CBP/TRS 118/94
July 1994
Chesapeake Bay
Atmospheric Deposition
Study, Phase II
Final Report
July 1990 - December 1991
Chesapeake Bay Program ^ 1
Printed on recycled paper
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Chesapeake Bay
Atmospheric Deposition Study
Phase II: Final Report
July 1990 - December 1991
July 1994
Printed by the U.S. Environmental Protection Agency for the Chesapeake Bay Program
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THE CHESAPEAKE BAY ATMOSPHERIC DEPOSITION STUDY
PHASE H: July 1990 - December 1991
Sponsor:
U.S. Environmental Protection Agency, Chesapeake Bay Program Office
Personnel (alphabetical order)
Principal Investigators:
Joel E. Baker1, David Burdige2, Thomas M. Church3, Gregory Cutter2, Rebecca M. Dickhut4, Dianne
L. Leister1, John M. Ondov5, and Joseph R. Scudlark3
Co-Investigators:
Cheryl Clark1, Kathryn M. Conko3, Linda S. Cutter2
Technical Assistants:
Michael Granger1, Zhi Lin5, Sheila Moore3, Mike Newell6, Brenda G.T.J. Yates1, Zhong Y. Wu5
Chesapeake Biological Laboratory
Center for Environmental and Estuarine Studies
The University of Maryland System
Solomons, MD 20688
department of Oceanography
Old Dominion University
Norfolk, VA
3College of Marine Studies
University of Delaware
Lewes, DE 19958
'Virginia Institute of Marine Sciences
College of William and Mary
Gloucester Point, VA
'Department of Chemistry and Biochemistry
University of Maryland
College Park, MD 20742
6Wye Research and Education Center
University of Maryland
P.O. Box 169
Queenstown, MD 21658
Revision Date: May 24, 1994
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TABLE OF CONTENTS
FORWARD
EXECUTIVE SUMMARY . . .
a. Overview
b. Organic Contaminants . . .
c. Aerosol Trace Elements . .
d. Precipitation Trace Elements
e. Overall
INTRODUCTION
1.1 Background
1.1.1 Evidence of Atmospheric Deposition
1.1.2 Mechanisms of Atmospheric Deposition
1.1.3 Review of Previous Work
1.2 Statement of the Problem
1.3 Study Objectives
1.4 Study Limitations
THE STUDY
II. 1 Design
H.2 Sampling Site Locations and Descriptions ....
11.2.1 Wye Site
11.2.2 Elms Site
11.2.3 Haven Beach Site
METHODS
HI. 1 Organic Compounds in Air and Precipitation . .
HI.1.1.1 Air Sampling
in. 1.1.2 Precipitation Sampling
HI. 1.2 Analytical Procedures
in. 1.2.1 Sample Extraction
CD. 1.2.2 Quantification of Analytes
m.1.2.3 Detection Limits
HI. 1.3 Quality Assurance
m. 1.3.1 Extraction Efficiencies
HI. 1.3.2 Procedural and Field Blanks
ffl.2 Trace Elements in Aerosol
m.2.1 Sampling
m.2.2 Analyses
m.2.3 Quality Assurance
m.2.3.1 Estimation of Uncertainties
m.2.3.2 Evaluation of Uncertainties in Blank Corrections
m.2.3.3 Evaluation of Field Blanks
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III.3 Trace Elements in Precipitation 13
III. 3.1 Sampling 13
III. 3.2 Analyses 14
III.3.3 Quality Assurance Program 15
in.3.3.1 Operational Blanks 15
in.3.3.2 Reference Solutions 16
m.3.3.3 Intra-Laboratory Analytical Comparisons 16
in.3.3.4 Inter-Laboratory Analytical Comparison 16
III.3.3.5 Precipitation Collection Efficiency 16
IU.4 Major Ions in Precipitation 17
IV. RESULTS IV
IV. 1 Organic Contaminants 17
IV. 1.1 Spatial and Temporal Variations in Atmospheric
Concentrations 17
IV. 1.2 Spatial and Temporal Variations in Precipitation
Concentrations 19
IV. 1.3 Depositional Fluxes of Hydrophobic Organic Contaminants . 20
IV. 1.4 Annual Loadings of Hydrophobic Organic Contaminants
to the Chesapeake Bay 21
IV.2 Aerosol Trace Elements 22
IV.2.1 Spatial and Temporal Variations in Atmospheric
Concentrations 22
IV.2.2 Estimation of Dry Deposition 24
IV.3 Trace Elements in Precipitation 26
IV.3.1 Concentrations 26
IV.3.2 Wet Deposition 27
IV.3.3 Interpretation of Trace Elements in Precipitation 28
IV.3.3.1 Estimation of Uncertainty 29
IV.4 Major Ions 30
IV.4.1 Covariance w/Major Ion Data 30
V. CONCLUSIONS 32
VI. 1 Common Trends and Interpretations 32
VI.2 Atmospheric Deposition of Contaminants to Chesapeake Bay 32
VI.3 Future Research Initiatives 33
Vn. ACKNOWLEDGEMENTS 34
Vm. LITERATURE CITED 35
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LIST OF TABLES
Table
No. Title Page
n.2.1 Sampling Schedule 43
HI. 1.1 Organic Contaminants and Elements Analyzed in CBAD Study 44
IE. 1.2 Mean field measured vapor concentrations, pg/m3, and mean
analytical detection limits for PAHs and PCBs, Chesapeake
Bay, 1990 - 1991 45
in. 1.3 Summary of Laboratory Surrogate Compounds for Chesapeake Bay
Atmospheric Deposition Samples, Elms and Haven Beach Sites,
1990 - 1991 46
IE. 1.4 Mean Mass (ng) Summary of Polycyclic Aromatic Hydrocarbons
and Polychlorinated Biphenyls in Laboratory and Field Blank
Matrices, Chesapeake Bay Atmospheric Deposition Project,
1990 - 1991 48
HI.2.1 Concentrations of Elements Determined in NIST Standard
Reference Materials 50
HI.2.2 Comparison of Laboratory and Field Blanks, ng/filter 51
HI.3.1 Analytical Detection Limits (jiglL) for the Determination of
Trace Elements in Precipitation 53
m.3.2 Results of Quality Control Check Solutions for Trace Element
Wet Deposition 54
HI.3.3 Trace Element Wet Deposition Intercomparison 55
IV. 1.1 Mean Total (Vapor + Particulate) Air Concentrations of
Polycyclic Aromatic Hydrocarbons and Total Polychlorinated
Biphenyls, Elms and Haven Beach Sites, 1990-1991 56
IV. 1.2 Polycyclic Aromatic Hydrocarbons Concentrations in Air, pg/m3 58
IV. 1.3 Total Polychlorinated Biphenyls in Air, pg/m3 59
IV. 1.4 Mean Total (Particulate (filter + funnel) and Dissolved Rain
Concentrations of Polycyclic Aromatic Hydrocarbons and Total
Polychlorinated Biphenyls, Elms and Haven Beach Sites 1990 - 1991 . . 60
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IV. 1.5 Mean Dry and Wet Fluxes of Polycyclic Aromatic Hydrocarbons
and Total Polychlorinated Biphenyls, Elms and Haven Beach Sites,
1990 - 1991 62
IV. 1.6 Mean Dry Wet Loadings of PAHs and Total PCBs, Chesapeake Bay,
1990 - 1991 63
IV. 1.7 1991 Annual Loadings of PAHs and Total PCBs, Chesapeake Bay,
for Maryland and Virginia Areas 64
IV.2.1 Summary of Concentrations of Elements Determined at the Wye, Elms,
and Haven Beach Sites, ng/m3 (year 1) 65
IV.2.3 Concentrations of Airborne Elements Determined in Beltsville,
College Park, MD, and Lewes, DE, ng/m3 66
IV.2.4 Deposition Velocities Determined for Aerosol Particles Over Water ... 67
IV.2.5 Data Summary and Annual Flux Estimates for the Chesapeake Bay .... 68
IV.3.1 Comparative Precipitation Concentrations (jtg/L) at Five Mid-
Atlantic Sites (Volume weighted averages) 69
IV.3.2 Spatial Variability in Trace Element Wet Deposition at Three
CBADS Sites for 1991 (/xg/m2/year) 70
V.l Summary of Atmospheric Fluxes and Loadings of Trace Contaminants
to Chesapeake Bay, 1991 71
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LIST OF FIGURES
Figure
No. Title Pace
II.2.1 Chesapeake bay atmospheric deposition sites 72
HI. 1.1 Comparison of several PCB congeners in a precipitation sample to
field detection limits 73
HI.3.1 Comparison of absolute field blank contributions at 3 CBADS sites
to those measured at Lewes, DE 74
HI.3.2 A comparison of field blanks at 3 CBADS sites, shows as a percentage
of the average sample concentration 75
m.3.3 A comparison of laboratory blanks to field blanks at 2 CBADS sites ... 76
ni.3.4 A comparison of the predicted volume (from gauge) to the collected
volume as an indication of the efficiency of the collector 77
IV. 1.1 Fluorene concentrations in air collected at the Elms and Haven Beach
sites 78
IV. 1.2 Phenanthrene concentrations in air collected at the Elms and Haven
Beach sites 80
IV. 1.3 Anthracene concentrations in air collected at the Elms and Haven
Beach sites 82
IV. 1.4 Fluoranthene concentrations in air collected at the Elms and Haven
Beach sites 84
IV. 1.5 Pyrene concentrations in air collected at the Elms and Haven Beach
sites 86
IV. 1.6 Benz[a]anthracene concentrations in air collected at the Elms and
Haven Beach sites 88
IV. 1.7 Chrysene concentrations in air collected at the Elms and Haven Beach
sites 90
IV. 1.8 Benzo[b]fluoranthene concentrations in air collected at the Elms and
Haven Beach sites 92
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IV. 1.9 Benzo[k]fluoranthene concentrations in air collected biweekly
at the Elms and Haven Beach sites 94
IV. 1.10 Benzo[e]pyrene concentrations in air collected at the Elms and Haven
Beach sites 96
IV. 1.11 Benzo[a]pyrene concentrations in air collected at the Elms and Haven
Beach sites 98
IV. 1.12 Indeno[l,2,3-cd]pyrene concentrations in air collected at the Elms
and Haven Beach sites 100
IV. 1.13 Diben[a,h]anthracene concentrations in air collected at the Elms and
Haven Beach sites 102
IV. 1.14 Benzo[g,h,i]perylene concentrations in air collected at the Elms and
Haven Beach sites 104
IV. 1.15 Total trichlorobiphenyl concentrations in air collected biweekly at
the Elms and Haven Beach sites 106
IV. 1.16 Total tetrachlorobiphenyl concentrations in air collected biweekly at
the Elms and Haven Beach Sites 108
IV. 1.17 Total pentachlorobiphenyl concentrations in air collected biweekly at
the Elms and Haven Beach Sites 110
IV. 1.18 Total hexachlorobiphenyl concentrations in air collected biweekly at
the Elms and Haven Beach Sites 112
IV. 1.19 Total heptachlorobiphenyl concentrations in air collected biweekly at
the Elms and Haven Beach Sites 114
IV. 1.20 Total octachlorobiphenyl concentrations in air collected biweekly at
the Elms and Haven Beach Sites 116
IV. 1.21 Total PCB concentrations in air collected biweekly at the Elms and
Haven Beach sites 118
IV. 1.22 Total nonachlorobiphenyl concentrations in air collected biweekly at
the Elms and Haven Beach Sites 120
IV. 1.23 Fluorene concentrations in precipitation integrated biweekly at the
Elms and Haven Beach Sites 122
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IV. 1.24 Phenanthrene concentrations in precipitation integrated biweekly at
the Elms and Haven Beach Sites 124
IV. 1.25 Anthracene concentrations in precipitation integrated biweekly at
the Elms and Haven Beach Sites 126
IV. 1.26 Fluoranthene concentrations in precipitation integrated biweekly at
the Elms and Haven Beach Sites 128
IV. 1.27 Pyrene concentrations in precipitation integrated biweekly at the
Elms and Haven Beach Sites 130
IV. 1.28 Benz[a]anthracene concentrations in precipitation integrated biweekly
at the Elms and Haven Beach Sites 132
IV. 1.29 Chrysene concentrations in precipitation integrated biweekly at the
Elms and Haven Beach Sites 134
IV. 1.30 Benzo[b]fluoranthene concentrations in precipitation integrated
biweekly at the Elms and Haven Beach Sites 136
IV. 1.31 Benzo[k]fluoranthene concentrations in precipitation integrated
biweekly at the Elms and Haven Beach Sites 138
IV. 1.32 Benzo[e]pyrene concentrations in precipitation integrated biweekly
at the Elms and Haven Beach Sites 140
IV. 1.33 Benzo[a]pyrene concentrations in precipitation integrated biweekly
at the Elms and Haven Beach Sites 142
IV. 1.34 Indeno[l,2,3-cd]pyrene concentrations in precipitation integrated
biweekly at the Elms and Haven Beach Sites 144
IV. 1.35 Dibenz[a,h]anthracene concentrations in precipitation integrated
biweekly at the Elms and Haven Beach Sites 146
TV. 1.36 Benzo[g,h,i]perylene concentrations in precipitation integrated
biweekly at the Elms and Haven Beach Sites 148
IV. 1.37 Total Trichlorobiphenyl concentrations in precipitation integrated
biweekly at the Elms and Haven Beach Sites 150
IV. 1.38 Total Tetrachlorobiphenyl concentrations in precipitation integrated
biweekly at the Elms and Haven Beach Sites 152
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IV. 1.39 Total pentachlorobiphenyl concentrations in precipitation integrated
biweekly at the Elms and Haven Beach Sites 154
IV. 1.40 Total hexachlorobiphenyl concentrations in precipitation integrated
biweekly at the Elms and Haven Beach Sites 156
IV. 1.41 Total heptachlorobipheynl concentrations in precipitation integrated
biweekly at the Elms and Haven Beach Sites 158
IV. 1.42 Total octachlorobipheynl concentrations in precipitation integrated
biweekly at the Elms and Haven Beach Sites 160
IV. 1.43 Total nonachlorobipheynl concentrations in precipitation integrated
biweekly at the Elms and Haven Beach Sites 162
IV. 1.44 Total PCB concentration in precipitation integrated biweekly at the
Elms and Haven Beach Sites 164
IV. 1.45 Fluorene wet depositional fluxes measured at the Elms and Haven
Beach Sites 166
IV. 1.46 Phenanthrene wet depositional fluxes measured at the Elms and Haven
Beach Sites 168
IV. 1.47 Anthracene wet depositional fluxes measured at the Elms and Haven
Beach Sites 170
IV. 1.48 Fluoranthene wet depositional fluxes measured at the Elms and Haven
Beach Sites 172
IV. 1.49 Pyrene wet depositional fluxes measured at the Elms and Haven Beach
Sites 174
IV. 1.50 Benzo[a]anthracene wet depositional fluxes measured at the Elms and
Haven Beach Sites 176
IV. 1.51 Chrysene wet depositional fluxes measured at the Elms and Haven Beach
Sites 178
IV. 1.52 Benzo[b]fluoranthene wet depositional fluxes measured at the Elms
and Haven Beach Sites 180
IV. 1.53 Benzo[k]fluoranthene wet depositional fluxes measured at the Elms
and Haven Beach Sites 182
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IV. 1.54 Benzo[e]pyrene wet depositional fluxes measured at the Elms and
Haven Beach Sites 184
IV. 1.55 Benzo[a]pyrene wet depositional fluxes measured at the Elms and
Haven Beach Sites 186
IV. 1.56 Indeno[l,2,3-cd]pyrene wet depositional fluxes measured at the Elms
and Haven Beach Sites 188
IV. 1.57 Dibenz[a,h]anthracene wet depositional fluxes measured at the Elms
and Haven Beach Sites 190
IV. 1.58 Benzo[g,h,i]perylene wet depositional fluxes measured at the Elms
and Haven Beach Sites 192
IV. 1.59 Trichlorobiphenyl wet depositional fluxes measured at the Elms and
Haven Beach Sites 194
IV. 1.60 Tetrachlorobiphenyl wet depositional fluxes measured at the Elms
and Haven Beach Sites 196
IV. 1.61 Pentachlorobiphenyl wet depositional fluxes measured at the Elms
and Haven Beach Sites 198
IV. 1.62 Hexachlorobiphenyl wet depositional fluxes measured at the Elms
and Haven Beach Sites 200
IV. 1.63 Heptachlorobiphenyl wet depositional fluxes measured at the Elms
and Haven Beach Sites 202
IV. 1.64 Octachlorobiphenyl wet depositional fluxes measured at the Elms
and Haven Beach Sites 204
IV. 1.65 Nonachlorobiphenyl wet depositional fluxes measured at the Elms
and Haven Beach Sites 206
IV. 1.66 Total PCBs wet depositional fluxes measured at the Elms and Haven
Beach Sites 208
IV.2.1 Aluminum concentrations on aerosols, integrated weekly at each CBAD
site 210
IV.2.2 Arsenic concentrations on aerosols, integrated weekly at each CBAD
site 212
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IV.2.3 Bromine concentrations on aerosols, integrated weekly at each CBAD
site 214
IV.2.4 Cadmium concentrations on aerosols, integrated weekly at each CBAD
site 216
IV.2.5 Chromium concentrations on aerosols, integrated weekly at each CBAD
site 218
IV.2.6 Copper concentrations on aerosols, integrated weekly at each CBAD
site 220
IV.2.7 Iron concentrations on aerosols, integrated weekly at each CBAD
site 222
IV.2.8 Manganese concentrations on aerosols, integrated weekly at each
CBAD site 224
IV.2.9 Nickel concentrations on aerosols, integrated weekly at each
CBAD site 226
IV.2.10 Lead concentrations on aerosols, integrated weekly at each CBAD
site 228
IV.2.11 Sulfur concentrations on aerosols, integrated weekly at each CBAD
site 230
IV.2.12 Selenium concentrations on aerosols, integrated weekly at each
CBAD site 232
IV.2.13 Vanadium concentrations on aerosols, integrated weekly at each
CBAD site 234
IV.2.14 Zinc concentrations on aerosols, integrated weekly at each CBAD
site 236
IV.3.1 Aluminum concentrations in precipitation integrated weekly at each
CBAD site 238
IV.3.2 Arsenic concentrations in precipitation integrated weekly at each
CBAD site 240
IV.3.3 Cadmium concentrations in precipitation integrated weekly at each
CBAD site 242
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IV.3.4 Chromium concentrations in precipitation integrated weekly at each
CBAD site 244
IV.3.5 Copper concentrations in precipitation integrated weekly at each
CBAD site 246
IV.3.6 Iron concentrations in precipitation integrated weekly at each CBAD
site 248
IV.3.7 Manganese concentrations in precipitation integrated weekly at each
CBAD site 250
IV.3.8 Lead concentrations in precipitation integrated weekly at each CBAD
site 252
IV.3.9 Nickel concentrations in precipitation integrated weekly at each CBAD
site 254
IV.3.10 Selenium concentrations in precipitation integrated weekly at each
CBAD site 256
IV.3.11 Zinc concentrations in precipitation integrated weekly at each CBAD
site 258
IV.3.12 Monthly integrated wet deposition of aluminum at each CBAD site .... 260
IV.3.13 Monthly integrated wet deposition of arsenic at each CBAD site 262
IV.3.14 Monthly integrated wet deposition of cadmium at each CBAD site .... 264
IV.3.15 Monthly integrated wet deposition of chromium at each CBAD site .... 266
IV.3.16 Monthly integrated wet deposition of copper at each CBAD site 268
IV.3.17 Monthly integrated wet deposition of iron at each CBAD site 270
IV.3.18 Monthly integrated wet deposition of lead at each CBAD site 272
IV.3.19 Monthly integrated wet deposition of manganese at each CBAD site . . . 274
IV.3.20 Monthly integrated wet deposition of nickel at each CBAD site 276
IV.3.21 Monthly integrated wet deposition of selenium at each CBAD site .... 278
IV.3.22 Monthly integrated wet deposition of zinc at each CBAD site 280
IV.3.23 A comparison of the CBADS trace element average wet flux to other
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studies 282
IV.4.1.1 Concentrations of major ions in precipitation, integrated weekly at
Haven Beach site, 1991 283
IV.4.2.2 Monthly volume weighted average concentrations of major ions in
precipitation at the Haven Beach site, 1991 284
IV.4.3.1 Monthly fluxes for major ions in precipitation at the Haven Beach
site, 1991 285
IV.4.4.4 Monthly fluxes for major ions in precipitation at each CBAD site,
1991 285
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APPENDICES
A1 Organic Contaminant Supplemental Data A-l
A 1.1 PAHs in Air Samples, Elms and Haven Beach, 1990 - 1991 A-2
A1.2 PCBs in Air Samples, Elms and Haven Beach, 1990 - 1991 A-22
A1.3 PAHs in Precipitation Samples, Elms and Haven Beach, 1990 - 1991 A-81
A1.4 PCBs in Precipitation Samples, Elms and Haven Beach, 1990 - 1991 .... A-101
A 1.5 Mean Analytical Detection Limits in Air and Precipitation Samples,
Elms and Haven Beach, 1990 - 1991 A-154
A1.6 Quality Assurance Notes, Organic Contaminant Analysis, Elms and
Haven Beach Sites, 1990 - 1991 A-158
A1.7 Monthly Cumulative Precipitation and Temperature, Elms Site,
1990 - 1991 A-162
A1.8 Field Notes for Air and Precipitation Samples, Elms and Haven Beach
Sites, 1990 - 1991 A-174
A2 Trace Elements on Aerosols, Supplemental Data, Three CBAD Sites .... A-l78
A3 Trace Elements in Precipitation, Supplemental Data, Three CBAD Sites . . A-206
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i. FORWARD
This report describes the second phase of the Chesapeake Bay Atmospheric Deposition Study
(CBADS). Data resulting from the analysis of samples collected between July and December 1991 are
presented and integrated with previously reported CBADS data (Baker et al., 1992. Mr. Rich Batiuk of
the Chesapeake Bay Program Office, U.S. Environmental Protection Agengy served as the project officer
for CBADS Phase II. Results of this ongoing study are also described in several published papers (see
Leister and Baker, 1994a; Scudlark et al., 1994; Wu et al., 1992; Quinn et al., 1992).
The purpose of the study was to determine atmospheric loadings of selected trace elements and
organic compounds directly to the surface waters of the Chesapeake Bay. The work in this report
represents the first eighteen months of the Chesapeake Bay Atmospheric Deposition Study. Future
reports will describe and integrate results from the CBADS network through September 1993.
ii. EXECUTIVE SUMMARY
a. Overview. An 18 month field study (6/90 - 12/91), conducted to estimate the deposition of
atmospheric trace contaminants to the Chesapeake Bay, represents Phase II of the Chesapeake Bay
Atmospheric Deposition Study (CBADS). Data from Phase I (6/90 - 7/91), which was previously
presented (Baker et al., 1992) is presented here in concert with data from 7/91 - 12/91. The trace
elements (aluminum, arsenic, cadmium, chromium, copper, iron, manganese, nickel, lead, selenium, and
zinc), polychlorinated biphenyl (PCBs) congeners, and polycyclic aromatic hydrocarbons (PAHs) were
measured in the ambient atmosphere and in precipitation. In addition several major ions, (chloride,
sulfate, nitrate, sodium) were measured in precipitation at the three sites, either by us this study or by
others in co-located acid deposition networks. Weekly integrated samples of aerosol and precipitation
were collected for elemental constituents at three field stations, one on the northeastern shore (Wye), one
on the mid-bay western shore (Elms), and one on the southwestern shore (Haven Beach) of the
Chesapeake Bay. Organic contaminants in precipitation samples were collected bi-weekly and organic
contaminants in the ambient air were collected for twelve to twenty-four hours semi-weekly at the Elms
and Haven Beach stations. Measurements of organic contaminants in precipitation and in the atmosphere
at the Wye station commenced during the summer of 1992 and these data will be presented in our Phase
III report (1/92 - 12/92). Phase IV will include data from sampling through September of 1993.
Dry aerosol deposition fluxes were estimated from the measured aerosol concentrations for crustal
and noncrustal modes and literature-derived deposition velocities. As described in Section IV, these flux
estimates contain considerable uncertainties. Wet deposition was calculated directly from contaminant
concentrations in precipitation and the measured precipitation volume. The total atmospheric flux is
reported as the sum of the wet and dry depositional fluxes. Atmospheric loadings of contaminants to the
Chesapeake Bay were calculated as the total site-averaged atmospheric contaminant fluxes times the
surface area of the mainstem Bay, including the tidal tributaies below the fall-line (1.15 x 1010 m2). No
attempts were made to extrapolate our measured fluxes to the entire watershed, both because the
magnitude of deposition likely changes and because it is difficult to model the ultimate fate of atmospheric
contamiannts deposited to the watershed.
b. Organic Contaminants. To estimate loadings of organic contaminants from the atmosphere to the
Chesapeake Bay, ambient atmospheric concentrations and wet depositional fluxes of 14 polycyclic
aromatic hydrocarbons (PAHs) and 74 polychlorinated biphenyls (PCBs) were measured at two shore
based rural field stations (Elms and Haven Beach) between June 1990 and December 1991. Organic
contaminant sampling at Haven Beach did not commence until Summer, 1992. Mean concentrations of
individual PAHs in air ranged from 0.004 (dibenz[o/i]anthracene) to 1.4 ng/m3 (phenanthrene) at the mid-
bay Elms station and ranged from 0.002 ng/m3 (dibenz[a/i]anthracene) to 3.5 ng/m3 (phenanthrene) at the
southern Haven Beach station. The observed temporal variability in PAH levels in the air ranged from
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50% to almost 200% about the respective mean concentrations. The mean ambient atmospheric PCB
concentration over the Chesapeake Bay during the study period was 0.21 ng/m3 at the mid-bay station
and 0.30 ng/m3 at the southern bay station, with a relative standard deviation of about 60%. PCB
concentrations in the air were slightly correlated with air temperature.
Volume weighted mean (VWM) concentrations of individual PAHs in precipitation measured at
both field stations ranged from 0.33 ng/L (dibenz[o/z]anthracene) to 17 ng/L (pyrene). Concentrations
of PAHs in precipitation were slightly higher at the southern station than at Elms. The VWM r-PCB
concentration was 1.6 ng/L at the mid-bay station and was 1.1 ng/L at the southern station. The temporal
variability of hydrophobic organic contaminant (HOC) concentrations in rainfall was as large as one order
of magnitude, with no apparent seasonal trend, suggesting highly variable HOC scavenging processes.
Assuming a dry deposition velocity of 0.49 ± 0.23 cm/sec, dry particle fluxes of PAHs ranged from 1
± 0.4 /xg/m2/year (anthracene) to 21 ± 10 (fluoranthene) /*g/m2/year. Wet fluxes of PAHs at the Elms
and Haven Beach sites ranged from 1 (anthracene) to 20 (pyrene) ^g/m2/yr. Total (wet + dry) fluxes
ranged from 2 ± 0.4 (anthracene) to 35 ± 7 (pyrene) /ig/m2/yr. The r-PCB wet flux was 1.8 ^g/m2/yr,
with the estimated dry particle flux accounting for 49% of the total flux (3.5 ± 0.8 /*g/m2/year).
Combined wet and dry annual atmospheric loadings of individual PAHs to the surface waters of
the Chesapeake Bay were calculated by extrapolating the total flux to the surface area of the Chesapeake
Bay (1.15 x 1010 m2). Individual PAH loadings (wet + dry) range from 19 ± 4 (anthracene) to 330 ±
86 (pyrene) kg/yr and the r-PCB annual atmospheric loading is 40 ± 9 kg/yr. These estimates of annual
atmospheric deposition do not include gaseous exchange across the air-water interface, which has been
shown to be considerable relative to wet deposition and dry aerosol deposition in recent studies in other
water bodies (Achman et al., 1993).
c. Aerosol Trace Elements. In addition to samples analyzed during the first full year of the study,
more than 90 samples collected during June - December 1991 were analyzed for > 30 elements, including
Al, As, Cr, Fe, Mn, S, Se, and Zn by instrumental neutron activation analysis (INAA); for Pb, Ni, and
Cu by inductively-coupled plasma-atomic emission spectrometry; and for Cd and Ni by Zeeman/graphite
furnace-atomic absorption spectrometry.
Concentrations of anthropogenic elements such as As, Cr, Se, V, and Zn exhibited similar
seasonal trends, generally, increasing from summer to winter, in accordance with decreasing
environmental temperatures. Superimposed on this trend are peaks, especially in late summer and winter
months, which presumably reflect elevated emissions during peak air conditioning and heating, periods
of low precipitation scavenging, transport dynamics, and conditions of atmospheric stagnation.
Concentrations of elements associated with crustal material (e.g., Al, Fe, and Mn) tended to be elevated
in the spring and summer months, probably reflecting increased agricultural and construction activities.
Concentrations of S are characteristically elevated during the summer months when more photochemical
oxidants are available for the conversion of S02 to the particulate forms of S measured in this study.
Overall, 18-month average concentrations determined for the Wye and Elms sites differed by ^5% for
As, Cr, Cu, Mn, Pb, and Zn; < 10% for Br, Cd, Fe, S, and Se; and ^27% for Al, Ni, and V. Average
concentrations determined for the Wye and Haven Beach sites differed by < 10% for As, Cd, Cu, Mn,
Pb, Se, and Zn; <20% for Cr, Ni, and S; and approximatey 25% for Al, Fe, and V. Concentrations
observed at Haven Beach were quite similar, however, fewer data are available and the averaging period
is smaller due to the delayed start of sampling at this site.
Preliminary estimates of annual deposition fluxes to Bay waters were calculated for each element
as the product of the annual average airborne concentration and a deposition velocity (V,,) for each
element taken from the literature as described in the text (Section IV). Lower limits of Vd were taken
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to be 0.26 cm^s"1 for noncrustal components and 1.4 ernes'1 for crustal components. Upper limits of
Vd are taken to be 0.72 ernes ' for noncrustal components and 4 cm^s'1 for crustal components. The
average and ranges (in parentheses) of the high and low flux estimates for the three sites are as follows:
Al, 120,000 (58,000 - 170,000); As, 100 (50 - 140); Cd, 20 (12 - 32); Cr, 200 (99 - 280); Cu, 420 (190
- 520); Fe, 64,000 (32,000 - 91,000); Mn, 1,300 (650 - 1800); Ni, 600 (256 - 710); Pb, 670 (300 - 820);
Se, 250 (130 - 370); and Zn, 2,000 (1,100 - 2900) jtgTm"2»yh A slight north-to-south gradient is
evident in averages concentrations of a few of the noncrustally-associated elements (e.g., Cr, Cu, Nni,
Pb, and Zn), however, too few data are available for the Haven Beach site to make a valid comparison
at this time.
d. Precipitation Trace Elements. Eleven trace elements in precipitation were successfully collected and
accurately determined in over two hundred weekly-integrated precipitation samples at the Wye, Elms,
and Haven Beach sites. The annual wet flux averaged for the three sites were as follows:
Al (14,000), As (50), Cd (80), Cr (100), Cu (530), Fe (10,400), Mn (1,100), Ni (260), Pb (580), Se
(130), and Zn (1,600). For the majority of the elements, the average annual wet flux has not changed
significantly from the CBADS Phase 1 estimates (Baker et al., 1992), which did not include the Haven
Beach site. However, the average flux for Cd and Cu increased two-fold due primarily to a few high
concentrations found at the Haven Beach site, which may have resulted from contamination during
sampling. In contrast, the Se flux decreased approximately 50% at all of the sites during Phase II.
Typically, the average monthly wet depositional flux of an element at a given site varies by a
factor of 10-20, but can vary by as much as a factor of 90. On a decreasing time scale {e.g., weekly),
this temporal variability can be even greater. From an ecological perspective (e.g., periods of fish
spawning), such episodic inputs may be as significant as the cumulative annual loadings. A few spatial
trends were noted, for example, a decreasing Pb signal from north to south and, conversely, increasing
arsenic deposition from north to south. As indicated by these observations, the atmospheric wet
deposition of trace metals thus appears to be a very heterogeneous process with respect to space and time.
Consequently, an accurate assessment of bay-wide loading requires the employment of multiple sites over
a long time frame.
Most of the elements examined in precipitation appear to have a dominant anthropogenic source.
With the exception of Fe and Al (and, to a lesser extent, Cr and Mn), crustal sources do not provide an
important source of trace elements deposited by wet deposition. While weekly concentrations vary
spatially by as much as twenty times, the average monthly fluxes differ among the sites by a factor of
five to ten times during the same months. Based on the concurrent estimates of dry deposition, the
proportion of dry deposition for crustal elements (e.g., Al and Fe) appears greater than that for wet
deposition. For non-crustal elements (e.g., Pb), the relative contribution of wet and dry deposition
appear comparable. However, the inherent uncertainty in the dry deposition estimates, particularly for
the noncrustal elements, currently prevents a more accurate and quantitative apportionment of wet versus
dry atmospheric deposition.
e. Overall. Large variations in concentrations and fluxes for trace elements in precipitation and organic
contaminants in the atmosphere and in precipitation are observed around Chesapeake Bay. Temporal
variations in contaminant concentrations in both the air and in precipitation reflect the influence of the
local micrometeorology and emission source strengths on atmospheric deposition. For example, greater
concentrations of trace elements were observed in precipitation at the Wye and Haven Beach sites than
at the Elms site but not in aerosol particles indicating that below-cloud scavenging processes are highly
variable and driven by ambient meteorological conditions (e.g., wind speed and direction).
In general, the wet fluxes are similar in magnitude to the corresponding dry aerosol fluxes for
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trace elements of non-crustal origin and for organic contaminants. However, as described in the text,
there is considerable uncertainty in the dry deposition velocity. Future research needs to consider the
direct measurement of the dry deposition velocity, particularly over water. As micrometeorological
conditions over water differ greatly from those over vegetative surfaces, the extrapolations of our land
based measurements to water surfaces need to be further investigated over a fairly long time scale to
accurately assess contaminant dry deposition to the Chesapeake Bay. In addition, dry depositional fluxes
of gaseous organic compounds may be of considerable importantance to the overall flux of contaminants
to the Bay
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I. INTRODUCTION
1.1 Background
Atmospheric transport and deposition of anthropogenically-mobilized acids, trace elements, and
organic chemicals may be a significant source of contaminants to coastal waters, including the Chesapeake
Bay. Contaminants are released into the atmosphere from a variety of activities, including direct
emissions from stationary sources (e.g., combustion sources), mobile sources (e.g., motor vehicles), and
regional activities (e.g., agrichemical applications, and soil erosion). Once in the atmosphere,
contaminants may be chemically altered, partitioned between gaseous and particulate phases, and
transported great distances. Contaminants are removed from the atmosphere and delivered to the Earth's
surface by a variety of mechanisms, including scavenging during precipitation events (wet deposition)
and by diffusive and turbulent transport during dry periods (dry deposition). Estimating the potential
impact of atmospherically-deposited contaminants to surface waters requires not only an accurate
quantitative measurement but also a thorough understanding of the processes which transport and
scavenge these chemicals from the atmosphere.
1.1.1 Evidence of Atmospheric Deposition. The atmosphere is an important environmental
pathway for the transport and deposition of contaminants to surface water systems. Numerous trace
organic pollutants are dispersed worldwide predominantly due to atmospheric transport. Fish collected
from Siskiwit Lake, a small lake on Lake Superior's Isle Royale, contain residues of polycyclic aromatic
hydrocarbons (McVeety and Hites, 1988), polychlorinated biphenyls (Swackhamer and Hites, 1988),
toxaphene and other airborne contaminants (Swain, 1978). As there are no local sources of these
contaminants on Isle Royale, aerial transport and deposition is the source of contamination to this isolated
location. Recent evidence suggests that the Arctic food chains have become contaminated with
atmospherically-derived organochlorine contaminants (Bidleman et al., 1989).
Duce et al. (1992) have recently synthesized the available data quantifying atmospheric deposition
of trace elements, nutrients, and organic contaminants to the world's oceans. Atmospheric inputs can
also be important for small bodies of water in the vicinity of major atmospheric sources. For example,
both dry and wet deposition were found to be important sources of Pb to the 2 ha Skinface Pond located
about 5.5 km from the coal-fired Savannah River Power Plant (Weiner, 1979). Atmospheric deposition
is also an important source of Cu, Cr, Pb, Zn, and other metals to the Great Lakes (Sievering et al.,
1981) and other bodies of water characterized by low watershed area-to-water surface area ratios. Excess
Cu, Pb, and Zn in surface sediments of the Chesapeake Bay have been attributed to atmospheric
deposition (Helz et al., 1985a; Helz et al., 1985b), as well as salt-marsh sediments of Naraganesett Bay
(Bricher, 1993).
1.1.2 Mechanisms of Atmospheric Deposition. Chemicals are removed from the atmosphere
during precipitation events via various wet deposition processes. Particulate and gaseous contaminants
are scavenged by hydrometeors, in-cloud processes such as diffusion, nucleation, coagulation, and
coalescence, or below-cloud processes including impaction interception, and diffusion into hydrometeors.
The efficiency of particle scavenging depends on the ambient suspended aerosol particle concentration
and size, as well as the micrometeorology of the precipitation event. Gas phase species may be
scavenged from the atmosphere via dissolution into rain drops. If the mass transfer of the gas into the
drop is rapid, then gas scavenging by precipitation may be modelled as an equilibrium distribution
following Henry's Law. Because precipitation scavenges organic particles much more efficiently than
organic gases, the gas-particle distribution of many organic contaminants may control the magnitude of
wet depositional fluxes (Leister and Baker, 1994a).
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During dry periods, particle-associated chemicals are removed from the atmosphere as particles
deposited on water, soil, and vegetation surfaces. The magnitude of particle transport and deposition
depends in a complex way upon macro- and micrometeorological conditions, and has been modeled as
a series of resistances to transfer in the bulk atmosphere and across the stagnant boundary layer.
Combustion-derived contaminants are generally associated with submicrometer particles, which are not
efficiently dry deposited, while many soil-derived (particles) components are attached to large particles
which deposit rapidly. Gaseous contaminants actively exchange between the atmosphere and water and
terrestrial surfaces at rates proportional to their instantaneous concentration gradients. Recent evidence
suggests that the exchange of volatile organic contaminants is highly dynamic, with volatilization during
warmer months offsetting efficient deposition during the winter season (Baker and Eisenreich, 1990; Hoff
et al., 1992; Achman et al., 1993, Hornbuckle et al., 1993; Baker et al., 1993).
1.1.3 Review of Previous Work. Atmospheric deposition may supply significant quantities of
nutrients, organic carbon, and potentially-toxic trace metals and organic chemicals to the Chesapeake Bay.
A 1988 report suggested that atmospheric deposition of inorganic nitrogen provides 25% of the total
loading of this important nutrient to the Chesapeake Bay (Fisher et al., 1988; Fisher and Oppenheimer,
1991). An independent evaluation concluded that as much as 35% of the nitrogen loading to the bay is
derived from the atmosphere (Hinga et al., 1991). Studies sponsored by the United States Environmental
Protection Agency Chesapeake Bay Program Office during the early 1980's indicated that aerial loadings
of organic carbon to the southern Chesapeake Bay are of the same order of magnitude as the estimated
lower limit of organic carbon fixation by phytoplankton production (Velinsky et al., 1986). Also, these
studies determined that atmospheric deposition of hydrocarbons to Chesapeake Bay is comparable in
magnitude to the inputs from wastewater treatment plants and accidental discharges (Webber, 1983).
Anthropogenic hydrocarbons are estimated to account for approximately 50% of the hydrocarbons aerially
deposited to the lower Chesapeake Bay (Webber, 1983). In the early 1980's, the EPA-sponsored
Chesapeake Bay Aerial Precipitation Survey measured trace element wet fluxes in coordinated studies in
the Maryland (Conkwright et al., 1982) and Virginia (Wade and Wong, 1982) portions of the estuary.
Data from this one year "pilot project" are discussed in Section IV of this report.
Bulk deposition {i.e., wet and dry combined) of agrichemicals to the Chesapeake Bay region were
measured by Williams (1986), Glotfelty et al. (1990), and Wu (1981). In these studies, open collectors
were deployed for extended periods in locations adjacent to agricultural fields. While these studies
provide some important first measurements of agrichemical deposition rates, the close proximity of
sampling to agrichemical use areas likely result in overestimating the true, regional deposition fluxes.
Church and Scudlark (1992) have measured wet depositional fluxes of trace elements at a coastal site
adjacent to the Chesapeake Bay watershed (Lewes, Delaware) since 1982. This record of contaminant
deposition reveals distinct seasonal and annual trends. For example, concentrations and fluxes of many
trace elements peak in the summer months coincident with increased automobile and boat traffic. P levels
in precipitation have decreased by more than a factor of 7 during the 10 years of sampling, presumably
reflecting the phase-out of alkylated Pb in gasoline during this period.
12 Statement of the Problem
As tighter controls are exerted on conventional point source discharges, the relative contributions
of non-point contaminant sources are increasing. As is the case for nutrients, the inventory of 'toxic'
chemical sources includes several important non-point sources, including atmospheric deposition. The
Chesapeake Bay Basinwide Toxics Reduction Strategy outlines a plan to determine both the absolute and
relative contributions of a variety of sources of contaminants to the Chesapeake Bay, and specifically calls
for quantification of atmospheric loadings (U.S. EPA, 1988). The 1990 Amendments to the Clean Air
Act also recognize the importance of atmospheric deposition to coastal water quality, requiring that the
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Federal Government establish and maintain monitoring networks around Chesapeake Bay and other
coastal waters. The problem is simply stated: What quantity of inorganic and organic contaminants is
entering the Chesapeake Bay via atmospheric deposition? Beginning in 1990, we initiated a field study
to answer this question. Early results of this study are described in the CBADS Phase I report (Baker
et al., 1992) and in several peer reviewed publications (Leister and Baker, 1994a,b,c, Wu et al., 1994;
Scudlark et al., 1994). This report describes the second phase of the study, in which the fluxes of
atmospheric contaminants to the Chesapeake Bay were estimated for 18 months beginning in July, 1990.
1.3 Study Objectives
The overall objective of the Chesapeake Bay Atmospheric Deposition Study (CBADS) is to estimate
the atmospheric fluxes of trace elements and organic contaminants to the surface of the Chesapeake Bay.
To adequately address this question, we also focused on quantifying the spatial and temporal variability
in atmospheric concentrations.
Our primary objectives for Phase 2 of the CBADS study were:
a) to accurately measure the concentration of selected trace elements and
organic contaminants in precipitation and in the atmospheric aerosols,
b) to determine the temporal and spatial variability in precipitation
concentrations and, where feasible, fluxes,
c) to evaluate the relative magnitude of atmospheric depositional processes
(wet versus dry), and
d) to estimate the annual areal fluxes of the contaminants to the Chesapeake
Bay surface waters.
1.4 Study Limitations
This report covers the second phase of CBADS, and does not explicitly address several related
issues currently under investigation. Specifically, no attempt is made to model contaminant scavenging,
to determine the sources of the deposited contaminants, or to quantify recycling of organic contaminants
(i.e., revolatilization) from the Chesapeake Bay. In addition, because of the large uncertainties in
estimating the transport of chemicals through the watershed into the Chesapeake Bay and because our
sampling locations may not be representative of the entire watershed, we have not calculated the
magnitude of atmospheric deposition to the watershed. Finally, because highly heterogenous conditions
were anticipated, sampling within the urban environment was consciously avoided. The loadings in this
report are, therefore, only indirectly influenced by urban air masses and therefore, reflect conservative
estimates of bay-wide loadings. The role of urban areas in supplying chemicals to coastal waters via the
atmosphere remains unclear. In 1995, a field study, funded by U.S. EPA-AREAL, will be undertaken
to document atmospheric deposition of contaminants to Chesapeake Bay that originate in Baltimore.
II. THE STUDY
II.l Design
This field-based study was designed to estimate atmospheric depositional loadings of trace
elements and organic contaminants to the Chesapeake Bay. As such, this work was constrained both by
the limited understanding of depositional processes and by the available resources. Because little a priori
information was available to anticipate the regional-scale variations in deposition rates, we chose initially
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to establish two sampling stations in the Maryland portion of Chesapeake Bay in the summer of 1990.
In a collaborative study sponsored by the U.S. EPA, Chesapeake Program Office, a third site in Mathews
County, Virginia was established in December, 1990 (Dickhut et al., 1992). Sampling for organic
contaminants in the study has been conducted at the Elms and Haven Beach sites. To ensure that every
precipitation event was collected, we employed automated wet-only precipitation samplers to collect
integrated wet deposition samples over weekly (trace elements) or bi-weekly (organic contaminants)
intervals. Continuous aerosol sampling provided weekly-integrated trace element concentrations at each
site, while 12-16 hour integrated air samples were collected bi-weekly for organic contaminants (gas and
aerosol).
A key characteristic of this study was the co-deployment of specialized, high quality samplers for
trace elements and organic contaminants, with the subsequent analyses following stringent analytical
protocols. As described below, the sampling and analytical procedures employed in this study resulted
in reproducible data, with concentrations consistently well above our analytical detection limits with a
minimum of contamination resulting from sample handling.
II.2 Sampling Site Locations and Descriptions
All CBADS precipitation and aerosol sampling described within this report was conducted at two
sites in the Maryland portion of the Chesapeake Bay and one site in the Virginia portion of the southern
Chesapeake Bay, subsequently referred to as the Wye, Elms, and Haven Beach sites (Fig II.2.1). Table
II.2.1 summarizes the sampling activities at the sites.
II.2.1 Wye Site. The northern-most site is located on the grounds of the University of Maryland
Agriculture Experiment Station, Wye Research and Education Center in Queenstown, MD (38°53'N,
76°08'W), on the eastern shore of Chesapeake Bay. This site is located <5 km from the shoreline of
the Chesapeake Bay, in a primarily rural agricultural region. Under typical meteorological conditions,
this site is downwind from the heavily populated Washington, D.C./Baltimore, MD corridor,
approximately 65 km east of Washington and 45 km southeast of Baltimore. Trace elements in
precipitation and aerosol particulates were sampled at this location. The sampling equipment was co-
located at existing National Atmospheric Deposition Program (NADP)/acid rain station, in the middle of
a large, flat, open, grassy field. The nearest buildings and roads are approximately 200 m away. The
site operator, Mr. Mike Newell, was also responsible for the NADP site activities.
11J2.2 Elms Site. The mid-bay CBADS site is on the property of the State of Maryland Elms
Environmental Education Center, near St. Mary's City, MD (38°13'N, 76°23'W). The land use in the
vicinity of the site is generally a rural agricultural region, however, a local source of atmospheric
pollutants is the Patuxent River Air Naval Station, 4.5 km to the north. In addition to the high aircraft
traffic volume, the base operates a coal-fired power plant. The complete suite of organic contaminants
and trace element aerosol/precipitation sampling were conducted at this site, which is co-located at the
existing State of Maryland Department of the Environment acid rain monitoring network site. The
sampling equipment was deployed on the eastern edge of a flat, grassy 75 x 75 m. clearing, flanked by
woods to the north and west and a tidal marsh to the south. The Chesapeake shoreline is about 0.5 km
to the west. The site operators, Ms. Dianne Leister and Ms. Cheryl Clark (University of Maryland,
CEES/CBL), were responsible for all on-site sampling and processing activities.
II.2.3 Haven Beach Site. The southern-bay CBADS site is located at Haven Beach in Mathews
County, Virginia (37°26'N 76°15'W). This site is south of the mouth of the Rappahanock River and
approximately 100 km due east of Richmond, VA. The samplers are deployed on a wooden platform
in a salt marsh directly adjacent to the western shoreline of the bay. Prior to CBADS, there were no
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existing atmospheric monitoring stations in the southern Chesapeake Bay. Personnel from Old Dominion
University and the Virginia Institute of Marine Sciences operated the samplers at this site.
III. METHODS
III.l Organic Compounds in Air and Precipitation.
Atmospheric organic contaminants exist as vapors which adsorb to suspended particulate material.
Because the washout efficiencies of these two phases differ, the partitioning behavior of the contaminants
strongly influences their overall depositional fluxes. In an effort to assess the magnitude of these fluxes,
we used samplers which collected vapor and particulate organic contaminants from the atmosphere and
which isolated dissolved and particulate organic contaminants from precipitation. The sampling protocol
will be discussed in the following section, along with a detailed description of sample
extraction/fractionation methods, analyte analysis and quality assurance efforts made.
III.1.1 Sampling.
III.1.1.1 Air Sampling. A high-volume air sampler (General Metals Works, Cleves,
OH) was deployed to collect bi-weekly ambient air samples. This sampler operationally isolates the vapor
and aerosol phases of atmospheric contaminants by successively drawing air through a 20.3 x 25.4 cm
glass fiber filter (Schleicher & Schuell #25) to collect aerosols and a polyurethane foam plug (8.5 cm x
10 cm) to collect vapors (Bidleman and Foreman, 1987 and references cited within). This type of
sampler has been used extensively over the past decade for remote atmospheric sampling of organic
contaminants (Atlas et al., 1981, Eisenreich et al., 1981, Bidleman et al., 1988, McVeety and Hites,
1988, Baker and Eisenreich, 1990). The glass fiber filters utilized in this study are composed of 100%
borosilicate glass fibers, arranged in layers that entrap particles. The mean pore diameter is 2.9 /xm.
The filters are ~ 95% free of organic material and offer low background levels of contaminants to
samples (Grosjean, 1983). The filtration efficiencies of several brands of glass fiber filters have been
measured to be > 99.1 % (John and Reischl, 1978). Using a Berner low pressure impactor downstream
of our glass fiber filter, we observed no breakthrough of particles > 0.04 fim. The polyurethane foam
is an efficient adsorbent of hydrophobic organic contaminants and has been used extensively in remote
environments such as the Arctic (Bidleman et al., 1989), the Great Lakes (Baker and Eisenreich, 1990),
the western North Atlantic Ocean and the Adirondack Mountains (Knap and Binkley, 1991). The foam
has a density of ~ 0.022 g^cm'3 and its open structure allows air to flow through easily, permitting large
volumes of air to be sampled readily (Pankow, 1989).
Two potential sampling artifacts can occur with this type of air sampling. First, the measured
particulate concentrations of hydrophobic organic contaminants may be overestimated due to the
adsorption of low molecular weight vapor phase compounds onto the filter surface during sample
collection (Cotham and Bidleman, 1992). Second, evaporative losses of adsorbed contaminants may lead
to an underestimation of the filter-retained material. In effort to assess the extent of adsorption, a routine
back-up filter was deployed with each sample (Ligocki, 1985b). In this study, low molecular weight
polycyclic aromatic hydrocarbons (e.g., phenanthrene, fluorene) were occasionally detected on back-up
filters. In five air samples, average phenanthrene concentrations on the back-up filter were 19% of those
measured on the front filter. Back-up filter concentrations for fluorene, anthracene and fluoranthene were
similar. Because the back-up contaminant concentrations were low relative to the front filter
concentrations for those preliminary samples, we did not correct the remaining front filter data for vapor
adsorption. Evaporative losses occur due to the gas phase concentration differential between the surface
of the filter cake and the ambient air at the sampler inlet. This concentration gradient may result from
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a) changes in vapor phase organic contaminant concentrations during the collection period, b) the pressure
drop associated with the air flow across the filter and c) increases in ambient temperature. However,
Zhang and McMurry (1991) have published sampling efficiency curves for air samplers with pressure
drops equal to 10 Pa which suggest evaporative losses due to pressure drops are <, 10%. To minimize
losses resulting from temperature changes, samples in this study were generally collected begining in late
afternoon and continuing through the night.
Air sampling times ranged from 12-16 hours with flow rates between 0.5-0.8 m3»min."' Some
samples were collected for longer periods (16-24 hours), particularly those in the winter seasons. Flow
rates were estimated for each sample from the measured pressure drop across the sampling train. The
flow rate (m3/min.) is proportional to the square root of the pressure drop as measured with a manometer
(inches of water). The pressure drop was measured in the field at the beginning and end of each the
sample period and an average flow rate was calculated using a factory-supplied calibration curve. A flow
controller installed in the sampling train maintained a constant sampling rate independent of the amount
of aerosols collected. The door of the sampler house was kept ajar during sampling to allow for venting
of pump exhaust and a peaked lid above the sampler house repelled birds and prevented precipitation and
very large (>100 /xm) particles from entering the sampler.
Ambient samples were collected bi-weekly, concurrently with the rain sampling strategy. An air
sample was collected on the day the precipitation sampler was serviced (generally every other Tuesday).
Prior to sampling, the glass fiber filters were individually wrapped in aluminum foil and ashed at 450°C
for 24 hours. The polyurethane foam plugs were cleaned via 24-hour extractions with petroleum ether.
The extracted plugs were dried in a vacuum desiccator to remove any remaining solvent, wrapped in
aluminum foil and, along with the glass fiber filters, stored in the laboratory until used. The sampling
train was loaded in the laboratory with two glass fiber filters and one foam plug, covered with aluminum
foil and transported to the site. After sampling, the entire train was brought back to the laboratory, the
filters and plug were removed with stainless steel forceps, and then wrapped in foil and stored at 4°C
in the dark until analysis. Blank filters and foam plugs were routinely placed in the field to determine
if either matrix accumulated analytes during the sampling period. Appendix A. 1.8 lists the volume of
air collected and other field notes for each sample.
III.1.1.2 Precipitation Sampling. For the assessment of low level organic contaminants
in precipitation, a modified, wet-only collector was developed to a) collect large volumes of precipitation
and b) to operationally isolate the particulate and dissolved fractions of the contaminants during a
precipitation event. The collection area is a 1 m2 stainless steel funnel which is kept closed during dry
periods by a 1 m2 aluminum lid tightly sealed over the top flange of the funnel. At the onset of a
precipitation event, a moisture sensor activates a Campbell Scientific CR-10 data module, which in turn
energizes a pressurized pneumatic system to open the lid. Collected precipitation is channeled down the
funnel, filtered through a glass fiber filter (142 mm diameter, Schleicher & Schuell #25) and passed
through a stainless steel column (2.5 cm x 30 cm) which contains a slurry (250 ml, - 80 g dry weight)
of XAD-2 macroreticular resin (Amberlite, Rohm and Haas, Philadelphia, PA). The XAD-2 resin
isolates dissolved organic contaminants from the precipitation. A peristaltic pump prevents rainwater
from accumulating in the funnel and assures a constant flow rate through the resin column at 200 ml/min.
Liquid level sensors control the pump to ensure that the filter and resin remain wet, minimizing any
sampling artifacts caused by volatilization of contaminants from a dry filter or drying of the resin.
Contamination of the sample could result if the resin beads cracked or split open as a result of drying.
Precipitation samples were integrated over 14 days and changed every other Tuesday. Resin
columns were packed in the laboratory and transferred to the field capped with stainless steel fittings.
The XAD-2 resin was precleaned in the laboratory by sequential 24-hour extractions with solvents in this
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order: methanol, acetone, hexane, dichloromethane, hexane, acetone and methanol, then rinsed with
deionized water and stored in a 4L amber glass bottle as an aqueous slurry. All solvents were pesticide
residue grade (J. T. Baker Co.). The glass fiber filters were pre-cut and ashed at 450°C for 4 hours
before sampling and were transported to the field wrapped in aluminum foil and sealed in a plastic bag.
Upon arrival at the site, an immediate check was made to ensure the sampler was functioning by
wetting the moisture sensor with tap water. A portable computer was then connected to the CR-10
module to download the sensor data for the 14-day period. The resin column and the glass fiber filter
were then removed from the sampler. The filter was removed from the filter plate with stainless steel
forceps, folded in half and then wrapped in clean aluminum foil and labeled. The stainless steel funnel
was then scrubbed with pre-cleaned (solvent extraction, 24 hours, acetone:hexane, 50:50) glass wool and
deionized water in order to remove any adhering particles that were not effectively washed down the
sampling train during the precipitation event. Because the funnel remains "sealed" during dry periods,
particulate matter in the funnel originated from the atmosphere during precipitation events. The funnel
rinse, consisting of the wetted glass wool, was wrapped in foil, labeled, put into a plastic bag and
transported to the laboratory. The funnel rinse was analyzed as a separated sample to measure the
contribution of the funnel-retained particles to the total measured contaminant concentrations.
After the glass wool cleaning, the funnel was thoroughly rinsed with deionized water, methanol,
dichloromethane, and deionized water again to insure that the funnel surface and sampling train were
clean. The lid was then closed and a new filter and resin column were put in place. A small volume of
deionized water was then rinsed down the sampling train to make sure the water level was above the
liquid level sensors. The volume of precipitation collected in the reservoir was measured, recorded and
then discarded. The CR-10 data module was then reset and the system was ready for a new sampling
period. Before leaving the site, the moisture sensor was activated again to insure the sampler was
functioning and that the lid was closing properly. All samples were stored in the laboratory in the dark
either in the refrigerator (resin samples) or freezer (rain filters, air filters and air vapor samples) until
analyzed. The resin samples were removed from the stainless steel column and stored in glass jars with
Teflon-lined lids. All filters and foam plugs were stored wrapped in aluminum foil.
III.1.2 Analytical Procedures
III.1.2.1 Sample Extraction. All samples were analyzed for 14 polycyclic aromatic
hydrocarbons (PAHs) and 74 polychlorinated biphenyls (PCBs) (Table HI. 1.1). Target PAHs are listed
as EPA priority pollutants. These compounds were chosen because their molecular weights, vapor
pressures, and aqueous solubilities span a wide range and thus are expected to demonstrate variable
atmospheric deposition patterns. Resin samples were extracted for 24 hours with 1:1 acetone:hexane.
Filter samples were sequentially extracted for 24 hours in methanol followed by dichloromethane. Vapor
samples were extracted for 24 hours in petroleum ether. Resulting fractions of each matrix extraction
were combined and the more polar solvent was removed by liquid-liquid partitioning into deionized water.
The remaining non-polar fractions were then dried over anhydrous NazSQ, (J. T. Baker Co.) and
concentrated to < 10 ml in a Kuderna-Danish (KD) apparatus. The dichloromethane fractions were
exchanged for hexane during the evaporation process. The extracts were further concentrated to ~ 4
ml under a stream of chromatographic grade nitrogen, transferred from the KD apparatus to weighed
amber vials, and a 10-25% subsample was reserved for PAH analysis. The remaining extract was
concentrated to ~ 1 ml under nitrogen and further purified by fractionation on a 13 g magnesium
aluminum silicate column (Florisil, 60 - 100 mesh, J. T. Baker Co.). The Florisil, partially deactivated
with 1.25% deionized water, acts as a polar stationary phase to remove any polar interferences present
in the extract such as lipids, phthalates, and some of the more polar pesticides. The non-polar PCBs are
eluted through the column with 80 ml hexane. A second elution with 80 ml of a 10% (v/v) solution of
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diethyl ether/hexane removes the retained polar organic compounds such as lindane
(7-hexachlorocyclohexane), o,p' and p,p'- DDT and dieldrin. A small NajSO,, layer was placed on the
Florisil column prior to elution to remove any traces of water present in the extract and to prevent farther
deactivation of the Florisil. All Florisil was cleaned by extracting with a 1:1 acetone/hexane solution for
24 hours and was activated at 550°C for a minimum of 4 hours prior to use. Following the Florisil
separation, the fractions were concentrated to ~ 8 ml in a KD apparatus and further to 1 ml under
nitrogen. The concentrated extracts were then transferred to amber autosampler vials, sealed with a
Teflon-faced cap and stored at 4°C in the dark until analysis.
III.1.2.2 Quantification of Analytes. Concentrations of PCBs were determined by
capillary gas chromatography and electron capture detection using a Hewlett-Packard 5890 gas
chromatograph. Congeners that were not commercially produced in the Aroclor mixtures and hence, are
not present in the environment (2,4,6 trichloro- and 2,2',3,4,4',5,6,6' octochlorobiphenyl, Ultra
Scientific, North Kingstown, RI) were used as internal standards to quantify the individual congeners in
each sample. Five nanograms of each internal standard was added to each sample prior to injection. The
use of the internal standard method eliminates errors propagated by inconsistent sample injections and
it is independent of the final extract volume (Swackhamer, 1987). A single calibration standard was used
to generate response factors for each congener relative to the internal standards. The standard solution
was a mixture of three Aroclor commercial mixtures (1232, 1248 and 1262) which were obtained from
the EPA Repository for Toxic and Hazardous Materials, Research Triangle Park, NC. Following the
procedure of Mullin (1985), a 610 ng/ml PCB solution was made in a 25:18:18 ratio for the three
mixtures, respectively. Congeners were identified based on retention times and relative response factors
and were calculated from calibration standards. The congener masses in the samples were then calculated
and the corresponding concentrations were then calculated by dividing the mass in the sample by the
sample volume in liters for precipitation or cubic meters for air. In instances where congeners could not
be separated completely, their combined concentrations are reported. Total PCB concentrations were
calculated as the sum of the 74 congeners.
The PAH subfraction was quantified with a Hewlett Packard 5890A GC coupled to a 5970 mass
spectrometer. Five deuterated PAH internal standards (MSD Isotopes, Cambridge, MA; Supelco
Separation Technologies, Bellefonte, PA) were combined as a mixture and used to calculate relative
response factors for individual PAHs. Identification of individual PAHs was based on appropriate
retention times, and were confirmed by the abundance of a secondary ion relative to the molecular ion.
Ail 14 target PAHs were chromatographically resolved.
III.1.2.3. Detection Limits. In this study the limit of detection was based on the signal
to noise ratio of the baseline adjacent to expected analyte peaks. Individual sample analytical detection
limits were estimated by assuming a minimum quantifiable peak area of 400 for a GC/MSD
chromatographic peak and a minimum peak area of 100 for a GC/ECD chromatographic peak. In
general, for both the GC/ECD and the GC/MSD, the peak to peak noise ratio was ^ 2. A comparison
of the mean vapor concentrations of several PAHs and total PCBs to the mean analytical detection limit
is shown in Table ID. 1.2. PAHs that are generally absent from the vapor phase approach the analytical
detection limit such that the signal to noise ratio is closer to 1.
Precipitation sampler detection limits were calculated based on an annual precipitation of 75 cm
(2.88 cm/14 days), resulting in an estimated 28.8 L sample collected during a two-week period.
Dividing the analytical detection limit by this estimated volume gives field detection limits in ng/L. A
comparison of sample field detection limits to the measured concentrations in a precipitation sample from
early August in 1990 is shown in Figure in. 1.1 for several PCB congeners. Congeners are plotted in
order of decreasing vapor pressure. With the exception of congener 200, all matrices are generally well
8
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above the field detection limits. The detection limit of congener 136 is close to the dissolved
concentration. Congener 48 was not detected in the funnel sample. Generally the less volatile PCBs are
not present in the dissolved phase and as a result the sample concentrations are close to the field detection
limits. Congener 180 is an exception, in all three matrices its sample concentration is 10 times larger then
the field detection limit.
III. 1.3 Quality Assurance. In this study, quality assurance procedures specified the use of
surrogate spikes to all matrices, laboratory blanks and field blanks. These procedures help insure that
the data obtained is of acceptable quality and that they represent the true environmental signal.
III.1.3.1 Extraction Efficiencies. In effort to evaluate the efficiency of the analytical
procedures, recoveries of several perdeuterated PAHs and non-commercially produced PCBs which were
added to all samples as surrogates prior to extraction were measured. Surrogate compounds are listed
in Table IE. 1.3, along with average recoveries for each compound in each sample matrix for the organic
contaminant analysis of air and rain samples collected at the Elms and Haven Beach site. Because the
same surrogates were not used in all matrices, analyte concentrations were not corrected for sample
recoveries. Resulting recovery data for individual samples are listed in Appendix A 1.6.
In addition to analytical evaluations, we began using field surrogates in June of 1991 to assess
the efficiency of the sampling procedures. The efficiency of the XAD-2 resin was evaluated by adding
known amounts of deuterated PAHs to the column prior to deployment in the field. Average recoveries
of surrogates spiked onto two columns were: d-10 anthracene, 64% and d-10 pyrene, 65%. Volumes
of rain for these samples ranged from 0 (no precipitation) to 66 L. Junk et al. (1974), using similar
extraction procedures, reported an average recovery of a wide variety of organic compounds in water at
the 10 - 100 /xg/L level from XAD-2 resin of 78%±6%. Again, because field surrogates were not
routinely used in every sample, no attempt was made to correct existing data for field recoveries. The
retaining ability of the polyurethane foam was evaluated with the use of d-12 fluoranthene. Prior to
sampling, a foam plug was spiked with 371 ng of d-12 fluoranthene in hexane. The solvent was then
allowed to evaporate and the spiked plug was placed into the sampling train. The recovery for this
compound was 55% (N = 1). Based on the laboratory recovery of 56% for d-12 benzo[b]fluoranthene
in this single sample, we conclude that the 45% loss of the field surrogate occurred in the extraction and
concentration steps rather then in the field during sampling. The retention of several PCB congeners on
polyurethane foam has been investigated by an elution chromatography system such that recoveries of the
total quantity of isomer applied to the spike plug ranged from 76-95% (Simon and Bidleman, 1979) and
similar results are reported for several chlorinated pesticides (Turner and Glotfelty, 1977) in a similar
sampling apparatus. Thus, we are confident that the polyurethane foam is an efficient trap for
hydrophobic organic contaminant vapors.
III.l 3.2 Procedural and Field Blanks. Accurate trace chemical determinations require
accurate knowledge of the analyte blanks. Procedural matrix blanks were extracted with each set of
samples to characterize any laboratory sources of contamination and to determine if the pre-cleaned
filters, resin, and PUF plugs contributed significant interferences to the sample extracts. Listed in Table
m. 1.4 are the mean masses of PAHs and PCBs found in our laboratory and field matrix blanks. In cases
where a field blank was extracted with a group of samples, the laboratory blank was not used for
quantification purposes. Instead the field blank was used, as was the case with most of the air vapor
samples. The largest laboratory and field blank analyte in the polyurethane foam was phenanthrene and
these values were generally only 13% of the sample analyte. All other PAHs in the foam blanks were
insignificant compared to the samples. Total PCBs in the laboratory foam blank were about 18% of the
average vapor phase concentration, assuming an average sample volume of 800 m\
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In general, individual compounds in laboratory blanks were less than 20 to 33% of the analyte
in the sample, and often were less. In instances where the blank mass was larger then 33% of the analyte
mass in the sample, the analyte was reported as being "non-quantifiable," or "NQ." In those cases where
the blank contributed less than 33 % of the sample analyte, the blanks were not subtracted because the
blank data were generally not normally distributed. All matrix laboratory and field blank data are listed
in Appendices A1.1-A1.4. Because concentrations of PCBs and lower molecular weight PAHs (< 202
amu) on air and rain filters were very low, the relatively low laboratory blanks provide a substantial
contribution (> 33%) to the total analyte present. The blank value of PCB congeners 8/5 on the XAD-2
resin was extremely large, and precluded any dissolved phase quantification. If congeners 8/5 was
included in the total mass of dissolved sample analyte, its mass value would be at least 50% that of the
total PCB mass for that sample. A coeluting chromatographic peak for congeners 8/5 was present in
most of resin samples and as a result it could not be determined if the peak present in the sample
chromatogram were indeed congeners 8/5.
III.2 Trace Elements in Aerosol
111.2.1 Sampling. Samples at each site were collected continuously for 168 hours at a flow rate
of 10 L^m'\on 2-/tm-pore, 47-mm, Gelman "Teflo" filters using dichotomous samplers each equipped
with a single stage impactor to remove particles > 10 /xm in diameter. Each sampler was also equipped
with a "dry" gas meter with cumulative display to determine sample volume. As shown in Tables II.2.1,
sampling was initiated at the Wye and Elms sites on 5 June, 1990, and at Haven Beach on 23 November,
1990. Between 5 June, 1990, and 31 December, 1991, 77 of 82 possible aerosol samples were collected
at Wye and 76 were collected at Elms. Between 23 November, 1990, and 31 December, 1991, 27 of
59 possible samples were collected at Haven Beach. Field blanks, five each at Wye and Elms, and three
at Haven Beach, were collected by installing a second loaded sampling head beside the regular sampling
head and exposing it for the duration of the weekly sampling period.
111.2.2 Analyses. The 180 samples, 15 laboratory blanks, and 13 field blanks were divided into
two equal parts. Half of each filter was analyzed for more than 30 elements, including Al, As, Cr, Fe,
Mn, S, Se, and Zn, by instrumental neutron activation analysis (INAA). Particles on the other half of
the filters were dissolved and analyzed for Cu, Ni, and Pb, simultaneously by inductively-coupled plasma-
atomic emission spectrometry (ICP-AE), and for Cd by graphite furnace atomic absorption spectrometry
with Zeeman background correction (GFAA-Z).
To determine activities from the decay of short-lived nuclides, each filter portion was individually
heat-sealed in precleaned polyethylene film and irradiated along with 1-mg Ni monitors for 10 minutes
at a flux of approximately 4.5 x 1013 n*cm'2t s"1 in the NBS research reactor located at the National
Institute for Standards and Technology (NIST) in Gaithersburg, MD. Spectra of y-rays emitted by the
samples were collected after decay periods of 5 and 15 minutes with intrinsic Ge 7-ray detectors with
photopeak efficiencies ranging from 20 to 40% at an energy of 1332 kev. At least one week after the
first irradiation, the samples were repackaged and irradiated a second time for 4-6 hours at a flux of
approximately 1 x 10w n^cm"2* s"1, and 7-ray spectra were collected for 4 and 12 hours after respective
cooling periods of 3 days and 3-5 weeks. Analytical sensitivities were determined by irradiating prepared
elemental standards and checked for accuracy against NIST Standard Reference Material (SRM) 1633A
(Eastern Coal; Table ID.2.1). Spectral data were reduced on a personal computer with the Ortec
Ominigam analysis package, which corrected count rates for pulse pileup, decay during spectral
acquisition, and decay after irradiation. Multielement standards for INAA were prepared from NIST-
certified standard solutions, except for elements determined from short-lived activation products.
Standards for Al, Br, Ca, CI, In, K, Mn, Na, and V were made from high-purity laboratory reagents.
Calibrations for S and Ti were made by irradiating accurately-weighed aliquots of the these elements in
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their elemental forms. Forty-four of the samples, 6 laboratory blanks, and 4 field blanks were analyzed
for long-lived neutron activation products using similar procedures at the MIT reactor.
Prior to analyses by the atomic spectroscopy techniques, particles adhering to the filter portions
were dissolved in ultra-high purity ("Suprapur") acids under a clean-air fume hood located in a laboratory
Class-100 clean room. Each filter portion was placed in a 50-ml Teflon-covered Teflon beaker and
leached overnight at room temperature in a mixture of 6 ml of concentrated nitric and 0.1 ml 40%
hydrofluoric acids. After leaching, the Teflon covers were removed and the samples were allowed to dry
on a hot plate under low heat. The residues were then dissolved in a mixture of 4 ml concentrated HN03
and 0.2 ml 70% HC104) and refluxed for 24 hours, after which the filter was removed and rinsed with
a few drops of concentrated HN03. The resulting clear solutions were allowed to dry on the hot plate
at high heat, and then reconstituted with 2 drops of concentrated HN03. These were transferred to 15-ml
polyethylene bottles, dried with an infrared lamp, and stored in the UMCP clean room. Prior to analysis,
the residues were gravimetrically reconstituted by dissolution and dilution to a volume of 3 ml with 2%
HN03. Dissolutions were performed in batches of 24 samples along with two aliquots of the (NIST)
SRM No. 1648, "Urban Particulate Material."
The ICP-AE analyses required approximately 2.5 ml of each of the solutions, and the remaining
0.5-ml aliquots were used to determine Cd by GFAA-Z. For both ICP-AE and GFAA-Z analyses,
prepared standard solutions were aspirated into the instrument (ICP-AE, Jobin-Yvon, model JY70-Plus;
AA, Perkin Elmer, model 5000) at the beginning and end of each analysis session and at 1.5-h intervals.
At least two aliquots of SRM-1648 were analyzed during each analysis period. The ICP-AE instrument
provided for three replicate measurements of each sample and five replicate measurements for prepared
standards and SRMs. To prevent Cd vapor from escaping the graphite furnace tube during heating, a
0.8 n\ aliquot of a 0.1 /zg//*l solution of Pd(N03)2 in 6% citric acid was added to the graphite tube and
dried at 2450°C before injecting each sample. If two replicate determinations differed by more than 5%,
a third 15 fil aliquot of the sample was analyzed.
III.2.3 Quality Assurance. Analytical integrity was maintained through the use of prepared
single and multi-elemental standards for atomic and nuclear techniques, respectively, and by frequent
analyses of NIST-certified SRMs. Sensitivities for INAA were derived from spectra for more than 25
multielement standards and checked by analyzing more than 30 aliquots of SRM 1633A. As shown in
Table m.2.1, results of the SRM analyses are in excellent agreement with NIST certified and published
results. Results for additional elements determined by INAA are listed in Table A.2.2 in Appendix A.2.
Overall quality of the resultant data is evaluated from estimates of the net uncertainty for each reported
value, through comparisons with other data sets, and through the analysis and evaluation of laboratory
and field blanks.
III.2.3.1 Estimation of Uncertainties. For INAA, the uncertainty in the measurement
depends mainly on counting statistics, imprecision in positioning the samples and flux monitors (geometry
errors), spectral background, and the sometimes substantial concentrations of the various elements in the
blank filter substrates. The maximum relative uncertainty associated with geometry, 1.7%, was estimated
from the coefficient of variation of the corrected count rates of 8 Ni flux monitors. We assume that a
similar uncertainty applies to both flux monitors and standards, so that the total uncertainty in geometry
is >/2 ~ 1.7%. An additional uncertainty of approximately 1.5% arises for some elements from corrections
for coincidence error, when samples are counted very close to the detector. Uncertainties in prepared
standards and detector intercalibrations are approximately 5%. For ICP-AE and GFAA-Z analyses,
analytical uncertainties are derived from the deviation of replicate measurements, uncertainties in the
calibration data, and uncertainties in the analyses of filter and reagent blanks. All of these uncertainties
are reflected in the net reported uncertainty (SnJ.
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III.2.3.2 Evaluation of Uncertainties in Blank Corrections. The overall quality of the
resultant data may be strongly influenced by the magnitude of corrections for filter and, where applicable,
reagent blanks. Uncertainty arising from variations in the substrate blank concentrations are minimized
when sample-to-blank (S:B) ratios are sufficiently large. In the first year's data set, sample-to-blank
ratios for Al, As, Fe, Mn, S, Se, Zn, V, and Br, were quite large, averaging 54, 660, 70, 90, 360, 180,
70, 1400, and 270, respectively. For these elements filter blank corrections contributed less than 10%
for from 96% to 100% of the concentration values determined (see Tables A2.3a and A2.5b in Appendix
A.2). Uncertainties in the filter blank correction (Sb) often contributed significantly to Snet for Cd, Cr,
Cu, Ni, and Pb, for which the S:B ratios typically averaged 9, 7, 6, 23, and 11, for samples collected
at all three sites. The effect of S:B on the measurement uncertainty depends on the analytical precision,
Sa (derived from uncertainties in counting statistics, geometry, and preparation of standards), and the
uncertainty in the concentration of the various elements in the blank filters, Sb, as shown below:
SM,rel = (n + 1)/(N - 1) nSa2 + Sb2/(n - l)p (5)
where, n is the S:B ratio. In this work, Sas were <10% for all elements except S, for which Sa was
typically 10 to 20%. As shown in Table III.2.2, Sb was often quite large for Cd, Cr, Cu, Ni, and
Pb, and Sb contributed significantly to Srel ntI, which generally resulted in net uncertainties that were
substantially larger than those obtained for the other elements. For these elements, the percentages of
values for which nct was <20%, were approximately 79, 36, 80, 75, and 59-84%, respectively, in
the first year's data.
As shown in Table III.2.2, the average concentrations of the elements in laboratory blanks from
7/91 - 12/91 fell in the range of those determined in the blanks from 6/90 - 7/91. For example, S:B
ratios for Al, As, Fe, Mn, S, Se, Zn, V, Br, and in addition, Cd at all three sites were as good as or
better than their values for 6/90 - 7/91, exceeding 39, in every case. In addition, average S:B ratios for
Cr and Cd, were markedly improved, i.e., ^40 and ^ 14, respectively, at all three sites; however,
average S:B ratios for Cu, Ni, and Pb at the three sites, were as small as 6, 9, and 3. The latter is
attributed to the somewhat lower sample volumes recorded at Haven Beach as a result of difficulties with
sampling pumps. Sampling systems that operated almost flawlessly at the other sites were plagued with
problems attributable to the moist, marsh environment at Haven Beach. At Wye, Sreli Kt was <20% in
at least 85% of all cases for all elements. At Elms, this was true for all elements except Cd, Cu, and
Ni, for which the percentage of values with ^ >20% ranged from 50 to 60%, and for Pb, 36%.
At Haven Beach, where fewer numbers of samples were successfully collected and often with lower
sample volumes, uncertainties for Cd, Cu, and Pb were typically about 25%. Those for Ni and S were
<20% in 63 and 68% of the cases, respectively.
III.2.3J3 Evaluation of Field Blanks. Concentrations of elements in laboratory and
field blanks are compared in Table m.2.2. Results for the four field blanks collected at Wye from 6/90 -
7/91 fell within the range of those for laboratory blanks, as did most of the results for Elms. However,
the metal fitting above the filter holder was left open during field blank collections at Elms and evidently
caused contamination of Cd, Zn, V, Ni, and possibly Fe in some field blanks, but not samples. For
example, Cd was elevated in EFB2, for which the measured mass was approximately two-fold larger than
the maximum laboratory blank; Zn in EFB1 and EFB2, (5- and 50-fold larger); and V in EFB3, (6-fold
larger). Despite the possibility of sporadic contamination for Cd and Zn at Elms, the good agreement
between their average concentrations and those at Wye suggests that the Elms data set was not widely
affected.
Results for the two Haven Beach field blanks collected during 7/91 - 12/91 fell within the range
of those for laboratory blanks for all elements except Cu and Zn in VFB1, for which the amounts
observed exceeded their maximum laboratory blank concentrations by 3.5- and 8.5-fold (Table ni.2.2).
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The value for Zn in VFB1 is equivalent to an atmospheric concentration of 2.3 ng/m\ which is at most
about 20% of the average concentration observed for this element. The value for Cu corresponds to
about 30% of its average atmospheric concentration at Haven Beach. As discussed below, plots of
concentration vs. time for Haven Beach data occasionally show large excursions for Zn and Ni, that were
not observed at the other sites. In addition, atmospheric concentrations for Zn, Ni, and Cu were
substantially greater at Haven Beach than at Wye or Elms. Bay salinity is substantially elevated in the
southern Bay, and the marsh location provided an especially wet and corrosive environment. The site
is surrounded by a galvanized chain-link fence and the sampler is mounted on a galvanized metal tower.
In addition, corrosion was observed inside one of the "quick disconnect" fittings installed at the top of
the sampling head at Haven Beach. We conclude, therefore, that sporadic field contamination may have
occurred at this site for Zn and, possibly, for Ni and Cu as well.
Concentrations of elements in field blanks collected from 7/91 - 12/91 were similar to their
corresponding laboratory blanks, except for Cd, Zn, and Fe, for which the amounts observed exceeded
their maximum laboratory blank concentrations by 4.9-, 2.9-, and 7.4-fold in at least one of the field
blanks. Contamination by Fe at the worst field blank concentration is insignificant. Contamination by
Zn at the indicated level would have generally resulted in a bias of about 15%; and by more than 30%
at the lower values (5.05 ng/m3) determined at Haven Beach. Contamination by Cd at the indicated level
would amount to an average bias of about 30%. However, the effect of sporadic contamination is
probably much less than this.
III.3 Trace Elements in Precipitation
III.3.1 Sampling. Weekly-integrated samples were collected every Tuesday, coincident with
ongoing NADP (Wye), State of Maryland (Elms) and ODU CBADS (Haven Beach) acid rain/major ions
precipitation sampling. Trace element "clean" protocols developed by Tramontano et al. (1987) and
modified by Scudlark et al. (1992) were followed by the on-site operators (see Appendix A.3). At the
Wye site, due to the lack of an available clean bench, only steps 1-6 of the collection procedure were
conducted on site. The sample buckets with lids were sealed in plastic bags and frozen in a trace metals-
dedicated freezer on site pending retrieval and processing at the University of Delaware laboratory. At
the Elms site, all sample processing was conducted at the Chesapeake Biological Laboratory under a Class
100 clean bench. Site supplies (acid-cleaned collection buckets and bottles, ultra-high purity acid,
disposable gloves, etc.) were provided to the site by the laboratory at the University of Delaware. At
Haven Beach, the samples were retrieved by Old Dominion University personnel, sealed in plastic bags
and transported to the laboratory in Norfolk, VA for processing (in a class 100 clean laboratory) and
analyses. All supplies (trace metal and major ion) for the Haven Beach site were provided by the lab at
Old Dominion.
Precipitation was sampled using a commercially available, automated, wet-only collector which
was specially modified for trace metals sampling (Aerochem Metrics, Inc., Bushnell, FL). Details of
collection, sample processing and analysis can be found in Tramontano et al. (1987) and Scudlark et al.
(1992). Briefly, this involves collection in an acid-washed clear HDPE bucket, acidification with ultra-
high purity HC1 (to 0.4% v/v), followed by partitioning after a 24-hour desorption period into acid-
washed LDPE (or HDPE at Haven Beach) sample bottles. Samples were stored frozen until analysis.
Specific sample collection protocols employed by the CBADS operators are provided in Appendix A.3.
Sampling was initiated at the Wye site on 17 April 1990, and at the Elms site on 5 June 1990,
and at Haven Beach on 20 November 1990 (Table II.2.1). However, due to a persistent sampler
malfunction, for practical purposes the data record at the Wye site did not commence until 5 July 1990.
The Haven Beach trace metal record begins on 4 December 1990 due to insufficient precipitation for
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analysis. This report covers all sampling through 31 December 1991. At the Wye site, the 18 month
record yielded 64 precipitation samples, 12 field blanks (weekly samples with no measurable
precipitation) and 3 samples with insufficient volume to analyze. Collected during the 19 months of
sampling at the Elms site were 65 precipitation samples, 13 field blanks and 4 samples not analyzed for
various reasons (3 insufficient sample volume, 1 operator error). Sampling at Haven Beach for 13
months resulted in 40 precipitation samples, 8 field blanks, and 6 weeks insufficient volume for analysis.
The recorded precipitation amount averaged 7.7 cm/month at the Wye site (which equals 92
cm/year), 9.3 cm/month at the Elms site (112 cm/yr) and 9.4 cm/month at Haven Beach (113 cm/yr).
The 12-month total precipitation at Elms was more than 10% higher than the long term annual average
for this site, while the total at Wye was slightly below the average of the past 7 years [M. Newell,
personal communication]. The yearly precipitation total at Haven Beach agrees well with the 50 year
average of 109 ± 14 cm/yr for Virginia (Historical Climatological Series, 1983).
III.3.2 Analyses. To remove trace element contamination introduced via manufacture and/or
prior use, all plasticware (collection buckets and sample bottles) were rigorously cleaned. This cleaning
involved successive leaching in acids of varying composition and strength (see Appendix A.3). Ultra-pure
ASTM Type 1(18 megohm/cm) rinse water (Millipore Milli-Q) was used for all sample processing and
cleaning (subsequently referred to as Q-H20). Ultra-pure double quartz-redistilled HC1 (Qz-HCl) was
used for sample acidification, analysis and processing which included a final "polishing" leach in the
cleaning procedure. Analytical standards were prepared gravimetrically from certified standards, which
were prepared in turn from pure metal dissolution (SPEX Industries, Inc.). All other reagents were of
at least ACS quality. Every sample was carefully processed under a class 100 clean bench, in a dedicated
clean room.
At the University of Delaware, precipitation samples were analyzed for Al, Cd, Cu, Cr, Fe, Mn,
Ni, Pb, and Zn using a Perkin Elmer 1100-B Atomic Absorption Spectrophotometer, equipped with a 700
HGA graphite furnace (GFAA). This instrument was also equipped with deuterium background
correction, and a L'vov platform is utilized to minimize matrix (salt) suppression by delaying atomization.
For Al analysis, due to acidification with HC1, the char/ash step is limited to 170°C to prevent
volatilization of A1C13 (b.p. 185°C). Citric acid was used as a matrix modifier for Al and Fe to increase
analytical sensitivity. The standard analyte injection was 60 /zl for all elements except for Zn (10 /zl).
Multiple injections were used for Cd, Cr, Ni and Pb, increasing the volume of analyte to 120-180 fil and
thus augmenting the sensitivity 2-3 times. GFAA calibration curves included an analytical blank and at
least three standards. The accuracy of the calibration curve was confirmed by an EPA or NIST reference
standard (refer to Section HI.3.3., Quality Assurance). Replicate samples were run on separate days to
verify true analytical reproducibility (which included but was not limited to instrument reproducibility).
Reproducibility of less than 10% variation was deemed acceptable.
At Old Dominion University, precipitation samples from the Haven Beach site were analyzed for
Al, Cd, Cu, Fe, Mn, Pb, and Zn using a Perkin Elmer 4000 Atomic Absorption Spectrometer equipped
with a HGA 400 graphite furnace and AS 40 autosampler. A L'vov platform was used in the graphite
atomizer to minimize matrix suppression and deuterium background correction was employed to correct
for non-atomic absorption. For all elements except Al, an analyte volume of 20 /xL was used. The
determination of Al was modified to include the addition of citric acid as a matrix modifier to increase
analytical sensitivity. However, this necessitated the reduction of the analyte volume to 10/iL. The
GFAAS system at ODU was calibrated using an analytical blank and at least three standards.
Additionally, the standard additions method was used on one sample every 15 samples to verify the
calibration curve. Accuracy was confirmed using the analysis of a standard reference solution (see
Section IH.3.3) for every 15 samples. Each sample was split into two aliquots, with triplicate analyses
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of each.
The trace elements As and Se were present in precipitation at concentrations significantly lower
than the detection limits of commercially available hydride/AA systems. Accurate quantification of these
elements required the application of non-traditional analytical methods (Cutter, 1986; Cutter et al., 1991).
Methods for both As and Se involve hydride generation, preconcentration by cryogenic trapping and
subsequent volatilization. The As hydride was determined using gas chromatography-photoionization
detection, while the Se hydride was determined with an air/hydrogen quartz burner fitted to an atomic
absorption spectrometer. Larger analytical volume requirements limit metalloid analysis to precipitation
samples greater than 200 mis. (ca. 0.3 cm precipitation). Standard curves for the metalloid analyses
included a blank and at least four standards. Large volume events (about 30% of all analyses) were
analyzed by the method of standard additions. Samples were run at least in triplicate and 5-10% of the
samples were replicated on a second day to establish reproducibility. The calibration curve was verified
utilizing certified reference solutions (see Section ni.3.3., Quality Assurance). At ODU the standard
additions method was used for daily calibrations, and reagent blanks and samples were all analyzed in
triplicate. In addition, 5% of the samples were re-analyzed on a second day to evaluate reproducibility.
A standard reference solution was analyzed every 15 samples. Employing the above methodology, we
conservatively estimate our analytical detection limits for all of the elements determined (D.L. =3X std.
deviation of analytical blank) and are cited in Table III .3.1.
III.3.3 Quality Assurance Program. Recent reviews of the historical data on the concentration
of trace elements in precipitation (Galloway et al., 1982; Barrie et al., 1987) cast considerable doubt on
the reliability of previously reported values or the efficiency of the collection and analysis techniques
utilized. In many of these studies, it was apparent that the authors failed to observe proper sampling and
handling precautions, resulting in either gross contamination, or conversely, irreversible adsorptive losses
of certain elements to container walls. Based on more than 15 years of experience in precipitation
sampling and analysis, it was our conviction that strict adherence to a rigorous quality assurance program
was essential to establish and maintain data accuracy.
Our QA program encompassed all components of this study, from the initial site selection to final
data validation. Essential elements of our QA program were:
a) conducting and evaluating operational blanks on a regular basis,
b) use of externally-certified analytical reference solutions,
c) intra-laboratory analytical comparisons using
redundant analytical methods (GFAA and ICP-AE),
d) inter-laboratory analytical comparisons,
e) cross-checks on collection efficiency.
III.3.3.1 Operational Blanks. Most contamination associated with accurately
quantifying the trace elements in precipitation is associated with field deployment and sampling (see
Figure m.3.3). Thus, conducting and evaluating operational blanks on a regular basis was the most
critical component in our QA Program.
Three types of additive, diagnostic operative blanks were routinely conducted: a Field Blank,
Laboratory Blank, and Process Blank. Data from these blanks were interpreted both quantitatively, to
accurately determine the background trace element contribution from materials and methods, and
qualitatively to identify and remedy any source of severe contamination.
The Process Blank was 500 mL of Q-H20 in a sample storage bottle, to which was been added
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2.0 mL of Qz-HCl (i.e., 0.4% v/v, identical ratio as samples). The Process Blank was a measure of the
trace element contribution from the water, acid, leaching from the storage bottle and analytical
procedures. The Laboratory Blank was 500 mL of Q-H20 poured into a clean bucket under a clean
bench, acidified, and processed as a precipitation sample. The Laboratory Blank gauges trace element
input from all sources included the Process Blank, as well as metal leached from the collector bucket or
contributed from airborne dust during the additional steps. The Field Blank was conducted identically
to the Laboratory Blank, except for use of a bucket which was previously deployed in the collector for
a weekly interval without rain. In addition to the sources included in the Laboratory Blank, the Field
Blank will indicate contamination in the field from the input of fugitive dust to the sample bucket during
transport, deployment, and recovery. Usually, the entire suite of blanks were done with every Field
Blank, however, the Laboratory Blank and Process Blank were run at least quarterly, or if there was a
significant change in methods, reagents (e.g. new batch of acid) or personnel (new or substitute operator).
Because the Wye samples were processed at Lewes, the Wye Laboratory Blank and Process Blank were
conducted at Lewes as well.
The Field Blank provided the most comprehensive representation of contamination during actual
sample collection and processing. As an assessment of site suitability and operator proficiency, we
compared the absolute Field Blank contributions at the three CBADS sites with those measured at our
Lewes, DE site using identical protocols (Figure III.3.1).
At Lewes, sampling with a more experienced operator and with access to clean room facilities
for sample processing, the blank levels were consistently lower. The Field Blank levels at the three
CBADS sites were comparable, and do not indicate any severe contamination problem (Figure II.3.2).
Noteworthy were the somewhat lower blank levels of the crustal tracers A1 and Fe at the Wye site. Initial
concerns existed about the potential for high soil resuspension and potential contamination associated with
farming practices on the grounds of the agricultural research station where the Wye site is located. The
Field Blank concentrations for As and Se at both sites were consistently below our instrumental detection
limits, and were not presented graphically.
A comparison of the Laboratory Blanks with Field Blanks at the Wye and Elms sites (Figure
ni.3.3) revealed that almost all of the blank contribution was associated with field deployment. This
included the inadvertent capture of fugitive dust during bucket deployment/recovery, as well as aeolian
input associated with high winds during non-precipitating periods. For the most part, materials and
reagents provided a consistently minor contribution to the blank levels.
III.3.3.2 Reference Solutions. Externally-certified reference samples were regularly
included in analytical sessions only to verify the accuracy of the calibration curve. The results of these
quality assurance checks are included in Table III.3.2.
Ill.3.33 Intra-Laboratory Analytical Comparisons. To verify the accuracy of the
GFAA analyses, selected samples were analyzed by Inductively-Coupled Plasma Atomic Emission
Spectroscopy (ICP-AE) using an Instruments SA/Jobin-Yvon-70 Plus ICP. For Al, Fe, Mn and Zn, low
instrumental detection limits coupled with comparatively high precipitation concentrations allowed for
cross-checking determinations by both methods without preconcentration (Jickells et al., 1992).
I1I.3.3.4 Precipitation Collection Efficiency. The accuracy of the wet deposition
calculation depends equally on the accuracy of trace element concentrations as well as the corresponding
precipitation amount. Precipitation amount at the Wye and Elms sites were determined gravimetrically
using a Belfort continuously-recording rain gauge, with an approximate resolution of 0.01" precipitation.
Because of repeated malfunction with the tipping bucket rain gauge at the Haven Beach site, the collected
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precipitation volume was used as a measure of the incident precipitation for internal consistence. This
aspect is examined further in the following discussion.
To verify the accuracy of the Belfort precipitation gauge and to establish the collection efficiency
of the Aerochemetric collector, the gauge reading was compared to the precipitation volume collected (for
each of the three sites). This comparison (Figure III.3.4) revealed generally good agreement between
the predicted and actual precipitation amount. In about 10% of the cases, however, the precipitation
gauge reading was found to be inconsistent with the sample volume collected. In these cases, the larger
of the two values was employed for deposition calculations. Overall collection efficiency of the ACM
collector was determined to be >95% at both sites, which included samples not analyzable due to
insufficient volume, collector malfunction and operator error.
111.4 Major Ions in Precipitation. The major anions (CI, NO'3, and S04-2) were determined
in precipitation samples collected at the Haven Beach site by David Burdige at Old Dominion University
in Norfolk, VA via ion chromatography and conductivity detection. The system was calibrated with
analytical blanks and five standards. The calibration was verified via the analysis of NIST Simulated
Rainwater (SRM 2694a). The major cations (Na+, K+, Ca+\ and Mg+2) were determined in precipitation
samples collected the Haven Beach site at the University of Delaware utilizing an Inductively Coupled
Plasma-Atomic Emission Spectrophotometer that was calibrated with analytical blanks an five standards.
This calibration was also verified with NIST Simulated Rainwater. All major ion samples and blanks
were analyzed in triplicate. Samples from Haven Beach were analyzed for pH immediately upon return
to the Old Dominion University lab using a pH meter equipped with a liquid junction electrode. The pH
meter was calibrated using NIST buffers and NIST Simulated Rainwater was analyzed to verify this
calibration. For the Wye and Elms sites, data for major ions in precipitation (those listed above) were
provided through other co-located studies (Wye: NADP; Elms, MD MDE).
IV. RESULTS
IV.l Organic Contaminants
rV.1.1 Spatial and Temporal Variations in Atmospheric Concentrations. Concentrations of
polycyclic aromatic hydrocarbons and polychlorinated bipheny] homologs in air samples collected at the
Elms and Haven Beach sites are shown Figures VI. 1.1 through V. 1.22 and summarized in Table IV. 1.1.
Average total (vapor + aerosol-bound) PAH concentrations range from 34 (dibenz[a,ft]anthracene) to
1780 (phenanthrene) ng/m3 at Elms and from 19 (dibenz[a, Ajanthracene) to 3507 (phenanthrene) ng/m3
at Haven Beach. Not surprisingly, the more volatile PAHs are present in higher concentration in the
atmosphere, with phenanthrene having the highest inventories at both sites. PAH concentrations in the
air over the Chesapeake Bay are higher than those over other more remote water bodies (e.g., Lake
Superior, Mediterranean Sea), and are similar in magnitude to those over the Baltic Sea (Table IV. 1.2).
PAH levels measured in urban areas (e.g., Baltimore, Portland, Denver, Stockholm) are ten to 100 times
greater than those measured at the rural CBADS sites. This is generally due to washout and atmospheric
mixing processes, which decrease contaminant concentrations in the atmosphere during transport from
urban areas. In addition, decomposition of PAHs via photo-oxidation in the atmosphere is also suspected
to reduce levels reaching non-uitan areas (Korfmacher et ai, 1980).
Concentrations of PAHs in the atmosphere at both the Elms and Haven Beach sites varied
considerably with time (Figures VI. 1.1 through V. 1.22), with relative standard deviations typically
greater than 100% and ranges spanning 50-100 fold. Concentrations of higher molecular weight, less
volatile PAHs such as indeno[i2J-cd]pyrene have the highest variability, perhaps due to their high affinity
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for atmospheric particles. Such large variation in PAH concentrations is likely driven by several factors,
including variations in local and regional emission strengths, variations in wind direction and local
meteorology, and variations due to the cleansing of the atmosphere by precipitation immediately before
some air samples were collected. Several of the higher molecular weight PAHs (e.g.,
benzo[g,/z,/]perylene, benzo[a]pyrene, benzo[6]fluroanthene) exhibit seasonal changes in air
concentrations, with higher concentrations during the winter months. This may reflect the contribution
of wood and fuel oil combustion for home heating in the local areas. Elevated atmospheric concentrations
of many PAHs were measured during a six to eight-week span during summer of 1990 at the Elms site.
This enrichment, which was also measured in the precipitation samples collected during that period, was
not observed during the same months in 1991. The reason for this interannual variability is unclear, as
there were no obvious changes in local land use or in meteorology.
The distribution of PAHs between the vapor and aerosol phases broadly follows the behavior
predicted by the Junge-Pankow model (Junge 1977; Pankow 1987). PAHs more volatile than
benz[a]anthracene exist predominately in the vapor phase while those less volatile than chrysene are
aerosol-bound (Figures V.l.l through V.1.22). Due to their intermediate vapor pressures, the vapor-
aerosol distributions of chrysene and benz[a]anthracene are highly variable, often shifting from vapor-
to aerosol-dominated between consecutive sampling periods (Figures V.1.6 and V.1.7). Although the
vapor-aerosol distribution is predicted to vary with ambient temperature and the aerosol concentration and
composition, the PAH distributions at Elms and Haven Beach show no distinct seasonal variations.
The mean annual PAH concentrations were compared between the Elms and Haven Beach sites
to evaluate spatial variability. In order to make a direct comparison, mean values for calendar year 1991
were calculated for both sites (Table IV. 1.1). Mean annual concentrations at Haven Beach are
consistently higher than those determined at Elms for most PAHs, with the ratio of Haven Beach to Elms
averages ranging from near one (anthracene, benz[a]anthracene, benzo[£]fluoranthene, benzo[ejpyrene)
to as high as 2.5 for fluorene. The approximately double mean annual 1991 concentrations of fluorene
and phenanthrene at Haven Beach may reflect local sources of these volatile PAHs in the southern
Chesapeake Bay. Interestingly, when one uses the overall mean concentrations from Elms (including the
elevated Summer, 1990 concentrations) to make the comparison, the PAH concentrations at the two sites
are quite similar. This emphasizes the importance of obtaining consistent, long-term measurements in
order to accurately assess possible spatial gradients in these highly time-variable parameters.
The concentration of total PCBs in the atmosphere averaged 214 and 298 pg/m3 at the Elms and
Haven Beach sites, respectively (Table IV. 1.1). These concentrations are quite similar to those recently
reported over southern Ontario (Hoff et al., 1992), Lake Erie (McConnell, 1992) and Lake Baikal,
Siberia (McConnell et al., 1993), but are significantly lower than those over the northern Great Lakes
(Swackhamer et al., 1988; Baker and Eisenreich, 1990; Achman et al., 1993; Hornbuckle et al., 1993),
the Adirondack Mountains and Bermuda (Knap and Binkley, 1991; Table IV. 1.3). Total PCB
concentrations are highly variable with time, ranging from 17 to 508 pg/m3 at Elms and from 26 to 730
pg/m3 at Haven Beach during the study period. PCB concentrations in the atmosphere are higher during
the wanner summer months at both sites, consistent with the seasonal trends observed by Hoff et al.
(1992) for many organochlorines in southern Ontario. These elevated concentrations in summer likely
result from enhanced volatilization of PCBs from soils and surface waters, with subsequent reabsorption
during colder seasons.
PCBs in the Chesapeake Bay atmosphere are dominated by the more volatile tri- and
tetrachlorobiphenyl congeners. This distribution is remarkably close to that measured over southern
Ontario (Hoff et al., 1992), suggesting that PCBs have undergone significant geochemical transport and
are fairly evenly distributed over continental scales (Leister and Baker, 1994a). Due to their relatively
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high vapor pressures, PCB congeners exist predominately (i.e., > 99%) as vapors in the atmosphere over
the Chesapeake Bay. Despite not being able to measure aerosol-bound PCBs directly, their concentrations
can be estimated using the Junge-Pankow equation from the measured vapor concentration, the
temperature-corrected subcooled liquid vapor pressures, the total particulate concentration in the
atmosphere (Baker and Eisenreich, 1990; Leister and Baker, 1994a).
IV.1.2 Spatial and Temporal Variations in Precipitation Concentrations. Concentrations and
speciation of polycyclic aromatic hydrocarbons in precipitation collected at the Elms and Haven Beach
sites are shown in Figures IV. 1.23 through IV. 1.36 and summarized in Table IV. 1.4. Volume-weighted
mean concentrations (VWM = E[concentration x volume]/Evolume) of PAHs range from 1.1 ng/L for
dibenz[a,K\anthracene to 16.8 ng/L for pyrene at Elms and from 0.33 ng/L for dibenz[a,/i] anthracene to
7.9 ng/L for phenanthrene at Haven Beach. Although the surrounding air was always enriched in the
more volatile PAHs, precipitation contains relatively more of the less volatile, higher molecular weight
PAHs, suggesting perhaps the role of particle scavenging in supplying HOCs to precipitation (Ligocki
et al., 1985b; Leister and Baker, 1994b,c). As with PAH levels in the air, concentration measured in
precipitation varied greatly throughout the sampling period, with concentrations of individual PAHs
ranging more than two orders of magnitude at both sites. In general, PAH concentrations in precipitation
were greater during winter months relative to the summer, consistent with the observed seasonal trends
in PAH inventories in the atmosphere. Higher PAH concentrations during winter months likely results
both from increases in local emissions (e.g., wood burning for residential heating) and from enhanced
precipitation scavenging efficiencies at the lower ambient temperatures. Greatly elevated concentrations
of PAHs in precipitation were observed in several samples collected during the Summer, 1990 at the Elms
site, consistent with the higher concentrations measured in the atmosphere. As noted above, the cause
of these elevated levels is uncertain.
PAHs in precipitation are distributed between the operationally-defined 'dissolved' and
'particulate' phases (Figures IV. 1.23 through IV. 1.36). As expected, the more soluble, lower molecular
weight PAHs (i.e., fluorene, phenanthrene, anthracene) are predominately dissolved while the more
hydrophobic species are associated with particles in the precipitation. We observed considerable
variability in PAH speciation, however, presumably reflecting differences in washout resulting from
changes in meteorology and PAH speciation in the atmosphere. Leister and Baker (1994b,c) estimate that
only less than five percent of PAHs in precipitation collected from the Elms site are thermodynamically
dissolved, with approximately 30% associated with nonfilter-retained submicron particles.
Concentrations of total PCBs in precipitation averaged 1.6 ng/L at Elms (17 month volume
weighted mean) and 1.12 ng/L at Haven Beach (Table IV. 1.4, Figures IV. 1.37 through IV. 1.44). These
concentrations are perhaps 50% lower than those measured during the mid-1980's in the Great Lakes
region (Franz etal., 1991; Murray and Andren, 1992), perhaps reflecting a general decline in PCB levels
during the past decade. The observed temporal variability in total PCB concentrations in precipitation
was less than that of PAHs, supporting the argument that PCBs are globally distributed and less
influenced by local and regional sources. While there is some indication that PCB concentrations in
precipitation increased during the summer months at Haven Beach (Figure IV. 1.44), no such trend is
apparent in the Elms data.
PCB congeners exist predominately in the 'dissolved' phase in precipitation collected at Elms and
Haven Beach, as expected from their extremely high vapor/aerosol distributions in the atmosphere.
Nonetheless, a significant portion of PCBs in precipitation are associated with particles that are retainable
by a glass fiber filter, indicating that although only a very small fraction of atmospheric PCBs are
associated with particles, the washout of those particles contributes to the wet depositional fluxes of
PCBs. By comparing the measured dissolved and vapor-phase PCB concentrations, Leister and Baker
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(1994b,c) determined that the precipitation is apparently supersaturated with PCB congeners relative to
the surrounding atmosphere (i.e., PCB concentrations in precipitation are higher than those supported by
equilibrium partitioning of vapor-phase PCBs). They hypothesize that these enriched precipitation
concentrations are due to PCBs associated with submicron colloidal particles in the precipitation which
pass through the filter, resulting in an overestimation of the truly dissolved PCB concentration.
IV.1.3 Depositional Fluxes of Hydrophobic Organic Contaminants. Monthly wet depositional
fluxes for each PAH and for total PCB and homolog groups were calculated as follows. Monthly
volume-weighted mean concentrations were calculated by dividing the sum of the total mass of each
chemical in all precipitation which fell during the month by the total volume of precipitation. In cases
where the sampling period spanned a month's end, the precipitation gauge record was examined to
partition the contaminant mass into each month. When calculating the monthly volume weighted mean
concentrations, concentrations of compounds which were not detected were conservatively estimated to
be equal to the analytical detection limit. The total volume of precipitation which fell during "each month
was determined using a Belfort gauge at Elms and from the weight of the trace metal precipitation sample
at Haven Beach. Resulting monthly fluxes (ng/rrr-month) measured at the Elms and Haven Beach-sites
are shown in Figure IV. 1.45 through Figure IV. 1.66. Annual wet depositional fluxes at each site were
calculated as the sum of the twelve monthly fluxes (Table IV. 1.5).
Not surprisingly, monthly wet fluxes of PAHs and PCBs are less variable than the concentrations
measured in the semi-weekly precipitation samples. Interestingly, the higher PAH concentrations
observed during the winter months do not necessarily result in higher wet fluxes during the winter, as
the elevated concentrations are offset by lower amounts of precipitation during the winter. Total PCB
wet fluxes are approximately twice as high during April and June than in the other months, due primarily
to increased fluxes of tri- and tetrachlorobiphenyls. A similar increase was not seen at Elms, suggesting
either localized sources of volatile PCBs or enhanced depositional processes in the southern bay during
those months.
Dry aerosol depositional fluxes of PAHs and PCBs were calculated as follows. Due to the large
uncertainty in dry aerosol deposition velocities, we only present average annual dry aerosol deposition
fluxes for PAHs and PCBs. Arithmetic mean annual concentrations of aerosol-bound PAHs (ng/m3) were
multiplied by the non-crustal dry deposition velocity (0.49 cm/sec; 1.5 x 105 m/year) to estimate the
annual dry aerosol flux at each site. These fluxes are only order of magnitude estimates and further
refinements require a better understanding of the temporal variability in both the dry aerosol deposition
velocity and the vapor-aerosol partitioning of the PAHs. Because PCB congeners were not consistently
present in our aerosol samples above the analytical detection limit, their dry deposition fluxes were
estimated by modeling the aerosol-bound concentrations. Using the empirical relationship between vapor-
aerosol partitioning and ambient temperature determined by Foreman and Bidleman (1990) for PCBs in
Denver, we estimated the aerosol-bound PCB concentration at our sites under typical winter and summer
conditions. These t-PCB aerosol concentration estimates were then multiplied by the non-crustal dry
aerosol deposition velocity in order to estimate winter and summer PCB dry fluxes, which were then
added to generate an annual flux (/ig/mJ/yr). This estimate of PCB dry aerosol deposition is highly
uncertain.
It must be emphasized that CBADS did not address the issue of vapor exchange across the air-
water interface. This exchange, including volatilization and gaseous absorption, has been shown to be
quite substantial and temporally dynamic in other water bodies, including Lake Superior (Baker and
Eisenreich, 1990), Green Bay, Lake Michigan (Achman et al., 1993), and the lower Great Lakes
(McConnell et al., 1993). The overall direction and magnitude of volatilization and gaseous absorption
of organic contaminants is a function of several parameters, namely the season (as driven by water
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temperature) and the variability in the ambient air and water contaminant concentrations, which has been
found to be quite large in the air in this study. Estimates of vapor exchange require coupled air and
surface water sampling, which is beyond the scope of this study. Current efforts are underway to assess
the magnitude and seasonality of gaseous exchange of organic contaminants in the Chesapeake Bay.
IV.1.4 Annual Loadings of Hydrophobic Organic Contaminants. Atmospheric loadings of
HOCs to Chesapeake Bay are listed in Table IV. 1.6. The loads were calculated by extrapolating the
average measured wet fluxes and estimated dry fluxes from the Elms and Haven Beach data to the surface
area of the Chesapeake Bay (1.15 x 1010 m1). Since sampling at the Elms site began about six months
eariler than at the Haven Beach site, a cumulative average and a calendar year 1991 average loading is
calculated. Because of large uncertainties in estimating the transport of chemicals through the watershed
into Chesapeake Bay and because our sampling locations may not be representative of the entire
watershed, the magnitude of atmospheric deposition to the watershed is not estimated. Also, samples
were consciously not collected within the urban environment. Therefore, the loadings presented in Table
IV. 1.6 reflect conservative values. The uncertainty of the annual loading is the extrapolated uncertainty
in the dry flux to the total surface area of the Chesapeake Bay.
Individual PAH annual loadings to the surface of the Chesapeake Bay range from 19 ±4
(anthracene) to 330 ± 86 (pyrene) kg/yr. Total PCB loadings are estimated to be 40 ± 9 kg/yr. It is
interesting to compare the HOC loadings to point source loadings of similar compounds. Consider one
23 million gallons per day (MGD) wastewater treatment plant delivering total hydrocarbons to the bay
at a concentration of 100 /xg/L, resulting in a total loading of about 3200 kg/yr (Webber, 1983). PAHs
are estimated to be 35% that of the total hydrocarbon detectable in wastewater (Webber, 1983), giving
a PAH loading of 1120 kg/yr. The measured atmospheric loading of all 14 PAHs in this study comes
to be 2100 kg/yr. This loading is about two times larger then that from the small, but significant,
wastewater treatment facility. Another interesting comparison is to calculate the loading of an individual
PAH from a major tributary such as the Susquehanna River, which has an average flow rate of 1100
m3/sec. The VWM concentration of fluorene in precipitation was measured to be 2 ng/L, which is very
close to the mean dissolved concentration of fluorene in Chesapeake Bay (1.5 ng/L; Baker and Ko, 1993).
An annual loading of fluorene from the Susquehanna River tributary at 1.5 ng/L would be 52 kg/yr.
From this study, the atmospheric loading is estimated to be 43 kg/yr. Hence, over a one year period,
the atmosphere delivers fluorene to the Chesapeake Bay at the same rate as the Susquehanna River!
Warner et al. (1992) estimated that fluorene is delivered from industrial discharges to the mid-section of
the Baltimore Harbor at a rate of 3 kg/yr, a factor 20 times lower then what is delivered to the
Chesapeake Bay via atmospheric deposition or from the Susquehanna River. These estimated
comparisons demonstrate that the role the atmosphere plays in delivering contaminants to the Chesapeake
Bay may be quite significant. Estimated dry loadings of HOCs from the atmosphere are about half of
the total HOC loading, indicating that dry deposition of contaminant laden particles is a significant source
of these compounds to the Chesapeake Bay. This is consistent with recent evidence. Measured dry
fluxes of chlorinated dioxins and furans to Indianapolis, IN contribute at least 60% to the total
depositional flux (Koester and Hites, 1992b).
Interestingly, although there were differences in the air and rain HOC concentrations between
those measured at the mid-bay station and those measured at the Haven Beach site, the annual fluxes (wet
and dry) for most HOCs are very close (Table IV. 1.7). This indicates that the integrated atmospheric
HOC fluxes measured at both sites are representative of the Chesapeake Bay (Maryland and Virginia)
despite the spatial differences observed in the precipitation concentrations between samples. The relative
homogeneity of the measured flux at both sites suggests that surface air above the bay is influenced by
regional sources dispersed throughout the bay area and that the washout processes that remove
contaminants from the atmosphere are very similar in air masses influencing the region.
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IV.2 Aerosol Trace Elements
IV.2.1 Spatial and Temporal Variations in Atmospheric Concentrations. In this section, we
present data on the spatial and temporal concentrations of selected elemental constituents (Al, As, Cd,
Cr, Cu, Fe, Mn, Ni, Pb, S, Se, Zn) of aerosol particles and give preliminary estimates of their dry
deposition fluxes to the Bay's surface waters. Concentrations of the various elements are plotted against
Julian week in Figures IV.2.1 through IV.2.14 for all valid samples collected from 6/90 - 12/91. In
general, concentrations rise and fall with source activity, precipitation, and meteorological and surface
conditions. For elements carried on particles from anthropogenic sources, concentrations rise during
periods of low winds and temperature inversions, wherein pollutants are trapped, and fall during windy
periods and during periods of precipitation. The concentrations of elements associated with crustal
material rise during dry windy periods and during earth disturbing activities, such as plowing and
landscaping, and construction work. Based on Turekian and Wedepohl's compilation of average
concentrations of elements in the earth's crust (Turekian and Wedepohl, 1961), more than 99% of the
As, Cd, Pb, S, and Se, and > 95% of the Cu, Ni, and Zn observed in aerosol particles in this study were
of noncrustal, origin. Aluminum, Fe, and Mn have large (Al, 100%; Fe and Mn, each near 50%) crustal
components and, on average, nearly 20% of the Cr is associated with crustal material. Some of the
crustal material may be associated with coal, which cannot be distinguished from crustal material by
elemental ratios.
As indicated in Figures rV.2.1-IV.2.14, concentration vs. time profiles of many of the
anthropogenic elements are similar, especially those for Cr, Se, V, and Zn. Concentrations for nearly
all of the elements of anthropogenic origin are elevated in August, September, and November, 1990 and
in January and February, 1991. This behavior probably reflects a combination of increased emissions
corresponding to peak air conditioning and heating periods, low precipitation scavenging and transport
dynamics. Low concentrations observed in June, July, October, and April are consistent with elevated
precipitation, as shown, for example, by Mn in Figure IV.2.8. Concentrations of particulate S are
characteristically elevated during the summer months when more photochemical oxidants are available
for the conversion of gaseous sulfur. Concentrations of crustal elements, Al, Fe, and Mn are elevated
in the spring and summer months, which probably reflects agricultural and construction activities. This
behavior is consistent with data reported for College Park, MD, in which average summertime
concentrations for Al, Fe, and Mn reported by Kitto (1987) substantially exceeded those reported by
McCarthy (1988) for winter months (see Table IV.2.2).
In the latter part of 1991, i.e., in October, November, and December, there is a weak trend in
the profiles of anthropogenic elements towards larger concentrations. This trend is most evident in the
profiles of As, V, Br, and Se, and to a lessor extent, Zn, Ni, and possibly Cu, possibly reflecting
increased fossil fuel use in the fall months. Concentrations of crustal elements, e.g., Al, Fe, and Mn
show the opposite trend, i.e., their concentrations tend to decrease between summer and winter,
presumably, for the reasons discussed above. Sulfur concentrations decrease markedly in the fall months.
Profiles for elements with substantial crustal and noncrustal components show weaker trends. Various
discrete events appear to be superimposed on the data for both crustal and noncrustal elements.
Cumulative and calendar year 1991 average concentrations of Al, As, Cd, Cr, Cu, Fe, Mn, Ni,
Pb, S, Se, and Zn for samples collected at the three sites are listed in Table IV.2.1, along with their
standard deviations, average uncertainties, numbers of values determined, and their minimum, and
maximum values. The complete set of individual results are listed in Tables A2.6a through A2.8b, given
in Appendix A.2. In cases where the measured concentration was near the instrumental detection limit
(i.e., from 6/90 - 7/91: 4 for Cr at Wye; and 4 for Cd, 3 for Cr, 7 for Cu, 2 for Ni, and 1 for Pb at
Elms; 1 for Cd, Cr, and Ni, 2 for Cu and Pb, at Haven Beach; and, from 7/91 - 12/91: 1 for Cu, Pb,
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and Zn, and 3 for S at Wye; 1 for Pb, 2 for Cu, and 3 for Ni at Elms; and 1 for As and Cu, 2 for Ni,
3 for Cd, 4 for Pb, and 6 for S at Haven Beach) the data were divided by two and included in the
summary statistics in an attempt to minimize positive bias that would result from excluding small values.
Relative uncertainties in the upper-limit-values transformed for this purpose were taken to be 100%. Air
volumes determined for samples V4, V12, V16, and V27 are suspect, therefore, concentrations are not
reported for these samples. We attribute abnormally high concentrations of Al, S, and V in W9
(6400 ±380, 13,600±2000, and 26.5±2.2 ng~ m"3respectively) to local activities at Wye, and exclude
these values from averages and flux calculations. Aluminum in sample W9 is 50-fold greater than the
mean Al concentration computed without this value; including this value would nearly double the first
year mean.
The data were screened for potentially contamnated samples as follows: A concentration value
was considered to be an outlier if the following criteria were met: i) the ratio, r, of its concentration at
Wye or Haven Beach to its corresponding concentration at Elms was:
r > (X + 3a) (7)
where X and a were the average and standard deviation of the ratios for the full data set; and ii) its
concentration, C, exceeded the average of concentrations for the full data set by 3-fold. Note, however,
that the exclusion of valid data is possible. For example, the minimum Al concentration observed at
Elms, 11.8 ngTm"3,was eliminated by the criteria even though airborne Al concentrations as low as 12
ngTm%ere observed by Han (1992) in Beltsville. Thus, there may be no valid reason to remove these
data. Only a few outliers were identified by the first criterion, and except for Ni at Elms, and Ni and
Zn at Haven Beach, the differences in averages for the full and reduced data set were less than
approximately 10%. One value for Ni at Elms; all of the values for sample W12, and values for Ai, Cd,
and V in W9 at Wye, were identified as outliers by the criteria described above. Three to five outliers
were identified by Wye/Elms ratios for Pb, S, V, Fe, and Mn; and, based on the first criterion, the
remaining elements had fewer than 3. Five outliers were identified in the Haven Beach data for Cd; 4
for S; 3 for Fe, Se, and Mn; 2 for Zn, Cu, Ni, Pb, and As; and ^ 1 for the remaining elements. In
general, the Haven Beach data suffered from lower sample volumes resulting from pump failures and,
possibly, from contamination by corrosion products.
As shown in Table IV.2.1, average concentrations determined at Wye and Elms are quite similar
for most of the elements. Notable exceptions were average concentrations for Al, Fe, Cr, and Ni, which
were from 17 to 26% larger at Wye; and V, for which the concentration at Elms was 24% greater than
at Wye. Overall, 18-month average concentrations determined for the Wye and Elms sites differed by
£5% for As, Cr, Cu, Mn, Pb, and Zn; < 10% for Br, Cd, Fe, S, and Se; and £27% for Al, Ni, and
V. Average concentrations determined for the Wye and Haven Beach sites differed by < 10% for As,
Cd, Cu, Mn, Pb, Se, and Zn; <20% for Cr, Ni, and S; and approximatey 25% for Al, Fe, and V.
Concentrations observed at Haven Beach were quite similar, however, fewer data are available and the
averaging period is smaller due to the delayed start of sampling at this site.
The fact that the S concentrations at Wye often exceeded those at Elms, might reflect its
proximity to urban plumes from Baltimore and Washington, DC, and local sources. The large spikes in
Al at Elms might be attributable to traffic on the unpaved road at this site. Sulfur and V spikes suggest
the influence of fuel-oil combustion sources, such as oil-fired power plants, or perhaps ship traffic. The
relatively small differences in the median concentrations observed for the majority of the elements at the
three sites suggest that these atmospheric pollutants have a strong regional contribution, or that their
major sources, such as the Baltimore and Washington plumes, ubiquitous motor vehicle emissions, and
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regionally dispersed sources tended to influence the two sites similarly during most of the week-long
sampling periods.
Concentrations of airborne elements determined at the Bay sites may be compared with average
concentrations determined at Beltsville and College Park, MD, and Lewes, DE, listed in Table IV.2.2.
The Beltsville samples were collected in a large open grass-covered field surrounded by trees, several km
from the nearest road or urban area in the Fall of 1990. The College Park samples were collected in an
urban environment, during Summer months (1983 - 1985; Kitto, 1987) and in Winter months (1985 -
1986; McCarthy, 1988). The Lewes samples were collected in Cape Henlopen Park, a semi-remote rural
coastal environment, during July, August, and September of 1989 (Han, 1992). Concentrations averages
reported for Al, Cr, Cu, Fe, Mn, and Se are remarkably similar for the Beltsville and Lewes sites.
Those for As, Br, S, and V are about 2-fold greater at Lewes than at Beltsville, possible reflecting the
influence of ship traffic. Concentrations measured at the more urban College Park site are uniformly
greater (generally by a factor of 2) than those reported for Beltsville. Average concentrations for As,
Br, and Se in the Bay aerosol are similar to those measured in the more limited Beltsville data set.
However, Bay values are about 2.5-fold less than the Beltsville averages for Al, Cr, Cu, Fe, Mn, and
Zn. The Bay average concentration for S is nearly equal to the average of Summer and Winter
concentrations reported for College Park.
IV.2.2 Estimation of Dry Deposition. The dry deposition fluxes of particulate-borne elements
may be calculated for each sampling period as the product of the atmospheric concentration of each
element and a deposition velocity (VJ appropriate to water surfaces. In general, dry deposition rates over
water are expected to be smaller than over land, where turbulence-inducing vegetation, terrain, and
surface structures promote pollutant transport to the surface. Despite this, turbulence and deposition may
be enhanced at the land-water boundary, where temperature differences create updrafts. Deposition
velocities depend strongly on both particle diameter (Dp ) and atmospheric stability. However,
experimental measurements of Vd are few, contain large uncertainties, and are often reported without
supporting meteorological data. Although various methods may be used to extrapolate limited Vd
measurements to other meteorological conditions (for example, Dolske and Sievering, 1979), herein, we
attempt to provide preliminary estimates of the annual fluxes using only the average annual
concentrations.
Aerosol particles may be conveniently classified into crustal components, which comprise wind
blown dust from natural and anthropogenic dust-making activities, and noncrustal components, which are
typically derived from high-temperature combustion sources. Crustal components of the aerosol reside
in larger particles, with mass median aerodynamic diameters (MMAD) typically < 1 /im, whereas
anthropogenic components reside in aerosol with MMADs typically ranging from 0.1 to >0.5 /im,
depending on the proximity of major sources and the degree of atmospheric processing. At Deep Creek
Lake, a rural recreational area in western Maryland, most of the mass for anthropogenic elements most
often occurred in aerosol with modal aerodynamic diameters between 0.3 to 0.6 fim (Dodd et al. 1991).
Mass median aerodynamic diameters often ranged from 2 to 3 /im for aged crustal aerosol and are
typically 12-15 /im for urban crustal aerosol (Holsen et al., 1992). As indicated by the work of Sievering
et al. (1981) reported in Table IV.2.3, Vd s measured for elements with 50% crustal source (Fe and Mn)
may be five or six fold greater than those measured for an element with predominately noncrustal source
(Pb). In general, Vd is minimal for small particles (0.02 to 0.1 /xm) and increases for larger particles,
becoming equal to the gravitational settling velocity for particles with diameters ^40 /im (4.8 cm/s for
Dp of 40 /im).
The rate of pollutant transport to the Earth's surface increases inversely with atmospheric
stability. Stable conditions exist when the air is warmer than the water and the wind speed, U, is low.
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The atmosphere becomes more unstable as the temperature difference, (dT = (T^ - )), between the
air and water decreases and as wind speed increases. The most unstable conditions exist when the water
is warmer than the air and wind speeds are high. Under extremely stable conditions (dT, +8.5°C; and
U, 3.8±0.8 m^s'1 ), Sievering et al. (1981) reported Vds of 0.13 cm^ for Pb (noncrustal residence)
and 0.55 to 0.65 cm^s"1 for Fe and Mn (elements with large crustal components). Larger Vds are
estimated from these data by Dolske and Sievering (1979) for less stable conditions. Monthly average
wind speeds and temperature differentials derived for the Chesapeake Bay area from climatological
compilations (see Table A.2.9) range from -3.3 to +0.83°C and 3.7 to 5.0 mTs^espectively, suggesting
that Bay air is usually much less stable. For these conditions of average U and dT, Dolske and Sievering
(1979) estimated Vds of 0.47 and 0.72 ernes '.
Deposition velocity estimates from "box-model" calculations for phosphorous containing particles
depositing on Lake Huron over a 6-month period (Delumyea and Petel, 1979) ranged from 0.01 to 1.8
cmTS"1 and averaged 0.57 ±0.16 cm^s"1. The size distributions for phosphorous-containing particles were
often bimodal, with concentrations peaking in particles with diameters between 0.3 and 0.5 /mi, and 2.9
and > 4.6 fini; suggesting "fine" and coarse components, as is the case for Fe and Mn, which have nearly
equal noncrustal and crustal components. The fact that the average Vd reported for the Lake Huron
study, (i.e., 0.56 cm~s"1), was nearly identical to the values reported by Sievering et al. (1981) for Fe
and Mn (0.65 and 0.55 cm^s'1), is problematical, as the latter should be minimum values, in accordance
with the extremely stable conditions accompanying the Lake Michigan study. This demonstrates the
difficulties in using these data for the Chesapeake Bay. Excluding Cd, for which Vds appear to be
inconsistently low, Vds determined from a 12-day study in the North Sea using vaseline-coated plates
(Dedeurwaerder et al., 1983) averaged 0.26±0.16 cm^s"1 for noncrustal elements in aerosol with
MMAD ^0.75 fim and, 1.18 ±0.08 cm^s"1 for elements with both crustal and noncrustal components
in aerosol with an MMAD of 1.2 fim. The data of Dedeurwaerder et al. (1983) are in logical agreement
with those of Sievering et al. (1981) in that the mean Vd for their noncrustal elements, (0.26 ernes'1),
for a variety of stability conditions, is two-fold larger than the latter's value for Pb (i.e., 0.13 cm^s"1)
which was determined under extremely stable conditions.
Herein, we take the Vd of 0.26 crn^s"1 derived from the data of Dedeurwaerder et al. (1983) to
apply to noncrustal components of the Chesapeake Bay aerosol, noting that the value applied by Dolske
and Sievering (1979) to Lake Michigan during conditions appropriate to the Bay was substantially larger,
i.e., 0.72 cm*s"'. Combining the data of Dedeurwaerder et al. (1983) and Delumyea and Petel (1979)
for elements with roughly equal crustal and noncrustal components we obtain an average of 0.84 cmTS"1,
from which we infer a value of 1.4 cm^s'for totally crustal elements. To estimate atmospheric fluxes
to the Chesapeake Bay, we determine the fraction of each element associated with crustal and noncrustal
components and derive a weighted deposition velocity, Vd, accordingly. Annual fluxes, F; (kg/yr), for
each element, i, are calculated from
Fi = C,.Vd. .315 (9)
where, Q is the annual average concentrations of element i (ng^m3), F; is in yr, and Vd. in
cm^s"1.
Results of the calculation are reported in Table IV.2.4, wherein we list both low and high
estimates of the atmospheric fluxes. Low estimates are based on noncrustal and crustal Vds of 0.26 and
1.4 cm ~s'1 respectively and high estimates are based on respective Vd s of 0.72 and 4 cm^. The former
is that of Dolske and Sievering (1979), the latter is the limiting value for hygroscopic particles of
diameters near 2 fim under conditions of turbulence-limited transfer (Slinn and Slinn, 1980).
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Dry deposition estimates, however, remain uncertain. Keeler et al. (1992) observed that
concentrations of particulate-borne elements were typically greater in air over Lake Michigan than in air
over adjacent land site. If this were true for the Chesapeake Bay, then our land-based measurements may
underestimate Bay air loadings and deposition fluxes. Furthermore, recent evidence (Holsen et al., 1992)
suggest that large particles (i.e., aerodynamic diameter > 10 to 100 /im) may control the deposition of
anthropogenic and crustal elements. In our study, we considered only particles < 10 fim. If the large
particle hypothesis is true, then dry deposition to water might be severely underestimated. Finally, the
underlying physics suggests that dry deposition to water surfaces occurs episodically, i.e., during periods
of high turbulence and great atmospheric instability. The disparity between deposition velocities for
different wind speeds is so great that the deposition associated with a wind speed of 20 m^s'1 for 10
minutes a day would be equivalent to the deposition associated with an entire week at an average wind
speed of 5 mrs'1. Thus, a small fraction of periods of high turbulence could lead to substantially enhance
deposition relative to the estimates made herein.
IV.3 Trace Elements in Precipitation.
IV.3.1 Concentrations. The weekly measured trace element concentrations in precipitation
collected at three sites are summarized in Figures IV.3.1-IV.3.11. The atmospheric deposition of a
number of anthropogenically influenced elements (e.g., As, Cd, Cr) exhibited a seasonality whereby
maximum fluxes were observed during the summer, consistent with results nearby at Lewes, De (Church
and Scudlark, 1992). This seasonality parallels trends in the acid components (H+, SO"24, N0 3) in the
northeast U.S., although the acid seasonality has been attributed primarily to photochemically enhanced
rates of acid precursor oxidation during summer (Lindberg, 1981). For trace elements in precipitation,
other meteorological and physical processes are probably more important than chemical reactivity in
contributing to the observed seasonality. These processes would include seasonal differences in: a) storm
trajectory, favoring atmospheric transport from concentrated mid-west U.S. emission regions during
summer (Church and Scudlark, 1992), b) micrometeorology, whereby summer convective precipitation
events effectively scavenge a larger portion of the boundary layer (often 50-60,000 ft.), compared with
typical winter frontal storms, and c) precipitation amount, often lower in summer storms, which usually
yields samples with higher concentration (Lim et al, 1991). In fact, all of the "spikes" which appear in
the weekly concentration record correspond to low volume precipitation events. However, within the
scope of this study it is not possible to distinguish the degree to which of the above three factors is
responsible for the observed intra-annual trends.
In calculating bay-wide fluxes, we assume that the precipitation concentrations and wet fluxes
measured at the land-based sites are representative of those over the Bay surface. As previously discussed
in Section IV.2.2, atmospheric aerosol concentrations and fluxes (and presumably precipitation by which
they are scavenged) over water can be significantly different that those measured over land. Despite this
caveat for practical and logistical purposes it was not possible to conduct our routine sampling at stations
over the water. However, during this phase of the CBADS program we were afforded an opportunity
to sample a precipitation event (23 October 1990) on board ship in the Chesapeake Bay at a station off
the Potomac River (37°39.65'N, 76°17.58'W) coincidentally with several land-based sites, using similar
sampling and analysis protocols (Table IV.3.1). To our knowledge this simultaneous sampling of trace
elements in precipitation at five closely spaced sites, including over-water sampling, represents a unique
data set. While any conclusions based on this comparison of only one isolated set of samples would be
tenuous at best, an interesting pattern is evident:
(a) Crustally-derived elements (Al, Fe, and to some extent Mn and Cr) exhibited higher
concentrations over land than water. This seems reasonable for crustal elements which
are typically associated with ground-based, locally dominant emissions of large
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(>2.5^m) particles that tend to dry deposit close to their source.
(b) The precipitation concentrations of some (Cd, Ni, Pb), but not all anthropogenically
dominated elements were higher over water than land. This may indicate more effective
scavenging/convective meteorology over water for fine (submicron) particles enriched in
these elements.
More extensive sampling is obviously required to test the hypothesis that the deposition of some trace
elements over water differs from that which is observed over land.
IV.3.2 Wet Deposition. Monthly-integrated atmospheric wet fluxes, which appear in Figures
IV.3.1 l-IV.3.22, were directly calculated for each site based on the total measured precipitation amount
(gauge) and the monthly volume-weighted average trace element concentration. The total monthly
precipitation amount is utilized to calculate wet deposition whether or not the volume was sufficient for
analysis (i.e., insufficient volume occurs for less than 2% of all samples). Thus, this calculation
inherently assumes that the trace element concentrations in the events not analyzed (predominantly low
precipitation events) are equal to the monthly average concentration. In reality, this assumption probably
results in a somewhat conservative estimate for atmospheric wet flux, since low volume events typically
exhibited higher than average concentrations (Lim et al., 1991), as previously discussed.
On a monthly time scale, the inter-site variability can be as much as a factor of 10, and is even
larger on a weekly or event basis. The atmospheric fluxes for crustal elements (Al, Fe, and Mn) at all
three sites show dramatic peaks in wet deposition during spring (Mar/Apr) and summer (Jul/Aug),
although these peaks were not necessarily associated with the same events or weekly samples. The
differences in the timing of the "peak months" between the three sites could be caused by variations in
the local meteorological conditions. However, meteorological trajectories would be necessary to confirm
this speculation.
It is also interesting to note that the peaks evident in wet deposition do not parallel corresponding
peaks in aerosol concentrations. This inconsistency suggests that the aerosol and precipitation
composition may reflect different sources in that they tend to sample the lower and upper troposphere,
respectively. It is also possible that peaks in transport and deposition revealed by episodic precipitation
events are better resolved than weekly-integrated aerosol measurements. Furthermore, the Al/Fe ratios
at Wye (1.31), Elms (1.29) and Haven Beach (1.43) were somewhat less than would be predicted from
a shale source (1.69) (Turekian and Whedepohl, 1961). If this difference is significant within the
uncertainties of average verses global crustal abundances, this may indicate a secondary source.
Using Al as a crustal normalizer, we can factor out the crustal component of the observed fluxes
based on reported soil elemental ratios (Turekian and Wedepohl, 1961). As indicated in Table IV.3.2,
it is apparent that except for Al, Fe, Mn, and Cr, the crustal contribution is relatively minor at all three
sites. The crustal component for each element is rather consistent between sites.
For five elements examined (Al, As, Cd, Cu, and Zn), the wet depositional flux was higher at
the Haven Beach site than at the Wye or Elms site (Table IV.3.2). However, for the remainder of
elements (Cr, Fe, Mn, Ni, Pb and Se) the deposition was the highest at Wye, despite lower precipitation
amounts (92 cm at Wye vs 112 cm at Elms and 113 cm at Haven Beach). This trend may reflect the
influence of the Baltimore-Washington urban plume at the Wye site. At Elms the precipitation fluxes
were consistently the lowest on both a monthly and yearly time scale.
The spatial variability in annual wet fluxes, expressed at the Wye:Elms:Haven Beach ratio varies
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from 1.0:0.9:1.0 for Se, suggesting a fairly uniform deposition to 0.3:0.9:1.0 for As, which indicates
a possible "southern-source" [Table IV.3.2], The Pb ratio (1.3:1.3:1.0) as well as a comparison of the
spatial trends of the monthly fluxes indicates a slight decrease in Pb concentrations at the most southern
site. This is probably due to a strong Pb source from the Baltimore/Washington emission plume.
Although alkyl-Pb additions to automobile fuel are in the process of being phased-out, there seems to be
a slight residual signal from other sources {e.g., coal burning).
Wet deposition is controlled by two factors: the amount of rainfall and the concentration of
elements in the rainfall. Individual "peak" events can account for much of the annual flux for certain
elements. Anthropogenic elements (i.e., As, Cd, Pb) seem to be especially sensitive to high episodic
deposition. The highest 10% of the events with the highest concentrations (which account for less than
2% of the total rainfall) are responsible for as much as 15% of the total flux. Obviously, calculating only
an annual (or even monthly) flux into the Bay cannot truly indicate the actual environmental impact of
anthropogenic elements in the Bay.
The average monthly wet depositional flux for a given element at each site was also highly
variable, deviating by as much as a factor of 90 during the data record. Even the most consistent element
(Zn) exhibits a range in the monthly flux by as much as a factor of 10. The temporal variability of all
of the elements increased with a decreasing time scale (weekly or event). The average annual flux for
the three sites is in general agreement with the yearly deposition that was reported in Phase I (6/90 -
7/91) of this study. With the data set covering a longer time period and with the addition of a third site,
the average Se flux is 50% less than the original phase I estimate. The atmospheric wet flux of elements
to Chesapeake Bay appears to be a very heterogeneous process with respect to space and time, requiring
employment of multiple sites over a long time frame for accurate assessment of the source and magnitude
of atmospheric trace element inputs.
IV.3.3 Interpretation of Trace Elements in Precipitation. Due to the paucity of other reliable
measurements, it is difficult to put the CBADS fluxes in perspective either spatially or with respect to
long-term trends. However, the following precipitation trace element data have been reported both
nearby and in other regional water bodies which can be used as a basis of comparison (Figure IV.3.23):
a) Lewes, DE (Church and Scudlark, 1992) - The average wet fluxes for the period 1982-89
were reported at the mid-Atlantic coast, based on identical collection, processing and
analysis methods as the CBADS Network. This probably represents the only long-term
continual record of trace elements in precipitation in the U.S.
b) Chesapeake Bay (Wade and Wong, 1982 + Conkwright et al, 1982) - In two similar
studies sponsored by the U.S. EPA precipitation collections were conducted at four sites
in the lower Bay (Virginia), and six from the Maryland portion of the Bay (April 1981 -
April 1982). Several of the sites were in close proximity to the CBADS sites. Wet
fluxes were calculated from the arithmetic average concentrations of the sites, assuming
an average precipitation amount of 100 cm/yr.
c) GLADS; Great Lakes Atmospheric Deposition Study, (Klappenbach, personal
communication) - Wet fluxes were calculated from the arithmetically averaged
precipitation concentrations reported at 13 "rural" sites (no population center > 15,000
within 40 km) for the period 1982-1989 and assuming an average annual precipitation of
100 cm/yr.
d) Puget Sound - (EPA, 1991). Fluxes were calculated from the arithmetic average of the
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total (wet + dry) deposition from the two sites (Brown's Point and Riverside School)
identified as "background." Sampling was conducted using a custom designed bulk (wet
+ dry) collector.
These wet fluxes are summarized in Figure IV.3.23 (it should be noted that not all elements were
analyzed in all the studies). For most of the anthropogenically derived elements (notably Pb, Ni, Zn,
Cd, and Cu), the long-term average fluxes measured at Lewes were somewhat higher than those measured
in the CBADS Network. For Pb, this is not an unanticipated result, due to the phasing out of alkyl-Pb
additives in gasoline over this period. In fact, the eight-fold decrease in the precipitation Pb concentration
observed over the past decade at Lewes (Church and Scudlark, 1992) closely parallels the estimated
decrease in the atmospheric Pb burden over this period (Shen, 1991).
For the other elements of interest, it is not possible to discern if the discrepancies between the
Lewes and CBADS wet fluxes represented a spatial or temporal trend due to the different periods of
determining atmospheric trace element deposition. This inconsistency can only be resolved by
comparison of the CBADS data to Lewes data for an identical time period, of which analysis is currently
underway. However, it is possible that enhanced deposition at Lewes results from unique chemical
climatology in the marine coastal regime, which would be consistent with the hypothesis suggested by
the shipboard sample comparison previously discussed (Table IV.3.2).
Except for Al, Fe, and Mn, wet fluxes calculated from the ChesBay 1982 studies were 1-2 order
of magnitude higher than the CBADS data. If these differences are real, it would suggest that
precipitation trace element concentrations have decreased dramatically over the past decade. However,
this hypothesis is not supported by our own trace element record for this period at Lewes, which does
not indicate a decrease (except for Pb).
The GLADS fluxes (rural measurements only) are comparable to the Lewes, DE measurements
for the same time period. The Cu, Mn, and Ni fluxes also compare well to CBADS, even though the
GLADS sampling (1982-1989) was not contemporaneous with CBADS. However, the Pb and Zn fluxes
were about a factor of 3-4 times higher that what is found in the Chesapeake Bay area. The Puget Sound
fluxes that have been reported are total deposition which include wet + dry measurements. Even
including the highest estimates of the CBADS wet + dry deposition, the fluxes reported for Puget Sound
are higher than would be expected for clean "background " sites (Nriagu, 1992). It is possible that the
sites reported were not truly "background" or that the elevated depositions reflect sampling/analysis
contamination.
The total atmospheric loading (Table V.l) of trace elements to Chesapeake Bay can be
apportioned into wet and dry components using the data collected in this study. The data indicate that
with the exception of the crustally-derived elements, wet deposition is the major atmospheric input of
trace elements to Chesapeake Bay. Qualitatively, the proportion of dry deposition for crustal elements
(Al, Fe) appears greater than for wet deposition, while the wet deposition proportion for some noncrustal
elements (Pb, Cd) appears greater than dry. However, the range of dry deposition estimated, particularly
for noncrustal elements, is considerable which currently prevents accurate or quantitative apportionment
of wet versus dry atmospheric fluxes.
rv.3.3.1 Estimation of Uncertainty. There are two primary sources of uncertainty in
estimating trace metal wet deposition: the sample collection efficiency which include the analytical error,
and the spatial variability. The analytical error is conservatively estimated at ±10%. This error takes
into account the collection efficiency of the rain sampler, the analytical reproducibility of the instruments
and any possible contamination that is seen in the Field Blanks. It must also be noted that samples with
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insufficient volume for analysis will underestimate (conservatively) by approximately 5% due to higher
concentrations that are typically in small volumes (Lim et al., 1991).
The spatial variability is more difficult to estimate. The three CBADS sites were chosen to be
regionally representative. As such, urban areas were intentionally avoided. However, the localized
impact of urban plumes (e.g., Baltimore/Washington or Norfolk) would have much higher concentrations.
Accessing the input of urban deposition on the Chesapeake Bay and Lake Michigan is a current focus of
the U.S. EPA Great Waters Program.
IV.4 Major Ions. The major ion data from the Haven Beach site are listed in Appendix A 3.3
and summarized in Figures IV.4.1.1-4. In addition to our normal QA/QC procedures, an ion balance
was carried out with these data. The difference between the cation and anion equivalents in weekly
samples ranged form 0.07% to 16.3% with the average for the 1991 data being 3.4±2.9%. This
excellent agreement suggests that other possible "major" anions (e.g., formate) are not likely major
constituents in the precipitation at this site.
For brevity we have chosen here to discuss only a sub-set of the major ion data. Sodium has
been chosen as an indicator of sea salt contribution, nitrate as an indicator of (local) internal combustion
sources, and pH (or H+) as an indicator of general acidity. Concentrations from weekly samples are
shown in Figure IV.4.1.1 while monthly volume weighted average concentrations are shown in Figure
IV.4.1.2. In this data set, nitrate and non-seasalt (nss) sulfate appear to be highly correlated (r=0.8 for
the weekly concentration data) while both nss sulfate and nitrate appear to be highly correlated with H+
(r = 0.8 and 0.7 for the weekly concentration data). This suggests that the major contributors to acidity
in precipitation at Haven Beach are nitric and sulfuric acid. In contrast sodium appears not to be strongly
correlated with nitrate, H+ and nss sulfate (r = 0.2, 0.4, and 0.5, respectively). The behavior of sodium
is likely due to strong wind events (storms) that increase the formation of sea salt aerosols.
Monthly fluxes for these ions are shown in Figure IV.4.1.3. No strong trends are immediately
apparent although H+, nitrate and nss sulfate fluxes may be slightly higher in the summer months (June
through August). Sodium fluxes are high in the late summer/early fall (August through October),
although high monthly fluxes are also observed in individual monthly fluxes throughout the year (e.g.,
January, April, and June).
A comparison of the monthly fluxes of these ions from all three sites is shown in Figure IV.4.1.4.
For any given month, fluxes of H+, nss sulfate and nitrate are generally similar (±50%) at all three sites,
although clear departures form this trend can be seen. At one level, these observations suggest that there
may be a certain level of similarity in the sources of these anthropogenic components to the Bay region.
However, spatial heterogeneity in the fluxes of these anthropogenic ions to the Bay is also clearly evident
within this data set. Sodium fluxes clearly indicate the decreasing influence of marine sources to
precipitation as one moves up the Bay. In general, the Wye site has the smallest sodium flux, with the
Elms and Haven Beach site showing larger sodium fluxes. This observation is consistent with the
proximity of the sites of the Bay (Haven Beach is the closest) and the average salinity of the Bay waters
adjacent to each site (Haven Beach > Elms > Wye).
IV.4.1 Covariance with major ion data. Sources of the major ions in precipitation are
well known, and this fact can be employed to examine the behavior of the trace elements. For this
exercise, concentrations of the trace elements at each site were regressed against the concentrations of
three major ions: non-sea salt sulfate (nss S042), sodium, and nitrate. Sodium was selected as a tracer
of sea salt aerosols, nitrate is largely derived from internal combustion (e.g., automobile exhaust) and
is transported over relatively short distances, and nss S042- in the eastern U.S. is primarily from fossil
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fuel combustion and can be transported over long distances (i.e., the oxidation of S02 is slow, allowing
it to be transported far from its sources before removal.
Correlations (expressed as r, the correlation coefficient) between the trace elements and sodium
at all three sites did not exceed 0.4, indicating that the generation of sea salt aerosols did not appreciably
introduce or scavenge trace elements to precipitation over the Chesapeake Bay. In contrast, the
concentrations of many of the trace metals were well correlated with that of nitrate. Arsenic (r = 0.8),
copper (r = 0.6), manganese (r = 0.7), and selenium (r = 0.6) showed reasonable correlations with
nitrate, suggesting input from local combustion sources. Wye and Elms displayed similar correlations,
with the additions of cadmium (r = 0.5-0.8), iron (r = 0.5-0.7), Pb (r = 0.7-0.8), manganese (r = 0.5-
0.7), nickel (r = 0.6-0.7), and zinc (r = 0.7-0.9). The inclusion of iron and manganese in the
correlations with nitrate are likely due to the removal of nitrate onto mineral aerosols rather than these
parameters sharing similar sources (i.e., the correlation is due to similar removal processes, not similar
sources).
In general, correlations between the trace elements and non-sea salt sulfate at the three sites were
not as strong (i.e., r<0.5) as those with nitrate. The notable exceptions were arsenic at Elms (r=0.8),
copper at Wye and Elms (r=0.6), nickel at Wye (r=0.6), and zinc at Elms and Wye (r=0.6-0.7).
Assuming that non-sea salt sulfate is largely due to fossil fuel emissions transported over long distances,
these emissions do not appear to be a dominant source of trace elements to precipitation over the
Chesapeake Bay. Instead, more local sources may have a larger effect (as manifested in the nitrate
correlations). Interestingly, the correlations between major ions and trace elements are relatively uniform
for three sites, even though their wet depositional fluxes are more variable. This observation suggests
that the composition of precipitation at the three sites are effected by the same processes (i.e., sources
and removal mechanisms), but that the fluxes are driven by meteorological processes. Nevertheless,
considerably more data covering a longer time period will be needed to thoroughly investigate the sources
and fluxes of trace elements in precipitation over the Chesapeake Bay.
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y. CONCLUSIONS
VI.1 Common Trends and Interpretations. As observed during the first phase of this study
(6/90 - 7/91), great temporal variability was observed in the concentrations of organic contaminants and
elemental concentrations of aerosol particles and rain. Spatial differences were also observed for trace
elements in rain but not for elemental constituents in aerosol particles, suggesting that regional sources
of trace elements are fairly ubiquitous in the ambient air throughout the bay area and that local
meteorology strongly influences the overall washout and scavenging of contaminants from the atmosphere.
Similar observations were made for organic contaminants in the atmosphere and in precipitation.
Annual temporal variations in inorganic pollutants in both aerosol particles and rain reflect
seasonal fossil fuel usage, peaking in the winter heating and summer cooling seasons {i.e., As, Se, and
V). In addition peak photochemical activity in the summer months for sulfur was observed and peak
agricultural and construction activities in the spring and summer months was evident as shown by the
higher atmospheric inventories of Al, Fe, and Mn. A slight seasonal atmospheric signal was observed
for the polychlorinated biphenyls, indicating volatilization from the Earth's surface. Elevated PAH
concentrations were also observed in the winter time, reflecting the increased home heating and industrial
fossil fuel usage. Concentrations of organic contaminants in precipitation did not exhibit strong seasonal
trends, demonstrating the inherent influence of air masses on the region throughout the year (e.g. the
fairly ubiquitous nature of contaminants in the atmosphere as a function of air mass source) and the
relative driving of precipitation scavenging mechanisms by local meteorology (e.g., temperature, wind
speed and direction), air mass source, and emission strengths.
VI.2 Atmospheric Deposition of Contaminants to Chesapeake Bay. The annual atmospheric
deposition of contaminants to the Chesapeake Bay is summarized in Tables IV. 1.6 and V. 1 from the data
provided in this report. These data are updated from the Phase I (6/90 - 7/91) evaluation given
previously (Baker et al., 1992). The dry depositional fluxes should be reviewed with caution as there
is substantial uncertainty in the excised data, which results from the estimated dry deposition velocities
of particles to the surface of Chesapeake Bay (see Section IV.3). Dry deposition depends on the size
distribution of aerosol particles and the structure of atmospheric turbulence as driven by the stability of
the surrounding air column. In addition, the importance of large particle deposition cannot be accurately
assessed from data collected in this study. Mathematical models suggest that dry deposition occurs
episodically during highly unstable periods as determined by the ambient wind speed. Dry deposition
velocities are expected to increase nearly 200 fold as the wind speed increases by a factor of 4.
Fluctuations in ambient particle-associated contaminant concentrations with wind speed need to be
measured over very short time scales to address these uncertainties.
The proportion of dry deposition for crustal elements (Al and Fe) appears greater than that for
wet deposition (Table V.l), while the wet deposition proportion for some non-crustal elements (Pb and
Cd) appears greater than the dry. This is likely due to the large differences in the size distribution of
crustal and non-crustal elements. Soil derived elements are generally associated with larger particles and
have higher dry deposition velocities which are strongly influenced by gravitational settling. Organic
contaminant annual estimates of atmospheric deposition are given in Table V.l. In general, the dry
loadings of particle-associated contaminants are substantially larger for compounds with vapor pressures
less than 17 Pa. Compounds that are extremely volatile (e.g. fluorene, and many of the PCB congeners)
exist primarily as gases in the atmosphere, resulting in minimal dry aerosol depositional rates relateve
to precipitation scavenging. However, the dry depositional fluxes are highly uncertain due to the
estimation of the dry deposition velocity. Without having an accurate description of organic contaminants
as a function of particle size, it is highly uncertain to utilize a constant deposition velocity for all organic
compounds. Many of the less volatile particle-associated compounds are likely on very small particles
32
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with deposition velocities substantially lower than 0.49 cm/sec. Also, how the particle-size distribution
of insoluble particulate matter changes as air masses travel from the shore to over the water surface of
the Chesapeake Bay will strongly influence the dry deposition velocity of particles to the water.
VI.3 Future Research Initiatives. Recommendations for future research priorities for the
Chesapeake Bay Atmospheric Deposition Study Program are offered below. As mentioned above, there
needs to be a much better assessment of the dry fluxes. Reducing the uncertainty in the overall flux
estimates will come about by 1) measuring the dry deposition velocity directly in the field, over land and
water and 2) measuring the aerosol size distribution of particle-associated contaminants. In addition, the
resolution of the data needs to be greater, i.e., the affects of local meteorology on the flux need to be
evaluated. Sampling at a higher frequency {e.g. precipitation event) with a higher frequency will allow
us to describe contaminant removal mechanisms in greater detail. Atmospheric aerosol sampling on a
daily basis will enable us to do air mass trajectory analysis and chemical source assessments of the trace
elements. Unfortunately, due to the paucity of data for organic contaminant source signatures and
profiles, source assessments for organics in the atmosphere is highly unlikely at this point. In addition,
sampling atmospheric contaminants as a function of altitude should be considered since much of the
variation observed in atmospheric concentrations of contaminants results from differential transport and
scavenging regimes being altered as air masses traverse the lower stratospheric and upper tropospheric
atmospheric layers. These types of studies are beyond the pollutant concentration and flux assessments
described in this document and should be considered as in-depth atmospheric process studies.
Specific objectives for future atmospheric process studies could be to:
a) investigate atmospheric scavenging mechanisms and their relationship to local
meteorology (i.e., a modeling-based intensive sampling strategy),
b) identify atmospheric sources by geographic region and emission type, including
documenting organic contaminant source profiles and the influence of localized urban
atmospheric contaminant emissions on bay-wide deposition,
c) determine if atmospheric fluxes at land-based sites are truly representative of fluxes
observed over bay waters and waters within the watershed,
d) determine if atmospheric concentrations measured on the ground are representative of
those at cloud height
e) determine if scavenging mechanisms within clouds are similar to those operating below
the cloud layer,
f) improve estimates of dry deposition, including documenting deposition velocities, the role
of large particles and episodic atmospheric instability, and the size distribution of particle-
associated contaminants,
f) estimate the atmospheric fluxes of contaminants to other geochemical inputs such as
groundwater, fluvial, and watershed inputs that currently use data of limited quality and
quantity,
g) estimate the indirect atmospheric loading via watershed runoff from the drainage basin
to Chesapeake Bay, which requires the derivation of "transmission/retention factors" for
33
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each contaminant under different land use regimes (e.g. agricultural, commercially
developed, rural).
Objective (a), which focuses on intensive sampling strategies, is addressed in Year 3 of this study
(1/92 - 12/92). Achieving the remaining objectives will require ancillary studies of atmospheric
deposition to coastal and inland waters, which are presently being considered under funding from U.S.
EPA/AREAL under the Great Waters Program. The utility of the data presented in this report will really
only be essential for the mitigation of contaminant inputs to the Chesapeake Bay when contaminant assays
of equal quality to those determined herein are obtained from other routes of contaminant entry
(objectives (f) and (g)). These, along with the other objectives, will provide accurate quantification of
atmospheric inputs of trace atmospheric contaminants to the Chesapeake Bay, which will provide the
necessary background required for the investigation of environmental effects of contaminants to the Bay
ecosystem.
VII. ACKNOWLEDGEMENTS
This study was supported by a grant from the Chesapeake Bay Program Office that is
administered by the U.S. Environmental Protection Agency. The encouragement and enthusiastic support
of Mr. Rich Batiuk is gratefully appreciated.
We thank Dr. Russell Brinsfield at the University of Maryland Wye Research and Education
Station and Mr. Rob Chapman at St. Mary's County Board of Education, Elms Environmental Education
Center, for permission to deploy sampling gear on their locations. We are grateful for the cooperation
of the Maryland Department of the Environment in sharing precipitation chemistry data for the Elms site
and for lending us the total suspended particulate high-volume air sampler and for the analysis of this
parameter, which they graciously provided. In addition, NAPAP shared their precipitation chemistry data
from the Wye station and this is much appreciated.
34
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Table n.2.1. Sampling Schedule, CBADS 1990 - 1991
Date
Start End
Sampling
Frequency Interval
Wve
Trace Elements-Precipitation
Trace Elements-Aerosols
Organics-Precipitation
Organics-Air
5 July 1990
5 June 1990
14 July 1992
14 July 1992
31 December 1991
31 December 1991
7 Days
6 Days
14 Days
14 Days
7 Days
7 Days
14 Days
0.5-1 Day
Flms
Trace Elements-Precipitation
Trace Elements-Aerosols
Organics-Precipitation
Organics-Air
5 June 1990
5 June 1990
26 June 1990
12 June 1990
31 December 1991
31 December 1991
31 December 1991
31 December 1991
7 Days
7 Days
14 Days
14 Days
7 Days
7 Days
14 Days
0.5-1 Day
Haven
Trace Elements-Precipitation
Trace Elements-Aerosols
Organics-Precipitation
Organics-Air
4 December 1990
23 November 1990
18 December 1990
18 December 1990
31 December 1991
31 December 1991
31 December 1991
31 December 1991
7 Days
7 Days
14 Days
14 Days
7 Days
7 Days
14 Days
0.5-1 Day
43
-------
Table III. 1.1. Organic Contaminants and Elements Analyzed in CBAD Study.
Organic Contaminants - Polvcvclic
Polvchlorinated Biphenvls
Aromatic Hydrocarbons
74 Congeners listed in Appendix A 1.2 and
Fluorene
A1.4
Phenanthrene
Anthracene
Chlorinated Aerichemicals
Fluroanthene
Hexachlorobenzene
Pyrene
a-hexachlorocyclohexane
Benzo[a]anthracene
fl-hexachlorohexane
Chrysene
G-hexachlorohexane
Benzo[b]fluoranthene
Heptachlor
Benzo[k] fluoranthene
Heptachlor epoxide
Benzo[e]pyrene
Aldrin
Benzo[a]pyrene
Endrin
Indeno[123-cd]pyrene
p,p'-DDE
Benzo[ghi]perylene
p,p'-DDD; o,p'-DDD
Dibenzo[ah]anthracene
p,p'-DDT; o,p'-DDT
Elements*
Major Ions
Aluminum
Calcium
Arsenic
Potassium
Cadmium
Magnesium
Chromium
Chloride
Copper
Nitrate
Iron
Sulfate
Manganese
Sodium
Nickle
Ammonium
Lead
Selenium
Zinc
*An additional 20+ elements were quantified on aerosol samples by neutron activation
analysis (Appendix A2).
44
-------
Table m.1.2. Mean field measured vapor concentrations, pg/m3, and mean analytical detection limits for
PAHs and PCBs, Chesapeake Bay, 1990-1991.
Polycyclic Aromatic
Hydrocarbon
Mean Vapor
Concentration
Elms
Mean Analytical
Detection Limit
Elms
Mean Vapor
Concentration
Haven
Mean Analytical
Detection Limit
Elms
Fluorene
686
0.5
1626
0.3
Phenanthrene
2011
0.3
3424
0.3
Anthracene
52
0.3
69
0.3
Fluoranthene
337
0.3
425
0.6
Pyrene
413
0.3
509
0.6
Benzo[a]anthracene
9
0.8
9
0.6
Chrysene
24
1.2
50
0.6
Benzo[b]fluoranthene
10
1.0
7
0.6
Benzo[k]fluoranthene
6
0.8
5
0.6
Benzo[e]pyrene
7
1.1
7
0.6
Benzo[a]pyrene
4
1.0
5
0.6
Indeno[ 123-cd]pyrene
2
2.0
26
2.7
Dibenz[ah]anthracene
2
2.2
13
2.7
Benzo[ghi]anthracene
2
1.5
28
1.1
Total Polychlorinated
Biphenyls
330
1.1
273
1.2
45
-------
Table m. 1.3. Summary of Laboratory Surrogate Compounds for Chesapeake Bay Atmospheric Deposition Samples,
Elms Site, 1990-1991.
Deuterated PAH
Sample
Mean%
Relative*
N**
70% < N
Matrix
Recovery
STD Dev (%)
N < 130%
d-10 Anthracene
Funnel Wash
53.6
68
10
2
d-12 Benzo(b)Fluoranthane
82.1
13
12
10
d-10 Anthracene
Rain Filter
59.1
48
19
7
d-10 Pyrene
52.6
22
13
3
d-10 Fluoranthene
67.9
51
23
11
d-12 Benzo(b)Fluoranthane
72.6
35
30
15
d-10 Anthracene
Rain Dissolved
75.5
30
24
16
d-10 Pyrene
73.5
50
19
10
d-10 Fluoranthene
63.8
57
15
6"
d-12 Benzo(b)Fluoranthane
84.9
37
33
21
d-10 Anthracene
Air Filter
55.8
46
9
4
d-10 Pyrene
108.2
16
6
1
d-10 Fluoranthene
61.2
41
28
8
d-12 Benzo(b)Fluoranthane
111.7
24
22
14
d-10 Anthracene
Air Vapor
59.6
46
14
5
d-10 Fluoranthene
79.0
60
16
6
d-12 Benzo(b)Fluoranthane
118.7
35
22
10
Non-Commercial (PCB)
Sample
Mean %
Relative*
N«
70-% < N
Matrix
Recovery
STD Dev (%)
N < 130%
3,5-dichlorobiphenyl
Funnel Wash
88.2
38
11
8
2,3,5,6-tetrachlorobiphenyl
87.8
18
11
10
3,5-dichlorobiphenyl
Rain Filter
70.1
39
46
22
2,3,5,6-tetrachlorobiphenyl
90.3
34
12
8
3,S-dichlorobiphenyl
Rain Dissolved
75.4
35
39
23
2,3,5,6-tetrachlorobiphenyl
69.1
36
7
1
3,5-dichlorobiphenyl
Air Filter
62.4
52
15
6
2,3,5,6-tetrachlorobiphenyl
86.7
67
15
5
3,5-dichlorobiphenyl
Air Vapor
98.5
41
33
20
2,3,5,6-tetrachlorobiphenyl
83.3
30
10
5
~Relative STD DEV = STD DEV
* 100/fMean],
¦•"•"Number of Samples.
"70% < % Rec < 130%
46
-------
Table m. 1.3 (Cont'd). Summary of Laboratory Surrogate Compounds for Chesapeake Bay Atmospheric Deposition
Samples, Haven Beach Site, 1990-1991.
Deuterated PAH
Sample
Mean%
Relative*
N**
70% < N
Matrix
Recovery
STD Dev (%)
N < 130%
d-10 Anthracene
Funnel Wash
77.7
12.5
33
30
d-12 Benzo(a)Anthracene
107.0
12.6
32
29
d-12 Benzo(a)Pyrene
102.0
16.0
28
26
d-10 Anthracene
Rain Filter
81.7
12.0
32
30
d-12 Benzo(a)Anthracene
102.8
10.7
31
30
d-12 Benzo(a)Pyrene
97.3
5.3
31
31
d-10 Anthracene
Rain Dissolved
81.0
19.5
32
27
d-12 Benzo(a)Anthracene
(XAD-2)
102.0
16.3
32
29
d-12 Benzo(a)Pyrene
100.5
13.8
31
30
d-10 Anthracene
Air Filter
87.0
10.0
46
45
d-12 Benzo(a)Anthracene
110.5
15.1
45
42
d-12 Benzo(a)Pyrene
99.7
10.5
45
44
d-10 Anthracene
Air Vapor
81.9
13.2
49
41
d-12 Benzo(a)Anthracene
(PUF Plugs)
105.4
12.4
49
47
d-12 Benzo(a)Pyrene
101.1
11.6
49
48
Non-Commercial (PCB)
Sample
Mean %
Relative*
N**
70-% < N
Matrix
Recovery
STD Dev (%)
N < 130%
3,5-dichlorobiphenyl
Funnel Wash
41.4
27.1
28
1
2,3,5,6-tetrachlorobiphenyl
51.2
47.7
27
3
2,3,4,4' ,5,6-hexachlorobiphenyl
82.6
28.2
33
22
3,5-dichlorobiphenyl
Rain Filter
42.2
26.4
29
0
2,3,5,6-tetrachlorobiphenyl
40.8
42.7
27
2
2,3,4,4', 5,6-hexachlorobiphenyl
77.2
18.6
31
22
3,5-dichlorobiphenyl
Rain Dissolved
57.4
53.8
30
3
2,3,5,6-tetrachlorobiphenyl
(XAD-2)
50.1
38.5
28
4
2,3,4,4' ,5,6-hexachlorobipheny]
88.0
19.2
31
29
3,5-dichlorobiphenyl
Air Filter
46.9
30.1
46
2
2,3,5,6-tetrachlorobiphenyl
48.4
51.6
44
3
2,3,4,4' ,5,6-hexachlorobiphenyl
85.8
20.9
46
35
3,5-dichlorobiphenyl
Air Vapor
.
.
.
•
2,3,5,6-tetrachlorobiphenyl
(PUF Plugs)
48.4
64.4
41
4
2,3,4,4' ,5,6-hexachlorobiphenyl
76.3
18.6
48
32
~Relative STD DEV = STD DEV
I
8
*
"""Number of Samples.
47
-------
Table III. 1.4. Mean Mass (ng) Summary of Polycyclic Aromatic Hydrocarbons and Polychlorinated Biphenyls in Laboratory and Field Blank Matrices,
Chesapeake Bay Atmospheric Deposition Project, Elms, 1990 - 1991.
Laboratory
Field
Polycyclic Aromatic
Hydrocarbon
Mean
Resin
(N=9)
%Rel
STDA
Mean
Filter
(N = 11)
%Rel
STD
Mean
Foam
(N=3)
%Rel
STD
Mean
Resin
(N=2)
%Rel
STD
Mean
Filter
(N=3)
%ReI
STD
Mean
Foam
(N=2)
%Rel
STD
Fluorene
14.3
171
7.2
267
ND
--
1.7
141
0.5
134
48.6
126
Phenantharene
70.4
156
16.7
211
13.8
21
10.0
1
3.7
161
212.6
130
Anthracene
85.5
249
8.7
253
1.6
100
2.1
105
2.6
62
12.4
129
Fluroanthene
24.3
116
16.3
237
1.5
173
2.0
70
0.3
90
23.0
134
Pyrene
172.4
191
126.2
318
5.7
103
2.4
49
10.6
L68
8.5
123
Benzo[a] Anthracene
17.1
167
6.3
137
ND
--
0.4
141
2.2
143
0.8
141
Chrysene
16.4
109
7.7
154
ND
-
5.8
52
2.8
124
0.7
141
Benzo[b]Fluoranthene
20.1
122
8.5
156
ND
00
ND
--
4.2
153
0.9
141
Benzo[k]Fluoranthene
20.4
100
7.7
146
ND
--
ND
—
4.3
153
0.8
141
Benzo[e] Pyrene
4.3
139
0.1
225
12.0
126
0.2
141
ND
—
Benzo[a]Pyrene
22.4
163
6.9
136
ND
-
24.9
141
0.3
173
0.6
141
Indeno[ 123]Pyrene
21.9
300
8.3
188
ND
—
ND
--
ND
~
ND
—
Dibenzo [a] Anthracene
12.3
252
4.4
332
ND
~
2.7
141
0.3
173
ND
—
Benzo[ghi]Perylene
21.3
173
10.7
152
ND
—
ND
~
0.3
173
0.9
141
TOTAL PCB***
19.3
52
19.7
90
48.3
64
32.2
55
5.8
74
27.5
30
~Number of samples.
Relative STD DEV = STD DEV * 100/[mean].
— 74 congeners, N = 7 for lab resins.
-------
Tabic III. 1.4 (Conl'd). Mean Mass (ng) Summary of Polycyclic Aromalic Hydrocarbons and Polychlonnated Biphenyls in Laboratory and Field Blank Matrices, Chesapeake Bay Atmospheric
Deposition Project, Haven Beach, 1991.
Laboratory
Field
Polycyclic Aromatic
Hydrocarbon
Resin
(N=5)
Mean %Rel Std
Mean PPT
Filter % Rel
(N = 5) STD
Mean
FW % Rel
(N=6) STD
Mean Air
Filter % Rel
(N = 6) STD
Mean
Foam % Rel
(N=8) STD
Mean
Resin % Rel
(N=2) STD
Mean PPT
Filter % Rel
(N = 2) STD
Mean
FW % Rel
(N = 2) STD
Fluorene
1.9
150
0.5
6.2
0.8
80
0.9
54
1.5
21
4.5
100
2.9
61
0.9
19
Phenanlharene
9.4
87
4.6
67
4.0
75
3.1
43
6.1
26
51.4
56
2.4
29
7.6
54
Anthracene
0.1
200
N.D.
-
N.D
-
0.2
224
N.D
-
0.7
100
2.3
100
0.4
100
Fluroanthene
1.8
76
0.3
54
0.4
24
1.6
117
1.1
31
26.2
81
1.7
33
4.6
81
Pyrene
0.9
91
0.3
54
0.5
37
1.1
97
1.7
99
11.1
10
1.6
26
3.9
78
Benzo[a] Anthracene
0.4
114
0.1
123
0.2
72
0.2
102
0.3
108
1.8
68
0.5
36
1 3
85
Chrysene
0.8
114
0.2
97
0.3
72
0.3
90
0.4
76
1.7
19
1.2
36
3.2
83
Benzo[b]Fluoranthene
0.4
105
0.1
159
0.4
124
0.1
142
1 1
112
0.5
100
0.9
40
2.7
85
Benzo[k]Fluoranthene
0.1
200
<0.1
200
0.2
129
<0.1
224
0.5
112
0.2
100
0.6
56
1.8
81
Benzo[e]Pyrene
0.5
113
<0.1
200
0.2
102
<0.1
224
0.1
182
N.D.
.
0.7
35
2.1
85
Benzo[a]Pyrene
3.6
59
0.1
200
0.2
127
<0.1
224
0.5
112
7.2
20
0.6
34
1.2
79
Indenof123JPyrene
N.D.
-
N.D
-
0.2
224
N.D.
-
0.5
152
N.D.
-
0.8
100
3.1
100
Dibenzo[a] Anthracene
0.1
200
0.1
200
0.2
224
0.1
224
1.4
116
0.4
100
0.3
100
0.4
100
Benzo[ghi]Perylene
0.5
94
0.5
82
0.5
127
0.4
128
1.5
88
0.3
100
0.8
100
3.6
84
TOTAL PCB»**
12.0
84
16.1
103
16.4
69.5
12.9
103
23.6
43
2 6
-
1.6
8
1.9
50
~Relative STD DEV * 100/[mean],
"Number of samples.
***86 Congeners, N= for lab niters, N = 2 for lab foam; N = 1 for field filters; N = 2 for field foam.
-------
Table III.2.1 Concentrations of Elements Determined in NIST Standard Reference Materials
Element
Unit
SRM
Method
Literature
Cone. Sigma
This Work
Avg Sigma
N
A1
%
1632 A
INAA
2.95 ± 0.1
2.93 ± 1.80
7
As
Mg/g
1632A
INAA
9.3 ± 1*
7.6 ± 0.8
23
Br
ng/g
1632A
INAA
41+2
39 ± 4
23
Cd
Mg/g
1648
Zeeman -- AA
75 ± V
73 ± 3
7
Cr
Mg/g
1632A
INAA
34.3 ± 1.51
37+2
23
Cu
Mg/g
1648
ICP-AE
609 ± 27'
586 + 10
6
Fe
%
1632A
INAA
1.11 ± 0.021
1.16 ± 0.06
23
Mn
Mg/g
1632A
INAA
28 ± 2
31 ± 7
7
Ni
Mg/g
1648
ICP-AE
82 ± 31
88 ± 6
6
Pb
Mg/g
1648
ICP-AE
6550 ± 80'
6397 + 65
6
S
%
1632A
INAA
1.55 + 0.1
ND2
Se
Mg/g
1632A
INAA
2.6 ± 0.71
2.6 ± 0.5
23
V
Mg/g
1632A
INAA
44 ± 31
43 ± 3
7
Zn
Mg/g
1632A
INAA
28 ± 21
29 ± 6
23
'Nist certified value.
2ND = not detected.
50
-------
Table III.2.2 Comparison of Laboratory and Field Blanks, ng/filter
Laboratory Blanks
6*
.oTOpo
WFB3
1/I-R/9I
4?»
10/F£%90
l/#W/91
4/^-'l?f9l
1 l/YF-%/90
II INF 1990-
III.Y 1991
Ave. + Sipma
N
Min
Mux
Mass+ .Sipma
Mass + Sipma
Mass + Sipma
Mass + Sipma
Mass + Sipma
Mass + Sipma
Mass + Sipma
Mass + Sipma
Mass + .Sipma
Al
7*7+ ISO
10
7 7
S98
44S + 77
636 + 39
740+IS
7S 4+1 8
470 + 79
S89 + 3IS
347 + 71
IS3 + I0
768+17
As
0 088 + 0 OSS
4
cooi
0 088
0 48 + 0 04
0 S7+006
0 08 + 0 02
0 86 + 0 12
OS4 + 0 06
07 + 0 1
0 047 + 4 6
0 009 + 0 94
0 01+0 8S
Br
0.942 ±1.1
4
0.16
2.73
0.6±0.5
1 ±0.6
2.2 ±0.1
5.8±0.3
1.56±0.42
0.84±0.7
1.71 ±0.16
0.4±0.0
PH
I if.-)-1 1
7
-------
Table HI.2.2 (Cont'd) Comparison of Laboratory and Field Blanks, ng/filter
Laboratory Blanks
WFB5
11/26-13/3/91
EFB5
11/5-12/91
VFB2
6/4-11/91
VFB3
12/3-10/91
JULY 1991 - DECEMBER 1991
Ave. ± Sigma
N
Min
Max
Mass ± Sigma
Mass±Sigma
Mass ± Sigma
Mass ± Sigma
Al
204
94
5
9.7
362
173 ±11
198 ±14
203 ±13
104±7
As
0.034
0.012
4
0.02
0.050
0.01 ±0.77
0.003 ±0.001
0.05 ±0.02
NA
Cd
0.26
0.25
2
0.01
0.52
2.54±0.41
0.17±0.14
0.4±0.03
0.35±0.31
Cr
4.3
1.1
4
2.79
5.75
3.29 ± 1.00
4.79±0.55
16.0±0.72
Cu
22
15
5
7.94
40.9
41 ± 1
26±2.2
23.7±0.7
10± 1.4
Ni
27
18
<13
45.9
63.4±3.2
39.6±20
67.1 ±1.5
17.3 ±21
Pb
50
12
5
37.42
73.0
46.5±30
20.1 ±2.0
66± 16
30.3 ±10
S
31
16
5
12.7
51.2
<13
<49
<51
Se
1.0
0.4
0.95 ±0.49
0.46±0.24
110
0.49±0.26
Zn
28
8.5
5
20
43.5
21.8±3.4
117 ± 8.3
4.28
127±9.0
Br
0.26
0.22
5
0.079
0.65
<0.045
0.283 ±0.68
600 ±270
0.674±0.29
V
0.086
0.031
5
0.012
0.125
0.103 ±0.038
<0.015
0.063 ± 0 021
Fe
123
75
2
49
198
NA
1473 ±52
0.22±0.04
1354 ± 51
Mn
4.73
1.0
5
3.34
5.74
4.31 ±0.17
9.79 ±0.24
18.1 ± 1.7
5.84±0.23
Dates
11/26-13/3/91
11/5-12/91
6/4-11/91
12/3-10/91
Values without uncertainties are upper limits
-------
Table III.3.1 Analytical Detection Limits (jigIL) for the Determination
of Trace Elements in Precipitation
UDE
ODU
UDE
ODU
A1
0.12
0.29
Fe
0.05
0.64
As
0.007
0.008
Mn
0.10
0.10
Cd
0.006
0.02
Ni
0.12
4.0
Cr
0.10
NA
Pb
0.12
0.12
Cu
0.12
0.12
Se
0.009
0.002
Zn
0.14
0.06
53
-------
Table III.3.2 Results of Quality Control Check Solutions for Trace Element Wet Deposition
SRM 1643c
(Trace Elements in Water)
Certified Experimental
EPA WP 386
(Trace Metals I)
Certified Experimental
EPA TMA989
(Trace Metals I)
Certified Experimental
Value ± STD
Value ± STD
Value ± STD
Value ± STD
Value ± STD
Value ± STD
A1
114.6 ± 5.1
116.0 ± 3.0
500 ± 50
503.4 ± 13.6
As
50.0 ± 5.34
49.3 + 10.4
Cd
12.2 ± 1.0
11.7 ± 0.6
25 ± 1.97
22.5 ± 1.3
Cr
100 ± 10.20
84.5 ± 5.73
Cu
22.3 ± 2.8
22.8 ±1.1
100 ± 6.20
102.4 ± 17.2
Fe
106.9 ± 3.0
108.3 ± 1.0
100 ± 8.78
109.1 ± 22.4
Mn
35.1 ± 2.2
37.3 ± 1.2
100 ± 5.79
98.0 ±6.11
Ni
100 ± 7.89
81.8 ± 13.0
Pb
100 ± 8.40
98.2 ± 6.59
Se
50.0 ± 4.86
50.8 ± 11.78
Zn
73.9 ± 0.9
73.8 ± 0.5
100 ± 7.36
100.9 ± 11.13
-------
Table III.3.3 Trace Element Wet Deposition Intercomparison
A1
As
Cd
Cu
Fe
Mn
Pb
Se
Zn
Corr(r)
0.993
0.852
0.838
0.870
0.979
0.999
0.888
0.824
0.956
Slope(b)
1.10
1.02
0.45
1.31
0.34
0.97
0.68
0.33
1.28
55
-------
Table IV. 1.1 Mean Total (Vapor + Particulate) Air Concentrations of Polycyclic Aromatic Hydrocarbons and Total Polychlorinated Biphenyls,
Elms Site, 1990 - 1991
On
Polycyclic Aromatic
Hydrocarbon
18 Month
Mean
Cone
% REL
STD
DEV
1991
Mean
Cone
Minimum^
Maximum
% Particulate
Minimum Maximum
N**
Fluorene
573.2
121
664.0
56.0
2724.5
0.0
23
35
Phenantharene
1779.3
66
1771.9
357.0
5692.2
0.3
23
35
Anthracene
50.4
78
47.1
0.9
181.3
0.0
100
35
Fluoranthene
404.7
94
330.1
46.9
2274.9
1.0
100
35
Pyrene
482
79
426.1
34.4
1502.6
0.8
100
35
Benzo[a]anthracene
40.0
102
27.6
1.9
152.8
0.0
100
35
Chrysene
96.9
103
85.0
13.9
537.5
0.0
100
35
Benzo[b]fluoranthene
100.5
117
74.2
2.4
463.8
0.0
100
35
Benzo[k]fluoranthene
58.3
114
47.3
3.1
214.1
12.2
100
35
Benzo[e]pyrene
64.8
128
50.5
3.2
325.5
0.0
100
35
Benzo[a]pyrene
33.9
125
24.0
3.3
162.1
0.0
100
35
Indeno[ 123-cd]pyrene
58.0
141
62.6
6.8
304.5
7.3
100
35
Dibenz[ah]anthracene
33.9
175
9.2
7.3
58.9
6.0
100
35
Benzo[ghi]perylene
63.8
118
60.7
5.6
242.7
12.4
100
35
TOTAL PCBs***
213.9
56
185.6
17.4
507.8
n/a
n/a
38
AAAir concentrations in pg/m3.
**Number of samples.
***74 congeners.
Afor non-detectables, the detection limit is given, range over all data
-------
Table IV. 1.1 (Cont'd). Mean Total (Vapor + Particulate) Air Concentrations of Polycyclic Aromatic Hydrocarbons and Total Polychlorinated
Biphenyls, Haven Beach, 1991.
Polycyclic Aromatic Hydrocarbon
1991
Mean Cone
Range
% Particulate
Minimum Maximum
N**
Fluorene
1635.8
298.7
3671.8
0.2
1.4
27
Phenanthrene
3506.7
1218.4
8285.6
0.4
10.0
27
Anthracene
48.9
1.1
140.0
1.4
100.0
25
Fluroanthene
558.0
202.3
1591.5
2.7
67.3
27
Pyrene
622.1
177.4
1302.4
2.2
74.1
27
Benzo[a] Anthracene
31.7
3.2
213.6
14.9
100.0
24
Chrysene
122.2
13.7
548.5
9.7
97.1
27
Benzo[b]Fluoranthene
83.9
1.9
601.8
56.8
100.0
26.
Benzo[k]Fluoranthene
67.0
1.5
416.1
56.8
100.0
24
Benzo[e] Pyrene
53.6
2.7
375.3
29.1
100.0
27
Benzo[a]Pyrene
36.9
1.7
262.4
66.8
100.0
25
Indenof123]Pyrene
92.1
7.1
443.4
27.8
100.0
22
Dibenzo[a]Anthracene
19.4
8.8
51.0
38.5
100.0
9
Benzo[ghi]Perylene
71.9
3.7
369.1
50.7
100.0
23
TOTAL PCBs***
298.3
26
730
-
-
27
A*Air concentrations in pg/m3.
**Number of samples.
***76 congeners.
-------
Table IV. 1.2 Polycyclic Aromatic Hydrocarbons Concentrations in Air, pg/m'.
Polycyclic Aromatic
Hydrocarbon
Lake
Superior —
Lake
Superior — *
Denver
Colorado"
N iagara
River*
Portland
Oregon**
Baltimore
Maryland*"
Stockholm
Sweden — *
Baltic
Sea — *
Mediterranean
Sea
Chesapeake
Bay"
Fluorene
110
450
na
na
6100
na
na
na
na
570
Phenantherene
92
2600
38000
13800
27002
1800
2560
740
26
1780
Anthracene
5.6
na
3200
1000
28002
2900
120
20
3.7
50
Fluoranthene
na
180
12600
5100
8300
20000
1700
340
30
405
Pyrene
8
340
21200
4200
7500
27000
1370
180
24
480
Benzo|a]anthracene
22
130
na
28002
1500
7600
160
30
4 8
40
Chrysene
67'
6.3'
na
39002
1800
12000'
780'
110'
35'
97
Benzo[b]fluoranthene
na
23
na
na
3500
10600
na
na
na
101
Benzo[k]fluoranthene
na
20
830
1100
na
10600
480
1 10
na
58
Benzo[e]pyrene
44
6.3
na
4202
1200
5000
420
70
22
65
Benzo[a]pyrene
22
5
1700
2302
12002
5800
160
140
6.2
34
Indeno[123-cd]pyrene
50
18
3600
na
na
4600
410
110
6
58
Dibenz[ah]anthracene
na
nd
4200
na
na
na
na
na
na
9
Benzo[ghi]perylene
41
13
4200
5302
20002
8000
640
70
9.1
64
— McVeety, B.D. and Hites, R.A., 1988
—'Baker, J.E. and Eisenreich, S.J., 1990
"Foreman, W.T. and Bidleman, T.F., 1990
*Hoff, R.M. and Chan, K., 1987
**Ligocki, M.B. et al., 1985a, b
**Benner, B.A. et al., 1989
~*Broman, D. et al., 1991
Simo, R. et al., 1991
"This study (from the mid-bay Elms station)
1 = Chrysene and triphenylene
2 = Aerosol phase only
-------
Table IV. 1.3 Total Polychlorinated Biphenyls in Air, pg/m3
Location
Total PCBs
Reference
Arctic
17
Bidleman, et al., 1988
Siskiwit Lake
2700
Swackhamer et al., 1988
Lake Superior
1200
Baker and Eisenreich, 1990
Adirondacks
950
Knap and Binkley, 1991
Bermuda
600
Knap and Binkley, 1991
Chicago
13500
Holson, et al., 1991
S. Ontario
200
Hoff, et al., 1992
Green Bay, MI
250 - 2300
Achman, et al., 1992; McConnell, 1992; Hornbuckle, et al.
1993
Lake Erie
370
McConnell, 1992
Lake Baikal
200
McConnell. et al., 1992
Chesapeake Bay
210
This study; Elms Site
59
-------
Table IV. 1.4. Mean Total (Particulate (Filter + Funnel) and Dissolved) Rain Concentrations of Polycyclic Aromatic Hydrocarbons and Total
Polychlorinated Biphenyls, Elms Site, 1990 - 1991.
Polycyclic Aromatic Hydrocarbon
Jun 90 - Dec 91
17 Months
VWM~ -
1991 VWM
Minimum^
Cone
Maximum
Cone
% Particulate
Minimum Maximum
Fluorene
1.8
1.4
0.1
48
0.8
76.0
Phenanthrene
6.7
5.3
1.3
89
2.8
76.8
Anthracene
1.2
0.7
0.1
30
19.0
99.8
Fluroanthene
9.0
4.9
0.6
20.8
10.4
97.1
Pyrene
16.8
2.6
0.5
912
16.4
98.4
Benzo [a] Anth racene
1.3
0.9
0.2
14
12.0
94.7
Chrysene
3.4
2.7
0.6
25
10.5
91.9
Benzo[b]Fluoranthene
5.7
3.1
0.9
265
16.8
92.6
Benzo [k] F1 uo ranthene
3.1
1.5
0.0
34
6.1
98.2
Benzofe] Pyrene
2.4
2.1
0.3
30
0.8
96.8
Benzo [a] Pyrene
1.9
1.2
0.0
185
11.2
95.9
Indeno[123]Pyrene
2.1
2.4
0.2
9
19.0
99.0
Dibenzo [a] Anth racene
1.1
0.8
0.1
29
5.1
97.3
Benzo[ghi]Perylene
2.3
2.4
0.6
11
36.2
99.0
TOTAL PCBs«*«
1.6
1.2
0.1
34
7.1
95.0
""Rain concentrations in ng/L.
Volume weighted mean concentration.
Total volume ppt, PAH samples, 17 months = 1.51 m\ 1991 = 0.960 m3.
Total volume ppt, PCB samples, 17 months - 1.29 m3, 1991 = 1.00 m3.
Number of samples, 17 months = 32; 1991 = 26
ARanges given for 17 months data.
**74 Congeners.
-------
Table IV. 1.4 (Cont'd). Mean Total (Particulate (Filter + Funnel) and Dissolved) Rain Concentrations of Polycyclic Aromatic Hydrocarbons
and Total Polychlorinated Biphenyls, Haven Beach, 1991.
Polycyclic Aromatic Hydrocarbon
1991
VWM~ ~ Cone
Minimum
Cone
Maximum
Cone
% Particulate
Minimum Maximum
N«*
Fluorene
1.78
0.18
15.99
1.12
100.00
26
Phenanthrene
7.91
2.40
78.95
1.55
100.00
26
Anthracene
0.42
0.09
6.66
4.56
100.00
26
Fluroanthene
4.67
1.72
29.35
11.77
85.59
26
Pyrene
3.57
1.44
21.92
14.04
90.49
26
Benzo[a] Anthracene
0.68
0.23
5.70
43.70
100.00
26
Chrysene
2.07
0.61
14.00
28.55
95.13
26
Benzo[b]Fluoranthene
1.77
0.35
15.80
45.23
97.71
26
Benzo[k]Fluoranthene
1.28
0.32
10.68
37.13
100.00
26
Benzo[e]Pyrene
1.29
0.30
10.40
45.00
97.31
26
Benzo[a]Pyrene
1.14
0.22
9.56
11.12
100.00
26
Indeno[123]Pyrene
1.90
0.42
16.29
39.47
98.26
26
Dibenzo[a] Anthracene
0.33
0.05
3.25
14.45
100.00
26
Benzo[ghi]Perylene
1.80
0.41
12.40
41.90
100.00
26
TOTAL PCBs***
1.12
0.34
5.84
0.51
72.58
26
AARain concentrations in ng/L.
Volume weighted mean concentration; total vol = 1011.2L.
**Number of samples.
***74 congeners.
-------
Table IV. 1.5 Mean Dry and Wet Fluxes of Polycyclic Aromatic Hydrocarbons and Total Polychlorinated Biphenyls, Elms and Haven Beach, 1990 - 1991
Polycyclic Aromatic
Hydrocarbon
Elms Dry Flux
Jun 1990- Jan 1991-
Dec 1991 Dec 1991
Elms Wet Flux
June 1990- Jan 1991-
Dec 1991 Dec 1991
Total Flux— Elms
Jun 1990- ±* Jan 1991- ±
Dec 1991 Dec 1991
Haven
Beach Dry
Flux
Jan 1991-
Dec 1991
Haven
Beach Wet
Flux
Jan 1991-
Dec 1991
Haven
Beach Total
Flux -
Jan 1991-
Dec 1991
Fluorene
1.6
1.3
2.6
2.1
4.2
1
3.4
1
1.5
1.8
3.3
Phenantharene
12
10
8.9
6.7
21
6
17
5
12
8.0
20
Anthracene
0.90
0.80
1.3
0.8
2.2
0.4
1.6
0.6
0.74
0.4
1.2
Fluroanthene
16
9.6
15
5.2
31
7
15
4
21
5.4
26
Pyrene
15
7.6
20
3.1
35
7
11
4
18
4.3
22
Benzofa] Anthracene
5.6
4.0
1.7
1.0
7.3
3
5.0
2
4.2
0.8
5.0
Chrysene
12
9.1
5.3
3.0
17
5
12
4
11
2.3
13
Benzo[b]Fluoranthene
15
11
7.6
3.4
23
7
14
5
13
2.0
15
Benzo|k]Fluoranthene
8.2
7.3
5.0
1.6
13
4
8.9
3
10
1.5
11
Benzo[e]Pyrene
9.0
7.6
2.3
2.2
11
4
9.8
4
8
1.5
9.5
Benzo[a]Pyrene
4.3
3.5
2.4
1.8
6.7
2
5.3
2
5.5
1.3
6.8
lndeno[123]Pyrene
9.6
11
2.1
2.5
12
5
13
5
14
2.2
16
Dibenzo[a] Anthracene
1.8
1.7
1.1
0.8
2.9
1
2.5
1
3
0.4
3.4
Benzo[ghi]Perylene
11
9.7
2.4
2.6
5
12
5
10
2.2
12
Total PCBs**
1.4
1.3
1.9
1.4
3.3
0.6
2.7
1
2.1
1.6
3.7
*AFluxes are in /tg/m2/year and include dissolved, particulate and funnel matrices dry fluxes are aerosol only.
— Total flux = dry + wet.
**74 Congeners.
*Error represented by the largest assumed dry deposition velocity of 0.72 cm/s (to one significant figure).
-------
Table IV. 1.6 Mean Dry and Wet Loadings1 of PAHs and Total PCBs, Chesapeake Bay, 1990 - 1991
Dry Loading Wet Loading Total Loading2
Polycyclic
Aromatic
Hydrocarbon
June 1990-
Dec 1991
Jan 1991 -
Dec 1991
June 1990-
Dec 1991
Jan 1991 -
Dec 1991
June 1990-
Dec 1991
±*
Jan 1991 —
Dec 1991
±
Fluorene
18
16
25
23
43
10
39
10
Phenantharene
138
127
97
85
235
69
211
63
Anthracene
9.4
8.9
10
7.0
19
4
16
5
Fluroanthene
213
176
114
61
327
98
237
81
Pyrene
190
147
140
43
330
86
190
69
Benzo [a]
Anthracene
56
47
14
10
71
29
57
23
Chrysene
132
116
44
31
176
58
146
52
oBenzo [b]
w Fluoranthene
161
138
55
31
216
75
169
63
Benzo [k]
Fluoranthene
105
99
37
18
142
52
117
46
Benzo [e] Pyrene
98
90
22
21
120
46
111
46
Benzo [a]
Pyrene
56
52
22
18
78
29
70
29
Indeno [123]
Pyrene
136
141
25
27
161
63
168
63
Dibenzo [a]
Anthracene
28
27
8.4
6.7
36
12
34
12
Benzo. [ghi]
Perylene
121
113
26
27
147
58
141
58
Total PCBs3
20
20
20
17
40
9
37
9
1 Kg/yr
2 total loading = dry + wet
3 74 congeners
*error represented by the largest assumed dry deposition velocity of 0.72 cm/s to one significant figure
-------
Table IV.1.7. 1991 annual loadings1 of PAHs and Total PCBs, Chesapeake Bay,
for Maryland and Virginia areas
Annual Loading Kg/yr
PAH
MD1
+
VA1
+
Baywide
+
Fluorene
18
5
21
4
39
10
Phenantharene
90
27
127
37
217
64
Benzo[a]pyrene
28
11
42
19
70
29
lndeno[123-cd]pyrene
69
27
98
43
166 "
70
Dibenz[ah]anthracene
13
6
20
6
34
12
Benzo[ghi]perylene
65
27
78
31
143
58
1 area is 0.53 x 10e10 m2 for MD portion of the Bay; 0.62 x 10e10 m2 for VA
2 baywide = sum of Maryland and Virginia loading
* error represented by the largest assumed dry deposition velocity of 0.72 cm/s
64
-------
Table IV.2.1. Summary of Concentrations' of Trace Elements on Aerosols Determined at Wye, Elms, and Haven Beach
Cummulative
1991
Average
Average
ng/m3
Sigma
Avg Error
N
Minimum
Maximum
ng/m3
Sigma
Avg Error
Elms
6/5/90 -
12/31/91
Al
155
114
12
76
12
570
150
120
11
As
0.62
0 27
0.05
76
0.11
1.6
0 56
0.20
0.03
Br
32
1.2
0 28
76
0.70
6.2
3.3
1.1
0.29
Cd
0.14
0.08
0.03
74
0.0025
0.4
0.13
0.08
0 03
Cr
0.66
0.33
0.17
75
0.0710
1.40
0 65
0 34
0.17
Cu
1 9
1.5
0.22
73
0.080
83
1.5
1 1
0.20
Fe
150
106
6.0
76
140
507
150
109
4.5
Mn
2.7
1.5
0.09
74
0.55
13
2.7
1.7
0.09
Ni
2.6
2.2
0.25
64
0.1100
9 1
2.4
2.1
0.24
Pb
3.6
2.4
0 48
71
0.35
12
27
1.8
0 43
S
3000
1500
470
69
736.00
6638
3000
1500
450
Se
1.72
0.72
0.15
76
031
3.80
1.8
0.71
0.13
V
4.40
2.1
0.56
76
1 1
13
47
22
0.68
Zn
13 0
6.7
0.9
76
3.20
36
12
5.4
0.65
Wye
6/5/90-
12/31/91
Al
114
60
10
75
25
300
109
56
8.3
As
0.64
0.33
0.05
76
0.11
2.0
0.61
0.30
0 028
Br
29
1.3
0.21
75
0 06
8.4
3.0
1.1
0.20
Cd
0.14
0.07
0 02
75
0 01
0 43
0.13
0.05
0 017
Cr
0.77
0 45
0 19
75
0 04
2.3
0.75
0 43
0 19
Cu
2.1
1.6
0.24
74
0.31
9.2
1.8
1.2
0.22
Fe
114
48
4.9
76
33
283
107
42
37
Mn
2.9
1 3
0 13
76
0 05
8.2
27
0.91
0.084
Ni
3.0
2.5
0.29
76
0.16
11.4
2.7
2.0
0 29
Pb
3 9
2.3
0.48
76
0.11
13.6
3.4
1.8
0.42
S
2600
1600
380
70
27
7400
2600
1600
340
Se
1.6
0.62
0.14
76
0.42
3 5
1.7
0.56
0.13
V
3.3
1.3
0 24
75
0 56
70
3.4
1.1
0.24
Zn
14
7.4
1 4
76
4.7
48
14
5 9
1.2
Haven
11/23/90-
Beach
12/31/91
Al
129
103
11
34
11
540
130
109
11
As
0.52
0 34
0.031
34
0.0001
1.4
0.47
0.28
0.03
Br
3.7
1.8
0.27
34
0.26
8.4
36
1.9
0 25
Cd
0.14
0.09
0.037
31
0 002
0.424
0.13
0.076
0.04
Cr
0 63
0.46
0 34
32
0.04
1.9
0.52
0.36
0.30
Cu
2.2
1.2
0.40
24
0.3
5
2.1
1.2
0.39
Fe
116
65
4
33
6.3
300
120
67
4.4
Mn
2.8
1.4
0 15
31
0.2
6.9
2.9
1.5
0.2
Ni
2.8
2
0.45
22
0.5
6.20
2.9
1.5
0 45
Pb
3.0
2.3
0.71
29
0.2
11
2.4
1.6
0.68
S
2100
1300
390
24
35
4700
2100
1500
370
Se
1.6
0.88
0.12
33
0.18
3.9
1.5
0.86
0.11
V
4.7
1.9
0.34
34
0.42
10
4 8
2.0
0.33
Zn
11
7
1.1
23
1.5
28
11
7.0
1.1
1 concentrations reported to two significant figures
65
-------
Table IV.2.2 Concentrations of Airborne Elements Determined in Beltsville, College Park, MD, and Lewes, DE, ng/m'.
Beltsville
9/22 - 12/1990'
Ave. ± Sigma Min Max N
College Park
Summer Months, 1983 - 19851 Winter Months, 1985 - 1986'
Ave. ± Sigma Min Max N Ave. ± Sigma Min Max N
Lewes
7/24 - 9/8/89
Ave. ± Sigma N
A1
230 ± 222
12.4
868
(23)
1230 ± 810
420
4140
(31)
420 ± 280
90
1400
(24)
272 ± 265
(91)
S
1690 ± 1425
384
4863
(24)
4000 ± 2380
900
11000
(30)
2100 ± 1100
910
5600
(24)
3771 ± 3225
(92)
Cd
0.53 ± 0.22
0.29
0 86
(5)
0.52 ± 0.39
0.069
1.5
(18)
Cr
2.01 ± 1.60
0.150
7.77
(24)
5 ± 2.8
1.5
13.2
(29)
3 9 ± 2.2
1.7
9.6
(24)
2.08 ± 1.54
(92)
Cu
5.90 ± 3.19
1.52
10 7
(9)
12 ± 5
4
18
(8)
(24)
6 21 ± 5.06
(56)
Fe
238 ± 175
33.4
733
(24)
830 ±430
280
2200
(30)
440 ±310
41
1600
(24)
203 ± 197
(92)
Mn
5.07 ± 5.55
1.07
28.4
(23)
20 ± 8
6
43
(31)
14 ± 7
6
36
(24)
5.32 ± 4.66
(89)
Se
1.55 ± 1.12
0.183
4.75
(24)
2.1 ± 1
0.37
4.4
(30)
2.4 ± 1
1 2
5.7
(24)
1.99 ± 1.78
(92)
V
3.47 ± 3.74
0.513
13.7
(20)
10 ± 10
1
56
(31)
9.1 ± 4.6
3.2
21
(24)
7 44 ± 5.06
(90)
Zn
25.9 ± 24.2
2.41
96.24
(24)
43 ± 17
18
100
(30)
41 ± 17
18
94
(24)
17 4 ± 13.2
(92)
As
0.518 ± 0.536
0.0993
2.38
(19)
1.01 ± 0 59
0.25
2.56
(30)
0 87 ± 0 4
0.39
1.7
(24)
1 11 ± 1.16
(83)
Br
4.00 ± 2 49
0.957
10.8
(24)
41 ± 26
11
140
(31)
28 ± 23
9 2
120
(24)
10.7 ± 12 2
(91)
'Han, 1992.
'Kitto, 1987
'McCarthy, 1988.
-------
Table IV 2.3 Deposition Velocities Determined for Aerosol Particles Over Water
Investigator
Stability
Species
vd
cm/s
MM AD
Mm
Sievering et al., 1979
Aerometric mass balance
over Lake Michigan
May 18-20, 1979
extremely stable
Tair 15.8°
Twater 7.3"
u 3.8 ± 0.8 m/s
S04
Pb
Fe
Mn
0.2 ± 0.16
0.13
0.65
0.55
88% < 1 jim
82% < 1 jim
47% < 1 jim
49% < 1 jim
Dolske and Sievering, 1979
estimated from diabatic drag coef.
Vd = Cdd* iiair - uwater)
over Lake Michigan
May - Sept., 1977
3.6 to 5.2 m/s
<0.9 to+0.9 unstable
dT = + 1.0 to + 2.7
+2.8 to +8.2 stable
Aerosol
0.47 ± 3x
0.72 ± 3x
0.51 ± 3x
0.39 ± 3x
0.1 to 2 fitn
0.1 to 2 jim
0.1 to 2 jim
0.1 to 2 jim
Delumyea and Patel, 1979
mixing box model
April - October, 1977
over Lake Huron
variable1
aerosol
P
0.57 ± 0.16
(0.79 to 1.22)
(6 month ave.)
1 jim
(28% < 1 jim)
Dedeurwaerder et al., 1983
vasaline - coated plates
12 days, 1980- 1981
Souther Bight, North Sea
not reported
Cu
Zn
0.19 (5)
1-0 (2)
0.20 (7)
0.23 (2)
0.38 jim
1.2 jim
0.20 jim
0.66 jim
Pb
0.42 ± 0.01 (9)
0.68 to 0.75 jim
Cd
0.04 (7)
0.10 (2)
0.52 jim
1.1 jim
Fe
1.35 ± 0.05 (9)
1.25 ± 0.05 jim
Mn
0.49 (7)
0.77 (2)
0.84 jim
0.98 jim
'Air and surface temperatures and wind speed not reported
67
-------
Table IV.2.4. Data Summary and Atmospheric Dry Flux Estimates for Trace Elements to Chesapeake Bay
Cummulatve Depositor! flux, pg/m2/yr
Cummulative Average1, ng/m3 Crustal Component % (Low estimates) (High estimates)
Elms
Wye
Haven
Beach
Elms
Wye
Haven
Beach
Elms
Wye
Haven
Beach
Elms
Wye
Haven
Beach
Al
155
114
129
100%
100%
100%
68197
50274
56889
194848
143640
162540
As
0.62
0 65
0 52
0 55%
0.38%
0 54%
52
54
44
143
150
121
Br
3.2
2 90
3.66
0 18%
0.15%
0 13%
262
239
301
724
662
835
Cd
0 14
0.14
0.14
0 14%
0.10%
0 12%
11
12
12
32
32
32
Cr
0.66
0.77
0 63
20.88%
13 24%
18 31%
104
100
93
293
280
262
Cu
1 90
2.10
2.2
3 12%
2 08%
2 25%
177
188
198
492
521
550
Fe
150
114
116
46.61%
45 21%
50 28%
37391
27845
30444
106256
79107
86567
Mn
2.7
2.9
2 8
49.58%
34 64%
40.60%
714
598
638
2031
1696
1810
Ni
2.60
3
2 8
3.33%
2.13%
2 58%
244
269
255
679
746
710
Pb
3.60
3 9
3
0 82%
0.56%
0.82%
305
327
255
847
907
706
S1
2983
2600
2100
0.02%
0 02%
0 02%
244509
213102
172173
677126
590146
476808
Se
1.72
1.6
1.6
0.01%
0 01%
0 01%
141
131
131
391
363
363
V
4.36
3.3
4 7
4 30%
4.19%
3 33%
424
320
441
1183
891
1228
Zn
12.65
13.5
11
0 94%
0 65%
0.90%
1079
1137
936
2992
3152
2597
oo 1991 Average Concentration ng/m3 Crustal Component % Low Flux Estimates 1991 High Flux Estimates 1991
Haven Haven Haven Haven
Elms Wye Beach Elms Wye Beach Elms Wye Beach Elms Wye Beach
Al
150
109
130
100%
100%
100%
66150
48083
57330
189000
137379
163800
As
0 56
0.61
0 47
0 52%
0 37%
0 53%
47
51
39
129
140
108
Br
3.3
3 0
3.6
0 17%
0 14%
0 15%
273
249
293
756
690
811
Cd
0 13
0 13
0.13
0 15%
0 11%
0 13%
11
11
10
29
30
29
Cr
0 65
0 75
0 52
20 38%
13 24%
18 24%
101
97
77
284
272
217
Cu
1 5
1 8
2 1
2 69%
2.00%
2.02%
134
162
185
371
450
513
Fe
150
107
120
51 53%
46.37%
58.62%
40040
26580
35138
113876
75529
100037
Mn
27
2.7
2 9
48 78%
33 05%
44.94%
705
545
700
2004
1543
1989
Ni
2 4
2.7
2.9
3.47%
2 24%
1 82%
230
246
255
640
682
709
Pb
27
34
2 4
0 67%
0.54%
0.71%
231
283
205
641
785
569
S1
3000
2600
2100
0 02%
0.02%
0.02%
245928
213117
172159
681056
590191
476767
Se
1.8
1.7
1.5
0 01%
0.01%
0 01%
150
143
120
415
395
331
V
47
3.4
4 8
4.82%
4.55%
4 04%
462
338
463
1288
942
1290
Zn
12
14
11
0 95%
0.66%
1.07%
1066
1173
982
2957
3252
2724
aerosol particle data only, Elms and Wye 6/5/90 -12/31/91, Haven Beach 11/23/90- 12/31191
-------
Table IV.3.1 Comparative Precipitation Concentrations (^g/L) for a Single Rain Event (23
October 1990) at Five Mid-Atlantic Sites (Volume weighted averages)
A1 Cd Cr Cu Fe Mn Ni Pb Zn
,,0/1...
L
Chesapeake Bay
(Shipboard)
1.9
0.013
0.025
0.09
1.4
0.07
0.66
0.27
0.16
Wye CBADS
3.8
0.007
0.199
0.18
2.7
2.65
0.29
0.17
0.77
Elms CBADS
2.5
0.001
0.081
0.10
3.2
0.34
0.14
0.13
0.23
Beltsville, MDa
1.9
0.007
0.140
0.13
3.6
0.14
0.05
0.09
0.56
Lewes, DE
1.3
0.067
0.032
0.17
0.8
0.10
0.10
0.13
0.19
"USDA Experimental Station, collection and analysis methods identical to CBADS
(Scudlark et al., 1994).
69
-------
Table IV.3.2 Spatial Variability in Trace Element Wet Deposition at Three CBADS Sites for 1991 [/xg/rrr/year].
Element
WYE
Total (% Crustal)"
ELMS
Total (% Crustal)"
HAVEN BEACH
Total (% Crustal)'
Flux Ratio
(Wye: Elms:
Haven)
A1
16,042
(100)
8,411
(100)
17,524
(100)
0.9:0.5:1.0
As
37
(7)
54
(3)
60
(5)
0.6:0.9:1.0
Cd
46
(*)
55
(*)
151
(*)
0.3:0.4:1.0
Cr
104
(17)
87
(11)
NA
1.2:1.0:-
Cu
210
(4)
216
(2)
1,176
(t)
0.2:0.2:1.0
Fe
12,290
(77)
6,498
(76)
12,277
(84)
1.0:0.5:1.0
Mn
1,230
(14)
891
(10)
1,236
(15)
1.0:0.7:1.0
Ni
271
(5)
240
(3)
NA
1.1:1.0:-
Pb
633
(*)
623
(*)
480
(1)
1.3:1.3:1.0
Se
133
(*)
• 115
(*)
128
(*)
1.0:0.9:1.0
Zn
1,358
(1)
1,377
(1)
2,030
(1)
0.7:0.7:1.0
(*) = less than 1 %
{" A1 normalized]
70
-------
Table V.1 Summary1 of Atmospheric Fluxes and Loadings of Trace Contaminants to Chesapeake Bay. 1991
Fluxes (jg/mVyr
Organic
Contaminant
Dry
Wet
Fluorene
1.4
2.0
Phenantharene
11
7.4
Anthracene
08
0.6
Fluroanthene
15
5.3
Pyrene
13
3.7
Benz[a]anthracene
4.1
0.9
Chrysene
10
27
Benzo[b]fluoranthene
12
2.7
Benzo[k]fluoranthene
8.7
1.5
Benzo [e] Pyrene
78
1 9
Benzo[a]pyrene
4.5
1 6
lndeno[123]pyrene
12
2.4
Dibenz[ah]anthracene
2.4
06
Benzo[ghi]perylene
9.9
24
Total PCBs1
1.7
1.5
Trace Element
Dry Flux
Wet Flux
Al
110290
14000
As
86
50
Cd
20
80
Cr
175
100
Cu
302
530
Fe
65200
10000
Mn
1247
1100
Ni
460
260
Pb
452
580
Se
259
130
Zn
2026
1600
Loadings (Kg/yr)*
Total
Dry
Wet
Total
. ±3
3.4
16
23
39
10
18
127
85
211
63
1 4
9
7
16
5
21
176
61
237
81
17
147
43
190
69
5.0
47
10
57
23
13
116
31
146
52
15
138
31
169
63
10
99
18
117
46
10
90
21
111
46
6.1
52
18
70
29
15
141
27
168
63
2.9
27
7
34
12
12
113
27
141
58.
3.2
20
17
37
9
Total Flux
Dry Loading
Wet Loading
Total Loading
±
124290
1300000
160000
1460000
680000
136
1000
580
1800
630
100
130
920
1200
130
275
2000
1100
3100
1300
832
3500
6100
11000
2600
75200
750000
120000
870000
450000
2347
15000
12700
30000
8600
720
5300
3000
10000
3800
1032
5200
6700
12000
3000
389
3000
1500
4500
1600
3626
23000
18000
41000
14000
1 average of the bay sites (Elms and Haven Beach for organics; Wye, Elms, and Haven Beach for trace elements)
2 sum of 74 congeners
1 represents the uncertainty represented by the largest assumed dry deposition velocity (to one significant figure)
"loadings calculated by extrapolating the average flux to the surface area of the Chesapeake Bay below the fall line (1.15E10 m2)
71
-------
Baltimore
( / /
Wye Institute
WashingftmJJ. C.
Elms
S
Haven '
Beach
Richmon
3J
Atlantic Ocean
CHESAPEAKE BAY
Figure 11.2.1. Chesapeake Bay atmospheric deposition sites.
Organic contaminant data collected at the Elms and Haven
Beach stations only.
72
-------
"i i i i rn i r
i i i i i
III
-rn—i—r~i—i—r~r
Precipitation
Sample 8/8 —
8/15/90
Funnel Sample
_ J] _~ _0 _~ -L
J].nJUl
Field Detection Filter Sample
Limit, Vol = 28.8 L
J J
_~ jj
. _ M
JD JJ
J]JI
JJjJ]. J.
ill
il
XAD —2 Resin Sample
J.
J] *=} J_
J] J] J] J1
i i i i i i i i i
I 1 I I L
CMt^a3CT)'*l-r^CT)t£)(OCMCM|\CTl"— O'-untD'^-r^O'-CMrOtD
'-'-¦r-T-Tj-Tj--
-------
nMoles
100
10
-j
¦p.
0.1
0.01
Al
Cd
Cr
Cu
Fe
Mn
Ni
Pb
Zn
Wye (18)
Elms (16)
Haven Beach (6)
Lewes
Figure III.3.1 Comparison of absolute field blank contributions at 3 CBADS sites to those
measured at Lewes, DE.
-------
16%
Ui
10% -
Elms
Haven Beach
~As & Se FB est from Detection Limits
Figure III.3.2 A comparison of field blanks at 3 CBADS sites, shown as a percentage of the average
sample concentration.
-------
Wye
100% -r
75%
50%
25%-
Al Cd Cr Cu Fe Mn Ni Pb Zn
Lab Blank (7) Km Field Blank (18)
Elms
100% -i
75%
50%
25% -
Al Cd Cr Cu Fe Mn Ni Pb Zn
Lab Blank (14) IfflSJ Field Blank (16)
Figure III.3.3 A comparison of laboratory blanks to field blanks at
2 CBADS sites.
76
-------
WYE Site
Collecetd Volume (ml*)
6.000
S.000
4.000
3.000
2,000
1.000
1 l.S 2
Gauge (inches)
HAVEN BEACH Site
Collected Volume (mis)
12.000
10,000
8.000
6,000
4,000
2,000
2 3 4
Gauge (inches)
7,000
6.000
S.000
4,000
3,000
2,000
1,000
0
ELMS Site
Collected Volume (mis)
-
*
*¦
' 1
Gauge (inches)
Figure III.3-4 A comparison of the predicted volume (from gauge) to the collected volume as an indication
of the efficiency of the collector.
-------
Figure IV.1.1 Fluorene concentrations in air collected at the Elms and
Haven Beach sites. (l=not quantifiable in vapor phase,
2 = not quantifiable on filter, 3 = not detected in vapor
phase, 4 = not detected on filter, ~ = lost vapor sample,
** = lost particulate sample)
6000
i 1 1 1 1 1 1 r
Fluorene - Haven Beach, VA 1991
5000 -
vapor
— aerosol
"i r
^ 4000
3000 -
c
2000
1000 -
J
2 2
i i I i i i i l i i r
uu
10 15 20 25 30 35 40 45 50
Julian Week
78
-------
3000
2500
m
cn 2000
CL
Fluorene
Elms, 1 990
vapor
aerosol
.2 1500
O
S 1000
u
c
o
CJ
500 -
6000
-i—i—|—i—:—i—!—i—I"
La
**
ill I I i
5000 -
n
cn 4000
CL
Fluorene
Elms, 1 991
vapor
aerosol
.2 3000
2000
u
c
o
CJ
1000
U
I I I I ... I I . ' I
10 15
20 25 30
Julian Week
35 40 45 50
79
-------
Figure IV.1.2 Phenanthrene concentrations in air collected at the Elms
and Haven Beach sites. (l=not quantifiable in vapor phase,
2 = not quantifiable on filter, 3 = not detected in vapor
phase, 4 = not detected on filter, * = lost vapor sample,
** = lost particulate sample)
10000
8000
i 1 1 1 1 1 r
Phenanthrene — Haven Beach, VA 1991
— vapor 1 1 — aerosol
6000
4000
2000
' I T I
10 15 20 25 30 35
Julian Week
40 45 50
80
-------
10000
m
cn
Q.
c
o
c
a;
u
c
o
o
ro
8000 -
6000
4000
2000
cn
o.
c
o
10000
8000
~i 1 r
Phenanthrene
Elms, 1 990
HI vapor
aerosol
i . i 'Ti i i i r -t ¦ I I I
Phenanthrene
Elms,1991
6000 -
c
-------
Figure IV.1.3 Anthracene concentrations in air collected at Elms and
Haven Beach sites. (l=not quantifiable in vapor phase,
2 = not quantifiable on filter, 3 = not detected in vapor
phase, 4 = not detected on filter, * = lost vapor sample,
** = lost particulate sample)
200
150
i i i r
Anthracene — Haven Beach, VA 1991
HI ~~ vapor r~] — aerosol
1 oo
50
o
3 3 3 3 3 3
n—r-1—1 1 1—r
10 15
"" ' T
3 3
1 1 1 I I T I T |
I
u
20 25 30
Julian Week
40 45 50
82
-------
Anthracene
Elms, 1 990
vapor
aerosol
Anthracene
Elms, 1991
^|[| vapor
aerosol
JLi
H
4 4
I
10 15
20 25 30
Julian Week
35
83
-------
Figure IV.1.4 Fluoranthene concentrations in air collected at the Elms and
Haven Beach sites. (l=not quantifiable in vapor phase,
2 = not quantifiable on filter, 3 = not detected in vapor
phase, 4 = not detected on filter, * = lost vapor sample,
** = lost particulate sample)
2000
Fluoranthene-
¦i - vapor
1500
"i i i i r
Haven Beach, VA 1991
— aerosol
1000
500
i
5
20 25 30 35
Julian Week
84
-------
i r
i i
Fluoranthene
Elms, 1 990
IB vapor
aerosol
1 iil I ¦
I 1 '1 1 T
i r
Fluoranthene
Elms, 1 99 1
|B| vapor
aerosol
¦ r
*
**
I il.illl.ii.l.
10 15
20 25 30
Julian Week
35 40 45 50
85
-------
Figure IV.1.5 Pyrene concentrations in air collected at the Elms and
Haven Beach sites. (l=not quantifiable in vapor phase,
2 = not quantifiable on filter, 3 = not detected in vapor
phase, 4 = not detected on filter, * = lost vapor sample,
** = lost particulate sample)
1 I I I 1 1
Pyrene— Haven Beach, VA 1991
H — vapor ["~ — aerosol
1 r
o
u
1 1 1 I 1 1 1 ' I
5 10
**
A a
15 20 25 30 35 40 45
Julian Week
n
50
86
-------
Pyrene
Elms, 1 990
HI vapor
aerosol
*~
Jj
• • > 1 • •
ill I i
I : ^
i i ; r
Pyrene
Elms, 1 99 1
Hi
u
Julian Week
87
-------
Figure IV.1.6 Benz[a]anthracene concentrations in air collected at Elms
and Haven Beach sites. (1= not quantifiable in vapor phase,
2 = not quantifiable on filter, 3 = not detected in vapor
phase, 4=not detected on filter, * = lost vapor sample,
** = lost particulate sample)
250
200 -
"I T
Benz[a]anthracene- Haven Beach, VA 1991
HI — vapor | | — aerosol
150 -
100 -
50
o
2*
IL
4 2 2 4 2
^ i H i ^ , f? i ? . ¥
1
4
jjj
1
4
¦ML
n 1
**
JU
-I—l—I—I T |
50
0
10 15 20 25 30
Julian Week
35
40
45
88
-------
250
200
150
100
50
250
200
150
100
50
Benz[ a] anthracene
Elms, 1 990
vapor
aerosol
"T T1 : I t :—I I I—!—! I i ; I
* *
i T ¦
Benz[ a] anthracene
Elms, 1 991
vapor
aerosol
M-
* 3
** n
4 3 3^3
t n n 4 „
u
3 n* y
9 . n . f
. 3
3
n
1
10 15
20 25 30
Julian Week
35 40 45 50
89
-------
Figure IV.1.7 Chrysene concentrations in air collected at the Elms and
Haven Beach sites. (l=not quantifiable in vapor phase,
2 = not quantifiable on filter, 3 = not detected in vapor
phase, 4=not detected on filter, * = lost vapor sample,
** = lost particulate sample)
600
500 -
400
300 -
200 -
100 -
"1 i i i i i r
Chrysene- Haven Beach, VA 1991
— aerosol
vapor
j,y,y,y,u,u,g,i,g.a,g.u.i
n
i
I
Ui
0
I
10
15
r
20
25 30 35 40 45 50
Julian Week
90
-------
600
500
400
300
200
1 00
600
500
400
300
200
100
i r
i i i r
Chrysene
Elms, 1 990
vapor
aerosol
ijj
I i ¦
I 1 ' I
i i i i
i i
i i i i
I r
Chrysene
Elms, 1 991
vapor
aerosol
1
, I, U, 8, D. v, y,.
4
T I T ¦ • I
fl.
10 15 20 25 30 35 40 45 50
Julian Week
91
-------
Figure IV.1.8 Benzo[6]fluoranthene concentrations in air collected at Elms and
Haven Beach sites. (1=not quantifiable in vapor phase,
2 = not quantifiable on filter, 3 = not detected in vapor
phase, 4 = not detected on filter, * = lost vapor sample,
** = lost particulate sample)
600
i 1 1 1 1 1 1 r
Benzo[6]fluoranthene- Haven Beach, VA 1991
~ vapor | | — aerosol
450
300
150
1 1
n
3 1 n 3
n n n n
'i1 i 111 i ¦ i1 i ¦ i
1
n
3 n 1 n 1 n
t ¦ 7 ¦ T I ¦ ¦ ¥ ¦ I i ¦
T i 'i—i '| i i i r | T i i' i | i—r—i—r-|—r-i—i—i ']1 i—t-t
5 10 15 20 25 30 35
Julian Week
1
n
40
45 50
92
-------
6 00
450
300
1 50
600
450
300
150
5 10 15 20 25 30 35 40 45 50
Julian Week
Benzo[b]fluoranthene
Elms, 1 990
HI vapor
aerosol
-i—i—r—i—i—i-
y_a
3
aj
3
1
I ! I
Benzo[6]fluoranthene
Elms,1991
vapor
aerosol
1
XL
* 3
J^XL
^3^3 n
3.n,n!:;,ry
T i 'i
-------
Figure IV.1.9 Benzo[A;]fluoranthene concentrations in air collected at the Elms
and Haven Beach sites. (1=not quantifiable in vapor phase,
2 = not quantifiable on filter, 3 = not detected in vapor
phase, 4 = not detected on filter, * = lost vapor sample,
** = lost particulate sample)
500
400 -
Benzo[A;]fluoranthene — Haven Beach, VA 1991
|H1 ~~ vapor | - aerosol
300 -
200
100 -
0
n
3 1 1 3 1
n, ~, n, n, ?
3 1
1
Q-
2 3 ?
1 n 1
**
1
n
I T I T I I1 |—I—r-
45 50
0
i < i i
10
15
20 25 30 35
Julian Week
40
94
-------
500
400
300
200
100
500
400
300
200
100
n r
1 r
Benzo[fc]fluoranthene
Elms, 1 990
1^1 vapor
aerosol
n
"i—¦—¦—1—1—r
—i—i—i—i—i—l—r~
I ' '' I 1 l-lji ' ¦ ' |
"1 T
1 r
Benzo[A:]fluoranthene
Elms, 1991
vapor
aerosol
3 * 3
n fl n
3
33 3
I.I
3 *
n n
t—i—i 111 | V-r-T i ' |' i V i—i—jit—i—i—|—i r i r | i i ll
I ' ' 1 ' I ' ' ' ' I
10 15 20 25 30 35 40 45 50
Julian Week
95
-------
Figure IV.1.10 Benzo[e]pyrene concentrations in air collected at the
Elms and Haven Beach sites. (1=not quantifiable in
vapor phase, 2 = not quantifiable on filter, 3 = not de-
tected in vapor phase, 4 = not detected on filter, 5 = not
analyzed, * = lost vapor sample, ** = lost particulate sample)
500
400
"I T
Benzo[e]pyrene — Haven Beach, VA 1991
HH — vapor (~~l — aerosol
cn
Q.
c
o
o
c
CD
U
c
o
u
300
200 -
100 -
1
XL
i
5
3 3 3 3 3
~ , n , n, n, n
3 3
1 I I 'l' I I1 I
10 15 20 25 30
Julian Week
Ai
i i i i
**
35
40
45
1
n
50
96
-------
500
400
300
200
100
500
400
300
200
100
Benzo[e]pyrene
Elms, 1 990
vapor
aerosol
5 55|
1 1 i 1
4e *
3
3
n
i
Benzo[e]pyrene
Elms,1991
HI vapor
aerosol
1 ¦ 1 1 T
5
3
LO
*
**
n
3 3
i j i i i '¦ i J j j j i' i )
rn, n . 4.
JlJiL
I
10
15 20 25 30 35 40 45 " 50
Julian Week
97
-------
Figure IV.1.11 Benzo[a]pyrene concentrations in air collected at Elms and
Haven Beach sites. (1=not quantifiable in vapor phase,
2 = not quantifiable on filter, 3 = not detected in vapor
phase, 4 = not detected on filter, * = lost vapor sample,
** = lost particulate sample)
350
300
250
"i r
Benzo[a]pyrene - Haven Beach, VA 1991
~ vapor | — aerosol
200
1 50
100
50
3 1
1
n
3 3 3 n 3
n n n M
1 i1 i ¦ i i ¦ i ¦ i ¦
3 3 3 3
1
3 2
n
T I T I y I l i i |
1
1
n
i I i i ]ii
i1 i i i i i i i i
i i 'i' i | i i i i |
i i i i T i ii i
5 10 15 20 25 30 35 4-0 45 50
Julian Week
98
-------
350
300
250
200
150
100
50
350
300
250
200
150
100
50
I I
Benzo[a]pyrene
Elms, 1 990
¦I vapor
aerosol
I I
I I
^3
1 i i i I—i—1—r-
3
XL3'
3
¦41
3
XL
n..
I I
Benzo[a]pyrene
Elms, 1 99 1
vapor
I ! aerosol
1 1 ¦ ¦ • 1
1 1
3 n -
1
3
3
3
3
3 3
4
* 4
** ^
4
n
n 4
1 1 1 1 1
20
' ' i 1
25
1 , | ,
30
ij
1 ' " 1 r I
3 * 3
ajl
3
H
Julian Week
99
-------
Figure IV.1.12. lndeno[/,2,3 — cc£]pyrene concentrations in air
collected biweekly at the Elms and Haven Beach
sites.(1=not quantifiable in vapor phase, 2 = not
quantifiable on filter,3= not detected in vapor phase
4 = not detected on filter,* = lost vapor sample,
** = lost particulate sample.
600
500
I I I I I I I I
lndeno[7,£,3-cd]pyrene - Haven Beach, VA 1991
— vapor I - aerosol
400 -
300
200 -
1 oo
XL
13 3 3
n n n n
3
n
7 n
Ua-
2 2
3 3
1
n
1 3 !
2 n 2
1 1 1 ' ' I
*
1
I I I I I I'll I I I 111 I
T 1 1 I I ' I 1 1 1 1 1 'I' I 'I' I I 1 1 I i I 1
I I I I
10 15 20 25 30 35 40 45 50
Julian Week
100
-------
500
400
lndeno[7,£,,3-cd]pyrene
Elms, 1 990
H vapor
aerosol
300
200 -
100
33
_QQ
la
4 3
**3 (~|
3 3
3 _
500
400
lndeno[7,2,3 —cd]pyrene
Elms,1991
300
200
100
i'¦ vi 'j "J
5
3
IL
11 1 * * i
10 15
*
**
fl
3 3^ 33333
1 1 1 1 I
25
4 4 n 4 n. 4 n
1 1 1 1
30
¦4JL
n
3 3
JUL
r ¦ 1 1 1 1 1
45 50
20
35
40
Julian Week
101
-------
Figure IV.1.13. Dibenz[a,/i]anthracene concentrations in air collected
biweekly at the Elms and Haven Beach sites.(1 =
not quantifiable in vapor phase, 2 = not quantifiable
on filter, 3 = not detected in vapor phase, 4 = not
detected on filter, * = lost vapor sample, ** = lost
particulate sample.
200
ro
150 -
i i i i i i i r
Dibenz[a, hjanthracene - Haven Beach, VA 1991
¦I — vapor I | — aerosol
cn
Q.
c
o
100 -
c
a;
o
c
o
o
50 -
3
n
n
i 'i' i "i
3 2 3 4 3 2
4 3 4 | 4 3
—1—|—|—I—I—I ^
I I I I
11 13 1 2 2 2 2 1 *
4^423^3321
I I I I—| l l l l—| l l I l—| l l l—l | l
10
15
20
25
30
35
40
45
2
3
50
Julian Week
102
-------
200
150
° 100
50 -
200
150
100
50
Dibenz[a, h]anthracene
Elms, 1 990
vapor
aerosol
3 |434 4 4 4 4
n„|3f13 »«3 3 3 3
1 ! : j •
*
n 3
I 1 I 1 I 1 I ' I
1
Dibenz[
1 1 1 1 1 1 1
a, /ijanthracene
1
Elms, 1 99 1
IB vapor
-
aerosol
3 r
3
-
3
3
¦z
|
44 4 44444444*^"
"443
. n
J
3 3 3 33*3333 3 43
r-i—:—1—1—1—1—1—:—1—1—1—1—1—1—1—1—1—1—1—1—1—1—1—1—1—!—i—1—1—:—r—^
3 3 n
' 1 1 1 ! ! 1
10 15 20 25 30 35
Julian Week
40
45
50
103
-------
Figure IV.1.14 Benzo[g,/i,i]perylene concentrations in air collected at Elms
and Haven Beach sites. 1=not quantifiable in vapor phase,
2 = not quantifiable on filter, 3 = not detected in vapor
phase, 4- = not detected on filter, * = lost vapor sample,
** = lost particulate sample)
500
n
400 -
Benzo[sr,h,,i]perylene — Haven Beach, VA 1991
|H| — vapor I ] — aerosol
cn
Q_
C
o
300
c
a;
u
c
o
o
200
100 -
.0
3 1 1 3 3
n fl n n n
2
3
t—r r i—|—i 1 r i ' r | i1 i I I ~T"~i—i—i—i—I t " i—m—i—i—r
1 1
n . n
2
1
n 2 1
Bj.ij.;
i
T~T T-! I T
10 15 20 25 30
Julian Week
35
40
45 50
104
-------
500
400
300
200
100
500
400
300
200
100
I I
I I I I
Benzo[gr, fc,i]perylene
Elms, 1 990
HI vapor
aerosol
nng
3
3
4
I I
I I
Benzo[gr, /i,i]perylene
Elms, 1991
vapor
aerosol
3
J
3
3
A-
L.
In 3 3 3 3 3 3 3 3 3 ~ 3
1
3 3 "
rJ fL,
-
r-1—
5 10 15 20 25 30 35 40 45 50
Julian Week
105
-------
Figure IV.1.1 5. Total trichlorobiphenyl concentrations in air collected
biweekly at the Elms and Haven Beach sites.(1 =
not quantifiable in vapor phase, 2 = not quantifiable
on filter, 3 = not detected in vapor phase, 4= not
detected on filter, * = lost vapor sample, ** = lost
particulate sample.
500
400
Trichlorobiphenyls- Haven Beach, VA 1991
HI — vapor | — aerosol
300
200
10 0
u
I
X
**
10 15 20 25
30 35
40
45
50
Julian Week
106
-------
400
300
cn
CL
.2 200
Trichlorobiphenyls
Elms, 1 990
vapor
c
CD
O
c
o
CJ
1 00
400
t—r—i—r i i i i i |—i—i—r
Trichlorobiphenyls
Elms,1991
n
300
CD
Q.
9. 200
i i i i T i
u
c
a>
o
c
o
o
100
l i if i i i T | l
I
5 10 15 20 25 30
Julian Week
i l i
35 40 45 50
107
-------
Figure IV. 1.16. Total tetrachlorobiphenyl concentrations in air collected
biweekly at the Elms and Haven Beach sites.(1 =
not quantifiable in vapor phase, 2 = not quantifiable
on filter, 3 = not detected in vapor phase, 4 = not
detected on filter, * = lost vapor sample, ** = lost
particulate sample.
250
200 -
"i 1 1 1 1 r
Tetrachlorobiphenyls— Haven Beach, VA 1991
— vapor [~~j — aerosol
"i r
150 -
100 -
50 -
0
i
ll-.ll
I
llll III
**
¦ - II
T"~ i j i
0
10 15 20 25 30 35 40
l 1 11 1 l
45 50
Julian Week
108
-------
m
cn
Q.
c
o
-+-I
o
250
200
1 50
1 00
c
(D
O
c
o
O 50
n
250
200
Tetrachlorobiphenyls
Elms, 1 990
vapor
Tetrachlorobiphenyls
Elms,1991
1
cn
a.
c
o
1 50
o
^ 100
c
CD
-------
Figure IV. 1.17 Total pentachlorobiphenyl concentrations in air
collected biweekly at the Elms and Haven Beach
sites. (1=not quantifiable in vapor phase, 2 = not
quantifiable on filter, 3 = not detected in vapor phase,
4 = not detected on filter, * =lost vapor sample,
** =lost particulate sample)
350
300
Pentachlorobiphenyls— Haven Beach, VA 1991
HI ~ vapor | I — aerosol
250
200
150
100
n
2 1
n **
1
45
¦ i ¦
50
Julian Week
110
-------
300
250
200
150
100
50
I I
I I
Pentachlorobiphenyls
Elms, 1 990
jj^l vapor
1
l i
300
lilt
Pentachlorobiphenyls
250 h Elms, 1 99 1
200 -
I I
150 -
100 -
50
L.
I.' I I • ! ¦
5 10
20 25 30
Julian Week
40 45 50
111
-------
Figure IV.1.18. Total hexachlorobiphenyl concentrations in air
collected biweekly at the Elms and Haven Beach sites.
(1=not quantifiable in vapor phase, 2 = not quantifialbe
on filter, 3 = not detected in vapor phase, 4 = not detected
filter, *= lost vapor phase, ** = lost particulate sample.
200
n
CD
Q.
C
o
c
-------
200
ro
1 50
cn
CL
2 100
i i
Hexachlorobiphenyls
Elms, 1 990
¦I vapor
i i
i i
c
CD
(J
c
o
o
50
200
m
cn
Q.
c
o
° 100
o
L_
c
QJ
O
c
o
CJ
50
"i r
Hexachlorobiphenyls
Elms, 1 99 1
150 -
II-
1
,1
I I
i
,-l
¦ M,U
10
15 20 25 30 35 40 45 50
Julian Week
113
-------
Figure IV.1.19. Total heptachlorobiphenyl concentrations in air at
the Elms and Haven Beach sites. (1=not quantifiable
in vapor phase, 2 = not quantifiable on filter, 3 = not
detected in vapor phase, 4=not detected on filter,
* = lost vapor sample, ** = lost particulate sample)
75
60
Heptachlorobiphenyls- Haven Beach, VA 1991
— vapor 1 — aerosol
45
30
W
20 25 30
Julian Week
114
-------
80 -
r-O
Heptochlorobip'nenv-ls
Elms, 1 990
vapor
^ 60
Cn
Q.
c
o
o
40 -
QJ
U
c
o
o
20 -
80
ro
c 60
cn
Cl
O
o
c
(U
u
c
o
o
40
20
Heptachlorobiphenyls
Elms, 1 991
20 25 30 35
Julian Week
115
-------
Figure IV.1.20 Total octachlorobiphenyl concentrations in air
collected biweekly at the Elms and Haven Beach
sites. (1=not quantifiable in vapor phase, 2 = not
quantifiable on filter, 3 = not detected in vapor phase,
4 = not detected on filter, * =lost vapor sample,
** =lost particulate sample)
100
"i r
"i r
80 -
Octachlorobiphenyls— Haven Beach, VA 1991
— vapor | - aerosol
60 -
40
20
1 1
XL2
1
2
1
2
z
J
I
1 **
2 2 1
I I I l | i i i i J i i
I | I l i i I i i i i | i i l l | I I
10 15 20 25 30 35 40 45 50
Julian Week
116
-------
Octachlorobi phenyls
Elms, 1 990
H vapor
¦iilll .ll •. i I I LL
Octachlorobiphenyls
Elms, 1 99 1
¦ I _ ¦ I I ¦ I ¦
l ! ¦ I * ¦ | | l
45 50
10 15 20 25 30
Julian Week
40
117
-------
Figure IV.1.21 Total nonachlorobiphenyl concentrations in air
collected biweekly at the Elms and Haven Beach
sites. (1=not quantifiable in vapor phase, 2 = not
quantifiable on filter, 3 = not detected in vapor phase,
4 = not detected on filter, * =lost vapor sample,
** =lost particulate sample)
1.5
Nonachlorobiphenyls— Haven Beach, VA 1991
— vapor I I — aerosol
1.0
0.5
o.o
1 2 2 1 1 12 11 22121 221 1 123223 **
2^ 3 2 443243323233424343341
i i i I
I I I I I I I I I I I I I [ I I I I
| I I I I | I I I I | I I I
10
15
20 25 30 35
Julian Week
40
45
50
118
-------
Nonachlorobiphenyls
Elms, 1 990
IH vapor
1
J,.
1
1
I ' ' ' ' ! !
Nonachlorobiphenyls
Elms, 1 99 1
1
I I I ill
T,i,fil
10 15 20 25 30 35
Julian Week
40 45 50
119
-------
Figure IV.1.22. Total PCB concentrations in air collected
biweekly at the Elms and Haven Beach sites.(1 =
not quantifiable in vapor phase, 2 = not quantifiable
on filter, 3 = not detected in vapor phase, 4= not
detected on filter, * = lost vapor sample, ** = lost
particulate sample.
1000
800
"i 1 r
Total PCBs- Haven Beach, VA 1991
— vapor I I - aerosol
600
400
200
11
i ¦ ¦ ¦ ¦ ¦ i ¦ ¦ 1 i ¦ ¦ ¦ ¦ i
20 25 30 35 40
Julian Week
120
-------
1000
800
Total PCBs
Elms, 1 990
HI vapor
cn
CL
c
o
0
u
c
o
o
600
400
200 -
1000
800
Total PCBs
EI m s, 1 9 S 1
vQpor
cn
Q.
600
c
0)
u
c
o
o
400
200
I
I
ill I ¦ 1
10 15 20 25 30 35 40 45 50
Julian Week
121
-------
60
40
20
20
1 6
1 2
8
4
5 Fl
Ha
on
Fluorene
Elms, 1 990
HI dissolved
particulate
funnel rinse
I . I 1 ! I I I
l-^21
a 8 a ~7'
-t i i i i—|—r-
Fluorene
Elms, 1 99 1
3
*
3
Jul
-7-
3 3
I I. ¦ i i I .
8
**
10
15
20
25
30
35
40
45
50
Julian Week
orene concentrations in precipitation integrated biweekly at the Elms and
en Beach sites. (1=not quantifiable in dissolved phase, 2 = not quantifiable
filter, 3 = not quantifiable in funnel, 4=not detected in dissolved
se, 5 = not detected on filter, 6 = not detected in funnel, 7 = sampler
m, 8=field blank, * = lost dissolved sample, *+ = lost particulate
iple, ° = lost funnel rinse). Funnel rinse combined with particulate
:tions after week 30, 1991.
122
-------
20
1 6
12
8
4
0
20
1 6
1 2
8
4
0
i i 1 1—
Fluorene
Haven Beach,1990
— dissolved
— particulate
— funnel rinse
"i i i r
I > I I | I « I I | » I I I | I I I I j I I 1 1 j I I I I | I I I I | I 1 I I I J ' T" l"T I" J T"r I I | I
I I I i I I I I I T"
Fluorene
Haven Beach,1991
il
¦j .i
3 -7 ,
iiU -
I
20 25 30 35
Julian Week
40 45 50
123
-------
1 00
75
50
25
100
75
50
25
4. Pi
an
qu
ph
di:
7
i i i i i i
i i
Phenanthrene
Elms, 1 990
dissolved
particulate
funnel rinse
I I I I I I ! I i ¦ '1 ! I I
i • ¦ ¦ ¦ i
1:
^ i—i | i i .
I l . ^ T I
3 3
M-7'
i ¦ 1 1 1 i
1 r
Phenanthrene
Elms,1991
2 *
8
**
li-J
10 15 20 25 30
Julian Week
35
40
45
50
jnanthrene concentrations in precipitation integrated biweekly at the Elms
I Haven Beach sites. (l=not quantifiable in dissolved phase, 2 = not
ntifiable on filter, 3 = not quantifiable in funnel, 4=not detected in dissolved
se, 5 = not detected on filter, 6 = not detected in funnel,. * = lost
solved sample, ** = lost particulate sample, ° = lost funnel rinse,
• sampler down and 8 = field blank, no ppt.). Funnel rinse combined
i particulate fractions after 4&fek 30, 1991.
-------
1 00
75
50
25
0
100
75
50
25
0
i 1 1 i r
Phenanthrene
Haven Beach.VA 1990
IHI — dissolved
- particulate
- funnel rinse
"i r
[ I l I i | I l I I | I I I i—j i i i i | i i i i |—i i i i | i—i i i | i i i i | i i l l |
—i 1 1 1 1 1 r
_i r
Phenanth rene
Haven Beach.VA 1991
20 25 30
Julian Week
i 1 1 1 1 i 1
40 45 50
125
-------
40
30
20
10
Anthracene
Elms, 1990
dissolved
particulate
funnel rinse
ii.ii
6 6 4
4 -7- 2 5
-0- ___
-7-
I T , t } 'I' I I ¦ { i I
8
4
i 1 1 1 1 i • ¦ ¦ 1 i
6 -
Anthracene
Elms, 1991
I ' ' '1 I
2 -
*
2
hiw
4
5
-7-1
*
2 n 8
* **
10
15
20
25
30
35
40
45
50
Julian Week
Figure IV.1.25 Anthracene concentrations in precipitation integrated biweekly at the
Elms and Haven Beach sites. (1=not quantifiable in dissolved phase,
2= not quantifiable on filter, 3 = not quantifiable in funnel, 4 = not detected
in dissolvedphase, 5 = not detected on filter, 6 = not detected in funnel,
7 = sampler down, 8=field blank, * = lost dissolved sample, ** = lost
particulate sample,0 = lost funnel rinse). Funnel rinse combined with
particulate fractions after week 30, 1991.
126
-------
8
6
4
2
0
8
6
4
2
0
Anthracene
Haven Beach.1990
HI — dissolved
- particulate
- funnel rinse
f=i
i ¦ ¦ i ¦ 1 ¦ 1 i 1 1 1 1 i 1
"i i i r
Anthracene
Haven Beach,1991
1
¦ I f i - .
UL
~ 1 '
4
n-C-
I I 1 | I
8
a
10 15 20
30
'i
35
40
45
50
Julian Week
127
-------
CJi
c
c
o
c
(D
O
c
o
o
200
150
100
50
Fluoranthene
Elms, 1 990
dissolved
particulate
funnel rinse
-7-
-7-
40
30
cn
c
c
o
20
c
-------
40
30
20
10
0
40
30
20
1 0
0
Fluoranthene
Haven Beach.VA 1990
— dissolved
I I - particulate
- funnel rinse
t—i i i [—i i i i—|—i i i i | i i i i | i i—i i | i i t i | i i i ¦ i i i i i i—i-
n r
1
Fluoranthene
Haven Beach,VA 1991
1,8,) I,i I
5 10 15
M-
20 25 30 35
Julian Week
129
-------
cn
c
c
o
800
600
400
-------
25
20
15
10
5
0
25
20
1 5
1 0
5
0
i i i i r
Pyrene
Haven Beach.VA 1990
HH - dissolved
- particulate
- funnel rinse
"i r
i 1 1 1 ¦ i
i i I i i i i I—i—i—r
I • ' • 1 I ' 1 1 1 I ' ' 1 • I
T—1 1 t i i I I | I I I—I | 1 I I I | I
1
"I T
III
"I 1 1 T
A
Pyrene
Haven Beach.VA 1991
U'
** I
xd
I
I T I i i i i T I I I ! I
i I I | r
10 15
20 25 30 35 40 45 50
Julian Week
131
-------
1 6
1 2
8
4
8
6
4
2
3 B
El
Pf
dc
o
Benz[ a] anthracene
Elms, 1 990
dissolved
particulate
funnel rinse
"i r
i1 T* r — j*1 t 'T -r r r | i i i i
i 1 1 1 1 i
-7-
Jul
8 ° -7-
i—l I i T i—I—| T i—i—i—|—i—r
1 r
Benz[a]anthracene
Elms,1991
1
I 6
u
6
JL
M
-7-
4
8n1 n1 n I
r
35
* 1
2 **
! I I
10
15
20
25
30
40
45
50
Julian Week
nz[a]anthracene concentrations in precipitation integrated biweekly at the
is and Haven Beach sites. (1=not quantifiable in dissolved phase, 2 = not
intifiable on filter, 3 = not quantifiable in funnel, 4=not detected in dissolved
ise, 5 = not detected on filter, 6 = not detected in funnel, 7 = sampler
m, 8 = field blank, * = lost dissolved sample, ** = lost particulate sample,
: lost funnel rinse). Funnel rinse combined with particulate fractions
er week 30, 1991.
132
-------
8
6
4
2
0
8
6
4
2
0
Benz[a]anthracene
Haven Beach,1990
HH - dissolved
- particulate
— funnel rinse
i i i i | i i i i | i i i i | i i i i |—i—i i i | i i i i | i i i i | i—i i i
Benz[a]anthracene
Haven Beach,1991
1
3
XL
*¦
3 6
i
**
I11 ¦ U ¦ ?
I I I I I I
10
15 20 25 30 35
Julian Week
40 45 50
133
-------
30
25
CP
c 20
c
o
•J3 15
c
a 10
o
c
o
o
cn
c
c
o
c
0
o
c
o
CJ
Chrysene
Elms, 1 990
dissolved
particulate
funnel rinse
i i i t I i i i i r : i ; r | ¦ i i i i , i i i
-7-
i i i | i
UJ
20
1 6
12
8
Ch rysene
Elms, 1 99 1
*
3
1 1
3 3
i.H.l.if.P.I.B.P. ?77t6 , g. 0? ?. b
1
3
1
jl
8 j -7-
I I T I I I " '
8
**
10 15 20 25 30 35 40 45 50
Julian Week
Figure IV.1.29. Chrysene concentrations in precipitation integrated biweekly at the
Elms site. (1=not quantifiable in dissolved phase, 2 = not quantifiable
on filter, 3=not quantifiable in funnel, 4=not detected in dissolved
phase, 5 = not detected on filter, 6 = not detected in funnel, 7 = sampler
down, 8 = field blank, 8 = lost dissolved sample, ** = lost particulate sample,
° = lost funnel rinse). Funnel rinse combined with particulate fractions
after week 30, 1991. 134
-------
20
16
12
8
4
0
20
1 6
1 2
8
4
0
"i 1 1 1 1 r
Chrysene
Haven Beach,VA 1990
HH - dissolved
- particulate
- funnel rinse
| i i—i i | i i i i | i i i i | i i i i—| ( i i i | i—i i i—|—i—i—i i | i i i i | i i i i
i 1 1 1 1 r
i
Chrysene
Haven Beach.VA 1991
1 - p
.1,
hoi
\
liinSoQe
\
! ? V 8 I ,
i,9,
i T i T | T i ¦
5
1 ™ T i 1
1 0
| 1 1 1 1 | 1 1 1 1 | 1 1 1 1 | < i i i |
15 20 25 30 35
40 45
r i J i
50
Julian Week
135
-------
cn
c
c
o
250
200
150-
c
Q)
O
c
o
o
1 00
50
Benzo[6]fluoranthene
Elms, 1 990
HI dissolved
particulate
funnel rinse
c
c
o
¦*->
o
-M
c
a)
o
c
o
CJ
20
16 -
12 -
Benzo[6]fluoranthene
Elms, 1 991
8 -
*
3
4 -
LlL
-7-
l I I | i I l . l I I I I i I I I I | . i I . , I i I I | I l
3 8 3 -7-
1 i 1 1
-7-
UJJ
* 1
2 **
10
15
20
25
30
35
40
45
50
Julian Week
Figure IV.1.30. Benzo[6]fluoranthene concentrations in precipitation integrated biweekly at the
Elms and Haven Beach sites. (1=not quantifiable in dissolved phase, 2 = not
quantifiable on filter, 3 = not quantifiable in funnel, 4=not detected in dissolved
phase, 5=not detected on filter, 6=not detected in funnel, 7=sampler down,
8=fieId blank, + = lost dissolved sample, **=lost particulate sample, 0 = lost
funnel rinse). Funnel rinse combined with particulate fractions after week
30, 1991.
136
-------
20
1 6
12
8
4
0
20
1 6
12
8
4
0
Benzo[fa]fluoranthene
Haven Beach.VA 1990
- dissolved
— particulate
- funnel rinse
i i i i i i i i i I i i i i I i i > i I i i i i
i i i I i i i i I i i i i I i i
I 1 1 1 1 I 1
Benzo[b]fluoranthene
Haven Beach.VA 1991
B.g.i.l.B.I.U.g.y
I
g.B.o.T.p.g.y.U.T.;*?.!
*
n
T I I r
10 15 20 25 30 35
Julian Week
40 45
50
137
-------
30
cn
c
c
o
c
c
c
o
c
Q)
(J
c
o
o
Benzo[fc]fluoranthene
Elms, 1 990
dissolved
particulate
funnel rinse
W
Benzo[fc]fluoranthene
Elms,1 991
n n n
f
4 a
3
2 1
" 6
4 *
2 0
5
1 j 1 1
10
15
20
25
30
35
40
45
50.
Julian Week
Figure IV.1.31. Benzo[ifc]fluoranthene concentrations in precipitation integrated biweekly at the
Elms and Haven Beach sites.(l=not quantifiable in dissolved phase, 2 = not
quantifiable on filter, 3 = not quantifiable in funnel, 4=not detected in dissolved
phase, 5 = not detected on filter, 6 = not detected in funnel, 7 = sampler down,
8 = fieId blank, * = lost dissolved sample, ** = lost particulate sample, ° = lost
funnel rinse). Funnel rinse combined with particulate fractions after week
30, 1991.
138
-------
1 5
12
9
6
3
0
1 5
1 2
9
6
3
0
Benzo|_fc]fluoranthene
Haven Beach.VA 1990
- dissolved
- particulate
— funnel rinse
~i~ i i i i i r i i i i i i i | i
-i—i i i—| i i i—i—|—I I I I I i—I I I I 1 I I I | T I I I
i -
Benzo[A:]fluoranthene
Haven Beach.VA 1991
13 15 20 25 30 35
Julian Week
40 45 ' 50
139
-------
cn
c
c
o
c
QJ
U
c
o
o
40
30
20
10
cn
c
c
o
c
-------
1 2
9
6
3
0
1 2
9
6
3
0
Benzo[e]pyrene
Haven Beach,VA 1990
WM - dissolved
- particulate
— funnel rinse
i I l I I I i i i—1 i I i i | 1 i i i
n—i i i | i i i i |—r-
i r
Benzo[e]pyrene
Haven Beach,VA 1991
)j.U,p.y.y.y.B,3.y.?.o.g,J.U.9.v.?,i
n
L
I
1 1 1 1 I
5
T l i r
10 15 20 25 30 35
Julian Week
40 45 50
141
-------
180
150
120
90
60
30
12
9
6
3
1.33
Benzo[a]pyrene
Elms, 1 990
HI dissolved
particulate
funnel rinse
6
4
-7-
i i I I i i
| i i i i
Benzo[a]pyrene
Elms, 1 99 1
*
6
*
3
fi 6 6 6
1 1 1
IS
-7-
_EL
4 4
1
~, n , n
4
JL
*
2 **
10
15
20
25
30 35
40
45
50
Julian Week
Benzo[a]pyrene concentrations in precipitation integrated biweekly at the
[Ims and Haven Beach sites. (1=not quantifiable in dissolved phase, 2 = n
quantifiable on filter, 3 = not quantifiable in funnel, 4 = not detected in diss
jhase, 5 = not detected on filter, 6 = not detected in funnel, 7 = sampler
Jown, 8 = field blank, * = lost dissolved sample, ** = lost particulate sample,
' = lost funnel rinse). Funnel rinse combined with particulate fractions
3fter week 30, 1991.
142
-------
1 1 1 1—
Benzo[a]pyrene
Haven Beach.VA 1990
- dissolved
- particulate
- funnel rinse
"i r
Benzo[a]pyrene
Haven Beach, VA 1991
A
i
li
a
1
n
I
Ji
' i r
i r
*
n
H
i T i—i—|—r
I n
* ¦ T
8
1
jD_
1 I 1 1 1 1 I
45 50
1
1 T
5
1 0
T
1 5
20
I ' 1
25
30 35 40
Julian Week
143
-------
20
cn
c
£Z
o
15
cn
c
c
o
iz; 10
c.
-------
20
15
10
5
0
20
15
10
5
0
"i i i i r
lndeno[/, 2,3-cd] pyre ne
Haven Beach.VA 1990
— dissolved
— particulate
— "unnel rinse
i i i | i i i i | i i i i i i i i" i | i " i11 "i i i i
i 1 1 1 1 i 1 • 1 1 i 1 1 1 1 i 1 11 1 i 1
i
. i .
¦ I,..
X
lndeno[/,£,3 — cdjpyrene
Haven Beach.VA 1991
g ,1
3
**
i.p.v. s,i
3
*
IL
10 15 20 25 30 35
Julian Week
40 45
I
50
145
-------
25
20
15
10
5
4
3
2
1
D i t
:lm
)ua
>ha
l = fi
Dibenz[a, h]anthracene
Elms, 1 990
dissolved
I particulate
funnel rinse
4
-7— «
_~ 1 HL.
4
-a.
Dibenz[a, h] anthracene
Elms, 1991
XL
ill
4
6
n
n
-7-
a 5 5
4 4 +
5 5 5 8
5 *
T"1"
40
A
5 **
Is1 rT
10
15
20
30
35
45
50
Julian Week
nz[a,/i]anthracene concentrations in precipitation integrated biweekly at the
and Haven Beach sites,(l=not quantifiable in dissolved phase, 2=not
ifiable on filter, 3=not quantifiable in funnel, 4=not detected in dissolved
5=not detected on filter, 6=not detected in funnel, 7=sampler down,
d blank, * = lost dissolved sample, ** = lost particulate sample, ° = lost funn<
Funnel rinse combined with particulate fractions after week 30, 1991.
146
-------
4
3
2
1
0
5
4
3
2
1
0
i I 1 1
Dibenz[a, h~\ anthracene
Haven Beach.VA 1990
- dissolved
- particulate
- funnel rinse
I l I "i" | I I I i | I I I I—| I I I I | I I I—I—|—I I I—I—j—1—I—I—1—|—I—I—I—i—|—i—i i i |
I
Dibenz[a, h]anthracene
Haven Beach.VA 1990
2
6
2
3
3
5
3
5 6
. 111 Vi111 [ 11
2
3 2
R l n |,4-
1
3 3
**
\
\
\
25
8
1
3 * 1
2 3
3 n
10 15 20
30
35 40 45 50
Julian Week
147
-------
1 5
1 2
9
6
3
1 5
1 2
9
6
3
6. E
E
q
P
8
Benzo[g, h, ijperylene
Elms, 1 990
dissolved
particulate
funnel rinse
5
4
-7-
y
8
-7-
I ' 1,1 I
Benzofg, h, i]perylene
Elms, 1 99 1
6 *
I r7rU, IIs ?, 0, U
4
JL
8
f—I—I—j 'I' l 'I' I
45
4
**
10
15
20
25
30
35
40
50
Julian Week
enzo[<7,/i,i]perylene concentrations in precipitation integrated biweekly at the
Ims and Haven Beach sites. (1=not quantifiable in dissolved phase, 2 = not
jantifiable on filter, 3 = not quantifiable in funnel, 4 = not detected in dissolvec
iase, 5 = not detected on filter, 6 = not detected in funnel, 7 = sampler down,
= fieId blank, *lost dissolved sample, ** = lost particulate sample, 0 = lost
nnel rinse). Funnel rinse combined with particulate fractions after
ek 30, 1991.
148
-------
15
1 2
9
6
3
0
15
1 2
9
6
3
0
Benzofgf, /i,i]perylene
Haven Beach.VA 1990
¦i — dissolved
- particulate
- funnel rinse
i i | i » i i [ i i i i | i i i i | i i i i |—i i i i | i i i i |
-1—i—r—i—|—i i i—i—|-
I I I I I I
Benzo[gr, h, ijperylene
Haven Beach.VA 1991
IX
**
8
1
a
10
I
15
20 25 30 35
Julian Week
40 45 50
149
-------
CD
CL
C
o
c
d)
CJ
c
o
CJ
4000
3000
cn
Q.
c
o
2000
£ 1000
1200
900
600 -
300 -
Trichlorobiphenyls, Rain
Elms, 1990
HI dissolved
particulate
funnel rinse
I i i i
-7-
Lag
-7-
: . i i ;
Trichlorobiphenyls, Rain
Elms, 1991
M
*
-P^J
10
15 20 25
30 3.5
40
45
50
Julian Week
Figure IV.1.37. Total trichlorobiphenyl concentrations in precipitation integrated
biweekly at the Elms and Haven Beach sites.1 = not quantifiable in dissolved
2 = not quantifiable on filter, 3 not quantifiable in funnel, 4- =
not detected in dissolved phase, 5 = not detected on filter, 6 = not
detected in funnel, 7 = samplgQ down, 8 = field blank, * = lost dissolved
samples, ° = lost funnel rinse). Funnel rinse combined with particulate
-------
1 200
900
600
300
0
1500
1200
900
600
300
0
i 1 1 r
T richlorobiphenyls
Haven Beach,VA 1990
- dissolved
— particulate
— funnel rinse
i i i i | i i i i | i i i i | i i i i | i i i i | i i i i [ » i i i | > I I I | I i I ) j i i I i | »
il
Trichlorobiphenyls
Haven Beach,VA 1991
3 1
111 1
2 2 2 ,3
I n 3 3 3 «« n I
T l T I l I I I I I I l t f™lTl | lTlT
2 2
3 3
1
I
10 15 20 25 30 35 40 45 50
Julian Week
151
-------
12000
CD
CL
c
o
c
-------
1 6Q0
1200
800
400
0
1600
1200
800
400
0
Tetrochlorobi phenyls
Haven Beoch.VA 1990
— dissolved
— particulate
— funnel rinse
T—I f—| [ I 1 1 1—| >—I—I !—f-
-]—i—i—i—i—j—i—i—c—i—|—i—i—i—i—|—i—i—i—i—|—i—i—r—i—I—i—r"
Tetrachlorobiphenyls
Haven Beach.VA 1991
20 25 30 35 40 45 50
Julian Week
153
-------
12000
9000
CD
CL
e
o
c
Q)
O
c
o
o
6000
3000
2400
2000
g 1600
c
•° 1 200
o
c
-------
2400
2000
1 600
1200
800
400
0
2400
2000
1 600
1200
800
400
0
1 1 1 1
Pentachlorobiphenyls
Haven Beach,VA 1990
— dissolved
— particulate
— funnel rinse
i i i i I r
-I—I—J—|—I—I—I—I—|—I—I—T—l—1—I—r—I—I—J—I—I—I—I—|—I—I—I—I—|—I—1—I—I | I 1—P—T—I—I—I 1—i \ i_H
Pentachlorobiphenyls
Haven Beach,VA 1991
3
3
5
s
s,
3
1 **
1 2 1 3 1
Ji u
5 10
l-rT-r"
15
1
2
3
1 i 1
20
3 3 I
B 0 ** 1 3
liUl
25 30 35
1 2
lilli
40 45 50
Julian Week
155
-------
CJI
Q_
C
o
c
CD
O
c
O
O
10000
8000
6000
4000
2000
cn
CL
c
o
c
-------
1 400
1200
1000
800
n 1 H 1 1
Total Hexachlorobiphenyls
Haven Beach, VA 1990
HI — dissolved
i r
"i r
- particulate
— funnel rinse
600
400
200
0
1400
1200 -
| I I I I | I I I I | I I I I | I—i I I j I I I I | I I I I | I I I I | I I I I | I I I I |
Total Hexachlorobiphenyls
Haven Beach, VA 1991
1000
0 5 10 15 20 25 30 35 40 45 50
Julian Week
157
-------
4000
3000
cn
CL
c
o
2000
c
¦1 i
50
Figure IV. 1 .41 .
Julian Week
Total heptachlorobiphenyl concentrations in precipitation integrated
biweekly at the Elms and Haven Beach sites. (1 = not quantifiable in
dissolved phase, 2 = not quantifiable on filter, 3 not quantifiable in funnel,
4 = not detected in dissolved phase, 5 = not detected on filter, 6 = not
detected in funnel, 7 = sampler down, 8 = field blank, * = lost dissolved
samples, ° = lost funnel 'inse). Funnel rinse combined with particulate
fraction after week 30, 19fc5§
-------
800
600
400
200
0
000
800
600
400
200
0
n 1 1 1 1 1 1 1 r
Total Heptachlorobiphenyls
Haven Beach, VA 1990
— dissolved
— particulate
— funnel rinse
#4
1^1
2 3
5
M-
Total Heptachlorobiphenyls
Haven Beach,VA 1991
ll.vil
1 4
2 5 n
2
3
8
2
6
X
-P-
10 15 20 25 30
Julian Week
35
40
45
50
159
-------
cr>
Q.
c
o
c
(U
U
c
o
o
1000
800
600
400
200
c
Q)
U
C
o
o
Octachlorobiphenyls
Elms, 1990
IH dissolved
particulate
funnel rinse
-7-
¦7 : i—r"
! ! I I I T
UJ
-7-
600
500
^ 400
c
o
300
~
200
100
Octachlorobiphenyls
Elms, 1991
jn
,n a,B
10
15
20 25 30 35
40
45 50
Julian Week
Figure IV. 1.42. Total octachlorobiphenyl concentrations in precipitation integrated
biweekly at the Elms and Haven Beach sites.(1 = not quantifiable in ,
dissolved phase, 2 = not quantifiable on filter, 3 not quantifiable in funnel,
4 = not detected in disso vsd phase, 5 = not detected on filter, 6 = not
detected in funnel, 7 = sampler down, 8 = field blank, * = lost dissolved
samples, ° = lost funnel rirse). Funnel rinse combined with particulate
fraction after week 30, 19360
-------
700
600
500
400
300
200
100
0
700
600
500
400
300
200
100
0
Octach I orobi phenyls
Haven Beach.VA 1990
— dissolved
— particulate
— funnel rinse
\
-i—j i i—n—|—i—n—i—|—i—i—i—i—|—i—i—i—i—|—i—i—i—i—J—i—r-1—i—f~i—i—i i |—i—i—i—i—|—r-i—i—i | i 1 i 1
i r
n 1 1 r
Octach I orobi phenyls
Haven Beach.VA 1991
10 15 20 25 30 35 40 45 50
Julian Week
161
-------
400
CD
CL
c
o
c
CL
c
o
200
o
c
0)
o
c
o
o
1 00
Nonachlorobiphenyls
Elms, 1990
dissolved
particulate
funnel rinse
4
5
4
6
-7-
2
1 60
Nonachlorobiphenyls
Elms, 1991
1 20
80 -
40
1
3
i-H
n
8
MP
20 25 30
Julian Week
n,fl
a
35 40 45 50
Figure IV. 1.43.
Total nonachlorobiphenyl concentrations in precipitation integrated
biweekly at the Elms anc Haven Beach sites. (1 = not quantifiable in
dissolved phase, 2 = not quantifiable on filter, 3 = not quantifiable in funm
4= not detected in dissolved phase, 5 = not detected on filter, 6 = not
detected in funnel, 7 = sampler down, 8 = field blank, * = lost dissolved
samples, 0 = lost funnel fji^e). Funnel rinse combined with particulate
fraction after week 30, 1
-------
1 6
1 2
8
4
0
30
25
20
1 5
10
5
0
Total Nonachlorobiphenyls
Haven Beach, VA 1990
IH - dissolved
- particulate
- funnel rinse
4
5
6
I I I I I I I I I I I I I I I I
I I I I I I I
1 1 I ' ' ' ' I
Total Nonachlorobiphenyls
Haven Beach, VA 1991
2
6
2
6
1
3
3
4
3
4
1
3
**
1 ° 1
6 1 2
n 5 6
1
3
3
4
4
5
6
i i r i r i—i—i—i iii i
3
* *
I
3
4
_a
4
6
4 1 4
5 5 5
6 6 6
4
5
6
2
4
4
6
4
5
6 8 6
4
5
6
4
6~
n—i—i—i—| i i 'i' i |—rnr
)
1 o
15
20
25
30
35
40
45
50
Julian Week
163
-------
40000
30000
cn
Q.
c
£ 20000
o
-t-j
c
0)
u
° 10000
8000
Total PCBs
Elms, 1990
1^1 dissolved
particulate
funnel rinse
n a
-7- a I s
8
-7-
Total PCBs
Elms, 1991
6000
CT>
CL
c
5 4000
o
-i—i
c
a)
o
J 2000
10 15 20 25
30 35
* 8
i 1 l 1 i i
*
n
40
45 50
Julian Week
Figure IV.1.44. Total PCB concentration in precipitation integrated biweekly at the Elms
and Haven Beach sites. (1=not quantifiable in dissolved phase, 2 = not
quantifiable on filter, 3 = not quantifiable in funnel.4 = not detected in
dissolved phase, 5 = not detected on filter, 6= not detected in funnel,7 =
sampler down, * = lost dissolved samples). Funnel rinse combined with
particulate fractions after 30, 1991.
-------
8000
6000
4000
2000
0
8000
6000
4000
2000
0
Total PCBs
Haven Beach.VA 1990
— dissolved
— particulate
— funnel rinse
i—i—i—|—i—i—i—i—|—i—i—i—i—|—i—m—i—|—i—m—i—|—i—i—i—i—j—i—i—i—i—|—i—i—r—i—j—i—i—i—i—|—i i i i—p
1
4t
Uilo
1
Total PCBs
Haven Beach,VA 1991
\ r—j
I I - III
10 15 20 25 30 35 40 45 50
Julian Week
165
-------
Figure IV.1.45. Fluorene wet depositiona fluxes measured at the Elms and Haven
Beach sites. (l=not quantifiable in dissolved phase, 2 = not quantifiable on*
filter, 3 = not quantifiable in funnel, 4 = not detected in dissolved
phase, 5 = not detected o~ filter, 6 = not detected in funnel, 7 =
sampler down, * = lost dissolved samples). Particulate fraction
after June, 1991 includes funnel rinse.
c
o
£
CM
500
400
300
"i 1 1 1 1 1 1 1 r
Fluorene - Haven Beach, VA 1991
HB — dissolved
"i r
— particulate K\N ~ funnel rinse
ai
c
X
=3
CD
200
100
*L-
i i^Pi i i i^Pi i i i^Pi i i i i i i n i i i i i r" T i i i i I i i i i
J FMAMJ JASOND
Month
166
-------
800
-C
C 600
CM
Cn
c
X
3
c
X
-------
Figure IV.1.46. Phenanthrene wet depositional fluxes measured at the Elms and Haven
Beach sites. (1=not quantifiable in dissolved phase, 2 = not quantifiable on
filter, 3 = not quantifiable in funnel, 4 = not detected in dissolved
phase, 5 = not detected on filter, 6 = not detected in funnel, 7 =
sampler down, * = lost dissolved samples). Particulate fraction
after June, 1991 includes funnel rinse.
c
o
E
cr>
c
X
=3
(0
2400
2000
1 600
1200
800
400
"i 1 1 1 1 1 1 1 r
Phenanthrene — Haven Beach, VA 1991
- dissolved
— particulate
1 r
— funnel rinse -
1-
i i i i i r I' i i i i 1 i—i—i i f i i—i—i | i—i—i—r
J F M A M J J
Month
168
-------
2500
2000
1500
1000
500
i 1 1 1
Phenanthrene
Elms, 1 990
HH dissolved
particulate
funnel rinse
1 r
i i r
\
"T—1 I—I—1 !—I I" I I I I I—I 1 I 1—I—1—1—I—I PI I I 1 T~
"i r
"i i r
2500
2000
1500
1000
500
Phenanthrene
- Elms.1991
1 r
J F M A M J J
Month
A S 0 N D
169
-------
Figure IV.1.47. Anthracene wet depositional fluxes measured at the Elms and Haven Beach
sites.(1=not quantifiable in dissolved phase, 2 = not quantifiable on
filter, 3 = not quantifiable in funnel, 4 = not detected in dissolved
phase, 5 = not detected on filter, 6 = not detected in funnel, 7 =
sampler down, * = lost dissolved samples). Particulate fraction
after June, 1991 includes funnel rinse.
125
100
1 1 1 1 1 1 1 1
Anthracene - Haven Beach, VA 1991
HI — dissolved
- particulate
~i r
— funnel rinse
-------
C 300
o
CM
en
c
X
=3
CD
200
100
c 300
o
E
CM
en
c
X
3
0)
200
100
0
I I
Anthracene
Elms, 1 990
dissolved
particulate
funnel rinse
i i i r
Anthracene
Elms, 1 991
N
I l
I 1 1 1 1 I
B B I g 8 y g n- n B
'¦III'
I ' ' ' 1 I ' ' ' ' 1 1 ' ' ' 1
I 1 1 1 1 I
M
M
J A
Month
0
N D
171
-------
Figure.IV. 1 .48. Fluoranthene wet depositional fluxes measured at the Elms and
Haven Beach sites. (1 =not quantifiable in dissolved phase, 2 =
not quantifiable on filter, 3 =not quantifiable in funnel, 4= not
detected in dissolved phase, 5= not detected on filter, 6= not
detected in funnel, 7= sampler doan, *= lost dissolved sample).
Particulate fraction after June,1991 includes funnel rinse.
c
o
E
CN
cr>
c
X
D
a;
1 800
1500
1200
900
300
i r
~i 1—
Fluoranthene— Haven Beach, VA 1991
HH - dissolved
1 1 1 r
- particulate K\N ~ funnel rinse
600
-
s
Month
172
-------
12000
o 9000
E
CN
£ 6000
cn 1500 7
I I I I
I I
Fluoranthene
Elms, 1 990
dissolved
particulate
funnel rinse
X
1000
Li_
0)
500
1 800
1500
c
o
E 1200
CM
cn
c
X
rj
900
3 600
-------
Figure IV.1.49. Pyrene wet depositional fluxes measured at the Elms and Haven
Beach sites. (l=not quantifiable in dissolved phase, 2 = not quantifiable on
filter, 3 = not quantifiable in funnel, 4 — nat detected in dissolved
phase, 5 = not detected on filter, 6 = not detected in funnel, 7 =
sampler down, * = lost dissolved samples). Particulate fraction
after June, 1991 includes funnel rinse.
1200
1000
8 00
600 -
400 -
200 -
0
~i 1 1 1 1 1 r
Pyrene Haven Beach, VA 1991
- dissolved
i r
— particulate \\\ — funnel rinse
Month
174
-------
C 9000
o
E
CM
C7>
C
X
3
-------
Figure IV.1.50. Benz[a]anthracene wet depositional fluxes measured at the Elms and Haven
Beach sites.(l=not quantifiable in dissolved phase, 2 = not quantifiable on
filter, 3 = not quantifiable in funnel, 4 = not detected in dissolved
phase, 5 = not detected on filter, 6 = not detected in funnel, 7 =
Isampler down, * = lost dissolved samples). Particulate fraction
after June, 1991 includes funnel rinse.
c
o
£
en
c
X
D
a;
1 "75 1 1 1 1 1 1 1 1 1 i i i
Benz[a]anthracene —Haven Beach, VA 1991
- funnel rinse
150 -
125 -
100 -
75 -
50 -
25 -
— dissolved j_^j — particulate
J FMAMJ JASOND
Month
176
-------
1 200
c
o
E
900
CM
cn
c
X
3
c
X
3
-------
Figure IV.1.51. Chrysene wet depositional fluxes measured at the Elms and Haven Beach
sites. (1=not quantif able in dissolved phase, 2 = not quantifiable on
filter, 3 = not quantifiable in funnel, 4 = not detected in dissolved
phase, 5 = not detected on filter, 6 = not detected in funnel, 7 =
sampler down, * = lost dissolved samples). Particulate fraction
after June, 1991 includes funnel rinse.
c
o
E
Di
C
X
J3
Li_
(D
675
600
525
"I 1 1 1 1 1 1
Chrysene —Haven Beach, VA 1991
¦¦ - dissolved
1 1 r
— particulate K\N — funnel rinse
Month
178
-------
_c
c 3000
o
E
CM
cn
c •
X
D
-------
Figure IV.1.52. Benzo[6]fluoranthene wet depositional fluxes measured at the Elms and Haven
Beach sites. (l=not quantifiable in dissolved phase, 2 = not quantifiable on
filter, 3 = not quantifiable in funnel, 4 = not detected in dissolved
phase, 5 = not detected on filter, 6 = not detected in funnel, 7 =
sampler down, * = lost dissolved samples). Particulate fraction
after June, 1991 includes funnel rinse.
1 1 1 1 I 1 l
— Haven Beach, VA 1991
- particulate K\N - funnel rinse
i r
600
500
400
300
200
100
0
Benzo[6]fluoranthene
¦i - dissolved
i
i i i i^Pi i i i^Pi i i i^Pi i i i^Ti i i i V i i v i I i i i i
i
[V
\
X
¦
x:
A M J J A S
Qr
0 N D
'i I I i i i I I q'l I i i^Pi i I I I" I I I I I I I I I
Month
180
-------
I I
~ i i i i r
i i
c
o
E
CNJ
C7>
c
X
D
4000
3000
2000
«? 1000
Benzo[6]fluoranthene
Elms, 1990
MM dissolved
particulate
K\\| funnel rinse
\
\
\
\
\
t\
0 200
Month
2
3 3
-IZL
-7-
I 1 1 ' 1 I
Benzo[6]fluoranthene
Elms, 1 991
0 N D
181
-------
Figure IV.1.53. Benzo[ifc]fluoranthene v^et depositional fluxes measured at the Elms and Haven
Beach sites. (1=no: quantifiable in dissolved phase, 2 = not quantifiable on
filter, 3 = not quantifiab e in funnel, 4 = not detected in dissolved
phase, 5 = not detected on filter, 6 = not detected in funnel, 7 =
Isampler down, * = lost dissolved samples). Particulate fraction
after June, 1991 induces funnel rinse.
400
300 -
200 -
100 -
~l I I I I I I 1 l I I I
Benzo[fc]fluoranthene —Haven Beach, VA 1991
- funnel rinse
— dissolved
— particulate
I J l^~T—r-T Til 1 I I
,p,,, ,y,,, ij,,, ,g,
I 1 I I I I ! I
JFMAMJJASOND
Month
182
-------
4000
c
o
E
cn 3000
E
cn
c
X
u
0)
2000
1000
400
-C
C 300
o
E
CM
cn
c
X
3
-------
Figure IV.1.54. Benzo[e]pyrene wet depositional fluxes measured at the Elms and Haven
Beach sites. (1=not quantifiable in dissolved phase, 2 = not quantifiable on
filter, 3 = not quantifiable in funnel, 4 = not detected in dissolved
phase, 5 = not detected on filter, 6 = not detected in funnel, 7 = not
analyzed, 8 = sampler down, * = lost dissolved samples). Particulate
fraction after June, 1991 includes funnel rinse. .
500
400 -
300 -
200 -
100 -
l l l l ll l l
Benzo[e]pyrene -Haven Beach, VA 1991
— dissolved
— funnel rinse
- particulate
9
Month
184
-------
600
500
c
o
E 400
C\l
cn
c
300
Z 200
Li_
0)
100
i i i i i i i~
Benzo[e]pyrene
Elms, 1 990
dissolved
particulate
funnel rinse
I I
7
600
500
c
o
E 400
CM
cn
c
300
J 200
(D
100
i i i i | I i i i | i ¦ i i | i i . i | ~—r-i—i—[—, . , ,—j—:—. . .—| i i i i
1 1 1 1 1 1 i
\
i 1 1 1 r
Benzo[e]pyrene
Elms, 1 991
i i i i
¦i i i i i . .
i i i—r^^i—i—i——r-i—r
M A M J J A
Month
i 1 1 i 1 1 1 i 1
S 0 N D
185
-------
Figure IV.1.55. Benzo[a]pyrene wet depositional fluxes measjred at the Elms and Haven
Beach sites. (l=not quantifiable in dissolved phase, 2 = not quantifiable on
filter, 3 = not quantifiable in fjnnel, 4 = not defected in dissolved
phase, 5 = not de-.ected on filter, 6 = not detected in funnel, 7 =
Isampler down, * = lost dissolved samples). Particulate fraction
after June, 1991 includes funnel rinse.
1 T
c
o
CN
cr>
c
X
=3
Q)
300 -
200 -
100 -
—i 1 1 i i i n
Benzo[a]pyrene -Haven Beach, VA 1991
jj^H - dissolved
l l r
- particulate NNN - funnel rinse
r-rJpi—n J | 1
0 N
| I I I I
D
Month
186
-------
800
c
o
E 600
CM
C7>
sS 400
X
3
CD 200
i i I i
Benzo[a]pyrene
Elms, 1 990
dissolved
particulate
funnel rinse
1(1'
3
4
1 1 1 ¦ i 1 ¦ 1 1 i 1 ¦ ¦ ¦ i
i—i—i—i—i—m—r-f
i 1 I
\
\
[\
\
\
3
O.
i , i . . ,
•7-
i i i ¦ '
800
c
o
E 600
CM
CP
v5 400
X
¦D
a> 200
ss
~i r
i 1 i r
T
Benzo[a]pyrene
Elms, 1 991
M A
1 4 1
¦a
| i i i 'i i i h i I | m i f p
M J J A S
i 1 1 i
0 N
M-
D
Month
187
-------
Figure IV.1.56. lndeno[ 1,2,3 — cdjpyrene wet depositional fluxes measured at the Elms and
Haven Beach sites.(1=not quantifiable in dissolved phase, 2 = not quantifiable
on filter, 3 = not quantifiable in funnel, 4 = not detected in dissolved
phase, 5 = not detected on filter, 6 = not detected in funnel, 7 =
sampler down, * = lost disso ved samples). Particulate fraction
after June, 1991 includes funnel rinse.
700
600
1 I I I I I I I I I I I
lndeno[ 7,2,3 — cdjpyrene —Haven Beach, VA 1991
— funnel rinse
- dissolved
— particulate
500
400
300
200
100
I
i » i iTi i i i
s:
riiiTiiii
F M
S 0 N D
Month
188
-------
I
700
600
_c
c
o
500
E
/
CN
400
E
/
en
c:
300
X
D
iZ
200
CD
100
700
600
,—\
s:
-*->
c
o
500
E
/
/
CM
400
E
/
cn
c
300
X
13
Li_
200
a)
100
r
1 r
till
lndeno[7,2,3-cd]pyrene
Elms, 1 990
dissolved
particulate
funnel rinse
i i I i i i i | i i i i | l i i i I i < < • I i • < . I • • • • I • • i i |
—i 1 1 1 1 1 1—
Lo
-7-
i r
lndeno[7,2,3 — cc£]pyrene
Elms,1991
UJ
-T—j-
i i
« i . t i i
JFMAMJJASOND
Month
189
-------
Figure IV.1.57. Dibenz[a,/ijanthracene wet depositional fluxes measured at the Elms and Haven
Beach sites. (1=not quantifiable in dissolved phase, 2 = not quantifiable on
filter, 3 = not quantifiable in funnel, 4 = not detected in dissolved
phase, 5 = not detected on filter, 6 = not detected n funnel, 7 =
sampler down, * = lost dissolved samples). Particulate fraction
after June, 1991 includes funnel rinse.
1 00
\ r
c
o
E
cn
c
X
D
-------
I I
Dibenz[a, h]anthracene
Elms,1 990
dissolved
particulate
funnel rinse
i 1 1 1 ! i
i—n—;—|—;—i—i—i—i—i—i—r
"1 1 1 T
i r
\
i 1 1 1 ¦ i 1 1 ¦ 1 i • 1 ¦ 1 i
u
I I
3 3
Li
-7-
, , , , ,-pi I I I , , I , I
1 1 1 1 1 r
Dibenz[ a, h~\ anthracene
Elms, 1 99 1
M A M J J
Month
i ¦ ¦ ¦ 1 i
A S 0 N
2
D
191
-------
Figure IV.1.58. Benzoffir./i.-ijperylene wet depositional fluxes measured at the Elms and Haven
Beach sites. (l=not quantifiable in dissolved phase, 2 = not quantifiable on
filter, 3 = not quantif able in funnel, 4 = not detected in dissolved
phase, 5 = not detected on filter, 6 = not detected in funnel, 7 =
sampler down, * = lost dissolved samples). Particulate fraction
after June, 1991 includes funrel rinse.
600
1 1 1 1 1 1 1 1 1 1 1 I
Benzo[g,/i,i]perylene -Haven Beach, VA 1991
— funnel rinse
500 -
- dissolved
- particulate
c
o
E
CTi
C
X
D
-------
600
_ 500
sz
c
o
E 400
CM
cn
c
300
x
2. 200
Li-
QJ
100
I I
Benzo[flr, Ai,i]perylene
Elms, 1 990
1^1 dissolved
particulate
funnel rinse
i I i i i . i i i I I i i i I I I i i I i i I I
600
500
c
o
E 400
CM
cn
c
300
x
_2 200
-------
Figure IV.1.59. Trichlorobiphenyl wet depos'tional fluxes measured at the Elms and Haven
Beach sites. (1=not quantifiable in dissolved phase, 2 = not quantifiable on
filter, 3 = not quantifiable in funnel, 4 = not deiected in dissolved
phase, 5 = not detected on filter, 6 = not detected in funnel, 7 = not
analyzed, 8 = sampler down, * = lost dissolved samples). Particulate
fraction after June, 1991 includes funnel rinse.
80
1 r
"i 1 1 1 r
n 1 r
60
40
20
Trichlorobiphenyls — haven Beach, YA 1991
— funnel rinse
— dissolved
— particulate
I
n
I T T^f I I I | I I I l| i I I i
I I
F M A M J
A S 0 N D
Month
194
-------
80
c
o
60
CM
CP
c
X
=3
0)
40
20
80
i i
Trichlorobiphenyls
Elms, 1 990
WM dissolved
particulate
funnel rinse
i r
Trichlorobiphenyls
Elms, 1 991
174'. 2
in1 > I >
' 1 1 I 1 ¦ ' M • ¦ ¦ ' i 1 ¦ 1 1 i 1 1 1 • i 1 ¦ ¦ ' I ' ' • 1 i ' • ' ~
I ii
-7-
n r
c
o
E
60
CM
cn
c
40
x
13
-------
Figure IV.1.60. Tetrachlorobiphenyl wet depositional fluxes measured at the Elms and Haven.
Beach sites. (1=not quantifiable in dissolved phase, 2 = not quantifiable on
filter, 3 = not quantifiable in funnel, 4 = not detected in dissolved
phase, 5 = not detected on filter, 6 = not detected in funnel, 7 = not
analyzed, 8 = sampler down, * = lost dissolved samples). Particulate
fraction after June, 1991 includes funnel rinse.
c
o
E
CN
cn
c
X
=3
CD
100
80
60
40
20
l r
"I 1 1 I 1 1 1 1 1 1
Tetrachlorob'phenyls - Haven Beacn, VA 1991
- funnel rinse
- dissolved
- particulate
IXL
t—i i i I i i i i ii i i i
J F M
N
^
I
*
i—i—i i I i—i—i i I i—i—i iT'i—rn—r~
0 N D
Month
196
-------
1 50
1 00
50 -
1 50
100
50
Tetrachlorobiphenyls
Elms, 1 990
dissolved
particulate
funnel rinse
i i
Tetrachlorobiphenyls
Elms, 1 991
Month
197
-------
Figure IV.1.61. Pentachlorobiphenyl wet depositional fluxes mecsured at the Elms and Haven
Beach sites. (1=not quantifiable in dissolved phase, 2 = not quantifiable on
filter, 3 = not quantifiable in funnel, 4 = not detected in dissolved
phase, 5 = not detected on filter, 6 = not detecteo in funnel, 7 = not
analyzed, 8 = sampler down, * = lost dissolved samples). Particulate
fraction after June, 1991 includes funnel rinse.
1 75
"I r
1 r
"i r
c
o
E
CN
D1
C
X
3
a>
150
125
100 -
75 -
50 -
25
Pentachlorobiphenyls — Haven Beacn, VA 1991
— funnel rinse
- dissolved
— particulate
J FMAMJJASOND
Month
198
-------
1 75
150
1 25
100
75
50
25
1 75
1 50
125
100
75
50
25
~i 1 1 1 i r
Pentachlorobiphenyls
Elms, 1 990
dissolved
particulate
funnel rinse
I I
N
B
1 1 • ¦ i 1 1 ¦ 1 i 1 1 • 1 i 1 ¦ 1 1 i ¦ ¦ 1 ¦ t 1 1 1 1 i - 1 1
1 1 1 1 1 1
¦ I i
la
i r
-7-
I I j 11 11 I I
Pentachlorobiphenyls
Elms, 1 991
J FMAMJJASOND
Month
199
-------
Figure IV.1.62. Hexachlorobiphenyl wet depositional fluxes measured at the Elms and Haven
Baech sites. (1=not quantifiable in dissolved phase, 2 = not quantifiable on
filter, 3 = not quantifiable in funnel, 4 = not detected in dissolved
phase, 5 = not detected on filter, 6 = not detected in funnel, 7 = not
analyzed, 8 = sampler down, * = lost dissolved samples). Particulate
fraction after June, 1991 includes funnel rinse.
100
"I 1 1 T
i r
c
o
E
cn
c
X
=3
Q)
80 -
60 -
40 -
20
0
Hexachlorobiphenyls — Haven Beach, VA 1991
— funnel rinse
- dissolved
— particulate
JFMAMJJAS0ND
Month
200
-------
1 00
80
c
o
E
CM 60
I I I I
Hexachlorobiphenyls
Elms, 1 990
M dissolved
particulate
funnel rinse
i i
i i i i
cn
c
X
D
40
0 20
100
80
c
o
E
^ 60
' ' I ' ' • ' 1 1 '
I ¦ I • i i . I . i i
i r
\
Li
\
1
-7-
i : 1 1 ¦ i 1 1 ¦ ¦ i ¦ ¦ ' ¦i 11¦ | | ,
Hexachlorobiphenyls
Elms, 1 991
i 1 1 1 i 1 1 r
CD
c
X
D
40
a) 20
Month
201
-------
Figure IV.1.63. Heptachlorobiphenyl wet depositional fluxes measured at the Elms and
Haven Beach sites. (l=not quantifiable in dissolved phase, 2 = not
quantifiable on filter, 3 = not quantifiable in funnel, 4 = not detected in
dissolved phase, 5 = not detected on filter, 6 = not detected in funnel, 7 =
not analyzed, 8 = sampler down, * = lost dissolved samples). Particulate
fraction after June, 1991 includes funnel rinse.
60
i 1 1 1 1 r
c
o
E
CD
C
X
13
CD
50 -
40 -
30 -
20
10 -
Heptachlorobiphenyls — Haven Beach, VA 1991
— funnel rinse
dissolved
- particulate
J FMAMJ JAS0ND
Month
202
-------
I I I I
I I
I I
Heptachlorobiphenyls
Elms, 1 990
HI dissolved
particulate
funnel rinse
i ! 1 1 ¦ i • 1 ¦ • i
¦ , i t i i
\
X
i 1 1 1 1 i • ¦ ¦ 1 i
\
Jj
N
-7-
I 1 ' 1 1 I 1 1 1
n r
"i r
Heptachlorobiphenyls
Elms,1991
i i
Month
i 1 1 ¦
A S 0 N D
203
-------
Figure IV.1.64. Octachlorobiphenyl wet cepositional fluxes measured at the Elms and Have_
Beach sites. (l=not quantifiable in dissolved phase, 2 = not quantifiable on
filter, 3 = not quantifiable in funnel, 4 = not detected in dissolved
phase, 5 = not detected cn filter, 6 = not detected in funnel, 7 = not
analyzed, 8 = sampler down, * = lost dissolved samples). Particulate
fraction after June, 1991 includes funnel rinse.
20
"i i i i i i i i i r
1 6
Octachlorobiphenyls - Haven Beach, VA 1991
— funnel rinse
— dissolved — particulate
12 -
8
I 1 I 7 I I
TT-ffn-TT
0 N D
Month
204
-------
I I
I I
< t I I
Octachlorobiphenyls
Elms, 1 990
dissolved
particulate
funnel rinse
i ¦ 1 1 1 i
i 1 ¦ 1 1 i
"i r
N
\
\
¦ ¦ - -
' ' ' ' I 1 1 ' ' I 1
-7-
1 i 1
"i i i i i r
Octachlorobiphenyls
Elms, 1 991
A S 0 N D
205
-------
Figure IV.1.65. Nonachlorobiphenyl wet depositional fluxes measured at the Elms and
Haven Beach sites. (1=rot quantifiable in dissolved phase, 2 = not
iIter, 3 = not quantifiable in funnel, 4 = not detected in dissolved
phase, 5 = not detected cn filter, 6 = not detected in funnel, 7 = not
analyzed, 8 = sampler cown, * = lost dissolved samples). Particulate
fraction after June, 1991 includes funnel rinse.
2.0
1.5
1.0
0.5
0.0
"i 1 1 r
"i 1 r
Nonachlorobiphenyls — Haven Beach, VA 1991
— funnel rinse
— dissolved — particulate
i i i i
I
i ¦ 1 1 1 i
i i i r ii i i r i i i i i ii i i >
|i i i r J 'i i i r | i i i r |
FMAMJ JASOND
Month
206
-------
"i r
Nonachlorobiphenyls
Elms, 1 990
HH dissolved
particulate
funnel rinse
n i r
N
\
I 1 I I—I" '("I I I I I I I I I I I I
0
.
J
-7-
I I I i
Nonachlorobiphenyls
Elms, 1 991
N
i r
ju
1
3
¦j—i—i i i | i i i i | i i ' i J
J F M A M J J
A S 0 N D
Month
207
-------
Figure IV.1.66. Total PCBs wet depositional fluxes measured at the Elms and Haven Beach
sites. (1=not quantifiable in d'ssolved phase, 2 = not quantifiable on
filter, 3 = not quantifiable in funnel, 4 = not detected in dissolved
phase, 5 = not detected on filter, 6 = not detected in funnel, 7 = not
analyzed, 8 = sampler down, * = lost dissolved samples). Particulate
fraction after June, 1991 includes funnel rinse.
500
c
o
E
CM
CP
c
X
D
-------
500
o 400
E
CM
300
cn
c
X 200
~
•
1 I 1 1 1
I I
l—i—i——i—i——¦—1——¦—¦—;^i
-7-
i i i ' i i
"i r
n i r
I
—:—•.——:—i——>—:—i(l—:—:—^—>—i—^—i—>—I—i—:—
JFMAMJJAS
Month
• • -T. • • 'T1- ¦ • It
0 N D
209
-------
600 -
400 -
Wye
1 990
Al j Tiinum
(aerosol particles)
200 -
i i i i i i i"~r i ] i i i i | i" i i i i "i i i i
ffl
1*
nl.ll.lon
ro
£ 600 -
cn
c
§ 400
S 200
o
c
o
o
Elms
1990
I
1.
600 -
i i i—i—j—i—i—i—i | i—i—i i |—i—i—i—i—j—i—i—rf
Haven Beach
1990
-2-
1 1 I '¦
nl
400 -
200 -
la
2 • 2
-i—i—i—|—i—n—i—| 1—i—i—|—i—i—i—i—|—i—i—i—i—|—i—i—i—i—|—i—i—i—i—|—i—i—i—i—|—i—i—i—i 11" i i—i i '|
10 15 20 25 30 35 40 45 50
Julian Week 1990
Figure IV.2.1. Alumirum concentrations on aerosol
particles, integrated weekly at each CBAD site. 1 =
detected, 2 = pump down, * = outlier/no data.
not
210
-------
600
Aluminum
(aerosol particles)
Wye
1 991
400
X
200
E 600
en
Elms
1991
400
v 200
M
600
Haven Beach
1991
400
200
X
— 2 —
25
30
35
50
5
10
15
20
40
45
Julian Week 1991
Figure IV.2.1. (Cont'd) Aluminum concentrations on aerosol
particles, integrated weekly at each CBAD site. 1 = not
detected, 2 = pump down, * = outlier/no data.
211
-------
6
2
8
4
6
2
8
4
6
2
8
4
i r
i r
n r
Wye
1 990
Arsenic t T
(Aerosols)
I
I
I
i I
I
* ~ 2 *
-i—i—i—i—|—i—i—i—i—|—i—i—i—i—|—i—i—i—i—|—i—i pi¦ ¦ i¦ ¦ |¦ i"i"i"i"|"i i i' i Y 1 • 1 i |'ii ¦ | ' > i"i y i 1
I
I
II
I
I
I
I
I
Elms
1 990
I
I
ii
ul
I
-2-
-T—| I I 1—I—f—I—I—I I I—I I I—I—I—I—IT
Haven Beach
1990
i i i i i | i i 11 | i i i i i i i i i i i ' ' ' i' ' 1 ' i ' ' ' ' i ' * ' ' i * ' 1 ' i 1
5 10 15 20 25 30 35 40 45 50
Julian Week 1990
Figure IV.2.2. Arsenic concentrations on aerosols,
integrated weekly at each CBAD s te. 1 = not
detected, 2 = pump down, * = no sample.
212
-------
1.6
1.2
0.8
0.4
1.6
cn
c 1 .2
c
o
0 0.8
c.
-------
Wye
1990
Bromine
(aerosol particles)
Elms
1 990
Haven Beach
1990
50
45
35
40
30
25
20
1 5
5
10
Julian Week 1990
Figure IV.2.3. Bromine concentrations on aerosol
particles, integrated weekly at each CBAD site. 1 = not
detected, 2 = pump down, * = outlier/no data.
214
-------
9
I l
\ Wye
1 99
i i i
1
i i i i i
Bromine
(aerosol particles)
6
-
-
-i- n i
I S
i
n fi nn
3
- |
fjsnxfrSSf1
pz
n ?q m n Pi-
rn;!: p?
W Pi x
n k n
Pi Pi Pi Pi
2 2 n
9
1 1
Elms
1 991
1 1 1
i i i i i
6
3
I
~ | i
fffi
fl fa fa fi
*
*
I
fa
I I
nrnl ll
SE
£ si
n n fi isOO ft
sPi fix s PjpiPiPipcn Hm
3C
9
1 111' 11' 1 p I 1 1 1 | 1 1 I
1 | 1 1 1 1 | 1 1 1 1 | 1 ( 1 1 | 1 1 1 1 | 1 1 1 1 | 1 1 1 ¦ | 1 1 1 1 | 1 1
Haven Beach I
I
1991 j
6
-
i
I
I
T
S T
T
T S
p;
3
JL *
22 2*2 2 2 •
n *
y I
»
nn n ft
c
2 2 2 2 2 2 2
5 10 15 20 25 30 35 40 45 50
Julian Week 1991
Figure IV.2.3. (Cont'd) Bromine concentrations on aerosol
particles, integrated weekly at each CBAD site. 1 = not
detected, 2 = pump down, * = oulier/no data.
215
-------
4
3
2
1
4
3
2
1
4
3
2
1
Wye
1 990
Cadmium
(aerosol particles)
I
fi
T—I—I—I—I—I—I—I—I—I—I—I | 'i' , 111111' |' |
I
I
Elms
1 990
is
5l.ll.lt
I
I
i—j—i—i—i—i—j—i—i—i i | i—n——| i i i 'i"!' i 1 i i | i i i i | i i i i | i i i—i—[¦
Haven Beach
1990
I
I-
2 » 2
5
i i i i |—r
10
I I I I I I
I 1 1 1 1 I
I I I I—I—I—I I I I I I—I I I I I
15 20 25 30 35 40 45
Julian Week 1990
rigure IV.2.4. Cadmium concentrations on aerosol
^articles, ntegrated weekly at each CBAD site. 1
detected, 2 = pump down, * = outleir/no data.
50
= not
216
-------
Cadmium
(aerosol particles)
0.4
Wye
1 991
0.3
IJ,
0.2
Si
ii
0.1
Elms
1991
0.5
0.4
0.3
0.2
Is
0.1
Haven Beach
1991
0.4
0.3
0.2
0.1
30
20 25
35
15
40
45
50
10
5
Julian Week 1991
Figure IV.2.4. (Cont'd) Cadmium concentrations on aerosoi
particles, integrated weekly at each CBAD site. 1 = not
detected, 2 = pump down, * = outlier/no data.
217
-------
2.5
Chromium
(aerosol particles)
Wye
1 990
2.0
1.5
1.0
0.5
2.5
Elms
1990
2.0
1.5
1.0
0.5
-2-
Haven Beach
1990
2.5
2.0
1.5
1.0
0.5
45
50
35
40
30
20
25
15
5
10
Julian Week 1 990
Figure IV.2.5. Chromium concentrations on aerosol particles,
integrated weekly at each CBAD site. 1 = not detected,
2 = pump down, * = outlier/no data.
218
-------
Chromium
(aerosol particles)
Wye
1 991
2.5
2.0
1.5
1.0
0.5
Elms
1991
2.5
2.0
1.5
1.0
0.5
Haven Beach
1991
2.5
2.0
1.5
1.0
0.5
— 2 —
50
40
45
35
25
30
15
20
10
5
Julian Week 1991
Figure IV.2.5. (Cont'd) Chromium concentrations on aerosol
particles, integrated weekly at each CBAD site. 1 = not
detected, 2 = pump down, * = outlier/no data.
219
-------
8
6
4
2
12
10
8
6
4
2
1 2
1 0
8
6
4
2
n r
Wye
1 990
i i i—i—r~i—i—m—|—i—¦" i i—| i i i—i—|—i—r
n
Copper
(aerosol particles)
i -
X PR
a
4-3-r^
n
Elms
1 990
SPi PisxPix
i—i—i—i—|—i—r—i—i—|—i—i—i—i—|—i—i—i—i—|—i—i—i T |—i—i ii|iiii|iiii|ii i—i—| 'i'ii i | i
I 1 1 1 T I
011111 1.10a
Haven Beach
1 990
In
2-2.2
T—I—i—1—|—I—I—I—I—|—l—i—I—I—|—I—I—I—I—|—:—i—I—I—|—I—I—i—i—|—I—I—i—I—|—I—i—i—I—|—i—i—I—I 11"1' i—I—i—|—r
5 10 15 20 25 30 35 40 45 50
Jihian Week 1990
igure IV.2.6. Copper concentrations on aerosol particles,
itegrated weekly at each CBAD site. 1 = not detected,
= pump down, * = outlier/no data.
220
-------
12
10
8
6
4
2
12
10
8
6
4
2
12
10
8
6
4
2
Fic
i r
i r
Wye
1991
Copper
(aerosol particles)
* -Pi*
nlllllfilUllnMlifln
I I I I | I I I I | I I I I | I I I I | I I I I | I I I I J I I I I J Tli i |
I
z
pc
Pi
M
'i"i"r i 11'11
c
2
"in f
In 1
nOnDnDf
r-rSr-T
n
Elms
1991
i i t i i i i I I i i i i i | i t '^ i
-fi;^nfaiT=ci1ac n,nn*n
nnHfinfinn
I I J ! I I I | I
I 1 1 1 1 I
7—I—I I I I I I
I 1 1 1 1 I
Haven Beach
1991
22*2*t2t22*»
I
I
J
rjr
p
p
c
pc
C
•
1 1 1
~
1 1
n • • —2—
11 ¦'' 11 ¦1. i''
n*n*2
11,11
,04,
An*
2
r i 'r
2 2*
i-1-
5 10 15 20 25 30 35 40 45 50
Julian Week 1991
jre IV.2.6. (Cont'd) Copper concentrations on aerosol
tides, integrated weekly at each CBAD site. 1 = not
ected, 2 = pump down, * = outlier/no data.
221
-------
400
300
200
1 00
400
300
200
1 00
400
300
200
100
Fi
in
2
"i r
i r
Wye
1 990
Iron
(aerosol particles)
n
I I I I I I I I I I I 1 I I I I I I I I 1 1 I I I
'r i 1» i '|
Elms
1 990
a
i
-2-
T-I—
n
i i i i | i i i i | i i i i | ii i i
Haven Beach
1990
2 • 2
e.
111111111.111111111111111111111111'''' i'''' i
5 10 15 20 25 30 35 40 45 50
Julian Week 1990
ure IV.2.7. Iron concentrations on aerosol particles,
sgrated weekly at each CBAD site. 1 = not detected,
= pump down, * = outlier/no data.
222
-------
400
300
200
100
400
300
200
100
400
300
200
100
Wye
1991
Iron
(aerosol particles)
a
! l l l j l l l l | i l l l | l l l l |
rr ¦ 1 ¦ r1 1
i
0.
I 'I
Elms
1 991
I ' ' 1 1 I
507 ± 11
| ii r i j i i i i | i i i f | t i i i | i i i i |
I rlilll t l | l I i i i i l
i rrrrrrrr
Haven Beach
1991
2 2
| r i 1 ¦'11111"i'111 'i111111
i i r i i i i 1 i
a
2 2*
5 10 15 20 25 30 35 40 45 50
Julian Week 1991
jure IV.2.7. (Cont'd) Iron concentrations on aerosol
rticles, integrated weekly at each CBAD site. 1 = not
tected, 2 = pump down, * = outlier/no data.
223
-------
8
6
4
2
8
6
4
2
8
6
4
2
Wye
1990
Manganese
(cerosol particles)
I j I I I
-|—i—i—|—i—i—i—i—|—i—i—i—r~
' i n
Elms
1 990
->—i—i—|—t—i—i—i—|—i—i—i—i—|—i—i i i | i—r
Haven Beach
1990
n
i 'r'r'r'i
0
2 • 2
a
i | i i i i—[—i—i i i—|—i i i—i—|—i i i i—|—i—i i i—|—i—n—i |-
I'll 1 I I I 1111 I I
5 10 15 20 25 30 35 40 45 50
Julian Week 1990
'igure IV.2.8. Manganese concentrations on aerosol particl
ntegrated weekly at each CBAD site. 1 = not detected,
[ = pump down, * = outiier/no data.
224
-------
8
6
4
2
8
6
4
2
8
6
4
2
'iq
Wye Manganese
1991 (aerosol particles)
^ i i i i i i 11 i i i i i i i i i i i
Elms
1 991
n
r'r'r'r i i
i i i i i i
12.65 ± 0.26
i i i i i i i i i i i i i i
Haven Beach
1991
2 2 2
2 2*
I I I"l"|"l —l—[
n
2«22»
i | I Wl'T i ' I i | i l 111111 | 11¦111 i l | i
r i i i | i 'i' i i
5 10 15 20 25 30 35 40 45 50
Julian Week 1991
jre IV.2.8. (Cont'd) Manganese concentrations on aerosol
tides, integrated weekly at each CBAD site. 1 = not
ected, 2 = pump down, * = outlier/no data.
225
-------
12
9
6
3
12
9
6
3
12
9
6
3
Nickel
(aerosol particles)
Wye
1990
B
nl
~fi*
a
nn-nn
-i—i—i i |—rn—i—r-j—i——i . | i—i—!—i—|—i—i ii|
Elms
1990
i i
nn
¦Jill I I I • I I I I I I I I I I I
Haven Beach
1 990
* ~ 2 • 2» •
—i—i—i—|—i—¦—i—i—|—i—r—i—i—|—i—i—i—|—i—i—i—i—|—i—i—i—i—|—i—i—> i | > i i i | i i 1 1 | 1 1 i i | ¦
5 10 15 20 25 30 35 40 45 50
Julian Week 1990
Figure IV.2.9. Nickel concentrations on aerosol particles
integrated weekly at each CBAD site. 1 = not detected,
2 = pump down, * = outlier/no data.
226
-------
12
9
6
3
12
9
6
3
12
9
6
3
i r
Wye
1991
Nickel
(aerosol particles)
el
55
nMfin
a
si
Elms
1991
n
a
nfln
n
nri:
I I I I ! I I I | I III |—TTTTTTt
Haven Beach
1991
]2 2 1 2 •
i i i i i
2.22
I I I | I 'I1 l I |—I I I I I '|
n
T—I—I I I I I | I 'I'
id
2 2 2
I | I I I I | I I
¦ ¦ i ¦ ¦
5 10 15 20 25 30 35 40 45 50
Julian Week 1991
jure IV.2.9. (Cont'd) Nickel concentrations on aerosol
rticles, integrated weekly at each CBAD site. 1 = not
tected, 2 = pump down, * = outlier/no data.
227
-------
12
9
6
3
1 2
9
6
3
12
9
6
3
Wye
1 990
Lead
(aerosol particles)
I
~j—I—I—I—I—|~~l I I I 1 ~ I • I | I I I T |
fi
S I
II
l' I 11 I 11 " 1" 1' I T'l
I
I-
I 1 1 1 1 T
I
I
Elms
1990
I
IB
¦2-
X-
i i i—r-|—i—iii)i—i—i i | 1 1 | i—1—i—i 'j' 1 1 11 |
T i l ¦ j I I 1 I | I I I I j
Haven Beach
1 990
r
2 » 2 1
i l i | l i i i | l i l i | i—n—i—|—i—i—i—i—|—i—»—i—i | ¦—i—i i |—i—> » 1 | 1 ' r-
5 10 15 2C 25 30 35 40 45 50
Julian Week 1990
igure IV.2.10. Lead concentrations on aerosol particles,
itegrated weekly at each CBAD site. 1 = not detected,
= pump down, * = outlier/no data.
228
-------
12
9
6
3
12
9
6
3
12
9
6
3
Fi<
Wye
1 991
Lead
(aerosol particles)
Ii
i Is
fl
is
I
1
n-
00
I 1 1 1 1 I
I
Elms
1991
XJ,
n
ii
i
0 rflfliiffljili
1 1 1
¦ r ¦ i ¦ ¦ i ¦ ¦ ¦ i" i ¦ ¦ i ¦ * i ¦ ¦ r i ¦ i ¦ ¦ i ¦ ¦ i ¦ ¦ i
n——i—I—i—r
Haven Beach
1991
• 2212*
2 2*2
I 1
5
T
Hill: "dw.
If
C
I
M
2
,5,
ft
122
| I 'I I 1 1 | I I I I |
5 10 15 20 25 30 35 40 45 50
Julian Week 1991
jre IV.2.10. (Cont'd) Lead concentrations on aerosol
tides, integrated weekly at each CBAD site. 1 = not
scted, 2 = pump down, * = outlier/no data.
229
-------
9000
Sulfur
(aerosol particles)
6000
Wye
1990
3000
9000
en
Elms
1 990
c 60 00
3000
-2-
9000
Haven Beach
1990
6000
3000
50
45
35
40
30
25
1 5
20
10
5
Julian Week 1990
Figure IV.2.11. Sulfur concentrations on aerosol particles,
integrated weekly at each CBAD site. 1 = not detected,
2 = pump down, * = outlier/no data.
230
-------
"i i r
"i r
9000 -
6000 -
3000 -
Wye
1 991
Sulfur
1 (aerosol particles)
II
I X
fi
11
I
I
I
J.J. I
I
IT*
Da
a
9000 -
6000 -
3000 - I
Elms
1 991
I I
I* I
ll I
I
II
I
T I
II
I
I
Si rl
I I I I I I j I 1 I I I I I I I J I I
I I I I I I I I I I I I I I I I I I
9000 -
6000 -
3000 -
Haven Beach
1991
5 10 15 20 25 30 35 40 45 50
Julian Week 1991
Figure IV.2.11. (Cont'd) Sulfur concentrations on aerosol
particles, integrated weekly at each CBAD site. 1 = not
detected, 2 = pump down, * = outlier/no data.
231
-------
4
3
2
1
4
3
2
1
4
3
2
1
Wye
1990
Selenium
(aerosol particles)
Sin
IlS
"I—| | |—I—I—I I I—I I I I—i I I I—I—I—I—I—TT
fi I I F
I
i i
s _
Elms
1990
i
n
i > i i i i i i i ij
fi i
i
i
l"| I I"! I
-2-
I X-
i i i i 1 i r
i 1 1 1 1 i
Haven Beach
1990
L
I ' 1 1 1 I 1 1 1 1 I
2*2
X '
i i i i | i i i i '|"i' i i i |
i i i I i i i i I i
I 1 1 1 1 I
5 10 15 20 25 30 35 40 45 50
Julian Week 1990
Figure IV.2.12. Selenijm concentrations on aerosol
particles, integ~atec weekly at each CBAD site. 1 = not
detected, 2 = Dump down, * = outlier/no data.
232
-------
4
3
2
1
4
3
2
1
4
3
2
1
ri
Wye
t 1991
I
Selenium
(aerosol particles)
n
I J Elms
1991
i
xi
Ex
x-
i i t i i r*V i i i r i | i i i i r i i
I r 1 I | I i i i | i i i I |
Haven Beach
1991
r i • • *
i ari 2 • 2 22
I 1 1 1
i r I i ii r | i i iii i i
2 2 • •
2 2 2
5 10 15 20 25 30 35 40 45 50
Julian Week 1991
jre IV.2.12. (Cont'd) Selenium concentrations on aerosol
tides, integrated weekly at each CBAD site. 1 = not
ected, 2 = pump down, * = outlier/no data.
233
-------
12
9
6
3
12
9
6
3
12
9
6
3
i r
Wye
1 990
Vanadium
(aerosol particles)
i—i—i—i—i i i i—i—i—i—i—r-i—i—i—i—i—i—i—i i rvT r r i
I 1 1 1 1 I
Elms
1 990
3l
T
rv i 'i't i i i i f i ¦ 111
-i—i—i—i—i—i i i—i i i—i i \—|—i—i—i—i—|—i i . 'i
§
ii
r
Haven Beach
1990
2 • 2
t—i i | i i i—i [ i—i i i ; i—i—i i |—i—i i i |—i i i i | i i i—r-|—i—r—i—i | i i—r
5 10 15 20 25 30 35 40 45 50
Julian Week 1990
Figure IV.2.13. Vanadium concentrations on aerosol
particles, integrated weskly at each CBAD site. 1 = not
detected, 2 = pump down, * = outlier/no data.
234
-------
12
9
6
3
12
9
6
3
12
9
6
3
"i r
i r
Wye
1991
Vanadium
(aerosol particles)
S I
* I
x
Pil
| I I | I I | I 11 I I | I I 11 I | ¦ 11 | | | | | ¦ lyhl | 1 1 | 1 1 | 1 1 | 1 1 | | | | " , , "| , | | | | | | |
Elms
1991
i
a
¦ i ¦ ¦111
n
ifo
i
ii
Hi
I I
fTTTTTT
2 2n 2 . 2
2 2
Haven Beach
1 991
2 2 2
2 2 2
I I 11' |—I 1 I 'I' |—I—i ¦ 11¦ i¦ >|¦ ¦,¦ ¦ i¦ ¦ |¦ i¦ ¦ i¦ i—i—| I I—I—I—|—I—|>¦ i¦ ¦ |¦ j¦ | ¦ i¦ ¦ i¦ i [¦ i—i—i—i—j-
5 10 15 20 25 30 35 40 45 50
Julian Week 1991
;ure IV.2.13. (Cont'd) Vanadium concentrations on aerosol
rticles, integrated weekly at each CBAD site. 1 = not
tected, 2 = pump down, * = outlier/no data.
235
-------
50
40
30
20
10
50
40
30
20
10
50
40
30
20
10
"i 1 1 1 r
Wye
1990
-|—i—n—[—i—i—i—i—j—i i i •—| i i i—r—j—i i 'i
w
Zinc
(aerosol particles)
i i
rr
i i i i i i I i i J I I i it I
Elms
1 990
i i i i—j—i—i i i j i—ii | i—i i i | i—\ \ 'i
Haven Beach
1 990
ni
i
J
1111111••1111111
n
-2-
3L
n
i i i i I i i i i I i i i i I—i i i i |—i—i—i > | i—i i i | i i i i | i i i i | i i i i—pi—i—i i | i i
5 10 15 20 25 30 35 40 45 50
Julian Week 1990
Figure IV.2.14. Zinc concentrations on aerosol particles,
integrated weekly at each CBAD site. 1 = not detected,
2 = pump down, * = outlier/no data.
236
-------
50
40
30
20
10
50
40
30
20
10
50
40
30
20
10
n 1 1 r
Wye
1991
Zinc
(aerosol particles)
T
I ' 1 1
Fi Sw s
T
XI
fl l l l !
j I | I I | I I I I J
Sl-
Elms
1991
spi
mm™
Haven Beach
1 991
. 2 2 n 2 •
I I I 11' 1 1
2 2*
I l 1 | l i I 'i' j—i—l Vi
fl
• 2-
1**1* I—I—I I I
I ' ' ' ' I
~ ~ ~ 2 ~ 2 2
"ill"
5 10 15 20 25 30 35 40 45 50
Julian Week 1 991
jure IV.2.14. (Cont'd) Zinc concentrations on aerosol
rticles integrated weekly at each CBAD site. 1 = not
tected, 2 = pump down, * = outlier/no data.
237
-------
Aluminum, 1990
60
40
20
Wye
I
i i i i | i i I i | i i i i | i—i—r~i | i i i i | r
60
40
o
-t->
ffj
H-J
d
a;
o 20
c
o
u
Elms
I
I
j.u.
X
IfM ¦ T*
i i i i I i i i i | l I i ' | i I I i |
60
Haven Beach
40
20
-I—i—i i |—i—i—i—i—|—i—i—i—i—|—i—I—i—r—|—i—i—i—i—|—i—i—i—i—| i i i i | i i i i | i ' i 1 I-1 '
10 15
20 25 30
Julian Week
35 40 45 50
Figure IV.3.1. Aluminum concentrations in precipitation,
integrated weekly at each CBAD site.
238
-------
Aluminum, 1991
400
200
400
200
1
Wye
-llli.l. ¦¦¦I- 1 a.l ¦_ _ ¦ - l-_
1 1 1 1 1 1 1 1 1 1
Elms
¦ ¦ 1¦11 _l_ ¦¦¦ — — _ ¦ ¦
Haven Beach
i i ^ l—| I ^ P I T i i | l iTi i—iTi 1 —i—|—i ? ¥ P | P l
400
200
10 15
20 25 30
Julian Week
35 40 45 50
Figure IV.3.1 (Cont'd) Aluminum concentrations in precipitation,
integrated weekly at each CBAD site.
239
-------
Arsenic, 1990
0.20
0.1 5
0.1 0
0.05
(it)
d
o
• i-H
-t-i
od
(h
-t->
C
-------
Arsenic,1991
0.3
0.2
0.1
L
0.3
3,
a
o
• H
cd
I-,
0.2
c
QJ
O 0.1
G
o
u
0.3
0.2
0.1
Wye
i
I
Jl.
Iiil.ulil,
Elms
in il
1,1 I II
llllllili
I
il ,, ,H
Haven Beach
In ll i.l
4-
I II II
iwJ
j
if**
ini
j i [~
10 15 20 25 30 35 40 45 50
Julian Week
Figure IV.3.2 (Cont'd) Arsenic concentrations in precipitation,
integrated weekly at each CBAD site.
241
-------
0.5
0.4
0.3
0.2
0.1
0.5
~4
\ 0.4
ISO
3
a 0.3
0
• r-H
-------
Cadmium, 1991
0.8
0.6
0.4
0.2
60
3
£
o
• r4
cd
C
0)
o
CI
o
o
0.8
0.6
0.4
0.2
0.8
0.6
0.4
0.2
Wye
TtI i | i ll-|.l.ll.|l, fllllf , I, If rill i I, Mf, 11 i f
T.ft**
Elms
•iL
u
ii
tM , f ¦
I
1.8
2.0
I
1,1
*¦
lljJf
f ¥¦¦If¦
I
Haven Beach -
¦1 ¦ ¦ i ¦1111 ¦1
10 15 20 25 30
Julian Week
, U | !¦
35
40
45
50
Figure IV.3.3 (Cont'd) Cadmium concentrations in precipitation,
integrated weekly at each CBAD site.
243
-------
Chromium, 1990
Wye
JL i
—i—i i [ i i i i | i i i | i i i i | i i i i | i i i i | i i i i t i i i | i i i i | i i i i | i i
Elms
—i—i—i—|—i—i—i—i—|—i—i—i—i—|—i—i—¦—i—|—i—i TT i—iT.llTili i iTi | i i T i | i l
~J 6
\
60
=1
§ 4
• rH
a}
U
4-J
fl
-------
Chromium, 1991
0.6
0.5
0.4
0.3
0.2
0.1
3 0.6
\
bo
3 05
g 0.4
• H
S 0.3
*->
c
« 0.2
CJ
C
O 01
Wye
lil...it
¦iiil.li iiiLi
xil
-*
1 I I I
Elms
1-L.ll
II
till
1
Figure IV.3.4. (Cont'd) Chromium concentrations in precipitation,
integrated weekly at each CBAD site.
245
-------
Copper, 1990
Wye
J
ii» I
IllL
t—i—i—|—i—i—i—i—|—i—i—i—r-j—i—i—i—i—|—i—i—i—i—j—r
• 'i i r
~ 2
c
O
• H
-t->
«5
-t->
a l
a)
o
C
o
u
Elms
jJil
i
T ,
i
-i—| i i i i |—i—i—r—i—j—i i i i—r
Haven Beach
i i i i i i i i i i i—|—i i i i i i i i i 1 ' ' ' i ' ' 1 1 i 1 1 1 1 i 1 1 1 1
5 10 15 20 25 30 35 40 45 50
Julian Week
Figure IV.3.5. Copper concentrations in precipitation,
integrated weekly at each CBAD site.
246
-------
4
3
2
1
4
3
2
1
4
3
2
1
;u]
ef
Copper, 1991
Wye
ItI, i ll.
Jou
Jill ifItIp|I.IffiTi .lilrfffT
Elms
ui
4lf , , f r li
|4
ifiii f | i jl
Haven Beach
it illlMl 11 III
10 15
20 25 30
Julian Week
35 40
-rr
45
111
T
50
ll
IV.3.5. (Cont'd) Copper concentrations in precipitation,
ated weekly at each CBAD site.
247
-------
120
90
60
30
120
90
60
30
1 20
90
60
30
Iron, 1990
Wye
Elms
il.i.
.1
llHi.
i i i I i i i i | i l i i | i 1
¦¦1 ,1 |T| I ¦ l|-
Haven Beach
I
-i—i—i—| i i i i—| i i i i | i—i—i—i—|—r~i—i—i—|—m—i~i—|—i i i—i | i i i ' | ' i i i | 1 i "Tj i T
5 10 15 20 25 30 35 40 45 50
Julian Week
; IV.3.6. Iron concentrations in precipitation,
¦ated weekly at each CBAD site.
248
-------
350
300
250
200
150
100
50
350
300
250
200
150
100
50
350
300
250
200
150
100
50
Iron, 1991
Till | i f f f
Wye
I i F i I ^ ^ T T T | ¥ i P I Y i T )—i ^ P*P T ¥ ^ ¥ '
Elms
fifi|tT^T|T
I
If if I
i T ' Tf
f ¥ i ¥
i 'i P i i—i ^ i
Ttt^tt
Haven Beach
M,, JMl.l, ,f
f I I 1T1T
III
'f f P I f T [ Et i i | i If ¦
| UlT| I TTTJTTTTJT I TT | ¦ . ¦ , |
10 15 20 25 30 35 40 45
Julian Week
+T#-
50
3 IV.3.6. (Cont'd) Iron concentrations in precipitation,
•ated weekly at each CBAD site.
249
-------
Manganese, 1990
Wye
4
'tIt ¦ T
1*1
~i—r—i—| i i—i—r—|—i—i—i—i—|—i—r—i—1—7—1—1 1 1
g 9
c
o
5 6
cd
f-i
-fj
ti
-------
40
30
20
10
40
30
20
10
40
30
20
10
Manganese, 1991
I i i i f f ¦
Wye
I
i f Ml*
T J -I t¥tIT¦WIfIT¦,fTiITTT
Elms
¦f I I
f i i i J I TT i ^ T I ¥ i T^T I I P I
Haven Beach
¦tT i i T
li.ll
HlyTfTTfT ¦ W
i
f rf ¦ T
]
10
l i r
15
¦ i ¦
20
25 30
Julian Week
35 40 45
r
50
2 IV.3.7. (Cont'd) Manganese concentrations in precipitation,
•ated weekly at each CBAD site.
251
-------
Nickel, 1990
Wye
-|—J—l—m—I—| I I—I—I—|—I—I I I—|-
n—i—i—|—r
3 2
o
• H
aS
t-,
+>
a l
0)
o
C
o
o
Elms
I I I | I I I I | I I I I | I I I
4
U
it
Haven Beach
(not analyzed)
I I I 1 I I I I
-i—|—r~i—i i |—r-
45 50
i i I i i—i i | i i i i | i i i—i | i i i—i i i i i i | i
5 10 15 20 25 30 35
Julian Week
40
Figure IV.3.8. Nickel concentrations in precipitation,
integrated weekly at each CBAD site.
252
-------
2.0
1.5
1.0
0.5
\ 2.0
M
3
fi 1.5
o
• H
-------
Lead, 1990
3
G
o
¦ rH
a}
d
a)
o
C
o
u
Wye
1 I I | ! I I i | i I i i | ¦ ¦ < ' |
t—n—i—|—r
1
Elms
-1—|—i—i—i—i—|—i—i T T T "r
1
iiii—i i i—«—|—r—?-
Haven Beach
-i—i—r—|—i—i—i—i—|—i—i—i—i—(—i—i—i—i | i i 1 >"
¦ i ¦ ¦
' 1 I
f*
10 15 20 25 30 35
Julian Week
I I | I I I I | I 1 I I
40 45 50
Figure IV.3.9. Lead concentrations in precipitation,
integrated weekly at each CBAD site.
254
-------
5
4
3
2
1
5
4
3
2
1
5
4
3
2
1
Lead, 1991
Wye
MM Mil II1 lliili, 11JI lih
Elms
wi
Haven Beach
20 25 30
Julian Week
; IV.3.9. (Cont'd.) Lead concentrations in precipitation,
ated weekly at each CBAD site.
255
-------
4
3
2
1
4
3
2
1
4
3
2
.1
Selenium, 1990
Wye
Jjl
I
T—i—i—i—|—i—i—i—I—|—i—i—I—i—|—i—i—i—i | i i i i | r
Elms
i i
I
Id
I
I | I I I I |—I I I I—J—I—I—I—I—|—I—I T T |
Haven Beach
i i i | i i i i | i i i i i i i ' ' i
i i i—i—I—i—i—r
T
10 15
20 25 30
Julian Week
35 40 45 50
s IV.3.10. Selenium concentrations in precipitation,
¦ated weekly at each CBAD site.
256
-------
Selenium, 1991
Wye
llUJl
I,ill ll
I
IU
J]
Elms
uJliUIH
i ii III j T|
Ml, M
Haven Beach
Ii, ,i
lljlllhl
20 25 30 5
i*
10 15
r
25 30
Julian Week
¦ ¦
35 40 45 50
Figure IV.3.10. (Cont'd) Selenium concentrations in precipitation,
integrated weekly at each CBAD site.
257
-------
Zinc, 1990
» 9
PI
o
• H
-fj
a}
(h
•fJ
C3
CD
o
a
o
CJ
6 -
Wye
-i—i—i—i—|—i—i I I | l I I—I—|—I—I—I—i—[—r
i
Elms
1 1 1 I
I ! I I I I I I I I I
iJiL
Haven Beach
I'll
IUi
i ll— -I llll
llllt
-l—l—I I I I I I I I I I I I »» I » I—I I I I I
I I I I I I I
10 15
20 25 30
Julian Week
35 40 45 50
Figure IV.3.11. Zinc concentrations in precipitation,
integrated weekly at each CBAD site.
258
-------
20
15
10
5
20
15
10
5
40
30
20
10
Zinc, 1991
Wye
Lji
¦iiii.li ill
Tfiliiiiiiii|l
Elms
III i ] i f
I*.
Il
I|U
Haven Beach
mI, llhfllr ,f ,|, | .T.if
I
106
ulllU
uUi
| f J|,||,|tt|Ti I II
#1
83
i
10 15
20 25 30
Julian Week
35 40
1 1 i 1
45
50
; IV.3.11. (Cont'd) Zinc concentrations in precipitation,
ated weekly at each CBAD site.
259
-------
6000
4000
2000
6000
4000
2000
6000
4000
2000
Fi{
at
Aluminum, 1990
Wye
Elms
Haven Beach
1 1 1 1 1 1 1 1 1 1 1 1
JFMAMJ JASOND
MONTH
re IV.3.12. Monthly integrated wet deposition of Aluminium
ach CBAD site.
260
-------
6000
4000
2000
6000
4000
2000
6000
4000
2000
ire IV
;ach (
Wye
Aluminum, 1991
Elms
Haven Beach
MONTH
J. 12 (Cont'd) Monthly integrated wet deposition of Aluminium
BAD site.
261
-------
Arsenic, 1990
Wye
10 -
5 -
1 1 1 1 r
llllll
g Elms
10
6
cm
3
g 5
E-
W
-i 1 1 1 r
hh-l
Haven Beach
10 h
MONTH
Figure IV.3.13. Monthly integrated wet deposition of Arsenic
at each CBAD site.
262
-------
Arsenic, 1991
Wye
Elms
JFMAMJ JASOND
MONTH
Figure IV.3.13. (Cont'd) Monthly integrated wet deposition of Arsenic
at each CBAD site.
263
-------
35
30
25
20
15
10
5
35
30
25
20
15
10
5
35
30
25
20
15
10
5
Fij
at
Cadmium, 1990
Wye
"i r
"i r
Elms
l I l l l
T" "T
Haven Beach
i r
J J
MONTH
J F
i
A
~r
M
i r
A S 0 N D
ire IV.3.14. Monthly integrated wet deposition of Cadmium
;ach CBAD site.
264
-------
35
30
25
20
15
10
5
35
30
25
20
15
10
5
35
30
25
20
15
10
5
Lre
Cadmium, 1991
Wye
Elms
54
Haven Beach
JFMAMJ JASOND
MONTH
r.3.14. (Cont'd) Monthly integrated wet deposition of Cadmium
CBAD site.
265
-------
40
30
20
10
40
30
20
10
50
40
30
20
10
Fij
at
Chromium, 1990
- Wye
1 1 1 r
Elms
Haven Beach
(not analyzed)
1 1 1 1 1 1 1 i i i i i
JFMAMJ JASOND
MONTH
ure IV.3.15. Monthly integrated wet deposition of Chromium
each CBAD site.
266
-------
40
30
20
10
40
30
20
10
50
40
30
20
10
Chromium, 1991
Wye
Elms
Haven Beach
(not analyzed)
~~r
F
~r
M
-1 r
J J
MONTH
~r
s
~r
D
M
i
0
i
N
f.3.15. (Cont'd) Monthly integrated wet deposition of Chromiun
CBAD site.
267
-------
200
150
100
50
200
150
100
50
200
150
100
50
Copper, 1990
- Wye
n 1 1 1 r
Elms
i 1 1 r
Haven Beach
T
F
T
M
T
A
M
T
J
T
A
MONTH
ii
0 N D
Figure IV.3.16. Monthly integrated wet deposition of Copper
at each CBAD site.
268
-------
200
150
100
50
200
150
100
50
200
150
100
50
Figui
at e<
Copper, 1991
Wye
Elms
Haven Beach
MONTH
IV.3.16. (Cont'd) Monthly integrated wet deposition of Copper
h CBAD site.
269
-------
3500
3000
2500
2000
1500
1000
500
3500
3000
2500
2000
1500
1000
500
3500
3000
2500
2000
1500
1000
500
Iron 1990
Wye
i 1 1 1 1 r
Elms
i r
Haven Beach
T
M
T
A
M
i
J
"i 1 r
S 0 N D
MONTH
Figure IV.3.17. Monthly integrated wet deposition of Iron
at each CBAD site.
270
-------
3500
3000
2500
2000
1500
1000
500
3500
3000
2500
2000
1500
1000
500
3500
3000
2500
2000
1500
1000
500
Figu
at e
Iron 1991
Elms
Haven Beach
MONTH
j IV.3.17. (Cont'd) Monthly integrated wet deposition of Iron
ch CBAD site.
271
-------
400
300
200
100
400
300
200
100
400
300
200
100
Fi|
at
Manganese, 1990
¥ ye
n r
i 1 r
Elms
T 1 1 1 r
Haven Beach
n 1 1 1 1 1 i i r
JFMAMJJAS
MONTH
M
i r
0 N D
ire IV.3.18. Monthly integrated wet deposition of Manganese
sach CBAD site.
272
-------
400
300
200
100
400
300
200
100
400
300
200
100
; IV.
Manganese, 1991
Wye
Elms
Haven Beach
MONTH
.18. (Cont'd) Monthly integrated wet deposition of Manganese
JAD site.
273
-------
Nickel, 1990
Wye
1 r
i r
Elms
i r
i r
Haven Beach
(not analyzed)
—i 1 1 1 1 1 1 1 1 1 i i
JFMAMJ JASOND
MONTH
Figure IV.3.19. Monthly integrated wet deposition of Nickel
at each CBAD site.
274
-------
Nickel, 1991
60
40
20
a
o
6 60
\
CM
B
*60 40
3
x
3 20
P«H
H
W
£
60
40
20
Wye
Elms
Haven Beach
1 1 1 1 1 1—
jfmamj jasond
MONTH
Figure IV.3.19. (Cont'd) Monthly integrated wet deposition of Nickel
at each CBAD site.
275
-------
120
100
80
60
40
20
120
100
80
60
40
20
120
100
80
60
40
20
Lead. 1990
Wye
i 1 1 1 r
Elms
Haven Beach
1 1 1 1 1 1 1 1 i i i I
jfmamjjasond
MONTH
Figure IV.3.20. Monthly integrated wet deposition of Lead
at each CBAD site.
276
-------
120
100
80
60
40
20
120
100
80
60
40
20
120
100
80
60
40
20
Fig
at
Lead, 1991
Wye
Elms
Haven Beach
MONTH
re IV.3.20. (Cont'd) Monthly integrated wet deposition of Lead
ach CBAD site.
277
-------
Selenium, 1990
30
Wye
20 -
10 -
-| 1 1 1 1 r
lill.i
30 - Elms
20 -
10 -
lll.i.l
30 -
20 -
10 -
Haven Beach
MONTH
Figure IV.3.21. Monthly integrated wet deposition of Selenium
at each CBAD site.
278
-------
selenium, 1991
Elms
jfmamjjasond
MONTH
Figure IV.3.21 (Cont'd) Monthly integrated wet deposition oi Selenium
at each CBAD site.
279
-------
400
300
200
100
400
300
200
100
400
300
200
100
Zinc, 1990
Elms
Haven Beach
—i 1 1 1 1 1 i i i i r
J FMAMJ JASOND
MONTH
Figure IV.3.22. Monthly integrated wet deposition of Zinc
at each CBAD site.
280
-------
400
300
200
10 0
400
300
200
100
400
300
200
100
Fij
at
zjiiic, iyyi
Wye
IfMIbpIfIpwI
Elms
1200
Haven Beach
MONTH
ure IV.3.22. (Cont'd) Monthly integrated wet deposition of Zinc
each CBAD site.
281
-------
A Comparison of CBADS Trace Element
Wet Fluxes (mg/m2/yr) with Other Studies
to
oo
K>
14
12
10
Cu, Ni & Pb Flux
Fe, Mn & Zn Flux
8
6
4
2 i
0
p
4
%
I
4
35
- 30
- 25
20
15
10
h 5
0
Lewes,DE
CBADS Ave ChesBay(1982) GLADS
Puget Sound
Figure IV.3.23. A comparison of the CBADS trace element wet fluxes with
other studies.
-------
6
x
Q.
3 ¦ ' ¦ 1 ¦I'MlLl.l.lll.l.l.ll .1.1.lll.1.1.III.1.1.III.1.1.Ill.l.I.III.1.1.III.1.1.III.1.1.III.1.1.III.I.I. I .1.1.III.1.1.Il
40 44 46 52 56 60 64 66 72 76 80 84 88 02 96 100 104
5000
4000 -
CO
o
3000 -
3 2000 -
CO
1000 -
3000
40 44 48 52 56 60 64 68 72 76 60 84 88 02 96 100 104
2000 -
¦ ¦ 111 * < rrl^lrl~JlIiTil7i i ig£ i TOJin.. T,.
24000
n 1
5000
_ 4000
H 3000
CD
Z 2000
1000
¦ ¦ ¦ 1
He
Tli i^Ji
¦ i.i.urn.
¦*-" 11 ¦ ¦ ¦ ¦ ¦ m ¦ i ¦
tL
X
40 44 48 52 56 60 64 66 72 76 80 84 88 92 08 100 104
<-199011091->
Julian Weeks (since Jan. 1990)
Figure IV.4.1.1. Concentrations of major ions in
precipitation collected at Haven Beach. Concentrations
are from weekly samples.
283
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5
1600
10
11
12
1200
£ 800 -
400
600
10
11
12
~ 600
400 -
200 -
5000 r-
4000 y
1600
1200
10
11
12
600
400
_L
_L
_L
J.
_L
_L
_L
6
8
10
11
12
liilian Mnnthe /cinoo Ian iQQi\
Figure IV.4.1.2. Volume weighted monthly concentrations
of major ions in precipitation collected at Haven Beach.
284
-------
16
12
8
4
0
240
200
160
120
60
40
0
60
50
40
30
20
10
0
240
200
160
120
80
40
0
J 1 I I I » ' i i i i i
1 2 3 4 5 6 7 6 9 10 11 12
J 1 1 1 1 I I I I I ¦ I ¦ I '
2 3 4 5 6 7 6 9 10 11 12
J 1 1 1 I ¦ ' i ' i
3 4 5 6 7 6 9 10 11 12
—1 1 1 " L-1 I 1 I 1 ' ¦ ¦ I »
1 2 3 4 5 6 7 8 9 10 11 12
litlian Months teinpp .Ian 1QQ"h
Figure IV.4.1.3. Monthly fluxes of major ions in
precipitation collected at Haven Beach.
285
-------
16
12
8
4
0
200
160
120
80
40
0
80
60
40
20
0
240
200
160
120
80
40
0
CD Haven Beach
EHH Elms
10
11
n
§
12
Julian Months (since Jan. 1991)
Figure IV.4.1.4. Compar ision of monthly fluxes of maj or
ions in precipitation collected at the three CBAD sites.
286
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