皮革中六价铬的研究进展

对国内外有关皮革中六价铬形成的原因、检测方法和预防措施的研究现状进行了总结 ,并提出了一些自己的观点     

深色皮革中六价铬含量测定方法的研究

在不改变DIN5 3 3 1 4检测方法的前提下 ,采用特效脱色剂对深色皮革的提取液进行脱色 ,解决了深色皮革中六价铬含量的测定难题     

Reduction of hexavalent chromium with the brown seaweed Ecklonia biomass

A new type of biomass, protonated brown seaweed Ecklonia sp., was used for the removal of Cr(VI). When synthetic wastewater containing Cr(VI) was placed in contact with the biomass, the Cr(VI) was completely reduced to Cr(III). The converted Cr(III) appeared in the solution phase or was partly bound to the biomass. The Cr(VI) removal efficiency was always 100% in the pH range of this study (pH 1 to approximately 5). Furthermore, the Cr(VI) reduction was independent of the Cr(III) concentration, the reaction product, suggesting that the reaction was an irreversible process under our conditions. Proton ions were consumed in the ratio of 1.15 +/- 0.02 mol of protons/mol of Cr(VI), and the rate of Cr(VI) reduction increased with decreasing the pH. An optimum pH existed for the removal efficiency of total chromium (Cr(VI) plus Cr(III)), but this increased with contact time, eventually reaching approximately pH 4 when the reaction was complete. The electrons required for the Cr(VI) reduction also caused the oxidation of the organic compounds in the biomass. One gram of the biomass could reduce 4.49 +/- 0.12 mmol of Cr(VI). From a practical viewpoint, the abundant and inexpensive Ecklonia biomass could be used for the conversion of toxic Cr(VI) into less toxic or nontoxic Cr(III).     

Co-removal of hexavalent chromium through copper precipitation in synthetic wastewater

The mechanisms of hexavalent chromium [Cr(VI)] co-removal with copper [Cu(II)] during homogeneous precipitation were studied with batch tests using a synthetic solution containing Cr(VI) and Cu(II). Metal precipitation was induced by adding Na2CO3 stepwise to different pH, and the respective removals of Cu(II) and Cr(VI) were measured. At the same time, the relative quantities of Cu(II) and Cr(VI) in the precipitates were also analyzed to establish their stoichiometric relationship. The results indicated that, in a solution containing 150 mg/L Cu(II) and 60 mg/L Cr(VI), the initial co-removal of Cr(VII with Cu(II) began at pH 5.0 and completed at pH 6.2. At pH 5.0-5.2, coprecipitation took place through the formation of copper-chromium-bearing solids [such as CuCrO4 and/or CuCrO4 x 2Cu(OH)2]. Thereafter, the remaining soluble copper started to react with carbonate in a heterogeneous environment to form the negatively charged basic copper carbonate precipitates [CuCO3 x Cu(OH)2], which subsequently adsorbed additional Cr(VI) (or HCrO4-) at pH 5.2-6.2. The maximum Cr(VI) co-removal took place at pH 6.2. Between the two mechanisms, co-precipitation accounted for about 29% of the total chromium's co-removal while the remaining 71% was attributed to surface adsorption, mainly through electrostatic attraction and ligand exchange. When the solution pH was increased to beyond 7.5, a surface charge reversal took place on the basic copper carbonate solids, and this led to some Cr(VI) desorption. Thus, the extent of Cr(VI) adsorption is highly pH dependent.     

番茄红素中总铬和六价铬本底值分析及健康风险评估

了解保健品中化学污染物的本底水平,有利于科学地进行综合判定,为制定相关的标准和法规提供理论依据。本文采用微波消解-离子交换分离-石墨炉原子吸收法对12种番茄红素胶囊中铬本底值水平进行测定和分析。结果表明,番茄红素样品中Cr本底值为401⁴521μg/kg,Cr(VI)本底水平为0.74521μg/kg,Cr(VI)本底水平为0.7²66μg/kg,仅占Cr的0.9%266μg/kg,仅占Cr的0.9%⁷%,番茄红素中的铬主要以Cr(Ⅲ)形式存在;Cr、Cr(VI)暴露健康风险指数分别为0.007和0.0006,无健康风险。本研究为正确认识番茄红素中铬天然水平及健康风险评估提供了数据支持。     

Removal of hexavalent chromium by biosorption process in rotating packed bed

Removal of hexavalent chromium ions from an aqueous solution by crude tamarind (Tamarindus indica) fruit shell was examined in a rotating packed bed contactor by continuously recirculating a given volume of solution through the bed. Reduction of Cr(VI) to Cr(III) within the biosorbent appeared to be the removal mechanism. Depletion rate of Cr(VI) from, and release of reduced Cr(III) ions into the aqueous phase, was influenced by mass transfer resistance besides pH and packing depth. A mathematical model considering the reduction reaction to be irreversible and incorporating intraparticle and external phase mass transfer resistances represented the experimental data adequately. The study indicated that the limitations of fixed bed contactor operating under terrestrial gravity in intensifying mass transfer rates for this system can be overcome with rotating packed bed due to liquid flow under centrifugal acceleration.     

Reduction of hexavalent chromium by H2O2 in acidic solutions

The rates of the reduction of Cr(VI) with H2O2 were measured in NaCl solutions as a function of pH (1.5-4.8), temperature (5-40 degrees C), and ionic strength (I = 0.01-2 M) in the presence of an excess of reductant. The rate of Cr(VI) reduction is described by the general expression -d[Cr(VI)]/dt = k2[Cr(VI)](m)[H2O2](n)[H+](z), where m = 1 and n and z are two interdependent variables. The value of n is a function of pH between 2 and 4 (n = (3 x 10(a))/(1 + 10(a)), where a = -0.25 - 0.58pH + 0.26pH2) leveling off at pH < 2 (where n approximately = 1) and pH > 4 (where n approximately = 3). The rates of Cr(VI) reduction are acid-catalyzed, and the kinetic order z varies from about 1.8-0.5 with increasing H2O2 concentration, according to the equation z = 1.85 - 350.1H2O2 (M) which is valid for [H2O2] < 0.004 M. The values of k2 (M(-(n+z)) min(-1)) are given by k2 = k/[H+](z) = k1/[H2O2](n)[H+](z), where k is the overall rate constant (M(-n) min(-1)) and k, is the pseudo-first-order rate constant (min(-1)). The values of k in the pH range 2-4 have been fitted to the equation log k = 2.14pH - 2.81 with sigma = +/- 0.18. The values of k2 are dependent on pH as well. Most of the results with H2O2 < 3 mM are described by log k2 = 2.87pH - 0.55 with sigma = +/- 0.54. Experimental results suggest that the reduction of Cr(VI) to Cr(III) is controlled by the formation of Cr(V) intermediates. Values of k2 and k calculated from the above equations can be used to evaluate the rates of the reaction in acidic solutions under a wide range of experimental conditions, because the rates are independent of ionic strength, temperature, major ions, and micromolar levels of trace metals (Cu2+, Ni2+, Pb2+). The application of this rate law to environmental conditions suggests that this reaction may have a role in acidic solutions (aerosols and fog droplets) in the presence of high micromolar concentrations of H2O2.     

Carbothermal synthesis of carbon-supported nanoscale zero-valent iron particles for the remediation of hexavalent chromium

Nanoscale, zero-valent iron is a promising reagent for in situ reduction of a variety of subsurface contaminants, but its utility in full-scale remediation projects is limited by material costs. Iron nanoparticles (20-100 nm diameter) supported on carbon (C-Fe0) were synthesized by reacting iron salts, adsorbed or impregnated from aqueous solutions onto 80 m2/g carbon black, at 600-800 degrees C under Ar. Similar products were obtained by heating the reactants under air in a covered alumina crucible. X-ray powder diffraction patterns show that Fe3O4 particles are formed at 300-500 degrees C in the initial stage of the reaction and that these particles are reduced to a mixture of alpha- and gamma-Fe nanoparticles above 600 degrees C. When C-Fe0 was combined with carboxymethylcellulose in a 5:1 weight ratio in water, the resulting material had similar transport properties to previously optimized nanoiron/polyanion suspensions in water-saturated sand columns. At a 10:3 Fe/Cr mole ratio, C-Fe0 reduced a 10 ppm Cr(VI) solution to approximately 1 ppm within three days. The surface area normalized first-order Cr removal rate was 1.2 h(-1) m(-2) under these conditions. These results demonstrate that reactive nanoiron with good transport properties in water-saturated porous media can be made in a scalable process from inexpensive starting materials by carbothermal reduction.     

Removal of hexavalent chromium with a lignocellulosic substrate extracted from wheat bran

In this paper, a new recovery system of the toxic hexavalent chromium Cr(VI) is proposed that uses a lignocellulosic substrate derived from the industrial treatment process of wheat bran. We studied the adsorption mechanism of Cr(VI) onto the lignocellulosic substrate and showed that the adsorption reaction consumes a large amount of protons goes along the reduction of Cr(VI) into Cr(III). The oxidation of lignin moieties takes place concurrently to the chromium reduction and leads to the formation of hydroxyl and carboxyl functions. The latter contribute to an increase in the number of ion-exchange sites for the reduced chromium. The maximum adsorption capacity for hexavalent chromium was found at about 35 mg g(-1) in an acidic medium. This is comparable to other natural substrates and ordinary adsorbents.     

Removal of hexavalent chromium from wastewater using a new composite chitosan biosorbent

A new composite chitosan biosorbent was prepared by coating chitosan, a glucosamine biopolymer, onto ceramic alumina. The composite bioadsorbent was characterized by high-temperature pyrolysis, porosimetry, scanning electron microscopy, and X-ray photoelectron spectroscopy. Batch isothermal equilibrium and continuous column adsorption experiments were conducted at 25 degrees C to evaluate the biosorbent for the removal of hexavalent chromium from synthetic as well as field samples obtained from chrome plating facilities. The effect of pH, sulfate, and chloride ion on adsorption was also investigated. The biosorbent loaded with Cr(VI) was regenerated using 0.1 M sodium hydroxide solution. A comparison of the results of the present investigation with those reported in the literature showed that chitosan coated on alumina exhibits greater adsorption capacity for chromium(VI). Further, experimental equilibrium data were fitted to Langmuir and Freundlich adsorption isotherms, and values of the parameters of the isotherms are reported. The ultimate capacity obtained from the Langmuir model is 153.85 mg/g chitosan.     

Behavior of hexavalent chromium in a polluted groundwater: redox processes and immobilization in soils

This work describes the chemical mechanisms governing transport and reduction of hexavalent chromium in soils of a contaminated industrial waste landfill. Groundwater and soil analyses indicate that the main source of chromium is a slag heap essentially consisting of mill tailings. In the groundwater, downstream migration of Cr(IV) is limited thanks to a redox mechanism involving chromate ions and ferrous ions or Fe(II)-bearing minerals. High Fe2+ concentrations in the groundwater are a result of pyrite residues from old activities at the site. Analyses of soil samples reveal that chromium is preferentially located in the soil profile at the fluctuation of the groundwater level. Grain size fractionation of four soil samples was performed, and fraction analyses show that chromium is preferentially accumulated in the clay fraction (<2 microm) and more specifically associated with montmorillonite particles. This work is a demonstration of the reduction of Cr(VI) by Fe(II) studied previously in the laboratory (Buerge, I. J.; Hug, S. J. Environ. Sci. Technol. 1997, 31, 1426-1432; Fendorf, S. E.; Li, G. Environ. Sci. Technol. 1996, 30, 1614-1617; Sedlak, D. L.; Chan, P. G. Geochim. Cosmochim. Acta 1997, 11, 2185-2192) in a field setting. Cr(VI) migration into the groundwater is stopped vertically by the very thick green clay unit and horizontally by the presence of Fe(II) acting as a chemical barrier. The specific site conditions safely prevent any extension of the Cr pollution.     

Natural occurrence of aflatoxins in Korean meju

Aflatoxin B₁ (AFB₁) was found in 35 of 60 (58.3%) meju samples with an average concentration of 7.3ng/g by ELISA. Contamination of AFB₁ was confirmed in 25 of 60 samples (41.6%) using HPLC, with an average concentration of 6.9ng/g. Mean recoveries from meju ranged from 107% to 170% for AFB₁ using ELISA at a spiking range of 1 to 50ng/g. Over the same range, recoveries using HPLC were from 70% to 83%. The levels of AFB₁ determined by ELISA and by HPLC demonstrated a close relationship between the two methods (r2 = 0.9324) employed in this study. In order to evaluate the potential health risks of AFB₁ on Koreans consuming meju, we calculated the estimated probable daily intake (PDI) based on the average contamination levels and compared it with the estimated tolerable daily intake (TDI). The PDIs of AFB₁ from kanjang and dwenjang were determined to be 0.04 and 0.21ng/kg bw/day, respectively, and were higher than TDIs.     

Extraction of hexavalent chromium from chromated copper arsenate treated wood under alkaline conditions

Information on chromium (Cr) oxidation states is essential for the assessment of environmental and health risks associated with the overall life-cycle of chromated copper arsenate (CCA) treated wood products because of differences in toxicity between trivalent [Cr(III)] and hexavalent [Cr(VI)] chromium compounds. Hypothetical Cr(VI) fixation products were investigated in CCA type C treated sawdust of aspen and red pine during or following preservative fixation by extraction with Cr(VI)-specific extractants. Cr(VI) was found only in alkaline extracts of treated wood. A major source of Cr(VI) was method-induced oxidation of fixed Cr(III) during alkaline extraction, as confirmed by demonstrated oxidation of Cr(III) from CrCl3 treated wood. Oxidation of nontoxic and immobile Cr(III) to toxic and mobile Cr(VI) was facilitated by the presence of wood at pH > 8.5. Thermodynamic equilibrium between Cr(III) and Cr(VI) is affected by pH, temperature, rates of dissolution of CrIII) compounds, and oxygen availability. Results of this study recommend against alkaline extraction protocols for determination of Cr(VI) in treated wood. This Cr oxidation mechanism can act as a previously unrecognized route for generation of hazardous Cr(VI) if CCA treated wood is exposed to alkaline conditions during its production, use, or waste management.     

Precipitates on granular iron in solutions containing calcium carbonate with trichloroethene and hexavalent chromium

Mineralogical examination, using scanning electron microscopy (SEM), X-ray diffractometry (XRD), and optical microscopy, was conducted on the Fe0-bearing reactive materials derived from long-term column experiments undertaken to assess the treatment capacity of Fe0 under different geochemical conditions. The columns received either deionized water or solutions of differing dissolved calcium carbonate concentrations, together either with trichloroethene (TCE) or hexavalent chromium (Cr(VI)). The major reaction product in the columns receiving deionized water was magnetite-maghemite, and for the columns receiving dissolved calcium carbonate, the main products were iron hydroxy carbonate and aragonite. Replacement of Fe0 by reaction products occurred mainly at the edges of the Fe0 particles, and penetrative replacement was focused along cracks and along and around graphitic inclusions. Fibrous or flake-shaped iron hydroxy carbonate mostly replaced the edges of the Fe0 particles. Aragonite had needle-shaped morphology, and some occurred as clusters of crystals. Aragonite was deposited on iron hydroxy carbonate, thus providing at least a partial armoring effect. The mineral was also observed to cement groups of Fe0 particles into compact aggregates. The Cr was present mostly as Cr(III) in Cr(III)-Fe(III) (oxy)hydroxides and in trace amounts in iron hydroxy carbonate.     

天然红色素在肉制品中的应用

<正> 目前国内在肉制品中应用较多的天然红色素是红曲米粉、红曲红色素和高粱红。但是这些天然色素远远不能满足现代肉制品加工的需要,开发新的天然红色素,对原有工艺进行改进,已成为迫切的问题。而花生衣色素、枣皮红色素和荞麦皮红色素因其营养价值高、性质稳定、来源广泛,将在肉制品中有着良好的应用前景。 1、红曲米 红曲米义称赤曲、红米、福米。是将稻米清洗后用0.2％柠檬水溶液浸泡,蒸     

Pyrite oxidation by hexavalent chromium: investigation of the chemical processes by monitoring of aqueous metal species

Pyrite, an iron sulfide, occurs in many soils and sediments, making it an important natural reductant of toxic metal pollutants. This study investigated the processes leading to aqueous Cr(VI) reduction by pyrite in a closed thermostated (25 +/- 0.1 degrees C) system and under an argon atmosphere. Synthetic pyrite suspensions were reacted with a range of Cr(VI) solutions from 0 to 7 x 10(-4) M and at pH 2-8. Metal species concentrations were continuously monitored during a period lasting approximately 20 h. Preliminary experiments carried out in acidic media without Cr(VI) have shown that some pyrite dissolution occurred. Then, metal species concentration changes with time during pyrite oxidation by Cr(VI) solutions exhibited two distinct trends depending on the complete or incomplete Cr(VI) removal. As long as chromate existed in solution, the Cr-(Ill) to Fe(lIl) ratio was found to be an effective parameter to investigate the pyrite reaction stoichiometry with Cr(VI). Experimental values close to 2 suggest that sulfur compounds with oxidation states between 0 and 2 should be formed during pyrite oxidation by Cr(VI). If Cr(VI) was completely reduced from solution, then the pyrite oxidation by Fe(lll) ions took place to generate ferrous ions.     

Evaluation of hexavalent chromium extraction method EPA method 3060A for soils using XANES spectroscopy

Hexavalent chromium (Cr(VI)) occurrence in soils is generally determined using an extraction step to transfer it to the liquid phase where it is more easily detected and quantified. In this work, the performance of the most common extraction procedure (EPA Method 3060A) using NaOH-Na(2)CO(3) solutions is evaluated using X-ray absorption near edge structure spectroscopy (XANES), which enables the quantification of Cr(VI) directly in the solid state. Results obtained with both methods were compared for three solid samples with different matrices: a soil containing chromite ore processing residue (COPR), a loamy soil, and a paint sludge. Results showed that Cr(VI) contents determined by the two methods differ significantly, and that the EPA Method 3060A procedure underestimated the Cr(VI) content in all studied samples. The underestimation is particularly pronounced for COPR. Low extraction yield for EPA Method 3060A was found to be the main reason. The Cr(VI) present in COPR was found to be more concentrated in magnetic phases. This work provides new XANES analyses of SRM 2701 and its extraction residues for the purpose of benchmarking EPA 3060A performance.     

Natural occurrence of Alternaria mycotoxins in sorghum and ragi from North Bihar, India

The natural occurrence of major Alternaria mycotoxins i.e. alternariol (AOH), alternariol methyl ether (AME), altenuene (ALT), altertoxin-1 (ATX-1) and tenuazonic acid (TA) has been investigated in sorghum (Sorghum vulgare Pers.) and ragi (Eleusine coracana Gaertn.) collected from North Bihar. Nine out of 20 sorghum samples, and three out of eight ragi samples, were found to be contaminated with one to three Alternaria mycotoxins. The toxin elaborating potential of Alternaria alternata (Fr.) Keissler strains isolated from sorghum and ragi have also been investigated. Out of 16 isolates of A. alternata (Fr.) Keissler, mycotoxins were detected in only 10.     

Effect of set potential on hexavalent chromium reduction and electricity generation from biocathode microbial fuel cells

Setting a biocathode potential at -300 mV improved the subsequent performance of an MFC for Cr(VI) reduction compared to a control (no set potential). With this set potential, the startup time was reduced to 19 days, the reduction of Cr(VI) was improved to 19.7 mg/L d, and the maximum power density was increased to 6.4 W/m(3) compared to the control (26 days, 14.0 mg/L d and 4.1 W/m(3)). Set potentials of -150 mV and -300 mV also improved system performance and led to similarly higher utilization of metabolic energy gained (PMEG) than set potentials of +200 mV and -450 mV. We observed putative pili at -150 and -300 mV potentials, and aggregated precipitates on bacterial surfaces in both poised and nonpoised controls. These tests show that there are optimal potentials that can be set for developing a Cr(VI) biocathode.     

热处理对黑莓果酒香气的影响

用不同温度处理黑莓果酒后,通过顶空固相微萃取和GC-MS检测技术鉴定到77种香气成分,50℃/30 min、70℃/30 min与90℃/30 min处理的黑莓酒香气成分分别为22、46和35种。结果表明热处理能使黑莓原酒的醇类、酯类、酸类及萜烯类等香气物质向老化的程度发展,证实热处理对黑莓果酒有一定的催熟作用。