Peer Reviewed
Use of Sodium Thiosulfate to Quench Hypochlorite
Solutions Prior to Chlorate Analysis
AN DREW K. BO AL 1 A ND F O TIO S I. PATSA L IS 1
1Johnson Matthey, Albuquerque, N.M.
Sodium thiosulfate is a commonly used quenching agent
for sodium hypochlorite and has previously been deemed
acceptable when quenching hypochlorite solutions before
conducting chlorate analysis. However, using thiosulfate to
quench hypochlorite solutions with compositions similar
to those produced by electrolytic onsite generation process
(OSG; free available chlorine content of 0.8% with a pH
range of 8–10) can result in artificially low chlorate
measurements. Reactions between thiosulfate and
Keywords: chlorate, disinfection byproduct, hypochlorite, regulation
Chlorate (ClO3–) is an emerging water contaminant
that is a part of the Third Contaminant Candidate List
of the US Environmental Protection Agency (USEPA) and
is expected to eventually be fully regulated as a drinking
water contaminant (USEPA 2015, Stanford et al. 2011).
Extensive research has been conducted on the introduc-
tion of chlorate, along with bromate and perchlorate, into
drinking water as an unintended byproduct of chlorina-
tion with either bulk sodium hypochlorite (Snyder et al.
2009) or hypochlorite produced through electrolytic
onsite generation (OSG) processes (Stanford et al. 2013).
Chlorate introduction from bulk hypochlorite occurs as
a result of degradation of hypochlorite after production.
Chlorate concentrations in bulk hypochlorite increase
during storage, and the rate of increase is influenced by a
variety of factors, including the pH of the solution, initial
hypochlorite concentration, and storage temperature
(Adam & Gordon 1999). Conversely, in OSG-produced
hypochlorite solutions, chlorate is primarily introduced
as an unintended byproduct of the electrolysis process
with no currently known control mechanisms.
Commonly, studies of the chlorate content of hypochlo-
rite solutions are carried out by sampling concentrated
hypochlorite solutions at a water treatment plant,
quenching these solutions using a chemical that consumes
the hypochlorite but does not interfere with chlorate
measurement, followed by shipping the quenched samples
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hypochlorite can result in a substantial decrease in pH that
in turn causes the production of bisulfite ions from
thiosulfate. In turn, these ions react with chlorate ions,
resulting in artificially decreased measurements of chlorate
in the initial hypochlorite solutions. Malonic acid does not
cause a similar effect when used as a hypochlorite quenching
agent and should therefore be used in place of thiosulfate
when conducting chlorate analysis of hypochlorite solutions
produced through electrolytic OSG processes.
to an analytical laboratory where chlorate content is
analyzed. The hypochlorite ion is unstable and will
degrade into chlorate, potentially leading to a false posi-
tive measurement, making sample quenching a critical
step in this process. Several quenching agents have been
considered for this application, including ascorbic acid,
glycine, malonic acid, sodium thiosulfate, sodium sulfite,
oxalic acid, and hydrogen peroxide (Pisarenko et al.
2010). None of these quenching agents have been previ-
ously identified as causing an interference with chlorate
measurements; however, ascorbic acid, sodium thiosul-
fate, and sodium sulfite were found to decrease the appar-
ent concentrations of bromate when used to quench
sodium hypochlorite solutions when the liquid chroma-
tography/tandem mass spectroscopy method is used to
determine bromate concentrations.
The goal of recently conducted research by the authors
was to increase the understanding of the fundamental elec-
trochemical processes responsible for the production of
chlorate during chloride oxidation in OSG systems. In the
course of this research, the solutions would at times become
cloudy or have a sulfurous odor when sodium thiosulfate
was used to quench the free chlorine component before
chlorate analysis. In addition, solutions that exhibited these
characteristics had lower-than-expected chlorate concentra-
tions. To determine why these observed behaviors occurred,
this quenching process was investigated in further detail.
MATERIALS AND METHODS
General. Hypochlorite solutions used in these tests were FIGURE 1 Changes in solution FAC concentration
prepared from commercial bleach purchased with a nom- as a function of initial solution pH and
inal free available chlorine (FAC) concentration of 8.25%. molar ratio between reactants
Sodium thiosulfate was purchased and used as received,1
and malonic acid was purchased and used as received.2 pH
FAC measurements were made using the DPD method 8 8.2 8.4 8.6 8.8 8.9 9
9.1 9.2 9.3 9.4 9.6 9.8 10
with a colorimeter,3 while a probe and meter4 were used
to measure pH. Chlorate content was measured by 9,000
,000

FAC Concentration—mg/L
Hall Environmental Laboratories and Eurofins Eaton 8,000
Analytical using ion chromatography modeled on USEPA 7,000
methods 300.0 and 300.1. These methods are normally 6,000
used for the detection of relatively low levels of chlorate 5,000
4,000
in a typical drinking water sample as opposed to the high 3,000
concentrations found in a concentrated hypochlorite 2,000
matrix. Samples were diluted before measuring chlorate 1,000
0
using ion chromatography. Ethylenediamine was not used

0. .0
0. 5
in the preparation of these samples (1) to avoid additional

0. 5
0
02

5
0. .1
0

5
07

0. 15
0
12

5
2
3
17
chemical reactions that might interfere with the goals of

0.

4
0.

0.

6
0.

8
0
0.
0.
1.
this study and (2) out of caution because it has been Thiosulfate:Hypochlorite Molar Ratio
reported that other organic amines (glycine) react vio- FAC—free available chlorine
lently when used to quench high-concentration hypochlo-
rite solutions (Pisarenko et al. 2010).
FIGURE 2 Changes in solution pH as a function of
Sodium thiosulfate reactions with sodium hypochlorite.
initial solution pH and molar ratio
Aqueous chlorine solutions were prepared by diluting
between reactants
concentrated sodium hypochlorite solutions to an FAC
concentration of ~8,000 mg/L using deionized water.
pH
These solutions were then pH adjusted through the addi-
8 8.2 8.4 8.6 8.8 8.9 9
tion of hydrochloric acid or sodium hydroxide to the 9.1 9.2 9.3 9.4 9.6 9.8 10
desired pH value, and the FAC concentration of the pH-
adjusted solution measured before use. Both FAC content
11
and pH range of the test solutions were modeled after the
Final Reaction—pH
—

previously reported composition range of oxidant solu-

tions produced by OSG systems in the field (Stanford et 6
al. 2013). A 200 mL portion of the pH-adjusted solution
was transferred to a second flask, and the desired amount
of solid sodium thiosulfate or malonic acid was then 1
added to the flask. The solution was then mixed for a
0. .0
0. 5
0. 5
0
02

5
0

0. .1
0. 5
07

0. 15
0

5
12

minimum of 5 min past the point at which the sodium

3
17
0.

4
0.

6
8
0.

0
0.
0.
1.

thiosulfate or malonic acid was completely dissolved. FAC
content and pH of the post-reaction solution were then
measured and recorded, along with observations regard-
ing the physical appearance of and any odors produced
by the solution. Samples for chlorate analysis in selected
reactions were refrigerated before submission to the Hall
Environmental Laboratory for analysis.
RESULTS AND DISCUSSION
Observations on the reaction of hypochlorite with thiosulfate.
Preliminary testing focused on documenting the changes
in composition and physical characteristics of hypochlo-
rite solutions after reaction with varying amounts of
sodium thiosulfate. In these reactions, the initial pH of
the hypochlorite solution varied between 8 and 10, and
the molar ratio between sodium thiosulfate and sodium
hypochlorite ranged from 0.025:1 to 1:1. Hypochlorite
Thiosulfate:Hypochlorite Molar Ratio
consumption by added thiosulfate was found to occur
similarly regardless of the initial pH of the hypochlorite
solution, with full hypochlorite consumption occurring
once the thiosulfate:hypochlorite (S2O32–:ClO–) molar
ratio reached 0.2:1 (Figure 1) in all reactions.
Changes in solution pH as a result of the reaction
between hypochlorite and thiosulfate were complex and
dependent on both the initial pH of the hypochlorite
solution, as well as the relative amount of thiosulfate
added to the solution (Figure 2). When the initial pH of
the hypochlorite solution was 8.9 or less, a drop in the
solution pH was observed to occur at all S2O32–:ClO–
molar ratios studied, with final pH values <1.2 observed

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in some reaction conditions. Minimum post-reaction molar ratio was 0.2:1, and generally were less intense
solution pH values were seen when the S2O32–:ClO– as the pH of the initial hypochlorite solution increased.
molar ratio was 0.2:1 in nearly every case, which was Reaction solutions were observed to become turbid for
the same molar ratio that resulted in complete con- all reactions with an initial pH less than 8.9 and a
sumption of the hypochlorite. Hypochlorite solutions S2O32–:ClO– molar ratio of 0.3:1 or greater, which cor-
with an initial pH of 8.9 and greater exhibited a more relates to an excess of thiosulfate present in the reaction
complex response in terms of changes in solution pH. relative to the amount required to quench the hypochlo-
When the initial pH of the reaction ranged from 8.9 to rite. When the initial reaction pH was 8.9 or greater,
9.4, the reaction between thiosulfate and hypochlorite turbidity was observed when the S 2O32–:ClO– molar
resulted in decreased solution pH if the S2O32–:ClO– ratio typically was in the range of 0.3:1 to 0.4:1, but
molar ratio was less than 0.4:1, with an increase in was absent when a higher amount of thiosulfate was
solution pH observed when higher amounts of thiosul- used. Turbidity was observed only qualitatively and not
fate were added to the hypochlorite solution. When the quantified in these tests.
initial pH ranged from 9.4 to 10, the pH was seen to Impact of thiosulfate quenching reaction on chlorate con-
increase for most reactions when the S 2 O 3 2– :ClO – centration. Residual chlorate concentrations were mea-
molar ratio was less than 0.125:1, with decreases in pH sured in the solutions produced through a subset of the
observed when the S 2 O 3 2– :ClO – molar ratio was reactions described earlier (Figure 4). Reaction conditions
0.125:1 to 0.4:1, and pH increases when higher relative employed in this test included varying the initial pH of
amounts of thiosulfate were used. the hypochlorite solution between 8.6 and 9.6 and using
Physical changes in the solutions that occurred as a S2O32–:ClO– molar ratios of 0.2:1, 0.4:1, and 1:1. Chlo-
result of the reaction between hypochlorite and thiosul- rate was measured for the solutions produced by these
fate were also recorded, specifically following the evolu- reactions and reported as relative chlorate by dividing the
tion of odors, as well as the appearance of turbidity in raw chlorate concentration by the initial FAC concentra-
the solutions (Figure 3). For all reactions, the appear- tion of the solution. Control samples were prepared by
ance of sulfurous odors was observed in nearly every adding an excess of malonic acid to FAC solutions with
reaction with an initial pH of 8.9 or less, as well as for an initial pH of either 8.8 or 9.6, and the relative chlorate
most reactions with an initial pH greater than 8.9, and was measured to be 41.7 and 42.0 µg ClO3–/mg FAC in
the S2O32–:ClO– molar ratio of 0.4:1 or less. Sulfurous these solutions, respectively. Apparent relative chlorate
odors tended to peak in intensity when the S2O32–:ClO– content of thiosulfate-quenched solutions depended on

FIGURE 3 Reaction conditions that result in the appearance of sulfurous odors and turbidity in the reaction between
hypochlorite and thiosulfate

Clear and odorless solution Turbid solution with sulfurous odors

Clear solution with sulfurous odors Turbid odorless solution
Initial pH
8.0 8.2 8.4 8.6 8.8 8.9 9.0 9.1 9.2 9.3 9.4 9.6 9.8 10.0

0.025

0.05

0.075
Thiosulfate:Hypochlorite Molar Ratio

0.1

0.125

0.15

0.175

0.2

0.3

0.4

0.6

0.8

1.0

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both reaction conditions tested, with solutions quenched
using a S2O32–:ClO– ratio of 0.2:1 measured to range FIGURE 4 Measured relative chlorate
between 33.1 and 44.6 µg ClO3–/mg FAC. FAC solutions concentrations of thiosulfate-quenched
quenched with S2O32–:ClO– ratios of either 0.4:1 or 1:1 hypochlorite solutions as a function of
were found to have little or no chlorate when the initial initial solution pH and molar ratio
pH of the solution was 8.6 or 8.8, and relative chlorate between reactants
concentrations ranging from 30 to 45 µg ClO3–/mg FAC
when the initial pH was 9 or higher. 0.2:1 Thiosulfate:FAC
0.4:1 Thiosulfate:FAC
Mechanistic analysis of reaction outcomes. Chemical 1:1 Thiosulfate:FAC
reactions between the thiosulfate ion and aqueous oxy- 45
halide species have been extensively studied throughout 40
the years, revealing that very rich chemistry occurs in

Measured Chlorate Content—

35

µg Chlorate per mg FAC

these systems. Specifically, with regard to the reaction
between aqueous chlorine species and thiosulfate, a num- 30

ber of chemical reactions have been described with vary- 25

ing mechanisms based on pH. When the reaction is car- 20
ried out with a pH of 2, in which the primary aqueous
15
species of chlorine is molecular chlorine (Cl2), products
10
are bisulfate and hydrochloric acid (White 1999):
5
S2O3 2– –
+ 4 Cl2 + 5 H2O → 2 HSO4 + 8 HCl (1) 0
8.6 8.8 9.0 9.2 9.4 9.6
Initial Reaction pH
Under milder acidic conditions with a pH of 3.95, in
which the primary aqueous chlorine species is hypochlo- FAC—free available chlorine

rous acid (HOCl), there are two identified reactions that The black line represents the averaged relative chlorate
can occur. Main products from these reactions are tetra- concentrations measured for solutions quenched with malonic acid.

thionate (S4O62–) and sulfate (SO42–) along with hydrox-

ide (HO–) or hydrogen ions (H+) (Varga et al. 2006):

  2 S2O32– + HOCl → S4O62–+ Cl– + HO–  (2)
    S2O32– + 4 HOCl + H2O → 2 SO42– + 4 Cl– + 6 H+  (3)
When the reaction is carried out at a higher pH so that
the primary aqueous chlorine species is the hypochlorite
ion (ClO–), there are two main reactions that have been
proposed to occur, again producing tetrathionate and
sulfate as the main oxysulfide products, and either
hydroxide or hydrogen ions (Wilson 1935):
      2 S2O32– + ClO– + H2O → S4O62–+ Cl– + 2 HO–  (4)
     S2O32– + 4 ClO– + H2O → 4 Cl– + 2 H+ + 2 SO42–  (5)
Specific reaction pathways between thiosulfate ions and
aqueous chlorine in the reactions studied in this work are
dependent on both the initial pH of the hypochlorite
solution, as well as the molar ratio between the two reac-
tants. Critically related to the current study, reactions
between aqueous chlorine and thiosulfate ions can result
in significant changes in the solution pH. In the case of
Eqs (reactions) 1, 3, and 5, the pH of the reaction solution
will decrease, and Eqs (reactions) 2 and 4, the pH of the
reaction solution is predicted to increase.
Where the initial pH of the hypochlorite solution was
8.9 or less, reactions with thiosulfate always resulted in a
decrease in pH indicating that, under those conditions, Eq 5
occurs first, with potential contributions from Eqs 1 and
3 as the reaction proceeds. A similar scenario takes place
when the initial hypochlorite solution pH is greater than
8.9 and the S2O32–:ClO– molar ratio is 0.4:1 or less. When
the initial pH is greater than 8.9 and the S2O32–:ClO–
molar ratio is 0.6:1 or greater, the pH of the reaction solu-
tion is always seen to increase, indicating that Eq 4 is the
predominant reaction, although the modest increases in
pH that were observed indicate that Eq 5 still occurred to
a significant extent.
Changes in the reaction pH are critical with regard to
preserving the chlorate content of these solutions as a result
of the additional reactions, which can occur in these sys-
tems, especially in the case of solution acidification. In
aqueous solutions in which the pH is less than 3, thiosul-
fate ions will react with hydrogen ions through two differ-
ent mechanisms to produce the bisulfite ion (HSO3–) and
molecular sulfur (S), or the pentathiolate ion (S5O62–), as
shown in Eqs 6 and 7 (Dinegar et al. 1951):
       H+ + S2O32– → HSO3– + S (6)
          6 H+ + 5 S2O32– → 2 S5O62– + 3 H2O(7)
This reaction is known to proceed at a rate that
increases significantly when the reaction pH is decreased,

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2017 © American Water Works Association

with Eq (reaction) 6 being the primary reaction mecha-
nism. Molecular sulfur in Eq 6 is typically produced as a
colloidal solid, which causes turbidity in the reaction
mixture along with a rotten-egg odor. Reactions between
thiosulfate ions and hypochlorous acid in acidic solutions
have been postulated to produce bisulfite ions through a
variety of reaction mechanisms (Varga et al. 2006). Eq 6
can also be written in a form that shows the production
of sulfur dioxide gas (SO2), which has a strong burnt-
match odor and can then hydrolyze (according to Eq 9)
to produce bisulfite ions along with other sulfur species
(Zhang & Ewing 2002):
     2 H+ + S2O32– → H2O + SO2 + S
       SO2 + H2O ↔ H+ + HSO3–
Inferences about the acidic degradation of thiosulfate
ions can be made on the basis of observations made on
the changes in the physical characteristics of the post-
reaction solutions. When the S2O32–:ClO– molar ratio
was 0.2:1 or less, sulfurous odors were nearly always
observed to be produced, with the highest-intensity
odors occurring as the S 2 O 3 2– :ClO – molar ratio
approached 0.2:1. This indicates that some amount of
the added thiosulfate reacts with acid produced from
Eqs 1, 3, or 5 through Eqs 6 or 8 to produce enough
sulfur dioxide to be detectable, but the lack of an observ-
able turbidity in these reactions indicates that the
amount of thiosulfate consumed by Eq 6 or 8 is minimal.
Interestingly, the sulfurous smell was also detected in
reactions in which the S2O32–:ClO– molar ratio was less
than 0.2:1, but the final pH increased relative to the
initial pH. The observed pH change indicates that Eqs 2
and 4 were predominant under these conditions, but the
appearance of the sulfurous smell indicates that the reac-
tion solution was likely acidified at some point prior to
the final state of the reaction.
When the S 2O 32–:ClO – molar ratio was increased
greater than 0.2:1, and therefore thiosulfate was present
in stoichiometric excess of the amount needed to fully
react with the hypochlorite present in the initial solution,
turbidity and a sulfurous odor were usually observed
when the pH of the post-reaction solution was acidic.
These observations are consistent with the production of
molecular sulfur, which has an extremely low solubility
in water (Boulegue 1978). Turbidity, along with the sul-
furous smell, was not observed in solutions in which the
pH was increased as a result of the reaction, and thiosul-
fate was used in a stoichiometric excess of the amount
needed to quench the hypochlorite present in the initial
solution. This observation indicates that only Eqs 2 and
4 primarily occurred under these conditions, and that the
excess thiosulfate used remained in the solution after the
hypochlorite was consumed, although this was not veri-
fied in these tests.
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Production of bisulfate ions is critical in these solutions
because this species can rapidly react with and degrade
chlorate ions, producing sulfate and chloride ions along
with additional hydrogen ions (Gleason et al. 1957,
Nixon & Krauskopf 1932):
        ClO3– + 3 HSO3– → Cl– + 3 SO42– + 3 H+ (10)
As a result of this reaction, in hypochlorite solutions in
which bisulfite ions are generated as a result of the acid
degradation of thiosulfate, chlorate present in the initial
solutions can be expected to be partially or totally con-
sumed by Eq (reaction) 10. This effect was clearly seen in
(8) the chlorate analysis of the thiosulfate-quenched hypo-
chlorite solutions.
(9) Chlorate testing implications. Acidification of hypo-
chlorite solutions during quenching with thiosulfate,
and the resulting associated production of sulfur diox-
ide and bisulfite ions, is likely responsible for the lower
chlorate measurements made on solutions in which this
process occurs. While many quenching conditions can
result in chlorate measurements that are consistent
with control samples quenched with malonic acid, data
from these tests demonstrated that, even under what
could be considered optimal quenching conditions, the
reaction between thiosulfate and hypochlorite can
result in the production of some chlorate-quenching
byproducts even when not expected. Because FAC
content and pH of the solutions used in this study were
modeled after what is commonly seen for OSG-produced
hypochlorite solutions, results clearly demonstrate that
using sodium thiosulfate to quench hypochlorite solu-
tions produced using OSGs can result in unreliable
chlorate measurements.
CONCLUSIONS
In summary, unreliable chlorate measurements can
potentially be made on hypochlorite solutions produced
by OSG systems in which sodium thiosulfate is used to
quench the chlorine component of these solutions. Under
several quenching conditions, acidification of the solution
was observed, which in turn resulted in the acidic conver-
sion of sulfate ions into bisulfite ions, which can react with
and degrade chlorate ions present in the initial solution,
ultimately causing artificially decreased measurements of
chlorate content. Even under optimal quenching conditions
in which the end point of the reaction had no outward
appearance of the formation of chlorate-reducing sulfur
species, or when the precise amount of thiosulfate required
to consume the hypochlorite is used, depressed chlorate
measurements can be made. As a result of observations in
this study, it is recommended that malonic acid be used as
the primary hypochlorite quenching agent for measuring
the chlorate content of oxidant solutions produced through
OSG processes, and that sodium thiosulfate be avoided for
this application.

ENDNOTES
1Hach Co., Loveland, Colo.
2AlfaAesar, Haverhill, Mass.
3Pocket
Colorimeter II, Hach Co., Loveland, Colo.
4IQ Scientific Instruments Inc., Carlsbad, Calif.
ABOUT THE AUTHORS
Andrew K. Boal (to whom
correspondence may be addressed)
obtained his PhD degree in organic
chemistry from the University of
Massachusetts, Amherst, in 2002.
After graduating, he was a
postdoctoral researcher at Sandia
National Laboratory, a fellow of the
NASA Astrobiology Institute at the University of
Hawaii in Honolulu, and a senior member of the
technical staff at Sandia National Laboratory. In 2008
Boal joined MIOX, now a Johnson Matthey company,
5601 Balloon Fiesta Pkwy., Albuquerque, NM 87113
USA; andrew.boal@matthey.com. His focus is on
technology development in the water space. As MIOX’s
chief scientist, Boal is focused on working with partners
and customers to develop and deliver cutting-edge
water disinfection technologies. Fotios I. Patsalis is an
intern at Johnson Matthey. As full-time employees of a
company that makes onsite generation systems and that
also supported the costs associated with this research,
the authors have declared an affiliation that could be
perceived as posing a potential conflict of interest in the
publication of this article.
https://doi.org/10.5942/jawwa.2017.109.0097
PEER REVIEW
Date of submission: 03/07/2017
Date of acceptance: 04/27/2017
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