Photochemical reduction of hexavalent chromium in glycerol-containing solutions

Hexavalent chromium [Cr(VI)] in the form of potassium dichromate was photochemically reduced to trivalent chromium [Cr(III)] in aqueous solutions containing glycerol. This reaction occurred rapidly during irradiation with either unfiltered sunlight or a UVA-emitting light source. Photochemical reduction of Cr(VI) was pH-dependent and did not occur in dilute solutions of sodium hydroxide. In acidified solutions, the reduction occurred at elevated rates and at lower concentrations of glycerol. This reaction was found to be dependent on the unsubstituted alcohol groups of glycerol since alpha-phosphoglycerol and beta-phosphoglycerol did not support the photochemical reduction of Cr(VI). These findings suggest that glycerol or related polyols can be used for the remediation of hexavalent (toxic) chromium at contaminated environmental sites.     

Biological solids reduction using the Cannibal process.

A laboratory study of the Cannibal process was undertaken to determine if the Cannibal system would generate less sludge compared with a conventional activated sludge system. Side-by-side sequencing batch reactors were operated--one using the Cannibal configuration and the other as conventional activated sludge. It was found that the Cannibal process generated 60% less solids than the conventional activated sludge system, without any negative effect on the effluent quality or the settling characteristics of the activated sludge. The oxygen uptake rate for the centrate from the Cannibal bioreactor showed that readily biodegradable organic matter was released from the recycled biomass in the Cannibal bioreactor. It is proposed that the mechanism for reduced solids from the Cannibal system is that, in the Cannibal bioreactor, iron is reduced, releasing iron-bound organic material into solution. When the Cannibal biomass is recirculated back to the aeration basin, the released organic material is rapidly degraded.     

Spectroscopic investigation of magnetite surface for the reduction of hexavalent chromium

The reduction of Cr(VI) to Cr(III) by magnetite in the presence of added Fe(II) was characterized through batch kinetic experiments and the effect of Fe(II) addition and pH were investigated in this study. The addition of Fe(II) into magnetite suspension improved the reductive capacity of magnetite. Eighty percent of Cr(VI) was reduced by magnetite (6.5 g l(-1)) with Fe(II) (80 mg l(-1)) within 1 h, while 60% of Cr(VI) was removed by magnetite only. However, the extent of improved reductive capacity of magnetite with Fe(II) was less than that predicted by the summation of each reduction capacity of magnetite and Fe(II). The reduction of Cr(VI) in the magnetite suspension with Fe(II) increased with the increase of molar ratio of Fe(II) to Cr(VI) (0.6, 1, 1.5, 2.3) in the range of 0-2.3 and with the decrease of pH in the range of pH 8.0-5.5. The speciation of chromium, iron, and oxygen on the surface of magnetite was investigated by X-ray photoelectron spectroscopy. Cr 2p3/2, Fe 2p3/2, and O 1s peaks were mainly observed at 576.7 and 577.8 eV, at 711.2 eV, and at 530.2 and 531.4 eV, respectively. The results indicates that Cr(III) and Fe(III) were the dominant species on the surface of magnetite after reaction and that the dominant species covered the magnetite surface and formed metal (oxy)hydroxide.     

Influence of plants on the reduction of hexavalent chromium in wetland sediments

This work addresses the effect that plants (Typha latifolia and Carex lurida) have on the reduction of Cr(VI) in wetland sediments. Experiments were carried out using tubular microcosms, where chemical species were monitored along the longitudinal flow axis. Cr(VI) removal was enhanced by the presence of plants. This is explained by a decrease in the redox potential promoted by organic root exudates released by plants. Under these conditions sulfate reduction is enhanced, increasing the concentration of sulfide species in the sediment pore water, which reduce Cr(VI). Evapotranspiration induced by plants also contributed to enhance the reduction of Cr(VI) by concentrating all chemical species in the sediment pore water. Both exudates release and evapotranspiration have a diurnal component that affects Cr(VI) reduction. Concentration profiles were fitted to a kinetic model linking sulfide and Cr(VI) concentrations corrected for evapotranspiration. This expression captures both the longitudinal as well as the diurnal Cr(VI) concentration profiles.     

Kinetics of the reduction of hexavalent chromium with the brown seaweed Ecklonia biomass

The dead biomass of the brown seaweed, Ecklonia sp., is capable of reducing toxic Cr(VI) into less toxic or nontoxic Cr(III). However, little is known about the mechanism of Cr(VI) reduction by the biomass. The objective of this work was to develop a kinetic model for Cr(VI) biosorption, for supporting our mechanism. The reduction rate of Cr(VI) increased with increasing total chromate concentration, [Cr(VI)], and equivalent concentration of organic compounds, [OCs], and decreasing solution pH. It was found that the reduction rate of Cr(VI) was proportional to [Cr(VI)] and [OCs], suggesting the simple kinetic equation -d[Cr(VI)]/dt=k[Cr(VI)][OCs]. When considering the consumption of organic compounds due to the oxidation by Cr(VI), an average rate coefficient of 9.33 (+/-0.65)microM(-1)h(-1) was determined, at pH 2. Although the function of the pH could not be expressed in a mechanistic manner, an empirical model able to describe the pH dependence was obtained. It is expected that the developed rate equation could likely be used for design and performance predictions of biosorption processes for treating chromate wastewaters.     

还原稳定化法修复六价铬污染土壤的中试研究

为探索还原稳定化法修复六价铬污染土壤的工程可行性,以某化工厂铬渣堆存场内六价铬污染土壤为研究对象,开展还原稳定化法修复六价铬污染土壤的中试研究。结果表明,DARAMEND-M、硫酸亚铁(FeSO4)和多硫化钙(CPS)3种药剂对土壤中Cr(Ⅵ)的还原率超过了99%,糖蜜对Cr(Ⅵ)的还原率达93.9%。经糖蜜和DARAMEND-M处理的下层土壤,水溶态铬+交换态铬由原来的21.77%分别下降至6.26%和2.95%;经FeSO4和CPS处理的渣土混合物,水溶态铬+交换态铬由22.12%分别下降至4.58%和2.94%,铬的稳定性明显增强。采用糖蜜、DARAMEND-M和FeSO4处理后可以降低土壤pH值,而CPS处理则提高土壤pH值;糖蜜和DARAMEND-M有助于提高土壤微生物量碳含量。总体而言,糖蜜和DARAMEND-M适合修复低Cr(Ⅵ)污染土壤,在还原稳定化效果和长效性方面,DARAMEND-M药剂优于糖蜜;FeSO4和CPS在修复高Cr(Ⅵ)污染土壤方面具显著效果。     

Reliable evidences that the removal mechanism of hexavalent chromium by natural biomaterials is adsorption-coupled reduction

For the last few decades, over 200 papers have been published in the Cr(VI) biosorption research field. Most early studies have claimed that Cr(VI) was removed from aqueous phase through an anionic adsorption, but this approach has been lost old original position. It has been newly explained that these findings were misinterpreted due to errors in measuring the concentrations of different chromium species in the aqueous phase, insufficient contact time required for equilibrium and the lack of information about the oxidation state of the chromium bound to biomaterials. Although 'adsorption-coupled reduction' is now widely accepted as the mechanism of Cr(VI) biosorption by natural biomaterials, a number of researchers still believe that Cr(VI) is removed by anionic adsorption onto the biomaterials. Therefore, the objective of this study was to show reliable evidences that the removal mechanism of Cr(VI) by natural biomaterials is 'adsorption-coupled reduction'. Sixteen natural biomaterials were used to study the Cr(VI) biosorption. Not only Cr(VI) but also total Cr in the aqueous phase were analyzed. X-ray photoelectron spectroscope was also used to verify the oxidation state of the chromium bound to the biomaterials. Finally, the removal behavior of Cr(VI) by each biomaterial was described by a kinetic model based on a redox reaction.     

Microbial community response to addition of polylactate compounds to stimulate hexavalent chromium reduction in groundwater

To evaluate the efficacy of bioimmobilization of Cr(VI) in groundwater at the Department of Energy Hanford site, we conducted a series of microcosm experiments using a range of commercial electron donors with varying degrees of lactate polymerization (polylactate). These experiments were conducted using Hanford Formation sediments (coarse sand and gravel) immersed in Hanford groundwater, which were amended with Cr(VI) and several types of lactate-based electron donors (Hydrogen Release Compound, HRC; primer-HRC, pHRC; extended release HRC) and the polylactate-cysteine form (Metal Remediation Compound, MRC). The results showed that polylactate compounds stimulated an increase in bacterial biomass and activity to a greater extent than sodium lactate when applied at equivalent carbon concentrations. At the same time, concentrations of headspace hydrogen and methane increased and correlated with changes in the microbial community structure. Enrichment of Pseudomonas spp. occurred with all lactate additions, and enrichment of sulfate-reducing Desulfosporosinus spp. occurred with almost complete sulfate reduction. The results of these experiments demonstrate that amendment with the pHRC and MRC forms result in effective removal of Cr(VI) from solution most likely by both direct (enzymatic) and indirect (microbially generated reductant) mechanisms.     

锰掺杂硫化锌量子点LED蓝光灯光催化还原六价铬

通过共沉淀法合成了锰掺杂硫化锌量子点(ZnS∶Mn QDs),该催化剂可在450 nm LED蓝光灯下光催化还原Cr(Ⅵ)。采用TEM、XRD、PL分别对ZnS∶Mn QDs的形貌、物相和发光特性进行了表征,结果表明：ZnS∶Mn QDs的尺寸小于10 nm;Mn掺杂没有改变ZnS的晶体结构;ZnS在掺杂Mn后,可在598 nm处产生橘黄色荧光。UV-vis表征结果显示,与纯ZnS相比,ZnS∶Mn QDs具有更强的光吸收能力。考察了不同因素对光催化效果的影响。结果表明,Mn掺杂浓度3%较为合适,酸性pH有利于光催化反应。当Cr(Ⅵ)浓度为25 mg·L⁻¹,pH为5.8时,光催化25 min后Cr(Ⅵ)去除率为99%。与其他光催化剂还原Cr(Ⅵ)相比,ZnS: Mn QDs使用低能耗LED灯作为光源,催化速率高,且能够吸附还原产物Cr(Ⅲ)。探究了光催化机理,发现在450 nm光激发下,Mn²⁺自身能级⁴T₁→⁶A₁发生跃迁产生光生电子,Cr(Ⅵ)捕获光生电子被还原,价带上余留的空穴参与水的氧化。结合表征结果,ZnS可通过掺杂Mn离子改善光吸收能力提高光催化还原Cr(Ⅵ)的性能。     

Pilot-scale study of biomass reduction in wastewater treatment.

Pilot-scale experiments were continuously carried out for more than 9 months to study the excess biomass reduction effect using a biophase-separation bioreactor, which was designed based on food-chain theory. By separating the biophase in the wastewater treatment system, bacteria, protozoa, and metazoa could be separated from each other and dominated in different microbial communities. After degrading organic matter, bacteria were consumed by protozoa or metazoa in the following process in such a reactor. Thus, both chemical oxygen demand (COD) and biomass were reduced. During the process of treating restaurant wastewater, the excess biomass yield in this biophase-separation technique varied from 0.13 to 0.22 kg/kg COD removed, 50% lower than that from the reference system. Apart from low biomass production, this biophase-separation technique can simultaneously achieve a high COD removal efficiency and improve settleability of biosolids at a hydraulic retention time of 6 to 13 hours.     

采油污水生物处理技术

采油污水是石油工业中的重点污染源之一。本文论述了采油污水生物处理的难度和技术可行性 ,总结了国内外近年来采油污水生物处理技术的现状及研究进展。     

Biological and chemical assessments of zinc ageing in field soils

As zinc (Zn) is both an essential trace element and potential toxicant, the effects of Zn fixation in soil are of practical significance. Soil samples from four field sites amended with ZnSO₄ were used to investigate ageing of soluble Zn under field conditions over a 2-year period. Lability of Zn measured using ⁶⁵Zn radioisotope dilution showed a significant decrease over time and hence evidence of Zn fixation in three of the four soils. However, 0.01 M CaCl₂ extractions and toxicity measurements using a genetically modified lux-marked bacterial biosensor did not indicate a decrease in soluble/bioavailable Zn over time. This was attributed to the strong regulatory effect of abiotic properties such as pH on these latter measurements. These results also showed that Zn ageing occurred immediately after Zn spiking, emphasising the need to incubate freshly spiked soils before ecotoxicity assessments.     

Effect of sulfate reduction activity on biological treatment of hexavalent chromium [Cr(VI)] contaminated electroplating wastewater under sulfate-rich condition

Electroplating wastewater (EW) containing heavy metals was treated by a two-stage packed-bed reactor system. The EW was highly contaminated with hexavalent chromium and other heavy metals as well as sulfate because sulfuric acid had been mainly used to polish the surface of metals to be electroplated. This acidic EW was effectively neutralized in an alkaline reactor where limestone had been packed. The neutralized wastewater together with organic wastewater from a starch-processing factory (SPW) was fed to a bioreactor packed with waste biomass. The SPW was used to supplement the electron donor in the sulfidogenic bioreactor. During the whole operation, we investigated the stoichiometry of electron to see what could be a major factor to remove Cr in the wastewater. The removal rates of sulfate and Cr(VI) were dependent on the consumption rate of organic materials in the wastewater. The stoichiometric studies also showed that about 63% of electrons from oxidation of organic materials were used to reduce sulfate. When the electrons of sulfide oxidation to elemental sulfur was at least 1.3 times higher than that of Cr(VI) reduction to Cr(III), Cr(VI) was completely removed. This result suggests that Cr(VI) reduction can be expected to take place under sulfate-rich anaerobic conditions, and sulfide produced by sulfate reducing bacteria could be used to immobilize soluble chromium through Cr(VI) reduction.     

铁-苹果酸配合物对高价铬的光还原处理

研究了Fe(Ⅲ)-苹果酸配合物体系对Cr(Ⅵ)的光还原处理,考察了光源、初始pH值、Fe(Ⅲ)、苹果酸盐和Cr(Ⅵ)初始浓度等因素对Cr(Ⅵ)光还原效率的影响。结果表明:光照条件下,铁-苹果酸配合物能有效实现对六价铬的光还原。pH=3时Cr(Ⅵ)的光还原处理效果最佳;Fe(Ⅲ)和苹果酸盐初始浓度的增加可提高Cr(Ⅵ)的光还原效率;光还原的初始速率随各组分浓度的增大而增大,Fe(Ⅲ)浓度是影响反应速率的主要因素;Fe(Ⅲ)-苹果酸盐配合物光解产生的Fe(Ⅱ)是Cr(Ⅵ)的主要还原剂。     

Assessment of aliphatic-aromatic copolyester biodegradable mulch films. Part I: field study

The objective of this work was to study the use of new biodegradable films in agriculture under open field conditions. Three biodegradable mulch films made from modified biodegradable polyester of different thicknesses and colors (black and white) and a conventional low density polyethylene (LDPE) mulch film were used to cover the beds of tomato plants. Changes in physical appearance of the films were recorded as well as changes in their mechanical, optical, and physical properties. Once tomato harvest was completed, the conventional LDPE mulch film was removed and all the tomato plants were cut using a mower. The biodegradable mulch films were plowed into the soil. The change in the appearance of the film was recorded and samples of each film after plowing were characterized according to the properties mentioned above. After the biodegradable films photodegraded, cross-link formation occurred within the films which promoted brittleness. Titanium dioxide, an additive used to produce white color in the films, catalyzed the photodegradation, while carbon black used for black color stabilized the photodegradation. The white films started to degrade after two weeks while it took about eight weeks for the black films to significantly degrade. The black biodegradable film seems to be a more promising alternative as a mulch film because of the comparable yields and weed suppression ability to conventional mulch film.     

Relationship between mass-flux reduction and source-zone mass removal: analysis of field data

The magnitude of contaminant mass-flux reduction associated with a specific amount of contaminant mass removed is a key consideration for evaluating the effectiveness of a source-zone remediation effort. Thus, there is great interest in characterizing, estimating, and predicting relationships between mass-flux reduction and mass removal. Published data collected for several field studies were examined to evaluate relationships between mass-flux reduction and source-zone mass removal. The studies analyzed herein represent a variety of source-zone architectures, immiscible-liquid compositions, and implemented remediation technologies. There are two general approaches to characterizing the mass-flux-reduction/mass-removal relationship, end-point analysis and time-continuous analysis. End-point analysis, based on comparing masses and mass fluxes measured before and after a source-zone remediation effort, was conducted for 21 remediation projects. Mass removals were greater than 60% for all but three of the studies. Mass-flux reductions ranging from slightly less than to slightly greater than one-to-one were observed for the majority of the sites. However, these single-snapshot characterizations are limited in that the antecedent behavior is indeterminate. Time-continuous analysis, based on continuous monitoring of mass removal and mass flux, was performed for two sites, both for which data were obtained under water-flushing conditions. The reductions in mass flux were significantly different for the two sites (90% vs. approximately 8%) for similar mass removals ( approximately 40%). These results illustrate the dependence of the mass-flux-reduction/mass-removal relationship on source-zone architecture and associated mass-transfer processes. Minimal mass-flux reduction was observed for a system wherein mass removal was relatively efficient (ideal mass-transfer and displacement). Conversely, a significant degree of mass-flux reduction was observed for a site wherein mass removal was inefficient (non-ideal mass-transfer and displacement). The mass-flux-reduction/mass-removal relationship for the latter site exhibited a multi-step behavior, which cannot be predicted using some of the available simple estimation functions.     

Immobilised microbial reactor for the biotransformation of hexavalent chromium

Out of an array of bacterial strains isolated from soil contaminated with effluents from electroplating wastewater, Bacillus coagulans exhibited the maximum Cr(VI) reduction potential. The feasibility of an immobilized B. coagulans bioreactor for hexavalent chromium reduction was investigated. Experimental results demonstrated that near complete removal of Cr(VI) was achieved in the reactor with an initial Cr(VI) concentration of 26 mg/l and reactor time of 24 h. The removal efficiency in the bioreactor was significantly affected by the influent Cr(VI) concentration, the Cr(VI) loading rate, the reaction time and the amount of Cr(VI) reduced by the biomass.     

旋风除尘器流场及浓度场实验与模拟

在研究旋风除尘器内气固两相的运动状况及分离机理方面,计算机模拟替代部分实验的方法能够优化设计旋风除尘器结构参数,提高其对微细颗粒的捕集效率,减少运行压力损失。本研究采用RSM模型和随机轨道模型对旋风除尘器内流场及浓度场进行模拟及实验。研究表明,旋风除尘器压力损失模拟结果与实验结果吻合较好,对于大于5μm的颗粒其捕集效率模拟结果与实验结果基本吻合;旋风除尘器外壁的颗粒浓度呈螺旋带状分布;如将排气管管径减少至原直径0.8倍,可使其对2μm颗粒捕集效率提高6.6%,但压力损失提高36.5%;颗粒的凝并作用有利于提高旋风除尘器微细颗粒的捕集效率。