Journal of Environmental Management 90 (2009) 504e511

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Sulfate removal from waste chemicals by precipitation

Cláudia Telles Benatti a, Célia Regina Granhen Tavares a,*, Ervim Lenzi b
a
Departamento de Engenharia Quı́mica, Universidade Estadual de Maringá, Av. Colombo, 5790, Bloco D90, 87020-900 Maringá-PR, Brazil
b
Departamento de Quı́mica, Universidade Estadual de Maringá, Av. Colombo, 5790, Bloco 22, 87020-900 Maringá-PR, Brazil
Received 23 May 2006; received in revised form 26 October 2007; accepted 2 December 2007
Available online 28 January 2008

Abstract

Chemical oxidation using Fenton’s reagent has proven to be a viable alternative to the oxidative destruction of organic pollutants in mixed
waste chemicals, but the sulfate concentration in the treated liquor was still above the acceptable limits for effluent discharge. In this paper, the
feasibility of sulfate removal from complex laboratory wastewaters using barium and calcium precipitation was investigated. The process was
applied to different wastewater cases (two composite samples generated in different periods) in order to study the effect of the wastewater com-
position on the sulfate precipitation. The experiments were performed with raw and oxidized wastewater samples, and carried out according to
the following steps: (1) evaluate the pH effect upon sulfate precipitation on raw wastewaters at pH range of 2e8; (2) conduct sulfate precipitation
experiments on raw and oxidized wastewaters; and (3) characterize the precipitate yielded. At a concentration of 80 g L1, barium precipitation
achieved a sulfate removal up to 61.4% while calcium precipitation provided over 99% sulfate removal in raw and oxidized wastewaters and for
both samples. Calcium precipitation was chosen to be performed after Fenton’s oxidation; hence this process configuration favors the production
of higher quality precipitates. The results showed that, when dried at 105  C, the precipitate is composed of hemidrate and anhydrous calcium
sulfate (w99.8%) and trace metals (w0.2%: Fe, Cr, Mn, Co, Ag, Mg, K, Na), what makes it suitable for reuse in innumerous processes.
Ó 2007 Published by Elsevier Ltd.

Keywords: Waste chemicals; Fenton’s reagent; Sulfate; Chemical precipitation

1. Introduction There are significant differences between the two in terms of

Waste chemicals from academic laboratories are byprod-
ucts of research, teaching and testing activities. Collectively,
academic institutions account for only a small portion of the
produced hazardous wastes, less than 1% of the total generated
in the United States (Ashbrook and Reinhardt, 1985). Al-
though small-quantity generators, universities have the respon-
sibility of introducing a sense of ecological awareness in
students as well as of ensuring institutional compliance with
regulations (Ashbrook and Reinhardt, 1985; Schneider and
Wiskamp, 1994). Moreover, waste chemicals from academic
laboratories generally pose more problems for the treatment
and subsequent adequate disposal than those from industries.
* Corresponding author. Tel.: þ55 44 32614746; fax: þ55 44 32632652.
E-mail address: celia@deq.uem.br (C.R.G. Tavares).
waste volume produced and number of chemicals handled,
as well as in the associated potential environmental risks (Na-
tional Research Council, 2000). Therefore, academia has sev-
eral unique challenges in managing hazardous wastes as
compared with industry (Izzo, 2000; Ashbrook, 2001). First
is the wide variety of relatively small amounts of chemicals
that are handled in the laboratories. Second is the high turn-
over of workforce, relying heavily on graduate and postgradu-
ate students, which requires a commitment to training. Third is
the type of operations and waste generation changes frequently
as the focus of the research. These aspects create a relatively
large difficulty in terms of characterizing wastes and providing
adequate documentation for treatment and disposal by safe
and environmentally acceptable methods.
Because of the lack of specific legislation to regulate waste
chemicals treatment, the waste generated during the operations
of the Control and Environmental Prevention Laboratory at the

0301-4797/$ - see front matter Ó 2007 Published by Elsevier Ltd.

doi:10.1016/j.jenvman.2007.12.006
 C.T. Benatti et al. / Journal of Environmental Management 90 (2009) 504e511
Department of Chemical Engineering of the Universidade
Estadual de Maringá e Brazil, has been held for many years
at the laboratory site, waiting for acceptable disposal modes to
be developed. Three typical chemical waste streams prevail in
this setting: waste chemicals from routine chemical analysis,
from research activities, and an abundance of unused labora-
tory reagents. The research activities include chemical and
biological treatment experiments of a wide range of synthetic
and natural wastewaters arising from different chemical indus-
tries. Accordingly, these wastes are constituted of great diver-
sity of composition and volume, including refractory organics,
toxic compounds and heavy metals, and may offer potential
hazards to both health and environment.
In previous research work, chemical oxidation using Fen-
ton’s reagent was used as a treatment method for the laboratory
wastewaters (Benatti et al., 2004, 2006). The results showed that
the oxidative destruction of organic pollutants could be success-
fully accomplished by the Fenton’s oxidation, however, the con-
centration of certain inorganic constituents, such as sulfate, still
remained extremely high for effluent discharge. The next step
was to designing a treatment system for the removal of sulfate.
Sulfate is a common constituent of many natural waters and
wastewaters (Silva et al., 2002), which is present as a dissolved
compound in seas and oceans or as insoluble salt (e.g., gypsum-
layers). Industrial wastewaters are responsible for most anthro-
pogenic emissions of sulfate into the environment. Domestic
sewage typically contains between 20 and 500 mg L1 sulfate
(Lens et al., 1998) while certain industrial effluents may contain
several thousands of milligrams per liter. The main source of sul-
fate in the laboratory wastewaters is the use of sulfuric acid in
many routine chemical analyses. Sulfur compounds are also
present in wastewaters used in the research activities, such as
those from the pulp and paper industry, the food processing
industry, and the photographic sector, among others.
The damage caused by sulfate emissions is not direct, since
sulfate is a chemically inert, non-volatile, and non-toxic com-
pound. However, high sulfate concentrations can unbalance
the natural sulfur cycle (Lens et al., 1998; Silva et al., 2002).
The accumulation of sulfate-rich sediments in lakes, rivers
and sea may cause the release of toxic sulfides that can provoke
damages to the environment (Ghigliazza et al., 2000).
A number of methods are currently used to promote the re-
moval of dissolved sulfate. They include reversed osmosis,
electrodialysis, or nanofiltration, which are expensive, can be
poisoned by impurities, and require a post-treatment of the
brine (Lens et al., 1998). Ion exchange, biological treatment
and chemical precipitation are also systems used for sulfate-
rich effluents treatment. Chemical precipitation is a widely
used, proven technology for the removal of metals and other
inorganic compounds, suspended solids, fats, oils, greases,
and some other organic substances (including organophos-
phates) from wastewater (U.S. EPA, 2000). Previous investiga-
tors have reported successful reduction of soluble sulfate from
water by formation of calcium aluminate and sulfoaluminates
(Schaezier, 1978), and from pure and waste sulfuric acid/lime
suspension by formation of calcium sulfate (Gominšek et al.,
2005). Chemical precipitation through the addition of barium
505
or calcium salts is an alternative, mainly if applied to the treat-
ment of wastewaters that contain high sulfate concentrations.
In this case, systems for separation and appropriate disposal
of the solid phase are necessary (Silva et al., 2002).
The solubility of BaSO4 is extremely low
(1.14  105 mol L1 or 2.66 mg L1 at 25  C from solubility
product calculations). An effective sulfate removal is also
obtained with lead (PbSO4 solubility 1.26  104 mol L1 or
38.40 mg L1 at 25  C). In the presence of Ca2þ ions CaSO4
is produced, a compound of moderate solubility
(5.10  103 mol L1 or 694 mg L1 at 25  C). Solubility data
were calculated according to the Kps value reported by Meites
(1963). If the product of barium, lead or calcium ion and sulfate
ion concentration (mol L1) exceeds the solubility product, pre-
cipitation of either BaSO4, PbSO4 or CaSO4 will occur. The
solid precipitate can then be filtered, centrifuged, or otherwise
separated from the liquid portion.
Because of its low solubility, precipitation with lead or barium
is potentially a more effective method for complete conversion of
dissolved sulfates to a sulfate insoluble form. However, the major
disadvantages of precipitation with either barium or lead are the
handling of toxic compounds and the generation of a barium or
lead-containing waste that requires disposal. Moreover, the risks
associated with high concentrations of barium and lead impose
adequate effluent monitoring and generally the use of a post-
treatment system (Lens et al., 1998; Ghigliazza et al., 2000).
On the other hand, precipitation of sulfate with calcium ions
has no toxic risks and produces gypsum, which can be a replace-
ment for natural gypsum (Lens et al., 1998).
The purpose of this paper is to study the chemical precipita-
tion as an alternative for sulfate removal from complex waste
chemicals. Chemical precipitation using barium and calcium
is recognized method to reduce sulfates in industrial wastewa-
ters (Kabdasli et al., 1995), but this has not become standard
practice owing to high costs, mainly due to the need of shipping
out hazardous solids for additional treatment or disposal. There-
fore, precipitation appeared as a promising process for remov-
ing sulfates in sulfate-rich laboratory wastewater since the
produced sludge contains a reasonable level of impurities that
favors its reuse. Thus, precipitation experiments with barium
and calcium ions were conducted on raw and oxidized wastewa-
ter; moreover particular attention was paid to gypsum generated
from calcium precipitation. Furthermore, the process was ap-
plied to wastewaters generated in different periods in order to
study the effect of wastewater composition on the sulfate pre-
cipitation. Results are discussed and conclusions are drawn
with focus not only on the sulfate removal efficiencies but
also on the reuse of the solid phase obtained after treatment,
addressing possible alternative ways for its final disposal.
2. Materials and methods
2.1. Sample preparation
Two composite samples produced during the laboratory
operations in different periods were used in the experiments.
The initial characteristics of the wastes generated from July
506 C.T. Benatti et al. / Journal of Environmental Management 90 (2009) 504e511

Table 1 purchased from Quimibrás. Barium chloride (BaCl2$2H2O,

Main characteristics of raw laboratory wastewaters 99%), ferrous sulfate (FeSO4$7H2O, 99%), hydrogen peroxide
Parameter Units Sample 1 Sample 2 (33%), sodium hydroxide (95e100%), sulfuric acid (95e98%)
Apparent color Pt/Co 12 700 10 250 were purchased from Nuclear or Quimibrás. All solutions
Real color Pt/Co 7150 1020 were prepared in distilled/deionized water. Glassware was
Turbidity NTU 4010 2960 washed with detergent, rinsed with tap water, soaked with
COD mg L1 2345 2676
Total phenols mg L1 58.6 37.9
HNO3 (w50% v/v) for 24 h, and rinsed with distilled/deion-
Settable solids mL L1 4.5 4.0 ized water prior to drying.
Standard barium and calcium chloride stock solutions were
2001 to April 2002 (sample 1) and those produced from May to obtained by dissolution of solids (BaCl2$2H2O and CaCl2) in
November 2003 (sample 2) are presented in Table 1; and the distilled water at 25  C till saturation. The solutions were then
main characteristics of these wastewaters after separation of filtered. Barium concentration was determined by EDTA titra-
suspended solids by centrifugation at 2500 rpm by 5 min are tion (Merck). Calcium concentration was determined by
presented in Table 2. In both periods, the waste chemicals atomic absorption.
were generated fundamentally by chemical analysis residues Reagent grade H2O2 was standardized using iodometric ti-
originated from the laboratory routine analysis, such as COD, tration (U.S. Peroxide, 2003) and used as purchased. A 1 M
total phenols, nitrogen, protein, phosphate, sulfide, sample prep- FeSO4 stock solution was prepared and standardized (Pavan
arations and standards for atomic absorption, solutions standard- et al., 1992) just before Fenton’s experiments. Solutions of
ization, and an abundance of unused laboratory reagents. NaOH and H2SO4 were used for pH adjustments.
Experiments of Fenton’s oxidation were carried out under
optimal conditions established in previous work (Benatti 2.3. Sulfate precipitation procedure
et al., 2006): ratio [COD]:[H2O2] ¼ 1:9; ratio [H2O2]:
[Fe2þ] ¼ 4.5:1 and pH ¼ 4. The wastewater after Fenton’s treat- Chemical precipitation of sulfate before and after Fenton’s ox-
ment was taken for the sulfate removal experiments and its main idation was performed using barium and calcium ions. Firstly, the
characteristics are presented in Table 2. effects of pH on sulfate precipitation were investigated at a pH
range of 2e8 using non-treated wastewaters without solids sep-
aration. NaOH (w30% w/v) was used for pH adjustments. At this
2.2. Reagents and solutions stage, a calcium or barium dosage of 9.2 g L1 (0.23 mol L1 as
calcium and 6.70  102 mol L1 as barium) was used. Control
All reagents used in this work were analytical reagent experiments were carried out in parallel without addition of
grade, excepting calcium chloride (CaCl2, 75%) which was either calcium or barium ions. Secondly, precipitation tests
Table 2 were conducted with non-treated wastewaters without solids sep-
Main characteristics of non-treated laboratory wastewater supernatant after aration at pH 4 as well as with oxidized wastewaters, at a calcium
centrifugation, and of laboratory wastewater after the Fenton’s oxidation or barium dosage range of 20e80 g L1 (0.50e2.00 mol L1 as
process (N.D.: not detected) calcium and 0.15e0.58 mol L1 as barium).
Parameter Units Sample 1 Sample 2 Each precipitation experiment was conducted in a 22 mL
Non-treated Oxidized Non-treated Oxidized glass tube, with 5 mL of wastewater in which a pre-calculated
wastewater wastewater wastewater wastewater volume of stock solution was added to give the desired con-
pH <1 8 <1 8 centration of barium or calcium ions. The tube was sealed
Apparent color Pt/Co 308 137 503 352 with parafilm, and after a rapid mixing the sample was left
Turbidity NTU e 10 e 6 to settle for 24 h under quiescent condition. Aliquots of the su-
Soluble COD mg L1 1145 117 2576 167
pernatant were then removed with a pipet from each tube for
Total phenols mg L1 27.3 N.D. 39.8 N.D.
Sulfate g L1 263 152 296 164 sulfate analysis. The difference in the amount before and after
Sulfide mg L1 0.04 0.01 0.05 0.03 precipitation reveals the sulfate removals. All experiments
Ag mg L1 1.1 0.8 1.1 1.0 were run in three replicates, at room temperature.
Al mg L1 18.8 1.4 6.8 4.5 The solid obtained from the best-selected experimental
Ca mg L1 59.1 30.4 37.7 21.4
condition was filtered under vacuum, rinsed with distilled/de-
Cd mg L1 0.2 0.3 6.9 0.5
Co mg L1 1.2 0.8 1.3 1.0 ionized water to eliminate the excess of sodium hydroxide,
Cr mg L1 301.4 1.0 541.6 16.0 dried at 105  C, and stored for characterization.
Cu mg L1 1.7 0.6 4.5 0.3
Fe mg L1 131.9 4.4 114.0 1.7 2.4. Analysis of the solid phase
K mg L1 405.2 187.4 1084.8 645.3
Mg mg L1 3.5 1.7 10.6 3.0
Mn mg L1 0.7 0.5 0.8 0.1 The dried solids were first analyzed for water content. The
Na g L1 10.2 77.9 9.1 101.7 samples were dried in a 105  C oven for 24 h, cooled down in
Ni mg L1 0.9 1.1 1.1 1.1 a vacuum desiccator for 2 h and then weighed at each 30 s for
Pb mg L1 1.9 1.1 1.6 1.1 10 min. To set free the water of constitution, the samples were
Zn mg L1 0.9 N.D. 0.1 N.D.
dried in a 220  C oven for 2 h, cooled down in a vacuum
 C.T. Benatti et al. / Journal of Environmental Management 90 (2009) 504e511 507

desiccator for 2 h and promptly weighed after been removed
from desiccator. Total water content was determined as the dif-
ference in weight loss after drying samples at 105 and 220  C.
Dried precipitate samples (0.5 g) were then treated with
3 mL of 60% perchloric acid in 250 mL erlenmeyer flasks un-
til fumes of perchloric acid appear. For metal determinations,
the obtained extracts were diluted to 50 mL by distilled/deion-
ized water. For sulfate determinations, the extracts were
treated by aqueous solution of sodium carbonate based on
the methodology of Wolesensky (1929), and then diluted to
50 mL by distilled/deionized water.
Mineralogical analysis in dried precipitate samples was
also performed by X-ray diffraction (XRD) using a Shimadzu
D6000 diffractometer (Cu Ka radiation and l ¼ 1.54178 Å;
scanning speed 5 2q for the ranges 5e70 2q).
2.5. Analytical methods
pH was measured with a Digimed DM-20 pH meter cali-
brated with pH 4.01 and 6.86 Digimed standard buffers. The
analyses of COD, settable solids, and soluble sulfate (turbidi-
metric method) were performed in accordance with standard
methods (APHA, 1998). Total phenols were measured accord-
ing to the colorimetric method of FolineCiocalteu reagent
(Scalbert et al., 1989). Real and apparent color, turbidity,
and sulfide were measured spectrophotometrically (spectro-
photometer DR/2010, HACH, Loveland, CO) using the
APHA platinumecobalt standard method, the attenuated radi-
ation method (direct reading), and the HACH sulfide test,
respectively. Metal concentrations were determined by atomic
absorption spectroscopy (Varian SpectrAAe10 Plus). The de-
tection limit of the analyzed metals was determined according
to Skoog and Leary (1992) recommendations.
3. Results and discussion
Fig. 1 illustrates the influence of pH on the concentration of
dissolved sulfate in non-treated wastewater before and after
the addition of a fixed calcium or barium dosage of
9.2 g L1 (2.30 mol L1 as calcium and 6.70  102 mol L1
as barium). This was a chosen concentration once it was de-
sired to work with a known concentration close to 10 g L1.
Results of barium and calcium precipitation on both sam-
ples showed a similar behavior to control experiments on the
pH range studied. Large amount of NaOH was used for raising
the pH from below 1 to 2, and a significant decrease on the sul-
fate concentration was observed on both samples (see Table 2
and Fig. 1). However, the pH variation in range of 2e8
resulted in small changes in sulfate concentration. In fact, in
this pH range the amount of hydroxyls present does not inter-
fere in the precipitation of barium sulfate (Kps ¼ 1.3  1010)
and calcium sulfate (Kps ¼ 2.6  105), because the formation
of Ba(OH)2 and Ca(OH)2, due to their high solubility, requires
other conditions of interference.
Therefore, the pH 4 was chosen to perform the sulfate pre-
cipitation on raw wastewater, since this is the pH used for the
Fenton’s oxidation.

220 2.29
a
Sulfate concentration (mol L-1)
Sulfate concentration (g L-1)

control
200 barium 2.08
calcium
180 1.87

160 1.67

140 1.46

120 1.25

100 1.04
2 3 4 5 6 7 8
pH

220 2.29
b
Sulfate concentration (mol L-1)
Sulfate concentration (g L-1)

200 2.08

180 1.87

160 1.67

140 1.46
control

120 barium 1.25

calcium
100 1.04
2 3 4 5 6 7 8
pH

Fig. 1. Influence of wastewater pH on sulfate concentration: (a) sample 1; (b) sample 2. The calcium and barium concentration is 9.2 g L1.
508 C.T. Benatti et al. / Journal of Environmental Management 90 (2009) 504e511
100
90
80
Sulfate removal ( )
70
60
50
40
30
20
10
0
0,0 0,2
Precipitating agent concentration (mol L-1)
Fig. 2. Results of barium and calcium precipitation conducted on samples 1 and 2.
In Fig. 2, the results obtained for sulfate removal in raw and
oxidized wastewaters as a function of the concentration of bar-
ium or calcium ions are presented.
The raw wastewater at pH 4 presented an initial sulfate con-
centration of 142 and 151 g L1 for samples 1 and 2, respec-
tively. The tested concentrations of precipitating agent were
40, 60 and 80 g L1 which correspond to the molar concentra-
tions of barium and calcium plotted on Fig. 2. These also cor-
respond to Ca2þ:SO2 4 molar ratios of 0.68, 1.01 and 1.35 for
sample 1 and 0.63, 0.95 and 1.26 for sample 2, respectively,
and to Ba2þ:SO2 4 molar ratios of 0.20, 0.30 and 0.39 for sam-
ple 1 and 0.19, 0.28 and 0.37 for sample 2, respectively.
Because sulfuric acid and sodium hydroxide solutions were
used for pH adjustments, and ferrous sulfate was used as a cat-
alyst in the Fenton’s process, further amounts of sulfate
resulted from the wastewater oxidation. Thus, the oxidized
wastewater presented an initial sulfate concentration of 152
and 164 g L1 for samples 1 and 2, respectively. The calcium
concentration tested were also 40, 60 and 80 g L1 that corre-
spond to Ca2þ:SO2 4 molar ratios of 0.63, 0.95 and 1.26 for
sample 1 and 0.58, 0.88 and 1.17 for sample 2, respectively,
and to Ba2þ:SO2 4 molar ratios of 0.18, 0.28 and 0.37 for sam-
ple 1 and 0.17, 0.26 and 0.34 for sample 2, respectively. Based
on the results shown in Fig. 2, the components originally
existing in the wastewater as well as the products of oxidation
seem to exert similar influence on sulfate removal for precip-
itation conducted on both samples, achieving similar removal
efficiencies under the same experimental conditions. Thus, the
removal efficiency is dependent on the dosage of the two
agents, once sulfate removal increases with crescent additions
of calcium or barium above the equilibrium sulfate concentra-
tion, independently if it is conducted on raw or oxidized
wastewater. The maximum removals were achieved with a dos-
age of 80 g L1, using barium or calcium ions. Barium precip-
itation provided 61.4 and 52.4% (raw wastewater at pH 4), and
50.1 and 61.2% (oxidized wastewater), of sulfate removal for
samples 1 and 2, respectively. Calcium precipitation provided
over 99% sulfate removal for both samples (raw and oxidized
wastewater); with a final sulfate concentration up to
1000 mg L1. These results are in accordance with theory, as
the production of insoluble inorganic species BaSO4 or
CaSO4 formed during the sulfate precipitation is stoichiometric
Calcium precipitation
sample1:raw wast.
sample1:oxidized wast.
sample2:raw wast.
sample2:oxidized wast.
Barium precipitation
sample1:raw wast.
sample1:oxidized wast.
sample2:raw wast.
sample2:oxidized wast.
0,4 0,6 0,8 1,0 1,2 1,4 1,6 1,8 2,0
(1 mole of SO24 per mole of Ca
2
or Ba2). Although complete
conversion to sulfate form is desirable, partial precipitation of
sulfate may be sufficient for reaching the required standards
for wastewater discharge. Barium salts may be capable of re-
moving practically all sulfate due to the lower solubility of
BaSO4, however, the hazardous nature of the sludge formed
and the excessive cost of chemicals are important factors to
be considered in the choice of the treatment system. Therefore,
the calcium precipitation was selected for sulfate removal.
The most recent directives of the European Community
regarding solid wastes management give high priority to the
development of technologies addressed towards recycling
and reuse. The reuse of calcium salts wastes can be limited
by their impurities. Hence, the calcium precipitation per-
formed after Fenton’s oxidation may be preferable, achieving
higher quality product precipitates. In this sense, the analyses
of precipitates generated by calcium precipitation of oxidized
laboratory wastewaters have been performed to indicate the
possible final destinations of the solid phase according to its
composition.
Firstly, the amount of water of hydration and constitution
presented in the precipitate was estimated by measuring the
dry weight at 105 and 220  C. As CaSO4 is appreciably hygro-
scopic when dried at 105  C, it is feasible to obtain its dry
weigh by plotting weigh against time. From these data,
a straight-line fitting is obtained, and the dry weigh at this tem-
perature can be determined in the intercept of the y-axis of the
straight-line fittings. Fig. 3 presents the obtained plots at 79%
daily average relative air humidity. According to Mellor
(1952) when calcium sulfate is heated over 200  C it un-
dergoes anhydrous calcium sulfate (anhydrite). Thus, the wa-
ter content of the precipitate generated by calcium
precipitation conducted on samples 1 and 2, as determined
by the difference in weight loss after drying precipitates at
105 and 220  C, was 0.83 and 1.34%, respectively. The small
change in weight detected demonstrated that sulfate precipita-
tion occurred as CaSO4, which may be associated with other
forms of crystalline calcium sulfate.
X-ray diffraction analysis of both samples was used in or-
der to identify crystalline forms in the precipitates. Fig. 4 pres-
ents typical X-ray diffraction spectrums of precipitates
indicating that both samples present similar characteristics,
 C.T. Benatti et al. / Journal of Environmental Management 90 (2009) 504e511 509

5.35
sample 1
5.30 sample 2

5.25 y = 0.0034x + 5.2576

R2 = 0.9909

Mass (g)
5.20

5.15

5.10 y = 0.0045x + 5.0193

R2 = 0.9918
5.05

5.00
0 1 2 3 4 5 6 7 8 9 10
Time (min)

Fig. 3. Water absorbed by dried precipitates (105  C) with time.

with the presence of calcium sulfate anhydrite (CaSO4$1/
2H2O) associated with calcium sulfate hemihydrate (CaSO4).
The absence of other pure crystalline components, as shown
by X-ray diffraction, also indicates the presence of a low con-
tent of other metals in precipitates as impurities.
Also, the presence of impurities in the precipitates was
investigated by the decomposition of calcium sulfate. The de-
termination of sulfur in precipitates as well as the results of
acid-extractable metals determinations along with the
detection limits of each metal are presented in Table 3. The
proportion of calcium sulfate as well as of moisture and impu-
rities detected in the precipitate is also presented in Table 3.
The results show that the approach used in the precipitation
procedure was able to produce calcium salts with low impuri-
ties contents. This suggests the yielded precipitate may be use-
ful for applications in innumerous processes.
Among the impurities detected in precipitates, iron and
manganese are micronutrients essential for plants growth.

a 2 (1) calcium sulfate anhydrite

(2) calcium sulfate hemihydrate
2
1/2

1/2

1/2

2 2 2
2
1 2 1/2 2 1 1/2 1/2 2 2 2
2

10 15 20 25 30 35 40 45 50 55 60 65 70 75 80
2θ - CuKα

b 2 (1) calcium sulfate anhydrite

(2) calcium sulfate hemihydrate

2
1/2 1/2

1/2

2 1 2 2
2 1/2 1 2
2 1/2 1/2 2 2 2
2

10 15 20 25 30 35 40 45 50 55 60 65 70 75 80
2θ - CuKα

Fig. 4. X-ray diffraction pattern of precipitate: (a) sample 1; (b) sample 2.

510 C.T. Benatti et al. / Journal of Environmental Management 90 (2009) 504e511

Table 3
Detection limit and composition of precipitates (dried at 105  C) generated from calcium precipitation conducted on samples 1 and 2 after Fenton’s oxidation
Element Detection limit Results (mg g1) Results (%)
(ppm) Sample 1 Sample 2 Sample 1 Sample 2
Ag 0.6 0.012 0.008 0.0012 0.0008
Al 129.0 0.000 0.000 0.0000 0.0000
Ca 2.9 301.8 299.7 29.13 28.99
Cd 0.0 0.000 0.000 0.0000 0.0000
Co 5.7 0.006 0.006 0.0006 0.0006
Cr 26.8 0.033 0.062 0.0033 0.0062
Cu 0.0 0.000 0.000 0.0000 0.0000
Fe 26.8 0.039 0.033 0.0039 0.0033
K 0.4 0.008 0.024 0.0008 0.0024
Mg 0.1 0.004 0.003 0.0004 0.0003
Mn 0.8 0.004 0.004 0.0004 0.0004
Na 1.9 2.02 1.77 0.20 0.18
Ni 0.0 0.000 0.000 0.0000 0.0000
Pb 3.8 0.000 0.000 0.0000 0.0000
Zn 0.0 0.000 0.000 0.0000 0.0000
S (as SO2
4 ) e 691.5 690.7 69.83 69.48
H2O (associated to the hemidrate) e e e 0.83 1.34
Total (%) 100.00 100.00

Cobalt is termed phytotoxic and is more toxic to plants than
animals. From the standpoint of potential hazard to human
health, elements such as chromium and silver are among the
most toxic ones. The toxicity of trace elements to plants and
microorganisms depends, however, on their concentrations.
Nevertheless, if elemental concentrations of precipitates are
within of those expected for soil, they can be safely used in
agricultural applications. Typical contents in soil worldwide
of some elements of interest detected in the precipitates are
(McBride, 1994): Ag, 0.03e8 ppm; Co, 1.6e21.5 ppm; Cr,
7e221 ppm; Mn, 80e1300 ppm. Regarding to the metal con-
tent, it is not a limiting factor in the use of the precipitates as
a soil conditioner. Hence, dried calcium sulfate can be safely
used in soil treatment to neutralize alkali carbonates and to
prevent loss of volatile and dissolved nitrogenous compounds
by volatilization and leaching. Dried calcium sulfate can also
be used as a white pigment, filler or glaze in paints; for wall
plasters, wallboard, tiles and blocks for the building industry;
in the cement industry; moldings; statuary; in the paper indus-
try (The Merck Index, 1996). Finally, it is essential to empha-
size that the produced calcium sulfate still has an
economically viable application for on-site reusing in the man-
ufacture of chalk, which besides representing discrete costs
with no need of shipping, increases the value of the proposed
treatment system.
4. Conclusions
Barium and calcium ions have been used for sulfate re-
moval process in mixed waste chemicals. The results showed
that a partial precipitation of sulfates with calcium ions may
be enough to reach the required standards for wastewater dis-
charge. As the feasibility of sulfate precipitation lies in the re-
use of the sludge produced, calcium precipitation was chosen
to be performed after the Fenton’s oxidation in order to pro-
duce higher quality precipitates. The precipitates’ character-
ization showed chemical compositions with no toxic risks
that favors its reuse in innumerous processes applications.
Acknowledgements
The support provided by CAPES and by the State
University of Maringá is gratefully acknowledged.
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