •
OOOOd'OOO
<3 ^ S vo i-5 -H o. ^ ^ d> ci d
d d o* Cx o* d d d C> d d d o
• • * • V.rt • • * • W\ * • * ^ x • ^Sl • * * • \^^ • • * ^^ • * ^» • «^ "• • •
oooS-oooC'OOOoG/oooS'OooC'OoooC'OOO
ddd!£'dddC'ddddC'ddo'CldddS-dddd^'ddd?N
T-H-Ht^i-J-oi-; oo'do^-do"©1*
_: ^: x —; ^: fN. ^; ^-; ^:
' do d C- o° o' o o o o o O o c d , dddd-do'd
d V
«n
^ -o-o-a
• • "
, "a
TS-O-O -o-o-o-o
"" -
n
§ T3 T3 T3 -OTS-O •O'OTS'O •O'O'O -O-O-O -O-O-O-O T3-O-O
|"a"a"a , ~a"a ~a ."s^^-a , ~a"a"a , "a "a"a , "a"a~a "a , "a"a"a ,
|
JJ-O-O-O -O-O-O -O-OT3-O -O-O-O •O'O'O -O-O-O-O •O'O'O
I "a "a "a , 'a'a'a , -a-a^a-a , •a'a'a , •a'a'a , •a'a'a'a , "a"a"a ,
«ONONONS>ou^r^^m^HOOTf^oo«r»vo^(NgNO^i*ooN-^^^t--vD^
*S »—i »^ •** 8^ (s| t-H >—i oo <—, »-i»—i»—«O'~i'-^'-^t~"»™' O *—< VO <—i >—i o ^^ ^^ O O O VC
Eb ... ^^ ... ^v| .... f^l ... ff\ ... «^\ .... fxl ... «L
goooS-oooCJ-ooood-oooCioooC-ooooCJ-oooS-
08
«
•S*O-O-C» -O-O-O •O-OTD'O TS'O'O •O'O'O •O'O'O'O •O'O'O
2"a~a~a , -a-a*a , -a-a-a^ , 'a'a'a , •a'a'a , "a'a'a'a , 'a'a'a ,
o«n
-*ONO
•^HON^^
oo m O
^SS
-o-o-o
mr-
oo oo
•O'O'O •O'O'O'O d*od
-a-a-g , •a'a-a'a ,d"ad ,
vo ^ oo co tR
ovooo o
^HON^H-^ o\
o^t OPO^^
o o o ^oo\o
-H oo o\ ^* «— i o\ ^^
o
o
«n
cs oo in
-------
a
09
8
W
o\
g s .. . . _
o. odd odd dddddddddddddd"Sdd
oo
eu ddddddddddddddddddddsSdd
OH ddd-HddddddddddddddddlSdd
vo
o« d d "5 d c d d d d d d d d d d d d e d d c d d
M
PQ
U
£
S
5*
'•H fT) OO Q\ O
cn en en en en
O O O O O
-------
•o
t
's
co
a
• •
J5
"SL
s
J
ca
u-
§
I
c
1
g
'§
S
I
oo
03
X
I
• •
COO
OO VO (S
O< ~H ^H
odd
•£
j j j
aaa -egg
v v v , -2dd
v _• ^
agg
Vdd
aaa aaaa
V V V . V V V V
J _4 J
aaa
V V V
J J J J
aaaa
v v v v
oo vo t-
d d d
•a -a -o
-2-2*2
S
g a§§ aaa agag
o o
o o
,
V V V
V o V
,
•^ -o ^ 5 ;a -a
, c c c i c s 73 ,
OO VO (N
(S en en
odd
S£ in m in Co" (N r>» •* •*
f~poo«K;a*-<'-< -otsts -a -a
ddddSedd , a d d , "2 c
ON t^ en
CN en en
o* d o'
»-1 vo •^-
o" d d
o o o
d d d
Sen en a^ _ m m *•*
^^ ^^ ^O ^C3 ^™^ ^"H ^^
o o
oo 10000*000
ss
r^ • • • f^ • • •
CJ'OOOS'OOO
odoo
fe^2JQ
good
CO
.Jo o o
* >J
gsass
..d VCD
o o o
00
CO
^^V ^^V ^^V OO ^^\ ^^ s^^ ^^ ^^ ^^ (^^ OO ^^\
i ^^ O^ ^3 ^^^ C^ ^^ C^ ^^ ^^ ^^
o^ ^"^ ^^V ^^^ ^^ *^**^ ^^ €^ f^*4 ^O ^^ o^ ^^» ^O
C^S ^"^ ^"^ ^"^ ^3 ^"4 ^^ f^ ^^ C^ ^^ ^^ ^"H ^H
s^^ I ^? ^d ^^ ^^ ^^ ^^ ^5 ^^ ^^ ^^
^^ ^^ OO ^^\ ^^ ^^ ^^^ ^D ^^ ^"f *^f ^^ S^ ^^ ^^
^^ ^"^ ^5 ^^ ^^^ ^5 ^^ ^^ ^"^ PO f^ ^^J ^^ ^^ ^"^
^^ • • • _^ * • • p^s • • • r^% • •
sooOoooC-oooC-oo
6^ t^ ON en ^ ^~^ oo ^f ^^ *~< ON in ®^ en in
VQ in ^f in in CN c^ CN oo ^f 01 en en en CN
S-do'o'CdddCi'do'dC-dd
J J J
, 111 , v v v , HI , 11
O*l C1*1! ^"^ ^^ OO ^^ ^^ C^ Ol ^1 ^3 ^"^ ^O ^"^ C3
•"^ • • • ^H * ' • ^M^ • • • ^J\ • •
^5 ^5 ^^ ^^^ C^ ^^ ^3 ^^^ ^? ^5 ^3 ^^^ ^3 ^^
1111 ,
1111 ,
O O O O i
s?
3
d i
ON
M
"2 ,
' ON ^ in VO ON
d d d d C,
d d d d CJ-
•a -a TJ -o m
S
d
vo
oo*
rf
ON
oo'
m m m
\O vo »-
•*' T-I OO
00 OO
m in
ON t»«
OO* Tfr*
in m
oo
vo'
vo m vo
ON en vo
en* «n •*
— icncs
oo oo oo
en
oo
mr»-oo
r«-vor~
en ON oo r-
• • • •
^ OO OO O
vo in in vo
333
•511
S£
S
§
-------
I
H
Q
Q
H4 »—I »—I 1-^ I—I . I—I •—< I—I I—I I—4
oa^^^^-oaasaaa^^aaTa
vv-a-a-a"a"avvvdvvv^-gvv-a
"a v
j
hJ ^J ^J HH ^4 N^J HH ^J ^J nJ fr^J ^J
^as^^asa^agaaagaaaaa^Sw
•aVdddVdV-aVdVVVdVVVVVddV
V d d d d d d
'agaaagaaaa
VdVVVdVVVV
ooo
-S
W
•o -a
•O -O •« T3
"a "a "a "a
linn?
•o -o -o -o
"a "a-a "a
T3 -O -O "O T3
•a "a "a "a "a
o
Q
Q
CO OO CM
vo -o o co
o c o
^^ f^ *O ^H
-------
1
S
"3,
2
S
3
CO
c
£
o
I
I
1
H
Q
Q
s
§
£
3
Q
•o
3
§
2
1
|
03
§
n
u
S
CO
*«*
(3
•o-o-o O*O*O* -o-o-o-o -o-o-o -o-o-o -o-o-o -o 33 ;o
-5-5-5 ,vvv ,-5-5-5-5 ,"5-5-5 ,"5-5-5 ,"5-5-5 ,^^^
«n
o
__ •» » %
-H -! «=
J
p p O* p
d d v d
3 d d C' c d d i
-o-o-o-o
CN fS »""* OO IO ^^ CO CO
5-0-0 -o -H -^ CN p ~H pj p p
C C C i COO ' O O O •>—' O O
S
OOOOS'OOOC'OOOS-OOO
-*
COOO i
vo'O
So
•o-o-o -opppoopppfscsp-*
-5-5-5 , "5dddO'dddx2,ddd
f^ ^^ ^1 ^^ ^S ^^ ^> vM ^^ ^^ ^^ f^ ^3 ^^ ^^ I«M ^M
i
en
odd
Q) S"
Q) -o -O*O -O -O "O O O "O O O *O d ^^ O '•^ OO *O >—i «—i O O "O
§-5-5-5 ,-5-5"5 ,dd"5d i d "5 d idddSS-add , d d "5
•§-o-o-o o-oo -o-o-o-o -o-o-o -o-o-o -o-o-o -o-o-o
3-5-5-5 , d*ao ,-5-5-5-5 ,-5-5-5 ,-5-5-5 ,-5-5-5 , "a"a"a
o ,
S
d ,
1 ,
oo
.. -5 "a -5 , d V o ,
0*0*0* -o ^ ^
v v v , -5-5-5 ,
i
-So
•o-o-o SpScn-o-o-o O*O*Q
i C« C3 Gt i ^? CD ^3 ^^ C3 C3 CS i ^d
OO
d
q
d
cn«nON -^
GN 5?s ON
*^ wQ KD vO °^ xD
oovo^Ocn -MeseK e? ^ e?:
cnotsts -HP-ON o»-Hm
»-,•—ii—(i-H <—tOOON VO'—'OO
Crs
6x 6^ ON *~*
P- OO ^H —< ^H
O\
en ~*
V)
s s
2 2
. ON ON ON ON ^-^ ON ON ON
O^ONONON'SOOOOOO
oo od m v
T T-T-
ON ^-> ON ON ON
^*» 9 ^** ^*^ ^*»
r S^
ON
Tf
ON
S
-------
2
Q
T3 "O
''
ddddddddddddddddddd
8 -J
O O OOOOOOOOOOOOOOOOOO OO
oo oo oo r- -H re cr> -H r< «n t- rj- rf,
Q ooooooooooooooooooo oo
2
A ooooooo -^o oooooooooo
cs c*4 co ^ *"^ ^D ^^ *o *o *o ^5 -o *o ^? »•* ^^ c*^ ^5 ^^ *o "O ^^
ddddddd^^^dc"adddddd "a"aV
i_doodo~aVo'do"dddo'odoo"d "5"av
O S"Sddd"S"c"3"Sd"Sdo'"So'ddd"ad do*v
CO
U .s en ^ MD w oo
Q «i,m,iiiipimim
&
-------
APPENDIX C
1994 Trace-element Concentration Data
-------
N
A
G*
2
^
£
u
u
3
w
^
5
0?
Date/Time
00
«r>
cs
s
0
en
v>
cs
CN
§
00
en
OS
r~-
ON
O
t-»
O
o
ON
«
o
en
O
o
o
en
en
1 940224/1516
Os
O\
00
I-N
O
§
cs
en
t»
w>
t-»
o
00
w>
o
cs
o
5
o
o
IT)
S
0
cs
00
*r\
CS
§
O
o
cs
o
o
"I-
en
o
TT
ON
VO
00
CS
en
CS
o
o
T
cs
o
en
en
vo
en
vo
Os
00
Os
O
T
o
VO
TT
O
o
cs
Os
CS
o
1—*
t^
en
«r>
i
o
vS
1940323/1345
S
"«<
2°
<5>
§
N
S3
S
-i
•»<
Q>
1
«=>
^
^
«N
3
d
o
<2>
S
\940325/1630
^
-•«
S
^^
«^
«N
tx
tv
5$
«N
K
K
00
oo
o
rv
o
0
*n
S
<=>
>
•«•<
S
\940325/163S
S
•«^
•«<
*^
o
S
5
r>
f^
cs
o
00
VO
o
s
o
s
o
o
ON
m
en
0
cs
VO
«/•»
O
o
o
ON
VO
cn
1940327/1115
«n
•<*•
S
0
cs
cs-
cs
VO
«r>
cs
(•M
VO
VO
••*
*^
»r>
vo
O
CS
«-^
o
vo
S
o
T
OO
en
o
Os
v>
•*
m
S
o
cs
r-
en
1 940327/2130
m
cs
VO
O
5
cs
m
vo
m
o
m
O
t-
t^
o
oo
o
o
8
o
o
v^
cs
cs
o
(S
r-
S
o
s
Tf
VO
m
1940328/1130
S
cs
fM«
O
VO
vo
CS
rr
TT
ON
ON
CS
§!
cs
oo
o
fVM)
o
%
o
o
oo
cs
en
o
o
o
vo
r>
o
VO
O
o
m
en
o
o
t^
•
-------
F ' 1
O
HH
H
F ^
O
u
H
u 2
M)
O
fc«
!
i
a
s*
g<
(/)
CM
DAT
Q
C
S
«
•5
t
OS
o\
Q
fc
N
g
z
s
£
O
U
u
•o
U
99
^
of
Date/Time
o
ON
O
O
VO
cs
en
ON
^4
VO
00
rr
o
00
o
o
r-
o
o
rr
m
o
o
o
rr
o
o
o
en
940329/1730
2
~
o
o
en
en
«n
(N
vo
ON
oo
VO
00
o
oo
o
o
rr
O
0
o
en
o
00
ON
rr
O
o
o^
cs
940330/1000
rr
en
1—4
O
ON
en
ON
rr
in
ON
5
3
0
3
"^
5;
^
o
o
ON
940629/1130
^
^^
^^
<^^
£5
S
f-^
^^
^^
3
^S
JN
§
O
3
ON
o
S}
940629/1132
en
en
0
O
o
VO
. VO
rr
rr
en
en
^
ON
en
ON
O
en
o
V
cs
1—4
o
o
o
o
vo
ON
(S
o
o
00
en
940727/1215
o
en
O
O
V
o
ON
0
en
3
^
vo
ON
O
o
in
0
O
en
en
rr
o
ON
rr
r?
§
O
S
940820/1300
S
oo
cs
o
ON
VO
rr
rT
ON
•n
o
en
rr
-------
p ' ' ^
o
H
£
O
u
H
f
!
H .a
o s
&d c
> O
rf^
O H
«^
s°
^
as
s:
s
Q
"?
^>
a
?
«
s
ja
P*
fc
S
4>
to
U
U
•w
U
M
•<
5
^1
Date/Time
S
o
~
o
SO
CS
•
8
cs
f"^
so
co
?•*
r~»
0
o
00
3
o
CO
t«-
co
o
cs
«/1
co
co
o
o
•^
oo"
SO
1940901/1430
co
Tt
O
s
o
f— *
TT
00
CS
r^-
ON
O
T
co
O
o
£
o
o
t^
cs
co
o
00
«r>
cs
§
o
SO"
cs
1 9409 14/1248
«/s
c*i
o
S
o
m
cs
s
o
CO
00
t^
l»4
«r»
o
rr
o
o
OS
S
o
0
S
?
r^
S
o
SO
O
0
«r>
00
8
-------
o
N
u
CS
es
es
oo*
es
ON
ON
es
«r>
es
U
55
m
ON
es
es
es
i— *
NO
en
ON
NO
es'
rr
NO
00
O
t-
ts
«r>
oo
O
NO
oo'
NO
oo
ON
es
o
o
oo
NO
es
NO
m
«J
U
U
O
2
U
u
U
U
O
U
g
O
55
u
g
u
u
2
ts
cs
ON
CN
«/"»
NO
NO
S
r>
cs
ON
ON
NO
ts
g
O
g
g
g
g
g
00
ON
•JO
CO
ro
oo
O
NO
ON
cs
ON
to
oo'
NO
O
ts
ON
§
NO
oo
o
S
TT
g
U
o
ON
NO
VI
O
O
OO
NO
f~
OO
oo
g
g
O
U
55
g
oo
ON
m
cs
NO
8
Tf
m
m
en
O
ON
0
NO
es
O
O
O
*x
CO
CO
O
o
o
*\
o
es
o
*\
NO
ON
es
ON
es
o
o
o
A
ON
es
o
o
o
ON"
00
CO
O
O
O
ON"
vo
O
O
o
es"
s
en
o
8
oo
o
o
o
o"
CO
^
NO
V ^
S
o
o
8
3
es
8
o
NO
«n
es
ON
en
NO
es
ON
cs
O
CO
ON
NO
es
8
ON
es
8
I
8
ON
oo
es
8
oo
oo
es
ON
o
CO
oo
o
ON
es
8
o
CO
t^
ON
es
8
ON
-------
^
o
H
r i
O
U
H
M)
cs
u
o
L.
ON
ON
1
<
•I
*
a
S
.&
Q
i
•8
!
^i
A
f*
On
fc
0
£
u
J.,
u
*
<
^Q E3
o»S
4i
V
S
S
08
A
2
en
en
cs
^
en
O
1
ON
en
en
cs
o
o
2
VO
cs
VO
o
VO
8
o
o
ON
o
8
I 940330/1
VO
CS
cs
„.
cs
00
VO
VO
cs
cs
ON
00
^
f-H
00
o
E
o
2
en
ON
00
en
%
ON
cs
o
s
I 940406/1
cs
en
oo
vo
oo
en
en
O
en
en
en
oo
CS
o
vo
en
en
vo
1—1
£
cs
VO
cs
|
cs
en
O
en
I 940420/1
TT
TT
VO
cs
«n
en
CS
en
vo
O
cs
00
ON
o
o
cs
en
5
VO
g
en
vo
E
O
8
VO
VO
I 940504/1
§
^
en
en
en
O
oo
VO
o
o
o
o
VO
o
en
o
o
"•*
2
VO
S
oo
o\
o
o
oo
cs
i
I 940526/1
s
>
|
55
S
I 940629/1
§
o
e^
0
VO
1
1
^
3
^
8
tv
$
e^
I 940629/1
cs
en
cs
^
en
<3\
OO
CS
o
o\
en
^
O
en
ON
oo
in
"•"
£
oo
o
cs
o
o
o
oo
en
S
I 940727/1
cs
ON
3
oo
en
f-
O
cs
cs
oo
00
en
O
5
^H
VO
JS
*•*
$
3
?
S
8
o
en
8
en
\ 940820/1
s
CS
o
en
^
VO
en
cs
ON
O
en
oo
O
en
vo
51
en
en
2
o
2
8
o
il-
en
\ 940822/1
to
% X,
o
-------
r '"••^
O
H
U
O
u
H
2
&*
o
1
u
2
es §
^ a
z ?
~ H
i.
CN
ON
td
O.
O.
^
Pk
1
v
to
0"S
s
en
cs
VO
ON
VO
en
en
en
00
cs
TJ-
vO
ON
en
en
cs
vo
vo
en
oo
cs
en
cs
o
o
o
en
en
CS
o
t-'
o
00
en
O
ON
ON
cs
en
en
ON
cs
00
ON
VO
vd
cs
cs
en
en
cs
en
s
O
o
cs
ON
en
en
OO
00
8
1
ON
O
vo
00
•^f
VO
en
en
ON
r-
cs
S
00
vo
en
O
ON
8
en
cs
cs
00
ON
5;
«n
oo
cs
vo
vo
en
cs
*r\
ON
IT)
en
Tf
en
en
vo
ON
cs
en
en
vo
en
oo
cs
00
en
cs
vo
ON
•n
o
ON
VO
ON
VO
ON
O
cs
VO
O
CS
cs
cs
cs
o
00
oo
o\
es
o
cs
o
vo
en
ON
00
en
w>
ON
en
O
en
en
ON
CS
cs
oo
o
un
oo
g
rf
ON
o
O
n-
oo
r-
VO
in
oo
f-
VO
en
ON
oo
ON
CS
00
VO
ON
es
en
o\
ON
vo
ON
ON
cs
o
O
CS
o
cs
O\
cs
M
vo
VO
o
o
K
VO
I
oo"
vo
§
VO
cs
o^
00
00
I
00
I
00
8
cs'
oo
o
o
cs"
00
cs
O
en
en
cs
00
o
o
en
%
o
00
o
o
oo
cs
o
o
en
oo
o
en
cs
en
§
S
o
en
cs
O
o
cs
00
o
ON
o
ON
V
fri
-------
fl
N
X)
fe
*
d
§
«
ta
a
t«
•d
BB
^
•••J
~^<
&G
^Jj.
Date/Time
i
•
'
•
1
•
•
i
o
8
CO
CO
(940224/1516
co
Ov
00
wo
o
,_
TT
35
ON
00
r^
cs
•~*
f^.
ON
tt
oo
0
O
oo
CO
ON
*••*
O
8
o
cs
1
1
ON
__
oo
(-V
tN
8
wS
vo
r-
"*
o
CO
CO
Vl
Tf
CO
CO
-
«— <
0
p:
00
oo
r-
8
o
^
vo
(940323/1345
1
1
1
1
1
1
'•
1
1
1
1
o
8
!/•)
ON
940325/1630
i
i
'
\
'
'
i
i
!
8
o
If)
ON
CN
1940325/1635
•
i
'
I
I
1
1
I
i
8
o
*/~l
ON
cs
1940325/1640
»o
Ov
CS
CO
v>
ON
ON
?
*
vq
ON
CO
vo
vd
CS
t— »
0
£
00
o
8
ON
00
CO
1940326/1930
1
1
1
1
1
1
1
1
1
1
1
8
ON
vo
CO
1940327/1115
ON
••*
CO
CS
VO
cs
Tf
r-.'
vo
00
o
00
00
CO
CS
CO
'
vq
8
o
•o
00
Q
^
8
o
cs
^•lln
CO
1940327/2130
1
1
••
1
'
!
1
!
o
8
^
^D
CO
(940328/1130
VO
CO
TT
vO
o
CO
vq
^
cs
cs
00
CO
CO
o
ON
o
VO
VO
O
o
1
1
8
s
Q
' '
o
8
r—i
CO
CO
1940328/1830
1
1
1
1
1
1
1
5
1
',
o
8
00
CO
(940329/0830
-------
H
Q
O
H
H
O
H
ON
H
fc
u
o
H
I
W
U P
5
M
A
P*
•*»
z.
S3
^
V
u,
U
U
T3
u
09
•<
5
Of
Date/Time
«n
vO
ON
00
Tt
CO
CO
ts
«n
«n
«o
VO
t->
1—1
vo
•/•>
r-
VO
ts
co
w>
vo
•^~
(^
00
o
O
i
§
oo
o
ts
1
o'
CO
940329/1730
r-
co
<-«
0
>/•>
(^M
5;
rr
l>
co
CO
cs
r*H
«0
V~l
oo
CO
rr
ts
cs
s
CN
00
ts
o
o
1
00
r-
£
VO
ts
o
o
o^
o
ON
cs
940330/1000
P
1MH
^
*— t
ON
i— i
in
00
0
ts
<5T
i— i
00
r~-
T
00
00
CO
«r>
vo
ts
VO
Tt
O
O
:
3
S
v»
8
o^
ON
iri
ts
940406/1030
CO
ON
r»
•*
«/•>
0
VO
ts
•<1-
«n
»— 1
3
1—
TT
r>
r— >
00
r-
ts
i-"
ON
oo
O
%
o
0
1
1
t-«
W"»
&
CO
o
§
ts
CO
940420/1130
oo
•*
~
CO
ts
o
ts
«r>
ts
oo
r~
00
»r>
CO
«r>
r-
CO
ts
tr\
«n
f\
o
TT
O
i
i
W">
iri
X
^-1
8
vO
VO
1
«r>
O
3
£
~-
CO
I— •>
o
»-N
O
ts
VO
vO
t~-
«n
VO
1— 4
O
f"^
00
TT
ON
T
«<-H
O
3
o
1
o
CO
s
ts
o
s
00
ts
940526/1045
ts
oo
o
s
o
VO
rr
ts
s
ON
ts
CO
o
ts
•*
00
ts
r^
.— i
Tf
S
o
1
•«1-
CO
CO
«n
00
8
•*r
ON
v>
940629/1130
s
CO
•«•
•n
o
ts
CO
ts
3
5
I— 1
r<
ON
r-
co
ON
00
1— 1
T
r-
<—i
oo
o
o
1
1
CO
CM
*r\
J2
o
o
TT
ON
w*
940629/1131
ts
co
•
t^
CO
t^
o
o
•*»•
ON
>r>
940629/1132
o
00
ts
t-
o
o
$
!—*
CO
•
2
5
»— «
S
o
oo
s
o
!
S
g
ts
o
o
oo
co
«r»
940727/1215
00
ts
o\
f-H
ts
t^
CO
«r>
oo
o
TT
«r>
.^
TT
«n
r-«
NO
ts
CO
ts
ON
ts
TT
r*
o
!
ON
•
VO
00
•
«^>
«/•>
«^
CO
§
ON
CO
OO
c<
rr
o
«/•»
rr
CO
ON
«r>
0
«n
•t
o
1
in
CO
ts
««r
trt
l^
O
§
^~
w->
940822/1345
a
«
O **
1.3 « s
S .o jq eS
.-s an
4
-------
fc
o
H
U
55
O
H
O
H
ON
I
5 £
^^^
w
§
w
J
w
w
u
^
k.
o>
0-
ptft
wW
«
b
Of)
0
I*
u
• PM
c
I
1
a
k.
>
s
«>
!
a
N
A
»*
•••
Z
E3
S
£
u
u
•«
u
09
•<
5
af
§
?
08
A
CO
•
O
T— t
O
0
ON
i— i
CO
CO
•^~
TT
p-
o
o
1
1
«n
•«1-
00
cs
ON
i— i
O
o
t-
r*
NO
O
CO
CO
§
00
o
*
oo
r-
cs
NO
00
O
ON
CO
CS
s
o
00
ON
00
?!
l«4
00
Tf
CS
?!
o
o
!
5?
1
§
•*
00
NO
o
CO
^t
||94090 1/1
oo
w>
CO
•^r
o
ON
CO
f«4
TT
«r>
CS
NO
'oo
OO
r~
>r»
NO
«n
00
ON
o
0
1
1
00
c-»
00
CO
o
§
NO
cs
00
•
NO
0
CO
oo
l—«
•t
CO
p«-
cs
f-M
TT
NO
p-
co
oo
t— 4
cs
o
cs
cs
£
o
0
1
1
ON
CO
§
p^
o
£
«o
TT
o
o
1940928/1
r«4
o
•^«
o
w>
o
CO
r—>
NO
p*
ON
CO
ON
oo
5
CO
NO
CO
3
0
1
«r>
*rt
ON
cs
o
o
«rT
o
o
CO
1 941019/1
s
cs
ON
O
O
w>
1-^
ON
5
O
CO
0
co
o
cs
cs
co
co
T
0
1
1
%
ON
oo
«r>
O
o
«rT
o
o
co
00
r* *
i
cs
Tt
NO
oo
f^
o
00
o
cs
p^
r>
s
cs
3
p*
Tf
«n
Tf
cs
CO
TT
0
!
ON
NO
p-
NO
o
1-H
o
§
TT
00
o
CO
cs
^
CO
1— 1
i
ON
CO
NO
I/I
o
ON
«/•>
cs
^
TT
TT
^1-
co
p-
ON
p»
Tt
CO
ON
!«4
1
1
!
CO
w>
p*
oo
00
o
§
cs
00
o
o
co
S
o
o
NO
cs
NO
«o
«/•»
T
ON
w>
O\
CO
NO
NO
O
!
1
X
ON
NO
1
cs
oo
~N
o
«n
\941201A
NO
co
co
ON
O
o
V
ON
P~
CS
r^
oo
ON
«/•»
NO
ir>
•»«•
p-
o
ON
00
co
o
!
!
CS
cs
§
oo
o
&
cs
00
3
»n
\941201A
^
NO
ON
O
00
OO
CO
cs
NO
p-'
w>
NO
s
00
f~
ON
•
cs
00
o
m
"1-
1 941212/1
*•*
•D
cs
o
co
cs
00
o
p~
NO
oo
o
«/•>
«/•>
o
p>
cs
o
«/">
"•
s
«r>
o
oo
1
oo
00
I
CO
p*
cs
oo
8
cs
0950118/1
00
Tf
cs
oo
p^
^>
CO
NO
p^
cs
s
NO
oo
CO
rj-
•^t
«r>
cs
w>
•f
««4
o
•*
0
1
p*
CO
CO
«r>
2
8
s
i
I950122A
0>
-------
fc
o
N4
O
u
H
u
r i
Q
ON
»H
U
Q
(3D
Q £
!
I
I
0
N
.a
2
0
*
«
ta
a
U
U
U
Qw
^^C
M*
^^G
^
^s
Q>
S^"
«n
O
O
S
0
00
r-
cs
^
o
cs
M
o
ON
S
O
CS
VO
CS
o
«n
If)
\f)
§
1— 1
VO
5
•s
I
CO
00
o
0
— I
5
*»M
•n
cs
ON
00
0
oo
cs
o
o
cs
cs
o
Q
VO
in
cs
§
cs"
a
i
o-
ON
cs
0
oo
o
o
o
VO
CO
ON
t-
00
TT
VO
o
«n
s
0
cs
VO
o
^
oo
T^-
cs
§
vo"
o
*->
«*>
o
o
I
s
VO
VO
Tf
VO
o
£
0
cs
o
o
*n
00
o
o
oo
VO
8
~
o
s
1
a
1 *
c^
"*
VO
cs
o
cs
VO
r-
VO
cs
o
5o
m
cs
cs
0
m
0
o
^
c^
<— >
o
cs
m
VO
r-
00
^
•a
i
Ph
O
cs
cs
rr
en
O
O
00
O
vo
ON
ON
S
O
OO
cs
o
^
o
o
00
VO
o
00
o
ON
ON
f— 4
VO
"73
g
%
s
ON
"*
ON
O
ON
Jn
CO
vo
r~-
r-
0
00
cs
cs
m
cs
o
^
0
o
oo
cs
cs
o
ro
,— 1
—
i
Oi
ON
cs
r"
cs
o
cs
s
•^f
vo
ON
T
00
cs
o
00
o
o
00
^
o
m
oo
^f
—
t-
a
a
J8
u
VO
cs
ON
0
00
o
vo
^^
c*>
o
Tf
00
00
cs
0
ON
cs
o
^
oo
cs
o
cs
ON
vO
VO
00
a>
1
;t
z
o
I
-------
r i
O
H
H
fc
U
O
U
K. .Ml
> ^
?3^
O H
03 3
to s
** p
cu
0,
G .-,
2 I
DA e
£ I
H .a e>
a s a
£
N
PH
fc
a
£
U
U
g
«
*
-1
v.
S
ON
O
0
O
00
0
~
en
en
cs
00
vo
cs
en
r-
o
en
O
0
vo
en
O
o
vo
CS
1— «
o
o
ON
ON
8
1
3
CO
S
O
O
o
vO
O
CS
ON
0
cs
00
0
s
o
o
o
cs
en
O
£
—
1
cs
L
IJPotomac
o
o
s
v
o
r-
o
1
0
-
cs
o
o
0
en
00
O
O
en
CS
o
ON
ON
8
v>
O
0
O
o
o
cs
0
en
cs
&
?
0
o
o
s
o
00
o
o
en
00
vo
en
o
O
1
O.
4
$
VO
s
°
en
en
0
00
VO
00
cs
^
vO
en
O
O
~
^
O
00
VO
o
o
00
s
o
ON
o
cs
cs
1
§N"
o
en
o
en
0
en
ON
cs
VO
VO
CS
oo
r-
o
2
0
cs
o
0
S
o
00
o
00
ON
o
1
cs
00
"*
0
o
00
vo
o
ON
en
ON
^
cs
vO
vo
o
s
o
ON
O
o
tfl
o
00
en
00
S
i
PI
o
r-»
0
en
O
®
oo
O
ON
O
„.
ON
ON
—
0
en
O
o
o
o
o
o
VO
00
o
00
en
llchoptank
ON
00
0
^
cs
ON
00
en
oo
cs
en
O
oo
o
o
s
o
00
CS
0
CS
o
en
1
1
-------
fc
o
r •—^
ti
U
z<
o
u
H
as
ON
u
a
p-
C8
h*
a>
2
if
%<
K a
<§•
<^
I
I
A
A
Pk
a
&
*3
u
u
TJ
u
00
Wj
V Dfc
80 S
a|
V
2
S
cs
m
cs
vo
o
s
oo
ON
O
O
cs
en
^j-
•/->
VO
g
f*^
(^
ON
VO
£
O
§
VO
1
CT
CO
cs
V«N
o
^.
oo
«
cs
cs
ON
O
f-
VO
VO
!Q
cs
0
g
*^>
\o
^H
OO
oo
en
§
cs"
cs
II
HPotomac
o
VO
CS
5
^.
fT)
1 '
00
o
VO
cs
vo
VO
*/">
„.
ON
1—1
m
VO
g
t—
CO
00
-
o
o
vo"
tn
at
i—i
3
00
^
o
vo
00
ON
%
f *
00
cs
r-
_
•^-
cs
£
1—4
CS
^»
cs
-
s
•8
q
1
cs
vd
vO
vO
"*
oo
cs
en
^
^
2
oo
oo
-
£
f»*
ON
oo
r~
ON
vo
00
5?
pi,
cs
cs
VO*
vo
1—1
"*"
00
vo
o\
o
cs
o
cs
in
ON
ON
O
CS
g
cs
ON
0
cs
-
f-^
fMattaponi
0
vb
o
00
cs
ON
f>
o
o
cs
m
-
cs
o
'"'
r^
0
^
£
If}
CO
00
cs
cs
£
m
IPatuxent
CS
5
^
VO
^
^
$
O
cs
00
cs
cs
VO
o
o
cs
*""
vo
cs
CS
£
00
ON
cs
cs
00
vO
fChoptank
cs
oo
00*
VO
cs
o
1— <
oo
VO
cs
cs
cs
ON
,^
Tf
00
g
cs
00
^f
T^
cs
'
VO
OO
I
CS
»—i
6
-------
A
,a
0-
l^
^*-H
a
£
u
»> X
\0
*p*
u
n
^*
•s?
V M
^
af
0>
£
ON
P-
5
^.
i/^
C^l
vo
cs
o
00
CO
cs
o
•^
r-
*~l
o
CO
£
00
ON
cs
00
cs
0
•n
•8
3
in
2
ON
CS
o
5
00
ON
cs
cs
00
cs
VO
vo
CO
*""*
cs
"*
g
o
o
t-
o
o
cs"
8
2
o
o
cs
cs
o
00
vO
r-
ON
^_l
VO
vo
0
g
vo
VO
VO
vo
•8
^
co
jji
-T
00
cs
cs
o
vO
VO
cs
cs
CS
vo
VO
vo
ON
CO
in
cs
cs
1—1
£
1-H
£
^
f^
ON
cs
vO
^
o
n
1
o
o
CO
^
^^
fo
CO
o
CO
00
VO
1— 1
g
TT
i
o
00
cs
0
•/•>
o
*""*
en
HH
g
§
VO
oo
t-
CO
§
1
1
3
cu
§
CO
o
cs
^.
^
o
CO
cs
ON
1
VO
co
00
rr
*~
cs
o
<
CO
v^
l/^
CO
oo
ON
1
§
**ri
c-
co
CO
o
o
ON
cs
CO
vo
cs
CO
ON
s
VO
g
In
CO
-
CO
1
"5
Pi
ON
«n
vo
vo'
^
^>
CO
o
co
co
CO
oo
0
ON
VO
ON
-
g
oo
0
o\
CO
oo
CO
1
1
JC
VO
o
VO
CS
ON
o
cs
p-
Ov
CO
o
ON
co
p-
o
cs
g
00
ON
cs
CO
CO
1
'$
*5
CO
«M«
u
-------
H
<
Q
fc
O
H
u
fc
o
H
O
H
TT
ON
ON
U
Q
fc
W
a,
o.
f 1 T
§5
e^
DD
U
a
N
*
2
o
*
_
to
—
U
b,
S
on
^^
•"j
^^
af
w.
a
oo
-
eo
CS
o
cs
cs"
00
f-
oo
m
eo
£
r-
eo
cs
E
o
o
,
1
«/•>
^
ON
~
O
VO
ea
RSusquehan
t^-
TT
s
o
oo
f-*
00
cs
v*^
cs
cs
r-
r-
co
00
cs
ON1
oo
rr
o
o
1
1
r-
oo
!/•}
eo
eo
O
O
cs"
cs
[[Potomac
^
-"
cs
cs
o
o
VO
O
cs
oo
o
VO
00
00
2
r-
o
o
,
1
f-
m
CO
~
s
to
1— .
,
«n
o
ON
O
CS
o
00
VO
_«
oo
CO
oo
o
5
o
cs
s
o
1
1
s
f^.
oo
o
o
1
1
a
I
ON
"*"
s
o
oo
o
2
^*
cs
o
ON
oo
o
cs
5
o
s
f— «
0
1
rr
f— *
\0
CO
~
oo
amunkey
ON
CO
ON
O
O
oo
o
T
VO
VO
•0
O
VO
O
oo
o
s
o
cs
s
o
1
1
cs
cs
CO
^f
cs
s
llMattaponi
VO
VO
£
O
cs
eo
VO
ON
VO
CS
eo
r-
cs
cs
5
cs
vo
Tf
o
,
1
cs
CO
ON
"*"
-
llPatuxent
CO
ON
vo
0
oo
S
CO
t^
cs
o
oo
cs
CO
cs
1
0
,
1
CO
cs
ON
eo
VO
llChoptank
ON
ON
8
o
CO
cs
CO
o
cs
C^l
"*
ON
s
VO
oo
"
CO
vo
o
CO
r-
cs
o
1
1
oo
CS
~
vo
oo
II
BNanticoke
.2 *
II
§ o
3
8,1
IJa
v ~
-------
Q
fc
N
PN
*
fl
^
«
g
U
U
•o
U
OB
^
^—
^^
af
SJ
3
3
CS
ON
O
O
""^
ON
en
•^>
0
en
O
O
cs
cs
9
0
i
i
00
ON
00
*n
§
e
1
1
VO
"
VO
O
ON
o
09
ON
00
ON
O
O
O
~
o
00
o
0
o
o
r»'
cs
cs"
Potomac
CS
o
ON
O
o
f-
o
£
\Q
ON
cs
r-
o
5
o
VO
00
O
0
i
i
ON
ON
g
t-;
i
.
o
cs
o
p
o
ol
fl
^
s
o
oo
o
cs
0
ON
s
o
1
00
en
en
o
O
1
en
ON
cs
o
cs
en
~
£
ON
t^
2
ON
oo
en
0
i
i
i
ON
\f)
tn
s
HPamunkey
ON
00
5
0
S
~
£
I-**
en
vo
VO
O
ON
VO
O
£
0
en
en
O
i
i
ON
ON
oo
ON
|Mattaponi
00
o
«r>
~
o
{5
~
o
^^
ON
W>
ON
en
00
vo
O
ON
O
en
0
3
^f"
m
l-M
1
00
00
o
o
o
NO
oo
o
o
f-^
~
en
o
2
o
cs
o
8
0
00
en
00
en
HChoptank
!?
ON
3
o
o
cs
cs
oo
00
en
~
^
VO
CS
o
o
"
a
0
oo'
^f
en
flNanticoke
M a
§ *
'% •«
IJ
'!
§
*ii
o -a -g
\^ t V
ll*
8 1= »
« a 5
53*2 >
cLJ: o
^^ O ^*
4> W v5
«a -a «
.2*2 S
•s«-S
S -3
.2
"8
1^1
f^1
a2
U
H
-------
APPENDIX D
Susquehanna River Fall Line Field Blanks - Organic Constituents
-------
A. Chemical Abbreviations
Abbrev.
Appendix D.I
Sim
Pro
Atr
Diaz
Ala
Mala
Metol
Cyan
Hexa
Appendix D.2
Mnp
Dmn
Acy
Acn
Flu
Phn
Fin
Pyr
Chr
Bnz
Bzp
Per
Complete Compound Name
Simazine
Prometon
Atrazine
Diazinon
Alachlor
Malathion
Metolachlor
Cyanazine
Hexazinone
2-Methylnaphthalene
2,6-Dimethylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
Chrysene
Benz(a)anthracene
Benzo(a)pyrene
Perylene
Abbrev.
Appendix D.3
Aid
Non
DDE
DDT
PCB1
PCB2
PCB3
PCB4
PCB5
PCB6
PCB7
PCB8
PCB9
SPCBs
Appendix D.4
BHC1
BHC2
BHC3
Oxych
Chll
Chl2
Nona
Did
DDD1
Endr
DDD2
DDT
Methoxy
Complete Compound Name
Aldrin
trans-Nonachlor
4,4'-DDE
4,4'-DDT
Monochlorobiphenyls
Dichlorobiphenyls
Trichlorobiphenyls
Tetrachlorobiphenyls
Pentachlorobiphenyls
Hexachlorobiphenyls
Heptachlorobiphenyls
Octachlorobiphenyls
Nonachlorobiphenyls
total PCBs
alpha-HCH
beta-HCH
gamma-HCH
Oxychlordane
trans-chlordane
cis-chlordane
trans-Nonachlor
Dieldrin
2,4'-DDD
Endrin
4,4'-DDD
4,4'-DDT
Methoxychlor
D-l
-------
cd
1
§
I
e
c/5
V*
i
111111
•O -O 'O T3 -O -O
-a-a-a-a-a-a
11
•O T3 -O -O
O O -O -O -O O
00 C *C GO
•O
•o *o
•o -o -a -o -o TS
3 "a'a'a'c'a^
> *
o r~; -o -a -a -a ~+
I o^^o
g CO O
S o "a "a ^5 "a o
U O "O T3 "O "O "O
•s d "a "a "a "a "a
Tf "O "O "O "O •
o "a "a "a "a CL
§
I
U
•8
'3
§
1
•a
a
111
\J \J -O
V V *£
•O -O -O
"a "a "a
•O 73 "O
"a "a "a
5
•o
5
*a
11
•a -o (-r
'S'S v
111
•a -a -a
•a "a "a
•o-oO'
"a "a v
•a -a CX
•a "a v
•o -o -o
"a ~a ~a
T3 T3 ^
"a'aci
ts
Q
ctf ctf
en
°id
ON -*
en
ON
JS
oo
O
en *o oo
*. d 1 <*i -3 c>
J\ — Tf ON ^H -H
ON ON ON ON ON O\
'•H en oo jf o O
en en en «n ^ ^5
O O O O O »-*
«•* en
^ cs
ss
ON ON
O O
-------
£
3
ffl
O
E
i
1
o o
pi -O O;
o 13 o
o\
«
O
o o —
o o o
O
q ;
d
•A
O
•s
i
o
U
1
$
Q
i
o
d
o
d
ooo
O r*>
<=>. 5 °.
o c o
o «/•>
P5 -•
o c o
_ _ 2
^O ^O ^3
"&"& d
8§S
d o' d
ts cs
d ~3 o"
^ S o o
« ri
^C3 ^3 ^^ ^3
6 IM ^*) C^
ooo,
^ d d d
o o m «^>
o o o o
d d d d
« oo m
«s o t-_
d d d
q ; r»i o «s
d d d d
-o o o o
e d d o*
o —• o\
5 o o o
c d o' d
00 CS
O oo
o o o o
o ON o vo
m o o v»
vo oo i— i
Ov o^ cf^ e^1
~ ~* cn O
ON oo
oo vo vo ON ^r oo
ON *f *f ao 06 d
-------
2
S
N
3
J3
O
1
I
1
I
Q
CN
CO
O
•O'O'O'O'O'OO'O
---""-"
11111111
•o-o-o-o-oxjoS
-a "a "a "a "a *a d d
•OO'OO'O'O'OO
"^**. • ^^. « "^ *~^. ^-^ •
COGOCCCO
rn
o-o-o
- - -^ - *° 5 ^ R
d"S"cd"a"cdd
g
o
e
6
S
I
"c d d o" "e d o" d
•o o| o o 8 o -o o
"cddddd ed
8
vo O
•a2!c)I"a"a!
88^8^8888
vor~o\m3oocx3oo
CM'— i
oo
w
I
S
I
C
O
I
'§
a
§
•a
3
•a
•a *a -a "a -a -a -a "a
•a "a -a ^ ^ ^a v v
o c
v-a-a v v
"cdVV'c-VVd
^ j ^
"cdddd v"ad
-a v -s -a -a -a
v ^ v "a v v v v
«n en
O oo -^
I*"- >o en
9\ O\ O\ O\ ON 9\
OOO
-H en oo x _
-H (N
-------
PU
1
I
CO
U
§
i
CQ
2
E
.S
I
I
;o
1
Pu
U
e?
o
•o
S
I
1
i
-".•8
f*l ^
w •>
so
crt
CQ
IX)
8
U
OH
OO
CQ
U
OH
CQ
U
OH
CQ
U
OH
o^
U
OH
CQ
U
OH
CQ
H
Q
Q
Q
Q
cd
I
CQ
U
CO
CO
S
-H Vi —4 CS tS -H O «S
oooooooo
•O'O'O'OO'O'O'O
~a~e~a~ad~a~a~a
81— < i— i
•oo-a
""
en »-< o
•o o o -o o -o -o
"""""
i— i O\ «— i »— I ff\ O
o o o o o -o -o
""
S P! S o. S S S S
o'ddddddd
S^5 oo ^o i^ ^^ ro ^^
tsi o *-• o oi o -H
doo'ddodd
d"cododd
•o-o-o-oo-o-o-o
•'
•O'O'O'O'O'O'O'O
C'C'G'C'C'C'C'C
11111111
•OTS'O'O'O-O'O'O
•-
1
§
U
Detec
8 8 -o o -o S 8 S
dd^cd'cddd
OOO'O'O'OOO
• • • "^** "***» *s"»
-------
UH
1
I
CO
«
3
UH
C
i
8
cu
G
^
§
C?
•a
«
U
CO
I
I
co
w
oo
PQ
a
u
CL,
co
OQ
CQ
H
Q
Q
W
g
CO
5^
0 O O O O O
111111
lllll
T3 -o -o -a -a -o
c c c c c c
•O -O T3 -O
•a -a TJ -a -o -a
o
-o -o -a -o -a
''-'-
1
S8S335
O O O O O O
llllll
5 -a -o -a -a -a
c c "a c c c
•o -o -o -a -o -a
•o -o -o -o -o -o
c c "c "c "S "c
•o -o -o -o -o -o
C C ~G "a ^ ~G
0 o o o o o
llllll
oo ^S vo oo
O O O ^H
co oo oo cs cs ON
CS «-^ CO CO O OO
NO Vi CO NO F""
-------
"8
•»*
S
I
i
§
2
u
I
CO
'c''c'"a'
Q £8808883
Q
j ^ _^ ___ j
o^-rJS^SoS
Q
6 S82828S8 ^ ~
55 dddddddd
en
« S 8 S 8 § 8 3 S I
O dddddddd
^ dddddddd
^ I 88888888
C) g dddddddd
ffi c ^^^^^^^^ 'S !0!0?3!oS^OT3rO
cq § dddddddd .„
0 j
K
CQ "a oooooooo
g 1 S88S888S „ _
» Q dddddddd CX V ^ V V-5-5 ^ V
.^fc _._ . __ ^~ *£* _ . — — ^^r
Vj ^^N '•H v^ C^l ^^1 ^D ^^?
^S
O O O
OOO
-------
.c
CL,
,S
o
I
i
cd
j
0)
I
U.
I
S
•o
.s
$
I
cs
•
O
•S
ts
g
s
§
•S
m
U
CQ
CQ
U
K
>y
88888288
oddddddd
88888888
oddddddd
88883388
oddddddd
88888888
oddddddd
88S88888
oddddddd
888SS888
d d d d d o* d d
88888880
d d d d d
80888
o o o
sss
d d o
ooooo
88888888
oddddddd
88888888;
d d d d d d d d
1
I
•g
88888888 i
odd
sss
odd
o o o o o
35888
ooooo
s
•J3
3
•a
88888888
oddddddd
•O'O-O'O'O^'O'O
72d
•o-o-ooo-o-o-o
OOOO
en
•o-o-o-o-o-a-o-o
oo
cnooootscntsONO
O\O\O\OSONO\OS
OOO
oo
Q
-------
APPENDIX E
Tributary Synoptic Study Concentration Data - Organic Constituents
-------
A. Chemical Abbreviations
Abbrev.
Appendix £. 1
Sim
Pro
Atr
Diaz
Ala
Mala
Metol
Cyan
Hexa
Appendix E.2
Mnp
Dmn
Acy
Acn
Flu
Phn
Fin
Pyr
Chr
Bnz
Bzp
Per
Complete Compound Name
Simazine
Prometon
Atrazine
Diazinon
Alachlor
Malathion
Metolachlor
Cyanazine
Hexazinone
2-Methylnaphthalene
2,6-Dimethylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
Chrysene
Benz(a)anthracene
Benzo(a)pyrene
Perylene
Abbrev.
Appendix E.3
Aid
Non
DDE
DDT
PCB1
PCB2
PCB3
PCB4
PCB5
PCB6
PCB7
PCB8
PCB9
SPCBs
Appendix E.4
BHC1
BHC2
BHC3
Oxych
Chll
Chl2
Nona
Did
DDD1
Endr
DDD2
DDT
Methoxy
Complete Compound Name
Aldrin
trans-Nonachlor
4,4'-DDE
4,4'-DDT
Mbnochlorobiphenyls
Dichlorobiphenyls
Trichlorobiphenyls
Tetrachlorobiphenyls
Pentachlorobiphenyls
Hexachlorobiphenyls
Heptachlorobiphenyls
Octachlorobiphenyls
Nonachlorobiphenyls
total PCBs
alpha-HCH
beta-HCH
gamma-HCH
Oxychlordane
trans-chlordane
cis-chlordane
trans-Nonachlor
Dieldrin
2,4'-DDD
Endrin
4,4'-DDD
4,4'-DDT
Methoxychlor
E-l
-------
OS
OH
•8
1
S
8
"3,
CO
1
CO
o
•a
|
CO
.S
to
e
0
•o
1
S
1
c
1
— !
CN
.a
i
<7
co Q
00
a ^ a ^ o>
—
vo«n«ooot» —
«-> oo iri — r* ~
S(NJ —. TT fo — r- t-fv
»o q « o o r-; r-; t7
-^^^^(S^rr — V
SS SR vs «o
to fn co c*i ft
S£i
M SalsB
lhliiia
PL, 2 .--;
O\ O\ O\ C7\ O\ OS gN
j^ rj ts o o o o
55 S 8
111111
addadadd
addacsddcs
«o ^ ^ c\ \o
?4 — t3 p NO •=• 5 13
ddadddaa
US
8
i
-------
B. Concentration Abbreviations
Term Definition
Date Date sample was collected
-------
ft,
"8
8
CO
I
CO
t
CO
CO
U
1°
1
CX
1
S
m
.B
•5
i
»
J
Q
I
ca
11
d
'
O
o
S
00 S i-J
00
cs
S
fe2 zy
O
S,
o 55
-a-a-d-a^W^^
_. °*
O"Ot^r*^NOT3^S •
— dcJcJoaoes
oo
'^oo
rnco\rnooO\
•
«nv>ov»
HI l!|8s
S 5 BC ^ < U W
illllsp
^S5ol2o2p1
SSSSSSSScS £
en
-------
£
3
^ CH O c^ oo vo <*>
• O • -^ • • • •
f**i *~| c^ a oo oo o o
— 00 o
_, oo oo
~ « °°. q - 5 ^
o o — o — -H o
Sr^
_,
— oo-^r~
o~— -o
8»no\
-
mn^^ I
CO
55 *a
ss 3
-a-a-a^a-
aa° a
vvSv^-av^
S^l fO *™' *•• ^v O
t p xr q v> *j ^
O O O O fO " *^^*
dddV^Vdvo
85 — cJoo^Sfi
•—ooo — o^S"-
o a v o o
> d V V X
CXO
v v
o a o v
Sen ^5 t**
q — q
d d d d
O'O'O'O'O'O'O'O'
vvvvvvvv
o *-* o *—• *•"* i—* *-•
-------
I
I
I
CO
£
'w?
§
•g,
•§
I
en
IX]
a
B
03
k:
a
-
If
oo —'•fpr-oooo
oowjr^^^fjpp
dddddddd
ddd
eddddddd
o o o o o o o
nddddddd
S T, S S 5! £ 8 8. S
daddddddd
lllllllll
lllllllll
aaaddaddd
u
-:
ddddddddd
y.S'? o
^^J^JJ
dddVddVV
2ddV§dVV
t-fifjr-v^io*-1'-1
dddo'ddVV
CO f) CO
--Tf
CO CO
^ ^ ^ ^ S* ^
Ov 9(
"CJCJCJ999S9 a
«- sliissisi 1
-------
O-
1
8
"E<
CO
1
CO
o
t
CO
.S
n
ex
S
•|
1
U
.a
1
OQ
W
S
a
3
en
n
OQ
01
Q
Q
U
J
en"
co
«".
"
>
O. H
fl
2 a is 5 g s a 2
— -^0
•o p q o vq •* q q —
adddddddd
ooooooooo
-o-aopcsm—> — o
aaddddddd
•05822828513
"adddddddd
dad ad dado
co
en r*j en en en
l>coP6a.CL.UZlM«
iiiiiii
i
aaoonaaa
dad — dado
* 3 5 E: S -9 S 8
aad—dadd
CM OO 5 O
5 3 -: m. ®. 5 3 ~.
daoooaao
f> •* ^ ci
5005055—
dddaoaad
d*3dddddd
aaadoaoo
en en tn en en
cu 2 2;
111
S O 55 S
a
-------
1
£
1
Q
1
i
•Q
"3
CO
£
8-
c
CO
.S
1
•3
•a
8
CL,
-------
OS
£
i
3
'i
0,
$
0.
f
T§
CO
1
CO
—
'»H
8
3
jo
«
\
a a
a i
g-8
(S H
i
J
V
m tn oo P"> >« r- O
WO^OOClCNjciptS
dddddodod
dddddd
oppp—i 9 p o ri
dddddaddd
•a-a'O'B'O vo
555P«s — — S —
dddoooddo
111111111
5353^^533
ddddooddd
§ 8 8 2 •« § § 8. 2
ddddddddd
oo >n in
5533-15°. 1
ddddOdoo
11111111
^* ^N O\ fl Oi *••' P*
— pt>ip3p
-------
-------
APPENDIX F
Tributary Synoptic Field Blank Concentrations - Organic Constituents
-------
A. Chemical Abbreviations
Abbrev.
Appendix F. 1
Sim
Pro
Atr
Diaz
Ala
Mala
Metol
Cyan
Hexa
Appendix F.2
Mnp
Dmn
Acy
Acn
Flu
Phn
Fin
Pyr
Chr
Bnz
Bzp
Per
Complete Compound Name
Simazine
Prometon
Atrazine
Diazinon
Alachlor
Malathion
Metolachlor
Cyanazine
Hexazinone
2-Methylnaphthalene
2,6-Dimethylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
Chrysene
Benz(a)anthracene
Benzo(a)pyrene
Perylene
Abbrev.
Appendix F.3
Aid
Non
DDE
DDT
PCB1
PCB2
PCB3
PCB4
PCB5
PCB6
PCB7
PCB8
PCB9
SPCBs
Appendix F.4
BHC1
BHC2
BHC3
Oxych
Chll
CW2
Nona
Did
DDD1
Endr
DDD2
DDT
Methoxy
Complete Compound Name
Aldrin
trans-Nonachlor
4,4'-DDE
4,4'-DDT
Monochlorobiphenyls
Dichlorobiphenyls
Trichlorobiphenyls
Tetrachlorobiphenyls
Pentachlorobiphenyls
Hexachlorobiphenyls
Heptachlorobiphenyls
Octachlorobiphenyls
Nonachlorobiphenyls
total PCBs
alpha-HCH
beta-HCH
gamma-HCH
Oxychlordane
trans-chlordane
cis-chlordane
trans-Nonachlor
Dieldrin
2,4'-DDD
Endrin
4,4'-DDD
4,4'-DDT
Methoxychlor
F-l
-------
•"§
H
g
8
tin
2
£
.S
1
i
Q
1
c
c
6
«
'3
S
A-
M
I
!
8
•o
S .§
oo cu
1 Organonitro
dy: Dissolved
• 3
CO
'•o J3
c 'a.
O. g
< CO
S
a
1
u
1
S
(4
•a
.2
<
3
5
<
1
g
CO
19
-22
Q
a.
o "c
•o -o
~c "c
2-0 -
2~c S
c
5
•o -o "3
-a ~a S
e
8
•o -o c
^b "S
S -o -o S
^2 p^ ^? ^J
o o
'S W
C _^ '^—
£^ H^
U -o-o .1
1 "^^ S
H en '*
u • "O 3
r\ *~* ~^t cv
U i— i c *— '
O O
en en
*
* *
•<*• •*
O\ ON
So in
0 ^
i-H ^H
^s
V "c
T3 -0
"3*5
0*-a
v ^
11
•o -o
"c ^
•o -o
"3 "3
11
11
Si
ON ON
q q
en en
*
* *
O\ ON
So m
o ^<
S H
« s
3 i
2 ^
w >
S s
>» -S
u o
1* '5
i
•* *
ts
-------
u
•a
ex
1
CO
£
2
•e
H
1
6
1
1
•a
*«
tu
_c
*9
I
•g
Q
09
1
i
G
6
c
Jg
K*
0
•&
e8
|
8
1
O to
-i
ts "3
tu _2
g >>
ex's
a. 3
a,
&
PQ
N
a
VH
U
,,
&.
c
E
c
£
1
u
^
^^
4^
Q
ex
S
glo
Is
£
ctf
Q
11
•a -a
dl
•o -a
"c c
en -*
d d
Tt g
d d
o r-
-^ d
2" o d
1 228
g do
g ON O
S do
y
O no >/">
U in ON
"P CN •— '
3 "
8 so ON
^3 i^^ ^l
Q 06 TJ-'
^
r^ o
ON -•«
O O
en en
*
* *
ON O^
oo — i »— i
^H ~*
-^
td
e
§
•a
S
S
I
u
1
u
CO
^t
S
3
ititation
5
3
a
•a ^
•o 5
^^
,
§1
11
en -^
d d
S S
d d
O f~
~ d
CN» 00
d d
oo oo
-H O
d d
ON O
d d
oo in
in ON
vo ON
|^^ ^^
06 -^
r- o
ON -H
oS
en en
*
* *
ON O\
oo in
^H V«H
^ »— 1
S 1
•j d
1 1
§ 1
5 *
^** '••^
4> O
*i •
i ^
P-> *
* *
en
-------
u
•Z3
1
CO
1
3
.0
•c
H
1
S
p
fc*
s
S
2
"«3
• ^^
.S
i
1
a
CO
O^*
1
§
C
a
e
2
3
5c
•o
S*
1
§
8
,— 1
1
>•» eg
ft. £
^1 *3
fN 0
PU 'S
s »
P5
>% M
4) O
•S .«
§ *"?•
i z
&H *
* *
-------
1
•a
3
CO
_o
§*
M
PQ
W
c
CO
a
1
g
PH
£
Jl
•o
*d3
E
c
i
£
Q
•o
'S
1
CH
C
^
JC
o
03
&0
6
i
/TS
PQ
H
en
*>»
1
PQ
cd
C
|
"o
Jl
fT, P^
1|
S .2
S -a TJ
g "a "a
o
'^
S 11
y
3 88
1 do
I 88
Q o* o*
11
q q
«n Tt
en en
^
* *
ON ON
§^3
^5 ^5
^4 r-4
1
o
1
c
o
3
1
^
CO
1
nj
§
I
•a
a
88
d d
•a ^
^^
55
c c
vl
CX-o
v •§
ey
^* ^3
V "^
J J
ao
V V
J
v'5
G
11
11
11
11
11
1 v
_1 J
aa
v v
o ts
ON ON
q q
en en
*
* *
OO IT)
O -*
^5 ^
~4 •— <
U
u e
3 3
^™^ VM
& ^
•1 a
>, J2
1 i
OH *
* *
-------
CO
1
c
CO
1
JO
£
U
1
J2
§
CQ
•o
"S
£
.S
1
I
1
01
3
'8
cu
U
1
5
1
O
1
CQ
U
C/5
^H
1
.S4
CQ
1
•S
o
1
o
CN g
en jc3
a!
••5-3
8-1
o. a
< CU
en
CQ
U
cu
w
m
oo
CQ
CU
CQ
CQ
CU
|^K
8
en
CQ
CU
CQ
CU
CQ
U
H
Q
Q
Q
Q
«J
O
3
CQ
U
y
o^ en
S CO
eR co
13
a
c3
Q
o ^
d d
88
d d
81^^
^^
d d
88
d d
88
d d
8S
d d
d d
88
d d
88
d d
88
d d
•o -o
2* "^
~3b
•B ^^
"° "°
e
o
O -o-o
I "^
H
Q "a"c
00 00
oo oo
tS vo
en en
*
* *
1§
T— 1 ^H
...
1
i
|
o
o
U
"8
CO
1
I-J
e
o
1
88
d d
*O "O
•o O*
"c V
1 v
T3 -0
^^
J i-J
aa
V V
i i
acx
V V
•o -o
^^
•o -o
"c ^3
11
5 5
e c
11
11
11
11
00 00
oo oo
fN VO
en en
*
* *
T TT
OS ON
oo in
o ^;
<-4 <— 1
<— 1 •— 1
(U
0> C
c *
1 *
(£4 l«
u. U
i 1
sr -o
•^ •«
I i
CU *
* *
tt.
-------
a
J
OH
1
S
tn
S
>»
3
CO
o
•o
ex
o
>»
CO
f
3
.O
•c
H
1
S
g
tL,
•i
s
s
"O
•s
S
c
13
1
8
&
Vi
O
1
CO
-r>
3
0
s
u
33
«
* \
S*
S M
8K CO
13
1
Q
8t-
cs
d d
S3
d d
88
d d
88
d d
88
d d
V^ O\
o 8
d d
88
d d
£ S
^^ ^^
d d
•^ en
cs O
CJ °' °'
g»
• «M
a
I
•a
s
3
O*
« S^
Id
11
11
11
G C
8-0
d^
NO Qs
O 0
d d
11
£3
d d
**• ff\
So
d d
2^
d*a
35 s
d ^
en en
CM —
d d
oo m
CS «-i
d d
* ifc
m cs
00 OO
o. o
in •«»
en en
*
* *
•^ ^
ON ON
oo in
O ^
v»4 f-H
9)
s 3
a d
= 73
« IX,
t SJ
I -1
(2 „
1 1
1 1
JA. Jt.
,-* -H -^
r-
-------
u
!
OU
i
s
•o
2
CO
o
ributary Sync
H
4)
6
s
i
1
•a
"S
E
.S
1
S
Q
8
•o
1
8
(X
0
2
8
i
00
6
(S
Tf
PM'
.a
•o
c
1
X*
0
H
s
fe
Q
a
Q
i
g
5
1
s
u
u
1
o
c^
u
OQ
cs
1
*«H
1
B
P^ S
^S c/i
^j
> C
I
88
d o
88
c> o"
88
d d
88
d d
88
d d
88
d d
88
* •
0 0
88
d d
8^^^
^^
2" do
1 ss
5 o o
o
'.3
1 88
§ do
e
a ss
•o do
£
1 88
Q do
** i*
S
OO OO
CN VO
• •
C^ C^
*
* *
O\ GK
oo in
/~^
!
c
1
§
§
U
1
u
CO
[s
"J
'I
.ta
a
•o -o
^ "S
•o -a
"S 'c
•o ^
"c c
11
11
•a TS
•c~c
11
dl
11
•a -a
"c "S
•o -a
"c^
11
11
*JS >J8
S un
00 00
rj vo
en en
*
* *
^" ^
^ ^
oo in
o ^
i-^ »— i
«
c
J
*"*j
fcn
u
52
^
0}
•^
s
g
*
oo
fct.
«
•o
-------
APPENDIX G
Susquehanna River FaU Line Loads - Organic Constituents
-------
-------
A. Chemical Abbreviations
Abbrev.
Appendix G.I
Sim
Pro
Atr
Diaz
Ala
Mala
Metol
Cyan
Hexa
Appendix G.2
Mnp
Dmn
Acy
Acn
Flu
Phn
Fin
Pyr
Chr
Bnz
Bzp
Per
Complete Compound Name
Simazine
Prometon
Atrazine
Diazinon
Alachlor
Malathion
Metolachlor
Cyanazine
Hexazinone
2-Methylnaphthalene
2,6-Dimethylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
Chrysene
Benz(a)anthracene
Benzo(a)pyrene
Perylene
Abbrev.
Appendix G.3
Aid
Non
DDE
DDT
PCB1
PCB2
PCB3
PCB4
PCB5
PCB6
PCB7
PCB8
PCB9
LPCBs
Appendix G.4
BHC1
BHC2
BHC3
Oxych
Chll
CW2
Nona
Did
DDD1
Endr
DDD2
DDT
Methoxy
Complete Compound Name
Aldrin
trans-Nonachlor
4,4'-DDE
4,4'-DDT
Monochlorobiphenyls
Dichlorobiphenyls
Trichlorobiphenyls
Tetrachlorobiphenyls
Pentachlorobiphenyls
Hexachlorobiphenyls
Heptachlorobiphenyls
Octachlorobiphenyls
Nonachlorobiphenyls
total PCBs
alpha-HCH
beta-HCH
gamma-HCH
Oxychlordane
trans-chlordane
cis-chlordane
trans-Nonachlor
Dieldrin
2,4'-DDD
Endrin
4,4'-DDD
4,4'-DDT
Methoxychlor
G-l
-------
V
o
8
1
OH
eo
|
8-
o
t
po
s
0)
CO
I
^o
.s
e^^ O
_ O]
O c/j
S Q
5 ••
II
11
w^
--J8
*"" P
d«g
11
Q,—
0.13
< £
3
S
I
00
ON
t* — —
O O
'-M^ONOOOTTtSOO^-.-. •—
-------
% S
>»
U
u
a
1
g
'co
1
ts o\ t^ oo -^ ts
«r>
O
o
o
-------
o
0>
CQ
I
u
PU
3
PL,
C
Q
I
I
§
oo
ON
OtStNOCNO
-* t- CS CN ^
o o o o d -H
3
oo
o
VO
CO
-H — OCJOOOCO
s;
94-01/31/9
ON ON ON ON ON ON ON ON
ON ON ON ON ON ON ON ON
ON ON ON
ON ON ON
3
-------
N
U
3
UN
8
Q
1
^5 *™^ ^5 O ^"^ ^3 ^5 *™^ ^? ^5 ^5 ^3 ^D
t^
OCSCMOtSO^OOOOO ~*
men _
vo «n "*. Tt °^ °i 9 <=> t -t o S
^^ ^^ ••••••••• CO
^^ *"^ ^^ ^^ CO ^"*^ CO ^3 C^ ^^ ^^? ^^* ^^5
-------
S'i
o
on
I
CQ
6
1
3
E
!
1
— in—*v>voooinr-csenTf
ts— «
. en
en
8
en
%
I
%
en
oo
en
SOON— *r--*
*-• ~* en
en
* en o ... in •
itscsONtsen—•« -*
vo . . m
« S » S 6
— •» -" S
ON
ON
ON
ON
TJ- ^ Tt ^t >n o
ON ON ON ON ON -»^
ON ON ON ON ON CS
VO
6
-------
•a >
ix
sq
&
CO
1
1
a
E
Q
ex
o^o— '
— «oo— «
en
o\
s
°
oo
en
'— i -* en
t-
6
oo —. oo
** °° °°
— oooo —
i
^
^ v, ^ ^ en
1-88SB1 §
ON ON ON ON ON ON ON ON ON ON ON ON •»»
ON ON ON ON ON ON ON ON ON ON ON ON CN
^^ V"4 »••* •«* v^ VH VM v«4 «-^ ^H 1—4 1—4 ^^
-------
8
a
w
oo
03
03
03
u
CL,
2
u
OH
i—i
03
i
g
Q
I
ffl
U
I
I
VO
*"". cs vo °°. "*. °. ^ *"". °. <**. ^ ^ c*^cscscSfr>O'~'f*^f>'^ ON
^T oo ON m
com ON vo —« o cs en
p p «o p p O p p p p «— -* p
o o o o o" o' o o o' o o o —'•
cs cs «n «n «/•>
o cs cs oo r-- «/•» OOON
— p r- o p o —i p p o o o ^r
o ^ o o o o' o o o o o o es
o ON cs p — p cs o —< co cs cs vq
o cs TT o o o o' o o o o o 06
ON
O ^ Tf CS T CS vq ^- CS «/"> P* 00 Q^
o r-' r*-' o o o o o" o o o o —«
o
TJ- Tf ooi pni Tt; eni «/"> cs[ p r* •**; «n cn
O 06 ON O O O O O O' •— O O CS
vo oo oo c**i ("•• r** vo cs ••* v"i r** ON ^^^
CS 00 00 ^ O O O O O O — ^ CS
^o ^«f co oo ^D fo ^^i **^ ^^ oo r^ ^^ «^
o fi ••a- o o o o d o o o o *-•
VO CS O
p p «n o p o p p p o p p vq
o o o o o o" o o o o o o o'
p p p p p p p p o o p p
o o o o o o o o o" o o o o
p o p p o p p o p p o p
o" o o o o o o o o o'oo o
oo o m
p m oo_ p p — cs p •—i vq cs_ cs p
o cs o' o o o o o o o o o vi
p o o o o p o p p o p p
o o o o o o o o o o o o' o
OO OO CS
SON m w% vo m
vq cs p — p p o p p p m
o o o o o o o" o o o o o ^
vo oo ^- vo «r> ON
O P- O O O O ~ O O — — — *r>
c5 o cs o o o o' o o o o o' en
fe to ^
>> £^
« ZZ
> 5 a °
O U t3 i
z
ONONONONONONONONONONONON
ONONONONONONONONONONONON
oo
6
-------
I
<*.
o
U
13
PL,
I
s
t
OH
CQ
•c
o
I
2
52
_g
09
1
1 &
•i|
§ ^
ii
31
ca .2
1s
o>
—*qt-;—*qq—*^'-^coqq »-<
o-^c>ooc5oooc>C)CJ co
SCO
co m co t^ O co
-<* co CN_ es ~H o CN q ^ co cs CM ^o
Oco'rrcJCJOCJOOOOCJ ON
ON
SOcoir»-*oovocs-«tc*-
TT «n «r> rf cs *o »-H cs »n r-_ oo _
CJt^-'t^OOOCJCJcJcJCJO •"*
o
O oomt^ocNt^ -*^
Tf •* oo co rt co in es q — Tt «n ^
OOOONOOOCJOO^OO CN
-^ •rj- •** o r~ co
NO oo oci co r-• r~ vc; cs| -^ \n r-• o\
csodo6-^ooooc>c>^« CN
oo "^•^ONCSOOCSONCN
VJ^COOONOCOON-^TfOOVOr-; _..
OcO-*OOC)C>OOCSC>O -^
cs oc^No»nNo-H cs r-^ •* ^ oo co •«* ON q cs ^
OCSCSCJOOOCJCJO — ^ ~*
q q q q q q q q q q q q q
oooooooooooo o
q q q q q q q q q q q q q
oooooooooooo o
•^- oo o co
S<^>W>C^ONO«OONQCOOO
co ON o q -^ cs ci -* NO cs CN «^
o'cs'odooooooo'o «ri
q q q q q q q q q q q q q
oddooodddodd d
cs oo ~*C^O\CSON^J-
^cSNOcoir>vOf^^^^^>rj
q CN| r-. cs| q -* q o o o q q t~-_
dddddddddodd ~
\o oo ^ NO «n ON
co^- CS-HCO-HCO^-NO-^NO
0^0000 — 00^-^'^ «n
d d cs' d d d d o o" d d d co'
CO
o
ON
6
ON ON OS ON ON ON ON ON ON ON
ON ON ON ON ON ON ON ON ON ON
-------
a
w
oo
1
U
u
PL.
0
u
O-
o
CD
U
cs o ON ^ t1^ r-» r^ •—' NO
dcscsddd-^ddddd ~*
oo ON cs w» o -* cs »-i '-'
n-oo^t-^-ent^Tfcsr-w^so .
• * * ,—* * /~z * _ • • • — • • ^r
oo ^ o cs ^ en en oo
• • •• • • • • • ••• O
-< ON
cs oo r* cs •* cs ON p p cs ^ ^ cs
en cs t^; «n —< cs en p p en -^ -^ en
^•^ o^ ^^ ^^ ^^ ^^ *^ ^^ ^^ ^^ ^^ ^^ f "^
^^) ^^ '"'^ CS ^"^ ^5 CS ^^ ^"^ V)D ^^ ^^ ^^
C^ ^^ ^^ ^^ ^^ ^5 ^^ ^^ ^^ ^^ ^^ ^^ ^^
p1 * CS ^^
<•* en cs •—< oo
p p •* O p p p p p p p p •*
dddddddddddd d
p p p p p p p p p p p p p
dddddddddddd d
p p p p p p 2 p p p p p 2
dddddddddddd d
O p cs ^ en cs ON »—• *—> m cs cs
en «n
p p p p p p p p p p p p p
dddddddddddd d
en r- cs oo
cs-^OenoooO'^enooooo
dddddddddddd cs
p^pppppppppp cs
dddddddddddd d
§
en
•5 •*-" 11 7! -O M t~ £1 ^
^ O *^ 9 U Ti fli Ai W f~*
I
O
s
I
-------
u
e
VhM
O
•!
3
PU
i
i
t/i
I
3
cd
I
I
S
Vfc,
O
en
2
S1
T-H
2
_G
an
>»
S
§
S
|fi
Is
3i
^
-!
en (X>
d S
.a 1
P
< GO
CQ
U
(X
w
a
u
O.
u
u
0,
£
u
a
a
OQ
S
Q
Q
Q
I
CQ
5
5
vo o ^ o en ON vq cs -^ «rj o •* ^
en' •* «s r- «n vo ^
o-*Ttooo-^oc5odo —«
oo ^QCS ^cn t^oo
oovoot^^«n»nrnrncnp^oo o
ovo'vioootsoo^oo ts
vo moo-^-t^c^-^-osr^
tsi oo t- tsi Tt; cs o\ O O cs| ^-H »-i r4
O^^OOOOCSOCSCJO v£)
CN
^tooo\ cst^ooom
en «Ni rt; »n ~-< ts en cs o •** —< -^ cs
~-*CN—OOO OO
•^ t~* vo ~* oo
VO OCN«£}O\vSo»n>OS
OTt-^CN—«OCNO—«VOOO —*
c5^^4c)c5oG>c5oc5c)O •*
•* ONcnrfo\«noo'«*en'-*
vci o\ vci Tt; en cs «n cs cs vo r~_ oo in
o^^ooooooooo od
cjoqooooooqqo q
dG>dc>dc>dc5G>c>c>c> d
q q q q q q 2 q q q q q 2
dddddddddddd d
Tfrr^-^tt^csr^csTfvo
q O ts •rt; en cs ON «-; ^ «n ts cs ^_
^•^•tsddddddddd —<
en vi
q q q q q q q q q q q q S
dddddddddddd d
ON «•* oo ^ oo
cso^tOenooootsenooooo
q CNi •* cri -« -^ rt q q -* q q -^
dddddddddddd «s
OO VOTfOOOO OO«-iTt
——i
O
-------
*
I
es
g
I
§
U
u
en
U
S
s
1
•S
1
oo
ppppppooppppp ON
dddddddddddd d
in
ON ON en en in
p oo <<* p p p p p p in in vo ~*
dddddddddddd •*'
OO ^4 •<* VO VO O
O t** oo o O O O O O en «•* es en
dddddddddddd en
pppppppppppp p
dddddddddddd d
cs
oo es ON ON vo es vo
p f; oo ^ p ON in p cs vo en en Q
des'^ddddddesdd -*
in inen^-esoovo^enoo
vo vo en en •* in oo en ^-« p en en ON
des'esddddddddd oo
es cs
T»- or-r^movo vocs
csoNr^csp^«nenp'-4CSen en
cj^^'odddddcs'dd 06
^vocsTrrtO'*vo-4 esm
p es ^t ^H cs in en •— —* es »-< ~* c*;
dddddddddcs'dd "*
oo
^^ OO ^^ ^^ ^^ C^ ^^ ^^
^5 ^^ ^* c^ C> ^o ^D co ^^ f** co co oo
des'^ddddddcs'dd oo
r^vooN—^^-en vooo
p en es en '-H in vo es —< in en en ON
o^'^odddddcs'dd t^
ON ON ^* in ON
vopONVooN-HCSTrenooONp ^
dencs'-^d^-^ddend-^ »^
^5 CO *"^
^5 ^^ ^^ ^3 ^^ ^^ ^5 ^3 ^3 ^5 ^5 ^3 ^^
dddddddddesdd en
ON ONCSON«-^t*-VO ^f*1
t—i psj ,—iTfCSVO^fi-4OOOVovo vo
des-Hodddddcsod ON
m
en
O
X
ON ON ON ON ON
in
ON
ON
O
§
cs
o
I
-------
•8
I
1
1
w
1
I
I
I
H
g
cs
§
•8
W
§
T3
5
s
o
cs
O
s
I
I
a
(X)
i
CQ
I
^f ON NO C""" C** en *^ ^f oo en
en o ON cs «—>'—• cs «-«'-« en en rr «<">
O —< O O O O —• O O O O O «n
*-> i-^ o\ r*» en
cs o ON NO «r> en ^ w> rj-«r>
•— cs r- o o o ~^ o o »/•> »/"> NO •—
o ^ o o o o cs o o -^ o o «ri
en O f- f- oo en •/•>
o oo oo o o o o o o en « cs w->
o o' o o o o o' o o —'• o o en
cs ooit-;• cs —• ~* cs| —•> — cs en en r-
O O O O O O O O O O O O en
«r^ ON CS
O oo oo ^t O O NO o cs NO en en o
oo
NO NO en en ^f *ri oo en -— O en en ON
O cs cs O C3 O O O O O o o ob
cs cs
•^- ot"-t^-*r»ONo r^cs
csor*»csO^f'oenO'--|CSen en
o cs <-* o o o o o o cs o o" ob
en
O en rr — cs «r> en •— <— cs •— — ON
o o o o' o o o o o cs o o •*
en oo
en oo oo cs t^* O en ^ c^
O •—' TT cs O *f\ NO en «—> l^ en en ON
o cs ^ o o o o o o cs o o ob
en C"** NO ON *~* ^ en NO oo
O en cs en •— «/"> NO cs <—> w> en en O
O « •-< O O O O O O «s O O ob
ON ON oo ^ i/^ ON
NO O ON NO ON O CS ^t en oo ON O QQ
O en cs »- O •— •— O O en O •— —*
\O NO «-< NO oo en
ONr^csON»/^w^ONen^ cscs
OenONOO^OOOO'"*'"" ^
o d o d d d d d d cs d d •*'
d cs — d d d d d d cs d d ON
8 ^
ft £ £
~H all
a S ^ § I
o. ° > o
g
§
o
ON ON ON ON ON
ON ON ON ON ON
ON ON ON ON ON
ON ON ON ON ON
-------
a
ts
8
a
3
&.
a
^
^
r°
i
I
dm'dddddddddd NO
CM CM
t^ CM ON oo t^ »n CM o
O Q
r- \o *—> cs ^ vo CN
vq p en -H p p csj ~* O »-; p p \o
~< o r-
10 en »—< en cs C4 *~* CM O "^ O O _
• ••• " « t-5 <-i o «
^•^ ^^ f^ ^^ W^ ^5 ^^ ^^^ ^"^
^^ i^^ ^^^ ^^ ^^ ^^ ^-f ^5 ^^ ^^ ^5 ^S c^
dddddddddddd en
ON CM oo rr
r^«nf»;ppp^f~*pppp oo
dcM'dddddddddd •*
SCM VO
ppppenppppp p
dddddddddddd —'
vi oo o r- en
en en ^^ ^^ ^^ ^^ CM ^^ ^^ c^ ^? ^^ ^^
^•9 *™^ ^5 ^5 ^^ ^5 ^^ ^5 ^^ ^^ ^3 ^5 CM
i
OOCMCM ^-OOCM-^
Ol>ppppcMppppp en
en en ON CM O
r-t f** OO *—I OO ~-<
dddddddddddd d
OO ^ O OO •*£
dddddddddddd ^
NO O O t** CM
en CM j£ ^ en »-H »—i o
dddddddddddd d
S
S
en
O
•^, ^^
ON O\ O\ O\ Ov Ov O/\ O\ OJ\ CT> O\ 5* ^~
ONONONONONONONONONONONON CM
»~< »—( 1-^ »~( «-H r—< »-H «-H »—t »—I t-H »-^ O
ON ON
ON ON
6
-------
8
a
I
CO
U
•o
1
§.
u
•c
o
1
e?
o
M
I
I
I2
la
5!
•I0-
1|
^
o S
*s *S
§ 2.
g ^
«< 5
1
I
s
Q
Q
Q
1
U
8?
o
m
8
OQ
U
i
-s
i
o o m -*
dddddddddddd CN
CN oo oo £•
^5 ^5 ^^ ^^ ^^ *"^ *^* * o CN
~* °C;C:!Cvo9t*c~H^:^;
^•irjV^OOO'^OO'—' O O cn
O cn oo ^ »o vo
r~; «o r^• q q q •<*; -H p q q q ON
dcNoddddddddd •*
CO 1^ OO C*J *^ ^^* f^i C** *^ C^l C^> Ol
q *o q q q q cn q q q q q •*
oo oo o r*1 ^ ON
d-^'dddddddddd CN
C^^ OO ^^ C^ OO CO v™^ ^^ ^^ C^
CO ^^? ^^ ^O ^^ ^^ ^^N ^O cO ^^ v^ ^"^
^^j ^^ ^^ C? ^5 C3 ^^ ^^ ^^ ^^ C^ ^^ ^^^
dddddddddddd ^
^^ CO t^* ^^ ^^ ^^ t^* CS C^
dddddddddddd ^
oo >^ oo oo o
qcNCNCNOq^*-''—icncsd o
dddddddddddd CN
\^^ ^O ^^N CO *"^ ^^ )^^ WO
CO f*^ ^^ ^^ ^^^ ^^ ^^P ^^ CO ^^ ^^ *"^
^^ co *™^ C? ^Z? ^^ *"H ^^ C5 ^? ^^ ^^ *™*<
dddddddddddd ^
•^ «3 « h ^
C JQ »- ja ^ .^ cn
Sx: t*6«Slb^
illiitplu! °
& 2 < S »? 5 < w O 2 Q ^ 3^
^ ^ """^ ^ Tf ^ ^ ^ ^ ^ ^
-------
-------
|