Journal of Environmental Science and Health, Part A

Toxic/Hazardous Substances and Environmental Engineering

ISSN: 1093-4529 (Print) 1532-4117 (Online) Journal homepage: http://www.tandfonline.com/loi/lesa20

Effect of wastewater quality parameters on

coliform inactivation by tin oxide anodes

Amy L. Teel & Richard J. Watts

To cite this article: Amy L. Teel & Richard J. Watts (2018) Effect of wastewater quality parameters
on coliform inactivation by tin oxide anodes, Journal of Environmental Science and Health, Part A,
53:5, 443-447, DOI: 10.1080/10934529.2017.1409020

To link to this article: https://doi.org/10.1080/10934529.2017.1409020

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JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH, PART A
2018, VOL. 53, NO. 5, 443–447
https://doi.org/10.1080/10934529.2017.1409020

Effect of wastewater quality parameters on coliform inactivation by tin oxide anodes

Amy L. Teel and Richard J. Watts
Department of Civil and Environmental Engineering, Washington State University, Pullman, Washington, USA

ABSTRACT ARTICLE HISTORY

The effect of six water quality constituents on wastewater effluent disinfection by tin oxide anodes (TOAs) Received 8 August 2017
was investigated in single cell laboratory reactors. Several concentrations of suspended solids, chemical Accepted 17 November 2017
oxygen demand (COD), alkalinity, ammonia–nitrogen, nitrite–nitrogen, and nitrate–nitrogen were added KEYWORDS
to media containing 106 total coliform bacteria mL¡1. Current was applied through the TOAs, and coliform Tin oxide anodes;
bacteria viability was analyzed over time. Over 99.9% inactivation of coliform bacteria was found over dimensionally stable anodes;
15 min in TOA reactors. Concentrations of the six water quality constituents typical of concentrations water quality; wastewater
found in wastewaters had no effect on TOA disinfection efficacy. The results of this research demonstrate effluent disinfection;
that TOAs, which could potentially be powered by solar panels, have potential as a sustainable electrochemical disinfection
disinfection process compared to chlorine, ozone, and ultraviolet light.

Introduction
Chlorine is the most commonly used disinfectant for wastewa-
ter effluents in the United States as well as throughout the
world. It is inexpensive and effectively inactivates most patho-
gens found in wastewater effluents. However, the use of chlo-
rine has several disadvantages. Chlorine is transported using
large tanks that sometimes rupture, resulting in the spread of a
low-lying toxic cloud.[1] Chlorination of water containing natu-
rally occurring organic compounds results in chlorinated prod-
ucts that are often mutagenic.[2,3] In addition, chlorination of
wastewater effluents results in the formation of trihalomethanes
and other disinfection byproducts.[4] Furthermore, the toxicity
of the treated effluent must be mitigated by dechlorination.[5]
The water quality of the effluent also deteriorates during chlori-
nation; chloride and total dissolved solids are increased while
the pH is decreased.[6]
Alternatives to chlorine have recently been developed,
including ozone and ultraviolet (uv) light. Ozone is an effective
disinfectant, but must be generated on site, and its generation
is energy-intensive and expensive.[7] It is also highly corrosive
and toxic, and the off-gas requires treatment. Because of main-
tenance difficulties, there are only about 10 ozone wastewater
treatment plants currently in the United States.[8] Disinfection
of wastewater effluents is often effective using uv light, which is
absorbed by, and destroys, the DNA and RNA of microorgan-
isms. Significant advances have been made in uv disinfection
with the development of new low pressure and medium pres-
sure uv lamps, ballasts, and contactors. Although uv disinfec-
tion is effective, does not generate disinfection byproducts, and
is safer than chemical disinfectants, it does have significant
shortcomings. It is energy-intensive and expensive, and some
configurations require significant maintenance, such as acid
washing lamps to remove scale.[9]
Advanced oxidation processes (AOPs), which generate the
highly reactive oxidant hydroxyl radical, have been investigated
for effluent disinfection at the laboratory level. AOPs such as
Fenton’s reagent, uv/ozone, uv/hydrogen peroxide, and tita-
nium dioxide mediated photocatalysis are effective in inactivat-
ing microorganisms; however, these processes are expensive
and have yet to be evaluated at full scale.[10–13]
An AOP that has significant potential for low cost disin-
fection with a low carbon footprint is electrode technology.
Numerous electrodes have been investigated for the oxida-
tion of organic compounds including platinum, titanium/
ruthenium oxide, titanium/platinum, and tin oxide.[14] All
of these electrodes are effective in oxidizing organic com-
pounds in two chamber electrochemical cells separated by a
Nafion membrane. However, tin oxide anodes (TOAs) have
a significant advantage over other electrode systems because
minimal back reactions occur at the cathode.[14] As a result,
TOAs can potentially be used in single cell systems such as
plug flow reactors. Furthermore, TOAs could potentially be
powered by solar panels mounted on the roof of a wastewa-
ter treatment facility to reduce the carbon footprint of the
disinfection process.
Wastewater effluent disinfection by chlorination is strongly
influenced by the concentration of various water quality con-
stituents such as alkalinity, nitrogen species, and suspended sol-
ids.[6] For example, chlorine reacts with ammonia to form
chloramines, which are classified as combined chlorine resid-
uals. Combined chlorine is less effective in inactivating some
viruses, spores, and cysts relative to free chlorine.[15] These
water quality constituents can also scavenge hydroxyl radical
and other reactive oxygen species, which could potentially
affect the efficacy of TOA disinfection. The objective of this
research was to investigate coliform disinfection using TOAs in

CONTACT Amy L. Teel amy_teel@wsu.edu Department of Civil & Environmental Engineering, Box 2910, Washington State University, Pullman, WA 99164-
2910, USA.
© 2018 Taylor & Francis Group, LLC
444 A. L. TEEL AND R. J. WATTS

a single chamber system and to evaluate the effects of common
water quality constituents on disinfection effectiveness.
Materials and methods
Materials
Sodium bicarbonate, sodium sulfate, ammonium chloride,
sodium nitrite, sodium nitrate, isopropanol, tin chloride pen-
tahydrate, antimony chloride, and tin sulfate were purchased
from Sigma-Aldrich. M-Endo broth, potassium dichromate,
sodium thiosulfate, hydrochloric acid, and sulfuric acid were
purchased from J.T. Baker. M9 medium was prepared as
described in Standard Methods for the Examination of
Water and Wastewater.[16] Chemical oxygen demand (COD)
analysis reagents were purchased from Hach Chemical. Tita-
nium rods (2 mm diameter) were purchased from GoodFel-
low Metals.
Preparation of TOAs
The method for preparing the TOAs was based on the proce-
dures of Lipp and Pletcher,[17] as modified by Loge et al.[18] and
Watts et al.[14] Titanium rods were pretreated by bead blasting,
sonication in isopropanol for 20 min, boiling in 11.5 M HCl for
1 min, rinsing in deionized water, and air drying. Eight coatings
of tin-antimony were then applied by dipping the rods eight
times in isopropanol containing tin chloride (SnCl4:5H2O; 20%
w v¡1) and antimony chloride (SbCl4; 1% w v¡1); the rods were
allowed to dry for 20 min between each dip. The anodes were
oven-dried at 1008C for 10 min, and annealed in a muffle fur-
nace at 5008C for 20 min. Each batch of anodes was tested after
preparation. The anodes were placed in a holder fitted to a
200 mL batch reactor matched with stainless steel cathodes.[18]
The anodes and cathodes were connected to a Tenma 72–
4045A DC power source with constant current of 200 mA. Any
anodes that did not support a current of 200 mA for 1 h were
discarded. TOAs prepared by this method have been demon-
strated to maintain optimal performance over a service life
of 30 d of continuous use[18] and over 1280 cycles of cyclic
voltammetry. [19]
Source of water quality constituents
Sodium bicarbonate, ammonium chloride, sodium nitrite, and
sodium nitrate were used as sources of alkalinity, ammonia–
nitrogen, nitrite–nitrogen, and nitrate–nitrogen, respectively.
The source of chemical oxygen demand was filtered primary
wastewater influent. It was analyzed for COD using the high
level ampule technique;[16] it was then added to reactors to pro-
vide a range of COD (10–50 mg L¡1). Secondary effluent col-
lected from the Pullman, WA wastewater treatment facility was
used as a source of suspended solids. A stock solution of settled
effluent was analyzed for suspended solids; the stock solution
was then diluted to 10–50 mg L¡1 suspended solids in M9
medium.
Reactor systems
A single chamber reactor was used to assess the effectiveness of
TOAs under the practical constraints of a typical effluent disin-
fection system; e.g., a plug flow reactor in which both the ano-
des and the cathodes are configured in the reactor (Fig. 1). The
anodes and cathodes were connected to a Tenma 72–4045A
DC power source. All reactions were conducted in triplicate,
and control systems were evaluated in the same reactors with-
out the application of current.
Effect of water quality constituents on the TOA
inactivation of coliform bacteria
Reaction solutions (200 mL) consisted of M9 medium with
1 mM sodium bicarbonate (to provide conductance) and 106
coliform bacteria mL¡1. In separate experiments, additional
alkalinity (0.25–2.0 mM [12.5–100 mg L¡1 as calcium carbon-
ate]), ammonia–nitrogen (0.25–2.0 mM [3.5–28 mg L¡1 nitro-
gen]), nitrite–nitrogen (0.25–2.0 mM [3.5–28 mg L¡1
nitrogen]), nitrate–nitrogen (0.25–2.0 mM [3.5–28 mg L¡1
nitrogen]), suspended solids (10–50 mg L¡1), or chemical oxy-
gen demand (10–50 mg L¡1) was added to the solutions.
Wastewater constituent concentrations were chosen to be in

Wastewater samples
Secondary effluent, primary effluent, and mixed liquor were
collected from the Pullman, WA, wastewater treatment facility,
a 18,950 m3 d¡1 (5 mgd) conventional activated sludge plant
that receives minimal industrial waste inputs.

Source of coliform bacteria

Settled primary effluent collected from the Pullman, WA
wastewater treatment plant was used as a source of coliform
bacteria. The primary effluent was allowed to settle for 30
min; the supernatant was then analyzed for total coliform bac-
teria using the membrane filter technique.[16] This stock coli-
form source was then added to reaction solutions to provide
106 coliform bacteria mL¡1. Figure 1. Single chamber reactor configuration for tin oxide anode system.
 JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH, PART A 445

the range commonly found in wastewaters.[15] Current was 1

Colony Forming Units (C/C0)

applied to the anode, and aliquots were collected every 2.5 min
and analyzed for total coliform bacteria.
0.1

Analysis 0.01
No Current
10 mg/L
Total coliform counts in the reactors after treatment were 20 mg/L
determined using the membrane filter technique.[16] The data 0.001 30 mg/L
40 mg/L
obtained featured counts of coliform bacteria as a function of 50 mg/L

time affected by different concentrations of water quality con- 0.0001

stituents. These data were analyzed using completely random- 0 5 10 15

ized design analysis of variance (CRD ANOVA) with one way
treatment structure and repeated measures using aD0.05 (95%
confidence interval).
Time (min)
Figure 3. Effect of chemical oxygen demand (10–50 mg L¡1) on coliform inactiva-
tion in tin oxide anode systems. Error bars represent the standard error of the
mean of three replicates.

Results and discussion These results are consistent with a non-hydroxyl radical path-
Effect of suspended solids on TOA disinfection way for disinfection in TOA systems.

When suspended solids were added to TOA reactors containing

M9 medium, statistical analysis showed that there was no effect
on coliform inactivation at concentrations from 10 mg L¡1 to
50 mg L¡1 (Fig. 2). Suspended solids can have significant effects
on disinfection effectiveness, especially for uv disinfection in
which solids shade the bacteria from the disinfecting agent.[20]
The results of Figure 2 demonstrate that there is a pathway for
TOA disinfection in the presence of suspended solids; a possi-
ble pathway is through superoxide, which can potentially dis-
rupt suspended solid particles.[21,22]
Effect of COD on TOA disinfection
The disinfection of coliform bacteria as a function of time in
TOA reactors containing six COD concentrations (0–50 mg
L¡1) is shown in Figure 3. The results indicate that COD has
minimal effect on disinfection by TOAs. Statistical analyses
confirmed that the coliform disinfection rates were not signifi-
cantly different (a D 0.05) when COD was added in increasing
concentrations to 50 mg L¡1. Hydroxyl radical is rapidly scav-
enged by the carbohydrates and amino acids that make up
COD,[23] and previous results confirmed that as expected, the
COD used in Figure 3 was oxidized in TOA systems.[24,25]
Effect of alkalinity on TOA disinfection
The effect of alkalinity on the disinfection activity of TOAs in
M9 medium was investigated by using six concentrations of
bicarbonate (0.25–2 mM [12.5–100 mg L¡1 as calcium carbon-
ate]) and then analyzing for total coliform bacteria (Fig. 4).
Alkalinity had no significant effect on coliform inactivation up
to 2 mM of bicarbonate (100 mg L¡1 as calcium carbonate) (a
D 0.05). Statistical analysis, using completely randomized
design analysis of variance (CRD ANOVA) with one way treat-
ment structure and repeated measures, confirmed that there
was no significant difference between the different concentra-
tions of alkalinity (a D 0.05). These results show that increasing
alkalinity within a range of concentrations typical of waste-
waters has a negligible effect on the disinfection activity TOAs.
Effect of nitrogen species on TOA disinfection
The inactivation of coliform bacteria by TOAs amended with
six concentrations of ammonia–nitrogen is shown in Figure 5.
Statistical analyses confirmed that the coliform inactivation
rates were not significantly different (a D 0.05) when ammonia
was added in concentrations up to 2 mM (28 mg L¡1

1 1
Colony Forming Units (C/C0)

Colony Forming Units (C/C0)

0.1 0.1

0.01 0.01
No Current No Current
10 mg/L 0.25 mM
20 mg/L 0.5 mM
0.001 30 mg/L 0.001 0.75 mM
40 mg/L 1.0 mM
50 mg/L 1.5 mM
2.0 mM
0.0001 0.0001
0 5 10 15 0 5 10 15

Time (min) Time (min)

¡1
Figure 2. Effect of suspended solids (10–50 mg L ) on coliform inactivation in tin Figure 4. Effect of alkalinity (0.25–2.0 mM [12.5–100 mg L¡1 as calcium carbon-
oxide anode systems. Error bars represent the standard error of the mean of three ate]) on coliform inactivation in tin oxide anode systems. Error bars represent the
replicates. standard error of the mean of three replicates.
446 A. L. TEEL AND R. J. WATTS

1 1
Colony Forming Units (C/C0)

Colony Forming Units (C /C0)

0.1 0.1

0.01 No Current 0.01 No Current

0.25 mM 0.25 mM
0.5 mM 0.5 mM
0.001 0.75 mM 0.75 mM
0.001
1.0 mM 1.0 mM
1.5 mM 1.5 mM
2.0 mM 2.0 mM
0.0001 0.0001
0 5 10 15 0 5 10 15

Time (min) Time (min)

Figure 5. Effect of ammonia–nitrogen (0.25–2.0 mM [3.5–28 mg L¡1 nitrogen]) on Figure 7. Effect of nitrate–nitrogen (0.25–2.0 mM [3.5–28 mg L¡1 nitrogen]) on
coliform inactivation in tin oxide anode systems. Error bars represent the standard coliform inactivation in tin oxide anode systems. Error bars represent the standard
error of the mean of three replicates. error of the mean of three replicates.

ammonia–nitrogen). The effect of nitrite–nitrogen on coliform
inactivation is shown in Figure 6. The results indicate that there
was also no significant difference in coliform inactivation with
nitrite–nitrogen concentrations up to 2 mM (28 mg L¡1
nitrite–nitrogen) (a D 0.05). The inactivation of coliform bac-
teria by TOAs amended with six concentrations of nitrate–
nitrogen is shown in Figure 7. Statistical analyses confirmed
that the coliform inactivation rates were not significantly differ-
ent (a D 0.05) when nitrate–nitrogen was added in concentra-
tions up to 2 mM (28 mg L¡1).
The results of Figure 7 are expected because nitrate is highly
oxidized and therefore should not compete with oxidants gen-
erated by TOAs. The results of Figures 5 and 6 are unexpected
because nitrite and ammonia are reduced species that should
scavenge oxidants generated by TOAs. Two disinfection path-
ways that are consistent with the results of Figures 5 and 6 are
disinfection by superoxide, a nucleophile, and disinfection by
direct oxidation on the TOA surface.
The results of Figures 2–7 are in agreement with the data of
Teel et al.[24] who found that the rate of loss of the oxidant
probe hexanol was also not affected by suspended solids, COD,
ammonia–nitrogen, nitrite–nitrogen, or nitrate–nitrogen. Four
of the water quality constituents investigated are reduced
(COD, suspended solids, ammonia–nitrogen, nitrite–nitrogen)
and would compete for hydroxyl radical if it is the dominant
reactant in contaminant destruction and disinfection in TOA
1 [1] White, G. C. Handbook of Chlorination and Alternative Disinfec-
Colony Forming Units (C/C0)
systems. These results suggest that another oxidation pathway
is present in TOA systems, such as electron holes on the anode
surface,[26,27] and that this pathway is not affected by common
water quality characteristics.
Conclusion
The results of this research show that alkalinity, ammonia–
nitrogen, nitrite–nitrogen, nitrate–nitrogen, suspended sol-
ids, and COD in concentrations typical of secondary
effluents have minimal effects on the inactivation of coliform
bacteria by TOAs. The characteristics of an ideal disinfectant
include the potential to deodorize while disinfecting and to
penetrate through suspended solids, and to be noncorrosive,
nontoxic to humans, and highly toxic to microorganisms.[15]
TOA disinfection has all of these characteristics, and there-
fore has the potential for full-scale disinfection. Furthermore,
TOAs could be powered by solar panels, which can lower the
carbon footprint of wastewater treatment and increase
sustainability.
Funding
Funding for this research was provided by the Water Environment
Research Foundation through Grant No. 02-CTS-6.
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