Draft Report: Air Toxics Deposition Monitoring in Galveston Bay, Texas (TRIADS)


TEXAS A&M UNIVERSITY
Geochemical and Environmental Research Group
College of Geosciences and Maritime Studies
30 January 1998
Mr. John M. Ackermann
US EPA/QAQPS
MD-15
Research Triangle Park, NC 27711
919-541-5687
Dear John:
Enclosed is the draft report "Air Toxics Deposition Monitoring in Galveston
Bay, Texas" for the TRIADS. I hope this report answers all of your questions
regarding our operation of this site since February of 1995. I look forward to your
comments.
If you need additional information, please contact me.
Sincerely,
Terry L. Wade, Ph.D.
Director for Environmental Chemistry
TLW/dep
enclosure
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S. Sweet, GERG
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TEXAS A&M UNIVERSITY
Geochemical and Environmental Research Group
College of Geosciences and Maritime Studies
February 20, 1998
Ms. Karen Foster
Battelle
397 Washington Street
Duxbury, MA 02332
781-934-0571
Dear Karen:
Enclosed is the draft report "Air Toxics Deposition Monitoring in Galveston Bay, Texas"
for the TRIADS and two CD containing the data to send to EPA. I have incorporated the changes
you suggested. The MQO arc discussed in the Executive summary. The instrument not being
calibrated after one year was added to the lexl. The four compounds that you say arc not listed in
Attachment A are there. The 2,3,5-lrimcthylnaphthalene is under its preferred name 1,6,7-
limcthyinaphthalene. For some sampling periods the site was sampled, but there was no rain and
therefor no sample to analyze. Tabic 1 has been corrected.
If you need additional information, please contact me.
Sincerely,
Terry L. Wade, Ph.D.
Director for Environmental Chemistry'
TLW/tlw
enclosure
xc: J. Ackermann, EPA
S. Sweet, GERG
833 Graham Road • College Station, Texas 77845-9668 • MS 3)49 . (409) 862-2323. FAX (409) 862-2361
http //www-gerg.tomu edu	Internet. director@gerg lamu edu
http //www-gerg.tomu edu

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Draft Report
for
Air Toxics Deposition Monitoring in Galveston Bay, Texas:
Texas Regional Integrated Atmospheric Deposition Study
(TRIADS)
EPA Contract No. 68-C2-0134
to
U.S. Environmental Protection Agency
Office of Air Quality Planning and Standards
February 20,1998
Prepared by
Geochemical and Environmental Research Group
Texas A&M University
833 Graham Road
College Station, TX 77845
(409) 862-2323
Under Contract to
Battelle
Ocean Sciences
397 Washington Street
Duxbury, MA 02332
(617) 934-0571

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Air Toxics Deposition Monitoring in Galveston Bay, Texas
EPA Work Assignment Manager: Dr. John M. Ackermann
Technical Area Leader: Dr. Carelton D. Hunt
Work Assignment Leader: Dr. Terry L. Wade
Executive Summary
This report provides the results of the operation of an Air Toxics Deposition
Monitoring Site at Seabrook, Texas on Galveston Bay. This is primarily a data report
with all the data supplied in the Appendices and in electronic format. The data is
accompanied by an initial discussion of the results of this study. Included in this
report are initial estimates of the deposition of nutrients and selected contaminants.
When possible, the atmospheric deposition rates are compared to other input
sources. An example of the use of the meteorological data generated by this study to
explain some of the events leading to the higher than normal nitrogen deposition
on selected data is provided.
The sampling site was established in Seabrook, Texas at an existing State of
Texas sampling site. The samplers were located inside a fenced area on platforms at
least 6 feet above the ground. The site was established following criteria established
for other Great Waters sampling sites. Galveston Bay is in a highly industrialized
and urbanized area and as such some local influences for some contaminants were
expected. However, these local sources would also be important input sources to
Galveston Bay and the selection of the sampling sit as representative of this area is
justified.
There were no specific data quality objective (DQO) acceptance criteria set for
this project. Instead the methods used were required to be as similar as possible to
those of other successful Great Waters studies. Field blanks are used to estimate
concentrations that are different than zero for this type of study. The data produced
for this study shows most analytes in the samples were at concentrations at least 3
times higher than those found for field blanks, with the exception of the trace
element air samples. The concentrations found are comparable to those found in
similar Great Waters and other studies. The results of duplicate analyses, where
applicable, were within acceptance limits set for other types of analyses. The data
were produced by reputable laboratories employing similar methods to other
laboratories that participated in the Great Waters program. The MQO provided
reliable data for most analytes based on the above stated criteria. The database
established by this study allows the estimation of atmospheric inputs of selected
contaminants to Galveston Bay

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Air Toxics Deposition Monitoring in Galveston Bay, Texas:
Texas Regional Integrated Atmospheric Deposition Study
Introduction
In order to fulfill the mandates of the Great Waters Program and the Clean
Air Act Amendments of 1990 (112 m), the US EPA initiated monitoring research in
important and representative water bodies, including coastal waters. As part of this
program the Texas Regional Integrated Atmospheric Deposition Study (TRIADS)
was established by the Geochemical and Environmental Research Group (GERG), of
Texas A&M University with funding from EPA Great Waters Program. The
sampling site is located in Seabrook, Texas (at an existing State of Texas, TNRCC site;
Figure 1) in order to monitor atmospheric deposition of contaminants to Galveston
Bay, a representative southern, coastal water estuary. Monitoring at the TRIADS
site started on February 2, 1995 and was in continuous operation until August 6,
1996.
The Clean Water Act as amended by the Water Quality Act of 1987 established
the National Estuary Program (NEP) to promote long term planning and
management in nationally significant estuaries threatened by pollution,
development, or overuse. Section 320 of the Clean Water Act describes the
establishment of a management conference in each estuary to develop a
Comprehensive Conservation and Management Plan. It also establishes
requirements to monitor the effectiveness of actions put in place by these plans.
Each estuary monitoring project must address the unique information needs for
that specific estuary, but all monitoring programs in the NEP should be based on
sound scientific principals and when possible employ comparable methods and
strategies. The EPA has established NEP in 28 of approximately 100 major US
estuaries. EPA established one of these NEP in Galveston Bay, Texas. In summary
the EPA NEP brings together citizens, business representatives, scientists, state and
local officials and environmental organizations to develop common-sense plans for
conservation and management of these estuaries. The need for information on the
importance of atmospheric deposition of nutrients and contaminants to Galveston
Bay is required to properly manage this resource.
Background
TRIADS samples were collected and analyzed for a group of contaminants of
concern to Galveston Bay and other coastal waters in the Gulf of Mexico. The
sampling and analytical design of TRIADS was similar to that of other EPA Great
Water program sites in the Great Lakes and Chesapeake Bay. The goal of TRIADS is
to provide an evaluation of the type and amount of selected contaminants entering
Galveston Bay from atmospheric deposition. A secondary goal is to evaluate long
range atmospheric transport of contaminants to Galveston Bay as well as the other
Great Waters. The research results will provide critical missing information on the
importance of atmospheric deposition of contaminants. Atmospheric transport and
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wet and dry deposition are important sources of many pollutants, such as
hydrophobic organic compounds (polycyclic aromatic hydrocarbons (PAHs),
pesticides, and poly chlorinated biphenyls (PCBs)), trace elements and nutrients, like
nitrogen, to terrestrial and aquatic ecosystems.
The TRIADS site was established to produce data comparable to existing Great
Waters atmospheric deposition sampling sites. Meteorological parameters
measured include: temperature; relative humidity; wind speed; wind direction;
solar radiation; total rainfall. Samples of rainfall were collected with a wet only
sampler that provides the large volumes of rain necessary to detect the low
concentrations of organic contaminants including, polynuclear aromatic
hydrocarbons (PAH), PCB and selected pesticides (including DDT's, chlordane,
HCH's etc.). An Aerochem Metrics wet/dry sampler is used to collect wet only
samples for trace metals/metalloids (Cu, Zn, Pb, Ag, Ni, Cd, Hg, Se, As, Fe, Mn, Al),
DOC, anions (CI, nitrate and sulfate) and nutrient analyses. A Graseby/Andersen
GPS1 polyurethane foam (PUF) sampling system is used for collection of air samples
to determine the concentration of PAH, PCB, and pesticides in the particulate and
vapor phases in ambient air. Atmospheric particulate samples for trace metal
analyses are collected with a Graseby/Andersen SAUV-1 flow controlled high
volume sampling system. Over one year of continuous data from samples collected
every 10 days or longer is provided for the contaminants listed above. The results of
air sample analyses allow for the calculation of "Dry" deposition of atmospheric
contaminants, while the rain sample analyses allow for the direct measurement of
"Wet" deposition.
Objectives
The main objective of TRIADS was to produce a data base that could be used
to provides estimates of atmospheric deposition to Galveston Bay and compare the
importance of these inputs to other sources of contaminant input. One of the
parameters that has been consistently found to be missing for most estuaries is an
estimate of the magnitude of atmospheric input of nutrients and contaminants.
This information is necessary if the determination of nutrient and contaminant
budgets are to be comprehensive. The use of the TRIADS data will complement
data from other historical and ongoing investigations in Galveston Bay, such as
through the Galveston Bay National Estuary Program (GBNEP), EPA-EMAP, NOAA
National Status and Trends program and Texas General Land Office Programs. The
results of these programs will be used along with the data from TRIADS to estimate
the cumulative, direct and indirect inputs of atmospheric nutrients and
contaminants to Galveston Bay. The TRIADS data is comparable to other ongoing
EPA Great Waters programs and should therefore, allow for an integrated
assessment of the relationship of atmospheric deposition of the measured nutrients
and contaminants to other input sources in cases where data is available.
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Justification
What are the pollutants of concern coming from the atmosphere to Galveston
Bay.
Previous research done at GERG ( GBNEP -20 and others) documents the
presence of combustion derived PAH in fish and shellfish from Galveston Bay.
Some of these contaminants may be coming from atmospheric inputs. The
presence of wide-spread PCB contamination in the fish and shellfish in all areas of
the Bay with the only point source permitted discharge (Rollins) in the Houston
Ship Channel also suggest that atmospheric deposition may be an important input
source for these contaminants. GERG (GBNEP-20 and others) also found pesticides
(DDT's, chlordanes, HCHs, etc.) trace elements (Hg, Pb) and dioxin/furans in
organisms from Galveston Bay. The TRIADS atmospheric deposition data allow for
the estimation of contaminant atmospheric inputs to Galveston Bay. This is vital
information for management decisions. The study also provides estimates for
atmospheric deposition inputs of trace elements, DOC and nutrients, including
nitrogen. While some of these contaminants are not a serious issue for Galveston
Bay, the information found in this study could be applied to other Gulf Coast
estuaries. For Example, while nitrogen loading is less of an issue for Galveston Bay
it is an issue for several tributaries (Houston Ship Channel, Clear Creek, Dickinson
Bayou, Cedar Bayou) and other estuaries (Corpus Christi, Tampa Bay).
*1,
What is the magnitude of atmospheric loading relative to other sources.
The question of the importance of atmospheric deposition to the pollutant
loading to Galveston Bay likely dates back to the early 1980's. It is listed as a research
need in the Research Action Plan of the Galveston Bay Plan. The existing TRIADS
data along with , GBNEP Non-point Source Loading Study (GBNEP-15) and GBNEP
Point source Loading Study (GBNEP-36) makes the calculations of the magnitude of
atmospheric loading and their comparison to other inputs possible for selected
contaminants. Even when data are not available from other sources for
comparison, at least there will be an estimated input from atmospheric deposition.
Contribution of this work to national air deposition information.
The sampling and analytical design of TRIADS is similar to that of existing
EPA Great Water program sites in the Great Lakes and Chesapeake Bay. TRIADS
site and analyses are done under a Quality Assurance Project Project Plan (QAPjP),
Analytical Deposition Monitoring in Galveston Bay, Texas (WA 1-222) approved by
EPA with the understanding that the TRIADS sampling site provides data
comparable to other EPA Great Waters sampling sites. TRIADS will assist in
determining the national extent and nature of the atmospheric deposition problem.
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Status of data gathering and ability to build on existing information.
Over one year of continuous data from samples collected every 10 days or
longer is available for selected contaminants (listed above). Data from other EPA
Great Waters Collection sites is available to put the TRIADS data into a national
context.
Sampling Status
The TRIADS site was set up at Seabrook, Texas (29° 34' 39.84"; 95° Y 1.4") in
January of 1995 and sampling commenced on February 2, 1995 with the collection of
air samples for organic analyses. The sampling site was serviced about every two
weeks in order to maximize the probability of collecting the maximum number of
individual precipitation events. During the period between February 2 and August
6, 1996, 23 sample collections visits to the site were made. Details of these site visits
are provided below.
Monitoring Data Status
The meteorological data that was collected is stored electronically and was
transferred to the GERG VAX computer following QA approval. Meteorological
data was obtained from a weather station close to the sampling site for periods when
data was not collected at the site .
Some samples were archived in excess of recommended holding times but
this is not expected to affect the validity of the results. Data indicate that all the
samplers were operating properly and that uncontaminated samples of sufficient
volume for the analytes to be detected were obtained. The meteorological, PAH and
PCB/pesticide and trace element data are provided in Appendix I, II, III and IV,
respectively. These data show that most contaminants of concern are detected in the
rain and air samples. The concentrations found are in the range of those reported
for other Great Waters studies. The QA/QC results indicate that the sampling and
analytical techniques provided reliable data.
Sampling History
1) January 12-13 1995 (Julian Day 12-13)
TRIADS site setup during this time period. Meteorological data logger and
weather station brought on line. The following sensors were connected to data
logger and data logged from 13 January 1995 at 1535 to 2 February 1995 at 1055.
Temperature (HMP35C Vaisala temperature and RH probe), relative humidity
(HMP35C Vaisala temperature and RH probe), wind speed (Met One anemometer
014A), wind direction (Met One wind direction sensor 024A), solar radiation (LICOR
Li200X pyranometer), total rainfall (Belfort model 5915) and CR-10 battery voltages
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were logged every 5 minutes to the SM192 storage module. The Baker sampler was
deployed and the Baker CR10 was set up to log Baker Sampler functions. The rain
gauge was initially calibrated. The organic air sampler (GMW PS-1) calibration was
attempted in the field, however; an inoperative magnahelic gauge prevented
calibration. The sampler was returned to College Station for maintenance and
replacement of the magnahelic gauge. The organic air sampler was subsequently
calibrated in College Station on 1 February 1995. The trace metal air sampler (GMW
SAUV-1) was calibrated in College Station on 27 January 1995.
2)	February 2-3,1995 (Julian Day 34-35)
Arrived on site to find Baker sampler inoperative with no battery power
remaining. Since the Baker CR-10 data logger lost data when power is interrupted,
all data associated with the Baker Sampler was lost over this time period. The
Aerochem Metrics sampler, the trace metal high volume air sampler, and the
organic air sampler were installed at the site. Two discrete organic air samples were
collected consisting of two glass fiber filters, a large and a small PUF for each sample.
The use of a large and small PUF in lieu of one large PUF sample was instituted to
get an indication of any breakthrough for lower molecular weight organic
compounds. One trace metal air sample and blank were generated as a result of this
visit. The data logging program was rewritten on site to ensure that all data will be
logged and saved using the weather station CR10 with the storage module (which
does not lose data when power is lost) and the Baker CR-10 not used. Numerous
modifications were made at this time which included using the Aerochem Metrics
sensor to operate the Baker sampler's opening and closing mechanism. The Belfort
rain gauge was calibrated again due to non-linearity at low volume. The GMW
metals sampler was programmed to turn on at 1700h every day for 2 hours.
3)	February 23,1995 (Julian Day 054)
Arrived on site at 0945. Collected Baker samples (XAD, Blank XAD, and glass
fiber filter), organic air samples (large PUF, small PUF, and two glass fiber filters) ,
metal air samples (sample and blank) and Aerochem Metrics trace metal sample.
Site appeared to be operating within specifications with reasonable data being
displayed using the CR10 key board/display. The storage module was returned to
College Station. It was discovered after return to College Station that no data had
been logged on the CR-10. Originally we thought the storage modules were
inadvertently switched in the field and calculated plenty of remaining storage space
on the one left in the field to allow us to wait until the next scheduled site visit.
The GMW organic sampler was programmed to sample for approximately 6 hours
beginning at 0845 to 1415 every Wednesday.
4)	March 10,1995 (Julian Day 69)
Arrived on site at 0800. Storage module in weather station checked for data,
none present. A software problem was responsible for the lack of logged data, and
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the problem corrected on site. Collected Baker samples (XAD sample, XAD field
blank, sampler glass fiber filter, and field blank glass fiber filter), organic air samples
(large PUF sample and blank, small PUF sample and blank, and two glass fiber
filters), metal air samples (sample and blank), Aerochem Metrics samples (2 trace
metal and 8 nutrient).
5)	March 15,1995 (Julian Day 74)
Arrived on site at 2045. Storage module checked for data and storage space
utilized. Sensor readings checked using CR10 keyboard/display on site. Collected
Baker samples (XAD sample, XAD field blank, and glass fiber filter), organic air
samples (large PUF, small PUF, and two glass fiber filters), metal air samples
(sample), Aerochem Metrics samples (1 trace metal and 2 nutrient). Data (no wind
speed and direction) logged from March 10, 1995 through March 15, 1995.
6)	April 7,1995 (Julian Day 97)
Arrived on site at 1018. Storage module checked for data and storage space
utilized. A problem was noted with the Belfort readings on the CR-10
keyboard/display on site. Reservoir for the Baker sampler overflowed due to
excessive rain, volume through XAD calculated using Belfort volume and surface
area for Baker sampler and Belfort sampler. . Collected Baker samples (XAD
sample, XAD field blank, and glass fiber filter), organic air samples (large PUF
sample and blanks, small PUF sample and blanks, and glass fiber filters both field
blanks and samples), metal air samples (sample and blank), Aerochem Metrics
samples (trace metal and 2 nutrient). Data (no wind speed or direction) logged from
March 15 1995 through April 7,1995.
7)	April 12,1995 (Julian Day 102)
Arrived on site at 0900. Belfort fuse-holder loose resulting in intermittent
readings. Wired around fuse which resulted in stable and reasonable readings.
Checking wind speed and direction indicated that while the readings obtained on
site were reasonable, the data was not logged for wind speed and direction due to
software problems. Moved the wind speed and directional inputs to another table
in the Campbell program and loaded revised program into the storage module.
Verified that wind speed and direction were actually logged in storage module prior
to departure. No samples collected during this site visit. Data (no wind speed or
direction) logged from April 7, 1995 through April 12, 1995.
8)	April 21, 1995 (Julian Day 111)
Arrived on site 1430. Verified all parameters logged from April 12, 1995
through April 21, 1995. Collected Baker samples (XAD sample, XAD field blank,
and glass fiber filter), organic air samples (large PUF both sample and blank, small
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PUF both sample and blank, and glass fiber filters both sample and blank), and metal
air samples.
9)	May 9, 1995 (Julian Day 129)
Arrived on site 1015. Maintenance personnel inadvertently removed tubing
from Baker reservoir during mowing/trimming operations. Re-plumbed the
tubing from Baker sampler to reservoir in order to avoid reoccurrence during
subsequent lawn maintenance operations. XAD sample volume calculated from the
rain volume collected in the Belfort rain gauge. Collected Baker samples (XAD
sample, XAD field blank, and glass fiber filter), organic air samples (large PUF, small
PUF, and two glass fiber filters), metal air samples sample, Aerochem Metrics
samples (trace metal and nutrient). Data logged from April 21, 1995 to May 9, 1995.
10)	May 27,1995 (Julian Day 147)
Arrived on site at 0830. Collected Baker samples (XAD sample, XAD field
blank, and glass fiber filter), organic air samples (large PUF, small PUF, and two glass
fiber filters), metal air samples (sample and 2 blanks), Aerochem Metrics samples
(trace metal and nutrient). Data logged from May 9, 1995 to May 27, 1995.
11)	June 8,1995 (Julian Day 159)
Arrived on site 0945. Collected Baker samples (XAD sample and glass fiber
filter), organic air samples (large PUF both sample and blank, small PUF both
sample and blank, and two glass fiber filters), metal air samples (sample and blank),
Aerochem Metrics samples (2 trace metal and 8 nutrient). Volume of rain during
sampling period was greater than the Baker sampler reservoir and the volume for
the XAD sample was calculated. Data logged from May 27,1995 to June 8, 1995.
12)	June 30,1995 (Julian Day 181)
Arrived on site at 1050. Collected Baker samples (XAD sample, XAD field
blank, and glass fiber filter), organic air samples (large PUF both sample and blank,
small PUF both sample and blank, and two glass fiber filters), metal air samples
(sample and blank), Aerochem Metrics samples (2 trace metal and 2 nutrient). Data
logged from June 8, 1995 to June 30, 1995.
12) July 23, 1995 (Julian Day 204)
Arrived on site at 0900. Collected Baker samples (XAD sample, XAD field
blank, and glass fiber filter), organic air samples (large PUF both sample and blank,
small PUF both sample and blank, and two glass fiber filters), metal air samples
(sample and blank), Aerochem Metrics samples (2 trace metal and 2 nutrient). Data
logged from June 30,1995 to July 30,1995.
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13)	August 2,1995 (Julian Day 214)
Arrived on site 1030. Collected Baker samples (XAD sample, XAD field
blank, and glass fiber filter), organic air samples (large PUF both sample and blank,
small PUF both sample and blank, and two glass fiber filters), metal air samples
(sample and blank), Aerochem Metrics samples (2 trace metal and 2 nutrient). Data
logged from July 23, 1995 to August 2, 1995. The organic air sampler program was
modified to take advantage of potential tropical storm (Erin) landfall in Galveston
area. The organic sampler was set up to sample from 0500 to 1700 on August 7,1995.
14)	August 14, 1995 (Julian Day 226)
Arrived on site 1000. Collected Baker samples (XAD sample and glass fiber
filter), organic air samples (large PUF both sample and blank, small PUF both
sample and blank, and two glass fiber filters), and metal air sample. Data logged
from August 2, 1995 to August 14, 1995.
15)	August 23,1995 (Julian Day 235)
Arrived on site 1015. Collected Baker samples (XAD sample and glass fiber
filter), organic air samples (large PUF, small PUF, and two glass fiber filters), metal
air samples (sample and 3 blanks), Aerochem Metrics samples (2 trace metal and 8
nutrient). No data logged due to storage module being cleared prior to downloading
in error resulting in no data from August 14, 1995 to August 23, 1995. The Belfort
rain gauge was calibrated using calibration weights.
16)	September 12,1995 (Julian Day 255)
Arrived on site at 1100. No rain samples collected. Organic air samples (large
PUF, small PUF, and two glass fiber filters), metal air samples ( delivered to G. Gill)
collected. Data logged from 1630 Day 235 to 1115 day 255.
17)	September 22, 1995 (Julian Day 265)
Arrived on site at 1040. Collected Baker samples (XAD sample and glass fiber
filter), organic air samples (large PUF, small PUF, and two glass fiber filters), metal
air sample, Aerochem Metrics samples (1 trace metal and 2 nutrient). Data logged
from 1121 day 255 to 1055 day 265.
18)	October 9,1995 (Julian Day 282)
Arrived on site at 1100. Collected Baker samples (XAD sample and glass fiber
filter), organic air samples (large PUF, small PUF, and two glass fiber filters), metal
air sample, Aerochem Metrics samples (1 trace metal and 2 nutrient). Data logged
from 1100 day 265 to 1115 day 282.
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19)	October 31, 1995 (Julian Day 304)
Arrived on site at 0920. Collected Baker samples (XAD sample and glass fiber
filter), organic air samples (large PUF, small PUF, and two glass fiber filters), metal
air sample, Aerochem Metrics samples (1 trace metal and 2 nutrient). GMW air
sampler returned to College Station for repair. Data logged from 1130 day 282 to 1015
day 304.
20)	November 22, 1995 (Julian Day 326)
Arrived on site at 0820. Collected Baker samples (XAD sample and glass fiber
filter), organic air samples (large PUF, small PUF, and two glass fiber filters),
Aerochem Metrics samples (1 trace metal and 2 nutrient). Returned GMW air
sampler to site. Data logged from 1030 day 304 to 0900 day 326.
21)	December 19,1995 (Julian Day 353)
Arrived on site at 0900. Collected Baker samples (XAD sample and glass fiber
filter), organic air samples (large PUF, small PUF, and two glass fiber filters), metal
air sample, Aerochem Metrics samples (1 trace metal and 2 nutrient). Data logged
from 0930 day 326 to 1000 day 353.
22)	January 14, 1996 (Julian Day 14)
Arrived on site at 0650. Collected Baker samples (XAD sample and glass fiber
filter), organic air samples (large PUF, small PUF, and two glass fiber filters), metal
air sample, Aerochem Metrics samples (1 trace metal and 2 nutrient). Data logged
from 1030 day 353 to 0700 day 14.
23)	February 25, 1996 (Julian Day 56)
Arrived on site at 0930. Collected Baker samples (XAD sample and glass fiber
filter), organic air samples (large PUF, small PUF, and two glass fiber filters), metal
air sample, Aerochem Metrics samples (1 trace metal and 2 nutrient). Data logged
from 0730 day 14 to 1000 day 56.
24)	March 15, 1996 (Julian Day 75)
Arrived on site at 1215. Collected Baker samples (XAD sample and glass fiber
filter), organic air samples (large PUF, small PUF, and two glass fiber filters), metal
air sample, Aerochem Metrics samples (1 trace metal and 2 nutrient). Data logged
from 1030 day 56 to 1255 day 75.
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25) June 2,1996 (Julian Day 154)
Arrived on site at 1030. Collected organic air samples (large PUF, small PUF,
and two glass fiber filters), metal air sample, Aerochem Metrics samples (1 trace
metal and 2 nutrient). Data logged from 1300 day 109 to 1100 day 154.
26) August 6, 1996 (Julian Day 219)
Arrived on site at 0830. Collected metal air sample, Aerochem Metrics
samples (1 trace metal and 2 nutrient). Data logged from 1130 day 219 to 1015 day
304.
Methods
Meteorological
Meteorological parameters measured include: temperature; relative
humidity; wind speed; wind direction; solar radiation; total rainfall. These
instuments were calibrated as received. They were not calibrated after one year of
service. These parameters are recorded directly from the corresponding
meteorological instrument. Meteorological data collected at the Seabrook, Texas
TRIADS site were stored on storage modules that could be downloaded on-site or
brought back to the GERG facility for downloading. The parameters measured
included: date, time, year, temperature, relative humidity, light, precipitation,
battery voltage, grid voltage (indicating rain events), wind speed, and wind
direction. The TRIADS site used a Campbell Scientific CR-10 data logger with SM-
192 storage modules for data storage between site visits. Meteorological sensors
included a Vaisala temperature and relatively probe (HMP35C), a Met One wind
speed (014A) and direction (024A) sensors, a LICOR (Li200X) pyranometer, and a
Belfort (5915) rain gauge. The grid sensor normally outputted a voltage of zero
unless the sensor was wetted in which case the voltage was approximately one volt.
This signal was used as a control signal in the CR-10 for the Baker Sampler to open;
when the signal dropped back to zero volts, the Baker Sampler would close. The
data was logged every fifteen (15) minutes unless a rain event was occurring, then
the data was logged every three (3) minutes until the rain ceased. A summary of the
meteorological results are reported in Appendix I. The full data base is provide in
electronic format.
Sampling
Initial sampling took place from February 2, 1995 to August 6, 1996 at
Seabrook, Texas. Samples were collected for 2 to 3 weeks period in 1995 and 1 to 2
month long periods in 1996. Meteorological data, including temperature, relative
humidity, wind speed, wind direction, and total rainfall, were obtained during each
sampling event. Each precipitation sample was comprised of the all individual rain
events during the sampling period.
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For the analysis of PAHs, PCBs and some pesticides, samples of ambient air
were collected with an organic air sampler. The organic air sampler employed two
filters followed by a large PUF, and a small PUF. Particulate and vapor phases were
collected separately by glass fiber filter and cylindrical polyurethane foam (PUF)
plugs, respectively. Filters and PUFs were all cleaned before use. Rain samples for
organic analyses were collected with the Baker sampler, a wet-only collector which is
closed during dry periods. Rainwater was filtered through a glass fiber filter by
gravity flow. The rainwater then passed through a XAD-2 resin cartridge. The
filtered rainwater is collected in a reservoir. The total volume of collected rain was
measured. Contaminants of interest are retained by the filter and/or resin.
Wet only deposition samples were collected in separate pre-cleaned
containers for trace elements and nutrient analysis with an Aerochem Metrics
sampler (Miami, Fl). Normally the dry bucket is open. However, when precipitation
begins, a grid-plate conductor designed-sensor detects precipitation and activates a
motor that moves a lid from over the wet bucket to cover the dry bucket, and vice
versa when precipitation stops. Blank filters, PUFs and XADs were collected from
the field site for each sampling event. Filters, PUFs and XADs were carried to the
field, installed in the sampler, removed immediately, and returned to the laboratory
for analysis. Laboratory blanks were clean, unused filters and PUFs. After
sampling, the samples for organic analyses were sealed in pre-cleaned glass jars and
samples for trace element analyses in sealed in plastic containers. Samples were
returned with the field blanks to the laboratory for analyses.
Organic Analyses
The XAD, sodium sulfate-dried filter samples, and PUF plugs were Soxhlet-
extracted. The XAD was extracted with 400 mL acetone:hexane (1:1) for 24 h. The
filter samples were extracted with methylene chloride (CH2C12) for 24 h. The PUF air
samples were extracted with pentane for 24 h(GERG, 1989a). Before extraction,
internal standards were added. To facilitate the gas chromatographic analysis and
remove interferences, extracts were cleaned-up by silica gel/ alumina column
chromatography. The columns consisted of 5 g anhydrous sodium sulfate, 20 g silica
gel, 10 g alumina, 5 g sand, and glass wool. The sample was added to the column
containing pentane in 1 mL of hexane, and eluted by 200 mL of a mixture of
pentane:dichloromethane (1:1). The elutes were concentrated and exchanged to 1
mL hexane (GERG, 1989a) which was separated into two 500 mL aliquots for the
analysis of organochlorine pesticides, PAHs, and PCBs. For the analysis of the
pesticides/PCBs, the 500 mL aliquot was evaporated to 100 mL using nitrogen before
analyses. Analysis for PAHs and pesticides/PCBS were conducted using a gas
chromatograph with capillary columns, equipped with either a mass selective
detector (MSD) or an electron capture detector (ECD). individual PAH, pesticides,
and PCB congeners were identified by their retention times relative to standard
solutions. The organic contaminants results are provided in Appendix II.
11

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Nutrients
Rainwater samples collected with an Aerochem Metrics sampler were
analyzed for nitrate, nitrite, ammonium, and urea using a Technicon
AutoAnalyzer. Samples were frozen until being analyzed. For analysis of
nitrate/nitrite, the sulfanilamide-NEDA (naphthylethylenediamine
dihydrochloride) method was used (Armstrong et al., 1967; Atlas et al., 1971). A
cadmium reduction column was used to reduce nitrate to nitrite. Phenol-
hypochlorite (Grasshoff, 1970) and diacetlmonoxime methods (Aminot and
Kerovel, 1982) were respectively used for analysis of ammonium and urea.
Nitrate/nitrite were analyzed at room temperature while ammonium and urea
analyses were being heated to 80°C and 90°C, respectively. Colorimeter interference
filters in the spectrophotometers of the AutoAnalyzer were 550 nm for
nitrate/nitrite, 635 nm for ammonium, and 520 nm for urea. The peaks recorded on
a flow chart were measured and converted to the concentration values relative to
standards. The P04 and Si03 were also determined using Technicon AutoAnalyzer
techniques (Murphy and Riley, 1962; Brewer and Riley, 1966). Blanks and standards
were run at the beginning and end of each batch of samples.
Major, Minor, Trace Elements and Nutrients
An Aerochem Metrics wet/dry sampler was used to collect wet only samples
for trace metals/metalloids (Cu, Zn, Pb, Ag, Ni, Cd, Hg, Se, As, Fe, Mn, Al), TOC, and
anions (CI, nitrate and sulfate). Atmospheric particulate samples for trace metal
analyses were collected with a Graseby/Andersen SAUV-1 flow controlled high
volume sampling system. Samples were collected every 2 to 3 weeks is provided for
the contaminants listed above. Dissolved organic carbon in rain samples was
determined on a Shimatzu TOC-500 analyzer. Major ions (chloride, nitrate and
sulfate) in rain were determined by a Dionnex Ion Chromatograph. Trace element
concentrations in the rain samples were determined with a Perkin Elmer PE5100
GFAAS and a Perkin Elmer Elan 500 Inductively Coupled Mass Spectrometer (ICP-
MS) equipped with ultrasonic nebulizer and flow injection sample introduction
system. The ICP-MS employs Sc, Bi, Tb and Rh as internal standards and a
qualitative analyses program. Air filters were microwave digested after they were
placed in Teflon bombs with 20 mL of Q-HC1, 30 mL of Q-HN03 and 10 mL of Q-HF.
Standard reference material (SRM 2074, Buffalo River Sediment) from the National
Institute of Standards and Technology (NIST) was analyzed to establish precision
and accuracy. Field blanks were also monitored. Analyte concentrations were
determined by ICP-MS and GFAAS. The results of the major, minor trace element
TOC, anions and nutrients analytical results are provided in Appendix III.
Results and Discussion
The results of air sample analyses allow for the calculation of "Dry"
deposition of atmospheric contaminants, while the rain sample analyses allow for
12

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the direct measurement of "Wet" deposition. Due to funding and time constrains
only a preliminary discussion of the results of the study are presented here.
Nutrients
Nitrogen compounds can have both beneficial (e.g., soil fertility, plant
nutrient) and harmful effects (ozone destruction, greenhouse effect, air pollution,
acid rain, acidification and eutrophication of surface waters, and contamination of
ground water). EPA took these deleterious effects into account and has a mandate to
evaluate and regulate nitrogen compounds under the Clean Air Act, the Clean
Water Act, the Drinking Water Act, etc. Beside agricultural and sewage loadings of
nitrogen via river and direct discharge, deposition of atmospheric nitrogen is a
major fraction of anthropogenic nitrogen loadings to coastal ecosystems (Fisher et
al., 1991; Hinga et al., 1991), which may cause harmful eutrophication (See collection
of papers of eutrophication in the Baltic. In: Ambio, 19(3), 1990).
Since fossil fuel burning, automobile exhaust gas, etc., contribute significantly
to atmospheric nitrogen (Duce et al., 1991), such human activities could potentially
influence the productivity in the ocean (Owens et al., 1992). The concentrations of
nitrate and ammonium depend on the amount of precipitation (Liken et al., 1987)
and on the character of the air mass (Shon, 1994). Nitrate and ammonium appears
to be derived primarily from gaseous constituents of the atmosphere (Gambell and
Fisher, 1964). Different air masses reaching the sampling site appeared to cause
temporal variations in inorganic and organic nitrogen concentrations in the
precipitation (Loye-Pilot et al., 1990; Shon, 1994). The natural sources of nitrate in
rain are lightning, causing the formation of nitric oxide, photochemical oxidation in
the stratosphere of NzO to NO and N02, chemical oxidation in the atmosphere of
ammonia to NOx, and soil production of NO by microbial processes. The
anthropogenic sources of nitrate in rain are fossil fuel burning, mainly in
automobile engines and power plants and biomass burning (Logan, 1981).
Another important nitrogen compounds, ammonium is found as gaseous
NH3 and NH4+ in aerosol formed in the atmosphere, which can be used by plants as
a nutrient. Ammonium results from the reaction of ammonia gas (NH3) with water
(NH3 + H20 = NH4+ OH-). Thus the presence of gaseous ammonia in the
atmosphere has been inferred by the measurement of the NH/ ion in rainwater
(Junge, 1963; McConnel, 1973). Shon (1994) summarizes that atmospheric ammonia
is produced mainly by 1) decay of animal and human excrements, 2) bacterial
decomposition of natural nitrogenous organic material in natural soils, 3)
volatilization from nitrogen fertilizer, and 4) combustion of coal.
Urea is produced by plankton excretion and decomposition (Van Vleet and
Williams, 1983; Carlson, 1983). Healy et al., (1974) suggested that the major source of
ammonia appeared to be urea in animal urine in the U.K. Urea is likely to be
directly volatilized from land and water surfaces into the atmosphere. High urea in
13

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the total dissolved organic nitrogen (DON) concentrations have been reported in
New Zealand, Japan (Timperley et al., 1985), and Texas (Shon, 1994).
However, it is often difficult to estimate the source of atmospheric nitrogen
by evaluating the chemical composition of wet deposition, because of other removal
mechanisms such as adsorption by plants (Hutchinson et al., 1972; Denmead et al.,
1976) and oxidation by OH radical (McConnell, 1973). Thus Lenhard and
Gravenhorst (1980) conducted aircraft measurements over rural area in western
Germany, in order to compare the result with theoretical estimations of ammonia
emissions from the ground by natural and anthropogenic processes. They found
that about half of the total ammonia emitted to the atmosphere is not rained out in
the same area.
Dry deposition has been variously estimated to account for from about one
half to four times the wet deposition contribution for nitrogen (Sirois and Vet, 1985;
Riggan et al., 1985; Vet et al., 1988). Of the total dry deposition, 75% would be by
adsorption of nitric acid to surface (Lovett and Lindberg, 1986). Although a common
assumption is that dry deposition equals wet deposition (Fisher et al., 1991; Tyler,
1988; Schwarz, 1989), Galloway (1985) observed that wet deposition of DIN species
(i.e., N03" and NH4+) in continental areas was much greater than dry deposition of
particulate and gas phase nitrogen (N03", HN03, NOx, NH3, and NH4+). The
measurement of only inorganic forms of nitrogen (e.g., nitrate and ammonia) may
sometimes underestimate the total nitrogen deposition. Dissolved organic nitrogen
(DON) may be a large fraction of atmospheric nitrogen in wet deposition and
contribute to the input of atmospheric nitrogen to the land and the oceans (Sidle,
1967; Timperley et al., 1985; Bottenheim and Gallant, 1987; Mopper and Zika, 1987;
Pedulla, 1989; Gorzelska and Galloway, 1990). However, it is still difficult to assess
the importance of atmospheric organic nitrogen, due to the lack of reliable data. Few
studies have considered the nature, origin, or ecological significance of DON.
Atmospheric nutrient nitrogen may be important in some marine ecosystem
(Paerl, 1985; Fanning, 1989; Loye-Piolt et al., 1990; Hinga et al., 1991; Owen et al, 1992)
particularly where nitrogen is the limiting nutrient (Smith, 1984), even though
there are some contrary reports (Knap et al., 1986; Michaels et al., 1993).
A study conducted on the Rhode River, sub-estuary of the Chesapeake Bay,
found that all forms of atmospheric nitrogen (including ammonium) to the surface
of the estuary contributed 40 % of the total annual nitrogen loading (Corell and
Ford, 1982). Patwardhan and Donigan (1995) estimated the contribution of
atmospheric nitrogen deposition to Chesapeake Bay, Galveston Bay, and Tempa Bay,
with respect to the nitrogen contribution from nonpoint and point sources. Their
estimation was based on the method of Fisher et al. (1991) applied to Chesapeake Bay
which estimates 23% from point sources, 39% from atmospheric deposition
(including both nitrate and ammonia), 34% from fertilizers, and 4% from animal
wastes.
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The air mass back-trajectory model developed by NOAA (the National
Oceanic and Atmospheric Administration) is sometimes used to evaluate transport
of air mass on a regional, continental or global scale (Harris, 1982; Likens et al., 1987;
Shon, 1994). The model can produce forward or backward trajectories in time and
may aid in determining the source region for selected anthropogenic components.
The nutrient concentrations in |imol/L determined for the TRIADS study in
rain samples collected between February 25, 1995 and August 6, 1996 are reported in
Table 1. Total nitrogen is the sum of NH4, Urea, N03, and NOz. The predominant
nitrogen species is either N03 or occasionally NH4. The reported concentration are,
in most cases, averages of replicate analyses. The replicates agreed very well in most
cases (Appendix III). The concentrations for P04 and Si03 were low and do not have
a simple relationship to total nitrogen. The ratio of total nitrogen to P04 is over 100
indicating that contamination of rain samples from bird feces was minimal. The
P04 concentrations were low and ranged from 0.02 to 0.22 |imol/L. The Si03
concentrations were also low and ranged from 0.01 to 0.25 jimol/L. By comparison,
total nitrogen concentrations ranged from 7.72 to 365 |imol/L. The highest
concentration was present predominantly as N03 (357 |imol/L) and this
concentration was confirmed by separate analyses of the trace element sample for
N03 (385 |imol/L). The second highest total nitrogen concentrations was 70 (imol/L
(Table 1). The amount of rain recorded during the collection period is also provided
in Table 1.
The rainfall amount (mm) and the total nutrient nitrogen (|imol/L) are
plotted versus Julian Day when the samples were collected (Figure 2). The interval
between sample collection ranged from 5 to 70 days, but generally was less than 30
days. There is no apparent correlation between rainfall amount and nutrient
nitrogen concentration.
Cumulative rainfall (mm) is plotted versus Julian Day (1995 plus 1996) in
Figure 3. Cumulative rainfall is simply the total rainfall collected after sample
collection on February 23, 1995 (Day 69) and the last sample collection August 6, 1996
(365+Day 219=584). The cumulative rainfall was linear with an equation of the line
of y=-39.268+2.7449X and a correlation coefficient(R2) of 0.956. The average rainfall
calculated from this equation was 963 mm/year. The average rainfall to the
Galveston Bay area is 50 inches or 1270 mm/year (Stanly, 1989). Therefore the
rainfall amount for the 1995 to 1996 sampling period was less than average by about
25%.
Cumulative nutrient nitrogen deposition in Kg N/hectar versus Julian Day is
plotted in Figure 3. The plot would likely provide a linear line fit, except for the
large rain nitrogen deposition between Julian Days 147 to 159 and 159 to 181. The
concentration of nutrient nitrogen in the rain from Julian Day 147 to 159 was
average (24.21 (imol/L), but the rainfall amount was the highest recorded (200 mm).
The 200 mm or 7.87 inches of rainfall is above the 21-year high average of 4.89
inches reported for Galveston Bay (Newell et al., 1992). The rain for Julian Day 159
15

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to 181 had the highest reported nutrient nitrogen concentration (365 |imol/L) and
was ten times higher than the next high reported concentration and also had a
higher than average rainfall amount (92.6 mm). The cause of this high nitrogen
deposition during this 45-day period will be discussed later. If the total number of
days (530) is divided by the total nutrient nitrogen deposition (8.95 Kg/hectar) then
multiplied by 365 days/year, the yearly deposition rate is calculated to be 6.16
Kg/hector-year. This is the average yearly rate. The 2 deposition event between
Julian Day 147 to 181 was eliminated and the remaining data are plotted in Figure 4.
The cumulative deposition is linear with an equation of the line of
y=0.43772+0.00712X and a line fit coefficient (R2) of 0.972. Using this equation, the
nutrient nitrogen deposition rate is calculated as 3.04 Kg/hectar-year. This indicates
that the rain events from Julian Day 147 to 181 double the yearly wet nutrient
nitrogen deposition estimate.
Sources of nutrient nitrogen to Galveston Bay including atmospheric
deposition have been estimated by Patwardhan and Donigian (1995). These
estimates were done using methods developed for and applied to Chesapeake Bay
(Fisher et al., 1988). The estimates for atmospheric deposition to Galveston Bay were
incorrect due to an error in the surface area that was used for Galveston Bay and its
drainage basin. Patwardhan and Donigian (1995) used an area of 10.84 and 1.40
million hectares for the drainage basin and the surface are of Galveston Bay,
respectively. These areas are ten times higher than the actual surface areas. The
correct areas are 1.08 and 0.14 million hectares for the drainage basin and surface
area, respectively. When the correct surface areas are used with the Patwardhan and
Donigian (1995) method, the total direct atmospheric deposition of nutrient
nitrogen to Galveston Bay is estimated as 1.406 million Kg per year. The
atmospheric deposition to the watershed that reaches Galveston Bay is 0.576 million
Kg per year for a total atmospheric input of 1.982 million Kg of nutrient nitrogen per
year.
Patwardhan and Donigian (1995) use atmospheric deposition data from the
average of 1983 to 1991 at Attwater Prairie Chicken NWR National Atmospheric
Deposition Program (NADP) sampling site. Based on the data collected from
TRIADS a more appropriate estimate based on Patwardhan and Donigian (1995)
method of atmospheric deposition to Galveston Bay is presented.
The yearly atmospheric wet deposition of nutrient nitrogen determined from
this study is 6.16 Kg/hectare-year. This number can be used in the model developed
by Patwardhan and Donigian (1995) to provide an estimate of the nitrogen budget
for Galveston Bay. This model assumes that wet deposition is equal to dry
deposition so total deposition would be 12.32 Kg/hectare-year. Based on the surface
area of Galveston Bay (0.143xl06 hectare), the total input from atmospheric
deposition of nutrient nitrogen directly to the Bay is estimated as 1.76xl06 Kg/year.
It is estimated that point sources deliver 6.74xl06 Kg/year of nutrient nitrogen
directly to the Bay and an additional 10.80xl06 Kg/year is delivered by rivers that
enter the Bay for a total from point sources of 17.54xl06 Kg/year. Based on
16

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Patwardhan and Donigian (1995), an additional 0.58xl06 Kg is added from
atmospheric deposition to the water shed and 0.63xl06 Kg from fertilizer application
to croplands. This would be a total input of 20.51xl06 Kg/year. The direct
atmospheric input calculated from the TRIADS data is 8.6% of the total nutrient
nitrogen input to Galveston Bay with another 2.3% from atmospheric input to the
watershed. Therefore, atmospheric inputs supplies about 10% of the nutrient
nitrogen to Galveston Bay. This percentage will likely increase as point sources
directly to the water of nitrogen inputs are regulated.
One use of the meteorological data provided from the TRIADS sampling site
is to look at what might have been the cause of specific deposition events such as
the high nitrogen deposition between June 8 (Day 159) and }une 30 (Day 181). The
main rain event during this period occurred between June 11 and 12, 1995 (Figure 6).
This event was due to the forcing caused by a synoptic front. The wind direction
(Figure 7) shifted from southeasterly to northwesterly just before the rain event and
continued from the northwest during the rain event. This is not a common
occurrence. These conditions provided air over the sampling site that was advected
from the heavily industrialized Houston area northwest of the sampling site. This
advected air could be the source of the nitrogen. The dissipation of nitrogen while
enroute was minimized due to decreased winds (Figure 8) and the subsidence
caused by the high pressure that followed the front. Subsidence over the Houston
area would inhibit upward mixing of the lower atmosphere maintaining high
nitrogen concentrations as the air moved over the Seabrook sampling site. These
conditions are documented in the air mass trajectories. The air mass trajectory for
June 11, 1995 (Figure 9) shows air mass passed from the Gulf of Mexico to the
Galveston Bay area then turned from its southeasterly flow to the northwesterly
flow at the time of the rain event. The trajectory for June 12, 1995 (Figure 10) shows
prevailing northwesterly winds and strong subsidence over the region. Therefore,
this unusual post frontal rain event is a likely explanation of this high nitrogen
deposition event.
The phosphate concentrations were much lower than the nitrogen
concentrations. The phosphate cumulative wet deposition is plotted versus Julian
Day (1985 plus 1996) in Figure 11. The cumulative distribution is linear with a
correlation coefficient of the line fit (R2) of 0.833 and an equation Y(g/hectare) equals
2.4684+0.0519Q9X. The deposition rate calculated from this equation is 21.4
g/hectare-year for phosphate. The deposition rate can also be estimated from the
cumulative deposits for the sampling period (26.5 g/hectare) divided by the total
sampling day (530 day) then multiplying by 365 day/year. This provides an estimate
of the deposition of 18.3 g/hectare-year. Therefore the phosphate deposition rate is
approximately 20 g/hectare-year. Based on the surface area of Galveston Bay of
0.143xl06 hectares, this represents a direct phosphate input from wet deposition of
2.86xl03 Kg of phosphate per year. The annual non-point source input of phosphate
to Galveston Bay is estimated as l,110xl03 Kg of phosphate per year (Newall et al.,
1992). The phosphate input from direct wet deposition to Galveston Bay is only
0.26% of the total non-point input.
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The silicate concentrations were also much lower than the nitrogen
concentrations. The silicate cumulative wet deposition is plotted versus Julian Day
in Figure 12. The cumulative distribution is linear with a correlation coefficient for
the line fit (R2) of 0.929 and an equation of the line of Y (g/hectare) equals
2.0433+0.067937X. The deposition rate calculated from this equation is 26.8
g/hectare-year for silicates. The deposition rate can also be calculated from the
cumulative deposition as explained for phosphate. The deposition for silicate
estimated from the cumulative deposition is 24.1 g/hectare-year. Therefore, the
silicate deposition rate is about 25 g/hectare-year and the estimated wet deposition to
Galveston Bay for silicate is 3.58xl03 Kg/year which is similar to the phosphate wet
deposition.
Organic Contaminants
Organic compounds in the atmosphere have been investigated in terms of
total organic carbon (TOC), dissolved organic carbon (DOC), amino acids, pesticides,
PCBs, hydrocarbons, vitamins, carboxylic acids, etc. Organic carbon is abundant and
ubiquitous in rain. Precipitation contains very complex organic compounds in very
low concentrations.
PAHs, PCBs, and pesticides
The atmosphere plays an important role in the transport, deposition, and
cycling of natural and anthropogenic (volatile and non-volatile) organic compounds
(Eisenreich et al., 1981; Bidleman, 1988; Duce et al., 1991; Leister and Baker, 1994). For
example, it has been estimated that when all inputs, including direct industrial
discharge, are considered, more than 80% of PCBs entering the Great Lakes came
from atmosphere deposition (Eisenreich et al, 1981). Thus atmospheric deposition is
a significant source of pollutants to surface waters, especially coastal waters of
industrialized areas, including Texas.
Polycyclic aromatic hydrocarbons (PAHs) are emitted by incomplete fuel
combustion (e.g., domestic heating, industrial plants and automobile traffic, etc.).
Pesticides (e.g., DDT) and synthesized chemicals (e.g., PCBs) are mobilized into the
atmosphere from agricultural and industrial activity (Bidleman, 1988). Thus, they
are ubiquitous in the atmosphere, especially near urban and industrialized areas.
These organic contaminants are characterized by their physicochemical properties of
low water solubility, high octanol-water partition coefficients, the ability to
bioconcentrate, and their chemical/microbiological stability (Eisenreich et al., 1981).
Some PAHs (benzo(a)anthracene, chrysene, benzo(b and k)fluoranthene,
benzo(a)pyrene, and others) and oxygenated and nitrated PAHs have been reported
to be carcinogenic in fishes, mammals, and humans (Menzie et al., 1992).
Organic contaminants can be removed from atmosphere by dry deposition,
wet removal, and air-water gas exchange (Bidleman, 1988; Duce et al., 1991). The dry
18

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deposition includes the sorption by the direct impact of particles and gaseous
molecules on land, water, or vegetation. Wet scavenging includes the removal of
aerosols and gases both within and below clouds during precipitation events, such
as rain, snow, hail, fog and mist. Although there have been some reports that at
least 50% of PAHs and organochlorines are removed from the atmosphere by
precipitation scavenging (Murphy, 1981; Andren and Strand, 1981; Strachan and
Eisenreich, 1986), insoluble compounds such as highly chlorinated PCBs and high
molecular weight PAHs may not be readily washed out by precipitation, due to their
hydrophobicity. Therefore, dry deposition of some PCBs and PAHs could be a
significant mechanism of atmospheric deposition to land and water surfaces.
Estimates of the total deposition of pollutants require assessment of both wet and
dry deposition.
The distribution of atmospheric organics between vapor and particle phases
strongly affects atmospheric removal processes (Eisenreich et al., 1981). The vapor to
particle ratio is controlled by the compounds vapor pressure, ambient temperature
and the total suspended particle concentration (Bidleman, 1988). Therefore,
precipitation contains dissolved and particulate contaminants. With a high volume
air sampler, the filter-retained organics are usually the high-molecular-weight and
low-vapor pressure species (Murphy and Rzeszutko, 1977; Cautreels and Van
Cauwenberghe, 1977). However, since a large fraction of high-molecular-weight
species (e.g., PAH, phathalate esters) could occur in the vapor phase in urban
atmospheres, trace organics distribution between the particle and vapor phases
needs to be interpreted carefully (Eisenreich et al., 1981).
Higher molecular weight aromatics have been reported in smoke plumes
from the TAMU Fireman's Training School and in ambient air in College Station,
Texas (Atlas et al., 1985). Some higher molecular weight chlorinated hydrocarbons,
such as chlordane, toxaphene, hexachlorocyclohexanes (HCH) and DDTs were found
at concentrations of 1-100 ng/L in rain in College Station, Texas (Atlas and Wade,
1988). Similar concentrations to toxaphene and HCH were measured in the air
along the Texas Coast (Change et al., 1985), though chlordane and DDTs were much
lower. A local or regional source was suggested for higher chlordane and DDT
concentrations in College Station (Atlas and Wade, 1988). PAHs concentration in
rainwater from College Station was reported to be lower than those for urban areas,
but higher than some west coast sites (Mazurek and Simoneit, 1983).
Molecular markers have been used in distinguishing biogenic and
anthropogenic sources of atmospheric organic material (Lunde et al., 1977; Georgii
and Schmitt, 1983; Pankow et al., 1984; Kawamura and Kaplan, 1984; Atlas and
Wade, 1988). For example, distributions of alkanes and PAHs in rural and urban
locations illustrate the different patterns characteristic of petrogenic and biogenic
sources. The presence of primarily unsubstituted PAHs provides additional
evidence of input from combustion sources.
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Organic Rain Samples
Organic rain samples were collected with a "Baker" sampler that collects the
rain falling into aim2 surface area. The rain is then gravity filtered through a glass
wool plug and a glass fiber filter that remove particles and then a column
containing XAD-2 resin that collects the dissolved organic contaminants. Results
from this study indicate that generally most contaminants in the rain were found
on the XAD-2 resin. The contaminants on the XAD-2 resin are operationally
defined as dissolved, while the contaminants on the filter are operationally defined
as particulate.
The concentration of dissolved and total (dissolved plus particulate) PAH in
the rain samples are plotted as a bar graph for each sample collection day in Figure
13. The rain data was censored to remove all rain events (4) when less than 9 L of
rain was collected. The concentrations of the sum of all PAH detected on the filter
and XAD-2 resin ranged from 5.5 to 161 ng/L and 52 to 247 ng/L, respectively. The
sum of the particulate and dissolved PAH or total PAH ranged from 50 to 277 ng/L.
There is no apparent seasonal trend in PAH concentration and no relationship to
rain volume was found.
The cumulative total PAH (dissolved and particulate) in wet deposition in
(ig/m2 is plotted versus Julian date in Figure 14. The distribution can be described by
a straight line with the equation, total PAH (|ig/m2) = -5.7147 + 0.35670 (days) with a
correlation coefficient R2 of 0.960 (Figure 14). Using this equation the total PAH wet
deposition is estimated as 124 |ig/m2-year and the yearly direct wet deposition to the
surface (1.43 xl09m2) of Galveston Bay is 177 Kg total PAH/year.
The concentrations of dissolved total HCHs and PCBs are plotted as bar graphs
versus Julian day in Figure 15. There is no seasonal trend and these two
contaminants do not covary. It is interesting to note that the high total HCH on day
181 corresponds to the high nutrient nitrogen concentration for the same rain
event. Total PCB ranges from not detected to 1,731 pg/L. The total HCH ranges
from 83 to 7,171 pg/L. The cumulative PCB wet deposition (ng/m2) is plotted versus
Julian day in Figure 16. The distribution is a straight line with the equation, PCB
(ng/m2) = -94.277 + 2.1038 (day). The yearly wet deposition of PCB as determined by
this equation is 674 ng/m2-year. The yearly input of PCB from wet deposition,
directly to Galveston Bay, is estimated to be 0.96 Kg/year.
The dissolve concentrations of chlordane and 4,4'-DDE (pg/L) is plotted as a
bar graph versus Julian day in Figure 17. The concentrations of 4,4'-DDE are low
(range not detected to 61 pg/L) and it was only detected in 9 of 19 (47°/)) of the events
collected. Chlorine concentrations ranged from not detected to 402 pg/L.
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Organic Air Samples
The organic air samplers were set to sample for 1 to 2 hours each day for the
entire sampling period. The air sampler was calibrated so that the number of cubic
meters of air the sampler pulled through the filters and plugs could be determined.
The air sample concentrations are reported on a m3 basis for pesticides and a ng/m3
basis for PAH.
The concentration of compounds found in the vapor phase of the air sample
is operationally determined by the concentration that passes through the filter and is
retained by the large PUF plug. The total PAH concentration in the vapor phase
ranged from 2.9 to 140 ng/m3. The PAH vapor concentrations versus Julian data are
provided in Figure 18. The sample collected on day 33 and 34 were 12 hr continuous
samples. These samples indicate a constant PAH concentration in the air over the
two day period. There is no clear seasonal trend in the PAH vapor phase
atmospheric concentrations. The concentrations of individual PAH were also
determined and that data is available in Appendix IV.
The concentration of selected pesticides in the vapor phase were also
determined (Appendix IV). The concentration of 4,4'-DDE in the vapor phase
ranged from the MDL (<1 pq/m3) to 38 pg/m3 (Figure 19). The concentration for the
two samples collected on consecutive days were very similar (Figure 19) and were
the two highest concentrations determined. The next highest 4,4'-DDE
concentration was 24 pg/m3.
The vapor concentrations for total HCHs, total PCBs, and total chlordane are
plotted versus Julian Day of sample collection (Figure 20). The range in
concentration for total HCH, total PCBs, and total chlordane are 68 to 666, 71 to 501,
and 31 to 286 pg/m3, respectively. There is no apparent seasonal trend in these
contaminant concentrations and the relative abundance of these contaminants at
various collection times are different (Figure 19). This data for contaminants in the
vapor phase will allow the estimation of dry deposition and gas exchange to be
made.
Trace Elements
The concentrations found in the rain samples collected at the Seabrook site
are reported in Table 3. In addition to the trace elements, dissolved organic carbon
(DOC), chloride, nitrate, and sulfate are reported. The results of duplicate analyses
indicate the precision of the analyses was acceptable (Table 3). DOC in the rain
samples ranged from 0.6 to 13.3 mg C/L. The value weighted average DOC
concentration for Chesapeake Bay is 4.3 mg/L (Velinsky et al., 1986). These DOC
concentrations are within the range of reported values.
The concentrations of Al (|ig/L) and total rainfall (mm) are presented as a bar
graph in Figure 21. There is no apparent correlation between rainfall amount and
21

-------
A1 concentration. The A1 concentration is plotted versus the Fe concentration in
rain samples in Figure 22. The concentrations have a linear correlation (R2=0.980)
and a line fit equation of Fe=3.5199+0.5562 Al. A linear correlation is expected if
crustal material is the major source of these elements. The same type of plot was
done for the other trace elements and only Mn and Pb had a linear relationship with
Al (Figure 23). Therefore, the presence of Mn and Pb appear to be primarily related
to the presence of crustal material.
The Zn concentrations ranged from 1.8 to 36.8 fig/L. It does not have a linear
relationship when plotted versus Al. The cumulative Zn deposition versus Julian
Day (1995 plus 1996) is provided in Figure 24. The cumulative Zn deposition is
linear and the equation of the line allows for an estimate of the yearly deposition to
Galveston Bay for Zn to be calculated. The deposition of Zn based on this equation
is 52 g/hectare-year. The total wet deposition input to the surface of Galveston Bay
(0.143xl06 hectares) is 7.4xl06 g/year.
The concentration of Cu ranged from ND to 2.8 fig/L. The concentration of
Cu was below the detection limit in 35% of the rain events analyzed. The Cu
cumulative deposition has a linear relationship when plotted versus Julian Day
(Figure 25) using the equation of this line fit. The deposition of Cu is estimated as
7.3 g/hectare-year. The Cu input directly to Galveston Bay from wet deposition is
then estimated as 1.05xl06 g/year. The annual non-point source load of Cu
(dissolved) to Galveston Bay in an average year is estimated as 10.9xl06 g/year
(Newell et al., 1992). The estimated input from Cu from wet deposition is 9.6% of
the total input and if dry deposition of Cu is approximately equivalent to wet
deposition, the total atmospheric deposit input of Cu directly to Galveston Bay is
about 20%.
The trace metal data for air samples is presented in Table 3. This table also
contains the results of the analyses (8) of a sediment SRM (NIST 2704) analyzed with
the samples. Also reported are several filter blanks. It is apparent that the filter
contained too much of several of the trace elements making the data not high
enough above the background to make any interpretation for Al, Fe, Ni, Zn, Ag, Se,
and As. There was no Cd or Hg detected in any of the air samples. That leaves only
the Cu data and perhaps the Fe and Mn data that can be interpreted. In future air
studies for trace elements, different filters with lower background should be used.
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27

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Table 1. TRIADS Nutrient Concentration (u mole/L) and Rainfall Amount (mm), 1995-1996.
Collection
Period
Julian Date
Days
File Numbers
nh4
Urea
no3
NO,
Total N
po4
Si03
Rain
(mm)
54-69
15
C18674-7
11.14
0.39
17.41
0.03
28.97
0.05
0.12
103.28
69-74
5
C18793-4
5.47
0.44
4.71
0.03
10.65
0.08
0.05
43.01
74-97
23
C19945-6
10.25
0.73
4.11
0.04
15.13
0.07
0.20
18.47
97-129
32
C20343
24.61
1.08
41.7
0.19
67.58
0.21
0.28
44.24
129-147
18
C20821
28.93
1.92
32.81
1.06
64.72
0.31
0.72
9.64
147-159
12
C20991-2
17.72
0.7
5.6
0.18
24.2
0.07
0.01
200.07
159-181
22
C21171-2
7.41
0.34
357.35
0.02
365.12
0.07
0.26
92.55
181-204
23
C21648-9
8.9
0.35
17.08
0.03
26.36
0.03
0.01
84.72
204-214
10
C21709-10
6.1
0.34
27.85
0.03
34.32
0.22
0.04
44.8
214-235
21
C21967-8
5.37
0.48
64.1
0.03
69.98
0.08
0.15
1.17
235-265
30
C22195-6
2.24
0.22
17.63
0.03
20.12
0.03
0.14
61.16
265-282
17
C22316-7
6.14
0.3
45.5
0.04
51.98
0.03
0.07
21.26
282-304
22
C22519-20
4.64
0.26
38.03
0.03
42.96
0.02
0.01
23.7
304-326
22
C22654-5
6.58
0.3
3.84
0.06
10.78
0.03
0.07
171.61
326-353
27
C23152-3
5.02
0.29
8.4
0.04
13.75
0.03
0.07
140.19
353-365-14
26
C23286-7
3.3
0.15
14.33
0.03
17.81
0.02
0.03
50.59
14-56
42
C23444-5
3.16
0.51
21.4
0.03
25.1
0.08
0.13
79.76
56-75
19
C23563-4
0.11
0.24
7.35
0.02
7.72
0.02
0.2
15.84
75-154
79
C25383-4
15.29
0.46
18.58
0.02
34.35
0.03
0.03
86.73
154-219
65
C25389-90
0.12
0.22
10.32
0.02
10.68
0.02
0.03
89.85

-------
Table 2. Inorganic and DOC Concentrations in Rain.
lollection
Period
Days
File
Numbers
DOC
PPM
CI
PPM
N03
PPM
S04
PPM
A1
PPB
Mi
PPB
Fe
PPB
Ni
PPB
Cu
PPb
Zn
PPB
Ag
PPB
Cd
PPB
Pb
PPB
Se
PPB
As
PPB
Hg
PPB
54-69

C18680
2.14
6
5.8
2.3
19.5
1.4
3.4
ND
ND
5.9
ND
ND
0.4
ND
ND
ND
54-69

C18681
1.35
5.9
5.4
2.2
10.9
1.2
ND
ND
ND
6.1
ND
ND
0.4
ND
ND
ND
54-69
15
Average
1.745
5.95
5.6
. 2.25
15.2
1.3
1.7


6


0.4



69-74
5
C1S792
2.4S
6.9
5.2
1.8
7.8
1.3
ND
ND
ND
36.8
ND
ND
0.2
ND
ND
ND
74-97
23
C19449
1.6
5.6
2.6
1.7
13.5
1.4
ND
ND
ND
2.1
ND
ND
0.1
ND
ND
ND
97-129
32
C20342
2.63
12
5.9
2.7
84.9
6.2
35.3
0.2
ND
5.9
ND
ND
0.5
ND
ND
ND
129-147
2S
C20S20
13.3
1.1
3.2
4.5
345
9.9
191
0.9
0.3
18.6
ND
0.8
1.9
ND
ND
ND
147-159
12
C21004
1.52
4.9
3.6
1.4
136
1.6
71
ND
ND
3.2
ND
ND
0.5
ND
ND
ND
159-1S1
22
C211S3
0.71
1.1
23.9
0.9
45.8
2.7
35.4
0.5
3.9
2.9
ND
0.06
0.3
2.7
ND
0.4
159-181
22
C211S4
0.76
2.9
23.8
0.8
32.9
2.1
24.1
0.1
1.7
3.1
ND
0.07
0
1.4
ND
0.3
159-1S1
22
Average
0.735
2
23.85
0.S5
39.35
2.4
29.75
0.3
2.8
3

0.065
0.15
2.05

0.35
181-204
23
C21661
0.S3
2.9
5.9
1.5
11.5
1.6
10.1
0.6
1.9
3.7
ND
0.06
0.3
1.2
ND
ND
1S1-204
23
C21662
0.96
2.6
6
1.5
20.4
1.7
20.1
0.4
2.2
3.2
ND
0.16
0.3
0.7
ND
ND
181-204
23
Average
0.S95
2.75
5.95
1.5
15.95
1.65
15.1
0.5
2.05
3.45

0.11
0.3
0.95


204-214
10
C21707
0.99
1.3
3.7
1.3
20.1
0.8
ND
ND
ND
3.1
ND
ND
0.1
ND
ND
ND
204-214
10
C21708
0.62
1.9
5
1.2
22.3
1.5
1.2
ND
ND
3.6
ND
ND
0.2
ND
ND
ND
204-214
10
Average
0.805
1.6
4.35
1.25
21.2
1.15
0.6


3.35


0.15

-------
Table 2. Cont.
Collection	Days File	DOC	CI	N03	S04	A1	Mn	Fe	Ni	Cu	Zn	Ag	Cd	Pb	Se	As	Hg
Period	Numbers	PPM	PPM	PPM	PPM	PPB	PPB	PPB	PPB	PPb	PPB	PPB	PPB	PPB PPB	PPB	PPB
214-235	21	C21976	3.73	23.7	16.1	2.3	85.4	1.6	48.5	0.2	2.9	18.4	ND	ND	0.8	ND	ND	ND
235-265	20	C22194	0.7 1	5.1	1.4	14.5	0.4	ND	ND	1.2	5.5	ND	ND	0.4	ND	ND	ND
265-2S2	17	C22314	4.61	14.4	4.7	1	5.7	ND	ND	ND	ND	1.8	ND	ND	0.1	ND	ND	ND
2S2-304	22	C2251S	5.02	5.4	1.9	1.2	4.7	0.6	2.4	0.1	1.2	4	ND	0.29	0	1.4	ND	0.6
304-326	22	C22653	0.67	2.3	0.8	0.9	4	1	1.5	0	0.5	2.7	ND	0.04	0.3	2.6	ND	0.9
326-353	27	C23151	0.6	1.4	0.7	1.1	1.8	1.7	0.5	0.6	1.2	3.1	ND	0.1	0.2	1.3	ND	1.7
353-365-14	26	C23285	0.67	3.3	1.2	2.1	2.9	0.7	4.3	0.1	0.4	2.9	ND	0.07	0.2	1.5	ND	0.3
14-56	42	C23443	0.46	2.4	1	1.6	8.3	2.5	1.1	0.5	1.2	3.2	ND	0.06	0.1	0.5	ND	ND
56-75	19	C23560	1.47	3.2	1.5	2.6	43.3	4.9	5.8	0.5	0.5	4.1	ND	0.06	0.3	1.8	ND	ND
75-154	79	C25387	0.94	10	1.5	1.9	39.7	2.9	15	0.6	2	5.5	ND	0.08	0.4	2.6	ND	0.8
154-219	65	C25392	0.75	2.3	1.2	1.3	18.3	1.9	1.8	0.2	1.1	3.5	ND	0.06	0	1.4	ND	1.1

-------
Table 3. Inorganic Concentrations in Air Samples.
lollection
Days
File
A1
Vfri
Fe
Ni
Cu
Zn
Ag
Cd
Pb
Se
As
Hg
Period

Numbers
™S
MB

MS

MP
MS
LIS

MS
MS
Mf?
54-69

C18678
43.4
94.5
4.33
32.5
304
301
8.5
ND
147
4.9
15.2
ND
54-69
Blank
C18679
38
13.5
1.64
24.3
4.8
259
5
ND
105
ND
15.2
ND
69-74
5
C18791
35
30.5
2.15
1
42.5
238
6
ND
101
0.5
13.6
ND
74-97
23
C19451
15.5
206
12.9
31
378
291
9
ND
163
4
19.9
ND
97-129
32
C20344
44.4
183
12.3
25.5
184
279
10
ND
150
4.3
16.9
ND
129-147
2S
C20815
39.3
103
6.48
16.5
171
277
11.5
ND
134
4.9
16.4
ND
129-147
Back Filter
C20816
41.3
29.5
2.1
32.9
43.3
287
8.5
ND
99.5
ND
15
ND
129-147
Blank
C20817
39.1
13.5
1.79
29.6
8.8
268
8.5
ND
98.5
ND
17.6
ND
147-159
12
C21003
36.4
82.5
5.71
10.5
120
271
8
ND
124
1.3
14.4
ND
159-181
22
C211S1
45.3
132
7.53
24.5
345
294
11
ND
117
9.1
16.4
ND
159-181
Blank
C211S2
33.1
11.54
1.64
31
7.4
253
8
ND
97
ND
14
ND
181-204
23
C21657
47.3
157
9.36
25.5
397
280
8.5
ND
137
5.2
14.6
ND
181-204
Blank
C21658
40.1
11.5
1.68
27.8
7
271
8
ND
109
ND
34.1
ND
204-214
10
C21694
40.3
101
6.55
7
125
286
6.5
ND
132
0.7
16.2
ND
204-214
Blank
C21695
38.9
14.5
1.8
24.2
5
270
8
ND
121
ND
15.7
ND
214-226
12
C21S90
44.3
50.5
3.81
5.5
117
264
9
ND
110
2.2
13.8
ND
226-235
9
C21977
43.7
60.5
4.22
3.5
123
295
9.5
ND
130
1.5
14.8
ND
226-235
Blank
C2197S
43.2
14
1.78
25.3
4.9
275
9
ND
107
13.1
15.6
ND

Blank
C21979
41.4
10.5
1.62
25.6
4.7
264
11
ND
103
ND
14.1
ND

Blank
C21980
42.1
17.5
1.9
27.9
6.3
296
11.5
ND
109
ND
16.5
ND
235-265
20
No Data

-------
Table 3. Cont.
Collection Days File A1 Mn Fe Ni Cu Zn Ag Cd Pb Se As Hg
Period	Numbers nig ig nig ig	ug	ig	ig	ig	tg	tig ug	ug
265-2S2
17
No Data
282-304
2S2-304
304-326
326-353
22
Blank
22
27
Blank
C22509
C22510
No Data
C23147
C23148
22.2
29
22.8
25.1
63
16
50
106
2.8
1
2.2
5
34
10
24
661
70
?
113
18
76.9 ND
83.1 ND
82.9
57.5
ND
ND
44
34
44
34
53
60
85
35
29
28
38
21
ND
ND
ND
ND
353-365-
14
14-56
14-56
56-75
75-154
154-219
26
Blank
42
Blank
19
79
Blank
65
C23281
C232S2
C23439
C23440
C25380
C25395
21.5
30.8
17.2
33.1
C23557 24.5
12.4
27.3
C25388 18.7
56
16
109
16
197
172
15
134
2.2
0.9
4.5
0.9
8.4
0.9
7.3
25
9
31
9
10.4 1173
45
8
32
97
?
127
1
244
1
233
80.2
76.3
79.6
84.8
123 65.3
79.8
75.3
71.6
ND
ND
ND
ND
ND
ND
ND
ND
59
36
48
40
42
61
33
48
66
45
92
72
97
66
66
58
32
22
46
32
35
39
31
33
ND
ND
ND
ND
ND
ND
ND
ND
N1ST 2704
N1ST 2704
Certified
Determined
SRM
SRM
6.11
5.89
555
537
4.1 44.1
4.07 43.8
98.6
97.4
438
429
3.45
3.41
161
158
1.12
NC
23.4
23.8
1.47
1.35

-------
LOUISIANA
• ¦ •"	-J&J
TEXAS
Galveston Bay
• v . "< ¦ :

; -,
Gulf of
Mexico
9<>'W
94°W
92aW
90° W
Houston
Trinity Bay I
' Galveston Bay
;t.-w;,- -;
29°30'N
'• g-
Gulf of
Mexico
Galveston
0 km 5 10
94°30'W
Figure l.
TRIADS Galveston Bay sampling location, Seabrook, Texas.

-------
350
300
250
200
150
100
50
0
/jk	TRIADS RAINFALL AND NUTRIENT NITROGEN
¦ RAIN (mm)
E3 I N (umole/l)
"/ A
9 7 4 9 7 1 2 9 1 4 7 1 5 9 1 8 1 2 0 4 2 1 4 2 3 5 2 6 5 2 8 2 3 0 4 3 2 6 3 5 3 3 7 9 4 2 1 4 4 0 5 1 9 5 8 4
JULIAN DAY (1995 AND 1996)
I. Amount of rainfall (mm) collected and nutrient nitrogen concentration (|imol/L).

-------

1400 "
y
TRIADS CUMULATIVE RAINFALL (mm)

•
•

1200 -

y = - 39.264 + 2.7449X
RA2 = 0.956 •
• >
• y


?
E,
1000 -

•



z






<
GC
LU
>
H
800 -
/
/ •
•
<
-1
Z)
S
Z3
O
600 "
/


400 "
/






/
/ m m




200 "
~ • T
m
•




o -

	1	1	1	¦	1	"	1	¦	1	1	1	¦	1	>	r
,

—,—r
0	5 0 1 00 1 50 200 250 300 350 400 450 500 550 600
JULIAN DAY (1995 and 1996)
Figure 3. TRIADS cumulative rainfall amount.

-------
10
9
8
7
6
5
4
3
2
1
0
JULIAN DAY (1995 AND 1996)
Figure 4 Cumulative nutrient nitrogen deposition.

-------
4.0
TRIADS CUMULATIVE WET DEPOSITION "CENSORED" (kg/hectare)

3.5
y = 0.43772 + 7.1185e-3x
RA2 = 0.972
0.0
1 0 0
200
3 00
400
5 0 0
CUMULATIVE DAYS
Figure 5.
Cumulative nutrient nitrogen deposition (censored data).

-------
Precipatation (1995)
Day of Year
Figure 6.
Precipitation record for Julian day 159 to 169.

-------
Wind Direction (1995)

V
o
L_
CD
 r t m m r» i 11 rr'l i f i'i'i r1
t t •t-fYTT^rrnrmmf^mW't1r f t r rmiWriT
Wlrffrmmh'V1
Figure 7.
Wind direction record for Julian day 159 to 169.

-------
Wind Speed (1995)
-------
nunri nj.r nesuurues Lduui atui y
This product was produced by an Internet user on the NOAA Air
Resources Laboratory's web site. See the disclaimer for further
information 
-------
This product was produced by an Internet user on the NOAA Air
''SjgStflgy Resources Laboratory's web site. See the disclaimer for further
' information 
as
02
E-i
Sz;
o
(H
&
w
o
02
p
o
07
z
a
s
K
m
H
H
o
po
o
Q
r-i
o
U
25
>•
a,
33-
700
900
Figure 10. Back air mass trajectory for June 12, 1995.
A 10O0HPA
¦ IOO0HPA
~ 9WHPA
-------
30
a>
k_
re
o
0)
.c
O)
UJ
I-
<
X
Q.
(/)
O
X
0.
Hi
>
I-
<
_l
3
S
3
O
25

20
15
10
TRIADS CUMULATIVE PHOSPHATE WET DEPOSITION (g/hectare)
y = 2.4684 + 5.1909e-2x
RA2 = 0.833
• •
• •
• •

/_
1 0 0
2 00
300
400
5 0 0
600
JULIAN DAY (1995 AND 1996)
Figure 11. Cumulative phosphate deposition.
-------
40
35
30
25
20
15
10
5
0
JULIAN DAY (1995 AND 1996)
Figure 12. Cumulative silicate deposition.
-------
400
TRIADS RAIN PAH DISSOLVED (XAD) AND TOTAL CONCENTRATIONS
o>
c
Z
o
h-
<
CC
I-
z
LU
o
z
o
o
350
300
250
200
150
100
B PAHng/l
S PAH XAD ng/l
Figure 13.
JULIAN DAY
Dissolve and total PAH concentrations in
rain samples.
-------
200
180
160
140
120
100
80
60
40
20
0 ¦
JULIAN DAY (1995 AND 1996)
Figure 14. Cumulative total PAH wet deposition.
-------
8000
7000
6000
5000
4000
3000
2000
1000
0
TRIADS RAfN CONCENTRATIONS HCHs AND PCBs
JULIAN DAY
Figure 15. Dissolved total HCH and PCB concentrations in rain samples.
-------
1000
900
800
700
600
500
400
300
200
100
0
JULIAN DAY (1995 AND 1996)
Figure 16. Cumulative PCB wet deposition.
-------
450 | TRIADS RAIN CONCENTRATIONS CHLORDANE AND 4,4'-DDE

CT>
<3-
r>.
o>

o>
T-


<0
in
CM
<*
<0
CO
o>
T-
o>
in
to
h-
o>
CM

in
00
O
y-
CM
<0
CO
o
CM
in

CM
T-




t-
y-

r-
CM
CNI
CM
CM
CM
CO
co
CO
CO

U)
JULIAN DAY
Figure 17. Dissolved chlordane and 4,4'-DDE concentrations in rain samples.
-------
TRIADS PAH CONCENTRATIONS IN PUF AIR SAMPLES
Figure 18.
JULIAN DAY (1995 AND 1996)
Total vapor phase (PUF) PAH concentrations in air samples.
-------
Figure 19.
JULIAN DATE (1995 AND 1996)
4,4'-DDE vapor phase (PUF) concentrations in air samples.
-------
JULIAN DATE (1995 AND 1996)
Figure 20. Total HCH, 18PCB and chlordane vapor phase concentrations in air samples.
-------
400 */
TRIADS RAINFALL AND Al
69 74 97 129 147 159 181204 214 235 265 282 304 326 353 379 421440 519 584
JULIAN DAY (1995 plus 1996)
Figure 21. Rainfall amount (mm) and Al concentration (|ig/L) in rain samples.
-------
180
160
140
120
100
80
60
40 '
20 •
0 •
Al CONCENTRATIONS (ug/l)
Figure 22. Concentration of Fe versus Al in rain samples.
-------
10
9
8
7
6
5
4
3
2
1
0 ¦
Al CONCENTRATION (ug/l)
Figure 23. Concentration of Mn and Pb versus Al in rain samples.
-------
80
	
TRIADS CUMULATIVE Zn WET DEPOSITION (g/hectare)
JULIAN DAYS (1995 AND 1996)
Figure 24. Cumulative deposition of Zn in wet deposition.
-------
0)
(C
+•>
o
0)
SZ
O)
z
o
H
CO
O
CL
LU
O
3
o
UJ
>
p
<
—J
D
5
D
O
1 0 0
2 0 0
300
400
500
600
JULIAN DAY (1995 AND 1996)
Figure 25. Cumulative deposition of Cu in wet deposition.
-------
Attachment A
The required calibration from the W/QAPjP for this projected are
summarized in Table 1. The field instruments were either calibrated at the factory
or in the field for air sampling gauges (Table 1). Due to delay in initiation of
sampling and collection of samples in excess of one year, the meteorological sensors
were not recalibrated after one year. Comparison with meteorological data from
weather stations in. the vicinity of the sampling site indicates the meteorological
data is valid. The wind direction sensor was checked with a compass and the Belfort
rain gauge was calibrated with calibration weights.
Analytical instruments were calibrated as stated in Table 1 and described in
the Q/QAPjP. The final data was validated following the following QA checks.
The following internal QC checks were made.
1.	Field blanks were analyzed for all analytes. The levels of target
compounds in the field blanks were determined.
2.	The response of calibration standards, the background levels in field and
laboratory blanks, and the recoveries of surrogate/matrix spikes were
monitored.
3.	Every set of organic samples processed for ongoing analysis contained a
laboratory matrix spike (LMB). The LMB was monitored.
4.	Analytical calibration standards were analyzed to monitor retention
times as well as relative detector response. These responses were used
for qualitative and quantitative identification of the target compounds.
5.	Surrogate spikes were added to every organic sample and blank prior to
extraction, permitting recovery to be checked on 100% of the samples.
Matrix spike samples, containing the full suite of PCB congeners, PAHs,
or pesticides, were included with each set of samples processed.
Surrogate recovery of PCB congener 103, PAHs, and pesticides was
between 50% and 130%, or the data were flagged. In addition, if fewer
than 1/3 of the PCB or pesticides surrogates or <70% of the pesticide of
PCB, pesticide or PAH matrix spike target compounds were <50% or
>130% recovery, the data was flagged.
6.	Trace metal, TOC, major ion duplicate acceptance levels were a relative
% error of 33% or less for trace elements. The relative % error was
exceeded in some cases. This is likely due to the fact that the field
duplicates reflect analytical uncertainty as well as inhomogeneity of the
rain samples. The instrument for trace element analysis was calibrated
in the range from 2.5 to 150 ppb. Gallium and scandium were added and
-------
used for mass identification purposes. Selected samples were analyzed
in duplicate and the results agreed within the uncertainty of the method.
7.	Nutrients were determined by standard methods on an autoanalyzer.
Laboratory duplicates agreed within ±20% while field duplicates in some
cases had high variability.
8.	Mr. Steve Sweet acted as the internal work assignment Quality
Assurance Officer to validate the final data set.
-------
QUALITY ASSURANCE STATEMENT
Contractor Geochemical and Environmental Research Group	_
Work Assignment Title: 	Air Deposition for Galveston Bay. Texas	
Work Assignment Number: WA-0-26	Task Number: 	
Description of audit and review activities:
Checked initial installation of meteorological and sampling equipment and periodic
checks (at least every three months) to ensure equipment operating properly.
Reviewed analytical data in view of W/QAPjP (April 13, 1994) requirements. See
Attachment A for details.
Description of outstanding issues or deficiencies which may affect data quality:
1.	Meteorological sensors were not recalibrated after one year of operations.
2.	Nutrients held in excess of suggested holding times due to interruption of
funding.
3.	Air particulate filter background levels for trace metals analysis were high
compromising the data.
4. Other deficiencies are noted in individual databases.
_	Vr/?g
Signature of Subcontractor Task Leader	Date
or Work Assignment Leader
Dr. Terry L. Wade
-------
Table 1. Field Instrument Calibration.
Parameter

Sampling
Instrument
Calibration
Method
Frequency Corrective Action

Organics (PCB/PAH/Organochlorine
pesticides)
Air - PM10
Rain - Baker
Flow Gauges
None
3 months
28 days
Adjust flow
Check operation

Trace metal/major ions/nutrients/TOC
Rain - Aerochem
None
28 days
Check operatiQn

Wind speed

Met one
Factory
Annual
None

Wind direction

Met one
Factory
Annual
None

Solar Radiation

LI Cor
Factory
Annual
None

Temperature

Vaisala
Factory
Annual
None

Relative Humidity

Vaisala
Factory
Annual
None

Analytical Instrument Calibration
Parameter
Analytical Instrument
Calibration Method
Frequency
Corrective Action
PCBs

GC-ECD
ISTD

2 standards/sample set
Recalibrate
Organochlorine Pesticides

GC-ECD
ISTD

2 standards/sample set
Recalibrate
PAHs

GC-MSD
ISTD

2 standards/sample set
Recalibrate
Metals

ICP-MS
STD

3 standards/sample set
Recalibrate
Nutrients

AutoAnalyzer
STD

standard/sample set
Recalibrate
Major Ions

Ion Chrom.
STD

2 standards/sample set
Recalibrate
TOC
High temperature combustion with
IR spectrometry
STD

2 standards/sample set
Recalibrate
-------