Measurements of The Chemical Composition of
Western Washington Rainwater, 1982-1983
Richard J. Vong and Alan P. Waggoner
University of Washington
Seattle, Washington 98195
(206) 543-2044
Chemical Analysis
Performed By
Phillip R. Davis and Roy L. Arp
Environmental Protection Agency Laboratory
Manchester, Washington
July 29, 1983
Sponsored by U.S. Environmental Protection Agency, Region 10, Seattle.
U.S. Geological Survey, Tacoraa, loaned precipitation sampling eouipment
to tins program. Seattle Water Department provided three sampling sites.
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Contents
I Executive Summary 1
II Summary of Results of Precipitation Sampling and Chemical 6
Analysis In Western Washington
III Chemical Composition of Western Washington Rainwater 9
IV Chemical Relationships 1n Western Washington Precipitation 12
Y Seasonal Variability 39
VI Relation of Emissions to Rainwater Composition 44
VII Measurements by Other Investigators 48
VIII Conclusions and Recommendations 51
IX References 54
X Appendices 57
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I Executive Summary
Acid Rain is now an important environmental, political and
^economic problem for the United States. Environmental impacts,
have been reported including failure of fish populations to
reproduce, reduced growth rate or even die-back of forest tree
species and leaching of nutrient or toxic ionic species from soils
into water systems. In June of 1983,. reports on acid rain were
released by the National Research Council of the National Academy
of Sciences (NAS), by a review panel created by George Kenworth,
White House science advisor and by a federal Interagency Task
Force on Acid Rain. The three reports agreed that in impacted
areas such as the north-east United States and eastern Canada,
| acid rain is almost entirely caused by man with sulfur dioxide
emissions making a larger contribution than oxides of nitrogen.
The NAS and White House sponsored reports also concluded that acid
deposition over large areas is in direct proportion to the up wind
regional emission of acid forming species and that the effects of
acid rain are damaging to the environment and must be reduced.
The chairman of the White House panel, W. A. Nierenberg, speaking
about impacts of acid deposition on soil micro-organisms that
recycle nitrogen and carbon in the food chain, said that some of
the effects of acid rain are severe, perhaps irreversible
(Sciences 15 July, 19831 pgs 241, 242 and 254).
Acid rain is also a political and economic problem because
emissions in one area affect a large downwind region that often
extends across political boundaries and because control of
emissions will have high costs.
1
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because of its potential importance as an environmental,,
political and economic problem to this area, Region X of the U. E
Environmental Protection Agency -funded the University of
Washington to conduct the -first year of a continuing program to
determine the acid character of precipitation in Washington State
west of the Cascade mountains. Four sites, two in Seattle (Maple
Leaf and West Seattle Reservoirs of the Seattle water supply
system), one 50 km east of Seattle (Tolt Reservoir of the Seattle
water supply system) and one near the Canadian border (2 km north
of Bellingham), were chosen to measure wet deposition on regions
of sensitive lakes, on farming and forest areas and to measure
deposition in an area that could be affected by sources in both
the United States and Canada. The methods used in sampling and
analysis of samples were chosen to be compatable with the
nation-wide National Atmospheric Deposition Program•(NADP) so that
our rain quality could be compared to that in other areas. The
precipitation was sampled 25 January, 1982 through 15 February,
1963. Sampling continues at three sites (the West Seattle site
has been dropped) under support of EPA. The parameters measured
include: rain volume, pH and conductivity. The samples were
analyzed by the EPA laboratory at Manchester for sulfate, nitrate,
ammonium, chloride, calcium, sodium, potassium, magnesium.,
arsenic, lead, zinc, cadmium, copper and phosphate.
The precipitation in western Washington was found to be
acidified (average pH 4.5 to 4.7 at different sites; minimum pH
was 3.6), largely by sulfuric acid (65%) and to a lesser extent by
nitric acid (35%). Industrial sulfur dioxide emissions are the
2
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probable source o-F sulfuric acid -found in rain. Oxides of nitrogen,
largely emitted by autos and trucks are the probable source of
nitric acid. We -found 65*/. as much acid was deposited at Bellingham
near the Canadian border in comparison to the three sites in and
east o-f Seattle. This could reflect dispersion and removal of
pollutants as air moves to the Bellingham site from both the western
Washington urban population centers and from the two major sulfur
dioxide sources, the(ASARCO copper smelter and the Centralia coal
fired power plant.
Differences were found between summer and winter
precipitation. The concentration of dissolved materials in
precipitation was much higher in summer than in winter at all sites
and there was much more precipitation per week in winter than in
summer. Because of the relation of concentration and rainfall
amount, more acid was deposited per week in winter than in summer at
Seattle sites. At Tolt and Bellingham, more acid was deposited in
summer than in winter because these sites receive much more summer
rain than the other two sites. More acid was deposited at Tolt than
at any of the other three sites because of the higher rainfall at
this site. This indicates that the Cascades probably receive more
acid deposition than lowland sites because of their high rainfall.
This study was unable to identify any source or class of
sources that cause acid deposition in western Washington by chemical
analysis for trace materials emitted by a specific source.
Transport, conversion of emissions to sulfuric acid and wash-out of
acid in rain was modeled using existing industrial emission data.
The model suggests that the major source of sulfuric acid in rain at
our three southern sites is the ASARCO smelter.
3
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Acid concentration and deposition in western Washington is
generally less than that found in areas where environmental damage
has been observed but above the level where researchers have
suggested acid rain could cause some environmental impact. The
higher lakes in the Cascades are the most sensitive areas in wester
Washington because these lakes receive high deposition of acid and
have little ability to neutralize acid inputs. We suggest
continuation o-f the acid precipi tation sampling program and adding
measurements o-f the character of lakes expected to be sensitive and
to receive large amounts o-f acid deposition.
Complete site descriptions are included in the Quality
Assurance Plan prepared as part o-f this program. This QA document
and the complete data set o-f observations is available from the Air
Programs Section of U. S. Environmental Protection Agency? Region X;
Seattle, Washington.
4
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'WASHINGTON
A Cascade Mountains
TOLT MS I
S*~
Sttt Loc*ttBM, ASAKO Uc«ttM
Figure 1. Maps of site locations. Three sites
were In and near Seattle as shown above. One
site was 2 miles north of Belllngham, shown on
the left map. ASARCO's location Is shown above.
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II Summary ot Results from Sampling and Chemical Analysis of
Western Washington F'rec 1 pi tat 1 on
The data -from this program, combined with information
concerning the sensitivity of specific biological systems to acid
deposition, can be used to estimate the potential for damage by
emissions of acid forming pollutants in this region. This
estimate of damage could be used to guide future emissions policy
in which the advantages of industrial production will be balanced
against cost of emission control and environmental impacts.
Impacts are estimated by comparing current character of
precipitation in this region to that in areas with reported damage
from acid deposition.
Previous investigators have reported acid rainfall in westerr
Washington (Larson et al . , 1975; Logan et al . , 1982) with
substantial concentrations of sulfate and nitrate associated with
acidity of rainwater. We find that sulfate and nitrate account
for essentially all of the acidity in sampled rain with sulfate
supplying 757. in Seattle and 65"/. at Tolt and Bellingham. For the
average weekly sample, acid species are partially neutralized by-
ammonium (13 - 227.) and by calcium (9 - 1671) compunds.
Evans et al., (1981) and Glass et al., (1981) have suggested
that an annual rain volume weighted pH of less than 4.6 and/or
annual deposition above 1.5 gram of sulfate (S04) per square
merter are the thresholds for effects of acid deposition on fish
populations. We found that Western Washington received acidic
rainfall in 1982 -1983 with an annual volume weigted pH of 4.4 to
4.5 in Seattle and 4.6 at Tolt and Bellingham. The measured
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S04 annual deposition was 1.3 g/m* in Seattle, 1.7 g/m1 at
Tolt and about 0.9 g/m* at Bellingham (Bellingham deposition was
measured to be 0.7 g/m* in 42 weeks). The measured values of
mean pH and sulfate deposition are at or above the threshold of
damage to fish populations in sensitive lakes.
Failure of fish populations to reproduce have been reported
from high acid deposition areas such as NE United States, eastern
Canada and southern Sweden (EPA, 1982). Annual deposition of
S0« is higher in New Hampshire and southern Sweden (2 to 5
g/m*) than we have measured in western Washington <0.9 to 1.7
g/m*). (S0« from sea salt has been subtrtacted from these
deposition values.) The pH in western Washington averaged about
4.S, less acid than the pH of 4.3 reported in Sweden and 4.13
reported in New Hampshire. The acidity of western Washington
rainwater is due to the small concentrations of neutralizing
species such as ammonium and calcium as well as to the acid
associated with sulfate and nitrate. Western Washington rain is
characterized by its low concentration of dissolved ions as
indicated by the volume weighted conductivities of 10 uS/cm
(micro-Seimens per centimeter) in Bellingham and Tolt and 15 uS/cm
in Seattle. In Sweden the conductivity averaged 28 uS/cm. Sea
salt spray and soil materials contribute to the precipitation
conductivity in western Washington.
Added data on lake buffering capacity (ability to neutralize
acid input) and acid input is needed to predict impacts on
specific lakes. Specific forest tree species in north-eastern US
appear to be damaged by levels of acid deposition several times
7
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higher than we have -found here. Acid fog, probably not -found
here, may have a role in creating these forest impacts in the
northeastern United States. Effects of acid precipitation on farm
productivity have been studied by others and they have reported
some crop yields are increased and some decreased by acid
deposi ti on.
This study has found that rainfall in western Washington is
less acid and that less sulfate is deposited than in rain found in
areas with reported damage to fish and forest productivity. We
appear to be above the threshold level of acid precipitation
damage,but our rain is substantially below the levels of acidity
associated with obvious damage to fish and forest productivity.
Measured deposition levels are high enough to expect some damage.
Damage will be first found in sensitive lakes and in sensitive
forest systems located in regions of high acid deposition. Some
regions of western Washington, especially the higher Cascades, are
sensitive to acid deposition because the watersheds surrounding
these lakes are low in capacity to neutralize acid inputs. The
soils in the Cascades have some similarity to the soil types found
to be associated with acid impact on forest productivity.
Additional studies are needed to determine the sensitivity of
lakes to acid input, the sensitivity of species populating the
lakes and the amount of acid deposited in the lakes. To guide
emission control policy, additional information is needed relating
emissions by specific sources to acid deposition.
8
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Ill Chemical Composition of Western Washington Rain
Local sources may alter the chemical composition o-f
precipitation. Sites were chosen to represent regional rather
than local sources to characterize the regional character o-f
Western Washington precipitation. All o-f the samplers in this
study except -for the site at University of Washington were
located in grassy, dust free areas in an attempt to avoid
altering rainwater chemistry by interaction with the chemistry of
local soil dust. Sites were chosen for this study to detect
effects of transport wind direction, regional pollution sources
and estimate effects of wet deposition on specific locations.
The 1000-2000 foot level winds are representative of the
planetary boundary layer where transport of sulfur and nitrogen
pollutants takes place. Three years data collected at Portage
Bay (in North Seattle) by Washington State Department of Ecology
and six years data collected at Sea-Tac airport by N0AA indicate
that south to southwesterly aloft winds occur 73 percent or more
of days with rainfall. Figure 2 presents the winds at Sea-Tac
for days with rainfall in 1956-61 (Vong, 1982). Accordingly, the
sites for sample collection are oriented to the general
North-Northeast direction in order that during rainfall they will
be downwind of the urban Seattle SO* and NO. emissions and
the major sulfur dioxide emission sources in Tacoma and at
Centralia (Puget Sound Air Pollution Control Agency, 1983).
Limited aloft wind data collected at Portage Bay during this
1982-83 sampling period confirm that the prevailing aloft wind
direction for days with rain is from the south-southwest. Of 23
9
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SEA-TRC WIND ROSE
FREQUENCY OF OCCURRENCE (PERCENT]
NORTH
. EAST
SOUTH
1500FT ALOFT WINDS 195661
NUMBER OF OBSERVATIONS = 1062
FIGURE 2 :
Seattle-Tacoma Airport 1500 foot aloft winds for
rain days.
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rainy days of aloft wind observations in 1982 - 1903, 15 show
winds from the 5 to SW sectors indicating that under usual rain
conditions, pollutant transport in Puget sound is toward the north
and east and toward the Cascade Mountains.
Samples of precipitation were collected in the Wet - Dry type
of precipitation sampler used in the NAOP national rain sampling
network. A detector is used to activate a motor driven lid to
open the wet collection bucket to rainfall. Wet deposition falls
into one plastic, acid washed bucket and the liquid sample was
collected at weekly intervals, as specified by NAOP. The sample
bucket was replaced with an acid-washed bucket that has been
rinsed with distilled, deionired water. The rinse water was
analysed to detect contamination. The conductivity and volume
were measured at the sampling site and the sample transported to
the University of Washington. After 24 hours, the sample
conductivity and pH were measured and the sample sent to the EPA
Laboratory at Manchester, WA.
n
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Sulfate, nitrate, chloride and ammonium ion concentrations
were measured as -first priority, then other ionic species, pH ai
conductivity. Species analyzed were selected to provide
information on the chemical makeup of rain and the sources of
these contaminants. Chemical analysis provided concentrations t
the following species: arsenic, lead, zinc, cadmium, copper,
phosphate, sulfate, nitrate, chloride, sodium, potassium,
magnesium and calcium. Conductivity and pH were measured both i
the field and in the lab when there was sufficient sample volume
The effect of sea salt on precipitation composition can be
detected and subtracted from measured concentrations because the
concentration of major ions in sea water are in a constant ratio
assuming no fractionation occurs
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cumulative deposition of four major ions. Excess sulfate is
generally used as a measure of deposition because this removes
the ions from sea salt which is a relatively local, natural
source of sulfate. Excess sulfate is a measure of the impact of
man on rainwater composition (assuming negligible biological and
volcanic sources of sulfur emissions, an assumption that appears
reasonable for this area, except during periods of high volcanic
sulfur emission).
13
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TABLE 1
Northwest Rain Chemistry Measurements: February 14, 1982 - February IS, 1983
Sujiwitary o-f Data : Weekly Volume. Deposition, and Volume Weighted (lean
Concentrations ana (Standard Deviation)
Site
<~/-)
NO,/SO.
(Molar)
Volume (ml)
Rain
pH (field)
Lab Cond.
(uS/cm)
Lab pH (from
regression)
• o< Weeks with
Zero rain
Nest Seattle
1.17 (.29)
0.63 <.29)
1221
19.2 (24.3)
4.44
12.6 (6.6)
4.33
8o«S2
Maple Lea*
1.15 (.22)
0.72 (.30)
1236
19.4 (21.4)
4.41
13.3 (6.2)
4. SI
6o*32
Tolt Reservoir
1.21 (.40)
1.06 (.72)
2670
42.0 (37.9)
4.60
9.9 (7.0)
4.66
4o*S2
Bel 1ingham
1.19 (.29)
1.07 (.46)
1067
16.8(27.2)
4.37
10.3 (3.9)
4.64
7o«44
Deposition, g Per Square Meter Per Year
SO* (excess)
H+
NO, as N
NH. ai N
1.34 (1.6)
0.036 (.42)
0.10 (.1)
0.06 (.07)
1.29 (1.1)
0.039 (.30)
0.12 (.1)
0.08 (.08)
1.63(1.4)
0.036(.31)
0.21 (.18)
0.11 (.1)
0.73(0.43)*
0.019 (.29)*
0.1 (.!)«
0.07 (.06)*
•Deposition in 42 weeks at Bellingham.
14
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TABLE 1. Continued
Northwest Rain Chemistry Measurements: February 14, 1982 - February 12, 1983
Concentrations, mg Per Liter
Site
West Seattle
Maple Leal
Tolt Reservoir
BellIngham
(ug/1>
34.42 (23.4)
38.76 (24.2)
23.33 (24.0)
26.90 (22.3)
NH.
as N
.064 (.03)
.061 (.09)
.032 (.06)
.073 (.07)
SO.
(Excess)
1.34 (.83)
1.27 (.78)
0.76 (.61)
0.83 (.56)
S0«
(Total)
1.42
1.33
0.82
0.89
NO,
as N
0.101 (.073)
0.121 (.102)
0.100(.103)
0.113(.096)
CI
0.384 (.67)
0.441 (.43)
0.403 (.32)
0.408 (.42)
N«
0.263 (.32)
0.219 (.22)
.0.222 (.19)
0.225 (.20)
HQ
0.042 (.043)
0.033 (.040)
0.034 (.025)
0.031 (.028)
Ca
0.126 (.173)
0.098 (.103)
0.043 (.023)
0.052 (.039)
K«
0.027 (.031)
0.026 (.036)
0.028 (.031)
0.037 (.042)
pa.
<0.002
<0.002
<0.002
<0.002
ru
(ug/1)
3.34 (4.1)
3.00 (6.6)
1.83 (2.6)
1.S2 (2.1)
asm
(ug/1)
14
•
CD
*
0*
2.21 (2.8)
1.13 (2.3)
0.56 (1.4)
Cult
(ug/1)
4.47 (4.7)
3.07 (3.3)
1.86 (3.6)
2.09 (4.7)
Zn#
(ug/1)
3.36 (3.7)
4.37 (6.3)
1.83 (3.0)
3.13 (22.7)
Cd«
(ug/1)
O.JZ <0.72)
0.43 (2.3)
0.87 (2.9)
0.10 (0.26)
•This data should bo- used Mith caution. The concentrations of these ions are
detection limits.
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MAPLE LEAF
CM
s
SQ
\
2
s
Jan.1,83
SAMPLE WEEK
CM
N
8
s
TOLT RESERVOIR
11+
so^
i
N°3__
SRMPLE WEEK
FIGURE 3 : Cumulative Deposition of Major Ions
16
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40
WEST SEATTLE
35
30
25
20
10
5
• ••••
0' ' '
0 4
Jan.1.82
16
Jan.1,83
SAMPLE WEEK
BELLINGHAM
a 12
\10
NO
• •
• • •
• •
FIGURE 4 : Cumulative Deposition of Major Ions
17
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The observed rainwater composition reflects its initial
background composition plus the added species -from polluted air
To detect effects of added pollutants on precipitation quality,
we have compared rainwater data collected at the Hoh River Rang
Station, Olympic National Park to measurements of this program.
The Hoh River data were collected as part o-f the NADP network ai
were analyzed at the NADP laboratory in Illinois. Table 2
presents Hoh River volume weighted concentrations for 9 major
ionic species. Trace metal analyses (trace metals are those
other than Na, Mg, Ca and K) were not performed on these
sample?. Two years (July 1980-July 1902) of rainwater are
represented and used as background values.
TABLE 2
Hoh River NADP Rainwater Data
(July 1980-July 1982, weekly wet samples)
Volume weighted mean (Standard deviation)
Rainfal1
mm/wk
65
S0« (total)
mg/1
0.41
(.28)
S0« (excess)
mg/1
0.22
(.18)
NO*
mg/1
0.091
(.09)
CI
mg/1
1.36
(1.55)
Na
mg/1
0.72
(.80)
Mg
mg/1
0.090
(.09)
Ca
mg/1
0.062
(.09)
K
mg/1
0.033
(.03)
NH«
mg/1
0.005
(.01)
H+
ueq/1
4.06
(1.56)
pH(laboratory)
5.39
Conductivi ty
uS/cm
8.69
(6.2)
18
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Hoh River data and this study overlap by 19 weeks and are
presented graphically in Figures 5-6 -for comparison of the
concentrations in Seattle. Me assume that Hoh precipitation is
not affected by anthropogenic emissions and represent background
precipitation quality for this region. The nitrate and excess
sulfate at the Hoh River have similar time variability when
compared to the data collected in Puget Sound, perhaps
invalidating our assumption or perhaps showing the effect of
variable rainfall altering concentration of both backgound and
anthropogenic contaminants. The background values are subtracted
from our measured ionic concentration and deposition values to
estimate the effect of sources in the industrialized and
urbanized Western Washington.
Hoh River site precipitation has 2.5 times higher salt
concentration than Seattle rain and about 17 percent of the
average excess sulfate and 18 percent of the average nitrate
concentration in Seattle. Other investigators have reported
remote sulfate concentrations which are consistent with these
data from the Hoh River NAOP site (Galloway, 1982). Ammonium and
excess cation concentrations at the Hoh River are near zero.
Since transport distance for sea salt particles is limited (due
to the large size of particles), the sea salt is considered to be
a local influence on rain composition. Our use of Hoh River data
does not attempt to distinguish between natural sources and
transport of distant anthropogenic emissions, both of which could
contribute to Hoh River rainwater quality.
19
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MRPLE LEAF =OPEN
HOH RIVER NADP= BOLD
-6.4 cB
2.4 co
1.6"
Jan.!,83
Jan.1,82
20 25 30 35
SRMPLE WEEK
4.01
3.6*
3.2
\2.8:
o
= 2.4
2.0-
cc 1.&
h-
5 1.2
.8-
.4'
0,
MAPLE LEAF =OPEN
HOH RIVER NADP= BOLD
1
20 25 30 35 40
SAMPLE WEEK
i
SO 55 60
r4.0
3.6
•3.2
2.8 v!
O
2.4 =
h2.0 J±f
•1.6 c£
l-«s
.8
.4
0
FIGURE S : Weekly Concentration
20
-------
MAPLE LEAF =OPEN
HOH RIVER NADP= BOLD
\m
I,.4
a
flog
Jan.1,82
10 IS 20 25 30 35 40
SflMPLE WEEK
45 50 55 60
Jah•1,83
MAPLE LEAF =OPEN
HOH RIVER NADP= BOLD
l.Oi
rl.O
53
Z
o
n
o
CE
K 30 *
SAMPLE WEEK
FIGURE 6 : Weekly Concentration
21
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The 204 weekly rainwater samples collected in this program
have been analyzed for correlations within these data. Appendix
B presents the correlation coefficients by sampling site.
Hydrogen ion correlates with excess sulfate at Maple Leaf
-------
2S0
200
ISO
100
SO
West Seattle
West Seattle
west Seattle
Jan.1,82
WN*LE HEEK
FIGURE 7 : Weekly Concentration
Jan.1,83
23
-------
Maple Leaf
Maple Leaf
Maple Leaf
Jan.1,82
SO 60
Jan.1,83
FIGURE 8 : Weekly Concentration
24
-------
ToU Reservoir
Tolt Reservoir
1
Tolt Reservoir
10 20 SO 40
8fmJL MEEK
FIGURE 9 : Weekly Concentration
Jen.1,83
25
-------
BellIngham
Bell Ingham
Bell Ingham
FIGURE 10 : Weekly Concentration
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The multiple correlations of chemical composition have been
examined using a statistical program available at the University
of Washington, SPSS, for factor analysis. This program examines
the entire data set for mutual tendencies of variability in
chemical makeup. Factors are then computed which can be used to
help identify sources of variability in rainwater composition.
Factor analysis detected the following groupings in the data:
TABLE 3
Grouping Identified BY Factor Analysis
Site Factor 1 Factor 2 Factor 3 Factor 4
Bellingham CI, Mg, Na NH*, NO, Pb# H+, N0S
S04
West Seattle CI, Mg, Na NH*, NO, As#, Pb# H+, S0«
Maple Leaf H+, NH», CI, Mg, Na As#, Pb#,
Ca
Tolt H+, NH«, Pb# CI, Mg, Na
NO,, SO., Ca
#Pb and As are of low accuracy because of low concentrations
in precipitation.
Note that several factors (likely to be specific sources)
have been identified by this analysis. These include sea salt
(Na, CI, Mg) and sources related to man (H+, NH«V As, Pb,
NOj, SQ«). Within the last factor, different combinations
are detected at different sites. We found similar results for
factor analysis performed using both excess and total cation
concentrations and deposition.
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Spatial Variability of SeattleRain Composition
Rainwater composition within the Seattle area was examinei
to detect effects o-f non-uni-form emissions and transport of
pollutants in the city. Two or three rain collectors were
operated at different locations in Metropolitan Seattle. For
the period, April 27 - September 7, 1982 a sampler was operate®
at the Universiy ef Washington, on the roof of Wilcox Hall.
TABLE 4
Comparison o-f Seattle Collection Site Locations
Rainwater Composition, Summer (April 27-September 7, 1982)
Volume Weighted tiean Concentrations, mg/1
Site U. of Wash. Maple Leaf West Seattle
SO« (Total) 4.31 2.73 2.84
S04 (Excess) 4.17 2.64 2.77
NOi as N 0.43 0.29 0.26
NH. as N .28 .20 .17
CI .97 .67 .33
Na* . 48 .40 .34
rtg* .09 .07 .06
Ca •52 .18 .32
K# .09 .08 .08
Pb» (ug/1) 17.3 11.3 8.9
As# (ug/1) 2.3 1.6 2.0
Zn# (ug/1) 9.7 5.3 5.3
Cd# (ug/1) 1.7 0.7 0.4
Cu# (ug/1) 6.1 5.5 5.7
~Some missing samples because volume insufficient for
measurement.
~Values of questionable accuracy because low concentrations of
ions are near detection limit.
28
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TABLE 4, CONTINUED
Comparison of Seattle Collection Site Locations
and Rainwater Composition
19 Weekly Samples Taken in Summer (April 27-September 7, 1982)
Site U. of Wash. Maple Leaf West Seattle
Sum, <+/-) 1.07 1.21 1.28
N0,/S04 (Molar ratio) .37 .40 .34
Summer Deposition in quantity/M® Per Week
S dep (mg)
H (meq)
3.97
.40
3.77
. 38
N0S as N (mg)
1.85
1.26
NH« as N (mg)
1.22
.86
Average Summer
Values
H+ (field, ueq/1)
93.3
89.5
pH (field)
4.03
4.05
Conductivity
35.0
25.6
Average Volume (ml)
288
273
Rainrate (mm/wk)
4.5
4.3
Weeks with rain
14
14
Weeks, no rain
5
5
3.04
.29
.85
.56
87.9
4.06
23.0
209
3.3
13
6
Conclusions from Table 4
1) pH varies only slightly between the 3 locations.
2) Weekly Rainfall Volume mas variable between sites within
Seattle, especially in the summer.
3) Deposition is highest for all ions at the University of
Washington.
29
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The similarity in pH at University of Washington and Maple
Leaf dispite quite different concentrations of excess S0«,
and NO* suggests that some of the additional sulfate at
University of Washington may be in the form of calcium
sulfate. The observed elevation of lead and nitrate
concentrations was expected at the University of Washington
site because of proximity to the University district auto
traffic. The presence of additional sea salt, calcium, sulfate
and nitrate at University of Washington explains the higher
conductivity (33 uS/cm compared to 23-215 at other Seattle
Sites) at University of Washington. Similar pH indicates added
NH« neutralised the higher nitric acid concentrations which
were measured for summer rainfall at University of Washington
when compared to the two other Seattle sites.
These results illustrate effects of localized pollution
sources as site variability of collected rainwater
composition. To characterize rainfall quality for an entire
region and not just a local area, sites should be as free as
possible from local influences.
Comparison of Tolt Reservoir and Seattle Rainwater
Figures 11-13 present concentrations of 5 species for the
sampling period for the Tolt Reservoir sampling site in the
Cascade foothills South of Stevens Pass and for Maple Leaf
reservoir in Northern Seattle. The Tolt site receives lower
concentrations of all species except cadmium. Comparison of
correlations in these chemical data indicate that Tolt
Reservoir rainwater may be influenced by the same source
30
-------
MflPLE LERF = OPEN
TOLT RESERVOIR =BOLD
6.4 cB
A A
•2.4 co
. uj
i-6 y
i
1,82
20 "25" '30' 35 40
SAMPLE WEEK
Jan.1,83
4.0
3.6
3.2;
^2.8^
a _
= 2.4
tf 2.0
S| i.e
5 1.2
•8*
.4
0 !
MflPLE LEflF = OPEN
TOLT RESERVOIR =BOLO
+*2**
20
25
FIGURE 11
as 40
SflMPLE WEEK
Weekly Concentration
4.0
-3.6
-3.2
2.8
- &
t2.4 =
fc.Ofc!
¦1.6ti
1.2 5
: .8
• .4
»
; 0
31
-------
MAPLE LEAF = OPEN
TOLT RESERVOIR =BQLD
20 IS 90) 95 40
SAMPLE WEEK
Jfln¦1,83
CD
l.Ch
.9
•a
i
.7
.6
.5
.4
.3
.2
.1
<
G:
MAPLE LERF = OPEN
TOLT RESERVOIR sBOLO
Amidl
in r
20 25 30 35 40 45 50
SAMPLE WEEK
FIGURE 12 : Weekly Concentration
32
-------
250]
225;
,200-
O 175*
LU
3 150"
I125
o 100-
ai
° 75'
X 5Q
25;
Ot
MAPLE LEAF = OPEN
TOLT RESERVOIR =B0LD
n
20 25 30 35 40
SAMPLE WEEK
100 o
45 50 55
Figure 13: Weekly Concentration
33
-------
¦factors as North Seattle but experiences lower concentrations
due to dilution of airborne material and by topographically
¦forced higher rain-fall rates (Maple Leaf elevation, 50 meters;
Tolt elevation, 538 meters). Factor analysis indicates that
variability at both Maple Lea-f and Tolt is dominated by two
sources, industrial-auto and by sea salt. In contrast the
results o-f -factor analysis indicate that West Seattle appears
to have -four separate sources; sea salt, ammonium nitrate,
arsenic + lead, and acid sul-fate.
Comparison o-f Seattle and Bellingham Rainwater
To help assess the degree that Seattle area emissions
impact Northern Puget Sound, Bellingham data has been compared
to Seattle rainwater data. Figures 14 - 16 compare West
Seattle and Bellingham precipitation concentrations for 5
species. These results indicate much lower concentrations of
S0« and arsenic in Bellingham when compared to Seattle and
Tolt indicating that if Seattle and Tacoma area sulfur and
arsenic emissions are transported this far North that they are
considerably diluted. For most other ions, the concentrations
at Bellingham are similar to those measured at the other
sites. The Bellingham site is downwind during rain of most,
but not all of the Anacortes - Bellingham area sources of SO*
and NO.. Our Bellingham rainwater composition is similar to
the composition of rain just north of the U.S. - Canadian
border (McLaren, 1982).
34
-------
WEST SEATTLE =OPEN
BELLINGHAM =BOLD
c!) 6.4
6.4 ci
E 4.8
co 2.4
2.4 co
"1.6
1.6 <->
I
DO
I I I f
Jan.1,82
20 25 90 35 40 45
SAMPLE WEEK
50 55
Jan.1,83
liJ
I—
cr
tx.
4.0
3.6-
3.2-
2.8'
2.4-
2.0-
l.fr
WEST SEATTLE =0PEN
BELLINGHAM =B0LD
H
15 20 25 30 35
SAMPLE WEEK
FIGURE 14 : Weekly Concentration
ink!
;4
¦3
•3
2
2
2
¦1
1
.0
.6
.2
•8 s
O
.4 =
.0
UJ
40 45 50 55 60
e CL
•6 0C
h-
•2 2
.8
.4
0
35
-------
o
3.0i
2.7-
2.4-
2.1
I.8i
IxJ
o 1.5
| 1 -2;
x .9-
o
.6
.3
°L
Jan.
TTT
1,82
in
WEST SEATTLE =0PEN
BELLINGHRM =B0LD
il
J
iM
i
20 2S 30 35 40
SAMPLE WEEK
m
45 50 55
Jan.1,83
(fiM
55 60
O
O
C
WEST SEATTLE =0PEN
BELLINGHAM =B0LD
i
25 30 35 40
SAMPLE WEEK
FIGURE 15 : Weekly Concentration
36
-------
i
10
WEST SEATTLE =0PEN
BELLINGH
RM =B0LD
91 9*
20 2S 90 95 40
SRMPLE WEEK
Figure 16: Meekly Concentration
37
-------
VI Seasonal Variability
The data collected in this study have been analyzed to
determine whether rainfall acidity and composition vary with
the time o-f year. This information is of interest for several
reasons: 1) Variability in emissions, transport, atmospheric
chemistry or rainfall can alter deposition. 2) Sensitivity o-f
biological systems may depend on time of year. Relationships
between impacts and sources may require understanding of
seasonal variability of the parameters listed above.
Figures 17 and 18 display the weekly sample volume at each
of the four sites. The minimum in rainfall in the summer is
accompanied by higher concentrations of most species. A summer
season has been arbitrarily designated from April 27 until
September 7, 1982 with the remainder of the year referred to as
winter. Weekly volume weighted average sample concentrations
for each season are listed in Table 5 for four species of
interest: pH, nitrate, sulfate and calcium. The ratio of the
concentrations from the average summer sample to the average
winter sample has been calculated for each site. Seasonal
variation in emissions and atmospheric chemistry couple with
variation in precipitation amount to modulate deposition. In
the mid-western US, for example, the sulfate levels are highest
in summer as is precipitation amount. This produces a strong
maximum in acid deposition. By comparison, in western
Washington, the increase in concentration in Summer is balance^
by a decrease in precipitation to produce a relatively constant
level of deposition.
-------
West Seattle
10
20
Maple Leaf
40
50
60
10
20 30
Tolt Reservoir
40
50
_!
60
.1,82
10 20 30 40
SAMPLE MEEK
FIGURE 17 : Weekly Rainwater Sample Volume
Jan.1,83
39
-------
12000
Bell Ingham
10000
eooo
6000
4000
2000
April 13,82
Jan.!,83
HEEK
FIGUP.E 18 : Weekly Rainwater Sample Volume
40
-------
Table 5 shows that in 1982-83 there was a marked
seasonality to volume weighted concentration. We -find that
calcium, nitrate, sulfate and hydrogen ion are 2 to 5 times
more concentrated in summer than in winter in Western
Washington rainwater. Rainfall quantity decreased in the
summer: In the summer, Seattle sites received 12 to 16 percent
of average weekly winter rainfall, while the Tolt River and
Bellingham received about 33 percent of their weekly winter
rainfall. Figures 17 and IB show sample volume versus time for
each site.
The combined effect of higher concentration and low
rainfall rates in the summer produces different seasonal
deposition patterns *t the four sites monitored in this study.
Both Seattle sites received higher mean weekly wet deposition
of sulfate, nitrate, ammonium, and hydrogen ion in the winter.
The Tolt Reservoir received higher average weekly wet
deposition of all four species in the summer than in the
winter. For three species: sulfate, nitrate and NH4|
Bellingham received higher weekly wet deposition in the
winter. For hydrogen ion, Tolt Reservior and Bellingham
received higher weekly hydrogen ion deposition in the summer.
Table 6 presents ratios for the rainwater concentrations,
volume, and wet deposition for the average weekly sample at
each of the four sites.
-------
TABLE 5
Summer/Winter Variability in Precipitation Composition
Effects on Concentration (Weekly Volume Weighted Mean)
Site
Analyte
pH, field summer
pH, -field winter
W Seattle Maple Leaf Tolt R. Bellingham*
4.06
4.48
4.05
4.47
4.15
4. 79
4.21
4.75
SO* (excess) summer 2.77
(mg/1)
S0« (excess) winter 1.24
(mg/1)
!. 64
1.15
1 .76
1.33
0.55 0.70
N0» as N summer 0.26
(mg/1)
N0S as N winter 0.09
(mg/1)
0.29
0. 11
0.27
0.07
0.20
0.09
Ca (total) summer 0.32
(mg/1)
Ca (total) winter 0.12
(mg/1)
0. 18
0.09
0.08 0.08
0.04
0.04
Volume(ml) summer 209
Volume(ml) winter 1804
273
1790
1272
3475
516
1486
Summer Season ¦ April 27 to September 7, 1982 (19 weeks)
Winter Season = February 16, - April 26, 1982 and September 8,
1982 - February 15, 1983 (33 weeks)
~Winter Season -for Bellingham = 24 weeks
42
-------
TABLE 6
Summer/Winter Variability of Rainwater
Ratio of Weekly Average Concentrations
(summer/winter)
Site W Seattle Maple Leaf Tolt R Bellingham
Species
S0« (excess) 2.2 2.3 3.2 1.9
NO, 2.9 2.6 3.9 2.2
Ca 2.7 2.0 2.0 2.0
H+ 2.7 2.6 4.4 3.4
Volume Ratio * (winter/summer)
W Seattle Maple Leaf Tolt R Bellingham
Sample Volume 8.6 6.6 2.7 2.9
Deposition Ratio » (winter/summer)
W Seattle Maple Leaf Tolt R Bellingham
«
o
(0
3.9
2.9
.86
1.3
NO,
3.0
2.4
.68
1.3
H+
3.2
2.6
.63
.84
NH«
2.9
2.3
.65
2.0
43
-------
VI Relation of Emissions to Rainwater Composition
Previous modeling of .industrial influences an rain quality
have focused on sulfur emissions and subsequent wet deposition
because sulfate appears to dominate acid deposition in most
areas. We had hoped to use trace metals emitted by specific
souces to estimate contributions of ASARCO, other industries
and urban population centers to sulfate and nitrate deposition
in western Washington. This was not possible because of the
low levels of these trace metals. An alternate method has been
used to estimate the sulfate contributions by different sources
in western Washington. We have chosen to model sulfate
concentrations because sulfate contributes 65 to 75 percent of
the acidity in Western Washington rainwater from charge balance
and correlation of sulfate and hydrogen ion concentrations.
Sulfate deposition is calculated by dispersing emissions during
rain into a 16 segment wind rose and assuming a conversion rate
for SOt to S0« and a washout rate. An approximation of
other SQi contributions to sulfate in Western Washington rain
has been made by assuming two emission points located in Tacoma
and Seattle and applying the model used by Vong (1982). It
should be recognised that the calculation of diverse SO*
sources as single point sources in Seattle and Tacoma is only
intended to roughly approximate their contributions to local
rain chemistry. The calculated sulfate deposition from the
major point sources in Tacoma (copper smelter) and Centralia
(power plant) are most suitable for estimating long term
averages, one year or longer. The model predictions in Table 7
indicate that, for average wind and rain patterns, the Tacoma
copper smelter is the largest source of sulfate in Puget Sound
4 a
-------
rainwater, contributing about 60 percent in West Seattle, 45
percent at Maple Leaf reservoir, and approximately 33 percent
at the Tolt reservoir in the Cascade -foothills. The Tolt
calculation is uncertain since only 84 percent of measured
sulfate is predicted. This apportionment of Puget Sound
rainwater sulfate appears to account for 84 to 96 percent of
the measured concentrations for 1982-83 as shown in Table 7.
Figure 19 presents the results of calculations for sulfate
deposition from emissions of the ASARCO Copper Smelter in
Tacoma into 16 sectors of 100 km length from the emission
point.
-------
RSRRCG RCID WET DEPOSITION
HEDGE MODEL H2S04 WfiSHOUf (MILL I ON" KO/YEfiR HI THIN 100 Kfl)
NORTH
WEST
. ERST
SOUTH
SER-TRC DflTR FOR-
1500FT RLOFT HINDS
FIGURE 19 : Calculated Sulfate Wet Deposition for the
Tacoma Copper Smelter (Vong,1982)
-------
TABLE 7
Summary of Calculations of Contributions To S0«
¦from Sources of Sulfate in Rainwater
1. Measured:
Background (excess)
Sea Salt
W Seattle
(mg/1)
Maple Leaf Tolt R
(mg/1) (mg/1)
Rainwater Concentration:
0.22(167.)
.08(67.)
0.22(177.)
.06(57.)
0.22(277.)
.06(77.)
2. Modeled*
Tacoma Smelter
Centralia power pi
Pierce County S0a
King Co SO*
0.88(627.)
.09(67.)
.09(67.)
Negl.
0.60(457.)
0.08(67.)
.06(57.)
.23(177.)
0.28(347.)
.07(97.)
.03(47.)
.03(47.)
3. Total Predicted
1.36(967.)
1.25(947.) 0.69(847.)
4. Measured(1982-3) (mg/1) 1.42
Underprediction (mg/1) 0.06(47.)
1.33 0.82
0.08(67.) 0.13(167.)
~Reference: Hutcheson and Hall, 19745 Vong, 1982
Assumptions:
1. Emission rates: Pierce County S0i ¦ 1500 kg/HR
King County SO* ¦ 2670 kg/HR
Smelter S0i - 14273 kg/HR
Centralia Power plant SO* « 6213 kg/HR
(Vong, 19821 PSAPCA, 1983)
2. Meteorology and Scavenging efficiency: Winds are average
climatological values and Scavaging as
reported by Vong (1982).
3. Area S0a Sources: Pierce County SO* and King County
S0i are modeled as point sources located
in downtown Tacoma and the Duwamish Valley,
respectively.
47
-------
NADP data for the Hoh River indicate much lower
concentrations for sulfate, nitrate and hydrogen ion near the
coast of Washington than in the Puget Sound area. Sections III
and V utilize Hoh River data as background to be subtracted
from Seattle precipitation concentrations in this study. Our
data is compared to other measurements in table 8.
Table 8
Rain Chemistry Data Measured by Other Investigators
Comparison of Western Washington Rainwater Excess Concentrations
with Other Geographical Areas
53
82-113
3. 1
Reference: This study?
Granat, 197B;
Likens,1976; Galloway
,1982
#Concentration value of
questionable
accuracy.
-------
Enplanations for increased under-estimat 1 on of S0«
deposition with distance include:
1) Inability of model to predict increased nucleation
scavenging of S02 for large oxidation and transport
times and distances.
2) Errors from modeling Seattle SO* source emissions
as one point source.
VI Measurements by Other Investigators
The results of this study indicate that rainwater in
Western Washington is acidic with measureable concentrations of
heavy metals and sea salt. Comparison of our data with other
studies of rainwater chemistry indicate that the areas known to
experience damage from acid deposition such as southern Sweden
and New England receive 2 to 3 times more sulfate and 1.5 to 2
times more hydrogen ion than Western Washington (Likens, 1976;
Granat, 1978). Data collected in Vancouver, B.C. indicate
higher nitrate and calcium concentrations and lower hydrogen
ion concentrations than in Seattle rainfall (Barrie, 1983).
However, Seattle receives three times the hydrogen ion and 3-4
times the sulfate concentrations that were detected at a remote
site with low rainfall rates located in Poker Flat, Alaska
(Gal 1oway, 1982).
48
-------
Table 8 , Continued
Comparison of Western Washington Rainwater Excess Concentrations
with Nortwest Rain Data (Micro Equivalents / Liter)
Analyte
Port Hardy BC
1977-79
Vancouver BC
1980
Hoh River WA
1980-82
NOs
5.9
13.5
1.5
CI
81.4
26.4
38.3
S0«
28
36
8.5
NH«
6.4
10.9
0.3
Na
76.8
23.2
31.4
K#
3.0
3.4
0.8
Mg
17.4
6.2
7.4
Ca
11.2
27.4
3.1
H+
11.5
17.5
4.06
PH
4.94
4.76
5.39
#Concentration value of questionable accuracy.
Sulfate (Total)
H+
Reference: (Barrie, 1982)
1.37
0.014
(Barrie, 1982) (Yanish, 1983)
Deposition, gm/m* per Year
2.23 2.45
0.019 0.025
49
-------
A recent compilation of rain chemistry data indicates that
Western Washington rainfall has lower concentrations of
hydrogen ion, nitrate, lead, zinc, and sulfate than the
heavily polluted Chio Valley and Northeastern U.S., but Western
Washington receives higher concentrations of hydrogen ion and
sulfate than most of the northwestern U.S. (Hunger, 1982).
Comparison o-f our data with other investigations of
western Washington rainfall, shown in Table 8, found general
agreement. One event study in Seattle showed arsenic and
sulfate values similar to our data but observed higher zinc,
cadmium, potassium and calcium concentrations (Larson et al.,
31975). Dethier (1901) found higher copper, lead, and zinc but
less arsenic in the North Cascades than at the Tolt River site
in this study. A six month study near Snoqualmie Pass found
consistently higher calcium and nitrate concentrations than
detected at the Tolt in this study (Logan et al., 19B1).
Logan's samplers were located near automobile traffic on 1-90
and may have found a locally higher nitrate concentration for
this reason. Measurements of precipitation ionic
concentrations from month duration, wet only samples on the
roof of a nearby University of Washington building found lower
pH (4.2) and higher concentration values for all species than
we report (USDOE, 19791 1981). Their data may not be
representative of the Seattle area due to local sources of
nitrate, calcium and sulfate found in our precipitation samples
from the University of Washington. Our study found lower
calcium than other studies reviewed here. This could be due to
low dry deposition by use of the wet/dry rain sampler in this
project and locating the samplers in grassed areas.
50
-------
VIII. Conclusions and Recommendations
1) Deposition of acid in the Washington Cascades is
at or above the reported threshold -for acidificat-
ion o-f sensitive lakes with low capacity to
neutralise acid inputs. Sensitive lakes are common
in the Cascade Mountain Range.
2) Acid concentrations and acid wet deposition in
western Washington are less than one-half that
received in heavily impacted areas in the north-
eastern US and Southern Sweden but higher than most
of the northwestern U.S. The average pH in western
Washington was 4.4 - 4.6, about 0.25 pH units less
acid (higher) than in northeastern US and southern
Sweden. Western Washington rain acidity is at the
level reported to be on the threshold of damage to
aquatic populations.
3) Rainwater in north Seattle and at the Tolt
Reservoir show similar compositions, probably due
to similar sources impacting both areas.
4) At the Seattle sites, acid deposition was higher in
winter than in summer. Deposition was higher in
summer than in winter at Tolt and Bellingham.
This difference reflects the higher precipitation
in summer at Tolt and Bellingham compared to the
other sites.
SI
-------
5) Western Washington rainfall is acidic with
seasonally higher concentrations of most ionic
species in the summer.
6) Models suggest that the dominant acid sources -for
Seattle and Tolt rainfall appear to be the Tacoma
Copper Smelter for sulfate and transportatian
emissions for nitrate. This is largely based on
the contributions of ASARCO and transportation to
SOa and NOi emissions in Puget Sound.
7) Rain in Bellingham has lower concentrations
of sulfate and was less acid than that at Seattle
si tes.
B) Rain from oceanic air at Hoh River sampling site
contains about 16 percent of the sulfate
concentration and 17 percent of the nitrate in
Seattle rainwater.
9) The deposition and concentrations of major ions
were not appreciably degraded by sampling and
analysis procedures except for trace metal species,
potassium and phosphate. The precision and
sensitivity of analytic methods was not sufficient
to accurately determine trace metal concentrations
in western Washington rainwater.
32
-------
B. Suggestions -for Future Work
1> Analysis of the trends in acidic precipitation in
western Washington will require long term
monitoring of rainwater composition in western
Washington. A major problem in our understanding
o-F acid precipitation in eastern US and Canada is
lack o-f long term deposition data. This suggests
that the current program sampling rain in western
Washington should be continued in the long term.
2) Collection o-f event length precipitation samples
with more extensive transport wind—field
measurements would help to identi-fy source-receptor
relationships in western Washington rain quality.
Electric Power Research Institute (EPR1) plans such
a program for 19B3 - 19S4.
3) Improvements are needed in sensitivity o-f analysis
for trace metals. These measurements are useful to
trace acid deposition to specific sources or types
of sources in Western Washington. Trace metal
analysis of Hoh River rainwater would be useful to
to discover man's impact at this coastal site.
4) The existing data set indicates there may now be
damage to fish resources in Cascade lakes. To
clarify this problem, measurements o-f lake
buffering capacity, biology and acid input are
needed.
53
-------
Re-f erertces
Barrie> L.A. and A. Sirois, An Analysis and Assessment of
Precipitation, Chemistry measurements made by CANSAP,
Atmospheric Environment Service, Ontario, Canada 1982.
Bolin, 8., The Impact on the Environment o-f Sulfur in Air and
Precipitation, Royal Ministries for Agriculture and Foreign
Affairs, Stockholm, Sweden 1971.
Charlson, R.J. and H. Rodhe, Factors Controlling the Acidity of
Natural Rainwater, Nature, 295, &B3-6B3, 1992.
Charlson, R.J., R. J. Vong, and D.A. Hegg, The Sources of
Sulfate in lPrecipitation-Sensitivities to Chemical Variables,
JGR, 08 C2, 1375-1377, 1983.
Dethier, D.P., Atmospheric Contributions to Stream, Water
Chemistry in the North Cascade Range, Washington, Water
Resources Research, IS, 4, August 1979.
EPA, 1982, "Air Quality Criteria for Particulate Matter and
Sulfur Oxides, Volume II", EPA-BO0/8-82-029b
Galloway, J.N., Likens, G.E., Keene, W.C. and J.M. Miller, The
Composition of Precipitation in Remote Areas of the World, JGR,
8771-8786, 1982.
Granat, L., On the Variability of Rainwater Composition and
Errors in Estimates of Aerial wet deposition, unpublished
paper.
Granat, L., Sulfate in Precipitation as Observed by the
European Air Chemistry Network, Atm. Envir. 12, 413-424, 1978.
Harrison, H. H., University of Washington, Personal
Communication, 1983
Hegg, D. A., Sources of Sulfate in Precipitation, JGR 88/2,
1370-1374, 1983
Holland, H.D, The Chemistry of the Atmosphere and Oceans, Wiley
and Sons, NY, 1978.
Hutchinson, M., Hall, F., Sulfate Washout from a Coal-Fired
power-Plant, At. Env., B, 23-28, 1974
Junge, C.E., Air Chemistry and Radioactivity, Academic Press,
N.Y. 1963.
Knudson, E. J., Duewer, G. D., Christian and Larson, T. V.,
Application of Factor Analysis to the Study of Puget Sound
Region, Chemometrics, University of Wash., 1976
Larson, T.V. R.J. Charlson, E.J.Knudson, G.D. Christian, J.H.
Harrison, Influence of a SO* Point Source on Rain Chemistry
of a Single Storm in the Puget Sound Region, Water Soil St Air
Pollution, 4, 319,328, 1973.
54
-------
Likens, G.E., Acid Precipitation, Chemical and Engineering
News, 54, 41, 29-44, 1976.
Logan, R.M., J.C. Derby, and L.C. Duncan, Acid Precipitation
and Lake Susceptibility in the Central Washington Cascades,
Central Washington Univ., 1982.
McLaren, R.R., Lower Mainland Precipi tation Chemistry Data,
Atmospheric Environment Service, Pacific Region, Environment
Canada, Vancouver, B.C., 1982.
Hunger, J.W. and S.J. Eisenreich, Continental Scale Variations
in Precipitation Chemistry, Env. Sci. and Tech., 17, 1983.
Peden, M.E., L.E. Skowron and F.F. McGurk, Precipitation Sample
Handling, Analysis and Storage Procedures, Illinois State Water
Survey, Urbana, 111., June 1979.
Peden, M.E., L.E. Skowron, Ionic Stability o-f Precipitation
Samples, Atmos. Environment, 12, 2343-2349, 1978.
Pszenny, A. A., Maclntyre, P. F., Duce, R. A., Sea Salt and the
Acidity o-f Rain on the Windward Coast o-f Samoa, GRL, 9, 7,
731-734, 1982.
PSAPCA, Computer Printout o-f Alo-ft Winds at Portage Bay, 1983.
PSAPCA, Emission Inventory for S0» and NO,, 1980
Taylor, 6. S., Baker, M. B., Charlson, R. J., Atmospheric
Heterogeneous Interatcions o-f C, N, and S Cysles: The Role o-f
Aerosols and Clouds, SCOPE 22, Ed. by Bolin and Cook, J. Wiley
and Sons, London, 1983
Topol, L.E., G. Colovos, and R. Schwall, Precision o-f
Precipitation Chemistry Measurements, Proceedings APCA
Speciality Conference on Acid Precipitationj Detroit, Michigan;
Nov., 1982.
Topol, L. E., Ozdemir, S., Operationa and Maintence Manual for
Precipitaiton Measurement Systems; EMSL, ORD, EPA; 1982 (Draft)
USDOE, The Chemical Composition of Atmospheric Deposition?
Appendix to EML Environmental Report} Edited by Topol, L. E.5
EML-356, 276, 1979
USDOE, Some Preliminary Results from the EML Precipitation
Chemistry Network* Edited by Hardy, E. P.J EML-390, 269-284,
1981
USEPA, Air Quality Criteria for Particulate Matter and Sulfur
Oxides, Volume II (Draft), Chapter 7, Environmental Criteria
and Assessment Office, RTP, NC 1982.
Vong, R. J., Puget Sound Transport Winds with Application to
Sulfate Wet Deposition, M.S.E. Thesis, Univ. of Washington,
March 1982.
55
-------
Welch, E.G., and W.H. Chamberlain, Initial Detection of Acid
Lakes in Washington State, Report to National Park Service,
Seattle, Washington, 1981.
Whelpdale, D.M., Atmospheric Pathways o-f Sulphur Compounds,
MARC Report 7, Univ. o-f London, 1978.
Yanish, H., Site Operator, Hoh River NADP Monitoring Station,
Washington, Personal Communication, 1983.
-------
Appendix A: Accuracy of Data
The data that result -from this program must be
sufficiently accurate to satisify the anticipated applications
for the data: to characterize the precipitation in terms of
acid inputs to the land and to trace the acidifying species to
sources or classes of sources. The data will fulfill these
needs if the samples are collected and transported to the
analytic laboratory without contamination and the analysis is
done with sufficient accuracy and sensitivity to quantify the
dissolved species in the rain.
Samples of precipitation were collected in automatic rain
sensing wet-dry collectors using acid washed plastic buckets.
The sample duration was one week and samples were collected
over the period January 15, 1982 - February 15, 19B3. Volume,
temperature and conductivity were measured at the time of
collection; field pH and conductivity were measured after about
24 hours storage at room temperature at the University of
Washington. All sample handling and storage used Nalgene
plastic bottles and labware. The last rinse af each bucket was
analysed to detect contamination of the bucket. Samples were
sent to the EPA laboratory at Manchester for analysis and
storage at 4" C.
The analytic method and detection limits reported by the
EPA laboratory are listed in Table 9. Precision and accuracy of
the analytic methods were checked periodically with EPA Quality
Control and Performance samples.
57
-------
TABLE 9
Analytic Method and Detection Limits, EPA Manchester
Analyte Method Limit of Det. , ug/i*
SO* Auto Analyser - Colorimetric 500
NO, as N " 2
NH« as N " 2
CI - 2
P04 " 2
Analytic Instrument
PE5000/PE360
Na Flame Atomic Absorption (AA)*» 5/20
fig " 10/10
K " 1/10
Ca " 1 / 30
PESOOO-Zeeman/PE403-HGA2100
As Graphite Furnace (AA)** 0.1/2
Cu " 0.1 / .8
Pb " 0. 1 / 1
Zn " 1 / 10
Cd " 0.1/0.1
*Anal. Chem. 32, 2247 <1980)
**Two different AA instruments were used during this program.
The new analytic instrument that increased sensitivity was used
after October of 1982.
58
-------
Analytic accuracy was tested by comparing analytic results
against solutions prepared in our laboratory -for concentrations
and conductivity and NBS potassium phthalate pH reference -for
pH. The results of these comparisons o-f analysis to our test
solutions is given in Table 10 and -for rainwater in 11.
TABLE 10
Comparison o-f Analytic Results to Standards
Analytic Result ¦ (Slope) X (Standard) + Intercept
Analyte Method Slope Intercept R*
S0« Auto. Colorimetric 1.03 .114 .99
S0« Ion Chromatography 0.99 .065 .99
CI Auto. Colorimetric 0.78 0.83 .99
N0j Ion Chromatography 1.05 -0.015 .99
NO* Auto. Colorimetric 0.97 0.063 .99
Conductivity Pt Electrode 1.08 0.98 .99
Comparison o-f Uo-fW and EPA pH Against Standards
pH Glass Electrode pH(UofW) - pH(EPA) - 0.06
~Hegg, D. A.; Atmos. Sciences, Univ. o-f Wash.
TABLE 11
Comparison o-f Sulfate and Nitrate Analysis Techniques for
Rainwater Samples By Least Squares Regression
*Hegg(ion chromatograph)¦(SIope)X(EPA(colorimetric))+Intercept
Slope Intercept R*
Sulfate 1.15 -.054 .72
Nitrate .93 .010 .98
~Hegg, 0. A.5 Atmos. Sciences, Univ. of Wash.
59
-------
Me also tested precision by submitting split samples, two
duplicate samples from one precipitation collection identified
to the laboratory as different samples. The results of this
test is presented in table 12.
Table 12
Estimates of Analytic Uncertainty
by Split Samples of Rainwater
Least Squares Regression of Replicate Analysis,
(Sample 2) ¦ (Sample 1) X (Slope) + (Intercept)I mg/1
Analyte
SI ope
Intercept
R*
CD
o
•
1.06
-.029
.95
CI
1.03
-.023
.98
NO* as N
1.00
-.001
.99
NH« as N
1.02
-.001
.97
Na
1.0S
-.015
.99
Ca
.86
.006
.56
K
.22
.012
.03
rig
1.04
-.001
.98
Cu
1.53
.08
.45
As
.65
.40
.45
Pb
.87
.60
.39
Zn
.42
.56
.28
Cd
-.44
.55
.01
Conduct.
1.02
-.13
.99
Each analyte: 19 pairs of differently labeled identical samples
60
-------
Considering the requirements of this program, we find the
accuracy o-f chemical analysis acceptable for the major species
(except calcium) based on tests of accuracy and precision.
Ratios of reported concentrations indicate 8-13 percent
variability in the results for sulfate in the 0.6 to 2.0 mg/1
range which includes most Puget Sound rainwater concentrations
and 8 percent for nitrate. Therefore, the choice of techniques
by EPA -for these two critical anions appears to give good
results for the concentrations typical of Puget Sound rain.
Except calcium, potassium and the five trace metals, all
species have average differences of reported concentrations for
split samples of less than 20 per-cent of the average value.
The sensitivity of the analytic techniques used for the
trace metals and potassium was not sufficient to use the
results to trace acid deposition to specific sources or classes
of sources in this program. Analysis of the five trace metals
species (lead, arsenic, copper, zinc, and cadmium) was
performed on unfiltered, unacidified aliquots of rainwater.
All trace metal species, except lead, show poor reproducability
of measured concentration at the levels that exist in western
Washington rain. Zinc and cadmium also show poor correlation
of the data with the least squares regression line.
61
-------
Explanations -for the relatively poor analytic precision
for metals include:
1) Analytical insensitivity at the low concentrations
found in Washington rainwater,
2) Possible loss of metals to the walls of the sample
bottle for these species because sample was not
acidified prior to storage for later AA analysis.
Detection limit problems are real for rainwater and
explanation 1) probably is important to the calculated
precision. However, explanation 2) may be important. NADP
specifies acidification to pH ¦ 2 for these analyses (Peden et
al., 1979) and this should be done in future studies.
Due to analytical uncertainties, zinc and cadmium have
been omitted from the analysis in this report except for
inclusion in mean annual average volume weighted
concentrations. Data for potassium, lead, arsenic, and copper
were included in factor analysis although caution is suggested
in drawing conclusions from these data.
Hydrogen ion was measured with a glass pH electrode at the
University of Wash, (field) and at the EPA analytical labatory
(lab). Comparison of field (University of Wash.) pH
measurement of NBS and potassium phthalate pH reference
standards found a mean negative bias of 0.07 pH units by
University of Wash. Comparison of lab (EPA) and field
(University of Wash.) was made for rainwater H+ concentration
calculated from measured pH, shown in table 10, indicates that
field pH averages 0.06 to 0.10 pH units less than lab pH.
62
-------
Laboratory pH was not taken -for some summertime samples due to
low sample volume. Charge balances were calculated -For these
low volume samples using pH from regression of -field pH with
lab pH to generate the missing lab pH values.
TABLE 13
Relationship Between Field and Lab Rainwater
Hydrogen Ion Concentration, Calculated -from pH
H+(Lab> • H-MField) X (Slope) + Intercept
Least Squares Regression, Units * H+
-------
Bias about equal to the difference between UofW field and
EPA lab pH of rainwater samples was detected using standards.
Organic acids and effects of laboratory atmospheric gases are
expected to be fairly small in comparison to the strong acid
content and probably are not the cause of lower field pH. The
second explanation seems most plausable. Some insoluble
cations are present as indicated by comparison of filtered and
unfiltered aliquots. A ring appeared.in sample buckets after
collection on several weeks also indicating the presence of
small amounts of insoluble material in Western Washington
rainwater. Rainwater can contain basic, insoluble (often soil
derived) minerals due to below cloud scavenging of dust by
falling rain.
We examined the effect of ambient temperature storage in
terms of change in sample pH during the one day to one week
residence of the sample in the bucket prior to analysis. pH
measurements of rainwater stored at 20" C found a small pH
increase of within two weeks after collection and little change
between 2 and 8 weeks. These observations are consistent with
a previous study indicating replacement of hydrogen ion by
particulate calcium in room temperature storage of unfiltered
solutions. The samples collected in this study were not
refrigerated for 1-7 days in the field and during a 2 or 3
day period between collection and arrival at EPA lab. pH And
conductivity were measured at the EPA laboratory within 24
hours after sample delivery. The samples were then filtered
and analysis performed for sulfate, nitrate, ammonium, chloride
and phosphate. Unfiltered samples were reserved for
determination of sodium, potassium, calcium, magnesium and
64
-------
other metals. Samples were maintained at room temperature
until pH and conductivity were measured, the re*frigerated at
4s C until analysis.
The effect of insoluble materials on sample composition
was evaluated by comparison of 27 filtered versus unfi1tsrsd
aliquots of the four cations of primary concern the charge
balance. The results indicate that unfiltered aliquot
concentrations range from 1-27 percent higher than
concentrations in filtered aliquots. Table 14 presents a
regression analysis for filtered versus unfiltered cations.
TABLE 14
Comparison of Filtered vs Total Concentrations
For Important Cations
Least Squares Regression
Filtered ¦ (slope) X (Total) + (Intercept), mg/1
Species Slope Intercept R*
Na .893 .022 .61
Ca .737 .006 .43
K 1.04 -.003 .97
Mg .912 .002 .90
Note: 27 samples of rainwater were measured for each analyte.
The data in Table 14 is used in correcting charge balance for
particles as described on the following page and in table 15.
65
-------
A common test of the accuracy of the analytical methods
and completeness of the choice of analytes is the balance of
positive and negative ions. A ratio of 1.0 confirms
electro-neutrality and implies that the analysis scheme is
appropriate. Table 15 presents the mean and standard
deviations (by site) of this charge balance ratio. Measured
cations exceed anions by about 18 percent. Passible
explanations for this cation excess include!
1) Analytical error, considered unlikely as discussed
earlier.
2) Presence of low solubility particles detected by AA and
not the Technicon Auto-Analyzer is considered to be the
likely source of this charge inbalance.
Regression analysis of filtered versus unfiltered cations
Mas used in the charge balance equation to predict the charge
balance ratio in filtered aliquots as shown in the right column
of Table 15, below. The results of this analysis indicate that
most of the charge balance error is due to insoluble cations.
Table 15
Charge Balance of Rainwater Samples
Site
Measured
(+)/(-)
Predicted
<~)/(-)
Maple leaf
1. IS (.22)
1.00 (.23)
West Seattle
1.17(.29)
1.03(.28)
Tolt River
1.21 (.40)
1 • 08 (.38)
Bel 1ingham
1.19 (. 29)
1.00 (.29)
All Locations
(135 Samples)
1.18 (.29)
1*02 (.29)
Range of Values
(IBS Samples)
0.40-3.32
0.33-3.11
66
-------
Three acidic species which could be present in western
Washington rainwater were not measured in this study:
bicarbonate, bisulfite, and organic acids (such as formate or
acetate anions detected in rainwater by Galloway, 1982).
Organic acids can represent up to 25 percent of the acidity of
rainwater in very remote locations, especially where
agricultural burning is present. Qrganics are not expected to
be important in Western Washington rain except possibly at the
Hoh River. Analysis for organic acids was not performed.
Carbonic acid in equilibrium with 340 ppm atmospheric CO* can
be calculated to contribute less than 1.0 ueg/1 at pH ¦ 5.0 and
less than 0.5 ueq/1 at pH « 4.5. Bisulfite and sulfite are
more important where high atmospheric SO* concentrations
occur, as in Tacoma or locations in Seattle near industrial
sources. Many difficulties exist in determining HSOj in
rain:
1) SO* in Solution could partly oxidize to S0« during
the one day to one week that the sample remains in the
field or during transport to the EPA Lab.
2) SOi may desorb or absorb from the rain sample such
that analysis reflects atmospheric levels of S0» in
the laboratory rather than the sample environmental
conditions.
Since acidic solutions shift the partioning of the
SO»/HSOa/SO» equilibrium towards gaseous SO* (Taylor et
al., 1992), the HS0a contribution to the charge balance of
weekly samples of Western Washington rains is expected to be
small away from emission sources.
67
-------
The Wet-Dry Sampler as a Source of Rain Composition
Variabi1ity.
The sampler contributes to variability in measured
precipitation quality because o-f uncertainty in the operation
of the precipitation detector. If rainwater composition varies
during the period of rainfall, the measured composition will be
a function of the period during which the sample is collected.
The rainwater samplers used in this project detect
precipitation using a sensor grid overlying a heated plate.
Accumulation of a sufficient volume of rainwater bridges the
gap between the plate and sensor, completes an electrical
circuit which energizes a motor to move the lid from the wet
bucket exposing it to precipitation. The samplers used in this
study were of two slightly different designs. The samplers at
the Tolt Reservoir and West Seattle required a slightly larger
rain volume to actuate the lid than the other locations. To
test the combined effect of sampler design and bucket wash
consistency on measured rainwater composition, two samplers of
different sensor design were co-located at haple Leaf reservoir
during the Summer of 1982. The results of ths comparison are
presented in Table 16.
68
-------
Table 16 presents two types of sources o-f measurement
uncertainty in these rainwater data: analytical and sampling.
Co-located sampling variability includes both analytical and
sampling variability. With the exception o-f potassium and
trace metals, these results indicate that the combined sampling
and analysis related variability ranges from 8 to 29 percent
¦for the species analyzed. These tests show that two analyses
display lower relative variability for colocated samplers than
for identical split samples for unknown reasons. The potassium
analysis is not precise enough to justify any conclusions.
TABLE 16
Variability in Rain Sampling by Fraction Difference for Analysis,
Sampling and Site Location by Analyte
Species
S0« (mg/1)
Cl-(mg/l)
NOs as N(mg/1)
NH« as N(mg/1)
Na (mg/1)
Ca (mg/1)
K (mg/1
Mg (mg/1
Sample Volume (ml)
Conductivity
(uS/cm)
pH-lab (pH units)
pH-field(pH units)
Analytical*
X Y
.04 (.032)
.13 (.021)
.01 (.001)
.12 (.003)
.11 (.013)
.32 (.015)
.87 (.012)
.19 (.003)
.01 (.142)
(.03)
Co-located*~
X Y
.20 (.767)
.12 (.113)
.12 (.279)
.28 (.069)
.22 (.083)
.23 (.047)
.67 (.081)
.29 (.036)
.13 (18.4)
.08 (1.94)
(.03)
(.10)
Where: X ¦ Difference/Average and
Y ¦ Difference in Specified Units
(X and Y are absolute values)
~Analytical Uncertainty determined from split samples.
•~Colocated samples collected 5 meters apart at Maple Leaf.
69
-------
We have compared our precision and accuracy to that of the
Canadian program, CANSAP and to the EPRI program, SURE. CANSAP
reports uncertanties as about 0.1 pH unit, 20 per-cent on
chemical analysis, with variability due only to collection of
5—80 per-cent and variation due to siting -for nitrate and 10 to
30 pet—cent for sulfate. Calcium and potassium displayed the
largest relative variability for their data, similar to this
study CBarrie, 1982).
An analysis of EPRI-SURE precipitation chemistry data for
colocated samples indicated the following ratios or fractional
error in analysis for the following ions in table 17 (Topol,
1982).
Table 17
Fractional Error for Colocated Samples
Conduct. S0« N0» CI NH« Na K Ca fig A1
.06 .05 .05 .11 .08 .18 .43 .16 .13 .37
pH (error in pH units): 0.06
We conclude that the analyses used in this program suffice
to quantify the acid deposition in Western Washington. The
analytic precision for trace metals was low enough to reduce
confidence in assigning sources to the acid deposition.
Increased sensitivity is needed for trace metals and this may
be improved by acidifying the samples prior to storage and
analysis. Inductively coupled plasma analysis may also improve
sensitivity over AA for some trace metals.
70
-------
APPENDIX B
Frequency of Occurrence of Rainwater Concentrations, Volume, Conductivity,
and Deposition Quantity by Sampling Location
-------
HYDROGEN ICN DEPOSITION
FREQUENCY
.8 1.2 1.6 2.0 2.4 2.8 3.2 9.6
MCftOEQUXVflLENTS PER SOJflRE METER PER HEEK
fmSNIUH ICN DEPOSIT ICN (CALCULATED US N)
FREBUEJCY PERCENT
a
EU
1.0 2.0 3.0 4.0 S.0 6.0
27
*5
¦Z2
-20
18
16
14
13
11
9
7
5
4
2
0
H0-N/8QUPRE METER PER HEEK
FIGi'RE 21 : Frequency of Occurrence at Maple Leaf
-------
HYDROGEN ICN DEPOSITION
FREQUENCY PERCENT
¦29
*¦23
-26
¦24
¦22
¦20
¦11
• n~i n
HICROEOUIVflLENTS PER SQURRE METER PER HEEK
AMMONIUTI ICN DEPOSITION (CALCULATED BS NJ
FREQUENCY PERCENT
25 r r45
Q
¦27
18
9
1.0 2.0 3.0 4.0 5.0 6.0
MG-N/SOUflRE METER PER HEEX
FIGURE 20 : Frequency of Occurrence at West Seattle
-------
HYDROGEN ICN DEPOSITION
FREQUENCY
17,
urn
.4
1.2 1.6 2.0 2.4
PERCENT
-33
37
^34
¦32
¦20
Y28
¦2S
-23
-21
18
f-16
•14
11
9
7
5
2
0
HICROEQUIVflLENTS PER SQURRE METER PER MEEK
pmONIUH ICN DEPOSITION (CflLDJLflTED AS N)
FREQUENCY
IS
14
13
12
11
10
9
8
7
6
S
4
3
2
1
0
I
PERCENT
.5 1*0 1.5 2.0 2.5 3.0 3.S 4.0 4.5
HG-N/SQUflRE METER PER HEEX
FIGURE 22 : Frequency of Occurrence atBellIngham
-------
HYDROGEN ICN DEPOSITION
FREQUENCY
17
16
IS
14
13
12
11
10
9
6
7
6
5
4
5
2
1
0
•5 1.0 1.5 2.0 2.5 9.0 5.5 4.0 4.5 5.0 5.S
MCROEOUIYflLENTS PER SQUARE METER PER MEEK
PERCENT
—r33
-31
¦29
-27
¦25
¦23
¦21
19
17
H6
14
12
10
h 8
¦ 6
¦ 4
2
0
flMMONIUI ION DEPOSIT ICN (CALCULATED RS N]
FREQUENCY PERCENT
9i rl7
n
0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0
KG-M/SQURRE PETER PER MEEK
FIGURE 23 : Frequency of Occurrence at Tolt Reservoir
-------
SULFATE ICN DEPOSITICN CCfiLCULflTED RS 6)
FREQUENCY PERCENT
2S| r45
20
15
10
l~i <—' l
¦26
¦27
19
9
0 5 10 15 20 25 90 35 40 45 50
HG-S/SOUfiRE METER PER WEEK
N1TRRTE ION DEPOSITION (CALCULATED RS N)
FREQUENCY
PERCENT
1*0 2*0 9*0 4*0 5*0 6*0 7*0 9*0
KH4/SQURRE METER PER MEEK
FIGURE 24 : Frequency of Occurrence at West Seattle
-------
SULFATE ICN CEPOSITICN (CALCULATED AS 8)
FREQUENCY
13
m
OD-S/SOUARE METER PER MEEK
NITRATE ICN CEPOSITICN (CALCULATED AS N)
FREQUENCY PERCENT
10i ria
16
H4
13
11
9
7
5
4
2
0 1-0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0
MG-N/SQUARE METER PER MEEK
FIGURE 25 : Frequency ot Uccurrence at Maple Leaf
-------
SULFATE ICM CEPCSITICN (CALCULATED AS 8)
FREQUENCY
PERCENT
LL
0 2 4 6 e 10 12 14 16 18 20 22 24 26
MG-S/SOUARE METER PER MEEK
NITRATE ION DEPOSITION (CALCULATED AS HJ
FREOUENCY
12
>
nO-H/SQUARE METER PER WEEK
FIGURE 26 : Frequency of Occurrence at BellIngham
-------
SULFATE ICN GEPOSITICN ICSLOJLATcD AS S)
FREQUENCY
10
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32
MG-S/SQUARE METER PER WEEK
NITRATE ICN 0EP0SITICN (CALCULATED AS N)
FREQUENCY
12
HG-N/SQUARE HETER PER KEEK
FIGURE 27 : Frequency of Occurrence at Tolt Reservoir
-------
FREOUENCY
7,
PERCENT FREOUENCY
-23 »
4.00 4.30 4.
n
60 4.90 5.20
¦20
16
13
10 B
g
7
3
0
LAB PH
5000 10000
SAMPLE VOLUME (ML)
PERCENT FREQUENCY
19
4 8 12 16 20 24 28 32 38
LAB CONDUCTIVITY tUS/D1)
PERCENT
- 9
.20 4.50 4.80 5.10
FIELD PH
FIGURE 28 : Frequency of Occurrence at West Seattle
-------
PERCENT FREQUENCY
¦15 25
4.05 4.25 4.45 4.65
LAB PH
0 1000 2000 9000 4000 5000
SflMPLE VOLUME (ML)
PERCENT FREQUENCY
6 10 14 18 22 26 30 34 38
Lfi8 CCNCUCTIVITY (US/011
3.50
3.80 4.10 4.40
FIELD PH
4.70
FIGURE 29 : Frequency of Occurrence at Maple Leaf
-------
FREQUENCY
7.
£ 3
4.00 4.90 4.
PERCENT FRECUENCY
-23 30
II
60 4.90 5.20
¦20
-16
13
10
7
a
o
PERCENl
€8
LflB PH
smPLE voluhe cnu
FREQUENCY
6
PERCENT FREQUENCY
4 8 12 16 20 24 28 92 96
LflB CONDUCTIVITY tUS/Ot)
PERCENT
9.30 4.20 4.50 4.80
FIELD PH
5.10
FIGURE 30 : Frequency of Occurrence at Bell Ingham
-------
FREQUENCY
81
7
6
5
4
9
2
1
PERCENT
-18
FREQUENCY
PERCENT
IS
14
11
9
-• 2
3.80 4.20 4.60 5.00
LPS PH
5.40
14
r27
13
—
-25
12
-
¦23
21
•
-21
10
¦
•19
9
¦
•17
8
»
•15
7
•
¦14
6
•
•12
5
•
•10
4
•
• 8
3
»
—
• 6
2
1
ft
>
. . . H
¦ 4
* 2
°c
3000
6000
9000 12000
8PMPLE VOLUME (ML)
FREQUENCY
PERCENT FREQUENCY
0 5 10 15 20 2S 30 35 40 45 50
inn
LAB CONDUCTIVITY (US/CM
FIELD PH
FIGURE 31 : Frequency of Occurrence
at Tolt Reservoir
-------
aiTasTE
FREGUENCY
25
CHOICE
PERCENT FREOENCY
40 80 120 160
CONCENTRATION (UEQ/L)
40 80 120 160 2C0 240 230
CONCENTRATION (UEQ/U
SULFATE
FREQUENCY
13
12
11
10
8
8
7
6
5
4
3
2
1
AMMONIUM
PERCENT FREQUENCY
r28
PERCENT"
"tmn rfjj
•24
-22
19
n
is
13
11
9
6
« ¦ i
0 60 120 180 240 300 360
n IT
0 10 20 30 40 50 60 70
CONCENTRATION (UEQ/L)
CONCENTRATION (UEQ/LJ
FIGURE 32 : Frequency of Occurrence at West Seattle
-------
NITRATE
FREOZNCY
25
1
C2-2SIES
PERCENT FRE5UECT
52
0 20 40 60 80 100 120
CONCENTRfiTXCN (UEQ/L J
n . fl . .
0 40 80 120 160
CONCENTRATION CUEO/L)
SULFATE
AMMONIUM
PERCENT FREQUENCY
52 90
0 40 80 120 160 200 240
CONCENTRATION (UEQ/L)
0 20 40 60 80 100 120
CONCENTRATION (UEQ/L)
FIGURE 33 : Frequency of Occurrence at Maple Leaf
-------
NITRATE
FREQUENCY
7i
CKLCR1CE
PERCENT FRESLSCY
rZO 25
miL
2 6 10 14 18 22 26 30 34 98
CONCENTRATION (UEQ/U
17
14
11
9
6
9
0
0 10 20 90 40 50 60 70 80
CONCENTRATION (UEQ/L)
SULFATE
FREQUENCY
7
AMMONIUM
PERCENT FREQUENCY
L
15 25 95 45 55
CONCENTRATION (UEQ/L)
r20
7
¦17
K
•14
5
•11
i4
•9
I9
• 6
2
• 9
1
°0
PERCEN1
rZO
mi
17
14
11
9
6
4 8 12 16 20 24
CONCENTRATION (UEQ/U
FIGURE 34 : Frequency of Occurrence at BellIngham
-------
NITRfiTE
FREQUENCY
DLCRIDE
PERCENT FREQUENCY
fERCEN-
10 20 30 40 50 60 70
8 12 16 20 24 28 32
CCNCENTRflTICN (UEQ/L)
CCKCENTRflTICN (UE3/L)
SULFATE
FREQUENCY
13
AMONIUM
FREQUENCY
30
1
CONCENTRATION tUEQ/LJ
CONCENTRATION (UEQ/L)
FIGURF 35 : Frequency of Occurrence at Tolt Reservoir
-------
SCOIUM
LL
calcium
PERCENT FREQUENCY
85 2
40 80 120 160 200 240
CONCENTRATION (UEQ/L)
0 5 10 15 20253035404550
CONCENTRATION (UEQ/L)
POTASSIUM
FREQUENCY
25
MAGNESIUM
PERCENT FREQUENCY
63 a
2 4 6 a 10 12 14 18
CONCENTRATION (UEQ/L)
PERCENT
88
10 20 SO 40 50 80
CONCENTRATION (UEQ/L)
FIGURE 36 : Frequency of Occurrence at West Seattle
-------
sodium
FREQUENCY
25
CSLCIUM
PERCENT FREQUENCY
56 5
-22 g 10
0 40 80 120 160
CONCENTRATION (UEQ/L)
n
0 10 20 90 40 50 60
CONCENTRATION (UEQ/L)
POTASSIUM
FREQUENCY
25
MAGNESIUM
PERCENT FREQUENCY
0 2 4 6 8 10 12 14 16 18 20
CONCENTRATION (UEQ/L)
mo
4 8 12 16 20 24 28 32 36 40
CONCENTRATION (UEQ/L)
FIGURE 37 : Frequency of Occurrence at Maple Leaf
-------
SOOIUH
FREQUENCY
14
13
12
11
10
9
8
1,
6
5
4
3
2
1
0
CflLCIUI
PERCENT FREQUENCY
•
B
»
•
*
4
J
¦
9
•
•
¦
»
•
•
1 1
40
0 5 10 15 20 25 90 35 40 45
17
14
,1
9
6
3
0
]
CONCENTRATION (UEQ/U
CONCENTRATION (UEQ/U
POTASSIUM
FREQUENCY
MAGNESIUM
PERCENT FREQUENCY
5|-
4
3
2
lh
D
29
-26
¦23
-20
17
15
12
9
6
3
PERCENT
1.0 2.0 3.0 4.0 5.0
10 12 14 16
CONCENTRATION (UEQ/U
C0NCENTRAT1CH (UEQ/U
FIGURE 38 : Frequency of Occurrence at BellIngham
-------
sooiun
FREQUENCY
lOi
9
8
7
6
5
4
3
2
1
0
caxiun
PERCENT FREQUENCY
18
0 4 8 12 16 20 24 28
CONCENTRATION (UEQ/L)
10 12
CONCENTRATION (UEQ/L)
POTASSIUM
FREQUENCY
MAGNESIUM
PERCENT FREQUENa
42 jtj
0 1.5 3.0 4.5 6.0 7.5 9.0
CONCENTRATION (UEQ/L)
CONCENTRATION (UEQ/L)
FIGURE 39 : Frequency of Occurrence at 'iuit Reservoir
-------
APPENDIX C
Pa1rw1se Correlation Coefficients and Results of Factor Analysis
-------
varihax rotated factor hatrix
APfE* ROTATI3H WITH KAISER NORMALIZATION
fACTCa l" FACTOR 2 FACTOR 3" FACTOR 4
NH4
.74490
•25838
.95469
.38762
M03
.87429
. .2008 0
.25902
•16850
sotxs
•80215
• 29355
.35531
-•09453
AS
•C0923
•19821
.7018 6
•18456
~CU
.11144
-•OU334
.2865 4
-•06442
re
• 49102
•31907
.73492
•12640
CA
.29146
•49963
.76917
-.13178
PIG
.18813
•87375
.33789
-.12996
~K
" .55765
•*7440
-.06237
.20350
CL
.14196
. .93i
-------
VARIHAX ROTATED FACTOR MATRIX
AFTER ROTATION WITH KAISER NORMALIZATION
. FACTOR 1 FACTOK 2 FACTOR 3 FACTOR 4
NH4
• 90550
_ .01699 .
•10334
.21267
"H03 "
•*3352
•UU397
.11684
*15743
SQ4X*
*85514 ..
• 0U166 __
*00818
*28933
AS '
.23385
.07485
*10362
.49262
CU
-.02187
r?i7#3« ..
.32760 .
.18663
PB
• t6849
•10521
.49634
.19562
CA
.47845
.16201
•26102
.65288
HiS '
*(.2440
•949*6
-*00124
*06308
K
.*48113
... .*13724
• 83939
*08385
"£l
-.17022
.99362
-.09992
.02763
HA
.06749
.79712
.04135
.07181
44
* ".92389
-.033 84
.22692
.13*22
FACTOR EIGENVALUE »CT D* YAR __CUN PCT
1 5*22816 18.? 56,2
2 2*59861 29,9 87.2
3 .70977 7.9 95.1
4 .4*012 4.9 100*0
VARIABLE COftMJNAllTY
HH4 #87612. .
*03 "" .90990
£0*X$ . »81534
"AS .31370
CU _ .17445
>8 .74256
CA ...74955
HG .90916
_K *9.1247
CL 1.00296
NA_ .64653
"HH "* " *92396
Tolffcese/voir
-------
VARIHA X ROTATED FACTOR HATRIX
.A^U* .ROTATION with .kaiser normalization
FACT OR I "factor"" Z *F ACTOR~ 3 ~ fTcTOR ~ 4 FACTOR 9
NH4 .01109 .83599 .10166 .11960 .16035
"03 .02324 .95312 _ .10132 .26244 _#13292
S04XS .13632 .35803 ' .16297 .97197 .52272
AS .10768 , .02161 _ .76041 .Q3b94 -,02005
-U .03539 .11879 .03947 .06644 .75164
_£B • €6877 .41379 _ .04279 .. _ .22981. .23966
CA .17761 .50333 .31327 .12503 .36830
H6 . 94548 .05491 .12273 .09647 -.07327
K .<7897 .19392 .03127 .39940 .21313
Ct .954 1 8 -.1*5142 .04471 -.08393 .09654
HA .94407 .04067 " " .09452 ~ .03595 .03811
HH .06208 _ .20848 _.11401 .82751 .04672
FACTOR EIGENVALUE >CT 3F VAR "cuh >CT
Utef-SecfHe
VARIABLE C0MUNAL1TT
NH4 .74926
NQ3 _ 1.00579 .
S04XS"" " .77414
AS _ _ „ .99159
"CU~ ~ " .65353
l»B .99649
"CA * ~ - .53^30
-------
— __YAgIKAX ROTATED FACTOR HATRIX
AFTER ROTATION WITH KAISER NORMALIZATION
factor. i..._factor .2 ..factor 3 .factor 4 factor 3
NH4
-.03988
.07193 ..
.23614
•07096
.17369
N03
.(6391
.73406
.44187
•49263
.02269
S04XS
"> C1443
*36761)
.30169
_ ,95210
•43924
AS
.16126
-.06743
.09299
.04303
.43033
_GU
. 41472
.. 49270
.•00079
..11932
-.17463
FB
-.08819
.22633
.84304
.19347
.03271
. CA . ...
_ .. 16500
. »49J93
.28463
. .21273
.46083
HG
.93370
.00422
.09796
-.00164
.11329
*
. »16399
•09643
• 7668 3
•12937
•19244
CL
.99646
•037*6
-.U3063
-•08596
•06179
NA
• £6343
.13365
~06130
•09549
•12336
. ..HH
_ -.02767
•19436
.47424
•62820
•10228
FACTOR EIGENVALUE FCT.DF YAR CUH-ECT
1 - 4.33529 30.4 M.4
2 2.67514 31*1 81*9
3 *13112 .9.7 91.2
4 .47408 9.9 96.7
.3 — . ... *28278 3.3 inb.O.
_VAIUAIU6 COHHUNALXTT .
SM4_ .89377 .
N03 *98132
_S04XS #72060 .
AS .22019
_JLU .30U63
FB .80422
£i 07193
KG .90875
K .67798
Cl" 1.00647
_JA .79202
HH .79634
Htllwfham
-------
Coffe (dff&vj CoeffiaeAth
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111
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mi .Nin i.um -ki4iil .tint .Hill ,ithi .ii»ii " .*»}•* .•!>» ,imi
Cl •.Mill -.Mil* !.•»»• •.«!»» tltHi _-•>*»!» ftlUI .(istil .ONt .fUti
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1H"~
-------
Appendix D
Excess Cation Concentrations (mg/1) (based on C1-) *52 weeks
Bell Ingham
Volume Weighted Average
Na (-.001)
Mg .004
K .028
Ca .043
West Seattle *
Volume Weighted Average
Na -.067
Mg .002
K .012
Ca .112
Maple Leaf*
Volume Weighted Average
Na (-.022)
Mg .004
K .015
Ca .094
Tolt River
Volume Weighted Average
Na (-.003)
Mg .006
K .020
Ca .037
Linear Average
Nax .02
Mgx .006
Kx .045
Cax .068
Linear Average
-.018
.010
.034
.178
Linear Average
.008
.012
.042
.154
Linear Average
.024
.007
.032
.049
-------
Appendix E
King County Emission Inventory (tons/yr), 1980
Source SOx
Fuel Combustion 22024
Industrial
Processes 640
Solid Waste 1
Disposal
Transportation 3091
Slash burning
NOx
8700
1052
41796
67
King County
Total
25756 tons/yr 51617 tons/yr
Pierce County Emission Inventory, 1980
Source SOx NOx
1. Fuel Combustion 12102 6808
2. Industrial
Processes 88351 175
3. Solid Waste
Disposal 2 3
4. Transportation 1186 14575
5. Slash burning 1 26
Pierce County
Total 101,642 tons/yr 21,587 tons/yr
-------
1980 Two County SOx and NOx Emissions
SOx NOx
King 25,756 51,617
Pierce 101,642 21,587
Total 127,398 73,204 tons/yr
1979 Four County SOx and NOx Emission
King, Pierce, Kitsap and Snohomish Counties
SOx NOx
136,195 92,313
King and Pierce Counties, Percent of 4 County Total:
SOx ¦ 93.5%
NOx - 79.35
Comparison of Major Point Sources to Two County Total Emission
1. Auto/Transportat1on (NOx)* 14,575 Pierce
41,796 King
56,371 tons/year
775 of 2 County NOx ¦ transportation
2. Smelter (S02) ¦ 87,178 tons/yr
685 of 2 County S02 ¦ Smelter
-------
Appendix F
PROCEDURES FOR ACID RAIN SAMPLING
1. Scrub the inside of the collection bucket and lid, using a new or
very clean brush which will be set aside and used only for this
purpose. Disposable kimwipes may also be used. No tap water or
soaps should ever be used on any acid rain equipment. Only deionized
water shall be used and the conductivity of the deionized water should
be less them or equal to 1.5 umhos/cm. This check should be made
before any washing or rinsing is started. A small amount of baking
soda can be used as an aid in scrubbing. When scrubbing is completed,
rinse the bucket and lid with deionized water at least three times.
NOTE: To develop proper field and lab technique, great care should
be taken to prevent touching the inner surface and rim of
the bucket and lid. Disposable plastic gloves are reocmmended
for in-lab work with the buckets to prevent accidental con-
tact while scrubbing. For the same reason, the lid should
always be set down with the inside up.
2. After scrubbing and rinsing the bucket is ready for the acid rinse.
Add a workable amount of 0.5 N BC1 and carefully swirl. The dilute
acid should contact the entire inner surface of the bucket. Let
stand for 15 minutes. Slowly empty while turning the bucket to once
again cover the entire inner surface and the entire rim of the bucket.
Rinse thoroughly at least three times with deionized water contacting
all inner surfaces and entire rim. Allow the last rinse to sit in
the bucket for at least one hour. At the end of this time, check the
conductivity of the last rinse water. If the conductivity is greater
than 1.5 unhos/cm., repeat the deionized water rinse process. If
the conductivity is less than or equal to 1.5 unhos/cm, save an
aliquot of the final rinse in a new and previously (deionised water)
rinsed Nalgene sample bottle. Label this last rinse sample as it is
to be analyzed as a background for the rain sample later collected in
that bucket.
NOTE: Use only reagent grade hydrochloric acid for the acid rinse.
The bucket lid does not go through the acid rinse process
as it might damage thesealing gasket.
3. Check the conductivity of the deionized water before filling the
carboy and after the water domes out of the earboy spigot. The
readings should both be less than or equal to 1.5 umhos/cm. and no
more than a 10% difference between the two readings. Sample bottles
(new Nalgene only) should be rinsed in the lab, using only water from
the carboy as this is the only water touras in the field. Rinsing of
the sample funnel and graduate cylinder between samples should be
done only with water from the carboy. The "clean* or sample funnel
and graduate cylinder should be kept separate from other equipment
and stored in a clean plastic bag during transportation and storage
to prevent contamination.
-------
FIELD PROCEDURES FOR ACID RAIN SAMPLING
1. Check sampler operation. If closed, use a piece of metal to
short the sensor; it should ojSin. If it is raining at the time
of collection and the sampler is open, remove the water from the
sensor; it should close. Note the status of sampler (open/
closed), operability, weather conditions, date and time. Care-
fully remove wet-side sample bucket and repalce with clean acid-
rinsed bucket. Put the lid frSm the clean bucket on the just
removed wet-side bucket and caxxy the covered sample to the van
to prevent spillage or contamination. When handling the sample
buckets and lids, cue must be taken to avoid touching any
surface that may eventually come into contact with the sample.
2. Remove the chart paper from the rain gauge. Record the time and
date on the chart paper. Using the "dirty" or non-sample graduate
cylinder (and funnel if desired), measure the volume of the rain
gauge sample and record this on the chart paper. Do the sane with
dry-side bucket of the samplers These samples are discarded.
Replace the rain gauge chart paper carefully, wind the gauge chart
drive timer (do not overwind) and refill the pen with ink if needed.
The chart must start on Monday, to enable the gauge to record properly
for seven days. We will be collecting on Tuesdays, but agny cor-
rections will be made later. Do not engage new chart until the
guage bucket has been emptied. Engage pen to new chart and add a
starting spike with the pen to ensure proper ink flow. Close the
door to the rain gauge housing, and make sure the lid to the rain
gauge is secure.
3. Carefully replace sampler batteries with freshly charged batteries.
Disengage both used batteries, taking care to prevent shorting the
battery by touching contacts, and remove. Place fresh batteries
in position and carefully attach leads to posts. Replace and
secure battery lids. Finally, check to see that sampler is opera-
tional .
4. Wiile in the van, record in a bound log book the information pre-
viously recorded on the rain gauge chart paper. Do this while
your field conductivity meter i,s warming up. Also record the
sampler status (open/closed), operability and weather conditions.
Record also the field measurements about to be taken. Make a
note of the condition of the actual sample, looking for dust or
soil particles, leaves, bugs, bird excrement, a ring in the bucket
or anything notable. Remove the "clean" graduate cylinder^and
funnel from plastic bag and rinse with water from the carboy.
Rinse all inner surfaces of the graduate and slowly rotate while
emptying to rinse the entire rim. Carefully handle only the
outside surface of the funnel while riasing and only the upper
portion of the funnel as the outside surface of the spout will
contact the sample when filling the sample bottles. Be sure to
rinse the outside of the spout too. Rinse the graduate and
funnel three times. Do not jonpty the last rinse from the graduate.
Place the rinsed funnel ups
-------
Field Procedures for Acid Rain Sampling
contact) surface up.
Rinse the conductivity probe and tube used for measurements
several times and then take a reading. The conductivity of the
rinse water should be less than or equal to 1.5 umhos/cm, «n
------- |