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Calcium polysulphide, its applications and emerging risk of environmental

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Environ Sci Pollut Res
DOI 10.1007/s11356-016-7842-3
REVIEW ARTICLE
Calcium polysulphide, its applications and emerging risk
of environmental pollution—a review article
Saad Mohammed Dahlawi 1 & Samreen Siddiqui 2
Received: 25 April 2016 / Accepted: 4 October 2016
# Springer-Verlag Berlin Heidelberg 2016
Abstract Easy availability, preparation technique, and eco-
nomic value make calcium polysulphide (CaSx) a very useful
inorganic chemical for various field and industrial applica-
tions. In this article, disparate applications of CaSx solution
have been reviewed to suggest potential and future consolida-
tion. This article also encompasses the physiochemical prop-
erties and production of CaSx solution, with critical appraisal
on research focusing on CaSx application in agriculture indus-
tries and removal of potentially toxic elements (PTEs) from
the environment. The kinetics of CaSx, technical issues asso-
ciated with optimization of its dosage and environmental fate
is also discussed in detail. This study covers almost all of the
peer-reviewed research that has been performed since 1914.
Some of the critiques in this article include the lack of inte-
gration between the exposure effect and the efficiency of
Responsible editor: Philippe Garrigues
Highlights
• Physicochemical properties of CaSx and its chemical speciation.
• Application of CaSx in agriculture industries, removal of potentially
toxic elements (PTEs) from air, soil, wastewater, and groundwater.
• Reduction of Cr(VI) to Cr(III) in chromite ore processing residue
(COPR).
• Technical issues associated with the molar ration of CaSx.
• Detailed kinetics of CaSx.
• Environmental fate and toxicity aspects of CaSx.
* Saad Mohammed Dahlawi
smdahlawi@uod.edu.sa
1
Department of Environmental Health, College of Applied Medical
Sciences, University of Dammam, P. O Box 2435, Dammam 31441,
Kingdom of Saudi Arabia
2
Department of Physical & Environmental Sciences, The Coastal
Health and Water Quality (C-HaWQ) Laboratory, Texas A&M
University Corpus Christy, Corpus Christi, TX 78412, USA
treatment method, effects of oxidizing environments on the
long-term performance of CaSx solution, and kinetics of
CaSx solution with the PTEs. The working model of CaSx
with PTEs is still system dependent, and therefore cannot be
used with other applications. The kinetics of CaSx is described
in detail with various phase stoichiometric reactions.
Environmental fate is discussed based on applications, gov-
ernment reports, peer-reviewed articles and kinetics of CaSx,
which provides a clear picture of emerging contaminants in
the environment in relation to the insect resistance and eco-
toxicology. Real time, lab based research articles are needed to
identify toxicity limits of CaSx in environment in order to
describe its effective permissible limit in environmental sys-
tem. This review article provides a risk assessment of environ-
mental pollution by CaSx based on its physicochemical char-
acteristic, stoichiometry, kinetics, field, and industrial
applications.
Keywords Calcium polysulphide . Heavy metals . COPR .
Soil . Wastewater . Groundwater
Introduction
Calcium polysulphide (CaSx) (CAS no. 1344-81-6), also
known as Bcalcium sulphide (CaS)^ and Blime sulphur^, nat-
urally occurs as gypsum (CaSO4·2H2O) or plaster of Paris
(CaSO4.1/2H2O) (Knauf et al. 1973; Klein et al. 1985) in the
environment. Under required conditions CaSx (x = 2–7) can be
produced by oxidation of hydrogen sulphide (H2S) and calci-
um oxide (CaO) (density 2.61 g cm−3) (Borgwardt 1984).
Levchenko et al. (2015) identified a semi-industrialized meth-
od to synthesize CaSx solution with a Ca/S ratio of 10:23.2 at
100 °C in 200 l of distilled water resulting in 70–75 % CaSx
yield. CaSx is a dark orange solution with a volatile and

unstable nature, especially if exposed to air (Chrysochoou and
Ting 2011; Levchenko et al. 2015). CaSx molecules can exist
as chains of heptasulphide, octasulphide, and nanosulphide
species with a pH value ranging from 6.0 to 11.0 (Gun et al.
2004; Kamyshny et al. 2007a, b). This long chain tends to
breakdown into shorter chains as the pH decreases (Chen
and Morris 1972). CaSx solution contains only 10 % of ele-
mental sulphur at pH 12.0 in the form of polysulphides (S6
and S5) (Chrysochoou et al. 2010). Other species of sulphur
exist in the CaSx solution such as hydrosulphide (HS−),
thiosulphate (S 2 O 3 − ), dithionate (S 2 O 6 2 − ) and H 2 S
(Yahikozawa et al. 1978; Kelsall and Thompson 1993).
Some sulphur species like S52−, S42−, and H2S becomes the
dominant species at pH values less than 8.0 (Kelsall and
Thompson 1993; Chrysochoou et al. 2010).
CaSx solution has a strong reducing capability towards
heavy metals and radionuclides and acts by making precipi-
tates with insoluble metal in the form of their sulphides
(Jacobs 2001; Zhong et al. 2009). The minimum purity of
CaSx is between 290 and 320 g kg−1 required by EFSA with
boiling point of 104.8 °C and solubility in water above pH 8.5
(EFSA 2010; Table 1). CaSx is also regarded as one of the
most promising reductants, with field applications in soils and
for chromite ore processing residue (COPR) (Storch et al.
2002; IETEG 2005; Charboneau et al. 2006; Wazna et al.
2007; Bewley and Clarke 2010).
CaSx is used as BLiquid-Lime Sulfur^ (LLS) (EPA reg. no.
66,196–2) in agriculture where a typical solution contains a
mixture of 29 % (w/v) CaSx and small amounts of calcium
thiosulfate (Smilanick and Sorenson 2001). LLS is prepared
by the combination of hydrated lime (CaO·H2O) and elemen-
tal sulphur with water (Tartar 1914; Auld 1915).
The aim of this literature review is to combine all the avail-
able scientific papers on CaSx applications to provide a cross
section of major research related to CaSx. The goal of this
review is to summarize the physico-chemical properties of
CaSx, its different applications, study its kinetics, and provide
a critique on its environmental fate (Tables 1, 2, 3, and 4). The
range of applications include metal and organic pollutant
Table 1 Physical and chemical properties of CaSx in its pure form
(EFSA 2010)
Molecular formula CaSx (x = 2–7)
Molecular mass 200.4 g mol−1 (average, primary CaSx)
Boiling point 104.8° C
Appearance Amber liquid with rotten egg odor
Water solubility Soluble in water above pH 8.5, unstable
below pH 8.5
Surface tension 71.33 mN m−1 at 20° C
Flammability Not auto-flammable (29/30 % w/w)
Explosive properties Not explosive (29/30 % w/w)
Environ Sci Pollut Res
removal from the environment including air, water, soil, sed-
iments, and COPR, which makes it an attractive chemical for
research. The understanding of proper mechanism and kinet-
ics of CaSx can provide help to researchers and stakeholders in
its application. This review combines available scientific re-
search and suggests the harmful effects of CaSx residues in the
environment, which is commonly ignored by stakeholders.
Methods
This article covers peer-reviewed research papers, case stud-
ies, conference papers, and reports from EU government as
well as United States Environmental Protection Agency
(USEPA) dating as far back as 1914 to 2015. This review
intends to combine standard techniques and methods pub-
lished in peer-reviewed journals, summarize the supporting
data from available research and present the findings in tabular
form (Tables 1, 2, 3, and 4). The standard toxicity testing
results from USEPA and European Food Safety Authority
(EFSA) and the peer-reviewed articles were used to discuss
environmental fate and risk assessment of CaSx (Table 4).
Applications of CaSx solution
Application of CaSx in agriculture
Since the nineteenth century, CaSx solution has been used to
control fungus and molds (McCallan 1967; USEPA 2005;
Table 2). More recently, CaSx solution was used as an active
ingredient for insecticides in agricultural industries (Aratani
et al. 1978b) and in the form of LLS for spraying trees, fruits,
and rose bushes (Ganczarczyk et al. 1985). CaSx is known to
reduce up to 80 and 70 % of the mold caused by Penicillium
digitatum and Geotrichum citri-aurantii, respectively
(Smilanick and Sorenson 2001). In a similar study by Palou
et al. (2002), CaSx was studied with a range of other chemicals
in order to select the most effective fungicide agent against
P. digitatum or Penicillium italicum. The effectiveness of the
selected chemicals was tested either alone or in mixtures at
different temperatures. The results suggested that CaSx was
more effective as a mixture of potassium sorbate (0.1 M)
and sodium propionate (0.1 M) at pH 8.3 and potassium sor-
bate (0.1 M) and sodium acetate (0.1 M) at pH 7.0 compared
to 8.5 M CaSx solution at 6.0 pH.
LLS is characterized by yellow-orange liquid, pH 11.5,
with a density of 1.26 g mL−1 (Smilanick and Sorenson
2001). For a common recommended fungicide application,
LLS solution is diluted to 3 % (w/v) at pH 10.0. The present
lime sulphur formula was standardized in England and LLS
was rediscovered in 1800 and applied as a pesticide spray in
1850 shortly after a fungi disease grape powdery mildew
Environ Sci Pollut Res

Table 2 Application of various CaSx species at variable pH ranges

CaSx species Application pH range Reference

CaS5 Solid-phase Cr(VI) speciation in COPR, USA 12.0 for hard brown (HB) Chyrocochoou et al. (2009a)
cemented COPR
12.5 for gray black (GB)
COPR
Cr(VI) remediation of COPP, USA 7.5 Chyrocochoou et al. (2009b)
Cr(VI) removal from contaminated soil 6.8 Chyrocochoou et al. (2012)
Cr(VI) reduction from brine solution 1.6–6.4 towards 100 % Pakzadeh and Batista (2011)
Cr (VI) removal
6.4–10.3 towards 96 %
Cr (VI) removal
10.3–12.4 towards 72 %
Cr (VI) removal
Cr(VI) and Pb removal from contaminated soil 5.5 Chyrocochoou and Johnston (2015)
Cr(VI) removal from contaminated soil 6.0–6.3 Jacobs (2001); Storch et al. (2002);
IETEG (2005); Chaboneau et al. (2006);
Chyrocochoou et al. (2010);
Cr(VI) removal, lab-based study 5.5–8.5 Chyrocochoou and Ting (2011)
Cr(VI) removal from groundwater 7.0 Messer et al. (2004)
Growth inhibition and simulation of NR Bailey et al. (2012)
Shewanella oneidensis MR-1
Cr(VI) removal from COPR-contaminated soil 7.0 Kameshwari et al. (2014)
CaS6 and CaS8 Immobilizing metals (Pb, Cu, and Ni) from the NR Maletic et al. (2015)
soil
CaS5–9 Demercurization of objects contaminated with NR Patent RU(11) 2 400 545(13) C1
mercury containing sulphur-containing sub-
stance, complexing agents and water,
CaSx Hydrodechlorination and detoxification of NR Tabata et al. (2013);
dioxins from waste incineration Sun et al. (2010)
Preparation of sulphur nanoparticles >7.0 Massalimov et al. (2014)
(1–5 M)
Imroved hardening of Portland cement Alkaline Elesin et al. (2002)
Liquid Lime Sulfur Control of green mold, Penicillium digitatum, 11.5 Smilanick and Sorenson (2001)
(0.75 % CaS5 + and Sour rot, Geotrichum citri-aurantii
CaO3S2) Control of fungus and molds NR McCallan (1967);
USEPA (2005)
Control of gray mite, Calacarus citrifolia NR Dippenaar (1958)
Control of brown rot of peaches, caused by NR Haller (1952);
Monilinia fructicola Poulos (1949)

NR not reported

introduced from North America, devastate vineyards in
Europe (Large 1940). By 1900, LLS was commonly used in
California for apple scab, powdery mildew, San Jose scale,
aphids, mites, brown rot of peaches, and other diseases
(Tweedy 1967; Eckert and Eaks 1989). LLS was found highly
active against the gray mite, Calacarus citrifolia in South
Africa (Dippenaar 1958). At present, LLS is certified as an
acceptable pesticide by most Borganic^ grower organizations
and the United States Department of Agriculture (USDA).
Reports of its applications as a control of postharvest diseases
includes Thurston County review summary report (2012) by
USEPA (2005). In this report, LLS was used as a fungicide-
insecticide/miticide (spider mites) against Powdery mildew,
anthracnose, and scab (USEPA 2005).
The mode of action is described as metabolism disruption
and acts as a protectant by utilizing the fungicidal properties of
elemental sulphur during its degradation (IUPAC 2009).
Some studies suggest that LLS works by producing two toxic
components, H2S and elemental Sulfur. H2S is an inhibitor of
cytochrome oxidase and elemental Sulfur oxidizes cyto-
chrome b to cytochrome c with a byproduct release of H2S
(Smith et al. 1977; Dorman et al. 2002).
Among various energy metabolism enzymes, cytochrome
oxidase also plays an important role in regulating xenobiotics
in insects (Pant 1958). Smilanick and Sorenson (2001) report-
ed, that LLS deposits on P. digitatum spores, even after repeat-
ed rinsing. This causes long-term sub-lethal growth inhibition
by persistent residual deposits, suggesting that LLS works in a
 Environ Sci Pollut Res

Table 3 Summarized doses of CaSx with Potentially Toxic Elements (PTEs) analyzed by different techniques and methods

Target metal CaSx/PTE ratio Methodology and technique used References

Cr 2-8× Bulk X-ray powder diffraction (XRPD); micro X-ray powder Chrysochoou et al. (2009b)
diffraction (μXRPD);
micro X-ray absorption spectroscopy (μXAS); micro X-ray
fluorescence (μXRF) and lab analysis.
1:1 and 1:2 Synthetic precipitation leaching procedure (SPLP) and micro X-ray Chrysochoou et al. (2010)
analysis (MXA)
12× and 24× μXRF and adsorption analysis Chrysochoou et al. (2012)
1:1.8 Use of CaSx and mixed reductant solution (MRS) for Cr(VI) treatment Freedman et al. (2005)
1:5 Quantitative XRPD analysis of residues from treatment of COPR Graham et al. (2006)
1:2 In situ, lab based, toxicity characteristic leaching procedure (TCLP) Wazne et al. (2007a)
and X-ray absorption near edge structure (XANES)
1:2 TCLP and XRPD Wazne et al. (2008)
1×, 2×, 3×, 4×, and 8× Micro X-ray powder diffraction (μXRD), Micro-X-ray fluorescence Chrysochoou and Johnston (2015)
(μXRF) and X-ray absorption nearedge structure (μXANES)
1:2 and 3:4 TCLP leaching studies and extraction procedure toxicity (EP ToX) Kameshwari et al. (2014)
3× TCLP Kameshwari et al. (2015)
CN 1:2 Using NaOH to maintain high pH values during the CaSx precipitation Takaoka and Ganczarczyk (1985)
1:2 Lab based and thermodynamic analysis Ganczarczyk et al. (1985)
Ni 1.3 Chemical analysis and characterization of the sulphide slurry by XRD Mihara et al. (2008)
1.2–1.5 XRD and thermodynamics Soya et al. (2010)
Zn 1.2–1.5 XRD and thermodynamics Soya et al. (2010)
Cu 1.2–2.0 XRD and thermodynamics Soya et al. (2010)

continuous persistent way to inhibit the growth of P. digitatum
instead of killing them immediately. Haller (1952) reviewed,
LLS use on stone fruit and found that applications before
harvest substantially reduced the postharvest incidence of
brown rot of peaches, caused by Monilinia fructicola.
Poulos (1949) reported, postharvest applications of LLS to
the peaches reduced postharvest brown rot incidence about
60 % without injury to the fruit. The LLS solution needs
continuous maintenance and renewal because it is constantly
releasing small amounts of H2S gas that acidifies the solution
(Smilanick and Sorenson 2001; Hojjatie et al. 2011).
Application of CaSx for detoxification of organic
compounds
Another application of CaSx is to remove polychlorinated or-
ganic compounds from fly ash (Tabata et al. 2013; Table 2).
Fly ash can be produced by coal combustion in electricity

Table 4 Summarized acute toxicity values of wildlife and aquatic biota

Organism Toxicity test Value Reference(s)

Rat LD50 820 mg kg−1 Anon (1997); USEPA (2005a)

Birds LD50 560 mg a.i. kg−1 USEPA (2005a)
Honey bee or insect LD50 >25 μg a.i.bee−1 USEPA (2005b)
Contact 48 h >593 μg bee−1 IUPAC (2012)
Oral 48 h >69.8 μg bee−1 IUPAC (2012)
Annelida—worms LC50 >1000 mg kg−1 USEPA (2005a)
Earth worm (Eisenia foetida) 14 days >1000 mg kg−1 IUPAC (2012)
Fish LC50 0.97 mg a.i. l−1 USEPA (2005b)
Crustacean LC50 2.9 mg ai l−1 USEPA (2005)b
Aquatic organisms in surface water and sediments (96 h) LC50 2.67 mg sulphur l−1 ESFSA (2010); IUPAC (2012)
(from lime sulphur)
Algae EC50 >12.6 mg l−1 IUPAC (2012)
(Pseudokirchneriella subcapitata) (72 h)

LD lethal dose, LC lethal concentration, EC effective dose

Environ Sci Pollut Res
generation process, flue gas treatment, and municipal and in-
dustrial waste incineration (Nriagu 1988; Sun et al. 2010;
Kalogirou et al. 2010; Tabata et al. 2013). In a study by
Tabata et al. (2013), aqueous mixture of calcium hydroxide
(CaOH) and sulphur was used to reduce dioxin compounds
such as polychlorinated dibenzo-p-dioxins (PCSDDs),
polychlorinated dibenzofurans (PCDFs), and polychlorinated
biphenyls (PCBs) generated from industrial and municipal
waste incinerators. A rapid hydrodechlorination of chloroben-
zene and PCBs derivatives has been reported after CaSx ap-
plication. The study concluded that about 87 % of the PCDD/
Fs and PCBs were decomposed and detoxified at temperature
150 °C with 30- to 60-min agitation.
Application of CaSx for detoxification of metals
Detoxification of Cr(VI)
Chromium is one of the toxic and carcinogenic heavy metals
frequently detected in polluted areas with Cr metallurgy, leather
tanning, and metal plating industrial facilities (Syracuse
Research Corporation 1993; Katz and Salem 1994; Chen
et al. 1996; Chandra et al. 1997). Chromium occurs in various
oxidation states ranging from Cr (−II) to Cr(+VI) out of which
Cr(VI) and Cr(III) are the most stable species in the environ-
ment (Zayed and Terry 2003). Cr(VI) is mobile in soils with
acidic and alkaline pH (Adriano 1986). To remove Cr(VI) from
polluted area, it is reduced to Cr(III) in the presence of various
sulphides, ferrous iron and soil organic matter (Rai et al. 1989).
CaSx has been used as a rapid reductant of soluble Cr(VI) to
immobile Cr(III) and this reaction has been referred to as
Bgeochemical fixation^ (Fruchter 2002; Freedman et al. 2005).
Chyrosochoou et al. (2010) treated Cr(VI)-contaminated
glacial soil from a Cr plating facility using 1× and 2× stoichio-
metric ration of CaSx and analyzed the resultant Cr(VI) with
synthetic precipitation leaching procedure (SPLP) and micro
X-ray fluorescence spectrometry (Micro-XRF). The pH of
treated soil increased from 6.0 to 11.0 upon CaSx addition
and returned to 8.0–8.5 after 1 year. This suggests that CaSx
created an apparent Cr(VI) immobilization environment for the
first 60 days of treatment which subsequently decreased the
solubility of Cr(VI) for up to 1 year of monitoring. Similarly,
studies reported, CaSx as an effective agent to reduce Cr(VI) to
Cr(III) at a former wood treatment facility (Jacobs 2001;
IETEG 2005). Storch et al. (2002) reported Cr(VI) reduction
at a former chrome plating facility in Arizona using CaSx. One
of the case studies at Morsen pond Culvert, MA, USA, sug-
gests the successful application of CaSx to treat Cr in a railroad
embarkment with Cr laden pigment. CaSx also applied in
Hanford cite to remove Cr from soil (Chaboneau et al. 2006).
CaSx solution has been used for the treatment of wastewa-
ter, groundwater and effluents attributable to different indus-
tries containing high concentrations of toxic elements (Aratani
et al. 1978a, 1978b; Yahikowaza et al. 1978; Takaoka and
Ganczarczyk 1985; Messer et al. 2004; Chen et al. 2009;
Table 2). CaSx removed Cr contamination by reducing
Cr(VI) to Cr(III) within 30 min of CaS x treatment
(Yahikozawa et al. 1978). Cr(III) can be precipitated at alka-
line pH to Cr(OH)3 (Graham et al. 2006). CaSx solution also
studied in relation to the treatment of Cr by ion-exchange
method in waste brine solutions (Pakzadeh and Batista
2011). Authors concluded that a molar ratio of CaSx to
Cr(VI) between 0.60 and 1.40 at pH range 8.00–10.30 is
needed to obtain a final Cr concentration less than 5 mg l−1.
Messer et al. (2004) recommended CaSx as a permanent
remediation technique for Cr(VI) fixation in soil (alluvial fan
sediments) and groundwater, based on a study at a former metal
plating facility in Western Arizona. In this study, approximately
660 gal of 29 % CaSx was applied to the 20-ft2 test zone of
infiltration trenches for 24 h followed by 2500 gal of water to
disperse the chemical through test zone. Results for the first
30 days indicated a 90 % reduction in Cr(VI) concentration.
In the same study, authors applied approximately 9000 gal of
29 % CaSx in an aquifer at about 165 ft below the surface of the
soil followed by 79,000 gal of water. In this case, less than
1 mg l−1 Cr(VI) was observed after 35 h of CaSx treatment.
There were attempts to treat groundwater contaminated with
Cr(VI) in anaerobic conditions (Zhong et al. 2009). One study
considered the foamability of CaSx and determined the reducing
potential of CaSx when delivered as foam. CaSx was mixed with
surfactant sodium POE(3) laureth sulphate, or sodium
laurylether sulphate, to treat Cr(VI) in groundwater under anaer-
obic conditions. Delivery of CaSx as a foam was compared with
the direct flushing of the CaSx solution. It was concluded that
direct liquid flushing of CaSx solution was more effective than
the delivery of CaSx foam (>98 % of total water leachable Cr(VI)
was mobilized compared to 28 % mobilization, respectively).
Another study reported the reduction of Cr(VI) in solution under
anaerobic condition catalyzed with sulphur nanoparticles result-
ed in accelerated Cr(VI) reduction (Lan et al. 2005).
CaSx was also widely used as a strong reductant Cr(VI) to
Cr(III) in COPR which is generated as a waste by-product during
industrial chromite ore processing. COPR contains high amounts
of Cr(VI) (Freese et al. 2014). CaSx is used for the treatment of
COPR by reducing Cr(VI) to Cr(III) at variable pH (Lan et al.
2005; Graham et al. 2006; Farmer et al. 2006; Wazne et al. 2007;
Moon et al. 2008, 2009; Chrysochoou et al. 2009a, 2009b, 2010;
Jagupilla et al. 2009; Chrysochoou and Ting 2011; Freese et al.
2014). CaSx solution was directly applied on the COPR to treat the
Cr(VI).Theeffect ofthetreatment wasevaluatedbymeasuringthe
resultant Cr(III) either quantitatively or qualitatively. In each of
these studies, different molar ratios of CaSx solution to Cr(VI)
were used under different pH conditions (Table 2). Graham et al.
(2006) were first to use CaSx for the COPR treatment in Glasgow,
UK, in groundwater contamination from the chemical works and
suggested the pH range 8.0 to 12.5 was more effective.

CaSx requires suitable conditions to reduce Cr(VI) at dif-
ferent rates. COPR treatment is challenging in terms of speci-
ation and distribution of Cr(VI) specially when Cr(VI) occurs
in the solid phase. According to Chyrosochoou et al. (2009b)
solid phase made Cr(VI) inaccessible for CaSx to bind.
Therefore in order to react Cr(VI) with the added sulphur ions
(CaS5), it is essential to release Cr(VI) from solid matrix into
solution. Similarly, Cr(VI) was bounded as PbCrO4 in the
beginning that precipitated in the interspatial pores of soil
and had a long residence time in environment
(Chyrosochoou et al. 2010). Authors also concluded that in
situ reduction is not an efficient treatment method for high
Cr(VI) containing soils in surficial layers. The CaSx applica-
tion for Cr application has been summarized in Table 2.
Detoxification of other potentially toxic elements (PTEs)
Another application of CaSx is to remove PTEs from different
matrices such as fly ash, soil, wastewater, and groundwater
(Table 2). Fly ash generated from municipal waste incineration
facilities contains high levels of pollutants like dioxins and
heavy metals including Pb and Cr(VI) (Bosshard et al. 1996;
Nagib and Inoue2000; Hartmut et al. 2001; Kalogirou et al.
2010; Darakas et al. 2013). In a study by Sun et al. (2010),
the application of CaSx solution in fly ash precipitated Pb as
PbO/PbCO3. It was concluded that there was an overall de-
crease in soluble Pb concentration from the leachates of treated
fly ash by post-treatment leaching tests.
CaSx solution has also been used for the treatment of waste-
water, groundwater and effluents attributable to different indus-
tries containing high concentrations of toxic elements (Aratani
et al. 1978a, 1978b; Yahikowaza et al. 1978; Takaoka and
Ganczarczyk1985; Messer et al. 2004; Chen et al. 2009;
Table 2). Yahikowaza et al. (1978) utilized CaSx (x = 4.7–5.4)
as a single coagulant, to remove heavy metals (Hg2+, Cd2+,
Pb2+, Cu2+, Zn2+, Cr3+, and Cr6+) from wastewater. CaSx also
used as a potential treatment of industrial effluents containing
concentrated cyanide (CN) liquors in combination of other
polysulphides (Takaoka and Ganczarczyk1985). The study
suggested that the treatment was effective in a broad range of
CN concentrations and metal complexes.
Calcium sulphide (CaS) was studied in relation to the
sulphidation of Zn, Ni, and Cu from wastewater originating
from a plating facility (Soya et al. 2010). In this study, selec-
tive precipitation of metal sulphides achieved at different pH
values and CaSx was described as the most effective precipi-
tation agent for separation and recovery of Cu, Zn, and Ni.
Increasing the molar ratio of the filtrates resulted in increasing
pH value. In another study, CaSx solution was used for the
treatment of automotive wastewaters containing Cu, Ni, Pb,
and Zn (Kim et al. 2002). In this case, precipitation of metals
as sulphides were compared to metal hydroxide precipitation
in the presence of chelating agents and it was concluded that
Environ Sci Pollut Res
the presence of small amounts of chelating agents can de-
crease the solubility of metal sulphides. Chelating agents, such
as EDTA, can inhibit the precipitation of Ni, Zn and Pb above
the proposed standards. In a study by Mihara et al. (2008),
CaS was produced as a recycled product of waste gypsum.
CaS was then used for treatment of Ni containing simulated
wastewater. The produced CaS was utilized as a sulphuration
agent to treat simulated wastewater containing Ni. CaS to Ni
ratio of 1.30 was successfully decreased the concentration of
Ni from 100 mg l−1 to less than 1.0 mg l−1 (Table 3).
CaSx is also used for demercurisation processes as patented by
Russian institution. In this process, a mercury containing waste,
phosphor (the content is Tuti was determined according to GOST
C 51768–2001) was mixed in polyethylene containers with the
sample oxidizer (chlorine, lime, white, chloramine). To obtain a
thick concrete solution consistency, 25–50 wt% water was added
to the mixture and left for 7–8 h. CaSx (2.5 to 12 %) was added to
this mixture at room temperature and laid out on pallets for 2–
2.5 h until it dried out. Analytical analyses demonstrated a sig-
nificant reduction in Hg concentration (0.0022 mg/m3) (Patent
RU(11) 2 400 545(13) C1).
Application for CaSx as nanoparticle
Advancing technology and increasing consumer demand re-
sulted in the development of efficient and more effective
chemicals in the form of nanoparticles. One such chemical is
sulphur nanoparticles which can be prepared from aqueous
solution of CaSx with hydrochloric, oxalic, nitric, and sulphuric
acid (Massalomov et al. 2014). Sulfur nanoparticles produced
by polysulphides resulted in high-efficiency fungicide and
plant growth regulators (Massalimov et al. 2013, 2014).
Nanoparticle preparation from aqueous solution of
polysulphides of alkali and alkaline-earth metals is described
simple and ecologically safe (Massalimov et al. 2012). It is also
interesting to note that nanoparticles prepared from CaSx with a
mixture of hydrazine hydrate and monoethanolamine resulted
in an average particle size of 20–25 nm, which further coarsen
to 100–1000 nm after 10–15 min (Massalimov et al. 2014).
Technical issues associated with the molar ratio
of CaSx required for treatment of PTEs
The available literature where CaSx solution was applied for
environmental remediation primarily comprises case studies
involving the remediation of COPR and examined the kinetics
of CaSx reaction in greater depth (Graham et al. 2006; Wazne
et al. 2007; Moon et al. 2008; Tinjum et al. 2008). There was
little insight into the mechanism of CaSx reactions with other
PTEs. However, there have been empirical findings regarding
the stoichiometric ratio of CaSx to PTEs for an effective re-
moval of PTEs, especially for Cr(VI). The ratio of CaSx to
Environ Sci Pollut Res
Cr(VI) depends on many factors such as; type of matrices
(soil, water, COPR, or sediments), concentration of PTEs,
aerobic or anaerobic and the pH conditions. Most of the avail-
able literature working ratio of CaSx solution with PTEs and
their methodological approaches has been summarized in
Table 3.
Kinetics of CaSx
Kinetics of CaSx studied with methylation of polysulphide
suggests the higher concentration of hepta- and octasulphides
whereas, lower concentration of Nona-, deca- polysulphides
(Kamyshny et al. 2004). Yahikozawa et al. (1978) studied the
kinetics of CaSx in wastewater with the presence of heavy
metals (Hg2+, Cd2+, Cu2+, Zn2+, and Cr6+), O2 and CO2. The
simple reaction in the presence of O2 and CO2 is provided as:
. phide salts with Zn and Cu (Salvato1992).
CaSx þ3 2 O →CaS2 O3 þ ðx−2ÞS ð1Þ
2
CaSx þCO2 þH2 O→CaCO3 þH2 S þ ðx−1ÞS ð2Þ
Equation (2) suggests the presence of H 2 S in CO 2
contained solution. CaSx decomposes rapidly in the presence
of CO2 compared to O2 and produce H2S, CaCO3, CaSO4,
and solid sulphur particles. In wastewater containing heavy
metals, the precipitating reactions can be explained as:
M2þ þCaS2 O3 þH2 O→MS þ CaSO4 þ2Hþ ð3Þ
M2þ þH2 S→MS þ 2Hþ ð4Þ
Where;
M represents the heavy metal cations
MS represents the precipitated metal sulphides.
Hg removal from soil and other open surfaces described by
a Russian patent (Patent RU(11) 2 400 545(13) C1) follows
the following reaction without CO2 and O2:
CaSx þnHg2þ ¼ xHgS↓þCa2þ ð5Þ
CaSx þ nHg0 þ ½Ox ¼ xHgS↓þCa2þ ð6Þ
According to the batch test experiment, Eq. (3) was found
to be faster compared to equation (4). The precipitation rate
was determined by the CaS x decomposition in former
reactions (steps 1 and 2). The reactions from Eqs. 1 to 4 evolve
with the formation of precipitate and known as Bhetero-
geneous gas-liquid reaction^. Similarly Graham et al. (2006)
suggested the following redox equilibrium reaction for COPR
treatment using CaSx
2CrO4 2− þ3CaS5 þ10Hþ →2 CrðOHÞ3
o developed resistance to LLS on various in situ experiments. In
þ 15S þ3Ca2þ þ2H2 O ð7Þ
Tabata et al. (2013) reported the mechanism based on
hydrodechlorination in which they used CaSx to reduce fly ash
waste. The authors postulated that Ca(OH) and sulphur reacted to
produce CaSx. The CaSx solution decomposed to provide a mix-
ture of Ca(SH)2, Ca(OH)2 and Ca(SH)(OH) in the presence of
water, which further produces CaS and CaSx. The resultant CaS
and CaSx acted as strong reducing agents in the reaction mixture
and reduced chlorinated compound to CaSO4 or CaSO3.
Ganczarczyk et al. (1985) studied the thermodynamic re-
action of CaSx conversion to CN, resulted in thiocyanate pro-
duction. In this study, a rapid moderately exothermic reaction
of CN with CaSx was detected, where CN concentration was
non-detectable within 2 weeks. CaSx was used for phosphate
removal by precipitating phosphate ions into calcium phos-
phate present in wastewater in the presence of calcium ions
(Aratani et al. 1978b). Similarly, LLS solves the water con-
tamination problem by forming irreversible and insoluble sul-
The environmental fate and toxicity aspects of CaSx
CaSx has a very high pH (about 11.5 which is corrosive) and
can cause irreversible eye damage (EPA Toxicity Category I)
and is considered mildly irritating to skin (EPA Toxicity
Category III) (USEPA2005). Chronic dietary toxicity hazard,
carcinogenicity, and mutagenic content have not been identi-
fied so far (USEPA 2005). CaSx exposure to midge eggs
caused embryogenesis although evaluation of the testing
methods indicates that the response may not cause by the
CaSx; therefore, endocrine disruption needs further research
(Thurston county report 2012). The primary safety hazards it
poses include burns from skin or eye contact with concentrat-
ed solution, or from exposure to H2S gas that can evolve from
LLS. Occupational health and safety administration work-
place limits for H2S are 10 μl l−1 for 8 h and 15 μl l−1 for brief
exposures of 15 min (Anon 1997).
As discussed earlier, CaSx is used widely as a pesticide and
insecticide in agriculture industries. About 500,000 tons of in-
secticides are now applied each year in the USA alone and insects
such as aphids continue to affect agricultural productivity by
developing resistance against these chemicals (van Emden and
Harrington 2007). Pesticide resistance is the adaptation of pest
populationsresultingindecreasedsusceptibility to thatchemical.
In other words, resistance is the key mode of survival which
evolves over time and gets genetically passed on to the offspring
(PBS 2001). Resistance can be developed in insects with time
and continuous usage of particular chemical. After 100 years of
LLS usage, Melander (1914) reported orchard pests, the San Jose
scale (Quadraspidiotus perniciousus) in the state of Washington,
the first experiment, all scales were killed with lime treatment

within 1 week in typical orchards. However, the survival rate
increased to 90 % after 2 weeks in an orchard with resistant
scales. In a second experiment, the author used 2° (1 lb.: 7 gal),
3° (1 lb.: 5 gal), 5° (4 × 3°), 1:1/2:5, 1:2:5 factory made sulphur-
lime in Clarkston, Walla Walla, Kennewick, Prosser, Sunnyside,
North Yakima, and Wenatchee, USA, to carry out experiments
with 350,000-scale insects. In a biweekly experiment, he found
50 % of the scales were still alive under the crust of dried spray.
LLS also reported damage to fruit quality as well as reduced the
number of harvested fruits with increasing application due to its
sulphide content (Palmer et al. 2003). Authors reported a delay of
maturity and fading of colors in apples treated with 12 % lime
sulphur as well as decreased photosynthesis activity in plants.
Another application of CaSx is metal binding which makes
it attractive for cleaning contaminants from wastewater and
groundwater facilities. However, water based CaSx applica-
tions are not suitable for deep vadose zones and can lead to
groundwater contamination by mobilizing the contaminant
through preferential pathways within the sediments (Dresel
et al. 2011). The Deep Vadose region is a zone of low perme-
ability, having preferential flow area that is determined by
gravity (Zhong et al. 2009).
Maletić et al. (2015) used many ameliorants to treat metal-
contaminated soils, where CaSx solution was one of the
ameliorants tested for its toxicity. The toxicity test was per-
formed on the extracted pore water samples after treatment
with different doses of CaSx solutions. For this purpose, a
genetically modified lux-based biosensor: Escherichia coli
HB101 (pUCD607) was used in a dose-response manner.
The luminescence was measured after 15-min exposure. It
was concluded that CaSx solution outperformed the other
ameliorants. Furthermore, CaSx demonstrated the least toxic
response as measured by the biosensor compared to other
ameliorants studied (namely bone meal, activated carbon,
and bentonite). Similarly, Bailey et al. (2012) exposed mi-
crobes, Shewanella oneidensis MR-1 to CaSx and other sur-
factants (sodium laureth sulphate (SLES), sodium dodecyl
sulphate (SDS), cocamidopropyl betaine (CAPB), and
NINOL40-CO). CaSx was found to be toxic at all the tested
concentration (1.45–7.25 mM) and stimulatory at lower con-
centrations (20–500 μM). Most of the standard toxicity tests
performed by IUPAC and USEPA used the LLS form. LLS
demonstrated moderate acute toxicity in mammals, fish, and
aquatic invertebrates and low acute toxicity in insects (Anon
1997; IUPAC 2009). Combined data with organisms is sum-
marized in Table 4.
Conclusion
CaSx is an inorganic chemical that gained popularity in agri-
cultural industries due to its effective insecticide and pesticide
properties. It is most commonly used in the form of LLS and
Environ Sci Pollut Res
applied towards post-harvest treatments. With increasing ap-
plication, recent technologies has developed sulphur nanopar-
ticles from CaSx, which demonstrated a higher efficiency and
improved regulation in plant growth. Although increasing use
of any chemical can cause resistance issues in insects, limited
research is available, making it difficult to identify the insect
species which have developed resistance and the amount
needed for successful application. There is a need of experi-
mental series describing ecological issues regarding LLS for
the effective measurements.
CaSx chemical properties to clean air, water, and soil pol-
lution make it a prominent chemical in treatment of wastewa-
ter, groundwater and superfund sites. Its easy availability, eco-
nomic cost, and successful application also adds value to-
wards its industrial applications (Kameshwari et al. 2015).
The hydrophobic nature of CaSx makes it a very applicable
coagulant against heavy metal pollution from the environ-
ment. The kinetics demonstrated that the mode of action high-
ly depends on pH, its physical state, and accessibility. The
ability of CaSx to react with other metals and make them less
soluble, nontoxic sulphides and hydroxides made it an ap-
proved reductant to clean contaminated land, wastewater,
and groundwater (Jacobs 2001; Lewis 2011).
While a range of PTEs such as Zn, Pb, Fe, and Ni can be
treated with CaSx; however, its area of major application is
Cr(VI) removal from groundwater, wastewater, soil, and
COPR sources. CaSx is very effective and economically feasi-
ble to remove Cr(VI), which makes it popular in Cr plating and
metallurgy industries. It works by precipitating heavy metals at
certain basic pH. According to the literature reviewed so far, the
chemical nature of CaSx makes it a very applicable chemical
against of heavy metal pollution in the environment. Further
successful applications in different industries can be identified
by kinetics described within this paper.
Even after a range of use and application of CaSx, their
molar ratio, dosage, and required chemical properties to work
effectively is not very well defined. The successful application
at defined pH is also missing in various prominent researches
(Table 2). Limited stoichiometry data and kinetics with each
metal makes it hard to implement its successful application
with various heavy metals.
The limited research on the fate of CaSx in environment
makes it a threat to living biota. Some government reports
and peer-reviewed articles identified CaSx toxicity in various
biota at certain quantity (Table 4), which requires attention and
further studies. The lack of toxicity information cannot be com-
pensated by field application and limited database reports by
individual agency. The physiochemical properties of every sin-
gle organism are different and highly depend upon their sur-
rounding environment. Real-time lab experiments are neces-
sary to identify its effects on living organisms in soil and water.
Dietary as well as exposure experiments with organisms are
required to define LC50 and LD50 values in living organisms.
Environ Sci Pollut Res
CaSx application ranges from agriculture, metal refineries,
leather tanning to construction industries. The wide range ap-
plications further expose it to the environment. So far, there is
no documented human health effects associated with CaSx,
which makes it an ecofriendly chemical against heavy metal
pollution and other industrial application. However, there is a
need to conduct some in depth studies related to the toxicity
and resistance to avoid any future health and environmental
hazards.
Acknowledgment Authors would like to thanks University of
Dammam for its support. Authors also like to thanks Miss Kelly
Corriea for her suggestions in this review article.
Compliance with ethical standards
Disclaimer The views expressed in this paper are those of the authors
and do not necessarily reflect the views or policies of any government
organization and peer-reviewed research article authors.
References
Adriano DC (1986) Trace elements in the environment. Chapter 5: chro-
mium. Springer Verlag, New York
Anonymous (1997) National Institute for Occupational Safety and Health
pocket guide to chemical hazards. US Department of human health
services (NIOSH) publication no. 97–140. US Government Printing
Office, Washington DC
Aratani T, Yahikozawa K, Matoba H, Yasuhara S, Yano T (1978a)
Conditions for the precipitation of heavy metals from wastewater
by the lime sulfureted solution (calcium polysulfide) process. Bull
Chem Soc Jpn 51:1755–1760
Aratani T, Yasuyuki N, Matoba H, Yasuhara S, Yano T (1978b) The
removal of heavy metals, phosphate, and COD substances from
wastewater by the lime sulfureted solution (calcium polysulfide)
process. Bull Chem Soc Jpn 51(9):2705–2709
Auld SJM (1915) LVII.—the reaction between calcium hydroxide and
sulphur in aqueous solution. J Chem Soc Trans 107:480–495
Bailey KL, Tilton F, Jansik DP, Ergas SJ, Marshall MJ, Miracle AL,
Wellman DM (2012) Growth inhibition and stimulation of
Shewanella oneidensis MR-1 by surfactants and calcium polysul-
fide. Ecotoxicol Environ Safety 80:195–202
Bewley RJF, Clarke S (2010) Field application of calcium polysulphide
for ex situ treatment of soils contaminated with chromite ore pro-
cessing residue. Land Contam Reclam 18:1–12
Borgwardt RH (1984) Surface area of calcium oxide and kinetics of
calcium sulphide formation. Environ Prog 3(2):129–135
Bosshard PP, Bachofen R, Brandl H (1996) Metal leaching of fly ash
from municipal waste incineration by Aspergillus niger. Environ.
Sci. Technol. 30(10):3066–3070
Chandra P, Sinha S, Rai UN (1997) Bioremediation of Cr from water and
soil by vascular aquatic plants. In: Kruger EL, Anderson TA, Coats
JR (eds) Phytoremediation of soil and water contaminants, ACS
Symposium Series #664. American Chemical Society, Washington
DC, pp. 274–282
Charboneau, B., Thomson, K.M., Wilde, R., Ford, B., Gerber, M. 2006
Hanford groundwater remediation. In: Proceedings of the WM’06
Conference, Tuscon, AZ, February 26–March 2
Chen K, Morris J (1972) Kinetics of oxidation of aqueous sulfide by O2.
Environ Sci Technol 6(6):529–537
Chen A, Qiu X, Sridharan K, Horne WG, Dodd RA, Hamdi AH,
Elmoursi AA, Malaczynski GW (1996) Chromium plating pollution
sources reduction by plasma source ion implantation. Surf Coat
Tech 82:305–310
Chen Q, Luo Z, Hills C, Xue G, Tyrer M (2009) Precipitation of heavy
metals from wastewater using simulated flue gas: sequent additions
of fly ash, lime and carbon dioxide. Water Res 43(10):2605–2614
Chrysochoou M, Johnston CP (2015) Polysulfide speciation and reactiv-
ity in chromate-contaminated soil. J Hazard Mater 281:87–94
Chrysochoou M, Ting A (2011) A kinetic study of Cr(VI) reduction by
calcium polysulfide. Sci Total Environ 409(19):4072–4077
Chrysochoou M, Fakra SC, Marcus MA, Deok HM, Dermatas D (2009a)
Microstructural analyses of Cr(VI) speciation in chromite ore pro-
cessing residue (COPR). Environ Sci Technol 43(14):5461–5466
Chrysochoou M, Moon DH, Fakra S, Marcus M, Dermatas D,
Christodoulatos C (2009b) Use of micro X-ray absorption spectros-
copy and diffraction to delineate Cr(VI) speciation in COPR. Global
Nest J 11(3):318–324
Chrysochoou M, Ferreira DR, Johnston CP (2010) Calcium polysulfide
treatment of Cr(VI)-contaminated soil. J Hazard Mater 179(1–3):
650–657
Chrysochoou M, Johnston CP, Dahal G (2012) A comparative evaluation
of hexavalent chromium treatment in contaminated soil by calcium
polysulfide and green-tea nanoscale zero-valent iron. J Hazard
Mater 201-202:33–42.199
Darakas E, Tsiridis V, Petala M, Kungolos A (2013) Hexavalent chromi-
um release from lignite fly ash and related ecotoxic effects. J
Environ Sci Heal A 48(11):1390–1398
Dippenaar BJ (1958) Concentric ring blotch citrus. Its cause and control.
S Afri J Agric Sci 1:83–99
Dorman DC, Moulin FJ-M, McManus BE, Mahle KC, James RA, Struve
MF (2002) Cytochrome oxidase inhibition induced by acute hydrogen
sulfide inhalation: correlation with tissue sulfide concentrations in the
rat brain, liver, lung, and nasal epithelium. Toxicol Sci 65(1):18–25
Dresel PE, Wellman DM, Cantrell KJ, Truext MJ (2011) Review: tech-
nical land policy challenges in deep vadose zone remediation of
metals and radionuclides. Environ. Sci. Technol. 42:4207–4216
Eckert JW, Eaks IL (1989) Postharvest disorders and diseases of citrus fruits.
In: Reuther W, Calavan EC, Carman GE (eds) The citrus industry, vol 4.
University of California Press, Berkeley, CA, pp. 179–260
EFSA (European Food Safety Authority) (2010) Conclusion on the peer
review of the pesticide risk assessment of the active substance lime
sulfur. EFSA J 8(11):1890–1935
Elesin MA, Pavlov AV, Berdov GI, Mashkin NA, Oglezneva IM (2002)
Mechanism of hydration conversion of portland cement in calcium
polysulfide solution. Russ J Appl Chem 75(6):883–887
Farmer JG, Paterson E, Bewley RJF, Geelhoed JS, Hillier S, Meeussen
JCL, Lumsdon DG, Thomas RP, Graham MC (2006) The implica-
tions of integrated assessment and modelling studies for the future
remediation of chromite ore processing residue disposal sites. Sci
Total Environ 360(1–3):90–97
Freedman DL, Lehmicke L, Verce MF (2005) Reductive dechlorination
of tetrachloroethene following abiotic versus biotic reduction of
hexavalent chromium. Bioremediation Journal 9(2):87–97
Freese K, Miller R, Cutright TJ, Senko J (2014) Review of chromite ore
processing residue (COPR): past practices, environmental impact
and potential remediation methods. Current Environ Eng 1:82–90
Fruchter J (2002) In-situ treatment of chromium-contaminated ground-
water. Environ. Sci. Technol. 36(23):464A–472A
Ganczarczyk JJ, Takoaka PT, Ohashi DA (1985) Application of polysul-
fide for pretreatment of spent cyanide liquors. Water Pollut Control
Federation 57(11):1089–1093
Graham MC, Farmer JG, Anderson P, Paterson E, Hillier S, Lumsdon DG
(2006) Calcium polysulfide remediation of hexavalent chromium

contamination from chromite ore processing residue. Sci Total
Environ 364(1–3):32–44
Gun J, Modestov A, Kamyshny A, Ryzkov D, Gitis V, Goifman A (2004)
Electrospray ionization mass spectrometric analysis of aqueous
polysulfide solutions. Microchim Acta 146:229–237
Haller MH (1952) Handling, transportation, storage, and marketing of
peaches. USDA Biograph Bull 21:1–105
Hartmut M, Baumann W, Becker B, Jay K, Paur H-R, Seifert H (2001)
Adsorption of PCDD/F on MWI fly ash. Chemosphere 42:803–809
Hojjatie, M., Feinstein, Y., Lockhart, C.L.F. 2011. Tessenderlo Kerley, Inc.
US patent no. US034318 B1/US20110262343 A1, Washington DC.
IETEG (Independent Environmental Technical Evaluation Group) 2005
In: Guertin J, Jacobs, JAC Avakian (Eds.), Chromium(VI)
Handbook, CRC Press, Boca Raton, FL
IUPAC (International Union of Pure & Applied Chemistry) 2015.
Pesticide Properties Database. Lime sulphur. EC Regulation 1107/
2009 (repealing 91/414). Accessed 11/16/2015.
Jacobs, J.A., 2001. In-situ delivery methods for remediation of hexavalent
chromium in soil and groundwater. Abstracts of the national meeting
of the national association of engineering geologists and American
institute of professional geologists, St Louis, MO; Oct 5.
Jagupilla SC, Moon DH, Wazne M, Christodoulatos C, Kim MG (2009)
Effects of particle size and acid addition on the remediation of chro-
mite ore processing residue using ferrous sulfate. J Hazard Mater
168:121–128
Kalogirou, E., Themelis, N., Samaras, P., Karagiannidis, A., Kontogianni,
ST., 2010. Fly ash characteristics from waste-to-energy facilities and
processes for ash stabilization. ISWA World Congress 2010,
Hamburg , Germany, 15–18 November 2010
Kameshwari KSB, Pedaballe V, Narasimman LM, Kalyanaraman C
(2014) Remediation of chromite ore processing residue using solid-
ification and stabilization process. Environ Prog Sustain Energy 34:
674–680
Kameshwari KSB, Narasimman LM, Pedaballe V, Kalyanaraman C (2015)
Diffusion and leachability index studies on stabilization of chromium
contaminated soil using fly ash. J Hazard Mater 297:52–58
Kamyshny AJ, Goifman A, Gun J, Rizkov D, Ovadia L (2004)
Equilibrium distribution of polysulfide ions in aqueous solutions at
25 °C: a new approach for the study of polysulfides’ equilibria.
Environ. Sci. Technol. 38:6633–6644
Kamyshny A, Gun J, Rikzov D, Voitsekovski T, Lev O (2007a)
Equilibrium distribution of polysulfide ions in aqueous solutions at
different temperatures by rapid single phase derivatization. Environ.
Sci. Technol. 41:2395–2400
Kamyshny A, Gun J, Rizkov D, Voitsekovski T, Lev O (2007b)
Equilibrium distribution of polysulfide ions in aqueous solutions at
different temperatures by rapid single phase derivatization. Environ
Sci Technol 41:2395–2400
Katz SA, Salem H (1994) The biological and environmental chemistry of
chromium. VCH Publishers, Inc., New York
Kelsall GH, Thompson I (1993) Redox chemistry of H2S oxidation by the
British gas Stretford process, part II: electrochemical behavior of
aqueous hydrosulphide (HS−) solutions. J Appl Electrochem 23:
287–295
Kim BR, Gaines WA, Szafranski MJ, Bernath EF, Miles AM (2002)
Removal of heavy metals from automotive wastewater by sulfide
preparation. J Environ Eng 128(7):612–623
Klein, C., Hurlbut, C. S., Jr. 1985. Manual of mineralogy (20th edn.),
John Wiley, pp. 352–353, ISBN 0–471–80580-7
Knauf, A., Hartmann, P., Schmidt, A., Wirsching, F., 1973. Process for
treating plaster of paris. US patent Publication number: US3770468
A, Washington DC.
Lan Y, Deng B, Kim C, Thornton EC, Xu H (2005) Catalysis of elemental
sulfur nanoparticles on chromium (VI) reduction by sulfide under
anaerobic conditions. Environ Sci Echnol 39(7):207–2094
Large EC (1940) The advance of fungi. Dover, New York
Environ Sci Pollut Res
Levchenko LM, Galitskii AA, Kosenko VV, Sagidullin AK (2015)
Development of semi-industrial synthesis of calcium polysulfide
solution and determination of the content of sulfide ions in solution.
Russian J Appl Chem 88(9):1403–1408
Lewis M, Pryor R, Wilking L (2011) Fate and effects of anthropogenic
chemicals in mangrove ecosystem: a review. Environ Pollut 159:
2328–2346
Maletić SP, Watson MA, Dehlawi S, Diplock EE, Mardlin D, Paton GI
(2015) Deployment of microbial biosensors to assess the perfor-
mance of ameliorants in metal-contaminated soils. Water Air Soil
Pollut 226:85
Massalimov IA, Gazizyanovich MA, Rifhatovn SA, Nailevich KA,
Maratovna ZR (2012) Obtaining sulfur nanoparticles from sodium
polysulfide aqueous solution. J Chem Chem Eng 6:233–341
Massalimov IA, Yanakhmetov MR, Chuykin AE, Mustafin AG (2013)
Protection of building constructions with sulfur impregnating solu-
tion. Int J Sci 2:25–30
Massalimov IA, Khusainov AN, Zainitdinova RM, Musavirova LR,
Zaripova LR, Mustafin AG (2014) Chemical precipitation of sulfur
nanoparticles from aqueous solutions. Russ J Appl Chem 87(6):
700–708
McCallan SEA (1967) History of fungicides. In: Torgeson DC (ed)
Fungicides: an advanced treatise. 1 Academic Press, New York,
pp. 1–37
Melander AL (1914) Can insects become resistant to sprays? J Econ
Entomol 7:167–173
Messer, A., Storch, P, Palmer, D. 2004 In-situ remediation of chromium
contaminated site using calcium polysulfide. Internal report. URS
Corporation
Mihara N, Soya K, Kuchar D, Fukuta T, Matsuda H (2008) Utilisation of
calcium sulfide derived from waste gypsum board for metal contain-
ing wastewater treatment. Global NEST J 10:101–107
Moon DH, Wazne M, Jagupilla SC, Christodoulatos C, Kim MG,
Koutsospyros A (2008) Particle size and pH effects on remediation
of chromite ore processing residue (COPR) using calcium polysul-
fide (CaS5). Sci Total Environ 399:2–10
Moon DH, Wazne M, Koutsospyros A, Christodoulatos C, Gevgilili H,
Malik M, Kalyon DM (2009) Evaluation of the treatment of chro-
mite ore processing residue by ferrous sulfate and asphalt. J Hazard
Mater 166(1):27–32
Nagib S, Inoue K (2000) Recovery of lead and zinc from fly ash gener-
ated from municipal incineration plants by means of acid and/or
alkaline leaching. Hydrometallurgy 56(3):269–292
Nriagu JO, Nieboer E (eds) (1988) Chromium in natural and human
environments. Wiley Interscience, New York, pp. 81–104
Pakzadeh B, Batista JR (2011) Chromium removal from ion-exchange
waste brines with calcium polysulfide. Water Res 45:3055–3064
Palmer JW, Davies SB, Shaw PW, Wünsche JN (2003) Growth and fruit
quality of BBraeburn^ apple (Malus domestica) trees as influenced
by fungicide programs suitable for organic production. New Zeal
Crop Hort 31:169–177
Palou L, Usall J, Smilanick J, Aguilar M, Vinas I (2002) Evaluation of
food additives and low-toxicity compounds as alternative chemical
for the control of Penicillium digitatum and Penecillium italicum on
citrus fruit. Pest Manag Sci 58:459–466
Pant, C.P. (1958) BStudies on the mode of action of insecticides^.
Retrospective Theses and Dissertations. Paper 2262.
Patent RU(11) 2 400 545(13) C1; Date of publication: 27.09.2010 Bull.
27. Method for demercuration of mercury-containing wastes for
recycling said wastes.
PBS, 2001. Pesticide resistance. Retrieved on December 06, 2015.
Poulos PL (1949) The use of sodium hypochlorite for the control of the
brown rot disease of peach in Delaware. Plant Dis Rep 33:413–415
Rai D, Eary LE, Zachara JM (1989) Environmental chemistry of chromi-
um. Sci Tot Environ 86:15–23
Environ Sci Pollut Res
Salvato JA (1992) Environmental engineering and sanitation, 4th edn.
Wiley-Interscience, New York
Smilanick JL, Sorenson D (2001) Control of postharvest decay of citrus
fruit with calcium polysulfide. Postharvest Biol Technol 21:157–168
Smith L, Kruszyna H, Smith RP (1977) The effect of methemoglobin on
the inhibition of cytochrome c oxidase by cyanide, sulfide and azide.
Biochem Pharmacol 26:2247–2250
Soya K, Mihara N, Kuchar D, Khbota M, Matsuda H, Fukuta T (2010)
Selective sulfidation of copper, zinc and nickel in plating wastewater
using calcium sulfide. Int J Civil Env Engg 2:93–97
Storch P, Messer A, Palmer D, Pyrih R (2002) Pilot test for in situ geo-
chemical fixation of chromium (VI) using calcium polysulfide, in:
proceedings of the third international conference on remediation of
chlorinated and recalcitrant compounds. Battelle Press, Monterey, CA
Sun Y, Watanabe N, Qiao W, Gao X, Wang W, Zhu T (2010) Polysulfide
as a novel chemical agent to solidify/stabilize lead in fly ash from
municipal solid waste incineration. Chemospeher 81:120–126
Syracuse Research Corporation, 1993. Toxicological profile for chromi-
um. Prepared for U.S. Dept. Health and Human Services, Public
Health Service, Agency for Toxic Substances and Disease
Registry, under Contract No. 205–88-0608.
Tabata M, Ghaffar A, Shono A, Notomi K (2013) Hydrodechlorination/
detoxification of PCDDs, PCDFs, and co-PCBs in fly ash by using
calcium polysulfide. Waste Manag 33:356–362
Takaoka PT, Ganczarczyk JJ (1985) Feasibility of polysulfide detoxifica-
tion of concentrated cyanide waste-water. Water Pollut Res J Can
20(1):118–128
Tartar HV (1914) The reaction between Sulphur and calcium hydroxide
in aqueous solution. J Am Chem Soc 36(3):495–498
View publication stats
Thurston County Review, 2012. Lime sulphur (calcium polysulphide).
CAS #: 1344–81-6.
Tinjum JM, Benson CH, Edil TB (2008) Treatment of Cr (VI) in COPR
using ferrous sulfate-sulfuric acid or cationic polysulfides. J Geotech
Geoenviron Eng 134(12):1791–1803
Tweedy BG (1967) Elemental sulfur. In: Torgeson DC (ed) Fungicides: an
advanced treatise, vol 2. Academic Press, New York, pp. 119–145
USEPA. Office of Prevention, Pesticides and Other Toxic Substances.
Reregistration eligibility decision for inorganic polysulfides. List
D—case no. 4054. September 30, 2005.
Van Emden H, Harrington R (eds) (2007) Aphids as crop pests. CABI,
Wallingford, Oxon, GBR
Wazne M, Jagupilla SC, Moon DH, Christodoulatos C, Kim MG (2007)
Assessment of calcium polysulfide for the remediation of hexavalent
chromium in chromite ore processing residue (COPR). J Hazard
Mater 143:620–628
Wazne M, Jagupilla SC, Moon DH, Christodoulatos C, Koutsospyros A
(2008) Leaching mechanisms of Cr(VI) from chromite ore process-
ing residue. J Environ Qual 37(6):2125–2134
Yahikozawa K, Aratani T, Ito R, Sudo T, Yano T (1978) Kinetic studies
on the lime sulfureted solution (calcium polysulphide) process for
the removal of heavy metals from wastewater. Bull Chem Soc Jap
51(2):613–617
Zayed AM, Terry N (2003) Chromium in the environment: factors affect-
ing biological remediation. Plant Soil 249:139–156
Zhong L, Qafoku NP, Szecsody JE, Dresel PE, Zhang ZF (2009) Foam
delivery of calcium polysulfide to the vadose zone for
chromium(VI) immobilization: a laboratory evaluation. Vadose
Zone J 8(4):976–985