&EPA
United States
Environmental Protection
Agency
Environmental Sciences Research EPA-600 4-80-004
Laboratory January 1980
Research Triangle Park NC 27711
Research and Development
Chemistry of
Precipitation from
Sequentially
Sampled Storms
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2 Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7 Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL MONITORING series.
This series describes research conducted to develop new or improved methods
and instrumentation for the identification and quantification of environmental
pollutants at the lowest conceivably significant concentrations. It also includes
studies to determine the ambient concentrations of pollutants in the environment
and/or the variance of pollutants as a function of time or meteorological factors.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/4-80-004
January 1980
CHEMISTRY OF PRECIPITATION FROM SEQUENTIALLY SAMPLED STORMS
by
J.K. Robertson, T.W. Dolzine, and R.C. Graham
The Science Research Laboratory
United States Military Academy
West Point, New York 10996
Interagency Agreement No. IAG-D6-0112
Project Officer
Herbert J. Viebrock
Meteorology and Assessment Division
Environmental Sciences Research Laboratory
Research Triangle Park, N.C. 27711
ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
-------
DISCLAIMER
This report has been reviewed by the Environmental Sciences
Research Laboratory, U.S. Environmental Protection Agency, and
approved for publication. Approval does not signify that the
contents necessarily reflect the views and policies of the U.S.
Environmental Protection Agency, nor does mention of trade names
or commercial products constitute endorsement or recommendation
for use.
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ABSTRACT
Sequential sampling techniques and applications to collect
precipitation are reviewed. Chemical data for samples collected
by an intensity-weighted sequential sampling device in operation
at the U.S. Military Academy, West Point, New York from October
1976 to April 1978 are presented and discussed. The problem of
dry deposition is explored. A newly designed intensity-weighted
sequential sampler that excludes dry deposition is presented.
The experiments have shown that intensity-weighted sequential
sampling is a viable technique for monitoring the rapid changes
in precipitation chemistry within a storm. Complete chemical
data are needed from individual storms to evaluate intensity
related scavenging.
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IV
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CONTENTS
Abstract
Figures
Tables
Acknowledgments
1. Introduction
2. Conclusions
3. Recommendations
4. Sequential Sampling
5. The West Point Sampler
6. Experimental Data
7. Discussion
References
Appendices
A. Tabulations of Measured Concentrations
B. Tabulation of Storm Information
C. Interpretation of Periods of Contamination
for the 22 Storms
D. Reagents Used for Standards
iii
vi
viii
x
1
3
4
5
12
22
26
59
63
64
112
113
116
v
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FIGURES
Number Page
1. Comparison of Sampling Strategies. 6
2. Comparison of Linked Bottle Samplers. 9
3. Schematic Diagram of the West Point Sampler. 14
4. The Closure Mechanism for the West Point Sampler. 15
5. Wiring Diagram for the West Point Sampler. 16
6. Siphon and Switch for the West Point Sampler. 17
7. Fractionator with Test Tubes in Place. 17
8. Changes in Storm Chemistry and Intensity, Rainstorm,
2 June 1977. 23
9. Changes in Storm Chemistry and Intensity, Rainstorm,
19 October 1977. 25
10. Changes in Storm Chemistry and Intensity, Rainstorm,
20 October 1976. 27
11. Changes in Storm Chemistry and Intensity, Rainstorm,
7 December 1976. 28
12. Changes in Storm Chemistry and Intensity, Snow/Rain,
17-18 March 1977. 29
13. Changes in Storm Chemistry and Intensity, Rainstorm,
22 March 1977. 30
14. Changes in Storm Chemistry and Intensity, Rainstorm,
28 March 1977. 31
15. Changes in Storm Chemistry and Intensity, Rainstorm,
4-6 April 1977. 32
16. Changes in Storm Chemistry and Intensity, Rainstorm,
23-24 April 1977. 33
vi
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Number Page
17. Changes in Storm Chemistry and Intensity, Rainstorm,
7 June 1977- 34
18. Changes in Storm Chemistry and Intensity, Rainstorm,
18 August 1977. 35
19- Changes in Storm Chemistry and Intensity, Rainstorm,
16-17 September 1977. 36
20. Changes in Storm Chemistry and Intensity, Rainstorm,
18 September 1977. 37
21. Changes in Storm Chemistry and Intensity, Rainstorm,
24-26 September 1977. 38
22. Changes in Storm Chemistry and Intensity, Rainstorm,
26 September 1977. 40
23. Changes in Storm Chemistry and Intensity, Rainstorm,
17 October 1977. 41
24. Changes in Storm Chemistry and Intensity, Rainstorm,
24-26 January 1978. 42
25. Changes in Storm Chemistry and Intensity, Snowstorm,
6-7 February 1978. 44
26. Changes in Storm Chemistry and Intensity, Snowstorm,
3 March 1978. 46
27. Changes in Storm Chemistry and Intensity, Rainstorm,
14-15 March 1978. 47
28. Changes in Storm Chemistry and Intensity, Snowstorm,
16-17 March 1978. 49
29. Changes in Storm Chemistry and Intensity, Rainstorm,
18-20 April 1978. 50
30. Processes Effecting the Number of Aerosol (Liquid & Solid)
Particles in the Air Column. 55
Vll
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TABLES
Number
1. Application of Sequential Precipitation Sampling. 11
2. Operating Conditions Used for the Atomic Absorption
Spectrophotometer and Carbon Rod Furnace. 21
3. Intensity and pH of Rainstorm, 20 Oct 1976. 65
4. Intensity and pH of Rainstorm, 7 Dec 1976. 67
5. Intensity and pH of Snow Followed by Rain,
17-18 March 1977. 69
6. Intensity, pH, and Chemistry of Selected Samples,
Rainstorm, 22 March 1977. 71
7. Intensity, pH, and Chemistry of Selected Samples,
Rainstorm, 28 March 1977. 76
8. Intensity, pH, and Chemistry of Selected Samples,
Rainstorm, 4-6 April 1977. 77
9. Intensity, pH, and Chemistry of Selected Samples,
Rainstorm, 23-24 April 1977. 80
10. Intensity, pH, and Chemistry of Selected Samples,
Rainstorm, 2 June 1977. 82
11. Intensity, pH, and Chemistry of Selected Samples,
Rainstorm, 7 June 1977. 84
12. Intensity, pH, and Chemistry of Selected Samples,
Rainstorm, 18 August 1977. 85
13. Intensity, pH, and Chemistry of Selected Samples,
Rainstorm, 16-17 September 1977. 87
14. Intensity, and pH of Rainstorm, 18 September 1977. 89
15. Intensity, pH, and Chemistry of Selected Samples,
Rainstorm, 24-26 September 1977. 90
viii
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Number Page
16. Intensity, pH, and Chemistry of Selected Samples,
Rainstorm, 26 September 1977- 96
17. Intensity, pH, and Chemistry of Selected Samples,
Rainstorm, 17 October 1977. 99
18. Intensity, pH, and Chemistry of Selected Samples,
Rainstorm, 19 October 1977. 100
19. Intensity, pH, and Chemistry of Selected Samples,
Rainstorm, 24-26 January 1978. 101
20. Intensity, pH, and Chemistry of Selected Samples,
Snowstorm, 6-7 February 1978. 104
21. Intensity, pH, and Chemistry of Snowstorm,
3 March 1978. 105
22. Intensity, pH, and Chemistry of Selected Samples,
Rainstorm, 14-15 March 1978. 106
23. Intensity, pH, and Chemistry of Snowstorm,
16-17 March 1978. 108
24. Intensity, pH, and Chemistry of Selected Samples,
Rainstorm, 18-20 April 1978. 109
IX
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ACKNOWLEDGMENTS
This research was conducted by scientific and technical personnel
of the U.S. Military Academy, West Point, New York under agree-
ment with the U.S. Environmental Protection Agency. The following
Academy personnel contributed significantly to this project:
J. Malcolm G. Wojciechowski
T. Hook M. Frann
D. Pickerell J. Dietzel
0. Dyes J. Hesson
The automated collection apparatus was designed by John Hesson
based on our requirements. The many versions of the collection
apparatus were built and serviced by Gary Wojciechowski to whom
we are deeply indebted.
Special thanks to Mrs. Shirley Bonsell and Ms. Susan Romano for
the many hours at the computer terminal juggling the text editor
to produce the many drafts of this paper.
x
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SECTION 1
INTRODUCTION
Considerable attention has been focused recently on the increas-
ing acidity of precipitation in the northeastern and north cen-
tral United States ,1«a
As a result of this concern, increased monitoring of precipita-
tion chemistry on a regional basis has been proposed.3'4'5 This
proposed network and others currently in operation (CANSAP,
MAP3S, and NADP)+collect precipitation samples on a weekly or
monthly basis. This frequency of collection provides an indica-
tion of how much material has been deposited on the earth's sur-
face by precipitation but fails to explore the instantaneous
acidity extremes and underlying ion chemistries within a storm
that may be potentially more damaging to the environment than the
averages reported.
The purpose of the research reported here was to examine the
changes in precipitation chemistry within individual storm
events. This research is part of a program of research designed
to investigate below cloud scavenging by precipitation. In this
portion of research, an attempt was made to test a number of
hypotheses using data collected by sequentially sampling
precipitation. These hypotheses are enumerated below:
1. The concentration of dissolved constituents in precip-
itation is inversely proportional to the intensity of preci-
pitation within the study pH range.
"""Canadian Network for Sampling Precipitation (CANSAP)
Atmospheric Environment Service, Ontario, Canada.
Multistate Atmospheric Power Production Pollution
Study (MAP3S) Precipitation Chemistry Network
sponsored by the Department of Energy.
National Atmospheric Deposition Program (NADP)
sponsored by the North Central Regional Association
of Directors of the Agricultural Experimental Research
Stations.
-------
2. The concentration of dissolved constituents in precipita-
tion decreases as the storm passes over the collector.
3. The relationships in 1 and 2 apply to both frontal storms
and convective storms.
4. A seasonal variation in the weighted-average pH of storms
ex ists.
5. The chemistry of precipitation within a storm is a result
of the source area from which the storm originated.
6. Values of pH above 5.6 are due to disequilibrium between
rain drops and the air pollutants rather than the presence
of basic ions.
Each of these hypotheses will be discussed more fully in Section
7 along with the data collected during the program.
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SECTION 2
CONCLUSIONS
1. Intensity-weighted sequential sampling is a viable technique
for monitoring the rapid changes in precipitation chemistry
within a storm.
2. Dry deposition in the West Point area is very acidic in
nature. Collection vessels left open to the atmosphere prior
to a storm, or after a storm become quickly contaminated by
dry deposition. During periods of light precipitation, dry
deposition is large and may exceed wet deposition as the
dominant process. Any precipitation chemistry data for storm
events in the West Point area in which dry deposition was not
specifically excluded must be viewed as being possibly conta-
minated by dry deposition or be considered as a bulk precipi-
tation sample (wet and dry precipitation combined).
3. Complete chemical data are needed from individual storms to
evaluate intensity related scavenging.
4. During periods of high intensity precipitation scavenging
causes pH to increase and the amount of dissolved constit-
uents to fall to low levels.
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SECTION 3
RECOMMENDATIONS
Sequential sampling of storms be continued with the following
restrictions:
a. dry deposition be excluded from collection by use of
an automated closure device, and
b. concurrent collection of meteorological parameters
be made.
Every sequential sample within
Na+, NH+ , K + , Ca*2 , Mg+s , Cl~
conductivity.
a storm should be
PO;3,
NO;, SOT",
analyzed
pH, and
for
Selected storms or the initial and intense portions of all
storms should be analyzed for:
a. heavy metals
b. organic acids
The ambient air should be sampled continuously before,
during, and after the sequential sampling of precipitation to
monitor gaseous and particulate pollutants to attempt to
evaluate scavenging of below cloud pollutants from the air
mass .
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SECTION 4
SEQUENTIAL SAMPLING
DEFINITIONS
The chemistry of precipitation has been monitored for many years.
Each researcher's objectives influence the choice of sampling
methods and observation frequency. Those interested in at-
mospheric loading to the environment sample on a monthly, weekly,
or perhaps single storm basis. Those interested in cloud pro-
.cesses and scavenging have used a sequential sampling method.
Sequential sampling produces a number of samples through the
course of a storm, each sample representing the portion of the
storm from which it was collected. A number of sequential
sampling strategies have been used. An analysis of these methods
shows the five basic approaches outlined below:
1. Grab Sampling: Samples are taken without respect to time
or volume, but usually to provide at least a minimal amount
for analysis. Generally samples are collected proportional
to intensity.
2. Time related grab sampling (Figure 1b): Samples of equal
volume are collected at fixed time intervals. Once the set
volume is collected the excess is allowed to spill until the
next time interval starts. An incomplete sample of the
storm will be collected.
3. Time weighted sequential sampling (Figure 1c): Samples of
unequal volume are collected consecutively for a predeter-
mined time interval. The volume of each sample varies de-
pending on the intensity of precipitation during its collec-
tion interval. The container volume is set large enough to
collect the volume from the most intense storm period
expected. Samples are collected without time break for the
whole storm period.
4. Intensity weighted sequential sampling (Figure 1d):
Samples of equal volume, collected at unequal time
intervals. Sampling frequency is proportional to the
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A. HYPOTHETICAL STORM INTENSITY AND CHEMISTRY
«
TIME
B. TIME RELATED GRAB SAMPLING
TIME
C TIME WEIGHTED SEQUENTIAL SAMPLING
TIME
TIME
I
TIME
§?
TIME
D. INTENSITY WEIGHTED SEQUENTIAL SAMPLING
TIME
E. CONTINUOUS MONITORING
TIME
TIME
TIME
FIGURE 1. COMPARISON OF SAMPLING STRATEGIES
See definitions in text.
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intensity of the storm or volume of precipitation. Samples
are collected consecutively without time break for the whole
storm period.
5. Continuous monitoring (Figure 1e). Precipitation is
routed through a sensor or sensors as it is collected. A
continuous record of the instantaneous response from the
sensor is recorded.
FACTORS LEADING TO THE CHOICE OF METHOD USED
The objective of any of the above sampling methods is to describe
the chemistry of the storm as accurately as possible. From this
standpoint continuous monitoring gives the best results, but the
unavailability of adequate sensors for all but a few ions of
interest and the problems of interference have limited its use.
Both intensity weighted sampling and time weighted sequential
sampling provide an average concentration value for the period of
collection of each individual sample. By shortening the time
between collections a closer approximation to the storm chemistry
is achieved. This presents a problem in time weighted sampling
since enough sample to perform all analytical tests of interest
may not be collected.
Intensity-weighted sequential sampling is used in this study
because it provides the following advantages:
1. Sample size is determined by the amount needed to perform
all analytical tests. This provides for easier sampler
design.
2. The volume of sample collected is related to the amount
of precipitation by the surface area of the collector. Thus,
as sample volume requirements change, adjustments are rela-
tively easy to accomplish by changing the siphon volume and
the volume of the collection vessel. Each sample reported
herein represented 0.015 to 0.025 inches of precipitation.
Although the amount of precipitation collected per sample
varied from storm to storm, the amount was constant within a
storm.
3. More samples were collected the harder it rained. Thus,
samples for low intensity periods give an average concentra-
tion value for the period of collection, but during intense
periods the time intervals were shortened to fractions of
minutes and give a good indication of changing chemistry
within the storm.
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REVIEW OF SEQUENTIAL SAMPLING
In the following paragraphs the sequential sampling methods used
by others and the application of the various techniques are re-
viewed and categorized.
Sequential samplers fit into four basic categories:
a. manually segmented samples.
b. linked collection vessels.
c. automatically segmented samples.
d. continuous monitors.
Each has its advantages and disadvantages which make it better
suited for the particular research program or for the analytic
technique employed.
Manual methods are the least expensive in terms of equipment
costs, but all require a researcher to change the collection
vessel at the appropriate time. Manual methods can be employed on
a time-weighted, intensity-weighted, or grab sample basis. The
simplest application is a funnel and bottle or an open wide
mouthed container. Gatz and Dingle6 used a 2.5 m2 funnel for 2
to 8 liter samples. Dana et al .7>8 used a 1 m2 funnel mounted
on the roof of an automobile for following convective storms.
Warburton and colleagues9'10'11 have used sheets of plastic
stacked in a frame and withdrawn one after another to sample snow
and hail. Perkins et al .ls used a large plastic sheet over a roof
to direct rain water to an ion exchange column which trapped the
radionuclides of interest. In this case the ion exchange column
was changed manually. Time of collection must be maintained
manually for all the manual methods.
Linked collection vessel samplers have been employed by three
research groups. They all consist of a series of bottles linked
together by tubing. When one bottle is full, the rainwater flows
into the next in line (Figure 2). Bottle filling time is propor-
tional to intensity. The groups differ in the precautions taken
to prevent mixing of incoming rain with that already in a bottle.
Cooper et al.13 have the simplest device (Figure 2a) which relies
on the narrow tubing leading to the bottle to prevent mixing.
Kennedy et al^14 use air vents on the bottles as shown in Figure
2b to prevent siphoning between bottles. The most sophisticated
is that used by Liljestrand and Morgan (Personal communication,
Figure 2c) in which air vents and a floating stopper are used to
prevent mixing. All three methods will segment a storm
unattended. If collection times are desired they must be moni-
tored by a researcher or calculated from intensity data and fun-
nel area. The automated methods can be divided into timer
actuated, volume actuated, or actuated by a related parameter to
segment the storm. The most widely used sampler is a tipping
bucket (weight)
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b.
FROM
FUNNEL
A-AIR VENTS
B- WATER LEVEL WHEN NEXT
BOTTLE BEGINS TO FILL
C-AIR-VENT TUBE,SERVES
TO LIMIT RISE OF WATER
IN BOTTLE.
AIR VENT
FLOAT
FIGURE 2. COMPARISON OF
a. Cooper et al.. 1976; b.
o. Liljestrand and Morgan,
LINKED BOTTLE SAMPLERS,
Kennedy et aI.. 1976;
personal communication
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actuated device developed at Argonne National Laboratory by Gatz
et al ,15 and used by Dingle16 and Adam et al ,17 in conjunction
with the Metromax study in St. Louis, Missouri. Raynor and
McNeil18 have designed a timer actuated device at Brookhaven
National Laboratory. Time periods are preset but^djustable be-
tween runs. Results reported by Raynor and Hayes are for one
hour collection periods. Krupa (personal communication) at the
University of Minnesota has designed a sampler which senses that
a bottle is full by means of a conductivity detector in the over-
flow port. The University of Minnesota sampler is the only
automated sampler which seals the bottle off from the atmosphere
to prevent exchange of gases after collection. The others utilize
open bottles in a rack which remain open after collection. A 20
sampler based on Krupa's design is now commercially available.
Stensland31 and Pickerell et al.3S have used a siphon to measure
fixed volumes of sample.
The automated methods vary in complexity. Some require manual
starting, but most now are sensor actuated. All have chart re-
corders to record sampling time and cover position. Gatz
(personal communication), now at the Illinois Water Survey, has a
new version of the tipping bucket sampler which operates in
either timer actuated or weight actuated mode. Semonin (personal
communication) reports that the device will operate in intensity
(weight) mode, but can be preset so that if an extended time
passes without a sample being taken a new collection vessel is
moved into place (and presumably the tipping bucket first
emptied).
Few cases of continuous monitoring have been reported.
Stensland illustrates a continuous pH monitor, but presents no
data. Falconer (personal communication) is currently using a
device similar to Stensland's. Most continuous monitoring has
been confined to looking at nuclei in air samples during rain and
snow storms. Radke et al ,33 have used an integrating nephelometer
for this purpose. Gradel and Franey2* have used a cloud nuclei
counter and optical particle counter for the same purpose.
Table 1 summarizes the applications to which sequential samplers
have been applied. Most deal with attempts at discerning cloud
processes or below cloud processes.
10
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TABLE 1. APPLICATION OF SEQUENTIAL PRECIPITATION SAMPLING
APPLICATION
AUTHOR
COLLECTION DEVICE
Opening Segmenting
Method Method
SAMPLING STRATEGY
REMARKS
Rainfall-Runoff
of a Watershed
Conveetive
Storm Processes
Scavenging
14
Kennedy et al. Manual
Linked Bottles
Acid Rain
Adam et al.17
Dana et al .8
Dingle1"6
Linkletter &
Warburton13
Warburton9
Dana et al .7
Ga'tz & Dingle
Gatz et al.1B
Perkins et al.13
Warburton 4
Owens10
West Point
Cooper et al .l3
Falconer^
Krupa*
Liljestrand &
Morgan*
Manual
Always Open
Manual
Manual
Manual
Always Open
Manual
Manual
Always Open
Manual
Manual
Automated
N/S
N/S
Automated
N/S
Raynor & Hayes19 Automated
Tipping Bucket
N/S
Tipping Bucket
Plastic Sheets
Plastic Sheets
Manual
Funnel & Bottles
Tipping Bucket
Ion-Exchange
Column
Plastic Sheets
Siphon
Siphon
Linked Bottles
Continuous
Overflow Sensor
Linked Bottles
Timer
Stensland31
Always Open Siphon
Intensity-Weighted
Intensity-Weighted
N/S
Intensity-Weighted
Grab
Grab
Grab
Grab
Intensity-Weighted
Grab
Grab
Intensity-Weighted
Intensity-Weighted
Intensity-Weighted
Continuous
Intensity-Weighted
Intensity-Weighted
Time-Weighted
Intensity-Weighted
N/S = not stated or not determinable from figures and text presented.
* = personal communication
Mattole River Basin
California
Metromax Study - Scavenging
Metromax Study - Modeling
Hail Suppression
Hail Storms
Power Plant Plumes
Cosmogenic Radionuclides
Lake Effect Storms-Tracer
In Service Oct 76 to May 78
In Service after Nov 78
Heated for Snow & Ice
Austin, Texas
Cloud Water pH
Minneapolis, Minn.
Pasedena, California
Upton, N.Y.;
Heated for Snow & Ice
Lake George, N.Y. ;
Concurrent Continuous pH
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SECTION 5
THE WEST POINT SAMPLER
DESIGN CRITERIA
Galloway's25 study of precipitation samplers provided a basis for
design and selection of construction materials for the West Point
sampler. Unattended automatic operation was one of the
requirements. On sensing precipitation, the sampler was to be
activated (funnel opened, first collection vessel positioned, and
a record of the time made). Dry deposition was to be excluded
prior to the storm, during interludes in the storm, and after the
storm. Since year round operation was desired, the sampler had to
be able to detect and collect rain and snow. The time of collec-
tion of each sample was to be recorded as well as the funnel
cover position (open or closed).
Intensity-weighted sequential sampling was chosen as the basis of
design (see Section 4). In this method of collection a fixed
sample volume, primarily determined by the amount of sample
needed to perform all analytical tests of interest, is the go-
verning design feature. Initial interest was in determining pH,
and the concentration of the common ions in solution (Na , K ,
NHt , Ca""3 , Mg+2 , Cr , F", NOg , SOJ2 , PO^3 ) . At a later time,
tests for conductivity and the concentrations of trace metals and
organics may be useful. Ion chromatography was chosen for the ion
analyses and an automated ion selective electrode for pH. These
selections allowed a design volume of 14 ml (5 ml for pH and 3 ml
for each of three runs on the ion chromatograph) to be chosen.
Any additional tests could be accomodated from the same 14 ml
sample by combining an automated flow-through conductivity meter
in series with the pH electrode (conductivity ahead of pH) and by
using an autoinjector to reduce the volume of the sample needed
for ion chromatography to 2 ml total. The remaining 7 ml could
be analyzed for metals by carbon-rod atomic absorption spectro-
photometry and for low molecular weight organic acids by ion
exclusion chromatography.
The sample volume (14 ml) had to be equivalent to a convenient
multiple of the amount of rain falling over the area of the
funnel. One-one hundredth of an inch of rain (0.254 mm) was
selected, but this required a funnel diameter of 9.43 inches
(264.10 mm). At the time of construction the only funnel avail-
12
-------
able was 7.5 inches in diameter. At 100% efficiency of
collection, each 14 ml of sample would represent 0.0193 inches
(0.491 mm) of precipitation with the 7-5 inch funnel.
THE SAMPLER
The current design of the sampler is shown schematically in
Figure 3. The funnel (c in Figure 3) is polyethylene and 7.5
inches in diameter. It is covered by a closure mechanism (Figure
4; b in Figure 3) activated by a Weathermeasure model 566 preci-
pitation sensor (a in Figure 3). The precipitation sensor (h in
Figure 3) is heated to:
1. melt snow and sleet in winter allowing all weather acti-
vation of the closure mechanism.
2. dry the sensor so that upon cessation of precipitation
the mechanism covers the funnel thus excluding dry
deposition.
The closure mechanism is powered by a reversible motor with li-
miting switches restricting its range of travel. The roof of the
cover is canted in the open position (Figure 4b) to reduce
splashing from the cover into the funnel and to allow snow and
ice to slide off (the roof will be heated if necessary to aid in
snow removal).
The precipitation sensor activates a double throw-triple pole
relay which performs four tasks:
1. provides power and directional control to the motor;
2. provides power to the fraction collector;
3. provides event marking for sensing of funnel cover
position;
4. changes recorder speed from 2.2 cm/hr to 11 cm/hr.
A schematic wiring circuit is provided in Figure 5. The funnel is
connected to the fractionator by a Tygon tube leading to the
Pyrex glass siphon (d in Figure 3; Figure 6) portion of the
fractionator. The siphon is attached by a rubber tube to a switch
operated by the air trapped in the siphon. This switch activates
a relay within the fractionator (f in Figure 3) which advances a
rack of disposable 16 x 150 mm polyethylene culture tubes below
the siphon and at the same time places a mark on the chart re-
corder (g in Figure 3). The fractionator is a commercially
available Buchler Fractomette 200 which will operate in volume,
time, or drop mode. The fractionator (Figure 7) has 20 racks of
10 culture tubes which move around the tray in race track
fashion. Dust is prevented from falling into the open tubes by a
plastic baffle. A magnet placed in the 200th culture tube acti-
vates a shutoff mechanism in the fractionator which prevents
culture tubes from passing under the siphon more than once.
The chart recorder is a Linear model 255 single pen chart record-
er with event pen. It is operated at a chart speed of 11 cm per
13
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SAMPLE RECORD
COVER
POSITION
FIGURE 3. SCHEMATIC DIAGRAM OF THE WEST POINT SAMPLER
14
-------
! I
< n
Fig 4a. The closure mechanism for the
West Point Sampler, closed position,
The precipitation sensor is on the
surface of the small box.
Fig 4b. West Point Sampler, open
position. Canted roof minimizes
splashing into funnel and prevents
snow accumulation.
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• POWER (Double Underline)
• ELEMENTS (Italics)
• CIRCUITS 8 DESCRIPTIONS (Single Underline)
HOLTZER-CABOT
2RPM
LIMIT
SWITCH
REVERSIBLE
MOTOR
PRECIPITATION
SENSOR
PRECIPITATION EVENT PEN CIRCUIT
RELAY
POTTER a BRUMFIELD
115V 50/60 C
CLOSING CIRCUIT
CHART DRIVE
CIRCUIT
BUCHLER
FRACTO METTE
200
FHACTIONATOR
LINEAR
255/MM
FRACTIONATOR
SIGNAL
EVENT)
POTTER a
BRUMFIELD
II5V 50/6OC
RELAY
POTTER 8 BROMFIELD
115 V 50/60C
//'/—A/W
9V BATTERY RESISTOR
FIGURE 5. WIRING DIAGRAM FOR THE WEST POINT SAMPLER,
16
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:
1
-
ll
Fig 6. Siphon and switch for the West
Point Sampler tube fron above drains
funnel on roof.
Fig 7. Fractionator with test tubes
in place. Two hundred test tubes
is a standard load. Magnet in last
tube activates a sensor which shuts
down the instrument.
-------
hour during sample collection and provides a resolution of 0.2 to
0.4 minutes. When the funnel is closed, the recorder operates at
a speed of 2.2 cm per hour. The event pen provides a record of
the opening or closing of the funnel and simultaneously the
change in chart speed.
A heater (j in Figure 3) provides heat to the funnel to melt snow
and sleet. The heater is controlled by a temperature controller
which activates the heater at 2°C. The heater is three laboratory
heater tapes (Fisher 11-463-49c) linked in series and taped to
the underside of the funnel. It was necessary to cover the full
extent of the funnel and not just the lower cone to prevent
bridging of the collector by snow. The funnel housing was insu-
lated to prevent freeze up in the Tygon line. Heat from the room
below the funnel is circulated into the housing by a blower to
aid the heating process.
STATION LOCATION AND OPERATION
The sampler is located on the roof of the fifth floor tower of
Bartlett Hall, at the U.S. Military Academy, West Point, New
York. This is a convenient location logistically, but its use as
a sampling location may not be good. The stack for the West Point
steam plant is 300 meters southeast of the collector, but down-
wind in the predominant wind direction. Bartlett Hall houses the
Academy's chemistry laboratories, but again the discharge from
the laboratory ventilators is downwind from the collector. Data
taken to date does not appear to be influenced by either of these
sources. Wind speed/wind direction instruments colocated with the
sampler since the summer of 1978 will allow more complete evalua-
tion of these as sources of contaminants in the future.
Earlier versions of the sampler are reflected in the data
presented. The earliest sampler was a simple 8 inch polyethylene
funnel 18 inches above the roof but below the parapet wall. It
was in operation from October 1976 until January 1977. It was
replaced in January 1977 with a glass funnel of the same diameter
when the polyethylene funnel was accidently melted by the heater
tapes. The glass funnel stayed in operation until October 1977.
At that time the data trends were promising enough that the fun-
nel was rebuilt using polyethylene. The funnel is now 18 inches
above the parapet; no longer shielded from the wind nor subject
to possible contamination from the parapet wall or loose material
on the roof.
In November 1978, the autoclosure device described .previously was
added to the funnel. The fraction collector and siphon mechanism
has remained unchanged from 1976 to the present time. The sampler
was out of operation from May 1978 to September 1978 due to re-
pair work being done to the roof.
18
-------
Prior to the addition of the autoclosure mechanism, the funnel
was opened and closed manually. The funnel was opened at the
onset of precipitation during the normal workday. In some
instances, if precipitation was predicted, the funnel was opened
at the end of the workday allowing a period of dry deposition on
the funnel prior to the beginning of precipitation. The funnel
remained open until the precipitation event ceased. The funnel,
tubing, and siphon were washed with distilled water after each
precipitation event. The last washing was collected and analyzed
to insure cleanliness.
Culture tubes are washed in an ultrasonic bath with Contrad-70
soap (Scientific Products C6327), rinsed in ]% nitric acid, then
in distilled water before being placed in the sampler. Samples
are removed each morning, again at noon, and at the end of the
day. Culture tubes are capped and refrigerated at 4°C until
analysis.
During operation, drops of sample remain on the siphon walls, but
the volume of these drops is small compared to the siphon volume.
Carry over between samples is considered negligible. Discussions
with Stensland, who operated a similar sampler containing a glass
siphon, led to agreement that carry over between samples was
negligible. In no case was storm intensity high enough to cause
continuous siphoning to occur.
The pH of samples was initially determined manually using an
Orion model 407A specific ion meter and Orion model 91-02 combi-
nation electrode. This combination was bedeviled with static
electricity problems after several measurements. A Corning model
476050 semimicro combination electrode was tried and solved the
problem for 30 minutes to an hour, after which static electricity
again became a problem. Static electricity was eliminated by use
of a Microelectrodes, Inc. model MI-410 microcombination pH
probe. The manual rinsing and wiping of electrodes proved to be
slow and consumed too many technician man-hours. In January 1978
a Technicon Ion Selective Electrode system which utilized a ther-
mostated flow-through combination pH electrode was put in use.
This system is used to run 30 samples per hour without static
electricity effects and with improved precision. All pH systems
were standardized daily against commercially available pH 4.0 and
pH 7.0 buffers. The time between sample collection and pH mea-
surement varies from storm to storm and from sample to sample
within a storm. Storms collected on weekdays will normally be
analyzed for pH within 6 hours after collection of the last
sample. Storms collected on Friday evening or a weekend will
normally be analyzed for pH by noon on the 1st workday after the
weekend. Other analyses on the refrigerated samples are per-
formed as soon as instrument time is available (normally within a
week or two, but in heavy rain periods it may take a month to
analyze all samples).
19
-------
Ion chemistries were determined initially using Hach powder pil-
lows and a Hach DR-2 speotrophotometer. Each Hach test required
25 ml of sample, requiring combination of samples to achieve this
volume. Once a sample was reacted for a particular colorimeteric
test it was not usable for further testing. These procedures
allowed some preliminary determination that measurable differ-
ences were present. New analytical methods were sought and in
August 1977 a Dionex model 14 Ion Chromatograph replaced the Hach
powder pillows. Initially the ion chromatograph was used to de-
termine only anions, but in January 1978 cation columns were +
added. The ion chromatograph is now utilized to analyze for Na ,
K+ , NHj , Ca"1^ , Mg+2 , F" , Cl~ , POJ3 , NO^ , and SO* . The above
analyses require only 9 ml of sample and the ion chromatograph
allows multiple analysis from the same sequential sample, a great
improvement over our previous techniques. Preliminary work is
underway to determine organic acids in the samples utilizing the
ion chromatograph.
Quality control on the Dionex ion chromatograph was ensured by
daily injections of a minimum of three standards which encom-
passed the range of concentrations expected in the samples.
Calibration curves are prepared by plotting concentration vs peak
height for these standards. Standards were prepared gravimetri-
cally from reagent grade chemicals, dried to constant weight, and
diluted to a known volume with Milli-Q deionized water
(conductance> 10 megohm). Appendix D contains a list of reagents
used for specific analytes. A sample of known concentration was
injected and peak height compared to the calibration curve ap-
proximately every tenth sample. A blank was injected daily to
detect possible contamination.
Some heavy metal analyses were performed on the sequential
samples. These were made using a Varian model 1280 atomic ab-
sorption spectrophotometer equipped with a Varian model 90 carbon
rod atomizer and Varian model 53 automatic sampling device. A
new non-threaded tube furnace (Varian 56-100157-00) was used
daily. A gas mixture of 99.5% argon-0.5% methane at a flow rate
of 5.0 liter/minute was used to prevent oxidation of the carbon
rod and to refresh the pyrolytic carbon coating thus prolonging
furnace lifetime. The average of four absorbance readings on each
sample was used in determining concentration. Absorbance data
from the 1280 was converted to concentration values automatically
utilizing a data link between the spectrophotometer and a Hewlett
Packard 9815 calculator driven by a Varian supplied curve fitting
program.
A 10 ul sample was used routinely for each analysis. Instrument
parameters and temperature programs for the carbon-rod furnace
are given in Table 2. Working standards were prepared daily for
concentrations below 10 ppm following the recommendations of
Begnoche and Risby.26 10 ppm standards were prepared from AA
standards bought from Varian-Techtron.
20
-------
TABLE 2. OPERATING CONDITIONS USED FOR THE ATOMIC ABSORPTION
SPECTROPHOTOMETER AND CARBON ROD FURNACE
^^^•^^^••^^^^•••^•••••••••••M-^^^^B^^^M
ELEMENT
Aluminum
Copper
Iron
Manganese
Nickel
Lead
^— ^^-^^^^••••••••••••^•••"•••••••••••M
LAMP
Current
mA
5
3
5
5
5
5
SPECTRAL
Bandwidth
nm
0.5
0.5
0.2
0.2
0.2
1 .0
•^•ta^^*^^^^^^^^^^^^^^^^— ^^^MB^^WM-MI
SPECTRAL
Line*
nm
309.27(5)
324.75(1)
371.99(2)
232.00(1 )
232. oo( 1 )
217.00(1 )
DRY
Temp/Time
C Sec
1 10/50
1 10/50
1 10/50
1 10/50
1 10/50
1 10/50
ASH
Temp/Time
C Sec
1700/20
500/20
600/20
700/20
900/20
500/20
ATOMIZE
Temp/Time
C Sec
2500/2/600
1200/2/400
2200/2/600
1900/2/400
2200/2/600
1200/2/400
^Numbers in parentheses are ranking of sensitivity of spectral line (1 = prime, 2 - 2nd
most sensitive, etc.).
-------
SECTION 6
EXPERIMENTAL DATA
Data from 22 precipitation events sampled over a 2-year period
are tabulated in Appendix A. Time between samples was measured
by converting the distance between sampling marks from the chart
recorder into time in minutes. The elapsed time is the cumula-
tive sum of the times between samples. Intensity is calculated
from the time between samples and the number of millimeters of
precipitation represented by the culture tube volume according to
the following equation:
mm of precipitation x 60 min/hr
Intensity, mm/hr = ~"~
Time between samples, min
This calculated intensity assumes a collection efficiency of
100?. The efficiency of collection will be evaluateg5against a
tipping bucket rain gauge in the future. Galloway's results
show that collectors of similar design have collection efficien-
cies of about Q5% for rain and 80% for snow. If this holds true
for the West Point Sampler then the intensities calculated above
are low. The pH and ion chemistry values are those obtained as
stated in Section 5. The data presented show the progression in
improved techniques and equipment. Early storms (Tables 3
through 5) present just pH data. Then Tables 6 through 12 add
chemical determinations using the Hach test kits. Three or more
consecutive samples were combined to allow these tests to be
made. The results are shown opposite each separate sample and
represent the average concentration for the three samples. Table
13 is the first of the ion chromatograph data. Tables 13 through
18 present pH, nitrate, and sulfate data. Tables 19 thru 22 add
light metals. Tables 23 and 24 are the most extensive containing
pH, anion, light metal, and heavy metal data.
Plots of the data from two storms are presented in this section
to illustrate and explain our plotting conventions. Figure 8 is
a plot of the data from the rainstorm on 2 June 1977 (Table 10).
The upper half of the figure is a hyetograph based on the calcu-
lated intensities and the elapsed time. Intensity values are
shown as the average for the time period during which they were
collected. Plotting difficulties forced plotting of intensities
22
-------
48
44-
40-
36
32
E
E24
CO
2O
16
12
8
4
O
HYETOGRAPH
129.6
50 100 150 200 250
ELAPSED TIME, MINUTES
NO;-N
300
350
12
10
o>
50 100 150 200 250
ELAPSED TIME, MINUTES
300 350
FIGURE 8.
CHANGES IN STORM CHEMISTRY AND INTENSITY, RAINSTORM,
2 JUNE 1977.
23
-------
for very short periods (period varies from plot to plot) as
points even though they are average values for the shorter
period. The lower half of the figure is a plot of pH versus
elapsed time. Again pH is shown as the average for its period of
collection except where resolution caused points to be used.
Superposed on the two halves of the figure are the chemical data
(in this case Hach powder pillow tests). Chemical data is shown
over its period of collection as the average value for the
period. Arrows indicate direction to the concentration scale
used. The grid on the lower half of the figure indicates inter-
preted periods of contamination by dry deposition (see Section
7).
Figure 9 is a plot of the data from the storm on 19 Oct 1977
(Table 18). It is basically the same as Figure 8 except that
more samples were analyzed by ion chromatography. In this
example, sulfate and nitrate values for individual samples are
plotted as the average value for the time of collection (other
plots use points where necessary because of time scales).
Sulfate and nitrate values are linked by a broken line to lead
the observer from one reading to another, not to indicate that
this is the chemical trend followed (on other plots where conse-
cutive samples were analysed, values are linked by solid line to
indicate the trend). In the early exploratory work, every 5th to
10th sample, samples at points where pH increased or decreased
markedly, samples at extended time between samples, or samples at
very short time between samples were analyzed. This was neces-
sary because it was too costly and time consuming to analyze all
samples in large storms. Criteria are being evaluated which will
enable one to pick which samples will be analyzed to give a good
representation of the species trends even though there are gaps
in the chemical data. This is being done by analyzing complete
storms and comparing the chemical trends produced using the se-
lection strategy with the trends produced using the full storm
chemistry.
Data for all storms are plotted and discussed in Section 7.
24
-------
50 75 100 125
ELAPSED TIME, MINUTES
FIGURE 9.
50 75 100
ELAPSED TIME, MINUTES
CHANGES IN STORM CHEMISTRY AND INTENSITY, RAINSTORM,
19 OCTOBER 1977. S = sulfate; N = nitrate.
25
-------
SECTION 7
DISCUSSION
When one quickly reviews the plotted storm data (Figures 8, 9,
and 10 to 29), several things immediately become apparent: (1)
the chemistry of precipitation varies widely within a storm; (2)
the chemistry within a storm can change very rapidly; (3) a sug-
gestion that there is a linkage between storm intensity and pre-
cipitation chemistry; (4) a parallelism in the chemical trends
within a storm when several chemical species are determined.
The following discussion will explore the above deductions and
test our hypotheses (Section 1) against the plotted data (Figures
8, 9, and 10 through 29). Examples from the full range of storms
will be cited where appropriate; however, the more recent storms
will be used more frequently since there is more chemical data
available from them to support the discussion.
FUNNEL CONTAMINATION
The manual opening/closing procedures for funnel operation repre-
sented in all the storms presented in this report are such that
periods of exposure to contamination by dry deposition are
present. It is believed that these contamination periods can be
identified. Also, that a period of precipitation following a
period of dry deposition will result in cleansing of the funnel
by washing the contaminants into the next few sequential samples.
This cleansing mechanism is highly efficient. A set of criteria
has been developed for identifying periods of dry deposition
contamination and for identifying the length of the cleansing
period. Utilizing these criteria, each of the twenty-two storms
has been analyzed for contamination and cleansing periods.
Appendix C presents the evaluation of each storm with respect to
the criteria. Only data from the contamination-free periods will
be utilized in subsequent discussion sections.
Periods of dry deposition are most likely identified in the data
by samples which have "long" times between samples. These dry
deposition periods must be distinguished from periods of low
intensity precipitation. Time alone will not make a good
discriminator, but time and the chemical data together may serve
this purpose. Since pH data is available for almost every sample
26
-------
18-
16-
CO
UJ
HYETOGRAPH
u
SO IOO 150 200 250
ELAPSED TIME, MINUTES
300
350
FIGURE 10.
50 100 ISO 200 25O 300 350
ELAPSED TIME, MINUTES
CHANGES IN STORM CHEMISTRY AND INTENSITY, RAINSTORM,
20 OCTOBER 1976.
27
-------
16
14
IK,
> 8-
UJ
Q.
6.4
6.2
60
5.8
5.6 H
5.4
5.2
5.0
4B
4.6
4.4
4.2
4.0
FIGURE 11
HYETOGRAPH
50
100
150
200
250
300
ELAPSED TIME, MINUTES
50
100
150
200
250
300
CHANGES IN STORM CHEMISTRY AND INTENSITY, RAINSTORM,
7 DECEMBER 1976.
28
-------
100
200
300
400
500
200
300
400
500
ELAPSED TIME, MINUTES
FIGURE 12 CHANGES IN STORM CHEMISTRY AND INTENSITY, SNOW/RAIN,
17-18 MARCH 1977.
29
-------
OJ
o
100 200 300 400 500 600 700 800
*
ELAPSED TIME, MINUTES
900
1000
1100
100
200
300
400
900
1000
1100
1200
I20JO
500 600 700 800
ELAPSED TIME, MINUTES
FIGURE 13. CHANGES IN STORM CHEMISTRY AND INTENSITY, RAINSTORM, 22 MARCH 1977
S = sulfate; A = ammonia as nitrogen; M = nitrate as nitrogen.
-------
O'
^ 4.
E
2-
^
— 0
Z
uj
1-
z
1 C"
1.5
1.4
1.3-
Z 1.2
UJ
O
Ol 1
1 .1
cr
i-
z l-u"
^ 09-
0"
£ 0.8
0 7
w .f
0.6
4 8
i • V
46
44
n
Q^
^^
-------
20
8-
6
4
HYETOGRAPH
A
400
I
600 BOO 1000 I2OO
ELAPSED TIME, MINUTES
MOO
N
•*-
-Mr
A '
200
400
600 800 1000 I20O
ELAPSED TIME, MINUTES
1400
FIGURE 15.
CHANGES IN STORM CHEMISTRY AND INTENSITY, RAINSTORM,
4-6 APRIL 1977. S = sulfate; A = ammonia as
nitrogen; N = nitrate as nitrogen.
32
-------
E
E
UJ
44
40-
36
32
28
24
20-
12-
HYET06RAPH
FIGURE 16.
100 200 300 400 500 600
ELAPSED TIME, MINUTES
700
800
100 200 300 400 500 600
ELAPSED TIME, MINUTES
700
800
CHANGES IN STORM CHEMISTRY AND INTENSITY, RAINSTORM,
23-24 APRIL 1977.
33
-------
E
E
z
Ul
HYETOGRAPH
_J\
100
200
300
400
500
600
700
ELAPSED TIME, MINUTES
iK>0
200 300 400 500
ELAPSED TIME, MINUTES
600
700
FIGURE 17.
CHANGES IN STORM CHEMISTRY AND INTENSITY, RAINSTORM,
7 JUNE 1977.
34
-------
IOO
8O-
60-
40
£
E
I0
w "
g *
HYETOGRAPH
J
25 50 75 100 125
ELAPSED TIME, MINUTES
25
150
50 75 100 125
ELAPSED TIME, MINUTES
150
FIGURE 18. CHANGES IN STORM CHEMISTRY AND INTENSITY, RAINSTORM,
18 AUGUST 1977. S = sulfate; A = ammonia as nitrogen;
N = nitrate as nitrogen.
35
-------
X
o.
4.8
4.6
4.4
42
40
3.8
3.6
34
12
3.0
so
,-2
"ioo 200 i5o
soo
\
ELAPSED TIME, MINUTES
\
100 200 300 400 500 600
ELAPSED TIME, MINUTES
700
800
36
32
28
24
20
16
12
8
4
0
FIGURE 19. CHANGES IN STORM CHEMISTRY AND INTENSITY, RAINSTORM,
16-17 SEPTEMBER 1977.
36
-------
16
14-
E 10-
CO
6
4
HYETOGRAPH
so
100 ISO " 600 650
ELAPSED TIME, MINUTES
700
75O
50
100 150 ' ' 600 650
ELAPSED TIME, MINUTES
700
750
FIGURE 20.
CHANGES IN STORM CHEMISTRY AND INTENSITY, RAINSTORM,
18 SEPTEMBER 1977-
37
-------
U)
00
E
E
14
12
10
8
UJ
HYETOGRAPH
RECORDER MALFUNCTION
UNKNOWN PERIOD OF TIME LOST
200 400 600 800 1000
1200
1400
1600
1800
2000
2400
2600
ELAPSED TIME, MINUTES
200
400
600 800
1800
2000
2400
2600
1000 ' ' 1200 1400 1600
ELAPSED TIME, MINUTES
FIGURE 21. CHANGES IN STORM CHEMISTRY AND INTENSITY, RAINSTORM, 24-26 SEPTEMBER
1977. a. Hyetograph; b. pH data.
-------
u>
40-
100
300
500
HOO 1300 1500
ELAPSED TIME, MINUTES
1700
1900
2100' 2400 2600
FIGURE 21.
CHANGES IN STORM CHEMISTRY AND INTENSITY, RAINSTORM, 24-26 SEPTEMBER
1977. c. Ion chemistry.
-------
200 300 400 500
ELAPSED TIME, MINUTES
200 300 400 500
ELAPSED TIME, MINUTES
600
700
FIGURE 22. CHANGES IN STORM CHEMISTRY AND INTENSITY, RAINSTORM
26 SEPTEMBER 1977- S = sulfate; N = nitrate.
40
-------
E
CO
z
o>
5.8
5.6
54
52
50
4.8
4.6
4.4
4.2
4.0
100 150 200 250
ELAPSED TIME, MINUTES
T
300
s s_
50 100 ISO 200
ELAPSED TIME, MINUTES
250
5OO
FIGURE 23. CHANGES IN STORM CHEMISTRY AND INTENSITY, RAINSTORM,
17 OCTOBER 1977. S = sulfate; M = nitrate.
41
-------
50
40
30
J= 20
1 '
6 10
V »
J- 6-
V) 4
Z
LJ
HYETOGRAPH
200
400
600
800
.000
1200
1400
1600
1800
2000 2200 2400
ELAPSED TIME, MINUTES
200
FIGURE 24.
400
600
800
1800
2000
2200
2400
1000 1200 1400 1600
ELAPSED TIME, MINUTES
CHANGES IN STORM CHEMISTRY AND INTENSITY, RAINSTORM, 24-26 JANUARY 1978.
a. Hyetograph; b. pH data.
-------
o
2.00-
20O 400 600 800 1000 1200 1400 1600
ELAPSED TIME, MINUTES
1800
2000
2200
n
24OO
200
400
1800
2000
2200
2400
800 1000 1200 1400 1600
ELAPSED TIME, MINUTES
FIGURE 24. CHANGES IN STORM CHEMISTRY AND INTENSITY, RAINSTORM, 24-26 JANUARY 1973
"c. Anion chemistry; d. Cation chemistry. S = sulfate; N = nitrate.
-------
2-
E
E
z
QJ
o.
HYETOGRAPH
100
800
1000
1200
1400
1600
1800
2000
2200
ELAPSED TIME, MINUTES
100 800 1800 1200 1400 1600
ELAPSED TIME, MINUTES
1800
2000
2200
FIGURE 25. CHANGES IN STORM CHEMISTRY AND INTENSITY, SNOWSTORM,
6-7 FEBRUARY 1978. a. Hyetograph; b. pH data.
44
-------
1200 I4'00 1^00 1800 2doO 2^00
ELAPSED TIME, MINUTES K +
100 ' 800 1000
0 100
800 IOOO
1200 1400 1600 1800
ELAPSED TIME, MINUTES
2000 2200
FIGURE 25. CHANGES IN STORM CHEMISTRY AND INTENSITY, SNOWSTORM,
6-7 FEBRUARY 1978. o. Ion chemistry.
45
-------
400
ELAPSED TIME, MINUTES
4.6
100 200 300 400 500
ELAPSED TIME, MINUTES
600
700
FIGURE 26. CHANGES IN STORM CHEMISTRY AND INTENSITY, SNOWSTORM,
3 MARCH 1978.
46
-------
44
40-
36
32
I 28-
I 24.
S 2°
UJ 16
Z
~ 12
8
4
0
HYETOGRAPH
200
3OO 400
ELAPSED TIME, MINUTES
200
300 400
ELAPSED TIME, MINUTES
500
FIGURE 27. CHANGES IN STORM CHEMISTRY AND INTENSITY, RAINSTORM,
14-15 MARCH 1978. a. Hyetograph; b. pH data.
47
-------
200
300 400
ELAPSED TIME, MINUTES
500
FIGURE 27. CHANGES IN STORM CHEMISTRY AND INTENSITY, RAINSTORM,
14-15 MARCH 1978. c. Ion chemistry.
48
-------
ELAPSED TIME, MINUTES
FIGURE 28,
150 200 250 300
ELAPSED TIME, MINUTES
350
400 450
CHANGES IN STORM CHEMISTRY AND INTENSITY, SNOWSTORM,
16-17 MARCH 1978. S = sulfate; N = nitrate; Fe =
iron.
49
-------
12
e
E
cn
z
UJ
8
6
4
2
0
2-
1.5
I
0.5
0-
600
1400 1600
ELAPSED TIME, MINUTES
800
2000 2200
so;'
\
NO;
,vr>
NH4
No
NH4
\
^~--*^s \
H— -h -^P^
Cl
\
•\".
600 800
1000 • 1200 1400 1600
ELAPSE TIME, MINUTES
BOO
20OO 2200
FIGURE 29. CHANGES IN STORM CHEMISTRY AND INTENSITY, RAINSTORM,
18-20 APRIL 1978.
50
-------
collected, it would be convenient if the time-pH data would be
sufficient to discriminate the contamination-free from the con-
tamination periods. Another factor which must be considered is
precipitation type. The intensity discriminator for a rainstorm
will probably not work for snowstorms which have a much lower
intensity.
The procedures used made contamination more likely at the start
of a storm when the funnel was uncovered in anticipation of rain.
As a first approximation, rainstorms with an elapsed time of
greater than 50 minutes (~0.5 mm/hr intensity) before collection
of the first sample were looked at for indications of
contamination. Four rainstorms, 16-.17 September 1977 (Figure 19,
24-26 January 1978 (Figure 24), 14-15 March 1978 (Figure 27), and
18-20 April 1978 (Figure 29) had elapsed times greater than 50
minutes at the start. In the samples following this possible
period of contamination, the pH starts from a low of 3.4 to 3.8
and rises slowly (15-17 Sep and 24-26 Jan are complicated by
severa|?early periods in excess of 50 minutes). Galloway and
Likens have shown that dry deposition in the northeastern U.S.
is acidic in nature, containing sulfate and nitrate salts. If
dry deposition occurred, one would expect the earliest samples
coming from the funnel to be very acid, and then as acid material
is washed off, the pH should rise. This expectation is borne out
in the four storms. In addition, chemical data from the storms
show high early sulfate and nitrate concentrations (16-17 Sept
and 24-26 Jan) and high early metal concentrations (14-15 Mar and
18-20 April). It appears that long (>50 min) elapsed time and pH
data are sufficient indicators for dry deposition contamination
at the beginning of a storm.
The above pH and elapsed time tests were extended to rainstorms
with elapsed times between 25 minutes (1.0 mm/hr intensity) and
50 minutes (~0.5 mm/hr intensity). Three rainstorms, 22 March
1977 (Figure 13), 4-6 April 1977 (Figure 15), and 7 June 1977
(Figure 17) fit in this category. Two, 22 March 1977, and 4-6
April 1977 show the slowly rising pH trend. Supportive chemical
data for the two storms are indicative of high early sulfate and
nitrate, but the sparseness of data does not allow a definitive
conclusion to be drawn. The other storm, 7 June, has high early
pH that drops following the initial "long" period. No supporting
chemical data are available. Rainstorms with an initial collec-
tion period less than 25 minutes (intensity greater than 1.0
mm/hr) have a random pH and chemistry pattern. Further analysis
of future storms is needed, but it appears that a working hy-
pothesis can be advanced which states that rainstorms with ini-
tial periods of intensity greater than 1.0 mm/hr are contamina-
tion free during this period and those with intensity less than
1.0 mm/hr are contaminated by dry deposition.
There is no reason why application of the intensity discriminator
should be confined to the early period of a storm only.
51
-------
Therefore, all rainstorms with periods of intensity less than 1.0
mm/hr during the course of the storm were identified. Of all the
rainstorms collected, only two, 17 October 1977 (Figure 23) and
19 October 1977 (Figure 9) show no possible period of
contamination. The others generally show a sharp drop in the pH
following a contamination period, which is indicative of the
acidic nature of dry deposition. Following the drop, the gradual
rise seen in the initial contamination period was exhibited (See
Figure 21 for example). Sulfate and nitrate data support this
conclusion, but are not plentiful enough to provide the desired
level of confidence. The intensity of 1 mm/hr for rainstorms is
a good discriminator for discerning periods of dry deposition
contamination throughout a rainstorm.
Dry deposition contamination in snowstorms was explored. Four
snowstorms are represented in our data, 17-18 March 1977 (Figure
12), 6-7 February 1978 (Figure 25), 3 March 1978 (Figure 26), and
16-17 March 1978 (Figure 28). All have periods with intensity
(using the water equivalent of snow) less than 1.0 mm/hr. The
6-7 February data has been used to establish an intensity limit
for snowstorms of 0.25 mm/hr (See Appendix C for the interpreta-
tion of the data). There are no periods in the other three
storms with intensity greater than 0.25 mm/hr which could be
interpreted as contaminated nor are there periods with intensity
less than 0.25 mm/hr which do not show evidence of dry deposition
contamination .
The cleansing period is harder to quantify. Assuming a uniform
deposition flux, more material will need to be removed from the
funnel the longer the period of exposure. Intensity of rainfall
will play a role too. A light drizzle will collect on the funnel
and remain longer as droplets coalesce to drops and run down the
funnel. Light rain will promote solution of soluble materials as
it will have a longer contact period. On the other hand, heavy
rain will tend to flush particulates because of the impact energy
of the drops. A complicating factor is a succession of contam-
ination periods each with samples between.
Examination of several storms indicates that the dry deposition
flux must not be uniform. In the 14-15 March 1978 rainstorm
(Figure 27), sodium ion concentration for a 200-minute period is
almost 5 mg/1 whereas the rainstorm on 18-20 April 1978 (Figure
29) had a 678-minute period yielding a sodium ion concentration
of 1.15 mg/1. Ammonium ion concentration was 1.45 mg/1 and 1.93
mg/1 in the two storms respectively and potassium ion concentra-
tion was 0.24 mg/1 and 0.35 mg/1. The trend for K+ and NHt is
as expected with the longer exposure time having the higher
concentration, but the Na+ data cannot be reconciled with this
interpretation. If the constant flux hypothesis were to hold
then one would expect 18-20 April to have three times more conta-
minant than 14-15 March since the contamination period is three
times longer.
52
-------
Storms with high intensity rain after periods of contamination
(e.g. 2 June 77, Figure 8) appear to wash their dry deposits off
the funnel in the 2 or 3 samples following contamination (e.g.
the intensity spike at 136 minutes of the 2 June data produces an
acid condition which recovers quickly). On the other hand during
less intense periods following contamination 5 or more samples
may be needed to cleanse the funnel. For example, the contamina-
tion period stretching from 372 to 420 minutes in the 14-15 March
storm (Figure 27) is followed by rains of low intensity which
slowly raise the pH and lower the pollutant concentrations.
Pollutants are not finally removed until the intensity spike at
472 minutes.
There does not appear to be any single discriminator which will
allow quantification of the cleansing period. The pH is not
suited for use. The ion concentrations for many samples from a
storm make interpretation easier, but not certain. Perhaps labo-
ratory experiments under controlled conditions would produce a
useful discriminator. The chemical data, when available, has
been used or in the absence of such data deletion of an arbitrary
3-8 samples following the suspected dry deposition depending upon
the intensity of rain. The deletion of these samples is to ac-
count for cleansing of dry deposition from the funnel.
This problem of funnel contamination will be eliminated with the
automated closure device, providing that the precipitation sensor
is sensitive enough to react quickly to rain stoppages. This
will be a function of the speed at which the sensor heater eva-
porates the rain. This heating rate cannot be too high, however,
or in very light rain the funnel may be closed prematurely.
A MODEL FOR INTERPRETING SEQUENTIAL PRECIPITATION CHEMISTRY DATA
Sequential precipitation chemistry data show the chemical compo-
sition of samples collected beneath a changing air column during
a storm event. The goal is to relate the changes in the chemistry
of these samples to processes occurring in the atmosphere above
the collector. The model below looks at atmospheric processes
which affect the number of aerosol particles or drops and the
composition of aerosols present in the atmosphere.
Clean dry air is composed of gases with relatively long residence
times, (N3, 02, He, Ne, Ar, Kr, Xe, H3, C02, 03, NS0, and CH4 ).
Pollutant gases (H30 vapor, N0g, NO, NH3, S02, H8S, CO, HC1, and
I8 ) from natural and anthropogenic sources; and aerosols of solid
and liquid particles suspended in the gaseous medium are also
present. These aerosols are typically extraterrestrial stony and
metallic meteoric material; volcanic material (ash); biological
material (bacteria, spores, and pollen); metal oxides; organic
combustion products; acids (H2S04, HN03); and salts (NaCl, MgCl2 ,
MgS04 , Na3S04, NaN03 , (NH4 )SS04 , NH4C1, NH4N03). The aerosol par-
ticles can be divided into water soluble and not soluble30.
53
-------
A number of processes (Figure 30) affect the number, size, and
composition of the particles of the aerosols present. The' pro-
cesses can be divided into those which bring particles into the
parcel, the input processes; those which remove particles from
the parcel, the output processes; and those processes which oper-
ate within the parcel to change the makeup of the aerosol
population, the internal processes. The inputs to the air column
result from material entering from an adjacent column due to: 1)
diffusional transport by either thermal agitation (Brownian
movement) or turbulent eddying of the air; 2) dry gravitational
processes from above (deposition, fallout, sedimentation); 3)
hydrometeors (rain, snow, drizzle, fog, sleet, hail, ice) carried
into the parcel by gravity or air turbulence.
Many processes occur that affect the size, composition, and
number of aerosol particles within the air parcel. A complete
review has been presented by Pruppacher .3l The following are
examples of these processes: 1) vapors condense to produce a
liquid aerosol particle; 2) condensed material evaporates, leav-
ing dry particulate aerosol; 3) gases are adsorbed on solids; 4)
particles, both liquid and solid, collide to produce larger
aggregate particles or perhaps breakup into smaller particles; 5)
chemical reactions occur between gases and solids, liquids and
solids, etc, to produce differing chemical composition; and 6)
water vapor nucleates on particles. In all of these processes the
material involved remains within the parcel.
Of prime interest to the precipitation chemist are the output
processes which remove aerosols from the parcel. These processes
will have the largest effect on the chemistry observed on the
ground. The dominant process is rainout, the removal of gases or
aerosols in a cloud by capture on cloud droplets or raindrops in
a cloud. Sedimentation occurs when particles have obtained suf-
ficient mass to fall out of the air parcel. The next two pro-
cesses are the scavenging of aerosol particles by other aerosol
particles falling through the parcel from above and by hydromete-
ors falling through the air column from above (washout). A
number of mechanisms have been proposed to explain how the ma-
terial is scavenged and incorporated into the falling mass..
Studies by Beard33 , Dana and Hales33, and Adam and Semonin34 have
shown that the scavenging efficiency is related to drop and par-
ticle size. Some authors have proposed wake capture as an impor-
tant process ,35 Hydrometeor type will affect scavenging
efficiency36'37 . Electrostatic processes play a role but the
extent is not known. The last output process is impaction on
buildings, trees, mountains, etc. as the wind impinges liquid and
solid aerosols on a surface. Impaction is largely a near surface
process.
54
-------
HYDROMETEOR
INPUT
SEDIMENTATION
DIFFUSIONAL
TRANSPORT
Ul
Ul
t
I.
2.
3.
CONDENSATION OF VAPORS TO
PARTICLES / EVAPORATION
ADSORPTION ON PARTICLES
COLLISIONS BETWEEN PARTICLES
5.
LOSS
CHEMICAL REACTIONS
A. BETWEEN GASES
B. ABSORPTION
WATER NUCLEATION ON PARTICLE
l
IMPACTION SCAVENGING RAIN
ON BY OUT
OBSTACLE HYDROMETEOR
(WASHOUT)
DIFFUSIONAL
TRANSPORT
SCAVENGING
BY
SEDIMENT
SEDIMENTATION
FIGURE 30.
PROCESSES EFFECTING THE NUMBER OF AEROSOL (LIQUID AND SOLID) PARTICLES
IN THE AIR COLUMN.
-------
The contents of the precipitation chemistry samples is the sum of
a number of processes operating above the sampling site. The
sample chemistry represents the integration of nucleation,
scavenging, dry deposition and impaction on the funnel. Gatz and
Dingle6 have summed this up as "the sum of (1) individual changes
within moving rain parcels, and (2) horizontal and vertical ad-
vection of concentration gradients in the three-dimensional rain
field ."
THE VARIATION OF CHEMISTRY WITHIN A STORM
One of the more interesting observations to come from the data is
the range of concentrations of dissolved constituents within the
precipitation of any storm. It is not unusual for pH to jump
from 1 to 2 pH units representing a 10 to 100X increase/decrease
in the hydrogen ion concentration of the rain. One storm, 22
March 1977 (Figure 13) has a 3-unit jump in pH, representing a
1000X increase in hydrogen ion concentration. Increases of 100X
or more are not found in the anion analyses. It is not unusual
for a change of 10 to 20X for sulfate or 5 to 10X for nitrate.
The cations show a similar pattern with sodium and calcium vary-
ing 5 to 10X, magnesium 2 to 5X, and potassium and ammonium 1 to
2X.
The pH data show significant jumps in level over the relatively
short period of minutes or fractions of minutes. The ion concen-
tration data show differences in levels but there is not suffi-
cient data to ascertain the rapidity of the changes.
INTENSITY AS A FACTOR IN PRECIPITATION CHEMISTRY
The sudden variations in rain water impurity concentrations from
convective storms have been previously observed.6 These observa-
tions pertain mainly to particulates. The data presented in this
paper extends the observations to frontal storms (See Appendix B)
and deals mainly with dissolved constituents.
There appears to be a correlation between peaks in pH and inten-
sity maxima. Regression and correlation analyses have been made
using this data (contamination periods excluded) with pH as the
dependent variable and intensity the independent variable.
Correlation coefficients were suprisingly low. The pH was con-
verted into hydrogen ion concentration and the coefficients im-
proved slightly. This was difficult to understand. A second
attempt was made using intensity and elapsed time as independent
variables and pH as the dependent variable. Multivariate regres-
sion analysis yielded correlation coefficients in some cases of
better than 0.7. Again using hydrogen ion concentrations rather
than pH yielded correlation coefficients that were improved from
5 to 10 percent. This better fit can be explained by the nature
of pH and hydrogen ion concentration - the first, pH, is a log
function, while hydrogen ion concentration is linear.
56
-------
Periods of high intensity precipitation, for example the 70 and
140 minute peaks of 20 Oct 76 (Figure 10), or the 2100 minute
peak of 24-26 Jan 78 (Figure 24) have a marked effect on the
precipitation chemistry. In almost every instance, pH jumps
several tenths of a pH unit, indicating a lowering of the
acidity. At the same time storms with additional chemical data
show a drastic lowering of the concentration of the dissolved
constituents (See the 2100 minute peak of Figure 24). This sug-
gests confirmation of the first hypothesis that intensity is
inversely proportional to the concentration of dissolved
constituents. Due to the limited data available positive confir-
mation is not possible at this time.
THE ACIDITY OF PRECIPITATION
An effort was made to try to correlate the concentrations of
dissolved constituents with the pH of the sample. Problems arise
in the application of multiple linear regression techniques to
the data. As mentioned previously, better regression coeffi-
cients are obtained if hydrogen ion concentration is used instead
of pH. There is a high correlation between the concentrations of
individual ionic species, a property called multi-colinearity. A
data set exhibiting multi-colinearity cannot properly use the
multiple linear regression technique because of violation of the
underlying assumptions. Techniques exist to manipulate the data
to reduce multi-colinearity28. One successful manipulation in-
volves conversion of nitrate and sulfate data from mg/1 to mi-
croequivalants and adding them together to form a single depend-
ent variable against either pH or pH converted to microequiva-
lents of H . The pH values produced are close to those expected
for COS gas in equilibrium with distilled water at the mean tem-
perature during the storm. No tests were made to see that auto-
correlation or heteroskedasticity assumptions are not violated.
EQUILIBRIUM OF PRECIPITATION WITH THE ATMOSPHERE
Distilled water in equilibrium with atmospheric C02 should have a
pH in the range 5.6 to 5.75 depending on the atmospheric
temperature. If acidic species dissolve in the rain, then the pH
should be more acid (lower). One could expect then, that rain
falling through an air mass containing acidic pollutants should
produce early samples which are acidic. Subsequent samples
should gradually show lower acidity as more and more pollutants
are removed from the air mass. The pH of the sequential samples
should gradually rise to an equilibrium value governed by the C02
water equilibrium. One storm, 17 October 1977 (Figure 23) shows
such a relationship. As long as equilibrium is maintained one
would not expect to find pH values above 5.75. There are many
occurrences in the data of pH values of 6.0 or higher (e.g. 22
March 1977, Figure 13).
57
-------
If disequilibrium is important, then the experimental techniques
would not allow the values to be detected. Once collected the
samples remain in open test tubes for several hours before
capping and refrigeration. During this time one would expect C02
from the laboratory air to enter the solution and bring the sam-
ple to an equilibrium pH. As Galloway et al ,39 point out, C02 is
more soluble in basic solutions and this would tend to bring a
high pH solution toward the equilibrium 5.6-5.75 value. Acid
solutions in the pH range 3 to 5 do not dissolve C02 and would
therefore maintain a stable pH value. That pH values of six or
more are found suggests that something other than disequilibrium
is important.
Cooper et al.13 present data from Texas which shows pH values in
the range 6.5 to above 7.0. They attribute this high pH to basic
components in the rain, mainly calcium and magnesium. New York
State has significant limestone and dolomite industries to the
north of West Point at Kingston and to the south of West Point at
Stony Point. As stated previously the predominant wind direction
at West Point is from the north. Wind data are lacking for the
period of data presented, but some calcium and magnesium data are
available for 6-7 February 1978 (Figure 25) and 14-15 March 1978
(Figure 27). Definitive conclusions cannot be drawn from the
data because of sparseness and dry deposition contamination.
THE SECTION 3 HYPOTHESES
Two of the hypotheses have been discussed indirectly to this
point. There does appear to be an inverse relationship between
concentration and intensity. Disequilibrium has pretty well been
eliminated. The other hypotheses mentioned in Section 3 lack
supporting or contradictory data. It is clear that chemical
analyses must be performed on every sample, that dry deposition
must be excluded, and that meteorological data are needed if the
hypotheses are to be fully tested.
58
-------
SECTION 8
REFERENCES
1. Likens, G.E., and F.H. Borman, 1974. "Acid Rain: A Serious
Regional Problem." Science 184: 1176-1179.
2. Likens, G.E., 1976. "Acid Precipitation." Chem. and Engr.
News 54.: 29-44.
3. Federal Interagency Work Group on Precipitation Quality,
1978. Research and Monitoring of Precipitation Chemistry in
the United States - Present Status and Future Needs. Office
of Water Data Coordination, Geological Survey, Res.ton,
Virginia.
4. Cowling, E.B., 1976. "Chemical Changes in Atmospheric
Deposition and Effects on Agricultural and Forested Land and
Surface Waters in the United States." Unnumbered Mimeographed
Report, dated October 29, 1976, submitted to Cooperative
State Research Service, U.S. Department of Agriculture,
Washington, D.C.
5. Galloway, J. , E. Cowling, E. Gorham, W. McFee, 1978. "_A
National Program for Assessing the Problem of Atmospheric
Deposition (Acid Rain): _A Report to the Council on
Environmental Quality." National Atmospheric Deposition
Program NC 141. Available from Publications Manager,
National Resource Ecology Laboratory, Colorado State
University, Fort Collins, Colorado 80523-
6. Gatz, D.F., and A.N. Dingle, 1971. "Trace Substances in Rain
Water: Concentration Variations during Convective Rains, and
Their Interpretation." Tellus 2J: 14-17.
7. Dana, M.T., D.R. Drewes, D.W. Glover, and J.M. Hales, 1976.
"Precipitation Scavenging of Fossil Fuel Effluents."
Environmental Protection Agency, Research Triangle Park,
North Carolina. Publication No. EPA-600/4-76-031.
8. Dana, M.T., J.M. Hales, C.E. Hane, and J.M. Thorpe, 1974.
"Precipitation Scavenging of Inorganic Pollutants from
Metropolitan Sources." Environmental Protection Agency,
59
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Research Triangle
EPA-650/3-74-005.
Park, North Carolina. Publication No.
11
12,
Warburton, J.A., 1973-
Precipitation From Two
Meteorol. 12: 677-682.
"The Distribution of Silver in
Seeded Alberta Hail Storms."_J_. Appl.
10. Warburton, J.A., and M.S. Owens, 1972. "Diffusional
Deposition of Ice on Silver Iodide in Seeded Lake Effect
Storms."_J_. de Researches Atmospheriques 1_0: 679-692.
Linkletter
of NHRE
Analysis
tter, G.O., and J.A. Warburton, 1977. "An
E Hail Suppression Seeding Technology Based
is."_J_. Appl. Meteorol. 16: 1332-1348.
Assessment
on Silver
13.
14.
Perkins, R.W., C.W. Thomas, J.A. Young, and B.C. Scott, 1970.
"In Cloud Scavenging Analysis From Cosmogenic Radionuclide
Measurements." In Precipitation Scavenging (1970). Richland,
Wash., June 2-4, 1970, R.J. Engelmann and W.G.N. Slinn (Eds),
AEC Symposium Series, No 22 (CONF-700601), pp 109-120.
Cooper, H.B.H., Jr., J.A. Lopez, and J.M. Demo, 1976.
"Chemical Composition of Acid Precipitation in Central
Texas." Water. Air, and Soil Pollution 6: 351-359.
Kennedy, V.C., G.W. Zellweger, and R.J. Avanzino, 1976.
"Composition of Selected Rain Samples Collected at Menlo
Park, California in 1971." Open-File Report 76-852 Geological
Survey, Menlo Park, California.
15. Gatz, D.F., R.F. Selman, R.K. Langs, and R.B. Holtzman, 1971.
"An Automatic Sequential Rain Sampler."^. Appl. Meteorol.
10: 341-344.
16. Dingle, A.M., 1977. "Scavenging and Dispersal of Tracer by a
Self-propagating Convective Shower System." In Precipitation
Scavenging (1974). Champaign, Illinois, October 14-18, 1974,
R.G. Semonin and R.W. Beadle (Eds), ERDA Symposium Series, No
41, (CONF-741003) , PP 395-424.
17. Adam, J.R., R.Cataneo, D.F. Gatz, and R.G. Semonin, 1973.
"Study of Rainout of Radioactivity in Illinois." Eleventh
Progress Report to U.S. Atomic Energy Commission. Contract
AT (11-D-1199, 157p.
18.
Raynor, G.S., and J.P. McNeil, 1978. "The Brookhaven
Automatic Sequential Precipitation Sampler." Report BNL
#50818 Brookhaven National Laboratory, Upton, New York,
29 PP.
19.
Raynor, G.S., and J.V.
Analysis of Sequential
Hayes, 1978. "Experimental Data from
Precipitation Samples at Brookhaven
60
-------
National Laboratory." Report BNL #50826 Brookhaven National
Laboratory, Upton, New York, 44pp.
20. P.B.S.K. Associates, P.O. Box 131, State College, Pa 16801:
Bulletin 177.6801
21. Stensland, G.J., 1976. "Precipitation Chemistry Studies at
Lake George: Acid Rains." Rensselaer Fresh Water Institute at
Lake George Newsletter 6: 1-4. Rensselaer Polytechnic
Institute, Troy, New York.
22. Pickerell, D., T. Hook, T.W. Dolzine, and J.K. Robertson, in
press. "Intensity Weighted Sequential Sampling of
Precipitation: A Technique for Monitoring Changes in Storm
Chemistry During a Storm." Proc. 2nd National Symposium on.
Ion Chromatographic Analysis of Environmental Pollutants,
Raleigh, N.C., Oct 11-13, 1978.
23. Radke, L.F., W.D. Scott, and C.E. Robertson, 1970.
"Interactions of Cloud Condensation Nuclei and Ice Nuclei
with Cloud and Precipitation Elements: A Review." In
Precipitation Scavenging (1970). Richland, Wash., June 2-4,
1970, R.J. Engelmann and W.G.N. Slinn (Eds), AEC Symposium
Series, No 22 (CONF-700601), p 37-48.
24. Gradel, T.E. and J.P. Franey, 1977. "Field Measurements of
Submicron Aerosol Washout by Rain." In Precipitation
Scavenging (1974). Champaign, Illinois, October 14-18, 1974,
R.G. Semonin and R.W. Beadle (Eds), ERDA Symposium Series, No
41, (CONF-741003), P 503-523.
25. Galloway, J.N., 1975. "Critical Factors in the Collection of
Precipitation for Chemical Analysis," Proc. First Specialty
Symposium on_ Atmospheric Contributions to the Chemistry of
Lake Waters. Internat. Assoc. Great Lakes Res., Sep 28- Oct
26. Begnoche, B.C., and T.H. Risby, 1975. "Determination of
Metals in Atmospheric Particulates Using Low-Volume Sampling
and Flameless Atomic Absorption Spectrometry." Anal. Chem.
4£: 1041-1045.
27. Galloway, J.N., and G.E. Likens, 1976. "Calibration of
Collection Procedures for the Determination of Precipitation
Chemistry." Water, Air, and Soil Pollution 6_: 241-258.
28. Chatterjee, S., and B. Price, 1977- Regression Analysis by
Example. New York: John Wiley & Sons.
29. Galloway, J.N., G.E. Likens, and E.S. Edgerston, 1976. "Acid
Precipitation in the Northeastern United States: pH and
Acidity." Science 194: 722-724.
61
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30.
Junge,
Press ,
C.E., 1963-
New York.
Air Chemistry and Radioactivity. Academic
31. Pruppacher, H.R., 1973- "The Role of Natural and Antropogenic
Pollutants in Cloud and Precipitation Formation." In
Chemistry of the Lower Atmosphere, S.I. Rasool (Ed), Plenum
Press, New York, pp 1-68.
32. Beard, K.V., 1977. "Rain Scavenging of Particles by
Electrostatic - Inertial Impaction and Brownian Diffusion."
In Precipitation Scavenging (1974) , Champaign, Illinois,
October 14-18, 1974, R.G. Semonin and R.W. Beadle (Eds), ERDA
Symposium Series, No 41, (CONF-741003), PP 183-194.
33. Dana, M.T., and J.M. Hales, 1977. "Washout Coefficients for
Polydisperse Aerosols." In Precipitation Scavenging (1974X,
Champaign, Illinois, October 14-18,1974, R.G.Semonin and
R.W. Beadle (Eds), ERDA Symposium Series, No 41,
(CONF-741003), PP 247-257.
34. Adam, J.R., and R.G. Semonin, 1970. "Collection Efficiencies
of Raindrops for Submicron Particulates." In Precipitation
Scavenging (1970) . Richland, Wash., June 2-4, 1970, R.J.
Engelmann and W.G.N. Slinn (Eds), AEC Symposium Series, No 22
(CONF-700601), pp 151-160.
35. Berg, T.G.O., 1970. "Collection Efficiency in Washout by
Rain." In Precipitation Scavenging (1970). Richland, Wash.,
June 2-4, 1970, R.J. Engelmann and W.G.N. Slinn (Eds), AEC
Symposium Series, No 22 (CONF-700601), pp 169-186.
36. Sood, S.K. and M.R. Jackson, 1970. "Scavenging by Snow and
Ice Crystals." In Precipitation Scavenging (1970) . Richland,
Wash., June 2-4, 1970, R.J. Engelmann and W.G.N. Slinn (Eds),
AEC Symposium Series, No 22 (CONF-700601), pp 121-136.
37. Knutson, E.G. and J.D. Stockhom, 1977. "Aerosol Scavenging
by Snow: Comparison of Single-Flake and Entire-Snowfall
Results." In Precipitation Scavenging C1974). Champaign,
Illinois, October 14-18, 1974, R.G. Semonin and R.W. Beadle
(Eds), ERDA Symposium Series, No 41, (CONF-741003), pp
195-207.
62
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SECTION 9
APPENDICES
A. Tabulations of Measured Concentrations
B. Tabulation of Storm Information
C. Interpretation of Periods of Contamination for the 22 Storms
D. Reagents Used for Standards
63
-------
APPENDIX A
TABULATIONS OF MEASURED CONCENTRATIONS
In the following tables, pH, time between samples, and ion
concentrations are all measured quantities. Elapsed time is
calculated by summing the time between samples. Intensity is
calculated from the time between samples and the number of
millimeters of precipitation represented by the culture tube
volume according to the following equation:
mm of precip x 60 min/hr
Intensity =
Time between samples, rain
Missing data indicate no measurement was made or measurement
(sample) lost. A pH of 0.0 indicates either a lost sample or
that an empty culture tube was in the rack at that position due
to wind pressure triggering the siphon switch and advancing the
tube rack. Using ion chromatography, the presence of ions will
show as a peak at the proper retention time. The symbol BDL
indicates that the analysis was below the established detection
limit for the analyte.
Symbols in the remarks column indicate the contamination and
cleansing periods detailed in Appendix C. Symbols used are:
X = Contamination
Cl= Cleansing
64
-------
TABLE 3. INTENSITY AND pH OF RAINSTORM, 20 OCTOBER 1976
SAMPLE
NUMBER
1
2
3
4
5
6
7
8
9
10
11
12
13
•
-------
TABLE 3 Continued
SAMPLE
NUMBER
41
42
43
44
45
46
47
TIME
BETWEEN
(Min)
7.
5.
12.
6.
22.
20.
33.
2
9
8
5
0
7
5
ELAPSED
TIME INTENSITY
(Min) (mm/hr)
266.
272.
285.
291.
313.
334.
367.
5
4
2
7
7
4
9
3-
4.
2.
3.
1 .
1.
0.
60
39
03
99
18
25
77
PH
4.
4.
4.
4.
4.
4.
4.
30
15
15
30
00
20
20
REMARKS
Cl
Cl
Cl
Cl
Cl
Cl
X
66
-------
TABLE 4. INTENSITY AND pH OF RAINSTORM,
7 DECEMBER 1976
' — - 1IHMI1J.....II
SAMPLE
NUMBER
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
*"" ^r
26
27
*••• i
28
29
*~~ ^
30
*p^
31
,J '
32
™^ *""•
33
->j ~j
34
^^
35
36
-J w
37
™/ i
38
-/ w
39
-/ -/
40
Continued
••••••^•"•••••"•••••••^•••••^^^•^^•••••i
TIME
BETWEEN
(Min)
2.3
3.6
4.5
4.4
2.8
1.8
2.3
2.9
2.7
2.3
2.4
2.5
2.9
2-3
2.8
2. 1
3.2
3-0
3.6
3.8
3-8
3.1
2.6
3.0
2.0
2.5
2.4
1.9
2.3
2.2
2.9
3.3
3.4
7-8
8.4
15.9
2.7
1.8
19.8
ELAPSED
TIME INTENSITY
(Min) (mm/hr)
0.0
2.3
5.9
10.4
14.8
17.6
19.4
21 .7
24.6
27.3
29-6
32.0
34.5
37.4
39.7
42.5
44.6
47.8
50.8
54.4
58.2
62.0
65.1
67.7
70.7
72.7
75.2
77.7
79.5
81 .8
84.0
87.0
90.3
93.7
101.5
109.9
125.9
128.5
130.3
150.0
11 .27
7.20
5.76
5.89
9.26
14.40
1 1.27
8.94
9.60
11.27
10.80
10.37
8.94
1 1 .27
9.26
12.34
8. 10
8.64
7. 16
6.82
6.82
8.31
9.89
8.64
12.96
10.37
10.62
13.86
11.27
11.52
8.82
7.83
7.53
3-34
3-07
1.63
9.64
14.81
1.31
^HM^^BHH_H^^^^^B^_^B,^HHBBIV^^^^^^_^BV^_^^^H
pH REMARKS
5.05
4.85
4.60
4.75
4.75
4.83
4.85
4.85
4.98
5. 10
5.00
4.55
4.95
4.85
4-80
5-30
6.35
4.80
5. 10
5.10
5.15
5.30
5.75
5.73
5.70
5.85
6.05
6. 10
6.30
6.20
5.80
5.85
5.90
6. 15
6.05
5.20
5.45
5.40
5.40
67
-------
TABLE 4 Continued
SAMPLE
NUMBER
41
42
43
44
45
46
47
TIME
BETWEEN
(Min)
21 .0
11.3
10.7
18.9
40.8
32.6
ELAPSED
TIME INTENSITY
(Min) (mm/hr)
171 .0
182.3
193-0
211.9
252.6
285.2
285.2
1 .23
2.30
2.42
1.37
0.64
0.79
PH
5.20
5.05
5.90
5.40
5.20
5.20
5.40
REMARKS
X
X
68
-------
TABLE 5. INTENSITY AND pH OF SNOW FOLLOWED BY RAIN, 17-18 MARCH
1977
SAMPLE
NUMBER
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
* */
20
21
22
23
^ _j
24
25
c— ^/
26
27
28
29
*- J
30
_J v
31
j i
32
33
— / -J
34
35
36
37
38
39
40
Continued
TIME
BETWEEN
(Min)
5.0
9.2
5.8
5.0
5.1
4.9
6.5
3.5
4.6
5.2
5.0
6.7
3.5
6.7
4.7
6.0
6.5
6.0
8.0
5.0
5.3
4.5
4.5
5.0
5.3
4.3
4.7
5-5
5. 1
6.4
5.8
7.0
7.1
10.8
16.0
61.3
6.0
1.7
ELAPSED
TIME INTENSITY
(Min) . (mm/hr)
0.0
5.0
14.2
20.0
25.0
30. 1
35.0
41.5
45.0
49.6
54.8
59.8
66.5
70.0
76.7
81.4
87.4
93.9
99.9
107.9
1 12.9
118.2
122.7
127.2
132.2
137.5
141.8
146.5
152.0
157.1
163.5
169.3
176.3
183.4
194.2
210.2
271.5
277.5
279.2
5. 18
2.82
4.47
5.18
5.08
5.29
3-99
7.41
5.63
4.98
5.18
3.87
7.41
3.87
5.51
4.32
3.99
4.32
3.24
5. 18
4.89
5.76
5.76
5.18
4.89
6.03
5.51
4.71
5.08
4.05
4.47
3.70
3.65
2.40
1.62
0.42
4.32
15.25
pH REMARKS
4.30
4.20
4.30
4.20
4.20
4.25
4.30
4.35
4.40
4.30
4.30
4.35
4.40
4.35
4.25
4.32
4.35
4.35
4.40
4.45
4.45
4.50
4.50
4.45
4.35
4.30
4.30
4.35
4.20
4.30
4.20
4.25
4. 25
4.30
4.30
4.30
4.20 X
4.10 Cl
4.20 Cl
69
-------
TABLE 5 Continued
SAMPLE
NUMBER
41
42
43
44
45
46
47
48
49
50
51
52
53
54
TIME
BETWEEN
(Min)
3.1
3.7
2.3
2.7
3-5
5.9
45.2
15.0
22.6
19.3
15.6
14.0
14.2
18.5
ELAPSED
TIME
(Min)
282.3
286.0
288.3
291.0
294.5
300.4
345.6
360.6
383.2
402.5
418. 1
432. 1
446.3
464.8
INTENSITY
(mm/hr)
8.36
7.01
11.27
9.60
7.41
4.39
0.57
1.73
1. 15
1.34
1.66
1.85
1.83
1 .40
PH
3-90
4.30
4.55
4.40
4.30
4.30
4.30
4.05
4.35
4.30
4.20
4. 10
4.00
4.00
REMARKS
Cl
Cl
X
Cl
Cl
Cl
Cl
Cl
Cl
Cl
70
-------
TABLE 6. INTENSITY, pH, AND
RAINSTORM
CHEMISTRY OF
22 MAR 1977
SELECTED SAMPLES
SAMPLE
NUMBER
1
2
3
4
5
6
7
8
9
10
1 1
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
ontinued
TIME
BETWEEN
(min)
32.0
15.6
10.9
6.0
8.0
5.4
4.7
5.3
6.7
6.9
4.4
4.5
3.0
3.9
4.0
4.7
6.0
6.3
5.0
5.0
3.5
5.2
6.0
6.0
2.4
6.0
6.5
4.0
3.0
ELAPSED
TIME
(min)
0.0
32.0
47.6
58.5
64.5
72.5
77.9
82.6
87.9
94.6
101 .5
105.9
1 10.4
1 13.4
117.3
121 .3
126.0
132.0
138.3
143.3
148.3
151.8
157.0
163.0
169.0
171 .4
177.4
183.9
187.9
190.9
INTENSITY
(mm/hr)
0.81
1.66
2.38
4.32
3.24
4.80
5.51
4.89
3-87
3-76
5.89
5.76
8.64
6.65
6.48
5.51
4.32
4. 11
5. 18
5. 18
7.41
4.98
4.32
4.32
10.80
4.32
3-99
6.48
8.64
PH
4.40
4.40
4.60
4. 70
4.55
4.00
4.60
4.50
4.62
4. 10
4.35
5.30
5.60
4.38
5. 10
5.50
5.80
5.32
5.80
5.30
5.90
5.00
5.20
4.90
5.25
5.40
5.90
4.95
4. 90
IONS (mg/1)
NO;-N SO"2 NH3-N REMARKS
X
Cl
Cl
Cl
3 Cl
3 Cl
3 Cl
Cl
Cl
0.08
0.08
0.08
0.3
0.3
0.3
-------
TABLE 6 Continued
SAMPLE
NUMBER
31
32
33
34
35
36
37
38
39
40
41
42
43
-j 44
10 45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Continued
TIME
BETWEEN
(min)
4.0
5.5
6.0
5. 1
5.2
5.2
5.5
5.2
3.0
3.0
3-0
3.2
3-0
3- 1
5.0
6.0
4.5
3-8
3.7
2.6
3.0
2.6
3-0
2.5
3.0
2.7
2.0
2.3
1.5
1.3
ELAPSED
TIME
(min)
194.9
200.4
206.4
21 1 .5
216.7
221 .9
227.4
232.6
235.6
238.6
241.6
244.8
247.8
250.9
255.9
261 .9
266.4
270.2
273.9
276.5
279.5
282. 1
285.1
287.6
290.6
293.3
295.3
297.6
299.1
300.4
INTENSITY
(mm/hr)
6.48
4.71
4.32
5.08
4.98
4.98
4.71
4.98
8.64
8.64
8.64
8. 10
8.64
8.36
5. 18
4.32
5.76
6.82
7.01
9.97
8.64
9.97
8.64
10.37
8.64
9.60
12.96
11.27
17.28
19.94
IONS (mg/lJ
NO~-N S0~ NH3 -N REMARKS
PH
5.20
5.80
5.95
5.90
5.30
5.48
6.02
5.84
6.00
5.60
5.35
6.60
6.55
5.70
4.90
4.60
4.43
6.07
6.20
6.30
6.35
6. 10
6.40
5.65
6.21
6.40
6.60
6. 15
6.48
7.30
-------
TABLE 6 Continued
-j
ui
SAMPLE
NUMBER
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
TIME
BETWEEN
(min)
2.5
1.7
1.5
1.5
3.5
5.5
2.5
5.5
1.5
2.0
3-4
5.0
4.7
3.8
3.5
4.0
2.7
9.5
2.7
3-0
1.0
1.5
2.5
3.6
1.7
2.3
1.5
1 .0
3-7
7.3
ELAPSED
TIME
(min)
302.9
304.6
306. 1
307.6
311.1
316.6
319.1
324.6
326.1
328.1
331.5
336.5
341 .2
345.0
348.5
352.5
355.2
364.7
367.4
370.4
371.4
372.9
375.4
379.0
380.7
383-0
384.5
385.5
389.2
396.5
INTENSITY
(mm/hr)
10.37
15.25
17.28
17.28
7.41
4.71
10.37
4.71
17.28
12.96
7.62
5. 18
5.51
6.82
7.41
6.48
9.60
2.73
9.60
8.64
25.92
17.28
10.37
7.20
15.25
11.27
17.28
25.92
7.01
3.55
IONS (mg/1)
NC£-N S0;s NH3 -N REMARKS
PH
6.85
6.85
6.55
6.65
6.75
6.62
6.55
6.00
6.42
6.65
6.54
6.60
6.70
6.47
6.35
6.30
6.30
6.20
6.25
6.62
6.46
6.60
6.50
6.75
6.75
6.60
6.68
6.73
6.73
6.80
Continued
-------
TABLE 6 Continued
SAMPLE
NUMBER
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
Continued
TIME
BETWEEN
(min)
2.2
3.7
2.3
1 .2
1.5
2.0
2.3
3.2
5.0
5.0
6.2
4.3
7.5
5.2
4.0
4.0
5.7
13-8
1 1.5
27.6
16.0
7.0
7.0
9.7
10.5
9.6
6.5
7.5
10.2
8.5
ELAPSED
TIME
(min)
398.7
402.4
404.7
405.9
407.4
409.4
411.7
414.9
419.9
424.9
431. 1
435.4
442.9
448. 1
452. 1
456. 1
461.8
475.6
487. 1
514.7
530.7
537.7
544.7
554.4
564.9
574.5
581 .0
588.5
598.7
607.2
INTENSITY
(mra/hr )
1 1.78
7.01
11.27
21.60
17.28
12.96
1 1.27
8. 10
5.18
5. 18
4. 18
6.03
3.46
4.98
6.48
6.48
4.55
1.88
2.25
0.94
1 .62
3-70
3.70
2.67
2.47
2.70
3-99
3.46
2.54
3.05
IONS (rag/1)
NOg-N SO^3
PH
6.60
6.90
6.60
6.50
6.60
6.70
6.60
6.90
6.50
6.50
6.60
6.40
6.40
6.40
6.80
6.50
6.40
6.30
6.30
6.20
6.20
6.20
5.90
5.70
5.60
5.20
4.90
4.50
4.50
4.90
NH3-N REMARKS
X
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
-------
TABLE 6 Continued
Ul
SAMPLE
NUMBER
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
TIME
BETWEEN
(min)
9.0
8.0
8.6
9.5
9.3
6.5
6.0
5.7
5.0
5. 1
5.0
6.4
7.3
6.0
7.5
10.7
12.5
29.5
31.5
54.0
34.0
53-0
172.5
50.5
53.0
43.0
ELAPSED
TIME INTENSITY
(min) (mm/hr)
616.2
624.2
632.8
642.3
651 .6
658. 1
664. 1
669.8
674.8
679.9
684.9
691.3
698.6
704.6
712. 1
722.8
735.3
764.8
796.3
850.3
884.3
937.3
1 109.8
1 160.3
1213.3
1256.3
2.88
3.24
3.01
2.73
2.79
3.99
4.32
4.55
5. 18
5.08
5. 18
4.05
3.55
4. 32
3.46
2.42
2.07
0.88
0.82
0.48
0.76
0.49
0.15
0.51
0.49
0.60
IONS (mg/1)
NO;-N SO;2 NH3-N
pH
5.40
5.90
5.80
5.70
5.80
5.63
5.80
6. 10
6.05
6.00
6.05
6.02
6.00
6.05 0.2
6. 10 0.2
6.10 0.2
6.00 0.06
6.3.0 0.06
6.20 0.06
6. 10
6.30
6.30
6.41
6.50 BDL
6.45 BDL
6.30 BDL
REMARKS
X
X
X
X
X
X
X
X
X
-------
TABLE 7. INTENSITY, pH, AND CHEMISTRY OF SELECTED SAMPLES
RAINSTORM, 28 MARCH 1977
-j
en
SAMPLE
NUMBER
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
TIME
BETWEEN
(min)
7.5
7.2
8.7
9.0
8.0
8.0
13.5
14.5
16.5
24.0
34.0
31.0
12.3
9.5
13.0
8.5
21.0
33.0
17.5
26.5
31.0
•MV«H«MIB^— ^^^^^K
ELAPSED
TIME
(min)
0.0
7.5
14.7
23-4
32.4
40.4
48.4
61.9
76.4
92.9
116.9
150.9
181.9
19U.2
203.7
216.7
225.2
246.2
279.2
296.7
323.2
354.2
•B^— ^^••^••HMM— «wa~P
INTENSITY
(mrn/hr)
3.46
3.60
2.98
2.88
3.24
3.24
1.92
1.79
1.57
1.08
0.76
0.84
2.11
2.73
1.99
3.05
1.23
0.79
1.48
0.98
0.84
^•"••^•^^^••^•••^^•••^^^^•M
PH
4.70
4.58
4.50
4.42
4.40
4.28
4.13
4.13
4.80
3.80
3.87
3.90
3.90
3-90
3.90
3.94
3.80
3.68
3.80
3-60
3.70
^ -M«a_MMB— •— —
IONS (mg/1)
NO^-N SOI2 NH3-N
5.0
5.0
0.6
0.6
0.6
0.7
0.7
0.7
0.7
1.0
1.0
1.0
1.0
1.5
1.5
1.5
11.0
11.0
11.0
_«^^_^^«^MHm^^MiM«t
REMARKS
X
X
Cl
Cl
Cl
Cl
Cl
X
Cl
X
X
-------
TABLE 8. INTENSITY, pH, AND CHEMISTRY OF SELECTED SAMPLES
RAINSTORM, 4-6 APRIL 1977
SAMPLE
NUMBER
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Continued
TIME
BETWEEN
(rain)
34.5
10.3
10.2
23.0
8.6
7.8
8.0
9.5
5.5
4.0
5.0
6.5
7.5
8.3
6.2
4.0
4.5
8.0
8.0
9.3
14.0
26.0
15.0
5.0
6.5
13-5
6.6
8.3
7.0
ELAPSED
TIME INTENSITY
(min) (mm/hr)
0.0
34.5
44.8
55.0
78.0
86.6
94.4
102.4
111.9
117.4
121.4
126.4
132.9
140.4
148.7
154.9
158.9
163.4
171.4
179-4
188.7
202.7
228.7
243.7
248.7
255.2
268.7
275.3
283.6
290.6
0.75
2.52
2.54
1.13
3.01
3.32
3.24
2.73
4.71
6.48
5.18
3.99
3.46
3.12
4.18
6.48
5.76
3.24
3.24
2.79
1.85
1.00
1.73
5.18
3.99
1.92
3.93
3.12
3.70
IONS (rag/1)
NO^-N SO 4 NH3-N
PH
3.79
4.10
4.00
3.99 7.0
4.12 7.0
4.22 7.0
4.23 1.0
3.81 1.0
4.21 1.0
3-90
4.10
4.10
4.60
4.90
4.91
4.40 0.12
3-81 0.12
4.40 0.12
4.48
4.50
4.33
4.15
4.22
4.60
4.99
4.58
4.90
5.35
5.44
REMARKS
X
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
-------
TABLE 8 Continued
GO
SAMPLE
NUMBER
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Continued
TIME
BETWEEN
(min)
4.7
6.4
8.0
4.0
4.0
6.0
3.2
6.3
2.3
2.3
1.2
1.5
2.0
2.5
3-0
2.0
2.6
2.7
3-0
2.5
3-0
2.5
3.5
3.5
3-0
4.5
40.5
17-0
96.5
22.5
ELAPSED
TIME
(min)
295.3
301.7
309.7
313.7
317.7
323.7
326.9
333-2
335.5
337.8
339.0
340.5
342.5
345.0
348.0
350.0
352.6
355.3
358.3
360.8
363.8
366.3
369.8
373.3
376.3
380.8
421.3
438.3
534.8
557.3
INTENSITY
(mm/hr)
5.51
4.05
3.24
6.48
6.48
4.32
8.10
4.11
11.27
11.27
21.60
17.28
12.96
10.37
8.64
12.96
9-97
9.60
8.64
10.37
8.64
10.37
7.41
7.41
8.64
5.76
0.64
1.52
0.27
1.15
pH
5.63
5.75
5.50
5.59
5.58
5.58
5.77
5.80
5.50
5.38
4.90
5.65
5.60
4.31
4.50
4.00
3.95
3.90
4.60
5.30
5.20
4.75
4.13
3.98
4.10
4.10
4.30
4.42
4.60
3.98
IONS (mg/1)
NO^-N SOI2 NH3-N REMARKS
0.7
0.7
0.7
X
Cl
X
Cl
-------
TABLE 8 Continued
SAMPLE
NUMBER
61
62
63
64
55
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
TIME
BETWEEN
(rain)
15.0
6.6
74.6
50.0
42.5
47.7
35.7
1.5
2.0
1.5
5.5
6.6
51.5
50.5
20.5
18.0
8.6
11.0
42.5
11.0
21.3
53-5
255.5
3.5
1.6
2.3
16.0
ELAPSED
TIME INTENSITY
(min) (nrn/hr)
572.3
578.9
653-5
703.5
746.0
793-7
829.4
830.9
832.9
834.4
839.9
846.5
898.0
948.5
969.0
987.0
995.6
1006.6
1049.1
1060.1
1081.4
1134.9
1390.4
1393-9
1395.5
1397.8
1413.8
1.73
3.93
0.35
0.52
0.61
0.54
0.73
17-28
12.96
17.28
4.71
3.93
0.50
0.51
1.26
1.44
3.01
2.36
0.61
2.36
1.22
0.48
0.10
7.41
16.20
11.27
1.62
IONS (rag/11
NO^-N SO" NH3-N REMARKS
PH
4.30
4.50
4.48
4.50
4.58
4.97
5.75
6.68
5.30
5.02
4.72
4.40
4.30
4.12
4.18
4.18
4.00
3.90
4.00
3.95
3.89
4.18
4.42
4.40
Cl
Cl
0.39 X
0.39 X
0.39 X
X
X
Cl
Cl
Cl
Cl
Cl
X
X
Cl
Cl
Cl
Cl
X
Cl
Cl
X
6.5 X
6.5 Cl
6.5 Cl
Cl
Cl
-------
TABLE 9. INTENSITY, pH, AND CHEMISTRY OF SELECTED SAMPLES
RAINSTORM, 23-24 APRIL 1977
oo
o
SAMPLE
NUMBER
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Continued
TIME
BETWEEN
(min)
3-2
5.0
59.8
93-7
90.7
6.2
5.8
4.5
6.6
193-0
25.9
9.6
3.2
1.8
2.3
2.0
1.3
3-2
16.6
4.7
3-6
4.9
2.1
8.2
21.9
1.1
0.6
0.8
46.8
ELAPSED
TIME
(min)
0.0
3.2
8.2
68.0
161.7
252.4
258.6
264.4
268.9
275.5
468.5
494.4
504.0
507.2
509.0
511.3
513-3
514.6
517-8
534.4
539.1
542.7
547.6
549.7
557.9
579.8
580.9
581.5
582.3
629.1
INTENSITY
(nm/hr)
8.10
5.18
0.43
0.28
0.29
4.18
4.47
5.76
3.93
0.13
1.00
2.70
8.10
14.40
1 1 . 27
12.96
19-94
8.10
1.56
5.51
7.20
5.29
12.34
3.16
1.18
23-56
43.20
32.40
0.55
pH
4.00
4.22
4.14
3.70
3-48
3.53
3-51
3.50
3.61
3.60
3-74
3.75
4.10
4.23
4.32
4.30
4.30
4.25
4.10
4.37
4.48
4.30
4.30
4.20
4.00
4.20
4.00
3.91
IONS (mg/1)
NOa-N SOl NH3-N REMARKS
12
12 X
12 X
X
>2.0 Cl
>2.0 Cl
>2.0 Cl
2.5 Cl
2.5 X
2.5 Cl
2.0 Cl
2.0 Cl
2.0 Cl
X
-------
TABLE 9 Continued
00
SAMPLE
NUMBER
31
32
33
34
35
36
37
38
39
40
41
42
43
TIME
BETWEEN
(rain)
5.4
1.7
1.3
0.7
0.9
1.0
2.8
9.2
2.7
5.2
3.7
72.4
81.8
ELAPSED
TIME
(min)
634.5
636.2
637.5
638.2
639.1
640.1
642.9
652.1
654.8
660.0
663.7
736.1
817.9
INTENSITY
(mm/hr)
4.80
15.25
19.94
37.03
28.80
25.92
9.26
2.82
9.60
4.98
7.01
0.36
0.32
PH
3.84
3.98
4.36
4.58
4.65
4.60
4.67
4.40
4.07
4.01
4.20
3.60
3.68
IONS (mg/1)
NOT-N SO? NH -N REMARKS
o ^* *^
Cl
Cl
Cl
X
X
Storm continued for several hours. Time data lost due to recorder malfunction.
-------
TABLE 10. INTENSITY, pH, AND CHEMISTRY OF SELECTED SAMPLES
RAINSTORM, 2 JUNE 1977
oo
to
SAMPLE
NUMBER
1
2
3
4
5
6
7
8
9
10
1 1
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Continued
TIME
BETWEEN
(min)
9.7
3.9
5.2
4. 1
1.8
2.6
3.0
10.7
1.8
1.9
21 .6
5.4
3.2
17.0
28.7
14.2
0.2
0.6
0.7
1. 1
31.4
0.6
0.7
1.3
2. 1
9.0
1.7
17-0
37.7
ELAPSED
TIME
(min)
0.0
9.7
13-6
18.8
22.9
24.7
27.3
30.3
41.0
42.8
44.7
66.3
71.7
74.9
91.9
120.6
134.8
135.0
135.6
136.3
137.4
168.8
169.4
170. 1
171 .4
173.5
182.5
184.2
201 .2
238.9
INTENSITY
(mm/hr )
2.67
6.65
4.98
6.32
14.40
9.97
8.64
2.42
14.40
13-64
1 .20
4.80
8. 10
1.52
0.90
1 .83
129.60
43.20
37.03
23-56
0.83
43.20
37.03
19-94
12.34
2.88
15.25
1.52
0.69
PH
3.60
3.70
3.43
3.65
3.80
3.86
3.70
4.00
4.20
4.30
4.15
3.88
3.92
3.99
4.05
4.04
3-98
3.66
3-63
3.46
3.82
4.00
3.95
3.87
3-65
3-73
3.82
4.09
4.03
IONS (mg/lj
NO;~N SOl NH--N REMARKS
o ^t o
12
12
12
0.7
0.7
0.7
0.85
0.85
0.85
X
Cl
Cl
Cl
7 X
7 Cl
7 Cl
0.9 Cl
0.9 Cl
0.9
1.73
1.73
1.73 X
-------
TABLE 10 Continued
SAMPLE
NUMBER
31
32
33
34
35
36
37
38
39
40
41
42
43
TIME
BETWEEN
(min)
2.2
46.5
2.2
5. 1
6.8
12.4
2.8
1.3
0.7
0.9
0.8
3.7
16.5
ELAPSED
* TIME
(min)
241 . 1
287.6
289.8
294.9
301 .7
314.1
316.9
318.2
318.9
319.8
320.6
324.3
340.8
INTENSITY
(mm/hr)
11.78
0.56
11.78
5.08
3.81
2. 09
9.26
19.94
37.03
28.80
32.40
7.01
1.57
IONS (mg/1)
NO~-N so;
PH
3.93
4. 32
4.93
5.08
5.00 2
5. 12 2
4.52 2
3-98
3.78
3. 18
3.36 1.15
3.50 1.15
3.66 1 . 15
NH3 -N REMARKS
Cl
X
Cl
Cl
Cl
Cl
Cl
0.7 Cl
0.7 Cl
0.7
00
OJ
-------
TABLE 11. INTENSITY, pH, AND
RAINSTORM,
CHEMISTRY OF
7 JUNE 1977
SELECTED SAMPLES
SAMPLE
NUMBER
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
TIME
BETWEEN
(Min)
25.6
22.4
298.2
47.2
8.0
8. 1
8.2
10.0
19.3
69.0
39.4
29.4
32.7
103.9
53.5
ELAPSED
TIME
(Min)
0.0
25.6
48.0
346.2
393-4
401 .4
409.5
417.7
427.7
447.0
516.0
555.4
584.8
617.5
721 .4
774.9
INTENSITY
(mm/hr)
1 .01
1 . 16
0.09
0.55
3.24
3-20
3. 16
2.59
1.34
0.38
0.66
0.88
0.79
0.25
0.48
pH
4.63
3.52
3.08
3. 16
3.69
3.80
3.70
3.86
3.60
3.40
3.46
3.30
3.40
3.30
3.00
REMARKS
X
X
Cl
Cl
Cl
Cl
Cl
X
X
X
X
X
X
84
-------
TABLE 12. INTENSITY, pH, AND CHEMISTRY OF
RAINSTORM, 18 AUG 1977
SELECTED SAMPLES
oo
Ul
SAMPLE
NUMBER
1
2
3
4
5
6
7
8
9
10
1 1
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Continued
TIME
BETWEEN
(min)
7.5
3.7
2.8
3.7
3-5
3.2
68.0
3.2
2.2
34.5
2.6
1.5
0.8
0.6
0.8
0.3
0.2
0.2
0.2
0.3
0.4
0.9
1.5
1.8
2.0
2.8
0.9
0. 8
1 .0
ELAPSED
TIME
(min)
0.0
7.5
11.2
14.0
17.7
21 .2
24.4
92.4
95.6
97.8
132.3
134.9
136.4
137.2
137.8
138.6
138.9
139.1
139-3
139.5
139.8
140. 1
141 .0
142.5
144.3
146.3
149. 1
150.0
150.8
151 .8
INTENSITY
(mrn/hr)
3.46
7.01
9.26
7.01
7.41
8. 10
0. 38
8. 10
1 1.78
0.75
9-97
17.28
32.40
43-20
32.40
86.40
129.60
129.60
129.60
86.40
64.80
28.80
17.28
14.40
12.96
9.26
28.80
32. 40
25.92
PH
5.00
4.73
4.80
4.80
4.98
5.05
4.41
4.41
4.28
4.50
4.72
4.95
4.95
5.20
5.20
5.50
5.31
5.50
5.45
5.45
5.43
5.28
5.20
5.05
5.00
5. 20
5.22
5. 10
IONS (mg/U
NO;-N SO; NH3-N REMARKS
5.0
5.0
5.0
0.7
0.7 I
0.7
0.9 X
0.9 Cl
0.9 Cl
X
Cl
Cl
Cl
2.0
2. 0
2.0
0.4
0.4
0.4
0.25
0.25
0.25
2.5
2.5
2.5
0.5
0.5
0.5
-------
TABLE 12 Continued
TIME ELAPSED TONS (rag/I)
SAMPLE BETWEEN TIME INTENSITY H0~3 -N S0~ NH3-N REMARKS
NUMBER (min) (min) (mm/hr) pH
31 1.6 153.4 16.20 5.09 0.3
32 3.9 157-3 6.65 4.97 0.3
33 4.7 162.0 5.51 4.80 0.3
34 13.5 175.5 1.92 4.46
CO
-------
TABLE 13. INTENSITY, pH, AND CHEMISTRY OF SELECTED SAMPLES
RAINSTORM, 16-17 SEPT 1977
TIME ELAPSED
SAMPLE BETWEEN TIME INTENSITY
NUMBER (min) (min) (mm/hr)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
*-/
35
36
37
38
•^ ^*
39
40
Continued
74.0
112.0
106.0
56.0
42.0
1.6
1.6
1 .6
4.0
32.5
12.0
5.4
9.0
7.8
8.2
2.0
2.8
6.6
4.2
3-0
2.4
2.9
2.3
1.0
0.8
1 .0
3.0
2.4
3.2
3.0
1.4
2.0
3.0
4.6
5.0
7.0
6.8
6.0
7.8
0.0
74.0
186.0
292.0
348.0
390.0
391.6
393-2
394.8
398.8
431.3
443.3
448.7
457.7
465.5
473.7
475.7
478.5
485. 1
489.3
492.3
494.7
497.6
499.9
500.9
501.7
502.7
505.7
508. 1
511.3
514.3
515.7
517.7
520.7
525.3
530.3
537-3
544. 1
550.1
557.9
0.35
0.23
0. 24
0.46
0.62
16.20
16.20
16.20
6.48
0.80
2. 16
4.80
2.88
3.32
3.16
12.96
9.26
3.93
6.17
8.64
10.80
8.94
1 1.27
25.92
32.40
25.92
8.64
10.80
8. 10
8.64
18.51
12.96
8.64
5.63
5. 18
3.70
3.81
4.32
3-32
IONS (mg/1) 2
N03 SOl
pH REMARKS
3.40 12.2
3-66
3.71
4.28
4.24 0.87
4.20
3-90
3.52 3.68
3-73
4. 19
4.20
3-97
4.09
4.46 3-04
3-90
3.80 1.49
3.87
3-91
4.32
4.14
3-70
4.09
4.22
3-99 0.49
4.01
4. 43
4.40
3-99
4.78 0.36
4.41
3-90
3-98
3.89
4.30 0.61
4.20
4. 17
4. 18
4.40
3-99
34.3 X
X
X
X
5.20 X
Cl
Cl
12.1 Cl
Cl
X
Cl
Cl
Cl
8.09 Cl
Cl
10.86 Cl
6.89
1 .63
3-57
87
-------
TABLE 13 Continued
SAMPLE
NUMBER
41
42
43
44
45
46
47
48
49
50
51
52
TIME ELAPSED
BETWEEN TIME INTENSITY
(min) (rain) (mm/hr)
10.
17.
17.
22.
20.
16.
21 .
55.
17.
22.
17.
21 .
0
0
6
0
0
0
0
0
0
6
0
0
567.
584.
602.
624.
644.
660.
681.
736.
753.
776.
793.
814.
9
9
5
5
5
5
5
5
5
1
1
1
2.
1 .
1 .
1 .
1 .
1 .
1 .
0.
1 .
1 .
1 .
1.
59
52
47
18
30
62
23
47
52
15
52
23
IONS (mg/1)
NO; so;2
pH REMARKS
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
3-
20
00 2.12
30
40 1.79
21
25
28
35
43
29 2.40
20
82 5.37
3.34
3.48
2.55
6.64
X
Cl
Cl
Cl
Cl
88
-------
TABLE 14.
INTENSITY AND pH
18 SEPT 1977
OF RAINSTORM,
SAMPLE
NUMBER
1
2
3
4
5
6
7
8
9
10
11
12
13
1 *j
14
TIME
BETWEEN
(Min)
75.0
608.0
11.0
2.4
1.8
5.8
6.6
4.0
3.6
5.0
6.2
6.6
11.0
ELAPSED
TIME
(Min)
0.0
75.0
683.0
694.0
696.4
698.2
704.0
710.6
714.6
718.2
723.2
729.4
736.0
747.0
INTENSITY
(mm/hr)
0.35
0.04
2.36
10.80
14.40
4.47
3.93
6.48
7.20
5- 18
4.18
3.93
2.36
pH REMARKS
4.90 X
3.70 X
3.70 ci
3.60 Cl
3.90 Cl
3.85
3-70
3.90
3.80
3-85
4. 10
3.90
3.70
89
-------
TABLE 15. INTENSITY, pH, AND CHEMISTRY OF SELECTED SAMPLES
RAINSTORM, 24-26 SEPT 1977
TIME ELAPSED
SAMPLE BETWEEN TIME INTENSITY
NUMBER (min) (mln) (mm/hr)
1
2
3
4
5
6
7
8
9
10
1 1
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
Continued
0.0
0.0
6.2
4.8
4.0
6.3
45.0
5.8
6.9
7-9
11.8
6.7
3.0
3-7
5.0
6.3
5.2
6.8
13-2
12.6
32.7
14.7
9.9
8.3
9.6
20.4
8.0
3-0
3.3
4.4
7.3
11.4
10.3
16.4
12.0
12.6
5.5
3.0
3.5
3.4
0.0
0.0
6.2
11.0
15.0
21.3
66.3
72. 1
79.0
86.9
98.7
105.4
108.4
1 12. 1
117. 1
123.4
128.6
135.4
148.6
161.2
193.9
208.6
218.5
226.8
236.4
256.8
264.8
267.8
271 . 1
275.5
282.8
294.2
304.5
320.9
332.9
345.5
351.0
354.0
357.5
360.9
4. 18
5.40
6.48
4.11
0.58
4.47
3-76
3.28
2.20
3.87
8.64
7.01
5.18
4.11
4.98
3.81
1 .96
2.06
0.79
1 .76
2.62
3. 12
2.70
1 .27
3.24
8.64
7.85
5.89
3-55
2.27
2.52
1.58
2.16
2.05
4.71
8.64
7.41
7.62
IONS (mg/1)
NO" SO;2
pH REMARKS
3.25 24.9
3-35
3.60 9-25
3.82
3.95
3-99 2.78
3.70
3-70
3.55 9.36
3.60
3.65
3-75
3.85
3.75
3.95
4.00
4.10 1.92
4.00
3.80
3-80
3-80
3.70
3.80
3.90
3-80 4.85
3.65
3.80
3.70
3.75
3.70
3.70
3.70
3-80
3.80
3.80 3-99
3.72
3.70
3.80
3-65
61.6
7.59
3.89 X
Cl
Cl
7.87 Cl
Cl
Cl
Cl
2.76
X
Cl
Cl
Cl
Cl
5.03 Cl
Cl
Cl
5.60
90
-------
TABLE 15 Continued
TIME ELAPSED
SAMPLE BETWEEN TIME INTENSITY
NUMBER (min) (rain) (mm/hr)
41
42
43 .
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
Continued
32.8
30.6
15.0
9.2
4.0
27.3
10.4
28.2
360.0
17.0
21.6
13.2
8.0
9.0
11.8
27.7
16.0
6.9
3.8
10.5
8.9
15.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
393.7
424.3
439.3
448.5
452.5
479.8
490.2
518.4
878.4
895.4
917.0
930.2
938.2
947.2
959-0
986.7
1002.7
1009.6
1013.4
1023.9
1032.8
1047.8
R
E
C
0
R
D
E
R
Q
U
I
T
0.79
0.85
1.73
2.82
6.48
0.95
2.49
0-92
0.07
1.52
1 .20
1 .96
3.24
2.88
2.20
0.94
1 .62
3.76
6.82
2.47
2.91
1.73
IONS (mg/1)
NO; so;2
pH REMARKS
3.70
3.60
3.50
3.60
3.65
3.75 2.65
3.70
3.90 2.78
3.75
3.20 16.67
3.45
3.60
3-75
3.75
3.65 2.29
3.70
3.55
3.55
3.65
3.55
3.65
3.65
3-65
3.70
3.40 5.04
3.60
3.80
3.85
3-85
3.55
3-70
3.80
3.75
3-75
3.80 1.56
3-80
4.00
4.00
4.05
4.15
X
X
Cl
Cl
Cl
6.02 X
Cl
3.89 X
X
32.76 Cl
Cl
Cl
Cl
Cl
9.44 Cl
X
Cl
Cl
Cl
Cl
Cl
Cl
13.6
6.73
91
-------
TABLE 15 Continued
TIME ELftPSED
SAMPLE BETWEEN TIME INTENSITY
NUMBER (rain) (min) (mm/hr)
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
1 1 1
112
113
114
115
116
117
118
119
120
Continued
0.0
0.0
0.0
0.0
0.0
0.0
90.0
6.7
3-0
2.0
1.9
5.0
9.6
3-5
3-6
5.4
6.4
12.3
11.2
16.7
10.0
9-0
4.3
1.9
2.0
2.8
3.8
4.6
3.2
3-6
3.6
4.8
3.7
2.3
2. 1
2.9
9-2
9.9
5.6
11.9
1137.8
1 144.5
1147.5
1149.5
1 151 .4
1156.4
1 166.0
1169.0
1173- 1
1178.5
1184.9
1 197.2
1208.4
1225. 1
1235.1
1244. 1
1248.4
1250. 3
1252.3
1255. 1
1258.9
1263.5
1266.7
1270. 3
1273.9
1278.9
1282.4
1284.7
1286.8
1289.7
1298.9
1308.8
1314.4
1326.3
0. 29
3-87
8.64
12.96
13.64
5. 18
2.70
7.41
7.20
4.80
4.05
2. 11
2.31
1.55
2.59
2.88
6.03
13-64
12.96
9-26
6.82
5.63
8. 10
7.20
7.20
5.40
7.01
1 1 .27
12.34
8.94
2.82
2.62
4.63
2. 18
IONS (mg/1) 3
N0~ SO"
pH REMARKS
4.25 0.34
4.25
4.20
4.40 0.54
4.35
4.35
4.50 0.65
4.40
4.40
4.35
4.50
4.50
4.60 0.54
4.50
4.50
4.50
4.50
4.35
4.28
4.30
4.40
4.35
4.30 1.83
4.30
4.35
4.35
4.40
4. 30
4.20
4.50
4.50
4.40
4.35 1.79
4.30
4.00 2.56
4. 10
4.35
4.40
4.35
4.30
2.05
2.02
2. 16 X
Cl
Cl
Cl
Cl
Cl
1.88 Cl
3.53
2.43
1 1 .20
92
-------
TABLE 15
TIME ELAPSED
SAMPLE BETWEEN TIME INTENSITY
NUMBER (rain) (mln) (mm/hr)
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
Continued
12.4
11.0
5.8
7.2
8.6
9-3
4.0
7.0
6.9
5.0
9-2
13.8
14.4
21 .7
43-5
69.9
50.5
8.7
12.0
5.0
4.4
5.6
5.0
6.0
6.0
6.7
5.4
9.0
5.9
6.8
6.8
5.0
4.9
4-3
4.8
6.3
6.5
7.5
6.4
4.7
1338.7
1349.7
1355.5
1362.7
1371.3
1380.6
1384.6
1391.6
1398.5
1403.5
1412.7
1426.5
1440.9
1462.6
1506. 1
1576.0
1626.5
1635.2
1647.2
1652.2
1656.6
1662.2
1667.2
1673.2
1679.2
1685.9
1691.3
1700.3
1706.2
1713-0
1719.8
1724.8
1729.7
1734.0
1738.8
1745. 1
1751 .6
1759-1
1765.5
1770.2
2.09
2.36
4.47
3.60
3.01
2.79
6.48
3.70
3-76
5.18
2.82
1.88
1 .80
1.19
0.60
0.37
0.51
2.98
2. 16
5. 18
5-89
4.63
5.18
4.32
4.32
3.87
4.80
2.88
4.39
3.81
3.81
5.18
5.29
6.03
5.40
4. 11
3.99
3.46
4.05
5.51
Continued
IONS (mg/1)
NO; so;2
pH REMARKS
4.40
4.40
4.80
4.80
4.89
4.95
5.20 0.28
4.99
4.80
4.95
4.75
4.50
4.65
4.65
4.85
4.60
4.50
4.80
4.85
5.00
4.90
5.00
4.60
4.30
4.70
4.90 0.35
5-00
4.80
4.75
5.05
4.95
4.99
5.10 0.17
5.00
5.05
4.70
4.80
4.90
5.25
5.30
1 .24
X
X
X
Cl
Cl
Cl
Cl
Cl
Cl
1 .40
1.33
93
-------
TABLE 15 Continued
TIME ELAPSED
SAMPLE BETWEEN TIME INTENSITY
NUMBER (rain) (rain) (mm/hr)
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
183
184
185
186
187
188
189
190
191
192
193
194
195
196
197
198
199
200
Continued
5.0
4. 1
5.9
5.0
2.7
3-0
3-2
4. 1
3.9
4.9
4.5
3-4
4.0
4.3
6.6
6.4
9.1
7.8
5.6
5.5
3.6
3.5
3.6
3.9
5. 1
4.7
8.8
5.2
42.0
9.1
11.4
8.5
7.0
4.8
6.2
4.6
9.0
10.3
12.2
12.3
1775.?
1779.3
1785.2
1790.2
1792.9
1795.9
1799. 1
1803.2
1807. 1
1812.0
1816.5
1819.9
1823-9
1828.2
1834.8
1841 .2
1850.3
1858.1
1863.7
1869.2
1872.8
1876.3
1879.9
1883.8
1888.9
1893.6
1902.4
1907.6
1949.6
1958.7
1970. 1
1978.6
1985.6
1990.4
1996.6
2001 .2
2010.2
2020.5
2032.7
2045.5
5. 18
6.32
4.39
5. 18
9.60
8.64
8. 10
6.32
6.65
5.29
5.76
7.62
6.48
6.03
3.93
4.05
2.85
3-32
4.63
4.71
7.20
7.41
7.20
6.65
5.08
5.51
2.95
4.98
0.62
2.85
2.27
3.05
3.70
5.40
4. 18
5.63
2.88
2.52
2. 12
2.03
IONS (mg/1) a
N0~ S0~
pH REMARKS
5.25
4.30
4.30
4.70
4.80
4.10 0.39
4.50
4.57
4.49
4.55
4.60
4.70
4.70
4.71
4.69
4.62
5.01 0.28
4.84
4.80
4. 12
4.10 3-30
3.72
3.67
3-61
3.96
3.89
3.99
4.00
4.06
3.85
3-51
3.61
4. 13
4.09
3.97
4.00
4.01
3.95
4.42
5.64
1.97
8.48
X
Cl
Cl
Cl
Cl
Cl
Cl
94
-------
TABLE 15 Continued
SAMPLE
NUMBER
201
202
203
204
205
206
207
TIME ELAPSED
BETWEEN TIME INTENSITY
(mln) (min) (mtn/hr)
14.8
430.0
110.0
14.3
5.0
11.7
9.5
2060.3
2490.3
2600.3
2614.6
2619.6
2631-3
2640.8
1.75
0.06
0.24
1 .81
5.18
2.22
2.73
IONS (mg/1) a
NO" sol
pH REMARKS
4.32
3-99
4.00
4.40
4.62
4.75
5.17
X
X
Cl
Cl
Cl
Cl
95
-------
TABLE 16. INTENSITY, pH, AND CHEMISTRY OF SELECTED SAMPLES
RAINSTORM, 26 SEPT 1977
TIME ELAPSED
SAMPLE BETWEEN TIME INTENSITY
NUMBER (min) (rain) (mm/hr)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
Continued
0.5
1 .0
1.5
1.3
1 .7
3-6
4.5
3.5
4.8
1.4
0.9
1 .2
2.0
1.6
0.3
0.7
2.3
2. 1
2.6
3.0
5.6
2.5
13.2
5.8
2. 1
1.8
1 . 1
2.0
1.7
1 .0
0.5
0.5
0.5
0.9
1 .0
2. 1
2.4
0.4
0.9
0.0
0.5
1.5
3.0
4.3
6.0
9.6
14. 1
17.6
22.4
23.8
24.7
25.9
27.9
29.5
29.8
30.5
32.8
34.9
37.5
40.5
46. 1
48.6
61.8
67.6
69.7
71 .5
72.6
74.6
76.3
77.3
77.8
78.3
78.8
79.7
80.7
82.3
85.2
85.6
86.5
51 .84
25.92
17.28
19.94
15.25
7.20
5.76
7.41
5.40
18.51
28.80
21 .60
12.96
16.20
86.40
37.03
1 1 .27
12.34
9.97
8.64
4.63
10.37
1 .96
4.47
12.34
14.40
23.56
12.96
15.25
25.92
51 .84
51 .84
51 .84
28.80
25.92
12.34
10.80
64.80
28.80
IONS (mg
NO;
PH
4.20
4.25
3-85 0.25
4.05
4.20
4.40
4.45
4.50
4.25
4.25
4.25
4.35
4. 30
4.40
4.45
4.60
4.80 0.25
4.60
4.40
4.35
4.33
3.90
3.85 1.37
3.90
3.70
4.00
3.84
4.00
5.02
5.14 0.08
4.50
3.80
3-84
3.82
4. 10
4.27
4.30
4.55
4.50
>/1} z
SO
4 REMARKS
4.89
1 .74
5. 11
1 .74
96
-------
TABLE 16 Continued
TIME E
SAMPLE BETWEEN
NUMBER (min)
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
Continued
1.3
0.6
0.5
0.4
1.8
6.7
3.0
196.5
2-3
0.9
1.2
0.9
1 .0
6.0
17.0
6.5
34.0
7.0
39.0
2.8
3-4
0.6
0.5
0.5
0.5
0.7
1.2
4.8
22.8
0.2
3.2
1.0
0.6
1.0
1.3
2.2
1.3
0.6
0.5
0.4
LAPSED
TIME INTENSITY
(min) (mm/hr)
87.8
88.4
88.9
89.3
91. 1
97.8
100.8
297.3
299.6
300.5
301.7
302.6
303.6
309.6
326.6
333.1
367.1
374.1
413. 1
415.9
419.3
419.9
420.4
420.9
421 .4
422. 1
423.3
428. 1
450.9
451 . 1
454.3
455.3
455.9
456.9
458.2
460.4
461 .7
462.3
462.8
463.2
19.94
43.20
51 .84
64.80
14.40
3.87
8.64
0.13
1 1 .27
28.80
21 .60
28.80
25.92
4.32
1.52
3-99
0.76
3-70
0.66
9.26
7.62
43.20
51.84
51.84
51.84
37-03
21 .60
5.40
1.14
129-60
8. 10
25.92
43.20
25.92
19-94
11.78
19-94
43-20
51.84
64.80
IONS (mg/1)
NO; so"2
pH REMARKS
4.84 0.20
4.90
4.93
5.27 0.17
5.00
4.91
4.09
3.66
3.70
3-91 3.50
3.90
3-98
3.89
3.62
3.61
4.00
4.58
4.50
4.70 0:36
4.22
4.45
4.49
4.01
4.60
4.58
4.71
4. 19
4.01
4.07 2.39
4.05
4.64
4.60
4.71
4.39
4.28
4.44
4.81
4.79
2.28
1 .96
X
Cl
7.80 Cl
Cl
X
Cl
X
Cl
3.20 Cl
Cl
Cl
3.93
97
-------
TABLE 16 Continued
SAMPLE
NUMBER
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
TIME ELAPSED
BETWEEN TIME INTENSITY
(min) (min) (mm/hr)
0.5
0.6
0.5
0.4
0.6
0.7
0.8
1 .2
0.6
0.3
4.0
107.0
1. 1
0.8
1.7
8.5
2.0
2.6
3-2
463-7
464.3
464.8
465.2
465.8
466.5
467.3
468.5
469. 1
469.4
473-4
580.4
581 .5
582.3
584.0
592.5
594.5
597.1
600.3
51.84
43.20
51.84
64.80
43.20
37.03
32.40
21.60
43.20
86.40
6.48
0.24
23-56
32.40
15.25
3.05
12.96
9.97
8. 10
IONS (rng/1)
NO; so;
pH REMARKS
4.90 0.32
4.45
4.79
4.71
4.57
4.42
4.35
4. 19
4.20
4.20
4.14 1.38
3.80
3-62
4.07
4. 11
4.08
3.80
4.00
4.01 2.95
1.60
4.02
X
Cl
Cl
Cl
3.47
98
-------
TABLE 17. INTENSITY, p'H, AND CHEMISTRY OF SELECTED SAMPLES
RAINSTORM, 17 OCT 1977
TIME ELAPSED
SAMPLE BETWEEN TIME INTENSITY
NUMBER (rain) (min) (mm/hr)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
*— _./
24
25
^- ^/
26
27
*^ i
28
29
*•— J
30
31
+J '
32
^/ *—
33
34
3.9
3.9
4.8
5.7
4. 1
4.8
4.8
5.2
2.8
2.9
3-8
4.2
4.5
7-9
8.9
5.4
5.5
6.2
5-0
6.6
7.1
6.5
6.5
8.3
8-9
10.5
12.9
14.7
13-6
12.3
11.9
14.2
0.0
3.9
7.8
12.6
18.3
22.4
27.2
32.0
37.2
40.0
42.9
46.7
50.9
55.4
63-3
72.2
77.6
83-1
89-3
94.3
100.9
108.0
114.5
121 .0
129.3
138.2
148.7
161.6
176.3
189.9
202.2
214. 1
228.3
228.3
6.65
6.65
5.40
4.55
6.32
5.40
5.40
4.98
9.26
8.94
6.82
6. 17
5.76
3-28
2.91
4.80
4.71
4. 18
5. 18
3-93
3-65
3-99
3-99
3. 12
2.91
2.47
2.01
1.76
1.91
2. 11
2. 18
1 .83
TONS (rag/1 )
NO: so;2
pH REMARKS
4.15 3.76
4.40 2.63
4.60
4.90 0.39
5.35
5.50
5.65 0.14
5.70
5.80
5.75 0.14
5.80
5.85
5.75
5.80
5.85 0.17
5.85
5.70
5.60
5.60
5.55 0.26
5.60
5.50
5.55
5.70
5.70 0.32
5.60
5.60
5.70
5.65
5.50 0.28
5.40
5.50
5.30 0.44
4.65 M
6.02 0
1 .27 C
0
N
0.58 T
A
M
0.57 I
N
A
T
I
0.66 0
N
0.70
0.90
1 .05
1.22
99
-------
TABLE 18. INTENSITY, pH, AND CHEMISTRY OF SELECTED SAMPLES
RAINSTORM. 19 OCT 1977
SAMPLE
NUMBER
1
2
3
4
5
6
7
8
9
10
1 1
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
TIME ELAPSED
BETWEEN TIME INTENSITY
(min) (min) (mm/hr)
0.8
0.8
0.9
1.5
5.8
1.9
2. 1
2.4
3-6
3.5
3.3
3.0
2.8
6.1
7.1
4.2
3-7
2.6
3-2
3.1
2.5
2. 1
2. 1
1.6
1.8
3.0
2.8
1.8
2. 1
2.0
2.2
2.9
3-0
1.9
2. 1
2.9
3.0
3.2
7.8
16.6
0.0
0.8
1.6
2.5
4.0
9.8
11.7
13.8
16.2
19.8
23-3
26.6
29.6
32.4
38.5
45.6
49.8
53-5
56. 1
59.3
62.4
64.9
67.0
69. 1
70.7
72.5
75.5
78.3
80. 1
82.2
84.2
86.4
89.3
92.3
94.2
96.3
99.2
102.2
105.4
1 13.2
129.8
32.40
32.40
28.80
17-28
4.47
13.64
12.34
10.80
7.20
7.41
7.85
8.64
9.26
4.25
3.65
6. 17
7.01
9.97
8. 10
8.36
10.37
12.34
12.34
16.20
14.40
8.64
9.26
14.40
12.34
12.96
11.78
8.94
8.64
13.64
12.34
8.94
8.64
8. 10
3-32
1.56
IONS (mg/1)
NO; so;
DH
4.30 2.51
4. 10
4.10
4. 10
4.20 1.38
4.20
4. 10
4.00
3-85
3.80 2.32
4.00
3.95
3.95
3.90
4.00 2.01
3.95
3.95
3.95
3.95
4.10 1.91
4.10
4.20
4.30
4.40
4.40 1.13
4.45
4.35
4.35
4.35
4.40 1.17
4.40
4.50
4.45
4.65
4.65 0.84
4.60
4.70 0.88
4.60
4.70 1.18
4.70
4.92
2.94
5.83
3-48
2.80
1.38
1.81
1.31
1 .49
1.38
REMARKS
N
0
C
0
N
T
A
M
I
N
A
T
I
0
N
100
-------
TABLE 19. INTENSITY, pH, AND CHEMISTRY OF
RAINSTORM, 24-26 JAN 1978
SELECTED SAMPLES
TIME ELAPSED
SAMPLE BETWEEN TIME INTENSITY Cl" N0~
NUMBER (min) (min) (mm/hr) pH
1
2
3
4
5
6
7
8
9
10
11
12
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Cont
804.0
16.5
19.8
95.9
52.7
75.0
27.9
16.7
13.4
12.4
15.8
17.0
17.9
21.3
15.7
15.1
11.9
12.8
12.9
9.7
9.2
9.3
6.5
8.1
3.8
10.6
13.0
16.8
16.3
inued
0.0
804.0
820.5
840. 3
936.2
988.9
1063.9
1091 .8
1 108.5
1121.9
1134.3
1 150. 1
1167. 1
1 185.0
1206.3
1222.0
1237.1
1249.0
1261 .8
1274.7
1284.4
1293.6
1302.9
1309.4
1317.5
1321.3
1331-9
1344.9
1361.7
1378.0
0.04
1 .81
1.51
0.31
0.57
0.40
1 .07
1.79
2.23
2.41
1.89
1 .76
1 .67
1.41
1.91
1.98
2.52
2. 34
2.32
3-09
3-25
3.22
4.61
3-70
7.88
2.82
2.30
1.78
1 .84
3-74 2.30 7.06
3.76
3.79
3.79 0.44 4.23
3.81
3.94 0.48 1.89
3-91 1.69 3-65
3-88
3.90
3.93
3.91 0.35 1.07
3.95
3-98
3.93
3.90 0.33 1 -07
3.90
3-87
3-94
4.02
3-99
3.94 0.33 2.37
4.03
4. 14
4. 18
4.20 0. 33 0.88
4.13
4. 17
4.09
4.00 0. 35 1 .78
IONS (mg/1)
SO'2 Na* NH+
4 4
13.54
0.44 0.55
0.44 0.55
2.80
2.28
4.35
0.40 0.30
0.40 0.30
2.54
0.26 0.14
2.99 0.26 0.14
1 .98
0.24 0.03
0.24 0.03
1 . 30
0.24 0.04
0.24 0.04
2. 11
•I
i
K* Ca+2 Mg+2 RMKS
X
0. 14 1.26 BDL Cl
0. 14 1.26 BDL Cl
X
X
X
Cl
0.16 Cl
0.16 Cl
Cl
Cl
Cl
0.09
0.09
0.09
0.09
BDL
BDL
-------
TABLE 19 Continued
o
to
SAMPLE
NUMBER
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
TIME ELAPSED
BETWEEN TIME INTENSITY Cl~ NO;
(rain) (min) (mm/hr) pH
7.4
5.4
6.4
5.3
5.6
9.3
8.2
6.6
6.3
6. 1
5.7
5.6
6.9
8.5
12.0
20.6
15.9
36.3
23.4
99.0
102.0
52.7
15.8
16.4
13.3
14.2
12. 1
5.8
6.5
6.8
1385.4
1390.8
1397.2
1402.5
1408. 1
1417. 4
1425.6
1432.2
1438.5
1444.6
1450.3
1455.9
1462.8
1471 .3
1483.3
1503.9
1519.8
1556. 1
1579.5
1678.5
1780.5
1833.2
1849.0
1865.4
1878.7
1892.9
1905.0
1910.8
1917.3
1924. 1
4.05
5.54
4.68
5.65
5.35
3. 22
3.65
4.54
4.75
4.91
5.25
5.35
4.34
3-52
2.50
1 .45
1.88
0.82
1 .28
0. 30
0. 29
0.57
1.89
1.83
2. 25
2. 11
2.47
5. 16
4.61
4.40
4.13
3.95
4.20
4.06
4. 10
4.15
3.93 0.34 0.65
4.10
4.22
4. 14
4.27
4.33 0.34 0.89
4.26
4.27
4. 17
4.12
3.95
3.92 0.35 2.53
3-94
3.70
3.69 0.47 4.73
3.83
3-92
4.06
4.09
4.15
4.10
4.15
4. 18
4. 19
IONS (mg/l)
SO;2 Na+ NHt K+ Ca+2 Mg+2 RMK3
0.28 0.04 BDL 0.88 BDL
0.28 0.04 BDL 0.88 BDL
5.84
1.11
0.27 0.03 0.04 BDL 0.05
0.27 0.03 0.04 BDL 0.05
3-27 X
Cl
X
6. 19 X
X
Cl
0.24 0.04 BDL Cl
0.24 0.04 BDL Cl
Cl
Cl
Cl
0.24 BDL BDL
0.24 BDL BDL
Continued
-------
TABLE 19 Continued
.0
u>
SAMPLE
NUMBER
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
TIME ELAPSED
BETWEEN TIME INTENSITY
(rain) (rain) (ram/hr) pH
4.6
4.9
8.0
29.0
17.2
79.2
39.6
2.8
1.6
1 . 1
1 .0
0.7
1. 1
11.8
67.3
30.5
6. 1
7.2
17.9
6.2
6.7
21 .0
1928.7
1933.6
1941 .6
1970.6
1987.8
2067.0
2106.6
2109.4
2111.0
2112. 1
2113- 1
2113.8
2114.9
2126.7
2194.0
2224.5
2230.6
2237.8
2255.7
2261 .9
2268.6
2289.6
6.51
6. 11
3-74
1.03
1 .74
0.38
0.76
10.69
18.71
27.22
29-94
42.77
27.22
2.54
0.44
0.98
4.91
4. 16
1 .67
4.83
4.47
1.43
4.28
4.32
4.26
4.02
3.82
3.82
3.62
3.75
3-99
4.27
4.39
4.43
4.59
4.57
4.24
4. 10
4.74
5.01
4.56
4.87
4.72
4.61
Cl"
BDL
1 .
0.
0.
0.
1 .
4.
0.
97
59
36
33
37
62
40
NOg
0.43
2.58
0.74
0.36
0.28
1 . 10
0.51
0.59
IONS (mg/1)
SO;2 Na NH* K Ca 3 Mg 2 RMKS
1 .
5.
1.
1 .
0.
4.
3.
2.
09
0.69 0.39
0.69 0.39
10
41
0.40 0.04
09
0.31 0.03
94
61
5.04 0.11
00
0.09 0.04
12
0.04 0.49 0.06
0.04 0.49 0.06
0.01 0.38 0.31
0.03 0.46 0.03
0.21 5.56 1 . 24
0.04 5.44 0.25
X
X
Cl
Cl
Cl
X
X
Cl
Cl
Cl
Cl
Cl
Cl
-------
H
O
TABLE 20. INTENSITY, pH, AND CHEMISTRY OF SELECTED SAMPLES
SNOWSTORM, 6-7 FEB 1978
SAMPLE
NUMBER
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
TIME ELAPSED
BETWEEN TIME INTENSITY
(min) (min) (mm/hr) pH
823.
48.
39.
10.
17.
25.
67.
87.
13.
13.
28.
62.
142.
41.
86.
184.
493.
0.
0
5
2
2
7
5
8
0
4
2
5
0
0
0
0
0
0
0
0.0
823-0
871-5
910.7
920.9
938.6
964.1
1031 .9
1118.9
1132.3
1145.5
1 174.0
1236.0
1378.0
1419.0
1505.0
1689-0
2162.0
2162.0
0.
0.
0.
2.
1 .
1.
0.
0.
2.
2.
1.
0.
0.
0.
0.
0.
0.
04
62
76
94
69
17
44
34
23
27
05
48
21
73
35
16
06
4.75
4.67
4.67
4.67
4.77
5.07
5.58
5.67
5.35
5.30
5.51
5.65
5.98
5.93
6.08
6.36
6.54
6.54
Cl"
1 .65
1 .64
0.85
BDL
1 .65
1. 19
0.95
BDL
1.17
6.81
NO;
3-72
2.84
1 .62
0.63
1 .07
0.62
0.88
0.55
2.06
4.09
so;3
3-58
3.44
3.26
3-14
3.41
3-23
3-99
3.34
5.53
18.23
IONS
Na+
3.20
1 . 17
1 .05
1 .09
0.96
0.67
0.58
1 .02
1 .36
1.39
1.04
1.73
0.87
0.61
0.71
1.02
2. 11
4.61
(mg/1)
NH+
1.46
0.38
0.31
0. 18
0.26
0. 16
0.26
0.32
0.25
0.28
0.27
0.53
0.58
0. 15
0.45
0.70
1 . 10
2.09
K+
1. 15
0.44
0.38
0.46
0.35
0.22
0. 17
0.42
0.61
0.65
0.44
0.80
0.34
0.20
0.21
0.22
0.71
2.56
Ca+2Mg + 2RMKS
6.04
1.32
1.73
2.26
1 . 10
1.48
2.79
10.72
BDL
0. 12
0. 12
0.08
0.05
0.09
0.07
0.30
X
Cl
Cl
Cl
Cl
Cl
X
Cl
Cl
X
X
Cl
-------
TABLE 21. INTENSITY, pH, AND CHEMISTRY OF SELECTED SAMPLES
o
01
SAMPLE
NUMBER
1
2
3
4
5
6
7
8
9
10
11
12
13
TIME
BETWEEN
(min)
227.0
33.0
16.8
22.0
34.5
48.5
41.5
33.2
42.2
27-4
21.4
49-2
ELAPSED
TIME INTENSITY
(min) (mm/hr) pH
227.0
260.0
276.8
298.8
333.3
381 .8
423.3
456.5
498.7
526. 1
547.5
596.7
0.0
0. 13
0.91
1.78
1.36
0.87
0.62
0.72
0.90
0.71
1.09
1 .40
0.61
5.70
5.55
5.26
5.10
4.77
4.85
4.77
4.80
4.66
4.76
4.72
4.77
Cl"
1.57
0.05
1.24
0.17
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
NO;
12.36
6.06
2.67
2.22
2.39
2.75
1.45
1. 16
1. 10
0.89
1.01
1.46
so;2
12.97
4.63
2.55
2.32
2.71
2.54
1.71
1.46
1.54
1.12
1.15
1.11
IONS (mg/1)
Na+ NH* K+
3.09
0.73
0.60
0.46
0. 15
0.08
0.08
0.05
0.05
0.05
0.40
0.43
0.40
0.47
0.33
0.17
0.31
0.24
0.29
0.33
1 .50
0.31
0.31
0. 15
BDL
BDL
0.91
BDL
BDL
BDL
po-3
0. 16
0. 12
0. 13
0. 11
0. 12
0. 10
0. 10
0. 10
BDL
BDL
BDL
BDL
RMKS
X
Cl
Cl
Cl
Cl
Cl
-------
TABLE 22. INTENSITY, pH, AND CHEMISTRY OF SELECTED SAMPLES
RAINSTORM, 14-15 MARCH 1978
TIME ELAPSED IONS +(mg/l) +
SAMPLE BETWEEN TIME INTENSITY Na NH4 K Ca
NUMBER (min) (min) (mm/hr) pH
1
2 1
3
4
5
6
7
8
9
10
1 1
12
13
14
15
16
17
18
19
20
21
22
23
24
25
Continued
99.5
7.5
8.9
7.4
9.8
6.9
6.0
9.4
9.7
8.0
24.7
6.6
16.7
16.8
18.8
16.2
47.6
16.6
9-0
6.9
5.8
6.9
3.8
1.9
0.0
199.5
207-0
215.9
223.3
233-1
240.0
246.0
255.4
265.1
273-1
297.8
304.4
321. 1
337-9
356.7
372.9
420.5
437.1
446.1
453-0
458.8
465.7
469-5
471.4
0. 15
3.99
3-36
4.05
3-06
4.34
4.99
3.19
3.09
3-74
1 .21
4.54
1.79
1.78
1.59
1.85
0.63
1.80
3.33
4.34
5. 16
4.34
7.88
15.76
3.60
3.49
3-55
3.50
3.54
3-61
3.69
3.74
3-73
3.56
3-55
3.51
3.54
3.51
3.58
3-60
3-57
3.50
3-60
3.77
3.98
4.05
3.96
4.26
4. 10
12.01
4.88
4.50
3-56
3.53
2.56
1 .81
1.21
1 .42
2.80
3-72
7.32
7.57
8. 12
7. 18
6.00
4.00
5.06
3-88
2.23
1.17
0.75
0.39
0.44
0.35
3.964
1.453
1. 196
1 . 128
1.099
0.982
0.801
0.612
0.707
1 , ^22
1.043
1.438
1 .210
1 .261
1.186
1 . 104
1 .219
1.467
1.033
0.657
0.381
0.322
0.394
0.439
0.348
0.87
0.24
0.25
0. 19
0. 15
0. 18
0. 10
0.08
0.05
0.09
0. 13
0.30
0.32
0.34
0.24
0. 19
0. 14
0.21
0. 15
0. 12
0.05
0.05
0.05
0.07
0.03
5.68
2. 16
1.51
1.35
3-94
BDL
1. 19
0.77
0.95
1 .04
1.27
1.39
1.14
0.65
0.95
0.86
+ 2
Mg
REMARKS
1 .51
0.71
0.67
0.52
0.59
0.45
0.42
0.37
0.41
0.53
0.60
0.96
0.94
0.62
0. 19
0.32
X
Cl
Cl
Cl
Cl
Cl
Cl
X
Cl
Cl
Cl
Cl
Cl
Cl
-------
TIME
SAMPLE BETWEEN
NUMBER (min)
ELAPSED
TIME INTENSITY
(rain) (mra/hr)
TABLE 22 Continued
IONS +(mg/l)
Na
NH,
K
Ca
+ 3
PH
Mg
+ 2
REMARKS
26
27
28
29
30
31
32
0.6
0.7
0.8
0.8
3-1
6.2
8.7
472.0
472.7
473.5
474.3
477.4
483.6
492.3
49-90
42.77
37.43
37.43
9.66
4.83
3.44
4.25
4.45
3-95
4.01
4.19
4.33
4.24
0.25
0. 10
0.08
0.05
0.06
0.05
0.05
0.248
0. 104
0.078
0.048
0.056
0.046
0.052
BDL
BDL
BDL
BDL
BDL
BDL
BDL
0.56
0.41
0.38
0.24
0.29
BDL
0.26
0.24
-------
TABLE 23-
o
00
INTENSITY, pH,
SNOWSTORM
AND CHEMISTRY OF SELECTED SAMPLES
16-17 MARCH 1978
SAMPLE
NUMBER
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
— «— •— "nni™— •.^—-••••••IM
TIME
BETWEEN
(min)
39-7
19.8
21 .4
31.0
22.0
16.3
11.4
11.5
8.4
12.9
8. 1
11.9
11.1
12.7
21.7
115.8
43.8
V^B^BHHVBH^^.V.,^^^^
ELAPSED
(min)
0.0
39.7
59.5
80.9
111.9
133.9
150.2
161.6
173. 1
181 .5
194.4
202.5
214.4
225.5
238.2
259-9
375.7
419.5
TIME INTENSITY
(mm/hr) pH
0.75
1.51
1 .40
0.97
1.36
1 .84
2.63
2.60
3-56
2.32
3-70
2.52
2.70
2.36
1.38
0.26
0.68
3-73
3.75
3.85
3-85
3.86
3.95
3-97
3.97
4.06
4. 16
4.23
4.07
4.03
4.08
4. 17
4.03
4.03
•^•••^••WWVBV^^^BWIWfltVH
cr
(mg/l)
0. 16
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
8.47
0.78
•^^••••••••Mri^^BW^MW^MV^^H^VMa^^MBHMMMWMWllBBBB'^BII**'*
IONS
NO; so;2
(mg/l) (mg/l)
9.41
5.31
4.09
4.41
3.14
2.95
2.81
2.57
1.93
1.04
0.92
1.38
1.00
0.94
1.06
2.39
2.33
6.36
5. 10
3.31
2. 11
1.69
1 .43
1 .27
1 .27
1 . 10
1.23
1.25
1 .71
1.95
1.97
1 .80
5.28
2.86
••••^•MHMH^HVVWHBVHIV^HHIIBPIIHBIIHMVIVIIHIHBVIVWI^^
Fe
(ug/l) REMARKS
145
1 10
82
55
63
33
30
20
24
11
15
21
16
21
22
35 X
340 X
-------
TABLE 24. INTENSITY, pH, AND CHEMISTRY OF SELECTED SAMPLES
RAINSTORM. 18-20 APRIL 1978
o
vo
SAMPLE
NUMBER
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
•MM^BMM^^HB^HHH
TIME
BETWEEN
(min)
687.0
22.2
13.5
14.8
11.4
11.6
23.2
10.0
6.6
9.8
9.6
7.5
8.6
6. 1
4.0
3.2
3.2
2.9
2.9
4.8
5.0
6.7
3.6
4.4
20.3
11.4
10.6
10.8
12.7
VMHMBBBM^^^^BBMMMH
ELAPSED
TIME
(min)
0.0
687.0
709.2
722.7
737.5
748.9
760.5
783.7
793.7
800.3
810. 1
819.7
827.2
835.8
841.9
845.9
849. 1
852.3
855.2
858. 1
862.9
867.9
874.6
878.2
882.6
902.9
914.3
924.9
935.7
948.4
••••MMMiHM^mMmiHBMV^
INTENSITY
(mm/hr)
0.04
1.35
2.22
2.02
2.63
2.58
1 .29
2.99
4.54
3.06
3. 12
3.99
3.48
4.91
7.49
9.36
9.36
10.32
10.32
6.24
5.99
4.47
8.32
6.80
1 .47
2.63
2.82
2.77
2.36
•••••^^••••nM
PH
3.61
3.83
3.82
3.93
3-99
3.92
4.06
3.87
3.97
3.94
4.04
4. 17
4. 12
4. 10
4. 10
4.08
3.85
3.90
3-92
4.01
4. 13
4.05
4.03
3.93
3.82
3.96
3.91
3-90
3-91
MMMMH^n^HVV^^MMHMHMBMMMMWMpnNBMMMMMMVHB
IONS (mg/1) 2
Cl" NOg S04
0.29 2.50
0.26 2.28
0.25 2.24
0.76 1.15
BDL 1.14
BDL 2.10
BDL 0.65
BDL 3-09
BDL 1.74
4.82
4.82
4.82
6.96
3.57
3.75
1 .61
2.50
2.68
••••^•••••MMBMM^
Na
1.14
0.62
0.40
0.60
0.28
0.13
0.08
0. 11
0.25
0. 10
0. 17
0. 12
I^H^^HMBB
1.
0.
0.
0.
0.
0.
0.
0.
0.
0.
••>•••••••••
NPU
93
67
37
29
09
17
12
14
11
32
BDL
0.
18
••••••MiMHHMBMM
•f
K
0.40
0. 19
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
BDL
••••MHMMMMHHM^^^
REMARKS
X
Cl
Cl
Cl
Cl
Cl
Cl
Continued
-------
TABLE 24 Continued
SAMPLE
NUMBER
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
TIME
BETWEEN
(min)
10.5
9.4
8.2
10.2
11.0
9.1
12.2
26.9
45.9
82.0
34.2
60.5
7-3
50. 1
6.6
5.2
8.7
7.6
376.4
16. 1
4.5
30.3
8.6
42.7
33.1
16.8
102.0
ELAPSED
TIME INTENSITY
(min) (mm/hr) pH
958.
968.
976.
986.
997.
1006.
1019.
1045.
1091 .
1173.
1208.
1268.
1275.
1325.
1332.
1337.
1346.
1354.
1730.
1746.
1751.
1781.
1789.
1832.
1865.
1882.
1984.
9
3
5
7
7
8
0
9
8
8
0
5
8
9
5
7
4
0
4
5
0
3
9
6
7
5
5
2.85
3.19
3-65
2.94
2.72
3.29
2.45
1.11
0.65
0.37
0.88
0.49
4. 10
0.60
4.54
5.76
3.44
3-94
0.08
1.86
6.65
0.99
3.^8
0.70
0.90
1.78
0.29
3.
3.
3.
3.
3.
4.
3-
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
3.
3.
3-
3.
3.
3.
3.
87
84
89
87
87
00
97
13
13
13
04
02
07
23
38
40
65
72
62
61
82
85
88
82
95
92
90
Cl"
BDL
BDL
BDL
BDL
BDL
0.18
BDL
BDL
BDL
0.46
0.34
0.21
IONS (mg/1
NO;
1.95
1.62
0.69
1.30
1. 18
1.70
0.91
0.37
1.43
4.91
2.83
2.38
3.
3.
2.
1 .
3-
3.
1.
0.
1.
4.
3.
2.
SO'2 Na* NH+ K+
4 4
21
0.19 0.09 BDL
0.11 0.09 BDL
04
85
61
0.41 0.17 BDL
0.27 0.17 BDL
0.28 0.17 BDL
93
04
38
75
34
64
0.45 0.35 0.04
48
86
REMARKS
X
X
X
X
Cl
X
Cl
Cl
Cl
Cl
X
Cl
Cl
X
Cl
X
X
Cl
X
Heavy metal ions analyzed in samples 10-14, 16, 20 and 21.
Continued
-------
TABLE 24 Continued
HEAVY METAL ANALYSES
SAMPLE
NUMBER
1
1
1
1
1
1
1
1
1
1
0
1
2
3
4
5
6
7
8
9
20
2
1
Fe
14.
0.
8.
8.
7.
0.
6
5
0
6
4
1
Al
35.
44.
26.
40.
55.
67.
101 .
52.
TONS (ug/l)
Ni Mn
1
1
8
1
8
4
1
1
33.
119-
200.
133.
158.
28.
17-
66.
3 4.5
2
?
6
0
5
4
5
Cu
3.
7.
12.
33.
4.
9.
7.
2.
5
7
8
4
5
7
2
4
Pb
244.
64.
28.
25.
39.
5.
45.
REMARKS
0
5
1
1
8
5
4
-------
APPENDIX B
TABULATION OF STORM INFORMATION
20 Oct 76
7 Dec 76
17-18 Mar 77
22 Mar 77
28 Mar 77
4-6 Apr 77
23-24 Apr 77
2 June 77
7 June 77
18 Aug 77
16-17 Sep 77
18 Sep 77
24-26 Sep 77
26 Sep 77
17 Oct 77
19 Oct 77
24-26 Jan 78
6-7 Feb 78
3 Mar 78
14-15 Mar 78
16-17 Mar 78
18-20 Apr 78
STORM TYPE
Cold Front
Cold Front
Warm Front
Low Pressure
Warm Front
Low Pressure
Cold Front
Cold Front
Convective
Cold Front
Warm Front
Convective
Low Pressure
Low Pressure
Low Pressure
Low Pressure
Low Pressure
Low Pressure
Low pressure
Low Pressure
Low Pressure
Low Pressure
DIRECTION OF MEAN
APPROACH TEMPERATURE
From Midwest
From Midwest
From Midwest
From Midwest
Undetermined
From Midwest
From Canada
Fr.om Midwest
Undetermined
Undetermined
From Midwest
Undetermined
From Midwest
From Midwest
Up Atlantic Coast
Undetermined
From Midwest
Undetermined
Up Atlantic Coast
From the Gulf
Midwest
From Great Lakes
Midwest
55
47
44
45
74
57
66
47
55
42
28
45
112
-------
APPENDIX C
INTERPRETATION OF PERIODS OF CONTAMINATION FOR THE TWENTY-TWO
STORMS
The following criteria were used in interpreting the storm data:
Dry Deposition Contamination Periods -
Rainstorm - all periods with intensity less than V. 0 mm/hr.
Snowstorm - all periods with intensity less than 0.25 mm/hr.
Cleansing: Chemical data has been used when available or an
arbitrary 3-8 samples following the suspected dry deposition
depending upon the intensity of rain. The deletion of these
samples is to account for the cleansing of dry deposition
from the funnel.
1 - Rainstorm - 20 October 1976 (TABLE 3 AND FIGURE 10)
Contamination at sample 40 and 47. Samples 41-46 represent
the cleansing period. Samples 1-39 are contamination free.
2 - Rainstorm - 7 December 1976 (TABLE 4 AND FIGURE 11)
Contamination of samples 45 and 46. No cleansing period as
the storm ends. Samples 1 to 44 are contamination free.
3 - Snow Changing to Rain - 17-18 March 1977 (TABLE 5 AND FIGURE
12) Contamination at sample 38, cleansing samples 39 to 42.
Contamination at sample 47, cleansing at 48 through the end
of the storm. Samples 1 to 37 and 43 to 46 are contamination
free.
4 - Rainstorm - 22 March 1977 (TABLE 6 AND FIGURE 13)
Contamination at sample 2; cleansing from sample 3 to 10.
Contamination at sample 110 with cleansing through sample
118. Contamination of samples 138 to 146. No cleansing as the
storm ends. Samples 11 to 109 and 119 to 137 are
contamination free.
5 - Rainstorm - 28 March 1977 (TABLE 7 AND FIGURE 14)
Contamination at samples 12, 13, 19, 21, and 22. No
opportunity for cleansing. Samples 1 to 11 are contamination
free.
6 - Rainstorm - 4-6 April 1977 (TABLE 8 AND FIGURE 15)
Contamination at sample 2; cleansing period samples 3 to 10.
113
-------
Contamination at samples 57, 59, 63 to 67. These are
sufficiently close together so that cleansing doesn't become
effective until 68. Contamination at samples 73, 74, 79, 82,
and 83, again close enough together so that good data is not
produced through the end of the storm. Samples 11 through 56
are contamination free.
7 - Rainstorm - 23-24 April 1977 (TABLE 9 AND FIGURE 16)
Contamination at samples 4 to 6 and again at 11. Cleansing
is effective at samples 12 to 15. Contamination at sample
30; cleansing 31 to 33. Contamination at samples 42 and 43.
Contamination free samples at samples 1 to 3, 16 to 29, and
34 to 41.
8 - Rainstorm - 2 June 1977 (TABLE 10 AND FIGURE 8)
Contamination at sample 16 and 22; cleansing in effect at
samples 17-19 and 23-26. Contamination at 30 and 32 with
cleansing in effect from 33 to 39- Contamination free
samples at samples 1 to 15, 20 and 21, 27 to 29, and 40 to
43-
9 - Rainstorm - 7 June 1977 (TABLE 11 AND FIGURE 17) Samples 2
and 3 are contamination free, all the rest are contaminated.
10 - Rainstorm - 18 August 1977 (TABLE 12 AND FIGURE 18)
Contamination at samples 8 and 11. Cleansing effective
samples 12 to 14. Samples 1 to 7 and 15 through 34 are
contamination free.
11 - Rainstorm - 16-17 September 1977 (TABLE 13 AND FIGURE 19)
Samples 1 through 11 are contaminated. Cleansing in effect
samples 12 through 17. Contamination at sample 48, cleansing
through the end of the storm. Samples 18 to 47 are
contamination free.
12 - Rainstorm - 18 September 1977 (TABLE 14 AND FIGURE 20)
Contamination at samples 2 and 3, cleansing in effect samples
4 to 6. Samples 7 to 14 are contamination free.
13 - Rainstorm - 24-26 September 1977 (TABLE 15 AND FIGURE 21)
Contamination at sample 7, cleansing at 8 to 13. More
contamination at sample 21, cleansing at 22 to 28.
Contamination in linked periods, samples 41, 42, 46, 48, 49,
and 56; cleansing through to sample 62. Contamination at 87,
with cleansing 38 to 93. Contamination again at 135, 136,
and 137 with cleansing up to 143. Another episode at 189
with cleansing up to 195. Contamination from 202 through the
end of the storm. Samples 1 to 6, 14 to 20, 29 to 40, 94 to
134, 144 to 188, and 196 to 201 are contamination free.
Samples 63 to 86 not considered because lack of intensity
data.
114
-------
14 - Rainstorm - 26 September 1977 (TABLE 16 AND FIGURE
Contamination at sample 48 with cleansing to
Contamination at 57 and 59; cleansing to 63. Once again
sample 92 with cleansing to 95. Samples 1 to 47, 52 to
64 to 91, and 96 to 99 are contamination free.
15 - Rainstorm - 17 October 1977 (TABLE
periods of contamination.
22)
51.
at
56,
No
16 - Rainstorm - 19 October 1977
periods of contamination.
17 AND FIGURE 23)
(TABLE 18 AND FIGURE 9) No
17 - Rainstorm - 24-26 January 1978 (TABLE 19 AND FIGURE 24)
Contamination samples 1 through 7; cleansing 8 to 13.
Contamination samples 48 through 52 with
through sample 58. Contamination at
cleansing 68 to 70. Contamination at 75
action as the storms end. Samples 14 to
to 74 are contamination free.
cleansing in effect
samples 66 and 67,
and 76; cleansing in
47, 59 to 65, and 71
18 - Snowstorm - 6-7 February 1978 (TABLE 20 AND FIGURE 25) An
intensity discriminator of 0.25 mm/hr was chosen as each of
the four time periods below showed jumps in the dissolved
constituent levels. Contamination at sample 2, cleansing in
effect 3 to 7. Contamination again at 14, 17, and 18 with no
opportunity for cleansing through the end of the storm.
Samples 8 to 13 are contamination free.
19 - Snowstorm - 3 March 1978 (TABLE 21
Contamination at sample 2, cleansing
Samples 8 to 13 are contamination free.
AND FIGURE 26)
in effect 3 to 7.
20 - Rainstorm - 14-15 March 1978 (TABLE 22 AND FIGURE 27)
Contamination at sample 2, with cleansing in effect through
sample 8. Contamination at sample 18 and cleansing 19 to 24.
Samples 9 to 17 and 25 to 32 are contamination free.
21 - Snowstorm - 16-17 March 1978 (TABLE 23
Contamination at sample 17 through the
Samples 1 to 16 are contamination free.
AND FIGURE 28)
end of the storm.
22 - Rainstorm - 18-20 April 1978 (TABLE 24 AND FIGURE 29)
Contamination at sample 2, cleansing 3 to 8. Contamination
at samples 39-42, 44, 49, 52, 54, 55, and 57. No period
sufficient for cleansing between these episodes. Samples 9
to 38 are contamination free.
115
-------
APPENDIX D
REAGENTS USED FOR STANDARDS
ION
Chloride
Nitrate
Phosphate
Sulfate
Floride
Sodium
Ammonium
Potassium
Magnesium
Calcium
cr
NO
SO
Na1
NH"
-3
>r
-2
MS*
REAGENT
NaCl
NH4N03
Na3P04.12H20
NaF
NaCl
NH NO
4 3
KC1
Ca
+ 2
CaCl
116
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
REPORT NO.
EPA-600/4-80-004
2.
3. RECIPIENT'S ACCESSION-NO.
TITLE AND SUBTITLE
CHEMISTRY OF PRECIPITATION FROM SEQUENTIALLY
SAMPLED STORMS
5. REPORT DATE
January 1980
6. PERFORMING ORGANIZATION CODE
AUTHOR(S)
O.K. Robertson, T.W. Dolzine, R.C. Graham
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
The Science Research Laboratory
United States Military Academy
West Point, NY 10996
10. PROGRAM ELEMENT NO.
1AA603A AE-008 (FY-79)
11. CONTRACT/GRANT NO.
IA6-D6-0012
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Sciences Research Laboratory - RTP, NC
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final Oct 1976 - Sep 1978
14. SPONSORING AGENCY CODE
EPA/600/09
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Sequential sampling techniques and applications to collect precipitation
are reviewed. Chemical data for samples collected by an intensity-weighted
sequential sampling device in operation at the U.S. Military Academy, West
Point, New York from October 1976 to April 1978 are presented and discussed.
The problem of dry deposition is explored. A newly designed intensity-weighted
sequential sampler that excludes dry deposition is presented.
The experiments have shown that intensity-weighted sequential sampling
is a viable technique for monitoring the rapid changes in precipitation
chemistry within a storm. Complete chemical data are needed from individual
storms to evaluate intensity related scavenging.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
West Point, NY
Dry Deposition
COSATI Field/Group
Air Pollution
*Scavenging
*Raindrops
*Sequential Sampling
Chemical Analysis
*Chemical Reactions
Reaction Kinetics
13B
13H
04B
12A
14B
070
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (ThisReport)'
UNCLASSIFIED
21. NO. OF PAGES
127
20. SECURITY CLASS (Thispage!
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
117
------- |