LRA, Vol. 12, pp.

149–156

Determination of Hydrogen
Peroxide in Natural Waters
by Stopped-Flow Injection
Analysis with
Chemiluminescence
Detection
S. H. Fan,1 B. T. Hart,2 and I. D. McKelvie2
1
Institute of Applied Ecology, Chinese Academia of Sciences, Box 417, Shenyang 110015,
China
2
Water Studies Centre and Chemistry Department, Monash University, Clayton, Victoria
3800, Australia

Received 25 August 1999

ABSTRACT: A rapid, sensitive flow injection (FI)
method with chemiluminescence (CL) detection for
the determination of trace amounts of hydrogen per-
oxide in natural water is described. This method is
based on the reaction of luminol with hydrogen per-
oxide catalysed by cobalt(II) in an alkaline medium.
Sodium dodecyl sulphate (SDS) was used as sensi-
tizer agent, and its presence greatly accelerated the
reaction and enhanced the CL intensity. An FI
stopped-flow technique was introduced to the CL re-
action to increase sensitivity. Optimal conditions for
the chemiluminescence reaction were examined.
The sampling frequency was 50 hrⳮ1 for injection vol-
umes of 100 lL. The detection limit of hydrogen per-
oxide, defined as 3 times the standard deviation of
the blank, was 0.5 nM in high purity water, and the
working linear range was 1 to 105 nM. For the deter-
Correspondence to: I. D. McKelvie.
Present address: Water Studies Centre, Monash University, Clay-
ton, Victoria 3168, Australia. Fax: Ⳮ61 03 9905 4196; E-mail:
I.McKelvie@sci.monash.edu.au
Contract Grant Sponsor: Water Studies Centre.
䉷 2000 John Wiley & Sons, Inc.
mination of 15 nM and 52 nM hydrogen peroxide, the
relative standard deviations were 2.8 and 2.3% re-
spectively (n ⳱ 11). The method has been applied to
the determination of hydrogen peroxide in natural
water samples. 䉷 2000 John Wiley & Sons, Inc. Lab
Robotics and Automation 12:149–156, 2000
INTRODUCTION
Hydrogen peroxide in aqueous solution can act as
either an oxidizing or reducing agent [1]. The pres-
ence of hydrogen peroxide has been reported in fresh
waters [2], marine waters [3, 4], and estuarine envi-
ronments [5]. Hydrogen peroxide affects redox chem-
istry in marine environments [5, 6], and it may also
be important in metal cycling in other natural waters
[7] and in the fate of pollutants in the environment
[8]. As a strong oxidant, it may effect both biological
[9, 10] and chemical processes and, as a result, may
influence ecosystem biogeochemistry.
The development of a sensitive method for the
determination of hydrogen peroxide is necessary to

149
150 Fan, Hart, and McKelvie
improve the understanding of its distribution and
flux in natural waters. A number of methods have
been proposed for the determination of hydrogen
peroxide, including methods involving tunable di-
ode laser spectrometry [11], fiber-array spectrometry
[12], and fluorescence and amperometry [13, 14] . Al-
though these methods are relatively sensitive, they
suffer from the disadvantages associated with com-
plex analytical equipment, reagent instability, and
high cost. Determination of hydrogen peroxide by
flow injection (FI) chemiluminescence (CL) detection
offers numerous advantages compared to other meth-
ods. The low cost, high sensitivity, precise timing,
high sampling frequencies, and excellent portability
makes the CL-FI method ideal for rapid determina-
tion of hydrogen peroxide.
A wide variety of CL reactions exist, and many
of these have been proposed for the determination of
hydrogen peroxide. These include the reaction of
periodate with hydrogen peroxide [15], the reaction
of 1,1’-oxalyldiimidazole with peroxide [16] and, (p-
hydroxyphenyl)acetic acid dimerization [17] as
chemiluminescence reagents.
Luminol (5-amino-2,3-dihydro-1,4-phthalazine-
dione) and peroxyoxalate are common chemilumi-
nescence reagents used for hydrogen peroxide deter-
mination. Both provide very low detection limits and
linearity over about four decades of concentration.
An advantage of peroxyoxatate CL is that it is also
useful over a wide pH range. However, a major lim-
itation of this reagent is the need to use an organic
solvent because of its limited aqueous solubility.
For this reason, luminol was used in the experi-
ments described here. In aqueous alkaline solution,
luminol is oxidized to 3-aminophthalate, with the
emission of blue light with kmax of 425 nm. The re-
action is optimal at pH 10–11 and is catalyzed by a
variety of metal ions and heme-containing enzymes.
Hexacyanoferrate(III), the most commonly used cat-
alyst, produces CL of high quantum yield, but with a
large background signal, which must be controlled in
order to achieve low detection limits. Cobalt (II) also
is a most efficient inorganic catalyst with high sen-
sitivity and low background for the luminol and hy-
drogen peroxide CL reaction [18].
Using this reaction system, Nieman [19] deter-
mined hydrogen peroxide in synthetic water with a
reported detection limit of 1 lM. Eremin et al. [20]
and Olssen [21] used the same CL reaction system,
with peroxidase and microperoxidase as catalysts,
and determined the contents of hydrogen peroxide
in synthetic samples with detection limits of 1 lM
and 3 nM, respectively. Nabi and Worsfold [18] re-
ported a detection limit of hydrogen peroxide at fem-
tomole level, while others [22, 23], have successfully
determined the ambient levels of hydrogen peroxide
in sea water in the range of 5–500 nM using cobalt(II)
as catalyst.
This article describes the modification and en-
hancement of the FI chemiluminescence reaction
with luminol as CL reagent and cobalt(II) as catalyst
[22, 23] and its direct application to the determina-
tion of hydrogen peroxide in natural waters.
EXPERIMENTAL
Reagent and Standards
All solutions were prepared from high purity water
(Continental Water System Pty Ltd.). All reagents
were of analytical grade. Luminol and cobalt(II) ni-
trate were supplied by Fluka A.G. and Merck Chem-
icals, respectively, and used without further purifi-
cation. Hydrogen peroxide [30%(w/v)] was obtained
from BDH chemicals. The reagent stocks and working
solutions were prepared in 0.1 M sodium carbonate
(Ajax Chemicals), and the pH was adjusted by addi-
tion of 1 M hydrochloric acid. Stock solutions of co-
balt(II) (10 mM) and luminol (10 mM) were used to
prepared working solutions by serial dilution and
keep refrigerated (4⬚C) to minimize decomposition.
Sodium dodecylsulfate (SDS) was obtained from
BDH Chemicals and a working solution of 0.1 %(w/v)
was prepared in high purity water. The standard so-
lutions of hydrogen peroxide were prepared daily by
serial dilution of a 2.11 M of stock solution that was
standardized against standard potassium permanga-
nate.
The metal ions used for the interference studies
included Ni(II), Zn(II), Fe(III), Fe(II), Mn(II), and
Cu(II) ion and these were prepared from analytical-
grade salts. Amounts of the potential interferent were
added to a 105 nM hydrogen peroxide standard so-
lution for comparison.
Instrumentation and Manifold
A custom-made luminometer consisting of a Hama-
matsu compact photomultiplier (H5783) with stabi-
lized high-voltage power supply and amplification
system housed in a light-tight box. The flow cell con-
sisted of a Teflon gasket sandwiched between a stain-
less steel backing plate and a Vitreosil window held
in a compression frame. Flow through the cell was
defined by an elliptical aperture cut in the Teflon gas-
ket. Two Ismatec peristaltic pumps (CA5E) and a
Rheodyne 5041 injector valve were used to construct
the FI system for reagent delivery and sample injec-
tion. The flow injection manifold is shown schemat-
 Determination of Hydrogen Peroxide in Natural Waters by Stopped-Flow Injection Analysis 151

ically in Figure 1. Poly(tetrafluoroethylene) (PTFE)
tubing (0.5 mm i.d.) was used throughout.
The sample (100lL) was introduced into the lu-
minol carrier stream by a valve switching module
with PTFE rotary injection valve, merged with the
cobalt(II) stream, and transported to the detector. The
two streams, after merging at a perspex T-piece
within the detector housing, passed into the flow-cell
situated immediately in front of the photomultiplier
tube (PMT) window. The distance from the injection
valve to merging point was 25 cm, and that from the
merging point to the flow cell was 2 cm. The peri-
staltic pumps and injection valve were controlled,
and the data were acquired and stored using the FCS
FI software package (A-Chem Technologies, Mel-
bourne, Australia) via a user interface to a computer.
The resulting signal was also recorded as voltage on
a strip chart recorder (Kipp and Zonen, BD111). Peak
heights were used to evaluate the experimental re-
sults.
In developing the stopped-flow CL method, the
same manifold was used as for normal flow injection
mode. Co(II) and luminol flows were halted simul-
taneously 11 seconds after injection, and the devel-
opment and decay of the chemiluminescence signal
was observed over a total period of 50 seconds. Peak
heights were used to evaluate the experimental re-
sults.
RESULTS AND DISCUSSION
Optimization of Manifold Parameters
The variables studied included the injection volume
and the reagent flow rates. The volume injected was
varied from 20 to 200 lL. The difference in peak
heights between blank and the sample increased with
increasing volumes injected. When the injection vol-
ume was 150 or 200 lL, doublet peaks were obtained.
Doublet peaks in FIA are usually associated with in-
complete reaction of the central portion of the sample
bolus because of inadequate sample reagent mixing
or a paucity of reagent [24]. The existence of doublet
peaks in this instance appears related to sample dis-
persion in the detection section of the manifold.
When a volume of 100 lL of injection volume was
used, a single large peak was obtained.
The flow rates of the luminol and Co(II) stream
were varied simultaneously over the range of 0.5 to
2.5 mL/min. At 18–20⬚ C, the peak height increased
with decrease of the flow rate, but the peak shape
broadened and a longer analysis time was necessary.

Figure 1. Schematic diagram of chemiluminometric flow-injection manifold for the determination of hydrogen. P, peri-
staltic pump (1.5 mL minⳮ1); S, injection valve with 100 lL loop; R1, 7 x 10ⳮ5 M luminol (in 0.1 M carbonate buffer, pH
10.3); R2, 4 x 10ⳮ5 M Co(II) solution in 0.1 M carbonate buffer, pH 10.3); FC, flow cell; IEC, ion-exchange column; W,
waste; PMT, photomultiplier tube; A, amplifier; C, personal computer; G, recorder.
152 Fan, Hart, and McKelvie
A 1.5 mL/min flow rate was chosen as a compromise
between the optimal sensitivity and maximum sam-
pling frequency.
Optimization of Reagent Concentration
The effect of varying the concentrations of luminol
and cobalt(II) was tested in the flow injection system.
The effect of luminol concentration was studied over
the range of 10 to 100 lM. As seen in Figure 2a, the
difference in peak height between sample and blank
increased with increasing luminol concentration up
to a maximum at 70 lM, and then decreased at higher
concentration. A 70 lM concentration of luminol so-
lution was therefore selected as being optimal.
A number of the metal ions—Co(II), Cu(II), Fe(II)
and Mn(II), Co(II)—have been tested as catalysts for
this reaction [25]. Consequently, Co(II) was selected
as a catalyst in the present CL system. The effect of
Co(II) concentration on the CL intensity was exam-
ined in the range of 6–80 lM. Figure 2b shows that
the CL intensity increased with increasing concentra-
tion of Co(II) up to 40 lM, and then decreased at
higher concentrations. A 40 lM Co(II) of working so-
lution was therefore selected as the optimal concen-
tration, based on the chemiluminescence intensity.
Previous studies [26, 27] have also shown that the
presence of carbonate in solution is also advanta-
geous; although carbonate serves as a buffer [28], it
also has the effect of enhancing the CL emission of
the luminol and hydrogen peroxide reaction. Based
on previous work in our laboratory [29], a 0.1 M (pH
10.3) of carbonate solution was used as the buffer so-
lution.
Figure 2. Effect of changes in the reaction variables (a) lu-
minol and (b) Co(II) on chemiluminescence reaction be-
tween luminol and hydrogen peroxide.
pH of Sample Solution
Experimental results (Figure 3) showed that the sam-
ple pH had an effect on the CL signal. Despite the use
of carbonate buffered reagents, samples at neutral pH
resulted in a slower CL reaction, with a correspond-
ingly lower peak height compared with alkaline sam-
ples at pH 10.3. The peak height of the alkaline sam-
ples was nearly twice that at neutral conditions. To
maximize the CL signal, the sample solution was
mixed with buffer solution as close as possible to the
entrance to the flow cell.
The observation that sample pH affects CL inten-
sity departs from other reported data [22]. The prob-
able explanation is that the sandwich-geometry flow
cell used in this study had a very small volume, and
much less effective mixing occurs than with the
coiled glass cells (volume ca. 240 lL) that have been
used by others [22]. Merged sample and luminol had
a very short residence time in the sandwich-geometry
flow cell, and maximum intensity was not achieved
before the solution left the cell even under conditions
of reduced flow rate.
Selection of Delay and Residence Times in
Stopped-Flow Mode
Most CL reactions are very fast, and it is normal for
the sample solution to be mixed with chemilumines-
cence reagent as close as possible to, or even within
the CL cell, to obtain the maximum intensity. How-
ever, in the work reported here, it was observed that
the luminol-H2O2 CL reaction in the presence of
Co(II) still required a finite time to reach maximum
intensity. For this reason, a stopped-flow technique
was adopted. Sample was injected, and after a pre-
determined delay time (the time elapsed after injec-
tion), the flow was halted for 50 seconds (the stop
Figure 3. Effect of increasing delay time before com-
mencement of stop-flow period on CL intensity.
 Determination of Hydrogen Peroxide in Natural Waters by Stopped-Flow Injection Analysis
time), to allow development of maximum CL signal
emission and subsequent signal decay to baseline. A
delay time of 11 seconds was found to give the op-
timum CL emission (Figure 3). When a delay time of
11 seconds was used, maximum signal output was
observed after 5.5 seconds and 7.2 seconds for alka-
line and neutral solutions respectively (Figure 4). A
calibration plot obtained using this stopped-flow ap-
proach was more than four times as sensitive (based
on calibration curve slope) as that obtained under
normal continuous flow FIA methods.
It was observed that the decrease in signal inten-
sity after the peak maximum was related to sample
pH, with a slower rate of CL emission being observed
in neutral samples compared with that under alka-
line conditions due to the difference in reaction ki-
netics (Figure 4).
The decrease in the signal observed for the re-
sponse curve shown in Figure 4 is not due to disper-
sion of the sample zone as is normally observed in
FIA, but rather to the decay of the CL emission under
stopped flow conditions.
Figure 4 shows that the peak intensity of neutral
and basic samples is reached within 16.5 seconds
and 18.2 seconds, respectively, under stopped-flow
conditions, and the flow could be resumed shortly
after this time. Therefore, a higher sample through-
put could theoretically be achieved than would be
the case where a stop time of 50 seconds was used.
Examination of the signal profiles in Figure 4 would
suggest that each sample injection cycle could be re-
Figure 4. CL intensity-time profiles obtained in the stop-
flow mode at different sample pH: A, sample pH 10.3; B,
sample pH 7.0. Condition: hydrogen peroxide, 0.105 lM;
luminol, 70 lM; Co(II), 40 lM. (See experiment section for
other experimental conditions.)
153
duced to ca. 30 seconds if the flow was resumed after
a stop time of 9 seconds. In the process of optimizing
all other aspects of this detection chemistry, we have
maintained a stop time of 50 seconds, and the re-
ported throughput of 50 hr-1 is therefore unnecessar-
ily conservative.
Signal Enhancement
In preliminary experiments, a detection limit of only
ca. 10-8 M was achieved even under optimized
stopped-flow conditions. A number of modifications
were made to the FI detection system to improve the
reaction sensitivity and the detection limit.
Bause and Patterson [30] found that concentrated
inorganic salt solutions, particularly halide ions, re-
sulted in enhancement of the CL intensity. Chen and
Patterson [31] similarly reported the results of stud-
ies of halide ion enhancement on chromium(III),
iron(II), and cobalt(II) catalyzed chemiluminescence
reaction. Other reagents used to enhance the reaction
intensity involved a mixed dye-sensitizer [32], ionic
surfactants [33], and perylene[28]. In our experi-
ments, we have evaluated the effect of sodium chlo-
ride and the anionic surfactant, sodium dodecyl sul-
fate (SDS), as a means of improving the sensitivity of
the CL reaction.
Figure 5 shows that the relative detector response
obtained for 0.21 lM hydrogen peroxide increased
with increasing concentration of sodium chloride in
the range of 0.5–2.0 M. At 2.0 M sodium chloride, the
magnitude of enhancement is about 1.6 times larger
than that in the absence of NaCl, but the reagent
blank also increased with the increasing concentra-
Figure 5. Chemiluminescence signal enhancement caused
by the addition of NaCl. The enhancement factor is the ratio
of CL signal in the presence of different concentrations of
NaCl to that in the absence of NaCl.
154 Fan, Hart, and McKelvie
tion of sodium chloride. Consequently, NaCl was not
used in the final manifold setup to provide signal en-
hancement.
The effect of SDS concentrations from 0.005 to
0.2% on the CL emission was also examined (Figure
6). Maximum CL emission was observed at ca. 0.1%
SDS, which gave a signal enhancement of ca. 2.4
times greater than that in the absence of SDS, with a
correspondingly small blank signal. Consequently,
0.1% SDS was added to the luminol reagent in fur-
ther experiments.
Background Chemiluminescence
Under the experimental conditions described, a con-
tinuous background CL emission was observed to re-
sult from the mixing of the two reagent streams. This
is apparently due to the presence of hydrogen per-
oxide in the high purity water used in the preparation
of reagents. The high blank signal makes the method
unsuitable for detection of hydrogen peroxide at
trace concentrations. To minimize the blank, Miller
et al. [34] used catalase to remove hydrogen peroxide.
When used under optimal conditions, this enzyme
can remove the hydrogen peroxide amount present
in a solution in a few minutes; however, in some
cases the catalase remains active in solution, and the
deionized water is therefore unsuitable for preparing
reagents. Price et al. [22] overcame this problem by
scavenging hydrogen peroxide from water used to
prepare reagents by passing it through a gravity-fed
column of either MnO2 chemically bound to Amber-
lite XAD-7 polymeric beads, or a column of solid
MnO2. A more convenient and economical method
Figure 6. Chemiluminescence signal enhancement caused
by the addition of SDS. The enhancement factor is the ratio
of CL signal in the presence of different concentrations of
SDS to that when no SDS is present.
to eliminate the low level of hydrogen peroxide in
blank solution is to use the deionized water that has
been stored for 6–7 days or more in a clean container
[35]. Because of the instability of hydrogen peroxide,
a storage period of 7 days was shown to be sufficient
to ensure degradation of residual hydrogen peroxide.
This practice was adopted in this study. After 7 days,
the signal intensity for high pure water stored was
decreased to 10–20% of that of fresh high purity wa-
ter, that is, signal of 2 to 3 mV decreased to ca. 0.3
mV, and its purity was deemed sufficient to deter-
mine low levels of hydrogen peroxide.
Cation Interference and Elimination
Liquid phase CL reactions based on the luminol or
other CL reagents in the present of catalyst suffer
from interference by transition metal ions [36, 37],
and there have been a number of attempts to develop
new CL reagents or catalysts for the CL determination
of hydrogen peroxide [38–40]. In the present exper-
iments, the interference of some transition metal ions
was evaluated at concentrations typically found in
natural water [41]. These metals included Fe(II),
Fe(III), Zn(II), Cu(II), Mn(II), and Ni(II). Their effect
on the CL signal at a specified concentration was
compared to that for the solution containing only hy-
drogen peroxide at the same concentration. The in-
terference effect of these ions on the determination
of hydrogen peroxide in the luminol-hydrogen-Co(II)
reaction is summarized in Table 1.
Among those metal ions, Zn(II) and Ni(II) had no
effect at concentrations typically found in natural
waters [41]. Cu(II) ions caused a slight suppression
(31–23%) of the CL signal when present at ca. 30
times the analyzed Cu concentration of samples.
Fe(III) ions, however caused a slight enhancement of
the CL signal in neutral samples, possibly due to a
small amount of Fe(II) ions present in the reagent,
whereas Fe(II) caused a serious positive interference
when present at 100 times the concentration of hy-
TABLE 1. Effect of Various Transition Metal Ions
on the CL Intensities of 10.5 lM Hydrogen Peroxide
at pH 7.0 and pH 10.33
Relative CL Intensity (%)
Ions Concentration
Added Present (lM) pH 7.0 pH 10.3
Ni(II) 8.5 110 Ⳳ 0.8% 104 Ⳳ 2.4%
Zn(II) 31 95 Ⳮ 4.3% 108 Ⳮ 1.6%
Fe(III) 18 130 Ⳳ 2.7% 103 Ⳳ 2.4%
Fe(II) 18 1760 Ⳮ 5.4% 240 Ⳮ 1.8%
Mn(II) 9.1 0 0
Cu(II) 3.1 69 Ⳮ 4.6% 77 Ⳮ 2.6%
 Determination of Hydrogen Peroxide in Natural Waters by Stopped-Flow Injection Analysis 155

drogen peroxide, possibly due to its catalytic effect,
especially under neutral solution conditions. Mn(II)
caused significant repression of the CL signal (de-
creasing the signal to zero) when at concentrations
100 times that of hydrogen peroxide. Based on the
reduction potentials for the following reactions:
H2O2 Ⳮ 2 HⳭ Ⳮ 2eⳮ r 2 H2O Ⳮ 1.78 V
MnO2 Ⳮ 4 HⳭ Ⳮ 2eⳮ r Mn2Ⳮ Ⳮ 2H2O Ⳮ 1.23 V
O2 Ⳮ 2 HⳭ Ⳮ 2eⳮ r H2O2 Ⳮ 0.69 V
the interference by Mn(II) ions is most likely due to
oxidation of Mn(II) by hydrogen peroxide under al-
kaline condition, that is,
Mn 2Ⳮ
Ⳮ H2O2 r MnO2 Ⳮ 2 H Ⳮ The proposed method was used to determine hydro-
However, under acid conditions hydrogen peroxide
reduces MnO2 to Mn2Ⳮ, thus:
MnO2 Ⳮ H2O2 Ⳮ 2 HⳭ r Mn2Ⳮ Ⳮ 2H2O Ⳮ O2
which is the basis of the technique used for removal
of hydrogen peroxide from reagent water discussed
previously [22]. Other common anions in natural wa-
ter, for example, chloride, sulphate, and nitrate ions,
at typical concentration, do not interfere with the de-
tection of hydrogen peroxide.
To eliminate the interference by cations, cation
exchange resins were employed. Using a column of
Dowex 50W-8 resin (70 mm x 5 mm i.d.), the Fe(II)
signal at pH 10.3 was decreased to 44% of the signal
obtained without cation elimination. Under neutral
pH conditions the Fe(II) signal was decreased by
97%, but the remaining signal was still at a relatively
high level (ca. 21 mV). When an IR-120 (Na-form)
resin was used (9 cm x 4.0 mm i.d. column) at 0.8
mL/min, the interference from 5 x lM Fe(II) solutions
was completely removed, and this column was in-
corporated into the sample line for on-line sample
conditioning (Figure 1).
Limit of Detection, Reproducibility, and Sample
Throughput
A limit of detection of 0.5 nM [H2O2] was determined
from the calibration graph corresponding to an S/N
ratio of 3. The reproducibility of the method was
tested by injections of 15 and 52 nM hydrogen per-
oxide, which gave relative standard deviations of
2.3% and 2.8 %, respectively, for 11 injections. The
results indicated that the precision is adequate for
low level determination of hydrogen peroxide. The
flow system could handle 100 samples per hour un-
der continuous flow injection condition and 50 sam-
ples per hour in the stopped-flow mode.
Analysis of Real Samples
gen peroxide in a number of natural waters. The re-
sults are shown in Table 2. To evaluate the validity
of the proposed method for the determination of hy-
drogen peroxide in water samples, in the absence of
suitable standard reference materials, recovery stud-
ies were performed on samples to which amounts of
hydrogen peroxide standards were added. Recovery
values of greater than 93% were found (Table 2).
The high sensitivity, simple operation, improved
selectivity, and rapid sample throughput make this
method suitable for detection of hydrogen peroxide
at low levels in natural waters.
Acknowledgments
S.H.F. thanks G. Cross, R. Shalders, B. Lovell, and P. Ellis
for their help.
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Analytical Performance TABLE 2. Determined Concentration of Hydrogen

Peroxide in Water Samples and the Recoveries
Linearity
Calibration data obtained using a two-line manifold Amount Standard Standard
Present Added Found Recovery
(Figure1) and a series of hydrogen peroxide stan-
Sample (nM) (nM) (nM) (%)
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The % recovery is the measured spiked concentration/added
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[H2O2, nM]; (r ⳱ 0.9987). b
Result for sample diluted 1:50.
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