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OCR for page 133
4
Assessment of Exposure to
Organophosphorus
Compounds, Carba mates, and
Volatile Organic Chemicals
This chapter reviews methods for assessing exposure to organophosphorus
compounds, carbamates, and volatile organic chemicals. It also provides
orientation on the concentrations that could be encountered in water and on
the resulting human exposures to them, and it indicates the importance of
considering not only ingestion but other routes of exposure, such as skin
contact and inhalation. Later chapters use these compounds to illustrate some
toxicologic considerations of mixtures in drinking water.
Analytic methods for organophosphorus compounds and carbamates in
water are well developed and standardized. An EPA method (EPA, 1984)
for the determination of carbamates uses direct-injection high-performance
liquid chromatography (HPLC). Less than 1 ml of a sample of filtered water
is directly injected onto a reversed-phase HPLC column, and separation is
achieved by gradient elusion chromatography. The eluted compounds are
hydrolyzed and then react with o-phthalaldehyde to form a fluorescent de-
rivative, which is analyzed with a fluorescence detector. Although the de-
tection limits for specific compounds in water vary, they are typically about
1 ~g/liter for aldicarb, propoxur, carbaryl, carbofuran, and methomyl. Fail-
ure to detect a pesticide of the organophosphate or carbamate class known
to be a potential contaminant of a specific water supply might not signify
its absence; the pesticide might have hydrolyzed or undergone other chemical
changes to other toxic substances, or the detection limit used in the analysis
might have been too high.
An EPA method (EPA, 1986) for the assay of organophosphorus insec-
ticides in water involves collection of a water sample, extraction of the sample
with 1 liter of methylene chloride, concentration of the extract, and analysis
133
OCR for page 133
134 DRINKING WATER AND HEALTH
by gas chromatography with a capillary column and a nitrogen-phosphorus
detector. For the typical organophosphorus insecticides diazinon, disulfoton,
fonofos, and terbufos, the detection limit is about 1 mg/liter. The organo-
phosphorus and carbamate insecticides hydrolyze at various rates in water,
and in some cases their hydrolysis products are of toxicologic concern.
Maximum contaminant levels (MCLs) ranging from 0.002 to 0.75 ma/
liter, depending on the compound, have been promulgated by EPA for the
following volatile organic chemicals (VOCs) and became effective January
9, 1989: benzene, vinyl chloride, carbon tetrachloride, 1,2-dichloroethane,
trichloroethylene, p-dichlorobenzene, 1,1-dichloroethylene, and 1,1,1-trich-
loroethane. There was already an MCL of 0.1 mg/liter for total trihalome-
thanes (THMs), a class of VOCs that includes chloroform, bromoform, and
the mixed chlorobromomethanes. The THMs and VOCs are measured by
purge-and-trap gas chromatography with estimated method detection limits
(MDLs) of about 0.2-1.9 ~g/liter (EPA, 1987a).
OCCURRENCE OF ORGANOPHOSPHORUS COMPOUNDS AND
CAR BAMATES I N OR I N Kl NG WATER
Several surveys have compiled data on concentrations of organophosphorus
compounds and carbamates in surface waters, groundwaters, and, in some
cases, completely treated ("finished'') or well waters. Typically, their con-
centrations are 1 ~g/liter or less (often undetectable), although substantially
higher concentrations have been found in isolated instances. Kelley et al.
(1986) showed that many commonly used pesticides, including carbamates
and organophosphorus compounds, leach into groundwater. Typical concen-
trations in ~groundwater in Iowa were 0.5-2.0 ~g/liter, although some wells
had total pesticide concentrations of 20 ~g/liter.
Data collected by various regulatory agencies are entered into the EPA
surface-water and groundwater data base, including data on several pesti-
cides. Such data have been summarized in health advisories prepared by
EPA (1987b) for some of these pesticides. These and other data on various
carbamate and organophosphorus insecticides are presented here to provide
perspective on the concentrations of pesticides encountered in drinking water
in several studies.
Aldicarb
In 17 of 106 wells sampled in California. aldicarb was detected at up to
14 parts per billion (ppb, equivalent to ~g/1) (NRC, 19861. In the 15 states
where aldicarb was found in groundwater~ it was found typically at 1-50
~g/liter (Cohen at al., 19861.
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Organophosphorus Compounds, Carbamates, and VOCs 135
Carbary'
Carbaryl has been found in 61 of 522 surface water samples and 28 of
1,125 groundwater samples in eight states (EPA, 1987b). In samples with
detectable concentrations, the 85th-percentile concentrations were 260 fig/
liter in surface water and 10 ~g/liter in groundwater. The highest concen-
trations were 180,000 ~g/liter in surface water and 10 ~g/liter in ground-
water.
Carbofuran
Carbofuran has been found in groundwater in three states, typically at 1-
50 ~g/liter (Cohen et al., 19861.
Dazlnon
Diazinon has been found in 13 wells (total number sampled not available)
in California at up to 9 ~g/liter (NRC, 1986, p. 201. It has been found in
7,230 of 23,227 surface-water samples and 115 of 3,339 groundwater sam-
ples in 46 states (EPA, 1987c). The 85th percentile of detectable concentra-
tions was 0.2 mg/liter in surface water and 0.25 ~g/liter in groundwater.
The highest concentrations were 33,400 ~g/liter in surface water and 84 fig/
liter in groundwater.
Fonofos
In Iowa, fonofos was detected in about 2% of the samples at a typical
concentration of 0.4 ~g/liter; the maximum was 0.9 ~g/liter (Kelley et al.,
1986).
It was detected in groundwater in California at 0.01-0.03 ~g/liter (EPA,
1987d).
Malathion
Malathion has been detected in five wells (total number sampled not avail-
able) in California at up to 23 ~g/liter (NRC, 1986, p. 201.
Methy' parathion
Methyl parathion has been found in 1,402 of 29,002 surface-water samples
and 25 of 2,878 groundwater samples in 22 states (EPA, 1987e). The 85th
percentile of detectable concentrations was 1.2 ~g/liter in surface water and
OCR for page 133
136 DRINKING WATER AND HEALTH
1 ~g/liter in groundwater. The highest concentrations were 13 ~g/liter in
surface water and 1 6 ~g/liter in groundwater.
Terbufos
In one study in Iowa, terbufos was found in 5% of the samples at a typical
concentration of 5.4 ~g/liter; the maximum was 12 ~g/liter (Kelley et al.,
19861. It has been found in 444 of 2,106 surface-water samples and 9 of
283 groundwater samples in five states (EPA, 1987f). The 85th percentile
of detectable concentrations was 0.1 ~g/liter in surface water and 3 ~g/liter
in groundwater. The highest concentrations were 2.3 ~g/liter in surface water
and 3 ~g/liter in groundwater.
OCCURRENCE OF VOLATILE ORGANIC COMPOUNDS IN
DRINKING WATER
There have been several surveys of THMs and VOCs in surface waters,
groundwater, and finished water supplies. The straight lines fitted to results
of an early EPA survey for THMs in finished water supplies of 80 U.S.
cities are shown in Figure 4-1 (EPA, 19751. The median total concentration
of THMs was about 20 ~g/liter, and chloroform usually dominated the other
THMs.
Results of several surveys of VOCs in surface waters and groundwater are
summarized in Tables 4-1, 4-2, and 4-3. Although Table 4-1 shows very
high concentrations of some specific organic chemicals (such as trichloroe-
thylene at 35,000 ~g/liter and 1, 1,1-trichloroethane at more than 400,000
~g/liter), "more commonly, contamination is found at less than 10 ~g/1 with
smaller percentages in the 10-100 ~g/1 and in the 100-1,000 ~g/1 range''
(EPA, 19821. In one national survey, the VOCs most frequently found in
finished groundwater supplies (other than the THMs) were trichloroethylene,
1,1,1-trichloroethane, tetrachloroethylene, cis- and trans-1,2-dichloroethy-
lene, and 1,1-dichloroethane (Westrick et al., 19841. Table 4-2 summarizes
the occurrences of the compounds detected at 186 randomly sampled sites
serving more than 10,000 people each. Differences in median concentrations
shown in Figure 4-1 and Table 4-2 arise largely out of the differences in
sampled supplies. Figure 4-1 includes surface-water supplies, some of which
are likely to be heavily chlorinated, whereas the data in Table 4-2 derive
from groundwater sources, which are less likely to be chlorinated. The dis-
tribution of the summed concentrations of these VOCs, shown in Table 4
3, demonstrates that large systems were likely to exceed a summed concen-
tration of 5.0 ~g/liter slightly more frequently than small systems, as might
be expected from purely statistical considerations. In both their random and
nonrandom samplings, the median concentrations of specific compounds in
OCR for page 133
Organophosphorus Compounds, Carbamates, and VOCs 137
300
100
50
-
z
o
Hi 10
LL
is
o
is
I
IL
o
6 1.0
I
tar
0.5
0.1
-
/
/
/
~1
o l
l
1 1 1 1 ~ I I 1 1 1 1 1 1
2 5 10 20 40 60 80 90 95 98 99
PERCENT EQUAL TO OR LESS
THAN GIVEN CONCENTRATION
FIGURE 4-1 Frequency dis-
tnbution of trihalomethane con-
centrations found in the National
Organics Reconnaissance Sur-
vey (NORS) of halogenated or-
ganic compounds in drinking
water in 80 U.S. cities. From
EPA, 1975.
the positive samples ranged from about 0.2 to 9 ~g/liter. One can conclude
that VOCs other than THMs are normally found at concentrations of less
than 10 ~g/liter- and often less than 1 ~g/liter in finished groundwater
supplies.
ROUTES OF HUMAN EXPOSURE TO CHEMICALS IN
DRINKING WATER
The usual estimates of exposure to contaminants in drinking water are
based on ingestion and are calculated from the standard of 2-liters/day inges-
tion of water by a 70-kg man. Ingestion of 2 liters/day is used to develop
MCLs when the dose-response relationships are known. There has been some
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138 DRINKING WATER AND HEALTH
TABLE 4-1 Occurrence of Volatile Organic Chemicals in Finished
Drinking Watera
No. No. Concentration
Compound SurveybSamples Positive Range, /liter
Trichloroethylene State data''2,894 810 Trace-35,000
NOMSd113 28 0.2-49.0
NSP~142 36e Trace-53.0
CWSS~452 15 0.5-210
Tetrachloroethylene State data''1,652 231 Trace-3.000
NOMSd113 48 0.2-3.1
ASPS142 24e Trace-3.2
CWSS~452 22 0.5-30
Carbon tetrachloride State data''1~659 166 Trace-170
NOMSd113 14 0.2-29
NSP"142 37'' Trace-30
cwsstl452 9 0.5-2.8
I.l~l-Trichloroethane State data''1.611 370 Trace-401.300
NOMS~113 19 0.2-1.3
NSP~142 32'' Trace- 21
CWSS'i452 19 0.5-650
1,2-lDichloroethane State data''1.212 85 Trace-400
NOMS113 2 0.1 - 1.8
NSP'~142 2e Trace-4.
CWSS~451 4 0.5-1.8
Vinyl chloride State data''1.033 73 Trace-380
NOMSd113 2 0.1 -0.18
NSPtl142 7" Trace-76
cwss~f I 1
UFrom EPA. 1982.
hNOMS. National Or~anics Monitoring Survey. 1976-1977: NSP. National Screening Program.
1977- 1981; CWSS. Community Water Supply Survey. 1978 (EPA. 1987~).
''All Round water sources; aggregated from various state reports on local contamination problems.
'~Surface-water and groundwater sources.
''Tentative identification by single-column gas chromatography.
fCompound not surveyed.
effort to determine the effects of variability in the quantities of water ingested
(Gillies and Paulin, 19831. Results of studies in Canada, Great Britain, The
Netherlands? and New Zealand indicate that mean daily intakes, including
those of beverages made with tap water, range from 0.96 to 1.34 liters/day.
In one of the New Zealand studies, the mean intake of 960 ml/day had a
standard deviation of 570 ml/day. A more recent study in the United States
indicated higher water intake (Ershow and Cantor, 19861. Thus, in estimating
the toxic effects of ingestion of water that contains pesticides, one should
consider both the mean and the variability in intake in the population of
interest. Most attention should be paid to persons with the highest intake.
Attention has recently shifted toward exposure to chemical contaminants
OCR for page 133
Organophosphorus Compounds, Carbamates, and VOCs 139
of tap water by routes other than ingestion, including skin contact with and
inhalation of chemicals that volatilize indoors and can be inhaled at the point
of water use or elsewhere or in moves from room to room. Very few data
are available on cutaneous exposure, although Brown et al. (1984) estimated
that bathing can cause exposures in the same range as those caused by the
daily ingestion of 2 liters of the same water.
Field measurements, experimental studies, and models have measured the
volatilization of chemicals found in water used for various purposes, in-
cluding showering and bathing (Andelman, 1985; McKone. 1987~. Estimates
of the resulting inhalation exposures vary, but suggest that showering can
cause about as much exposure as ingestion and that exposure due to all water
uses can be substantially higher than that due to direct ingestion, in part
because the intake of air (about 20,000 liters/day) is about 104 times that of
water.
How quickly and how completely a pesticide or other contaminant in
TABLE 4-2 Summary of Occurrences of Volatile Organic Chemicals at 186
Randomly Sampled Groundwater Sites Serving More Than 10,000 Persons
Eacha
Quantitation Occurrences Median of
Limit, Positives. Maximum.
~Doter /liter
Vinyl chloride 1.0 1 0.5 1.1 1.1
1.1-Dichloroethylene 0.2 5 2.7 0.28 2.2
1,1-Dichloroethane 0.2 8 4.3 0.54 1.2
cis- and trans
1 ,2-Dichloroethylene 0.2 1 3 7.0 1.1 2.0
1,2-Dichloroethane 0.5 3 1.6 0.57 0.95
1, 1,1-Trichloroethane 0.2 15 8.1 1.0 3.1
Carbon tetrachloride 0.2 10 5.4 0.32 2.S
1,2-Dichloropropane 0.2 5 2.7 0.96 21
Trichloroethylene 0.2 2 1 11.3 1 .0 78
Tetrachloroethylene 0.2 21 11.3 0.52 5.9
Benzene 0.5 2 1 . I 9.0 1 5
Toluene 0.5 2 1.1 2.6 2.9
Ethylbenzene 0.5 1 0.5 0.74 0.74
Bromobenzene 0.5 1 0.5 1.7 1.7
m-Xylene 0.2 2 1.1 0.46 0.61
o + p-Xylene 0.2 2 1.1 0.59 0.91
p-Dichlorobenzene 0.5 3 1.6 0.66 1.3
Chloroform 0.2 106 57.0 1.6 300
Bromodichloromethane 0.2 101 54.3 1 .6 7 1
Dibromochloromethane 0.5 96 51.6 2.9 59
Dichloroiodomethane 1.0 3 1.6 1. ~4.1
Bromoform 1.0 57 30.6 3.8 50
aAdapted from Westrick et al., ]984. with permission.
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140 DRINKING WATER AND HEALTH
TABLE 4-3 VOC Concentrations in Random Samples of Finished
Groundwater~
Water Supplies with Summed Concentrations
of VOCs Exceeding Value Shown at Left
Summed Systems Serving Systems Serving
Up to 10 000 Persons More Than 10 000 Persons
Concentrations of
VOCs, ~g/liter No. % No. %
Quantitation limitb 47 16.8 52 28.0
1.0 20 7.1 26 14.0
5.0 8 2.9 12 6.5
10 5 1.8 7 3.8
50 1 0.4 1 0.5
100 0 0 0 0
Adapted from Westrick et al.. 1984. with permission.
hQuantitation limits not same for all compounds. In most cases. quantitation limit is either 0.2
~/1 or 0.5 ~/1. This difference in quantitation limits can confuse interpretation of data somewhat
so results of survey should be viewed with differing quantitation limits in mind. Occurrence is
any specific finding at, or in excess of. the quantitation limit.
drinking water will volatilize depends on its physical and chemical properties,
including its solubility in water, its vapor pressure, its Henry's law constant
(H), and its coefficient of diffusion in water at the water-air interface (An-
delman, 1985), as well as physical characteristics of the water, such as
temperature, agitation, and spraying. The constant H is equal to the ratio of
the equilibrium concentration in air to the concentration in aqueous solution.
The vapor pressures of carbamates and organophosphorus compounds are
low, as are their H values. Other aqueous insecticides, such as dieldrin and
aldrin, can readily volatilize from water-air interfaces, although probably at
lower rates than compounds (such as benzene and toluene) that have higher
H values (Mackay and Leinonen, 19751. Polychlorinated biphenyls (such as
Arochlor 1242) and chlordane volatilized from water surfaces at about 20%-
30% of the rate of oxygen in reaeration studies, but dieldrin, which has a
substantially lower H value, volatilized at only 1%-5% of the oxygen reaer-
ation rate (Atlas et al., 19821. The H values of specific organophosphorus
and carbamate compounds vary, but many are low. On the basis of their
water solubilities and vapor pressures, one can calculate H values at room
temperature of 2 x 10-6 and 8 x 10-9 atm m3/mol for aldicarb and
carbofuran, respectively. Comparable values for dieldrin, aldrin, and Ar-
ochlor 1242 at room temperature are 2 x 10-7, 1 X 10-5, and 6 x 10-4
atm m3/mol (Mackay and Leinonen, 19751.
In contrast to the organophosphorus and carbamate compounds, the typical
VOC or THM has a relatively large H value at room temperature, generally
OCR for page 133
Organophosphorus Compounds, Carbamates, and VOCs 141
in the range of 10-2-10-3 aim m3/mol (Roberts and Dandliker, 19831.
The mass-transfer rate constants for the VOCs and THMs are also substan-
tially higher than those for the organophosphorus and carbamate compounds,
typically about 60% of that for oxygen reaeration. Thus, one would expect
that substantial fractions of these components would volatilize during typical
indoor water uses and thereby contribute to inhalation exposures, especially
of the person at the point of use, but perhaps of others if the volatile con-
stituents are disseminated by air movement. As has been shown for trichlo-
roethylene and chloroform, volatilization from both showers and baths is
substantial, usually greater than 50% and sometimes as high as 90%, de-
pending on temperature, air flow, and the geometry of the water system
(Andelman, 1985; Andelman et al., 1986, 19871. For the VOCs and THMs
with higher H values, Henry's law equilibrium is generally not attained, so
mass transfer at the water-air interface often limits the rate and extent of
volatilization. A recent attempt to detains whether a surrogate chemical,
sulfur hexafluoride, could be used to estimate the volatilization of such
constituents associated with indoor water uses (Giardino et al., 1988) was
encouraging, but additional research is required.
CONSI DERATIONS OF TOTAL EXPOSURE
The principal focus of this report is the assessment of toxicity associated
with exposure to mixtures of chemicals in drinking water. But other media,
such as food, are also potential sources of exposure. Exposures related to
nonwater sources, such as exposure to polycyclic aromatic hydrocarbons in
ambient air, can be much greater than those related to water. When human
toxicity associated with exposure through water is assessed, combined ex-
posures through other media have the potential for raising an apparently low
exposure through water to the point where a toxic threshold is exceeded or,
in the case of a carcinogen, a risk is increased.
An early multimedia-exposure analysis for some of the chemicals consid-
ered here addressed the multiple routes and variability of uptake of chloroform
and carbon tetrachloride (NRC, 19781. The exposure data on air, water, and
food in that analysis were often meager and not precise, but the analysis did
use what was known about variability in absorption after ingestion or in-
halation. Table 4-4 shows three hypothetical scenarios for uptake (based on
exposure and absorption) of carbon tetrachloride and chloroform from water,
food, the atmosphere, and the three together. It appears that most exposure
to chloroform at typical levels is by water, whereas air is typically more
important for carbon tetrachloride. However, in any given instance, almost
any route can dominate, so it is essential to consider all sources when one
is assessing individual exposure to a specific chemical and the associated
risk.
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142 DRINKING WATER AND HEAl TH
TABLE 4-4 Adult Human Male Uptake (Based on Exposure and Intake) of
Carbon Tetrachloride (CC14) and Chloroform (CHC13) from Environmental
Sources
Uptake, mg/year
Source CCI ~CHEW
At minimum exposure levelsh
Water and water-based drinks 0.73 0.037
Atmosphere 3.60 0.41
Food 0.21 0.21
Total 4.54 0.66
At typical exposure levels''
Water and water-based drinks 1.78 14.90
Atmosphere 4.80 5 . 90
Food 1.12 9.17
Total 7.70 92.3
At maximum exposure levels"
Water and water-based drinks 4.05 494
Atmosphere 618 474
Food 7.33 16.4
Total 629 9X4
"Adapted from NRC, 1978. pp. 180-181.
Minimum exposure and minimum intake for all sources.
''Typical conditions assumed. For CC1~: water and water-based drinks, exposure at 0.0095 my/
liter and reference-man intake; atmosphere. average of typical minimum and maximum absorption;
Mods average exposure and intake. For CHAIN water and water-based drinks. median exposure and
reference-man intake; atmosphere, average of typical minimum and maximum absorption; foods
average exposure and intake.
'iMaximum exposure and maximum intake for all sources.
CONCLUSIONS AND RECOMMENDATIONS
If joint exposure to THMs or to all VOCs with roughly equivalent potency
could be considered to have additive toxic effects, it would be useful to have
an analytic method for monitoring purposes that could be used as a measure
of the total concentration of members of the group. For example, the sum
of the volatile organohalide concentrations could be measured with a single
instrument, even though it would measure a group of compounds such as
vinyl chloride, carbon tetrachloride, 1,2-dichloroethane, trichloroethylene,
p-dichlorobenzene, 1,1-dichloroethylene, and 1, 1,1-trichloroethane with
widely varied toxic effects. The potential deficiency of such a method is that
other, possibly harmless volatile organohalide compounds in the water sample
would also be detected. In the case of the organophosphorus compounds, it
OCR for page 133
Organophosphorus Compounds, Carbamates, and VOCs 143
is unlikely that a single simple analytic measurement with a gas chromato-
graphic phosphorus detector can be developed that would depend only on
the presence of organophosphorus insecticides, because other, unidentified
phosphorus compounds could be present. The HPLC method described earlier
might be more successful in this regard, but it would have to be shown that
the derivatization procedure is specific to the hydrolysis products of the
carbamates of interest and that other naturally occurring chemicals and their
hydrolysis products would not introduce serious inaccuracies.
If a simple analytic process could be developed to provide a summary
measure of the concentrations of an entire class of toxicologically similar
constituents in drinking water, it is likely that it would also detect other,
potentially confounding constituents in the water.
In assessing the toxic impacts of individual or mixed constituents of drink-
ing water, it is essential to consider all forms of exposure to the constituents,
including exposure through water, soil, air, and food. For contaminated
drinking water, exposure by inhalation, skin contact, and ingestion should
be assessed. Whether organophosphorus and carbamate compounds volatilize
to a substantial extent during domestic indoor water uses should be deter-
mined, so that total exposures to these chemicals can be assessed. For the
THMs and VOCs, exposure due to volatilization can be substantial and should
be considered in assessing human toxic impact and risk.
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Andelman, J. B., S. M. Meyers, and L. C. Wilder. 1986. Volatilization of organic chemicals
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Andelman, J. B., L. C. Wilder, and S. M. Meyers. 1987. Indoor air pollution from volatile
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Atlas, E., R. Foster, and C. S. Giam. 1982. Air-sea exchange of high molecular weight organic
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Brown, H. S., D. R. Bishop, and C. A. Rowan. 1984. The role of skin absorption as a route
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Cohen, S. Z., C. Eiden, and M. N. Lorber. 1986. Monitoring ground water for pesticides.
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OCR for page 133
144 DRINKING WATER AND HEALTH
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Ershow, A., and K. P. Cantor. 1986. Population-based estimates of water intake. Fed. Proc.
45:706.
Giardino, N.~ J. B. Andelman~ J. E. Borrazzo. and C. I. Davidson. 1988. Sulfurhexafluoride
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