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Microbial reduction of Cr(VI) to Cr(III) can mitigate environmental chromium toxicity. A chromium, cadmium and nickel tolerating strain TCL with 97% 16S rRNA gene sequence homology to Bacillus cereus was isolated from a derelict open-cast, Tasra Coalmine Lake of Jharia, India. It could tolerate up to Cr2000 [2,000 mg L−1 Cr(VI)] and completely reduce Cr200 within 16 h under heterotrophic condition. TCL grown in ≥ Cr500 exhibited multifarious stress responses particularly in its prolonged lag-phase, like cell aggregation, up to two-fold elongation, increased exopolysaccharide production, and stress enzyme activities. These were relieved by increasing inoculum size or nutrient content. Chromium reduction was constitutive, with maximum activities detected in loosely-bound exopolysaccharides and membrane fractions, followed by cytoplasm and spent media. Cr(VI) was efficiently reduced to Cr(III) and >90% was released in spent media. Cells also expressed Cr-induced active efflux pumps. Growing cells or its crude enzyme extracts could efficiently reduce Cr(VI) in diverse temperatures (15–45 °C), pH (5–9); and in presence of other metals (Cd, Cu, Mo, Ni, Pb), oxyanions (SO4−2, NO2−), and metabolic inhibitors (phenol, NaN3, EDTA). Growth and reduction were also detected in nutrient-limited minimal salt media, and contaminated leather industry effluent thereby making TCL a potential candidate for bioremediation.

Chrome-free metal tanning agent has been considered as eco-friendly in the leather industry. However, extensive crosslinking reactions of metal species on the leather surface restrain their uniform penetration into the hierarchical nanoscale leather matrix. Thus, masking agents with appropriate coordination ability are needed. Herein, the selective degradation of hemicellulose in corncob was achieved with 92.5% of conversion in an AlCl3–H2O system, obtaining oligosaccharides masking agent with high purity and leaving cellulose and lignin in the solid residue for other valuable use. Subsequently, H2O2 oxidation was performed to introduce –CHO/–COOH into oligosaccharides and reduce their molecular weights, thereby enhancing coordination ability and reducing ligand dimension. The post-oxidized reaction fluids together with additional Zr species were subjected to leather tanning, in which the oligosaccharides could coordinate with Al/Zr species and promote the penetration of metal species into the leather matrix. By controlling the hemicellulose degradation and oligosaccharide oxidation, an appropriate concentration of oligosaccharides with proper –CHO/–COOH contents allowed the efficient masking effect of the oligosaccharides. As a result, a uniform distribution of Al/Zr species was observed on the cross section, and 83.5 °C of shrinkage temperature was obtained for the chrome-free tanned leather.

Tanning leather using green biomass-derived polyaldehyde (BPA) is a promising approach to eliminate the widespread Cr pollution in leather industry, but unsatisfactory thermal stability and mechanical strength of the correlated resultant leather limited its industrial application. Herein, we report a green methodology to strengthen BPA tanned leather via introducing chitosan derivatives to crosslink with free aldehyde groups on dialdehyde carboxymethylcellulose (DCMC) tanned leather. H2O2 was employed for purposely modifying chitosan to prepare low-molecular chitosan (LMC) with lower positive charge. The interactions between chitosan/LMC and DCMC were investigated to elucidate the strengthening mechanism. Owing to the weakened hydrogen bonding network and higher accessibility of amino groups on LMC, LMC could react much easier with aldehyde groups on DCMC. Moreover, LMC could efficiently penetrate into the internal fiber networks of leather for further interlocking, which enhanced the thermal stability and the lubricating degree of crust leather and, as a result, the tensile and tear strengths were significantly improved by 79.3% and 25.3%, respectively. Therefore, the use of LMC can promote the widespread application of BPA tanned leather, benefiting to the complete elimination of hazardous Cr pollution.

The effectiveness of heat-inactivated fungal biomass a fermentation waste of newly isolated laccase enzyme producer Leiotrametes flavida was studied for Cr (VI) removal in water and applied for Cr (VI) removal from tannery effluent. Adsorption parameters pH, biomass concentration and contact time were optimized using Box-Behnken design of response surface methodology. The adsorption process fits the Langmuir isotherm. Thermodynamic and kinetic studies showed that the process is spontaneous at ambient temperature and followed the second-order kinetics model, respectively. The values of the kinetic model indicated that the adsorption process is a combination of physisorption and chemisorption. Chromium adsorption onto the biomass was confirmed by SEM-EDAX, FTIR, XPS and XRD analysis. XPS analysis confirmed the reduction of Cr (VI) to Cr (III). The amount of chromium adsorbed was 72.38 % and 68.33 % for water and effluent, respectively. Chromium adsorbed onto biomass was desorbed at pH 9 with 1 M NaOH. Total chromium desorbed was 61.40 and 59.38 percent from water and effluent, respectively. The amount of Cr (III) in the desorbed sample was 71 and 68 percent, respectively. The heat-inactivated biomass of Leiotrametes flavida is a suitable material for efficient Cr (VI) removal and detoxification.

A tannery sludge, produced from physico-chemical treatment of tannery wastewaters, was incinerated without any pre-treatment process under oxic and anoxic conditions, by controlling the abundance of oxygen. Incineration in oxic conditions was performed at the temperature range from 300°C to 1200°C for duration of 2h, while in anoxic conditions at the temperature range from 400°C to 600°C and varying durations. Incineration under oxic conditions at 500°C resulted in almost total oxidation of Cr(III) to Cr(VI), with CaCrO4 to be the crystalline phase containing Cr(VI). At higher temperatures a part of Cr(VI) was reduced, mainly due to the formation of MgCr2O4. At 1200°C approximately 30% of Cr(VI) was reduced to Cr(III). Incineration under anoxic conditions substantially reduced the extent of oxidation of Cr(III) to Cr(VI). Increase of temperature and duration of incineration lead to increase of Cr(VI) content, while no chromium containing crystalline phase was detected.

Dual chambered microbial fuel cells with Potassium dichromate (22 g/L, MFC-1) and tannery effluent waste water containing 26 mg/L (MFC-2), 5 mg/L (MFC-3) of Cr(VI) as catholyte, sweet lime waste inoculated by cowdung as anolyte and graphite electrodes were used to reduce toxic Cr(VI) to Cr(III) with simultaneous power generation. Cr (VI) in the cathode chamber reduced to Cr2O3 within 24 h. Complete reduction of Cr(VI) from tannery effluents by microbial fuel cell is noticed within 10 days. The 16 s rRNA sequencing studies demonstrated presence of Geobacter Metallireducens in mixed culture bacteria in anaerobic anode. The power density of the device is 396.7 mW/m2on day1which is 7.2 times higher than literature data of 55.5 mW/m2. The processes involved on the biofilm/electrolyte interface and graphite/electrolyte interface is studied by Electrochemical Impedance Spectroscopy. Electrochemical studies demonstrated the active growth of biofilm on anode which reduces charge transfer resistance from day 1 to day 25. The concentration of Cr(VI) reduced in the present studies are approximately 1000 times higher than those reported in the literature.

The impact of ambient concentrations in the vicinity of a plant can only be assessed if the emission rate is known. In this study, based on measurements of ambient H2S concentrations and meteorological parameters, the a priori unknown emission rates of a tannery wastewater treatment plant are calculated by an inverse dispersion technique. The calculations are determined using the Gaussian Austrian regulatory dispersion model. Following this method, emission data can be obtained, though only for a measurement station that is positioned such that the wind direction at the measurement station is leeward of the plant. Using the inverse transform sampling, which is a Monte Carlo technique, the dataset can also be completed for those wind directions for which no ambient concentration measurements are available. For the model validation, the measured ambient concentrations are compared with the calculated ambient concentrations obtained from the synthetic emission data of the Monte Carlo model. The cumulative frequency distribution of this new dataset agrees well with the empirical data. This inverse transform sampling method is thus a useful supplement for calculating emission rates using the inverse dispersion technique.

This paper reports on the calorific value of synthetic gas (syngas) produced by gasification of dewatered sludge derived from treatment of tannery wastewater. Proximate and ultimate analyses of samples were performed. Thermochemical conversion alters the chemical structure of the waste. Dried air was used as a gasification agent at varying flow rates, which allowed the feedstock to be quickly converted into gas by means of different heterogeneous reactions. A lab-scale updraft fixed-bed steel reactor was used for thermochemical conversion of sludge samples. Artificial neural network (ANN) modeling techniques were used to observe variations in the syngas related to operational conditions. Modeled outputs showed that temporal changes of model predictions were in close accordance with real values. Correlation coefficients (r) showed that the ANN used in this study gave results with high sensitivity.

The organic and suspended solids present in soak liquor, generated from leather industry, demands treatment. The soak liquor is being segregated and evaporated in solar evaporation pans/multiple effect evaporator due to non availability of viable technology for its treatment. The residue left behind in the pans/evaporator does not carry any reuse value and also faces disposal threat due to the presence of high concentration of sodium chloride, organic and bacterial impurities. In the present investigation, the aqueous evaporated residue of soak liquor (ERSL) was treated by electrochemical oxidation. Graphite/graphite and SS304/graphite systems were used in electrochemical oxidation of organics in ERSL. Among these, graphite/graphite system was found to be effective over SS304/graphite system. Hence, the optimised conditions for the electrochemical oxidation of organics in ERSL using graphite/graphite system was evaluated by response surface methodology (RSM). The mass transport coefficient (km) was calculated based on pseudo-first order rate kinetics for both the electrode systems (graphite/graphite and SS304/graphite). The thermodynamic properties illustrated the electrochemical oxidation was exothermic and non-spontaneous in nature. The calculated specific energy consumption at the optimum current density of 50 mA cm−2 was 0.41 kWh m−3 for the removal of COD and 2.57 kWh m−3 for the removal of TKN.

Tannery operations consist of converting raw animal skins into leather through a series of complex water- and chemically-intensive batch processes. Even when conventional primary treatment is supplemented with chemicals, the wastewater requires some form of biological treatment to enable the safe disposal to the natural environment. Thus, there is a need for the adoption of low cost, reliable, and easy-to-operate alternative secondary treatment processes. This paper reports the findings of two pilot-scale wetlands for the secondary treatment of primary effluents from a full tannery operation in terms of resilience (i.e., ability to produce consistent effluent quality in spite of variable influent loads) and reliability (i.e., ability to cope with sporadic shock loads) when treating this hazardous effluent. Areal mass removal rates of 77.1 g COD/m2/d, 11 g TSS/m2/d, and 53 mg Cr/m2/d were achieved with a simple gravity-flow horizontal subsurface flow unit operating at hydraulic loading rates of as much as 10 cm/d. Based on the findings, a full-scale wetland was sized to treat all the effluent from the tannery requiring 68% more land than would have been assumed based on literature values. Constructed wetlands can offer treatment plant resilience for minimum operational input and reliable effluent quality when biologically treating primary effluents from tannery operations.

In the present study, green and sustainable method or eco-friendly approaches to tanning process based on unnatural D-amino acids (D-AA)-aldehyde (Ald) as a substitute for chrome-free tanning has been attempted. The distribution of optically active D-AA in tanned leather, the hydrothermal stability, the mechanical properties and resistance to collagenolytic activity of tanned leather, the evaluation of eco-friendly characteristics were investigated. Scanning electron microscopic (SEM) and Atomic force microscopic (AFM) analyses indicate the surface morphology and roughness, respectively, of the tanned leather collagen matrix. Shrinkage and Differential scanning calorimetric (DSC) analyses shows that the shrinkage temperature (T(s)) and denaturation temperature (T(d)) of tanned leather are related to the content of D-AA+Ald present in the leather matrix. It has been found that the T(s) of D-AA tanned leather is more than that of Ald tanned leather and also more or less equal to chrome tanned leather. Environmental impact assessment (EIA) shows that the developed process results in significant reduction in total solids content (TSC) and improves better biodegradability of organic compound present in the effluent compared to chrome tanning.

Chromium plating used for functional purposes provides an extremely hard, wear and corrosion resistant layer by means of electrolytic deposition. Typical layer thicknesses range between 2.5 and 500 μm. Chromium electroplating baths contain high concentrations of Cr(VI) with chromium trioxide (CrO 3 ) as the chromium source. When because of technical or economic reasons a bath gets exhausted, a waste containing mainly chromium as dichromate as well as other heavy metals is generated. Chromium may then be purified for use in other industrial processes with different requirements. In this work, a sustainable system for using galvanic wastes as reagents in the leather tanning industry, thus reducing quantity of wastes to be treated, is presented. Metal cations present in the chromium exhausted bath were precipitated with NaOH. Then, the solution containing mainly soluble Cr(VI) was separated. By means of sodium sulphite in acidic conditions, Cr(VI) was reduced to Cr(III) as chromium (III) sulphate. From chromium (III) sulphate a basic Cr(III) sulphate may be obtained, which is one of most used compounds in the tanning industry. Cr(III) concentration in the final solution allows its reuse without concentration, but with a slight dilution.

In this work, hydrogen peroxide decomposition and oxidation of organics in aqueous medium were studied in the presence of activated carbon prepared from wet blue leather waste. The wet blue leather waste, after controlled pyrolysis under CO(2) flow, was transformed into chromium-containing activated carbons. The carbon with Cr showed high microporous surface area (up to 889 m(2)g(-1)). Moreover, the obtained carbon was impregnated with nanoparticles of chromium oxide from the wet blue leather. The chromium oxide was nanodispersed on the activated carbon, and the particle size increased with the activation time. It is proposed that these chromium species on the carbon can activate H(2)O(2) to generate HO radicals, which can lead to two competitive reactions, i.e. the hydrogen peroxide decomposition or the oxidation of organics in water. In fact, in this work we observed that activated carbon obtained from leather waste presented high removal of methylene blue dye combining the adsorption and oxidation processes.

The reject water or retentate generated from membrane application for recovery of water from tannery wastewater treatment contains certain refractory organics. These refractory organics are present in substantial quantity in the condensate of reject water also. Hence the treatment of rejects using conventional methods is rather difficult. In this paper, an attempt has been made to treat the reject water from the reverse osmosis (RO) and nano filtration (NF) operation on tannery wastewater using ozonation treatment technique. Ozonation studies on RO and NF rejects indicate that ozone dose of 80 and 100 mg/min for 60 and 70 min contact time achieves 59 and 78% chemical oxygen demand (COD) reduction, respectively. The mass balance in ozone indicates the ozone consumption for RO and NF rejects varies from 2.4 to 3.4 and 2.8 to 4.5 g/g of COD removed respectively. The results suggest that ozonation of RO and NF rejects would significantly reduce the refractory organic pollutant loading into the environment from wastewater reuse facility.

In this study, various activation methods have been employed to examine the potential reuse of tannery residual biomass (TRB) obtained from vegetable tanning process for the removal of Cr(VI) and Rhodamine B (RB) from aqueous solution. The maximum BET surface area (10.42 m(2)/g), honey comb pore distribution and uptake of both Cr(VI) and RB were achieved when only 3-fold volume of HCl was used to activate the biomass. The pH and temperature experiment showed that they have considerable impact on the adsorption capacity of the used adsorbent. The presence of other ions (Na(+), Ca(2+) and NH(4)(+)) significantly reduces the metal uptake but marginal enhancement in the dye removal was observed when Na(+) and NH(4)(+) ions were present in the solution. The equilibrium data fitted satisfactorily with the Langmuir model and monolayer sorption capacity obtained as 177-217 and 213-250 mg/g for Cr(VI) and RB at 30-50°C, respectively. The sorption kinetics was found to follow the pseudo-second-order kinetic model. The increase in adsorption capacity for both metal and dye with increase in temperature indicates that the uptake was endothermic in nature. The results indicate that the HCl modified TRB (A-TRB) could be employed as a low cost adsorbent for the removal of both Cr(VI) and RB from the aqueous solution including industrial wastewater.

The leather industry produces a large quantity of solid waste (wet blue leather), which contains a high amount of chromium. After its removal from wet blue leather, a solid collagenic material is recovered, containing high nitrogen levels, which can be used as a nitrogen source in agriculture. In order to take more advantage of the collagen, it was enriched with mineral P and K in order to produce NPK formulations. The objective was also to evaluate the efficiency of such formulations as a nutrient supply for rice plants in an Oxisoil, under greenhouse conditions. The application of PK enriched-collagen formulations resulted in N contents in the vegetative parts and grains of rice plants which were equivalent or superior to those obtained with urea and commercial NPK formulations.

PubMed ID: 20940084 Two new methods for treatment of tannery sludge were studied to achieve cost-effective and environmentally acceptable remediation solutions for high chromium containing tannery sludge. Quillaja bark saponin, a plant derived biosurfactant, was applied to dewatered tannery sludge for chromium recovery and a comparative assessment with H2O2 oxidative treatment method is presented. Tannery sludge samples were treated on a laboratory scale with saponin in the pH range 2-3. The effects of various factors like time, concentration of saponin, pH, and temperature on the extraction of chromium were studied. The treatment with saponin extracted 24% of Cr from tannery sludge at a pH around2, performing multiple wash of 6h, at 33°C. On the other hand, the H2O2 treatment, which include Cr(III) oxidation to Cr(VI) and extraction with sulfuric acid solution at pH 2, enabled to extract 70% of chromium within less than 4h at room temperature (21°C). The results indicate that the extraction efficiency of saponin was strongly dependent on the organic matter content of the sample, which affects chromium mobility by its high adsorption capacity. On the other hand hydrogen peroxide treatment is effective and the duration of the process is short and requires cheap chemicals and moderate conditions. © 2010 Elsevier B.V.

In this present work, electrochemical treatment of saline wastewater with organic (protein) load was studied. The influence of the critical parameters of electro-oxidation such as pH, period, salt concentration and current density on the reduction of organic load was studied using graphite electrodes. It was found that current density of 0.024 A/cm(2) for a period of 2 h at pH 9.0 rendered best results in terms of reduction in COD and TKN. The energy requirement for the reduction of 1 kg of TKN and 1 kg of COD are 22.45 kWh and 0.80 kWh respectively at pH 9 and 0.024 A/cm(2). Reuse experiments were conducted at commercial scale. One of the saline waste streams in leather manufacturing process, pickling was treated and reused continuously thrice. The characteristics of the waste stream and the quality of the leathers indicate that the reuse of saline streams with intermittent electrochemical treatment is feasible.

In this study, the original causes for hexavalent chromium presence in the leather were first evaluated by ageing of chromium(III) solutions and chrome tanned hide powder (50 degrees C, UV lightening at 340 nm, 0-36 h). The results showed that the trivalent chromium at instable coordination state was easy to convert into hexavalent chromium in high pH environment, and the probability of the oxidation increased in this order: multi-coordinate chromium, mono-coordinate chromium, and free chromium. For this reason, the process for stabilizing chromium in the leather was designed with the specific material, which was mostly consisted of the reducers and the chelating agents. After treated with the developed process, these leathers were aged (50 degrees C, UV irradiance as 0.68 W/m(2) at 340 nm, 0-72 h) to estimate chromium(VI) presence. Hexavalent chromium was not found in these treated leathers even if the leathers were aged for 72 h. Moreover, the physical and mechanical properties for the leathers varied little after treating. In a word, an inherent safe and effective process was proved to avoid the formation of hexavalent chromium in the leather.

Collagen-tannin resin (CTR), as a novel adsorbent, was prepared via reaction of collagen with black wattle tannin and aldehyde, and its adsorption properties to UO(2)(2+) were investigated in detail, including pH effect, adsorption kinetics, adsorption equilibrium and column adsorption kinetics. The adsorption of UO(2)(2+) on CTR was pH-dependent, and the optimal pH range was 5.0-6.0. CTR exhibited excellent adsorption capacity to UO(2)(2+). For instance, the adsorption capacity obtained at 303 K and pH 6.0 was as high as 0.91 mmol UO(2)(2+)/g when the initial concentration of UO(2)(2+) was 1.0 mmol/L. In kinetics studies, the adsorption equilibrium can be reached within 300 min, and the experimental data were well fitted by the pseudo-second-order rate model, and the equilibrium adsorption capacities calculated by the model were almost the same as those determined by experiments. The adsorption isotherms could be well described by the Freundlich equation with the correlation coefficients (R(2)) higher than 0.99, the adsorption behaviors of UO(2)(2+) on CTR column were investigated as well. Present study suggested that the CTR can be used for the adsorptive recovery of UO(2)(2+) from aqueous solutions.

Leather wastes tanned with chromium are generated during the production process of leather, hence the wastes from hand crafted goods and footwear industries are a serious environmental problem. The thermal treatment of leather wastes can be one of the treatment options because the wastes are rich in chromium and can be used as a raw material for sodium chromate production and further to obtain several chromium compounds. The objective of this study was to utilize the chromium from leather wastes via basic chromium sulfate production to be subsequently applied in a hide tanning. The obtained results have shown that this is the first successful attempt to achieve desired base properties of the product. The result was achieved when the following conditions were applied: a molar ratio between sodium sulfite and sodium dichromate equal to 6; reaction time equal to 5 min before addition of sulfuric acid; pH of sodium dichromate solution equal to 2. Summarizing, there is an opportunity to utilize the dangerous wastes and reused them in the production scheme by minimizing or annulling the environmental impact and to attend a sustainable process development concept.

This study was conducted to evaluate the distribution and mobility of Cr in tannery waste that has been added to semi-arid soils. In addition, the amount of total oxidizable soil Cr (III), Cr (VI), pH and soil microbial activities were determined. Tannery sludge alone or mixed with fleshing waste was added to two types of soils, which were then incubated at 25 degrees C for 6 months and subsequently subjected to simulated rainfall. The highest total amount of Cr loss occurred due to infiltration, regardless of the treatments. The Cr loss ranged from 0.452 to 0.825 microg g(-1) soil for all soils from 1 to 3 months, with the exception of those that were located under the canopy and treated with tannery sludge and fleshing waste, which had the highest runoff (from 1.312 to 1.667 microg Crg(-1) soil). The pH of the soil increased from 1 to 3 months (from 7.35 to 8.46), while the total oxidizable soil Cr (III) (2.12-4.31 mg g(-1) soil) peaked after 1 month of treatment. The majority of the fractionated chromium was bound to carbonates at initial time, 3 and 6 months prior to and after application of the simulated rainfall. The microbial activities decreased in each of the treated soils from initial time to 3 months; however, after 6 months bacterial activity increased, while pH decreased (from 8.03 to 7.63). Overall, these data suggest that pH is responsible for Cr loss in response to infiltration and runoff, Cr speciation and the equilibrium of Cr fractionation.

This study describes biosorption of chromium (VI) by immobilized Spirulina platensis, in calcium alginate beads. Three aspects viz. optimization of bead parameters, equilibrium conditions and packed column operation were studied and subsequently modeled. Under optimized bead diameter (2.6mm), calcium alginate concentration (2%, w/v) and biomass loading (2.6%, w/v) maximum biosorption was achieved. 140 g l(-1) loading of optimized beads resulted in 99% adsorption of chromium (VI) ions from an aqueous solution containing 100 mg l(-1) of chromium (VI). The quantitative chromium (VI) uptake was effectively described by Freundlich adsorption isotherm. The immobilized S. platensis beads were further used in a packed bed column wherein the effects of bed height, feed flow rate, inlet chromium (VI) ion concentration were studied by assessing breakthrough time. The performance data were tested for various models fitting in order to predict scale up-design parameters such as breakthrough time and column height. Results were encouraging.

Two tanning units of Pakistan, namely, Kasur and Mian Channun were investigated with respect to the tanning processes (chrome and vegetable, respectively) and the effects of the tanning agents on the quality of soil in vicinity of tanneries were evaluated. The effluent and soil samples from 16 tanneries each of Kasur and Mian Channun were collected. The levels of selected metals (Na, K, Ca, Mg, Fe, Cr, Mn, Co, Cd, Ni, Pb and Zn) were determined by using flame atomic absorption spectrophotometer under optimum analytical conditions. The data thus obtained were subjected to univariate and multivariate statistical analyses. Most of the metals exhibited considerably higher concentrations in the effluents and soils of Kasur compared with those of Mian Channun. It was observed that the soil of Kasur was highly contaminated by Na, K, Ca and Mg emanating from various processes of leather manufacture. Furthermore, the levels of Cr were also present at much enhanced levels than its background concentration due to the adoption of chrome tanning. The levels of Cr determined in soil samples collected from the vicinity of Mian Channun tanneries were almost comparable to the background levels. The soil of this city was found to have contaminated only by the metals originating from pre-tanning processes. The apportionment of selected metals in the effluent and soil samples was determined by a multivariate cluster analysis, which revealed significant differences in chrome and vegetable tanning processes.

Ozonation of leather dye effluent for removal of color and COD reduction covering wide range in operating parameters forms the scope of the present work. The influence of parameters such as influent pH, ozone flow rate and initial effluent concentration on ozonation efficiency has been critically examined. It has been observed from the present investigation that a maximum of COD removal efficiency of 92% has been achieved under optimum operating conditions. Further the biodegradability index of the tannery effluent has increased from an initial value of 0.18 to 0.49 during ozonation indicating favorable adaptation of ozonation as a primer to the biochemical technique to enhance the efficiency of biochemical treatment.

The feasibility of the photobleaching of a leather acid dye, acid red 151, simultaneously to degradation of anionic surfactant, Tamol, and reduction of Cr(VI) to the less toxic Cr(III) was investigated by photoelectrocatalytic oxidation. The best experimental conditions were found to be pH 2.0 and 0.1 mol L(-1) sodium sulfate when the nanoporous Ti/TiO2 photo anode was biased at +1.0 V and submitted to UV-irradiation. The photoelectrocatalytic oxidation promotes 100% discoloration, reducing around 98-100% of Cr(VI) and achieving an abatement of 95% of the original total organic carbon. The effect of pH, the applied potential, the Cr(VI) concentration and the complexation reaction between Cr(VI) and acid red dye were evaluated as to their effect on the kinetics of the reaction.

The major limitation of direct application of tannery sludge compost in agriculture is the total heavy metal contents and their bioavailability to the soil-plant system. This study focused on the heavy metal characterization and the influence of changing the physicochemical properties of the medium throughout the composting on the concentrations, bioavailability or chemical forms of Cr, Cu, Zn, Pb and Cd in tannery sludge. The study shows that throughout the 60 days of composting, physicochemical analysis and Fourier-transformed infrared (FTIR) spectroscopic characterization show that all parameters elaborated and reached relatively stable levels reflecting the stability and maturity of the final product, and revealed the biodegradation of components that can be easily assimilated by microorganism. The C/N ratio reaches the optimal range of stable compost; inorganic nitrogen is transformed into stable organic forms. The total concentration of Cr, Zn, Cu, Pb and Cd is very low rendering final compost acceptable for agricultural use. The germination index for both Chinese cabbage and lettuce was 97% after 60 days of composting, showing that the final compost was not phytotoxic. Furthermore, in using a sequential extraction method in sludge compost at different phases of treatment, a less than 2% of metals bound to bioavailable fractions X-(KNO(3)+H(2)O). A large proportion of the heavy metals were associated to the residual fraction (75-85%) and more resistant fractions to extraction X-NaOH, X-EDTA, X-HNO(3) (15-25%). Mobile fractions of metals are poorly predictable from the total content. Bioavailability of all fractions of elements tends to decrease.

A simple extractive separation method has been developed for the determination of chromium based on the extraction of Cr (VI) as its ion-pair with tribenzylamine (TBA). The ion-pair is extracted at acidic pH using toluene as the diluent. The concentration of chromium in the organic phase was measured spectrophotometrically at 309 nm. The influence of experimental variables such as pH, sample volume, equilibration time, diverse ions etc. has been studied in detail. The extracted chromium (VI) could be stripped to the aqueous phase using NaOH as the stripping agent. The extracts were characterized using FT-IR spectroscopy. A detection limit of 0.08 μg mL −1 could be achieved and the validity of the method was checked in real tannery effluent, electroplating waste water and spiked water samples.

Chemically enhanced primary treatment (CEPT) is a technology that uses coagulants for enhanced pollutants removal at the primary stage of the wastewater treatment. This paper presents the detailed characteristics of tannery wastewater. It also explains effectiveness of CEPT in removing pollutants from tannery wastewater using various metal salts. The results of this study demonstrated that the tannery effluent had high concentrations of organic matter, solids, sulfates, sulfides and chromium. Alum, ferric chloride and ferric sulfate were tested as coagulants using jar test apparatus. Alum was found to be the suitable coagulant for tannery wastewater in a dose range of 200-240 mg/L as Al(2)(SO(4))(3). With alum, percentage removal efficiency for turbidity, total suspended solids (TSS), chemical oxygen demand (COD) and chromium was found to be 98.7-99.8, 94.3-97.1, 53.3-60.9, and 98.9-99.7%, respectively. National effluent quality standards for total suspended solids and chromium were met after CEPT. However, COD content was high, emphasizing the need of secondary treatment for the tannery effluent.

Due to large growth in leather and textile industries to cater for the needs of a growing world population, contamination of soil and water resources by chromium has become a great threat for humans and animals. In this work, Laser Induced Breakdown Spectroscopy (LIBS) was applied to monitor the remediation process of soil contaminated with Chromium metal. This study was conducted at a laboratory scale by setting up an experiment in a container holding soil contaminated with chromium. This setup represents actual field conditions where remediation process could be applied and monitored for the removal of toxic metals like Cr. For generation of LIBS spectrum, the plasma was produced by focusing a pulsed Nd: YAG laser at 1064 nm on the soil contaminated with chromium under remediation process. The evaluation of the potential and capabilities of LIBS as a rapid tool for remediation process of contaminated sites is discussed in detail. Optimal experimental conditions were evaluated for improving the sensitivity of our LIBS system for monitoring of remediation process through parametric dependence study. The minimum detection limit of our spectrometer for chromium in soil matrix was 2 mg Kg −1 .

The oxidation of organic and inorganic pollutants present in tannery effluents has been realised by electrochemical way. The influence of the electrochemical reactor parameters was carried out by the use of Doehlert matrix. The obtained results have shown that the current intensity and the electrolysis time were the main influent parameters on the removal ratio of chemical oxygen demand (COD), total organic carbon (TOC), electrochemical oxidation of trivalent chromium and sulphite ions.

In the present study, accumulation and distribution of toxic metals (Cu, Cd, Cr, Zn, Fe, Ni, Mn, and Pb) and their biochemical effect on wheat and mustard plants irrigated with mixed distillery and tannery effluents are reported. Analyses of effluents and soil samples have shown high metal content than the permissible limit except Pb. Further, analyses of plant samples have indicated the maximum accumulation of Fe (340 mg kg(-1) in wheat root and 560 mg kg(-1) in mustard leaves) followed by Mn and Zn in root>shoot>leaves>seeds. Maximum increase in photosynthetic pigment was observed between 30 and 60 days while protein content was found maximum between 60 and 90 days of growth period in both plants. An increase in malondialdehyde, cysteine and ascorbic acid antioxidants content was also observed in root and leaves of treated plants upto 60 and 90 days of growth. Hence, wheat and mustard plants irrigated with effluents without adequate treatment are health hazards for environment, humans and animals.

In this paper, the authors deal with the problem of processing various types of waste generated by leather industry, with special emphasis to chrome-tanned waste. The agent that makes this waste potentially hazardous is hexavalent chromium. Its compounds can have negative effects on human health and some CrVI salts are considered carcinogens. The authors present the risks of spontaneous oxidization of CrIII to CrVI in the open-air dumps as well as the possible risks of wearing bad quality shoes, in which the chromium content is not controlled. There are several ways of handling primary leather waste, but no satisfactory technology has been developed for the secondary waste (manipulation waste, e.g. leather scraps and used leather products). In this contribution, a new three-step hybrid technology of processing manipulation waste is presented and tested under laboratory, pilot-scale and industrial conditions. The filtrate can be used as a good quality NPK fertilizer. The solid product, titanium-chromium sludge, can serve as an inorganic pigment in glass and ceramic industry. Further, the authors propose selective collection of used leather products (e.g. old shoes), the hydrolysable parts of which can be also processed by the new hybrid technology.

Chromium in the effluent is a major concern for tanning industry. Chemical precipitation methods are commonly employed for the removal of chromium but this leads to formation of chrome-bearing solid waste, plus it is uneconomical when the concentration of chromium in the effluent is low. Ion exchange and membrane separation methods are relatively expensive. In this study, two algae namely, Spirogyra condensata and Rhizoclonium hieroglyphicum have been employed to remove chromium from tannery effluent. The effect of pH and chromium concentration showed S. condensata to exhibit maximum uptake of about 14 mg Cr(III)/g of algae at optimum pH of 5.0 whereas R. hieroglyphicum had 11.81 mg of Cr(III)/g of algae at pH of 4.0. Langmuir and Freundlich models were applied. Increase of initial concentration of Cr resulted to a decrease in adsorption efficiency. Dilute sulphuric acid (0.1 M) showed good desorption efficiency (>75%). Interference from cations negatively impacted on biosorption of chromium. Immobilized algae on Amberlite XAD-8 in a glass column, gave better recovery of chromium in tannery effluent compared to a batch method with unimmobilized algae. Fourier transform infra red (FT-IR) analysis of the two algae revealed the presence of carboxyl groups as possible binding sites.

This paper evaluated the effect of mixing the effluent of a pharmaceutical plant producing acetylsalicylic acid with tannery wastewater, on the biodegradation of the effluents. The evaluation involved the analysis of the oxygen uptake rate (OUR), profiles of each wastewater and the mixture by respirometry. Model calibration using the experimental OUR data identified major COD fractions and associated process kinetics for all samples analyzed. The tannery sample was a plain-settled effluent having a total COD of around 2200 mg/L with a readily biodegradable fraction of 15%. The same fraction was 57% in the pharmaceutical wastewater sample having a much stronger total COD content of 40,435 mg/L. Consequently, mixing of the pharmaceutical effluent with the tannery wastewater up to 38% of the total COD in the mixture increased the readily biodegradable COD fraction but had an inhibitory effect on the biodegradation kinetics. This effect was relatively lower on growth, but quite significant on the hydrolysis of the slowly biodegradable COD decreasing the maximum hydrolysis rate from 2.0 day(-1) to 1.2 day(-1). Model evaluation of the respirometric data, as performed in this study sets a workable protocol for the assessment of the compatibility of different wastewater mixtures for biological treatability.

In this study, leaching properties and pollution potential of chromium in chrome shaving (CS), which is a solid residue of leather industry, containing 2.27% Cr were investigated and thermal stabilization procedure was applied to the CS for chromium immobilization. For this purpose, firstly, effects of the liquid/solid ratio, contact time, pH and sequential extraction on the leaching behavior of chromium in the CS were studied. It was determined that the CS-caused chromium pollution is a hazardous material for environment. Thermal stabilization procedure was applied to the CS in the temperature range of 250-500 degrees C for the chromium immobilization. Effective stabilization of chromium in the CS was achieved by heating of CS at 350 degrees C under CO(2) atmosphere. Leaching experiments were also carried out with the samples obtained from the stabilization process and the results compared with that of the CS. Also, TCLP test method was applied to the samples to determine pollution potentials and discharge situations of the CS and its stabilization products. While the chromium concentrations in the test solutions of all samples stabilized thermally at above 350 degrees C were below the USEPA regulatory limit of 5 mg/l, the concentration of chromium leached out from the CS was 30-fold bigger than the USEPA regulatory limit.

The high concentration of trivalent chromium along with organic/inorganic compounds in chrome buffing dust (CBD), the solid waste discharged from leather industries, causes severe groundwater contamination on land co-disposal and chronic air pollution during thermal incineration. In the present investigation, CBD was subjected to starved air incineration (SAI) at 800 degrees C in a thermal incinerator under different flow rates of oxygen to optimize the oxygen required to incinerate the organic compounds and simultaneously preventing the conversion of Cr(3+) to Cr(6+). The energy audit of SAI of buffing dust under the external supply of oxygen was carried out under different incineration conditions. The bottom ash from SAI was effectively solidified/stabilized using Portland cement and fine aggregate. The solidified blocks were tested for unconfined compressive strength and heavy metal leaching. Unconfined compressive strength of the blocks was in the range of 120-180 kg/cm(2). The stabilization of chromium(III) in the cement gel matrix was confirmed using Scanning Electron Microscopy SEM, Electron Paramagnetic Resonance spectroscopy (EPR) and X-ray diffraction spectroscopy (XRD). Leachability studies through TCLP on solidified blocks were carried out to determine the degree of leaching of chromium and organic compounds (expressed as COD) under standard conditions.

Various single extractant (DTPA, EDTA, NH(4)NO(3), CaCl(2), and NaNO(3)) was used to evaluate the bioavailability of heavy metals from tannery wastewater contaminated soil and translocation of metals to the plant of Brassica juncea L. Czern. (var. Vaibhav). The extraction capacity of the metals was found in the order: EDTA>DTPA>NH(4)NO(3)>CaCl(2)>NaNO(3). Cluster analysis between different extractants showed close relationship between DTPA, CaCl(2), NH(4)NO(3) except EDTA and NaNO(3), which showed dispersed relationship. Principal components analysis (PCA) applied to metals extracted with EDTA showed different grouping of metals (i) Na, Co, Pb, Ni and (ii) K, Mn, Zn, Cr, in the loading plot which showed similar availability from contaminated soil. PCA applied on metals accumulation data in the plants also exhibited different grouping of variables (i) Cu, Co, Ni, Cd and (ii) Mn, Zn, Pb, Fe showed almost similar accumulation pattern in the plants. The data displayed positive loading for Mn and negative loading for Cr with PC(2). Cd and Zn have shown high loadings in PC(1) and PC(2), respectively. The translocation of most of the tested metals (Pb, Mn, Cd, Ni, Fe) in the shoot of the plant was found better except Cr, Cu, Co and K. The correlation analysis between different extractable metals and metal accumulation in the shoot of the plant showed significant positive correlation with Pb and Cr. Overall, extraction capacity and cluster analysis augmented that EDTA was found suitable extractant for tannery wastewater contaminated soil to B. juncea.

This study describes the feasibility of anaerobic ammonia removal process in presence of organic matter. Different sources of biomass collected from diverse eco-systems containing ammonia and organic matter (OM) were screened for potential anaerobic ammonia removal. Sequential batch studies confirmed the possibility of anaerobic ammonia removal in presence of OM, but ammonia was oxidized anoxically to nitrate (at oxidation reduction potential; ORP=-248+/-25 mV) by an unknown mechanism unlike in the reported anammox process. The oxygen required for oxidation of ammonia might have been generated through catalase enzymatic activity of facultative anaerobes in mixed culture. The oxygen generation possibility by catalase enzyme route was demonstrated. Among the inorganic electron acceptors (NO(2)(-), NO(3)(-) and SO(4)(2-)) studied, NO(2)(-) was found to be most effective in total nitrogen removal. Denitrification by the developed culture was much effective and faster compared to ammonia oxidation. The results of this study show that anaerobic ammonia removal is feasible in presence of OM. The novel nitrogen removal route is hypothesized as enzymatic anoxic oxidation of NH(4)(+) to NO(3)(-), followed by denitrification via autotrophic and/or heterotrophic routes. The results of batch study were confirmed in continuous reactor operation.

Tannery wastewater collected from a local leather industry in Peshawar, Pakistan was subjected to DC electrolysis in a simple cell having two static sheet electrodes and stirring assembly after proper dilution and adjustment to desired conditions. One percent HNO 3 and 1% NaHCO 3 were used as electrolytes and pH adjusters. The latter salt also worked as sodium source for anodic deposition of Na 2 Cr 2 O 7 . Various combinations of electrodes were tested and conditions optimized for best electrode couple with increased recovery and removal of chromium in the form of Cr(OH) 3 and/or Na 2 Cr 2 O 7 at cathode and anode, respectively. The recovery of 99% chromium was achieved after 2 h electrolysis at a cell potential of 1.0 V, pH 5.0 and stirring rate of 500 rpm using Pb sheet as anode and Cu sheet as cathode. The most interesting and novel finding of this work was the recovery of the mentioned salt(s) alone at Cu cathode or Pb anode or collectively at both electrodes by proper control of pH. Such treatment not only minimizes the environmental water pollution, but results in the formation of useful products employed for recycling purpose in tannery or other related industry to make the process economical.

In this paper, the ability of chrome shavings to remove motor oils, oily wastes and hydrocarbons from water has been studied. To determine amount of hydrocarbons sorbed on tanned wastes, a FT-NIR methodology was used and a multivariate calibration based on partial least squares (PLS) was employed for data treatment. The light density, porous tanned waste granules float on the surface of water and remove hydrocarbons and oil films. Wastes fibers from tannery industry have high sorption capacity. These tanned solid wastes are capable of absorbing many times their weight in oil or hydrocarbons (6.5-7.6g of oil and 6.3g of hydrocarbons per gram of chrome shavings). The removal efficiency of the pollutants from water is complete. The sorption of pollutants is a quasi-instantaneous process.

In this study, the chromium recovery conditions in the form of soluble chromate from chrome shaving (chromium-containing solid waste) by oxidation with air, oxygen and Na2O2 were investigated and basic Cr(III) sulphate solution using in the tanning was prepared from the chromate obtained. It has been determined that the oxidation agent is the most effective parameter affecting the chromate formation. While maximum oxidation yields in air and oxygen atmosphere at 850 °C were found to be 23.02 and 30.41%, respectively, the highest chromium recovery efficiency in the form of chromate (99.45%) occurred in the presence of eight times Na2O2 with respect to stoichiometric amount of chromium. The chromate generated in Na2O2 oxidation process where 99.45% of chromium in the chrome shaving can be recovered was leached with distilled water and pregnant chromate solution was prepared. The chromate ions in this solution were reduced by using Na2SO3 and Cr(III) sulphate solution was obtained.

Effluent and relevant soil samples from 38 tanning units housed in Kasur, Pakistan, were obtained for metal analysis by flame atomic absorption spectrophotometric method. The levels of 12 metals, Na, Ca, K, Mg, Fe, Mn, Cr, Co, Cd, Ni, Pb and Zn were determined in the two media. The data were evaluated towards metal distribution and metal-to-metal correlations. The study evidenced enhanced levels of Cr (391, 16.7 mg/L) and Na (25,519, 9369 mg/L) in tannery effluents and relevant soil samples, respectively. The effluent versus soil trace metal content relationship confirmed that the effluent Cr was strongly correlated with soil Cr. For metal source identification the techniques of principal component analysis, and cluster analysis were applied. The principal component analysis yielded two factors for effluents: factor 1 (49.6% variance) showed significant loading for Ca, Fe, Mn, Cr, Cd, Ni, Pb and Zn, referring to a tanning related source for these metals, and factor 2 (12.6% variance) with higher loadings of Na, K, Mg and Co, was associated with the processes during the skin/hide treatment. Similarly, two factors with a cumulative variance of 34.8% were obtained for soil samples: factor 1 manifested the contribution from Mg, Mn, Co, Cd, Ni and Pb, which though soil-based is basically effluent-derived, while factor 2 was found associated with Na, K, Ca, Cr and Zn which referred to a tannery-based source. The dendograms obtained from cluster analysis, also support the observed results. The study exhibits a gross pollution of soils with Cr at levels far exceeding the stipulated safe limit laid down for tannery effluents.

Sulfuric acid doped diaminopyridine polymers are synthesized in situ on graphene oxide surface via mutual oxidation–reduction technique. Exploiting large and highly porous surface, we have used this polymer composite as an adsorbent to remove high concentration of toxic Cr(VI) from water. It shows very high adsorption capacity (609.76 mg g −1 ) during removal process. The composite takes only 100 min to remove high concentration of 500 mg L −1 Cr(VI) from water. Interesting features for this material is the enhancement of removal efficiency at lower acidic condition due to the formation of acid doped emeraldine salt during polymerization. XPS and AAS measurements reveal that our prepared material mainly follows reduction mechanism at higher acidic condition while anions exchange mechanism at lower acidic condition during the removal experiments. Good recycling ability with ∼92% removal efficiency after fifth cycle is also noticed for this material. Easy preparation, superior stability in acidic condition, remarkable removal efficiency and excellent recycling ability make this polymer composite an efficient material for modern filtration units in waste water purification.