Characterization of primary precipitate composition formed during co-removal of Cr(VI) with Cu(II) in synthetic wastewater

BACKGROUND, AIMS AND SCOPE: Hexavalent chromium [Cr(VI)] cannot react with either carbonate or hydroxide to form chromium precipitates. However, by using a precipitation technology to treat plating wastewater containing Cr(VI), Cu(II), Ni(II) and Zn(II), approximately 78% of Cr(VI) (initial 60 mg/L) was co-removed with the precipitation of Cu(II), Ni(II) and Zn(II) (each 150 mg/L) by dosing with Na2CO3 (Sun 2003). Direct precipitation by forming Cu(II)-Cr(VI) precipitates followed by adsorption of Cr(VI) onto freshly formed Cu-precipitates was subsequently found to be the main mechanism(s) involved in Cr(VI) co-removal with Cu(II) precipitation by dosing Na2CO3 stepwise to various pH values (Sun et al. 2003). This study was. carried out to further characterize the formation of primary precipitates during the early stages of copper precipitation and simultaneous removal of Cr(VI) with Cu(II). METHODS: Test metal-solutions were prepared with industrial grade chemicals: CuCl2 x 2H2O, Na2SO4 and K2Cr2207. NaCO3 was added drop-wise to synthetic metal-solution to progressively increase pH. For each pH increment, removal of soluble metals was detected by atomic absorption spectrophotometer (AAS) and surface morphology of precipitates was analyzed by scanning electron microscope (SEM). To further characterize the formation of primary precipitates, a series of MINEQL+ thermodynamic calculations/analyses and equilibrium calculations/ analyses were conducted. RESULTS AND DISCUSSION: MINEQL+ thermodynamic calculation indicated that, for a system containing 150 mg/L Cu(II) and 60 mg/L Cr(VI) with gradual Na2CO3 dosing, if any precipitates can be formed at pH 5.0 or lower, it should be in the form of CuCrO4. Comparison tests using systems containing the same equivalent of Cu(II) plus Cr(VI) and Cu(II) plus SO4(2-) showed that the precipitation occurred at a pH of around 5.0 in the Cu(II)-Cr(VI) system and around 6.0 in the Cu(II)-SO4(2-) system. The discrepancy of the precipitation was indeed caused by the formation of Cu-Cr precipitates. The initiation of copper removal at pH around 5.0 for the Cu-Cr co-removal test was not attributable to the formation of Cu-CO3 precipitates, instead, it was most likely through the formation of insoluble Cu-Cr precipitates, such as CuCrO4 and CuCrO4 x 2Cu(OH)2. Experimental tests, equilibrium calculations, MINEQL+ thermodynamic calculations and surface morphologies for systems using higher concentrations of Cu(II) and Cr(VI) further verified the most probable composition of primary precipitates is copper-chromate. CONCLUSION: In the Cu-Cr co-removal test with Na2O3 dosing to increase pH and induce metal precipitation, copper-chromate precipitates are the primary precipitates produced and contribute to the initial simultaneous removal of copper and chromium.     

Heavy metal contamination in the vicinity of an industrial area near Bucharest

BACKGROUND, AIMS AND SCOPE: Chromium enters into the aquatic environment as a result of effluent discharge from steel works, electroplating, leather tanning industries and chemical industries. As the Cr(VI) is very harmful to living organisms, it should be quickly removed from the environment when it happens to be contaminated. Therefore, the aim of this laboratory research was to develop a rapid, simple and adaptable solvent extraction system to quantitatively remove Cr(VI) from polluted waters. METHODS: Aqueous salt-solutions containing Cr(VI) as CrO4(2-) at ppm level (4-6 ppm) were prepared. Equal volumes (5 ml) of aqueous and organic (2-PrOH) phases were mixed in a 10 ml centrifuge tube for 15 min, centrifuged and separated. Concentrations of Cr(VI), in both the aqueous and organic phases, were determined by atomic absorption spectrometry. The effects of salt and acid concentrations, and phase-contact time on the extraction of Cr(VI) were investigated. In addition, the extraction of Cr(VI) was assessed in the presence of tetramethylammonium chloride (TMAC) in 2-PrOH phase. Effects of some other metals, (Cd(II), Co(II), Cu(II), Ni(II) and Zn(II)), on the extraction of Cr(VI) were also investigated. RESULTS AND DISCUSSION: The Cr(VI) at ppm level was extracted quantitatively by salting-out the homogeneous system of water and 2-propanol(2-PrOH) using chloride salts, namely CaCl2 or NaCl, under acidic chloride media. The extracted chemical species of Cr(VI) was confirmed to be the CrO3Cl-. The ion-pair complex extracted into the organic phase was rationalized as the solvated ion-pair complex of [2-PrOH2+, CrO3Cl-]. The complex was no longer stable. It implied the reaction between extracted species. Studies revealed that salts and acid directly participated in the formation of the above complex. Use of extracting agents (TMAC) didn't show any significant effect on the extraction of Cr(VI) under high salting-out conditions. There is no significant interference effect on the extraction of Cr(VI) by the presence of other metals. The Cr(VI) in the organic phase was back-extracted using an aqueous ammonia solution (1.6 mol dm(-3)) containing 3 mol dm(-3) NaCl. The extraction mechanism of Cr(VI) is also discussed. CONCLUSIONS: Salting-out of homogeneous mixed solvent of 2-propanol can be employed to extract Cr(VI) quantitatively, as an ion-pair of [2-PrOH2+ * CrO3Cl-] solvated by 2-PrOH molecules. Then, the complex becomes 'solvent-like' and is readily separated into the organic phase. The increase of Cl- ion concentration in the aqueous phase favors the extraction. The 2-PrOH, salts and acid play important roles in the extraction process. There is no need to use an extracting agent at a high salting-out condition. RECOMMENDATIONS AND PERSPECTIVES: Chromium(VI) must be quickly removed before it enters into the natural cycle. As the 2-PrOH is water-miscible in any proportion, ion-pairing between 2-PrOH2+ and CrO3Cl- becomes very fast. As a result, Cr(VI) can easily be extracted. Therefore, the method is recommended as a simple, rapid and adaptable method to quickly separate Cr(VI) from aqueous samples.     

Chromium(VI) resistance and removal by actinomycete strains isolated from sediments

Forty-one isolated actinomycetes were used to study qualitative and semi-quantitative screening of chromium(VI) resistance. Chromate-removing activity was estimated using the Cr(VI) specific colorimetric reagent 1,5-diphenylcarbazide. Twenty percent of the isolates from El Cadillal (EC) and 14% of isolates from a copper filter plant (CFP) were able to grow at 13 mM of Cr(VI). All isolates from sugar cane (SCP) could grow up to Cr(VI) concentration of 17 mM. EC, CFP and SCP strains were able to remove 24%, 30% and more than 40% of Cr(VI), respectively. The highest and lowest Cr(VI) specific removal values were 75.5 mg g(-1) cell by M3 (CFP), and 1.5 mg g(-1) cell by C35 (EC) strains. Eleven Cr(VI) resistant strains were characterized and identified as species of the genera Streptomyces (10) and Amycolatopsis (1). Differences on actinomycete community composition between contaminated and non-contaminated soil were found. This study showed the potential capacity of actinomycetes as tools for Cr(VI) bioremediation.     

Chromium (VI) remediation by a native strain: effect of environmental conditions and removal mechanisms involved

A native bacterial strain with high capability for Cr (VI) removal was isolated from tannery sediments located in Elena (Córdoba Province, Argentina). The strain was characterized by amplification of 16S rRNA gene and identified as Serratia sp. C8. It was able to efficiently remove different Cr (VI) concentrations in a wide range of pHs and temperatures. The addition of different carbon sources as well as initial inoculum concentration were analyzed, demonstrating that Serratia sp. C8 could reduce 80 % of 20 mg/L Cr (VI) in a medium containing glucose 1 g/L, at pH 6–7 and 28 °C as optimal conditions, using 5 % inoculum concentration. The mechanisms involved in Cr (VI) removal were also evaluated. The strain was capable of biosorpting around 7.5–8.5 % of 20 mg/L Cr on its cell surface and to reduce Cr (VI). In addition, approximately a 54 and 46 % of total Cr was detected in the biomass and in the culture medium, respectively, and in the culture medium, Cr (III) was the predominant species. In conclusion, Serratia sp. C8 removed Cr (VI) and the mechanisms involved in decreasing order of contribution were as follows: reduction catalyzed by intracellular enzymes, accumulation into the cells, and biosorption to the microbial biomass. This strain could be a suitable microorganism for Cr (VI) bioremediation of tannery sediments and effluents or even for other environments contaminated with Cr.     

Chromium (VI) remediation in aqueous solution by waste products (peel and seed) of mango (Mangifera indica L.) cultivars

The surface group characteristics of mango cultivar peels and seeds were evaluated by infrared spectra, PZC, and functional group composition. The adsorption/reduction of chromium (VI) in aqueous solutions was investigated by varying pH, contact time, initial Cr(VI) concentration, and adsorbent amount. The results show that both peel and seed powders of the mango cultivars showed significant adsorption/reduction capacity for Cr(VI) and that the desorption process obeys pseudo-second-order kinetics. Optimal adsorption occurred at pH 1.0, using a Cr(VI) concentration of 100 mg/L. On average, at pH 1.0, and a concentration of 3 g/L, the maximum adsorption/reduction capacity of Cr(VI) was 83% (peels 76%, seeds 90%). Of the mango powders tested, the most efficient were Tommy seed (100%) and Coite peel (98%) followed by Coite seed (96%) and Tommy peel powders (95%). The adsorption/reduction of Cr(VI) was complete (100%) by the mango seed, in comparison to the peel powders (97%) after 180 min. The data indicates that mango waste products, such as seed and peel powders, are both excellent candidates for the remediation of Cr(VI) from aqueous systems and due to the higher concentration of gallates and galloyl glucosides, the mango seed powders should be the powders of choice for future remediation projects.

     

Simultaneous Cr(VI) reduction and phenol degradation using Stenotrophomonas sp. isolated from tannery effluent contaminated soil

This study presents simultaneous hexavalent chromium (Cr(VI)) reduction and phenol degradation using Stenotrophomonas sp., isolated from tannery effluent contaminated soil. Phenol was used as the sole carbon and energy source for Cr(VI) reduction. The optimization of different operating parameters was done using Placket–Burman design (PBD) and Box–Behnken design (BBD). The significant operating variables identified by PBD were initial Cr(VI) and phenol concentration, pH, temperature, and reaction time. These variables were optimized by a three-level BBD and the optimum initial Cr(VI) concentration, initial phenol concentration, pH, temperature, and reaction time obtained were 16.59 mg/l, 200.05 mg/l, 7.38, 31.96 °C and 4.07 days, respectively. Under the optimum conditions, 81.27 % Cr(VI) reduction and 100 % phenol degradation were observed experimentally. The results concluded that the Stenotrophomonas sp. could be used to decontaminate the effluents containing Cr(VI) and phenol effectively.     

Uptake studies of environmentally hazardous (51)Cr in Mung beans

Attempt has been made to study the accumulation behaviour of a common plant, Mung bean (Vigna radiata) towards Cr(III) and Cr(VI) to have an insight on the migration and bio-magnification of Cr. For this purpose healthy germinated Mung bean seeds were sown in the sand in the presence of Hoagland's nutrient solution containing measured amount of K(2)(51)Cr(2)O(7) and (51)Cr(NO(3))(3).9H(2)O. Growth rate was also studied in the presence and absence of phosphate salts in the medium. It has been found that the transfer of chromium from soil to plant is significantly low (maximum 5% for both Cr(III) and Cr(VI)). Maximum accumulation of Cr occurs in the root with respect to the total chromium accumulation by the plant. Other parts of the Mung bean plant, e.g. cotyledons, shoot and leaves, show negligible accumulation. Therefore, the chance of direct intake of Cr through food as well as through the grazing animals to human body is less.     

Characterization of a simple bacterial consortium for effective treatment of wastewaters with reactive dyes and Cr(VI)

A microbial consortia consisting of three bacteria isolated from tanning and textile wastewaters revealed high capacity to simultaneously bioaccumulate dye and Cr(VI). The identity of the bacteria were determined by 16S rRNA gene analysis to be closely related to Ochrobactrium sp., Salmonella enterica and Pseudomonas aeruginosa. Dependence of initial pH values and range of concentrations of the dye Reactive Black B (33.2-103.1 mg l(-1)) and Cr(VI) (19.9-127.6 mg l(-1)) were examined to find the effect of pH on the dye and Cr(VI) bioaccumulation. Optimal pH for growth of the consortia in media containing 35 mg l(-1) dye and 50 mg l(-1) Cr(VI) was determined to be around 8. The Cr(VI) bioaccumulation by the consortia was rapid in media containing molasses with or without reactive dye with a maximum Cr(VI) bioaccumulation yield ranging from 90% to 99% within a 2-4d period. A slightly lower yield for the dye bioaccumulation was measured with a maximum dye bioaccumulation of 80% at 59.3 mg l(-1) dye and 69.8 mg l(-1) Cr(VI). The highest specific Cr uptake value was obtained as 76.7 mg g(-1) at 117.1 mg l(-1) Cr(VI) and 50.8 mg l(-1) dye concentration. This ability to bioaccumulate dye and Cr(VI) was more efficient than the enriched sludge from which they were isolated.     

Remediation of Cr(VI) from chromium slag by biocementation

Here we demonstrate a calcifying ureolytic bacterium Bacillus sp. CS8 for the bioremediation of chromate (Cr(VI)) from chromium slag based on microbially induced calcite precipitation (MICP). A consolidated structure like bricks was prepared from chromium slags using bacterial cells, and five stage Cr(VI) sequential extraction was carried out to know their distribution pattern. Cr(VI) mobility was found to significantly be decreased in the exchangeable fraction of Cr slag and subsequently, the Cr(VI) concentration was markedly increased in carbonated fraction after bioremediation. It was found that such Cr slag bricks developed high compressive strength with low permeability. Further, leaching behavior of Cr(VI) in the Cr slag was studied by column tests and remarkable decrease in Cr(VI) concentration was noticed after bioremediation. Cr slags from columns were characterized by SEM–EDS confirming MICP process in bioremediation. The incorporation of Cr(VI) into the calcite surface forms a strong complex that leads to obstruction in Cr(VI) release into the environment. As China is facing chromium slag accidents at the regular time intervals, the technology discussed in the present study promises to provide effective and economical treatment of such sites across the country, however, it can be used globally.     

Differential Sensitivity of a Coccal Green Algal and a Cyanobacterial Species to Dissolved Natural Organic Matter (NOM) (8 pp)

Background

and Aim. In non-eutrophicated freshwaters, humic substances (HS) pose chemical stresses on aquatic organisms and, hence, separating sensitive from less sensitive or even tolerant species. One of the stresses, identified so far, is the reduction of photosynthetic oxygen production and reduction in growth in freshwater macrophytes and algae. In a previous paper, it has been shown that even closely related coccal green algae responded differently upon identical stress by HS, which is consistent with the hypothesis above. Due to their much simpler cellular ultrastructure, cyanobacteria are supposed to be more sensitive to HS exposure than eukaryote should be. One coccal green algal species (Desmodesmus communis) and one cyanobacterium (Chroococcus minutus) were exposed to four natural organic matter (NOM) isolates. One NOM has been isolated from a brown water lake (Schwarzer See) in Brandenburg State; three were obtained from a comprehensive Scandinavian NOM research project and originated from Norway (Birkenes), Finland (Hietajärvi), and Sweden (Svartberget).

Methods

Cultures of D. communis and C. minutus were obtained from the Culture Collection of Algae, Göttingen, and maintained in a common medium. The cultures were non-axenic. The algae and cyanobacteria were exposed under identical conditions to environmentally realistic NOM concentrations. Cell numbers were counted microscopically in Neugebauer cuvettes in triplicates. To avoid limitation by nutrient depletion, the experiments were terminated after 14 to 15 days. Until culture day 12, no growth limitation has been observed in the controls.

Results

All NOM isolates modulated the growth of the algae and cyanobacteria. During the early culture days, there was a slight growth promotion with the coccal green alga and to a much lesser degree with the cyanobacterium. Yet, the major effect were significant reductions in cell yield in both primary producer cultures. C. minutus was much more affected than D. communis. This applies particularly to the three tested Scandinavian NOM isolates, which were effective at concentrations even below 1 mg L-1 DOC.

Discussion

The growth promoting effect may be due to an increase in bioavailability of some trace nutrients in the presence of NOM, the release of some growth promoting substances by microbial or photochemical processing of the NOM, and/or a hormetic effect. The growth reducing effect can be explained as a herbicide-like mode of action that affects the photosystem II most prevalent by blocking the electron transport chain, absorption of electrons, or production of an internal oxidative stress after processing the bioconcentrated HS. Furthermore, it may be postulated that also photo-toxicity of these HS in the algal cells contributes to the overall toxicity; however, experimental evidence is lacking so far.

Conclusions

Upon exposure to HS, cyanobacteria appear to be much more sensitive than coccal green algae and respond in growth reduction. This high sensitivity of cyanobacteria to HS may explain phytoplankton patterns in the field. Eutrophic, humic-rich lakes do not support the cyanobacterial blooms characteristic of eutrophic, but humic-poor lakes. In the humic-rich systems, raphidophytes or, less frequent, specific coccal greens are more common. Obviously, cyanobacteria appear to be unable to make advantage of their accessory pigments (phycocyanin) to exploit the reddish light prevailing in humic-rich lakes.

Recommendation

. At present, no effective structure can be figured out which may be responsible for the adverse effect on the cyanobacterial species. It is reserved to future research whether or not HS may be applied more specifically (for instance, with elevated moieties of the effective structures) as a natural geochemical to combat cyanobacterial blooms.