Lignin and functional polymer-based materials: Synthesis, characterization and application for Cr (VI) and As (V) removal from aqueous media.

In this study, lignin derived from corncobs was chemically modified by substituting the hydroxyl groups present in its structure with methacrylate groups through a catalytic reaction using methacrylic anhydride, resulting in methacrylated lignin (ML). These MLs were incorporated in polymerization reaction of the monomer 2-[(acryloyloxy)ethyl trimethylammonium] chloride (Cl-AETA) and Cl-AETA, Cl-AETA/ML polymers were obtained, characterized (spectroscopic, thermal and microscopic analysis), and evaluated for removing Cr (VI) and As (V) from aqueous media in function of pH, contact time, initial metal concentrations and adsorbent amount. The Cl-AETA/ML polymers followed the Langmuir adsorption model for the evaluated metal anions and were able to remove up to 91 % of Cr (VI) with a qmax (maximum adsorption capacity) of 201 mg/g, while for As (V), up to 60 % could be removed with a qmax of 58 mg/g. The results demonstrate that simple modifications in lignin enhance its functionalization and properties, making it suitable for removing contaminants from aqueous media, showing promising results for potential future applications.

Novel method of removing metals from estuarine water using whole microbial mats.

This study addresses the limited understanding of chromium-microbial mat interactions in estuarine tidal flats. The aims were to evaluate (1) the efficiency of the microbial consortium in Cr(III) removal from seawater; (2) the elemental and mineralogical composition of the microbial mat as a natural system in the Cr removal, (3) the effects of metal on microphytobenthos, and (4) possible interactions of Cr with other metals present in the consortium. Microbial mats were exposed to Cr(III) solutions at different concentrations (2-30 mg Cr/L). Analysis such as metal concentration, organic matter content, chlorophyll a and phaeopigment concentrations, abundance of diatoms and cyanobacteria, SEM-EDS, and XRD were performed. Most of the Cr(III) was deposited, as chromium oxide/hydroxide, on the surface of all microbial mat components. The complete microbial mat, comprising sediments, detritus, EPS, and diverse microorganism communities, exhibited a remarkable capacity to accumulate Cr(III), retaining over 87% in the solution.

Biodegradable gelatin composite hydrogels filled with cellulose for chromium (VI) adsorption from contaminated water.

Biopolymers are promising materials for water treatment applications due to their abundance, low cost, expandability, and chemical structure. In this work, gelatin hydrogels filled with cellulose in the form of pristine eucalyptus residues (PER) or treated eucalyptus residues (TER) were prepared for adsorption and chromium removal in contaminated water. PER is a lignocellulosic compound, with cellulose, hemicellulose, and lignin, while TER has cellulose as a major component. FT-Raman Spectroscopy and FTIR analysis confirmed the crosslink reaction with glutaraldehyde and indicated that fillers altered the gelatin molecular vibrations and formed new hydrogen bonds, impacting the hydrogels' crystalline structure. The hydrogen bond energy was altered by the cellulosic fillers' addition and resulted in higher thermal stability (~10 °C). Hydrogels presented a Fickian diffusion, where gelatin hydrogel showed the highest swelling ability (466%), and composites showed lower values with the filler content increase. The chromium adsorption capacity presented values between 12 and 13 mg/g, i.e., featuring an excellent removal capacity which is related with hydrogel crosslinked structure and fibers surface hydroxyl groups, highlighting gelatin hydrogel TER 5% with better removal capacity. The developed hydrogels were produced from biomacromolecules with low-cost and potential application in contaminated water.

Bioreduction of Cr(VI) by Indigenously Isolated Bacterial Strains from Stream Sediment Contaminated with Tannery Waste.

The potential of indigenously isolated bacteria from the Estância Velha stream to reduce Cr(VI) was evaluated and also the chromium contamination over the past ten years was verified in one of the most important industrial centers of Brazil, the "Brazilian Capital of Tanneries," Estância Velha municipality in the Rio Grande do Sul State, South Brazil. Samples were collected from the Estância Velha stream at the source (P1), as well as at upstream (P2) and downstream (P3) of the most demographically area. The bacterial strains reduced between 52.5 and 61.6% of 250 mg L-1 Cr(VI) in 48 h. The genus Acinetobacter was the most abundant and could efficiently reduce 500 mg L-1 of Cr(VI); for example, P2.8 and P2.9 strains of Acinetobacter ursingii reduced 21.3 and 24.5% of 500 mg L-1 of Cr(VI), respectively, after 48 h. Moreover, an analysis of Cr levels in the stream sediment reported up to 3594 mg. L-1 of total Cr and up to 138 mg. L-1 of Cr(VI) in 2009. Acinetobacter strains were identified as the most abundant and efficient in reducing Cr(VI), makes them an ideal candidate for cleaning environments contaminated with tannery effluents, an approach that is more cost-effective than the traditional methods.

Nanocellulose and Polycaprolactone Nanospun Composite Membranes and Their Potential for the Removal of Pollutants from Water.

A composite membrane based on polycaprolactone (PCL) and cellulose nanofibers (CNF) with different compositions was prepared using the electro-spinning method, with the objective of developing organic membranes with good mechanical properties to remove contaminants from water. Water is a resource of primary importance for life and human activities. In this sense, cellulose obtained from agave bagasse and polycaprolactone nanofibers was used to prepare membranes that were tested by filtering tap water. The membranes obtained presented a porosity and structure on a nanometric scale. The water quality variables evaluated after filtration with the PCL/CNF membranes showed 100% turbidity removal, 100% conductivity, and heavy metal removal of the order of 75% to 99% for iron and chromium. CNF comprises biowaste derived from tequila production, and it has added value. Electro-spun CNF and PCL membranes can be applied as a "green" and eco-friendly filtration system for water purification.

Use of Salvinia sp on the adsorption of hexavalent chromium.

The remotion of hexavalent chromium in the form of chromate in aqueous solution was done using the aquatic plant Salvinia sp as biosorbent. The chemical modification of the Salvinia surface was performed by organosolv adapted method. The untreated Salvinia and the modified were characterized by infrared spectroscopy, Boehm titration, scanning electron microscopy, energy dispersive system, point of zero charge, surface area analysis, and porosity. Batch adsorption experiments were performed to observe the effects of pH, contact time, initial concentration, and temperature on the metal removal process. The characterization results show the chemistry modifically changed the modified Salvinia structure compared with untreated Salvinia. The adsorption test results showed the maximum adsorption capacity of 26.03 mg g-1. The kinetic equilibrium was reached in about 3 h, and the better temperature and pH were 298 K and 7, respectively. The adsorption and kinetic models were Freundlich and pseud-second order, respectively. This study showed the Salvinia sp after the chemical treatment can be used with biosorbent for hexavalent chromate in the form of chromate, being a natural material with low cost and plentiful in the environment.

Chitosan-iron oxide hybrid composite: mechanism of hexavalent chromium removal by central composite design and theoretical calculations.

In this study, the synthesis of iron oxide stabilized by chitosan was carried out for the application and optimization in the removal process of aqueous Cr(VI) by central composite design (CCD). The calculation of these effects allowed to know, quantitatively, the variables and the interaction between them that could affect the Cr(VI) removal process. It was also verified that the most favorable conditions for chromium removal were the following: pH 5.0, Cr(VI) concentration of 130 mg L-1, adsorbent mass of 5 mg, and Fe(II) content of 45% (w/w) in the CT-Fe beads. The adsorption kinetics performed under these conditions showed that the chitosan/iron hybrid composite is an adsorbent material with high chromium removal capacity (46.12 mg g-1). It was found that all variables were statistically significant. However, it was observed that the variable that most affected Cr(VI) removal was the pH of the solution, followed by the concentration of chromium ions in solution and the interaction between them. Therefore, the studied experimental conditions are efficient in chromium adsorption, besides the operational simplicity coming from statistical design. Theoretical calculations showed that the most stable chitosan was that with Fe(II) in the structure, that is, in the reaction mechanism, there is no competition of Fe(II) with Cr(III, VI) in the available sites of chitosan. Thus, the theoretical calculations show that the proposed Cr(VI) removal is effective.

Multi-resistant plant growth-promoting actinobacteria and plant root exudates influence Cr(VI) and lindane dissipation.

The aims of this study were (1) to isolate new multi-resistant actinobacteria from soil, rhizosphere and plant samples collected from an ancient illegal pesticide storage and (2) to elucidate the effects of these microorganisms developed with maize root exudates on lindane and Cr(VI) removal. Fifty-seven phenotypically different actinobacteria were isolated and four of them, belonging to the genus Streptomyces exhibit tolerance to a mixture of lindane and Cr(VI). Two rhizospheric strains named as Streptomyces sp. Z38 and Streptomyces sp. Z2 were selected to be grown with root exudates because they showed the highest Cr(VI) and lindane removal in co-contaminated medium. When root exudates were the only carbon source, metal dissipation increased significantly either as single or mixed contaminant, compared to metal dissipation with glucose. No significant differences were found on lindane removal with root exudates or glucose, so a higher lindane concentration was evaluated. Despite of this, lindane removal remained stable while metal dissipation was notoriously lower when lindane concentration was enhanced. In addition to a good performance growing with mixed contaminants, Streptomyces strains showed plant growth promoting traits that could improve plant establishment. The results presented in this study show the importance of the screening programs addressed to find new actinobacteria able to grow in co-contaminated systems. It was also evidenced that root exudates of maize improve the growth of Streptomyces strains when they were used as carbon source, being the dissipation of Cr(VI) considerably improved in presence of lower lindane concentration.

Adsorption mechanism of chromium(III) using biosorbents of Jatropha curcas L.

The removal of Cr3+ from water solutions by biosorbents from the rind, endosperm, and endosperm + episperm of the Jatropha curcas was evaluated. Adsorption tests were performed in batch systems for evaluating the influence of the solution's pH, adsorbent mass, contact time, initial Cr3+ concentrations, and solution temperature during the adsorption process. Kinetic, adsorption isotherm, and thermodynamic studies were performed to investigate the mechanisms that control adsorption. Ideal conditions for the adsorption process included pH of the solution of 5.5 and 8 g L-1 adsorbent mass, within 60 min time contact between adsorbent and adsorbate. Maximum adsorption capacities by Langmuir model for rind, endosperm, and endosperm + episperm of the J. curcas were, respectively, 22.11, 18.20, and 22.88 mg g-1, with the occurrence of chemosorption in mono and multilayers. Results show that the biosorbents obtained from J. curcas have a high potential to recuperate Cr3+ from contaminated water sources.

Integral use of sugarcane vinasse for biomass production of actinobacteria: Potential application in soil remediation.

The use of living actinobacteria biomass to clean up contaminated soils is an attractive biotechnology approach. However, biomass generation from cheap feedstock is the first step to ensure process sustainability. The present work reports the ability of four actinobacteria, Streptomyces sp. M7, MC1, A5, and Amycolatopsis tucumanensis, to generate biomass from sugarcane vinasse. Optimal vinasse concentration to obtain the required biomass (more than 0.4 g L-1) was 20% for all strains, either grown individually or as mixed cultures. However, the biomass fraction recovered from first vinasse was discarded as it retained trace metals present in the effluent. Fractions recovered from three consecutive cycles of vinasse re-use obtained by mixing equal amounts of biomass from single cultures or produced as a mixed culture were evaluated to clean up contaminated soil with lindane and chromium. In all cases, the decrease in pesticide was about 50% after 14 d of incubation. However, chromium removal was statistically different depending on the preparation methodology of the inoculum. While the combined actinobacteria biomass recovered from their respective single cultures removed about 85% of the chromium, the mixed culture biomass removed more than 95%. At the end of the reused vinasse cycle, the mixed culture removed more than 70% of the biological oxygen demand suggesting a proportional reduction in the effluent toxicity. These results represent the first integral approach to address a problematic of multiple contaminations, concerning pesticides, heavy metals and a regionally important effluent like vinasse.

Zeolitic tuffs for acid mine drainage (AMD) treatment in Ecuador: breakthrough curves for Mn2+, Cd2+, Cr3+, Zn2+, and Al3.

Zeolitic tuff constitutes a technical and economical feasible alternative to manage acidic waters in initial phases of generation. A study of cation exchange with two zeolitic tuffs from Ecuador and one from Cuba has been conducted using breakthrough curve methodology. Cations Mn2+, Cd2+, Cr3+, Zn2+, and Al3+ have been chosen owing to their presence in underground water in exploration activities (decline development) in Fruta del Norte (Ecuador). Zeolites characterized by X-ray diffraction and thermal stability after heating overnight as heulandites show a similar exchange behavior for the five cations studied. The clinoptilolite sample Tasajeras shows a relevant cation exchange performance expressed in the important increment of spatial time to reach the breakthrough point in comparison with heulandite samples. The maximum length of unused beds was found for Cr3+ and Zn2+ cations showing, therefore, a lower adsorption performance in relation with Mn2+ and Cd2+. A final disposal method of metal-loaded zeolites with cement is proposed.

Hexavalent chromium removal in contaminated water using reticulated chitosan micro/nanoparticles from seafood processing wastes.

Chitosan particles (CH) were obtained from seafood processing wastes (shrimp shells) and physicochemically characterized; deacetylation degree of CH was measured by Infrared Spectroscopy (FTIR) and potentiometric titration; polymer molecular weight was determined by intrinsic viscosity measurements. Reticulated micro/nanoparticles of chitosan (MCH) with an average diameter close to 100nm were synthesized by ionic gelation of chitosan using tripolyphosphate (TPP), and characterized by SEM, size distribution and Zeta-potential. Detoxification capacities of CH and MCH were tested analyzing the removal of hexavalent chromium Cr(VI) from contaminated water, at different initial chromium concentrations. The effect of pH on adsorption capacity of CH and MCH was experimentally determined and analyzed considering the Cr(VI) stable complexes (anions) formed, the presence of protonated groups in chitosan particles and the addition of the reticulating agent (TPP). Chitosan crosslinking was necessary to adsorb Cr(VI) at pH<2 due to the instability of CH particles in acid media. Langmuir isotherm described better than Freundlich and Temkin equations the equilibrium adsorption data. Pseudo-second order rate provided the best fitting to the kinetic data in comparison to pseudo-first order and Elovich equations. Chemical analysis to determine the oxidation state of the adsorbed Cr, showed that Cr(VI) was adsorbed on CH particles without further reduction; in contrast Cr(VI) removed from the solution was reduced and bound to the MCH as Cr(III). The reduction of toxic Cr(VI) to the less or nontoxic Cr(III) by the reticulated chitosan micro/nanoparticles can be considered a very efficient detoxification technique for the treatment of Cr(VI) contaminated water.

Removal of chromium and lead by a sulfate-reducing consortium using peat moss as carbon source.

The effect of pre-treated peat moss on the ability of a sulfate-reducing microbial consortium to remove chromium and lead in solution was evaluated. The most active bacterial community (235.7 mmol H2S/g VSS) was selected from among eight consortia. The peat moss was pre-treated with different HCl concentrations and contact times. The best combination of treatments was 20% HCl for 10 min. The constant substrate affinity Ks was 740 mg COD/L and the ratio COD/SO4(2-) was 0.71. At pH 5, higher production of biogenic sulfide was observed. The up-flowpacked bed bioreactor operated at a flow of 8.3 mL/min for 180 h to obtain removal efficiency (by sulfate-reducing activity) of 90% lead and 65% chromium. It is important to consider that peat moss is a natural adsorbent that further influences the removal efficiency of metal ions.

Removal and accumulation of As, Cd and Cr by Typha latifolia.

The removal from the solution and the accumulation of As, Cd and Cr by Typha latifolia was studied. Small plants of T. latifolia, collected from a non-contaminated site, were exposed to individual concentrations of As, Cd and Cr for 10 days. The ability of T. latifolia for the removal of toxic elements ranged from 23% to 54% for As, 43%-55% for Cd and 28%-73% for Cr. The accumulation of toxic elements in T. latifolia occurred mainly in the roots. The results suggest that T. latifolia can be considered as an interesting alternative for treating aquatic effluents polluted with toxic trace elements.

Application of the extraction induced by emulsion breaking for the determination of chromium and manganese in edible oils by electrothermal atomic absorption spectrometry.

This work reports the optimization of a method, based on the extraction induced by emulsion breaking, for the determination of trace concentrations of Cr and Mn in edible oils by electrothermal atomic absorption spectrometry (ETAAS). In the method, a water-in-oil emulsion was prepared by mixing the oil sample with an acid solution (HNO(3)) of Triton X-114 to allow the intense contact between the sample and the extractant acid solution. Afterwards, the emulsion was broken by heating and the acid aqueous phase deposited in the bottom of the flask was collected for the determination of the metals of interest. The method was optimized by studying the influence of several parameters such as the concentration of HNO(3) and the emulsifier agent (Triton X-100 and Triton X-114) in the extractant solution. The best results were verified when the procedure was performed with 5 mL of the sample and 1 mL of the extractant solution containing 15%m/v of Triton X-114 and 2.8 mol L(-1) of HNO(3). Also, the fastest emulsion breaking was verified when the emulsions were heated at 90°C. In these conditions, the emulsions were broken in approximately 10 min. The quantification of Cr and Mn in the extracts was carried out by external calibration with aqueous standard solutions, which simplified the procedure. The limits of detection for the determination of Cr and Mn in the oil samples were 66 and 36 ng L(-1), respectively, and the limits of quantification were 219 and 120 ng L(-1), respectively. The developed method was applied in the determination of Cr and Mn in twelve samples of edible oils produced with different oleaginous. Recovery tests were performed to attest the accuracy of the method, being observed recovery percentages in the range of 86-115%.

Removal efficiency of Cr6+ by indigenous Pichia sp. isolated from textile factory effluent.

Resistance of the indigenous strains P. jadinii M9 and P. anomala M10, to high Cr(6+) concentrations and their ability to reduce chromium in culture medium was studied. The isolates were able to tolerate chromium concentrations up to 104 µg mL(-1). Growth and reduction of Cr(6+) were dependent on incubation temperature, agitation, Cr(6+) concentration, and pH. Thus, in both studied strains the chromium removal was increased at 30 °C with agitation. The optimum pH was different, with values of pH 3.0 and pH 7.0 in the case of P. anomala M10 and pH 7.0 using P. jadinii M9. Chromate reduction occurred both in intact cells (grown in culture medium) as well as in cell-free extracts. Chromate reductase activity could be related to cytosolic or membrane-associated proteins. The presence of a chromate reductase activity points out a possible role of an enzyme in Cr(6+) reduction.

A review of chemical, electrochemical and biological methods for aqueous Cr(VI) reduction.

Hexavalent chromium is of particular environmental concern due to its toxicity and mobility and is challenging to remove from industrial wastewater. It is a strong oxidizing agent that is carcinogenic and mutagenic and diffuses quickly through soil and aquatic environments. It does not form insoluble compounds in aqueous solutions, so separation by precipitation is not feasible. While Cr(VI) oxyanions are very mobile and toxic in the environment, Cr(III) cations are not. Like many metal cations, Cr(III) forms insoluble precipitates. Thus, reducing Cr(VI) to Cr(III) simplifies its removal from effluent and also reduces its toxicity and mobility. In this review, we describe the environmental implications of Cr(VI) presence in aqueous solutions, the chemical species that could be present and then we describe the technologies available to efficiently reduce hexavalent chromium.

Removal, accumulation and resistance to chromium in heterotrophic Euglena gracilis.

The removal, uptake and toxicity of chromium in Euglena gracilis cultured in absence and presence of malate with Cr(VI) or Cr(III) was evaluated. The malate extrusion and the extra- and intracellular Cr(VI) reduction capacity were determined and the contents of molecules with thiol group and ascorbate were also evaluated. Absence of malate in the medium decreased cell growth, increased Cr(III) toxicity, induced faster Cr(VI) disappearance from medium, and increased intracellular and intramitochondrial chromium accumulation. Both chromium species induced soluble and particulate ascorbate-dependent chromate reductase activities. Cells also secreted large amounts of malate and increased intracellular contents of thiol-molecules to bind extracellular and intracellular Cr(III), respectively. The former process was supported by significant increase in malate-producing enzyme activities and the assessment of the Cr-complexes indicated the in situ formation with thiol-molecules. The present results establish new paradigms regarding chromium stress on algae-like microorganisms: (i) Cr(III) may be more toxic than Cr(VI), depending on the culture (or environmental) conditions; (ii) several simultaneous mechanisms are turned on to inactivate chromium species and their toxic effects. These mechanisms, now well understood may further optimize, by genetically modifying E. gracilis, and facilitate the development of strategies for using this protist as potential bio-remediator of chromium-polluted water systems.

Biological Cr(VI) removal coupled with biomass growth, biomass decay, and multiple substrate limitation.

In this work, a mathematical model for the biological reduction of Cr(VI), carbon and nitrogen sources consumption, and biomass growth under fully aerobic conditions was developed. The model comprises three types of aerobic heterotrophic cells (non-growing cells, growing cells with chromate reductase activity, and growing cells that have lost the chromate reductase activity), and five soluble compounds (organic substrate, ammonia nitrogen, non-metabolizable soluble products, dissolved oxygen, and hexavalent chromium). Two processes are considered responsible for the reduction of Cr(VI). The first one is the reduction of Cr(VI) coupled with growth, the second process is coupled with the endogenous decay of the biomass. The model was calibrated using the results obtained in batch cultures in the absence of carbon and nitrogen sources, using different initial Cr(VI) concentrations (0-100 mgCr L(-1)), two carbon sources (cheese whey and lactose), and different initial nitrogen to carbon ratio (0-50 mgN gCOD(-1)). The calibrated model was used to calculate steady-state values of TSS, soluble COD, TAN and Cr(VI) in continuous systems, obtaining a good agreement with the experimental data. The model also accurately predicted the transient concentration of Cr(VI) as a function of time in response to step changes of the inlet Cr(VI) concentration in continuous systems.

Chromium recovery from tannery sludge with saponin and oxidative remediation.

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 H(2)O(2) 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 H(2)O(2) 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.