Journal of Environmental Management 90 (2009) 504e511 www.elsevier.

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Sulfate removal from waste chemicals by precipitation

Claudia Telles Benatti a, Celia Regina Granhen Tavares a,*, Ervim Lenzi b
a

Departamento de Engenharia Qumica, Universidade Estadual de Maringa, Av. Colombo, 5790, Bloco D90, 87020-900 Maringa-PR, Brazil b Departamento de Qumica, Universidade Estadual de Maringa, Av. Colombo, 5790, Bloco 22, 87020-900 Maringa-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 Fentons 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 efuent 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 composition 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 Fentons oxidation; hence this process conguration 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. 2007 Published by Elsevier Ltd.
Keywords: Waste chemicals; Fentons reagent; Sulfate; Chemical precipitation

1. Introduction Waste chemicals from academic laboratories are byproducts 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). Although small-quantity generators, universities have the responsibility 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.: 55 44 32614746; fax: 55 44 32632652. E-mail address: celia@deq.uem.br (C.R.G. Tavares). 0301-4797/$ - see front matter 2007 Published by Elsevier Ltd. doi:10.1016/j.jenvman.2007.12.006

There are signicant differences between the two in terms of waste volume produced and number of chemicals handled, as well as in the associated potential environmental risks (National Research Council, 2000). Therefore, academia has several 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 turnover of workforce, relying heavily on graduate and postgraduate 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 difculty in terms of characterizing wastes and providing adequate documentation for treatment and disposal by safe and environmentally acceptable methods. Because of the lack of specic legislation to regulate waste chemicals treatment, the waste generated during the operations of the Control and Environmental Prevention Laboratory at the

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Department of Chemical Engineering of the Universidade Estadual de Maringa 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 laboratory reagents. The research activities include chemical and biological treatment experiments of a wide range of synthetic and natural wastewaters arising from different chemical industries. Accordingly, these wastes are constituted of great diversity 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 Fentons 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 successfully accomplished by the Fentons oxidation, however, the concentration of certain inorganic constituents, such as sulfate, still remained extremely high for efuent 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., gypsumlayers). Industrial wastewaters are responsible for most anthropogenic emissions of sulfate into the environment. Domestic sewage typically contains between 20 and 500 mg L1 sulfate (Lens et al., 1998) while certain industrial efuents may contain several thousands of milligrams per liter. The main source of sulfate 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 compound. 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 suldes that can provoke damages to the environment (Ghigliazza et al., 2000). A number of methods are currently used to promote the removal of dissolved sulfate. They include reversed osmosis, electrodialysis, or nanoltration, 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 sulfaterich efuents 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 organophosphates) from wastewater (U.S. EPA, 2000). Previous investigators 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 (Gominsek et al., 2005). Chemical precipitation through the addition of barium

or calcium salts is an alternative, mainly if applied to the treatment 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). extremely low The solubility of BaSO4 is (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 Ca2 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, precipitation of either BaSO4, PbSO4 or CaSO4 will occur. The solid precipitate can then be ltered, 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 efuent monitoring and generally the use of a posttreatment 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 replacement for natural gypsum (Lens et al., 1998). The purpose of this paper is to study the chemical precipitation as an alternative for sulfate removal from complex waste chemicals. Chemical precipitation using barium and calcium is recognized method to reduce sulfates in industrial wastewaters (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. Therefore, precipitation appeared as a promising process for removing 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 wastewater; moreover particular attention was paid to gypsum generated from calcium precipitation. Furthermore, the process was applied to wastewaters generated in different periods in order to study the effect of wastewater composition on the sulfate precipitation. Results are discussed and conclusions are drawn with focus not only on the sulfate removal efciencies but also on the reuse of the solid phase obtained after treatment, addressing possible alternative ways for its nal 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

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Table 1 Main characteristics of raw laboratory wastewaters Parameter Apparent color Real color Turbidity COD Total phenols Settable solids Units Pt/Co Pt/Co NTU mg L1 mg L1 mL L1 Sample 1 12 700 7150 4010 2345 58.6 4.5 Sample 2 10 250 1020 2960 2676 37.9 4.0

2001 to April 2002 (sample 1) and those produced from May to November 2003 (sample 2) are presented in Table 1; and the main characteristics of these wastewaters after separation of suspended solids by centrifugation at 2500 rpm by 5 min are presented in Table 2. In both periods, the waste chemicals were generated fundamentally by chemical analysis residues originated from the laboratory routine analysis, such as COD, total phenols, nitrogen, protein, phosphate, sulde, sample preparations and standards for atomic absorption, solutions standardization, and an abundance of unused laboratory reagents. Experiments of Fentons oxidation were carried out under optimal conditions established in previous work (Benatti et al., 2006): ratio [COD]:[H2O2] 1:9; ratio [H2O2]: [Fe2] 4.5:1 and pH 4. The wastewater after Fentons treatment was taken for the sulfate removal experiments and its main characteristics are presented in Table 2. 2.2. Reagents and solutions All reagents used in this work were analytical reagent grade, excepting calcium chloride (CaCl2, 75%) which was
Table 2 Main characteristics of non-treated laboratory wastewater supernatant after centrifugation, and of laboratory wastewater after the Fentons oxidation process (N.D.: not detected) Parameter Units Sample 1 Sample 2

purchased from Quimibras. Barium chloride (BaCl2$2H2O, 99%), ferrous sulfate (FeSO4$7H2O, 99%), hydrogen peroxide (33%), sodium hydroxide (95e100%), sulfuric acid (95e98%) were purchased from Nuclear or Quimibras. All solutions were prepared in distilled/deionized water. Glassware was washed with detergent, rinsed with tap water, soaked with HNO3 (w50% v/v) for 24 h, and rinsed with distilled/deionized water prior to drying. Standard barium and calcium chloride stock solutions were obtained by dissolution of solids (BaCl2$2H2O and CaCl2) in distilled water at 25  C till saturation. The solutions were then ltered. Barium concentration was determined by EDTA titration (Merck). Calcium concentration was determined by atomic absorption. Reagent grade H2O2 was standardized using iodometric titration (U.S. Peroxide, 2003) and used as purchased. A 1 M FeSO4 stock solution was prepared and standardized (Pavan et al., 1992) just before Fentons experiments. Solutions of NaOH and H2SO4 were used for pH adjustments. 2.3. Sulfate precipitation procedure Chemical precipitation of sulfate before and after Fentons oxidation was performed using barium and calcium ions. Firstly, the effects of pH on sulfate precipitation were investigated at a pH range of 2e8 using non-treated wastewaters without solids separation. NaOH (w30% w/v) was used for pH adjustments. At this 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 experiments were carried out in parallel without addition of either calcium or barium ions. Secondly, precipitation tests were conducted with non-treated wastewaters without solids separation at pH 4 as well as with oxidized wastewaters, at a calcium or barium dosage range of 20e80 g L1 (0.50e2.00 mol L1 as calcium and 0.15e0.58 mol L1 as barium). Each precipitation experiment was conducted in a 22 mL glass tube, with 5 mL of wastewater in which a pre-calculated volume of stock solution was added to give the desired concentration of barium or calcium ions. The tube was sealed with paralm, and after a rapid mixing the sample was left to settle for 24 h under quiescent condition. Aliquots of the supernatant were then removed with a pipet from each tube for sulfate analysis. The difference in the amount before and after precipitation reveals the sulfate removals. All experiments were run in three replicates, at room temperature. The solid obtained from the best-selected experimental condition was ltered under vacuum, rinsed with distilled/deionized water to eliminate the excess of sodium hydroxide, dried at 105  C, and stored for characterization. 2.4. Analysis of the solid phase The dried solids were rst analyzed for water content. The samples were dried in a 105  C oven for 24 h, cooled down in a vacuum desiccator for 2 h and then weighed at each 30 s for 10 min. To set free the water of constitution, the samples were dried in a 220  C oven for 2 h, cooled down in a vacuum

Non-treated Oxidized Non-treated Oxidized wastewater wastewater wastewater wastewater pH Apparent color Turbidity Soluble COD Total phenols Sulfate Sulde Ag Al Ca Cd Co Cr Cu Fe K Mg Mn Na Ni Pb Zn Pt/Co NTU mg L1 mg L1 g L1 mg L1 mg L1 mg L1 mg L1 mg L1 mg L1 mg L1 mg L1 mg L1 mg L1 mg L1 mg L1 g L1 mg L1 mg L1 mg L1 <1 308 e 1145 27.3 263 0.04 1.1 18.8 59.1 0.2 1.2 301.4 1.7 131.9 405.2 3.5 0.7 10.2 0.9 1.9 0.9 8 137 10 117 N.D. 152 0.01 0.8 1.4 30.4 0.3 0.8 1.0 0.6 4.4 187.4 1.7 0.5 77.9 1.1 1.1 N.D. <1 503 e 2576 39.8 296 0.05 1.1 6.8 37.7 6.9 1.3 541.6 4.5 114.0 1084.8 10.6 0.8 9.1 1.1 1.6 0.1 8 352 6 167 N.D. 164 0.03 1.0 4.5 21.4 0.5 1.0 16.0 0.3 1.7 645.3 3.0 0.1 101.7 1.1 1.1 N.D.

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desiccator for 2 h and promptly weighed after been removed from desiccator. Total water content was determined as the difference 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 asks until fumes of perchloric acid appear. For metal determinations, the obtained extracts were diluted to 50 mL by distilled/deionized 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 1.54178 A;   scanning speed 5 2q for the ranges 5e70 2q).

respectively. Metal concentrations were determined by atomic absorption spectroscopy (Varian SpectrAAe10 Plus). The detection limit of the analyzed metals was determined according to Skoog and Leary (1992) recommendations.

3. Results and discussion Fig. 1 illustrates the inuence of pH on the concentration of dissolved sulfate in non-treated wastewater before and after the addition of a xed 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 desired to work with a known concentration close to 10 g L1. Results of barium and calcium precipitation on both samples 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 signicant decrease on the sulfate 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 interfere in the precipitation of barium sulfate (Kps 1.3 1010) and calcium sulfate (Kps 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 precipitation on raw wastewater, since this is the pH used for the Fentons oxidation.
2.29 control barium calcium 2.08 1.87 1.67 1.46 1.25 1.04

2.5. Analytical methods pH was measured with a Digimed DM-20 pH meter calibrated with pH 4.01 and 6.86 Digimed standard buffers. The analyses of COD, settable solids, and soluble sulfate (turbidimetric method) were performed in accordance with standard methods (APHA, 1998). Total phenols were measured according to the colorimetric method of FolineCiocalteu reagent (Scalbert et al., 1989). Real and apparent color, turbidity, and sulde were measured spectrophotometrically (spectrophotometer DR/2010, HACH, Loveland, CO) using the APHA platinumecobalt standard method, the attenuated radiation method (direct reading), and the HACH sulde test,
220

200 180 160 140 120 100

pH Sulfate concentration (mol L-1)

220

Sulfate concentration (g L-1)

200 180 160 140 120 100

2.29 2.08 1.87 1.67 control barium calcium 1.04 1.46 1.25

pH
Fig. 1. Inuence of wastewater pH on sulfate concentration: (a) sample 1; (b) sample 2. The calcium and barium concentration is 9.2 g L1.

Sulfate concentration (mol L-1)

Sulfate concentration (g L-1)

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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. 0,0

Sulfate removal ( )

80 70 60 50 40 30 20 10 0

0,2

0,4

0,6

0,8

1,0

1,2

1,4

1,6

1,8

2,0

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 barium or calcium ions are presented. The raw wastewater at pH 4 presented an initial sulfate concentration of 142 and 151 g L1 for samples 1 and 2, respectively. The tested concentrations of precipitating agent were 40, 60 and 80 g L1 which correspond to the molar concentrations of barium and calcium plotted on Fig. 2. These also correspond to Ca2:SO2 molar ratios of 0.68, 1.01 and 1.35 for 4 sample 1 and 0.63, 0.95 and 1.26 for sample 2, respectively, and to Ba2:SO2 molar ratios of 0.20, 0.30 and 0.39 for sam4 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 catalyst in the Fentons 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 correspond to Ca2:SO2 molar ratios of 0.63, 0.95 and 1.26 for 4 sample 1 and 0.58, 0.88 and 1.17 for sample 2, respectively, and to Ba2:SO2 molar ratios of 0.18, 0.28 and 0.37 for sam4 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 inuence on sulfate removal for precipitation conducted on both samples, achieving similar removal efciencies under the same experimental conditions. Thus, the removal efciency is dependent on the dosage of the two agents, once sulfate removal increases with crescent additions of calcium or barium above the equilibrium sulfate concentration, independently if it is conducted on raw or oxidized wastewater. The maximum removals were achieved with a dosage of 80 g L1, using barium or calcium ions. Barium precipitation 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 nal 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

(1 mole of SO2 per mole of Ca2 or Ba2). Although complete 4 conversion to sulfate form is desirable, partial precipitation of sulfate may be sufcient for reaching the required standards for wastewater discharge. Barium salts may be capable of removing 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 performed after Fentons 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 nal 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 hygroscopic when dried at 105  C, it is feasible to obtain its dry weigh by plotting weigh against time. From these data, a straight-line tting is obtained, and the dry weigh at this temperature can be determined in the intercept of the y-axis of the straight-line ttings. 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 undergoes anhydrous calcium sulfate (anhydrite). Thus, the water 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 precipitation occurred as CaSO4, which may be associated with other forms of crystalline calcium sulfate. X-ray diffraction analysis of both samples was used in order to identify crystalline forms in the precipitates. Fig. 4 presents typical X-ray diffraction spectrums of precipitates indicating that both samples present similar characteristics,

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5.35 5.30 5.25 sample 1 sample 2 y = 0.0034x + 5.2576 R2 = 0.9909

509

Mass (g)

5.20 5.15 5.10 5.05 5.00 0 1 2 3 4 5 6 7 8 9 10 y = 0.0045x + 5.0193 R2 = 0.9918

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 content of other metals in precipitates as impurities. Also, the presence of impurities in the precipitates was investigated by the decomposition of calcium sulfate. The determination 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 impurities 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 impurities contents. This suggests the yielded precipitate may be useful 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 1/2

1/2

1/2

2 2 10 15 20 25 1 2 1/2 2 1 35 40

2 1/2 45 50

2 2 1/2 55 60 65 70 2 2 2 75 80

30

2 - CuK

b
2 1/2

(1) calcium sulfate anhydrite (2) calcium sulfate hemihydrate

1/2

1/2

2 1 2 10 15 20 25 30 2 1/2 1 2 35 40

2 1/2 1/2

2 2 2 2 2 60 65 70 75 80

45

50

55

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

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Table 3 Detection limit and composition of precipitates (dried at 105  C) generated from calcium precipitation conducted on samples 1 and 2 after Fentons oxidation Element Detection limit (ppm) 0.6 129.0 2.9 0.0 5.7 26.8 0.0 26.8 0.4 0.1 0.8 1.9 0.0 3.8 0.0 e e Results (mg g1) Sample 1 0.012 0.000 301.8 0.000 0.006 0.033 0.000 0.039 0.008 0.004 0.004 2.02 0.000 0.000 0.000 691.5 e Sample 2 0.008 0.000 299.7 0.000 0.006 0.062 0.000 0.033 0.024 0.003 0.004 1.77 0.000 0.000 0.000 690.7 e Results (%) Sample 1 0.0012 0.0000 29.13 0.0000 0.0006 0.0033 0.0000 0.0039 0.0008 0.0004 0.0004 0.20 0.0000 0.0000 0.0000 69.83 0.83 100.00 Sample 2 0.0008 0.0000 28.99 0.0000 0.0006 0.0062 0.0000 0.0033 0.0024 0.0003 0.0004 0.18 0.0000 0.0000 0.0000 69.48 1.34 100.00

Ag Al Ca Cd Co Cr Cu Fe K Mg Mn Na Ni Pb Zn S (as SO2) 4 H2O (associated to the hemidrate) Total (%)

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 content, 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, ller or glaze in paints; for wall plasters, wallboard, tiles and blocks for the building industry; in the cement industry; moldings; statuary; in the paper industry (The Merck Index, 1996). Finally, it is essential to emphasize that the produced calcium sulfate still has an economically viable application for on-site reusing in the manufacture 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 removal 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 discharge. As the feasibility of sulfate precipitation lies in the reuse of the sludge produced, calcium precipitation was chosen

to be performed after the Fentons oxidation in order to produce higher quality precipitates. The precipitates characterization 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 Maringa is gratefully acknowledged. References
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