Hexavalent chromium quantification by isotope dilution mass spectrometry in potentially contaminated soils from south Italy.

Due to carcinogenicity of hexavalent chromium [Cr(VI)], its accurate quantification in Cr-contaminated soils is of paramount importance. The aim of this work was to quantify Cr(VI) by species-specific IDMS in soil samples from two Italian case studies: A) farmland potentially contaminated by pseudo-total Cr and Zn and heavy hydrocarbons due to past illegal burial of tannery wastes; B) Solofrana valley where volcanic soils are potentially contaminated by pseudo-total Cr and Cu due to tannery activities. Hexavalent Cr extraction from soils was performed by focused microwaves (5 min at 80 °C) using 50 mM EDTA, followed by the separation of Cr species by IC and detection by ICP-MS. The Cr(VI) extracted from 20 soil samples of case study A ranged from 0.15 to 11.18 µg g-1, with 70% of samples exceeding the Cr(VI) screening value set by Italian Parliament for residential/urban soil to assess their potential contamination. Higher levels of Cr(VI) (22.0-107.1 µg g-1) were extracted from other 7 Cr-most-enriched soil samples, which required a pre-treatment with n-hexane to remove part of organic compounds from each sample, since these reducing agents made the quantification of Cr(VI) by IDMS more challenging because they caused an almost complete reduction of 50Cr(VI) used for IDMS quantification. Hexavalent Cr extracted from soil samples of case study B ranged from 0.70 to 5.79 µg g-1, with 42% of samples exceeding the value set by Italian legislation. In both case studies, the Cr(VI) extracted from soil was significantly correlated to the pseudo-total Cr content.

Experimental tests of co-combustion of pelletized leather tannery wastes and hardwood pellets.

This study examines the possibility of using pelletized leather tannery wastes (LTW) in the co-combustion process with hardwood pellets (HP). The experiments were carried out in a small-scale combustion reactor and were followed by thermogravimetric analysis (TGA) of fuels in the nitrogen and air atmosphere. The experimental investigation has indicated that the leather tannery wastes can be an interesting fuel with a relatively high heating value (HHV), at the level of 16 MJ/kg, and the volatile content of about 68%. Thermal decomposition of the leather tannery sample occurs at temperatures ranging between 220 and 420 °C, with the maximum of intensity at 320 °C. The experimental results indicated that the averaged maximum temperatures obtained during the combustion reached similar values for all samples, which indicates that doping wood pellets with leather waste pellets does not have a significant impact on the temperature characteristics of the combustion process. However, decreasing the amount of hardwood pellets in the mixture reduces the bulk density of the fuel bed and the combustion front velocity. The emission of nitrogen oxides for combusting blends is twice as high as for combustion of pure HP, which is related to higher nitrogen content in leather waste as well as higher ash content.

Modeling of Cr contamination in the agricultural lands of three villages near the leather industry in Kasur, Pakistan, using statistical and GIS techniques.

Kasur is one of the hubs of leather industry in the Punjab, Pakistan, where chrome tanning method of leather processing is extensively being used. Chromium (Cr) accumulation levels in the irrigation water, soil, and seasonal vegetables were studied in three villages located in the vicinity of wastewater treatment plant and solid waste dumping site operated by the Kasur Tanneries Waste Management Agency (KTWMA). The data was interpreted using analysis of variance (ANOVA), clustering analysis (CA), and principal component analysis (PCA). Interpolated surface maps for Cr were generated using the actual data obtained for the 30 sampling sites in each of the three villages for irrigation water, soil, and seasonal vegetables. The level of contamination in the three villages was directly proportional to their distance from KTWMA wastewater treatment plant and the direction of water runoff. The highest level of Cr contamination in soil (mg kg-1) was observed at Faqeeria Wala (37.67), intermediate at Dollay Wala (30.33), and the least in Maan (25.16). A gradational variation in Cr accumulation was observed in the three villages from contaminated wastewater having the least contamination level (2.02-4.40 mg L-1), to soil (25.16-37.67 mg kg-1), and ultimately in the seasonal vegetable crops (156.67-248.33 mg kg-1) cultivated in the region, having the highest level of Cr contamination above the permissible limit. The model used not only predicted the current situation of Cr contamination in the three villages but also indicated the trend of magnification of Cr contamination from irrigation water to soil and to the base of the food chain. Among the multiple causes of Cr contamination of vegetables, soil irrigation with contaminated groundwater was observed to be the dominant one.

Vermicomposting as an advanced biological treatment for industrial waste from the leather industry.

The leather industry (tanneries) generates high amounts of toxic wastes, including solid and liquid effluents that are rich in organic matter and mineral content. Vermicomposting was studied as an alternative method of treating the wastes from tanneries. Vermicompost was produced from the following tannery residues: tanned chips of wet-blue leather, sludge from a liquid residue treatment station, and a mixture of both. Five hundred earthworms (Eisenia fetida) were added to each barrel. During the following 135 days the following parameters were evaluated: pH, total organic carbon (TOC), organic matter (OM), cation exchange capacity (CEC), C:N ratio, and chromium content as Cr (III) and Cr (VI). The results for pH, TOC and OM contents showed decreases in their values during the composting process, whereas values for CEC and total nitrogen rose, indicating that the vermicompost reached maturity. For chromium, at 135 days, all values of Cr (VI) were below the detectable level. Therefore, the Cr (VI) content had probably been biologically transformed into Cr (III), confirming the use of this technique as an advanced biological treatment. The study reinforces the idea that vermicomposting could be introduced as an effective technology for the treatment of industrial tannery waste and the production of agricultural inputs.

Characterization of a novel lipase from Bacillus sp. isolated from tannery wastes

Kinetics of a lipase isolated from Bacillus sp. was studied. The enzyme showed maximum activity at pH 9 and temperature 60ºC. The Michaelis constant (K M 0.31 µM) obtained from three different plots i.e., Lineweaver-Burk, Hanes-Wolf and Hofstee, was found to be lower than already reported lipases that confirmed higher affinity of the enzyme for its substrate p-NPL (p-nitrophenyl laurate). Vmax of the enzyme was found to be 7.6 µM/mL/min. Energy of activation calculated from Arrhenius plot was found to be 20.607 kJmol-1. Activation enthalpy (ΔH*) had negative trend and the value for the hydrolysis of p-NPL by the enzyme at optimum temperature was -2.748 kJmol-1 . Activation entropy (ΔS*) and free energy of activation (ΔG*) of the enzyme were found to be 1.468 Jmol-1K-1 and -3.237 kJmol-1, respectively at optimum temperature. Low value of Q10 (0.04788) shows high catalytic activity of the enzyme. Mn2+, Fe2+ and Mg2+ enhanced the lipase activity whereas Cu2+, Na+ and Co2+ inhibited the enzyme activity. However, the enzyme activity was not affected significantly by K+ ions. EDTA and SDS also significantly inhibited the lipase activity. Activity of the enzyme was increased in n-hexane while decreased with increase in concentration of acetone, chloroform, ethanol and isopropanol.

Characterization of a novel lipase from Bacillus sp. isolated from tannery wastes.

Kinetics of a lipase isolated from Bacillus sp. was studied. The enzyme showed maximum activity at pH 9 and temperature 60°C. The Michaelis constant (KM 0.31 mM) obtained from three different plots i.e., Lineweaver-Burk, Hanes-Wolf and Hofstee, was found to be lower than already reported lipases that confirmed higher affinity of the enzyme for its substrate p-NPL (p-nitrophenyl laurate). Vmax of the enzyme was found to be 7.6 µM/mL/min. Energy of activation calculated from Arrhenius plot was found to be 20.607 kJmol(-1). Activation enthalpy (ΔH*) had negative trend and the value for the hydrolysis of p-NPL by the enzyme at optimum temperature was -2.748 kJmol(-1). Activation entropy (ΔS*) and free energy of activation (ΔG*) of the enzyme were found to be 1.468 Jmol(-1)K(-1) and -3.237 kJmol(-1), respectively at optimum temperature. Low value of Q10 (0.04788) shows high catalytic activity of the enzyme. Mn(2+), Fe(2+) and Mg(2+) enhanced the lipase activity whereas Cu(2+), Na(+) and Co(2+) inhibited the enzyme activity. However, the enzyme activity was not affected significantly by K(+) ions. EDTA and SDS also significantly inhibited the lipase activity. Activity of the enzyme was increased in n-hexane while decreased with increase in concentration of acetone, chloroform, ethanol and isopropanol.