~6981/80~1-0653 %02.
00/o
MEASUREMENTS OF HYDROGEN
IN RAINWATER
GREGORY L. KOK
Harvey Mudd College, Department of Chemistry, Claremont, CA 91711, U.S.A.
(First received 10 September 1979 and
Abstract -The hydrogen peroxide (H,O,) con~ntration of rainwater falling in Claremont, California has
been measured over a series of precipitation events. The H,Ot concentrations were typically l-160 ppb, but
on three occasions H202 levels in excess of 1 ppm were measured. The H,O, levels generally decrease with
time during the storms. The measured values of H,Or are lower than those which are predicted from the
uptake of ias phase H,Oz into clouds.
INTRODUCDON
Hydrogen peroxide (H,O,) is an important com-
ponent of both the polluted and clean troposphere. In
the gas phase it can act as a sink for hydroperoxyl
radicals or as a source of hydroxyl radicals when
photolyzed. Measurements of Ht02 under polluted
conditions in the California South Coast Air Basin
indicate levels between lo-30 ppb (Kok et al., 1978a).
In rural air H,O, levels between 0.3 and 3 ppb have
been observed (Kelly et nl., 1979). The levels of HzOz
in the gas phase are of significant importance for the
modeling of OH concentrations (Crutzen and Fish-
man, 1977).
In rainwater, H,02 can play a significant role in the
oxidation of sulfur dioxide (SO,) to sulfuric acid
(H$04) (Penkett et al., 1979). Assuming gas phase
con~ntrations of SO* and H,Ot of 5 ppb and 1 ppb,
respectively, the net production of H,SO, in rain
could be as high as 1 gg ml- min-.
Two previous studies of H,O, leveis in rainwater
are known. In Tokyo, Japan, H,O, levels in rainwater
were found to vary between 80 and 860 ppb (Matsui,
1949). More recently, measurements of H20, levels in
the Research Triangle area of North Carolina have
been published (Bufalini et al., 1979). These workers
found the summer rain to contain as much as 200 ppb
while the winter rains contained about 2-8 ppb H,O,.
In the study reported in this paper Hz02 levels in
rainwater have been measured over a wide range of
pr~ipitation events during 1978-79.
EXPERIMENTAL
Rain samples were collected at the Harvey Mudd College
campus, Claremont, California. The rain was collected in
beakers maintained at 0C. Samples were taken at appro-
ximately hourly intervals during daylight hours and over
longer periods at night. The analysis for H,O, was conducted
immediately after the samples were removed from the ice
bath. Under these sampling conditions the decomposition of
H,Or was minimal.
The H,O, content of the samples was determined using the
653
PEROXIDE
in jnal form 15 ~oue~~r 1979)
chemiluminescent analytical method for HrOs. This tech-
nique involves the reaction of H,O, with luminol @-amino-
2,3-dihydro-1,4 phtalazonedione) in the presence of a copper
(II) catalyst in basic aqueous solution. Complete details ofthe
analytical technique are given elsewhere (Kok et al., 1978b).
The instrumentation was calibrated using solutions of HIOz
prepared by serial dilution of a stock solution titrated with
standard KMnO*.
RESULTS AND DISCUSSION
The data presented cover H,O, levels for both
summer and winter precipitation events. The summer
precipitation is typically of short duration and is
preceded by large amounts of photochemical smog.
During the winter precipitation events can be of
several days duration.
In Table 1 the data for H,Or levels in rainwater
collected during the s~mer rain showers are given.
The rain shower of 5 September I978 was very intense
with a relatively large amount of rain falling in a short
time. The striking features of these data are the high
concentration of HzOZ in the initial rain and the rate of
decline of H,O, with time during the storm. It is
impossible to calculate what the H,O, concentration
was in the initial rain drops, but from the trend in
H202 levels observed during the storm, the initial
concentration of H,Oz in the rain would be much
higher than _the initial recorded value of 1590 ppb.
Table 1. Concentration of H,O1 in rainwater
H,Or con~ntration, Rain amount,
Time* ppb mm
5 September 1978
1400-1700
1700-1800 510 6
1800-2000 170 6
17 July 1979
~--
0800 1140 Trace
* Pacific daylight time.
654 &!XiORY L. KOK

/ I 1 4 1 1
IV00 24,,00 06 00 12.00 I8 00 24,;OO 06 00 12 00 1800 24800 06 00
12 00
30 I 79 31 I 79 I279 2 279
Pacific Standard Time

Fig. 1. Concentration of H,Oa in rainwater in Claremont, California during the period 30 January-2
February 1979. The amount of rain in mm is given above each of the sample intervals. The H,O,
concentration of 1090 ppb was measured immediately after a thundersto~.

On 17 July 1979 a trace of rain was collected and decreases in an irregular manner. From 0900 to 1430
analyzed for H,Oz content. This was an early morning there was a clearing of the overcast and an opportunity
shower and minimal photochemical activity had taken for photochemical smog production to take place. The
place. The level of Hz02 measured, 1140ppb, is ozone Ievel during this time reached SOppb. The
consistent with the September 1978 rain. These increase in H,Oz upon resumption of the rain is an
measurements are considerably higher than the indication of photochemical activity. The very high
100-200 ppb observed in North Carolina during the concentration of H,O, measured in the rain between
summer (Bufalini et al., 1979). This is certainly due to 1600 and 1700 is attributed to electrical storm activity
the larger amount of photochemical smog found in the in the area. The production of nitrogen oxides in
Southern California area. electrical storms is well known (Chamiedes et aI., 1977)
The remainder of the data were collected during and it is not surprising that H,O, would be produced
January and February 1979. Figure 1 shows H,02 in a similar way. Following the electrical storm the
levels for rain falling during the period 30 January-2 concentrations of H,02 return to a much lower level
February 1979. The initial concentration of H20, is and continue to decrease.
92 ppb and in subsequent samples the levei of HzOz Figure 2 shows HzOz levels for rain collected on

I80 ,

1.5
160 -

140 -

.a r-

8 120-

6
c, IO0

;
g 80-

r
0 60.
I
40 -
3.0 I5.0 2.8
- _!

20-

4 I I I I I i I
I2 01 18 00 24:OO 0600 12:oo 18:OO 2400 06:OO 12:oo
20.2 79 II 21.2 79 i 22 2 79
Pacific Standard Time

Fig. 2. Concentration of H,O, in rainwater in Claremont, California during the period 20-22 February
1979. The amount of rain in mm is given above each of the sampie intervals.
 M~surements of hydrogen peroxide in rainwater
20-22 January 1979. The initial rain contained
130 ppb of H,Oz and had a pH of 4.3. Each of the
successive rain fractions had pH values of 4.5-4.6.
Following the initial fraction the H,Oz level decreases
steadily and reaches an almost constant concentration
ofabout 40 ppb H,O,. In the two extended rain storms
which were observed, Figs 1 and 2, there appears to be
a constant lower limit for the H,O, content of the rain.
Corre~a~ia~ with gas phase H202 levels
Unfortunately, no data on gas phase H,Oz con-
centrations immediately prior to or during the rain
storms are available. Reasonable estimates can be
made from knowledge of gas phase HzO, levels during
similar atmospheric conditions.
On 7 September 1979, atmospheric conditions of
H20, were between 1.2 and 2.6 ppb. In addition, two
measurements of H,Ot were made by aircraft at an
altitude of 3.3 km. The concentration of H,Oz in the
gas phase was 2.0 and 1.8 ppb. From this the vertical
distribution of H,Oz can be assumed to be relatively
uniform for this date.
If the H,O, in rainwater is exclusively due to a
rainout process, an upper limit can be calculated for
expected levels of H,O, in rain. For the rainstorm of 5
September, assuming a gas phase concentration of
2 ppb (3 pg me3) and taking this up into 1 ml of liquid
water, which is the approximate amount of liquid
water contained in 1 m3 cloud (Mason, 1971), the level
of H,O, in rainwater is calculated to be 3000 ppb. The
initial concentration of H,O, in rain for this pre-
cipitation event was much higher than the initial
recorded concentration of 1590ppb. In this case the
measured levels of H,O, in rain give a reasonable
correlation with H,O, levels calculated from a rainout
process.
For the other precipitation events, the observed
levels of H,O, in rain are considerably lower than
predicted. Assuming a range of gas phase H,O,
concentrations to be 0.3-l.Oppb, levels of H,Oz in
rainwater are predicted to be 300-15OOppb. This is
more than one order of magnitude higher than the
observed values.
This loss of HzO, can be attributed to at least two
sources. The first is the reaction of the H,O, with SO2
or other species in the cloud water. There is evidence of
this in the rain collected on 20 February 1979 (Fig. 2).
The initial rain is lower in H,O, than the following
sample and is also lower in pH. This indicates that
additional acidic species are present and could either
have reacted with the H,Oz or catalyzed its de
struction. The other loss mechanism, and potentially
the major one, could be the destruction of H,O1
during the evaporation stages of the rainfall. In
aqueous solution, H,Oz is concentrated by distillation
(Schumb et al., 1955). In the evaporation of a raindrop
the H,Oz would be concentrated in the presence of the
nucleating species for the raindrop. Presumably a
majority of the H,O1 would be decomposed in this
655
process, thus greatly reducing the concentration of
H,Oz present in the final raindrops.
The decrease of H,Oz levels in rainwater during the
course of the rainstorm, coupled with the lower-than-
calculated values of H,O, in rainwater, suggest that
the predominant mechanism for the uptake of H,O, in
rainwater is the washout mechanism. The constant
value of H,O, observed after an extended period of
rainfall may be the contribution due to rainout which
would be expected to be constant during the course of
a rainstorm.
CONCLUSION
These observations show that rainwater can contain
substantial amounts of H,Or. The concentration of
the H,O, varies greatly depending on the amount of
photochemical activity present prior to the rainfall.
Most ofthe observed values for H,Oz are considerably
lower than predicted from the gas phase uptake of
H,Oz. If the oxidation of SO, is considered in the light
of these lower HzO, concentrations, the production of
H,O* will be at least an order of magnitude slower
than previously predicted via heterogeneous oxidation
(Penkett et al., 1979). The concentrations of H,O, in
rainwater are sufficiently high to make a substantial
contribution to oxidation processes in rainwater.
Additional data are needed on H,O, levels in both the
gas phase and in rainwater before the total significance
of the oxidation of SO, by HzO, will be known.
Acknowledgements - The author would like to thank M.
Lopez for help in the analysis of some of the rain samples.
This work was sponsored in part by the National Science
Foundation-ASRA (Grant No. PFR-76-14702). The con-
tents do not necessarily reflect the views and policies of the
NSF-ASRA, nor does the mention of trade names or
commercial products constitute endorsement or recom-
mendation for use.
REFERENCES
Bufalini J. J., Lancaster H. T., Namie G. R. and Gay B. W., Jr.
(1979) Hydrogen peroxide formation from the photo-
xidation of formaldehyde and its presence in rainwater. J.
enuir. Sci. Hlth Al4 (2), 135-141.
Chameides W. L., Stedman D. H., Dickerson R. R., Rusch D.
W. and Cicerone R. J. (1977) Nitrogen oxide (NO,)
production in lightning. J. ammos. fci. 34, 143-149.
Crutzen P. J. and Fishman J. (1977) Average con~ntrations
of OH in the troposphere and the budgets of CH&,CO, H,
and CH,CI,. Geopkys. Res. Lett. 4, 321-324.
Kelly T. J., Stedman D. H. and Kok G. L. (1979) Measure-
ments of HrO, and HNO, in rural air. Geopkys. Res. Lett.
6, 375-378.
Kok G. L., Damah K. R., Winer A. M., Pitts J. M., Jr and Gay
B. W. (1978a) Ambient air measurements of hydrogen
peroxide in the California South Coast Air Basin. Enuir.
Sci. Tech&. 12, 1077-1080.
Kok G. L., Holler T., Lopez M., Nachtrieb H. and Yuan M.
(1978b) Chemiluminescent method of the determination of
hydrogen peroxide in the ambient atmosphere. En&. Sci.
Tecknol12, 1072-1076.
Matsui H. (1949) On the content of hydrogen -peroxide of
656 GRPWRY L. KOK

atmospheric precipitates. J. met. Sot. Japan 2, 380-381.
Mason B. (1971) 7he Physics of Clouds. Clarendon Press,
Oxford.
Penkett S. A., Jones B. M. R., Brice K. A. and Eggleton A. E. J.
(1979) The importance of atmospheric ozone and hy-
drogen peroxides in cloud and rainwater. Atmospheric
Environment 13, 123-137.
Scchumb W. C., Sutterfield C. N. and Wentworth R. E. (1955)
Hydrogen Peroxide. Am. them. Sot. Monogr. Ser., Rein-
hold. New York