Low-temperature chromium(VI) biotransformation in soil with varying electron acceptors

Effective and low-cost strategies for remediating chromium (Cr)-contaminated soil are needed. Chromium(VI) leaching from contaminated soil into ground water and surface water threatens water supplies and the environment. This study tested indigenous Cr(VI) microbial transformation in batch systems at 10 degrees C in the presence of various electron acceptors. The effects of carbon addition, spiked Cr(VI), and mixing highly contaminated soil with less contaminated soil were investigated. The results indicated that Cr(VI) can be biotransformed in the presence of different electron acceptors including oxygen, nitrate, sulfate, and iron. Sugar addition had the greatest effect on enhancing Cr(VI) removal. Less dissolved organic carbon (DOC) was consumed per amount of Cr(VI) transformed under anaerobic conditions [0.8-93 mg DOC/mg Cr(VI)] compared with aerobic conditions [1.4-265 mg DOC/mg Cr(VI)]. Toxicity of high concentrations (< 160 mg/L) of spiked Cr(VI) were not evident. At Cr(VI) concentrations > 40 mg/L, aerobic conditions promoted faster Cr(VI) reduction than anaerobic conditions with nitrate or sulfate present. Biotransformation of Cr(VI) in highly contaminated soil (22,000 mg Cr/kg) was facilitated by mixing with less-contaminated soil. The study results provide a framework for evaluating indigenous Cr(VI) microbial transformation and enhance the ability to develop strategies for soil treatment.     

Distribution of chromium contamination and microbial activity in soil aggregates

Biogeochemical transformations of redox-sensitive chemicals in soils can be strongly transport-controlled and localized. This was tested through experiments on chromium diffusion and reduction in soil aggregates that were exposed to chromate solutions. Reduction of soluble Cr(VI) to insoluble Cr(II) occurred only within the surface layer of aggregates with higher available organic carbon and higher microbial respiration. Sharply terminated Cr diffusion fronts develop when the reduction rate increases rapidly with depth. The final state of such aggregates consists of a Cr-contaminated exterior, and an uncontaminated core, each having different microbial community compositions and activity. Microbial activity was significantly higher in the more reducing soils, while total microbial biomass was similar in all of the soils. The small fraction of Cr(VI) remaining unreduced resides along external surfaces of aggregates, leaving it potentially available to future transport down the soil profile. Using the Thiele modulus, Cr(VI) reduction in soil aggregates is shown to be diffusion rate- and reaction rate-limited in anaerobic and aerobic aggregates, respectively. Thus, spatially resolved chemical and microbiological measurements are necessary within anaerobic soil aggregates to characterize and predict the fate of Cr contamination. Typical methods of soil sampling and analyses that average over redox gradients within aggregates can erase important biogeochemical spatial relations necessary for understanding these environments.     

Leaching mechanisms of Cr(VI) from chromite ore processing residue

Batch leaching tests, qualitative and quantitative x-ray powder diffraction (XRPD) analyses, and geochemical modeling were used to investigate the leaching mechanisms of Cr(VI) from chromite ore processing residue (COPR) samples obtained from an urban area in Hudson County, New Jersey. The pH of the leaching solutions was adjusted to cover a wide range between 1 and 12.5. The concentration levels for total chromium (Cr) and Cr(VI) in the leaching solutions were virtually identical for pH values >5. For pH values <5, the concentration of total Cr exceeded that of Cr(VI) with the difference between the two attributed to Cr(III). Geochemical modeling results indicated that the solubility of Cr(VI) is controlled by Cr(VI)-hydrocalumite and Cr(VI)-ettringite at pH >10.5 and by adsorption at pH <8. However, experimental results suggested that Cr(VI) solubility is controlled partially by Cr(VI)-hydrocalumite at pH >10.5 and by hydrotalcites at pH >8 in addition to adsorption of anionic chromate species onto inherently present metal oxides and hydroxides at pH <8. As pH decreased to <10, most of the Cr(VI) bearing minerals become unstable and their dissolution contributes to the increase in Cr(VI) concentration in the leachate solution. At low pH ( <1.5), Cr(III) solid phases and the oxides responsible for Cr(VI) adsorption dissolve and release Cr(III) and Cr(VI) into solution.     

Genotypic Variation in the Phytoremediation Potential of Indian Mustard for Chromium

The term “phytoremediation” is used to describe the cleanup of heavy metals from contaminated sites by plants. This study demonstrates phytoremediation potential of Indian mustard (Brasicca juncea (L.) Czern. & Coss.) genotypes for chromium (Cr). Seedlings of 10 genotypes were grown hydroponically in artificially contaminated water over a range of environmentally relevant concentrations of Cr (VI), and the responses of genotypes in the presence of Cr, with reference to Cr accumulation, its phytotoxity and anti-oxidative system were investigated. The Cr accumulation potential varied largely among Indian mustard genotypes. At 100 μM Cr treatment, Pusa Jai Kisan accumulated the maximum amount of Cr (1680 μg Cr g⁻¹ DW) whereas Vardhan accumulated the minimum (107 μg Cr g⁻¹ DW). As the tolerance of metals is a key plant characteristic required for phytoremediation purpose, effects of various levels of Cr on biomass were evaluated as the gross effect. The extent of oxidative stress caused by Cr stress was measured as rate of lipid peroxidation. The level of thiobarbituric acid reactive substances (TBARS) was enhanced at all Cr treatments when compared to the control. Inductions of enzymatic and nonenzymatic antioxidants were monitored as metal-detoxifying responses. All the genotypes responded to Cr-induced oxidative stress by modulating nonenzymatic antioxidants [glutathione (GSH) and ascorbate (Asc)] and enzymatic antioxidants [superoxide dismutase (SOD), ascorbate peroxidase (APX), and glutathione reductase (GR)]. The level of induction, however, differed among the genotypes, being at its maximum in Pusa Jai Kisan and its minimum in Vardhan. Pusa Jai Kisan was grown under natural field conditions with various Cr treatments, and Cr-accumulation capacity was studied. The results confirmed that Pusa Jai Kisan is a hyperaccumulator of Cr and hypertolerant to Cr-induced stress, which makes this genotype a viable candidate for use in the development of phytoremediation technology of Cr-contaminated sites.     

Leachability of dissolved chromium in asphalt and concrete surfacing materials

Leachate metal pollutant concentrations produced from different asphalt and concrete pavement surfacing materials were measured under controlled laboratory conditions. The results showed that, in general, the concentrations of most metal pollutants were below the reporting limits. However, dissolved chromium was detected in leachate from concrete (but not asphalt) specimens and more strongly in the early-time leachate samples. As the leaching continued, the concentration of Cr decreased to below or close to the reporting limit. The source of the chromium in concrete pavement was found to be cement. The concentration of total Cr produced from leachate of different cement coming from different sources that was purchased from retail distributors ranged from 124 to 641 μg/L. This result indicates that the potential leachability of dissolved Cr from concrete pavement materials can be reduced through source control. The results also showed that the leachability of dissolved Cr in hardened pavement materials was substantially reduced. For example, the concentration of dissolved Cr measured in actual highway runoff was found to be much lower than the Cr concentration produced from leachate of both open and dense graded concrete pavement specimens under controlled laboratory study. It was concluded that pavement materials are not the source of pollutants of concern in roadway runoff; rather most pollutants in roadway surface runoff are generated from other road-use or land-use sources, or from (wet or dry) atmospheric deposition.     

Chemical and physical properties of dry flue gas desulfurization products

Beneficial and environmentally safe recycling of flue gas desulfurization (FGD) products requires detailed knowledge of their chemical and physical properties. We analyzed 59 dry FGD samples collected from 13 locations representing four major FGD scrubbing technologies. The chemistry of all samples was dominated by Ca, S, Al, Fe, and Si and strong preferential partitioning into the acid insoluble residue (i.e., coal ash residue) was observed for Al, Ba, Be, Cr, Fe, Li, K, Pb, Si, and V. Sulfur, Ca, and Mg occurred primarily in water- or acid-soluble forms associated with the sorbents or scrubber reaction products. Deionized water leachates (American Society for Testing and Materials [ASTM] method) and dilute acetic acid leachates (toxicity characteristic leaching procedure [TCLP] method) had mean pH values of >11.2 and high mean concentrations of S primarily as SO(2-)4 and Ca. Concentrations of Ag, As, Ba, Cd, Cr, Hg, Pb, and Se (except for ASTM Se in two samples) were below drinking water standards in both ASTM and TCLP leachates. Total toxicity equivalents (TEQ) of dioxins, for two FGD products used for mine reclamation, were 0.48 and 0.53 ng kg(-1). This was similar to the background level of the mine spoil (0.57 ng kg(-1)). The FGD materials were mostly uniform in particle size. Specific surface area (m2 g(-1)) was related to particle size and varied from 1.3 for bed ash to 9.5 for spray dryer material. Many of the chemical and physical properties of these FGD samples were associated with the quality of the coal rather than the combustion and SO2 scrubbing processes used.     

Accelerated weathering of biosolid-amended copper mine tailings

Application of municipal biosolids to mine tailings can enhance revegetation success, but may cause adverse environmental impacts, such as increased leaching of NO3- and metals to ground water. Kinetic weathering cells were used to simulate geochemical weathering to determine the effects of biosolid amendment on (i) pH of leachate and tailings, (ii) leaching of NO3- and SO4(2-), (iii) leaching and bioavailability (DTPA-extractable) of selected metals, and (iv) changes in tailing mineralogy. Four Cu mine tailings from southern Arizona differing in initial pH (3.3-7.3) and degree of weathering were packed into triplicate weathering cells and were unamended and amended with two rates (equivalent to 134 and 200 Mg dry matter ha(-1)) of biosolids. Biosolid application to acid (pH 3.3) tailings resulted in pH values as high as 6.3 and leachate pH as high as 5.7, and biosolids applied to circumneutral tailings resulted in no change in tailing or leachate pH. Concentrations of NO3--N of up to 23 mg L(-1) occurred in leachates from circumneutral tailings. The low pH of the acidic tailing apparently inhibited nitrification, resulting in leachate NO3--N of <5 mg L(-1). Less SO4(2-)-S was leached in biosolid-amended versus unamended acid tailings (final rate of 0.04 compared with 0.11 g SO4(2-)-S wk(-1)). Copper concentrations in leachates from acidic tailings were reduced from 53 to 27 mg L(-1) with biosolid amendment. Copper and As concentrations increased slightly in leachates from biosolid-amended circumneutral tailings. Small increases in DTPA-extractable Cu, Ni, and Zn occurred in all tailings with increased biosolid rate. Overall, there was little evidence of potential for adverse environmental impacts resulting from biosolid application to these Cu mine tailings.     

Trace Metal Concentrations in an Intensive Agricultural Watershed in British Columbia,Canada1

Abstract: Effects of agricultural intensification and a naturally occurring landslide of asbestos material upon water and sediment quality in a transboundary watershed were investigated. The water and sediments of the Sumas River watershed were analyzed for copper (Cu), zinc (Zn), chromium (Cr), and nickel (Ni) concentrations in 1993/1994 and 2003/2004 and differences within sites over time were examined. Based upon a review of the literature, Cu and Zn were used as indicators of agricultural impacts while Cr and Ni were used as indicators of impacts from an asbestos landslide. Animal unit equivalents (AUEs) were calculated on a per area basis as an indicator of livestock density using detailed statistical census data. Whatman #42 filtered metals, bioavailable metals, and sediment‐bound metals (in the <63 μm fraction) were determined at 22 sites along the mainstem and tributaries, including two reference sites. Temperature, pH, and dissolved organic carbon (DOC) were also measured. The bioavailable metal fraction was determined using the diffusive gradient thin film technique (DGT). Sediment‐bound results were compared with British Columbia’s Interim Sediment Quality Guidelines (ISQGs) and Severe Effects Levels (SELs). A Wilcoxon signed rank test was used to determine if the concentrations of metals changed significantly within sites between 1993/1994 and 2003/2004. Spearman rank correlation analysis was used to determine relationships between trace metals, water quality parameters, and AUEs/hectare. The results indicate that Cu and Zn levels in sediments increased significantly to concentrations above the ISQGs of 35.7 mg/kg and 123 mg/kg, respectively from 1993/1994 to 2003/2004 in streams, where associated land use was dominated by intensive agriculture. Higher AUEs/hectare were significantly correlated with greater bioavailable levels of Zn as well as higher sediment‐bound Zn concentrations. Neither Cu nor Cr were detected by the DGTs on any of the sampling occasions. The Cr and Ni sediment concentrations were highest in Swift Creek, the headwater tributary affected by the natural landslide of asbestos material, and decreased in the Sumas River downstream from the point of input. Cr and Ni concentrations have increased in the mid‐region of the Sumas River since 1993/1994, suggesting downstream movement of the asbestos material over time. DGT results indicated that bioavailable Zn is significantly positively correlated to sediment‐bound Zn and livestock density, and bioavailable Ni is significantly correlated to sediment‐bound Ni.     

Phosphorus release from a manure-impacted spodosol: effects of a water treatment residual

Long-term depositions of animal manures affect P dynamics in soils and can pose environmental risks associated with P losses. Laboratory studies were done on P solubility characteristics in a manure-impacted Immokalee soil (sandy, siliceous, hyperthermic Arenic Alaquod) and the effectiveness of water treatment residual (WTR) in controlling P leaching. Soil samples with contrasting initial total P concentrations were prepared by mixing samples of a manure-impacted surface A horizon and a minimally P-impacted E horizon. Effects of mixing various ratios of A and E horizons, WTR rates (0, 25, 50, and 100 g kg(-1)), and depths of WTR incorporation (mixed throughout the soil column or partially incorporated) on P leaching were determined. Between 62 and 77% of total P was released from the soil mixes by successive water extractions, suggesting a considerable buffering capacity of this manure-impacted soil to resupply P into solution. Between 224 and 408 mg kg(-1) P were leached during the 36-wk leaching period in the absence of WTR. Mixing WTRs with soil reduced soluble P concentration in leachates by as much as 99.8% compared with samples without WTR. Thoroughly mixing WTR with the entire soil column (15 cm) was much more efficient than mixing WTR with only the top 7.5 cm of soil. Calcium- and Mg-P forms appear to control P release in soils without WTR, whereas sorption-desorption reactions probably determine P leaching in WTR-treated samples. Soil P distribution in various chemical forms was affected by WTR additions. Data suggest that WTR-immobilized P is stable in the long term.     

Determination of toxic metals in discarded Liquid Crystal Displays (LCDs)

This study focused on the determination of the toxic metal content of Liquid Crystal Displays (LCDs) present in various Waste Electrical and Electronic Equipment (WEEE). The main objective was the identification and quantification of toxic metals detected in LCD panels. An experimental procedure which involved dismantling, shredding, pulverization, digestion and chemical analysis was followed for the sorting, separation and analysis of LCD monitors from various electronic devices that are currently on the market. Nine selected devices were examined, originated from four different types of e-waste (WEEE); TVs, computers, mobile phones and tablets. Eleven metals were measured in all examined samples. In addition, concentration values of chromium (Cr), cadmium (Cd), lead (Pb) and mercury (Hg) were compared with the respective limits set by the RoHS 2002/95/EC Directive that was recently renewed by the 2012/19/EU recast. The comparison revealed that the examined toxic metals on LCD panels did not exceed the limits set by the European Union (EU). Furthermore, when results were compared to the TTLC regulatory limits it was revealed that in three samples As concentrations were higher than the limit. Finally, when the TCLP test was implemented the aforementioned samples did not exhibit proportionally elevated values in their leachates.     

DISSOLVED HEAVY METALS IN SHALLOW GROUND WATER IN A SOUTHEASTERN MICHIGAN URBAN WATERSHED1

ABSTRACT: The occurrence of dissolved heavy metal concentrations in shallow ground water were measured at 126 sites within an urban watershed in southeastern Michigan. A total of 1,140 samples were collected from the first saturated zone, and the mean concentrations of 11 heavy metals (arsenic, barium, cadmium, chromium, copper, lead, mercury, nickel, selenium, silver, and zinc) were obtained and compared to their corresponding mean concentrations within surface soil. The results suggest that former and current land use processes have resulted in significant adverse impacts on the study region. Levels of Cr 20 to 30 times the maximum contaminant level (MCL) have been detected in the ground water beneath industrial sites. In addition, Cd and Pb have been found at levels exceeding their MCLs where surface soils are clay‐rich, and in sandy soils at more than 10 times their MCLs. The high levels of Cr in ground water strongly suggest that the chromium is in a hexavalent form, and this likelihood is supported by current studies. Given the hydraulic connection between the watershed's surface waters and the Great Lakes, these findings raise significant ecological and public health concerns.     

Chromate reduction by chromium-resistant bacteria isolated from soils contaminated with dichromate

Extensive use of hexavalent chromium [Cr(VI)] in various industrial applications has caused substantial environmental contamination. Chromium-resistant bacteria isolated from soils can be used to remove toxic Cr(VI) from contaminated environments. This study was conducted to isolate chromium-resistant bacteria from soils contaminated with dichromate and describes the effects of some environmental factors such as pH, temperature, and time on Cr(VI) reduction and resistance. We found that chromium-resistant bacteria can tolerate 2500 mg L(-1) Cr(VI), but most of the isolates tolerated and reduced Cr(VI) at concentrations lower than 1500 mg L(-1). Chromate reduction activity of whole cells was detected in five isolates. Most of these isolates belong to the genus Bacillus as identified by the 16S rRNA gene sequencing. Maximal Cr(VI) reduction was observed at the optimum pH (7.0-9.0) and temperature (30 degrees C) of growth. One bacterial isolate (Bacillus sp. ES 29) was able to aerobically reduce 90% of Cr(VI) in six hours. The Cr(VI) reduction activity of the whole cells of five isolates had a K(M) of 0.271 (2.61 mM) to 1.51 mg L(-1) (14.50 mM) and a V(max) of 88.4 (14.17 nmol min(-1)) to 489 mg L9-1) h(-1) (78.36 nmol min(-1)). Our consortia and monocultures of these isolates can be useful for Cr(VI) detoxification at low and high concentrations in Cr(VI)-contaminated environments and under a wide range of environmental conditions.     

The characterization of total and leachable metals in foundry molding sands

Waste molding sands from the foundry industry have been successfully used as a component in manufactured soils, but concern over metal contamination must be addressed before many states will consider this beneficial use. Since there is little data available on this topic, the purpose of this study was to characterize total and leachable metals from waste molding sands. A total elemental analysis for Ag, Al, As, B, Ba, Be, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb, Sb, V, and Zn was conducted on 36 clay-bonded and seven chemically bonded molding sands. Total metal concentrations in the molding sands were similar to those found in agricultural soils. The leaching of metals (i.e. Ag, As, Ba, Be, Cd, Cr, Cu, Ni, Pb, Sb, and Zn) was assessed via the toxicity characteristic leaching procedure (TCLP), synthetic precipitation leaching procedure (SPLP), and ASTM water leach test. Based on the TCLP data, none of the 43 molding sands would meet the Resource Conservation and Recovery Act (RCRA) characteristic for toxicity due to high Ag, As, Ba, Cd, Cr, and Pb. Compared to the TCLP results, the metal concentrations were generally lower in the SPLP and ASTM extracts, which is likely related to the buffering capacity of the extraction fluids.     

The treatment of textile wastewater including chromium(VI) and reactive dye by sulfate-reducing bacterial enrichment

Sulfate-reducing bacteria (SRB) that could grow on modified Postgate C medium (PC) containing chromium(VI) were isolated from industrial wastewaters and their chromium(VI) reduction capacities were investigated as a function of changes in the initial pH values, chromium, sulfate, NaCl and reactive dye concentrations. The optimum pH value at 50 mg l(-1) initial chromium(VI) concentration was determined to be 8. Chromium(VI) reduction by SRB was investigated at 22.7-98.4 mg l(-1) initial chromium(VI) concentrations. At the end of the experiments, the mixed cultures of SRB were found to reduce within 2-6 days more than 99% of the initial chromium(VI) levels, which ranged from 22.7 to 74.9 mg l(-1). The effects of the initial 0-9.0 g l(-1) concentrations of disodium sulfate and 0-6% (w/v) concentrations of NaCI to chromium reduction showed that the lowest concentrations of sulfate and NaCI were the best for chromium reduction in the PC medium including 50 mg l(-1) chromium(VI). Chromium(VI) reduction in 50 mg l(-1) and 25-100 mg l(-1) Remazol Blue, Reactive Black B or Reactive Red RB containing media were also investigated. In the experiments, 25-30% of the initial dye concentrations and 95% of the chromium(VI) was removed from the medium at the end of 72-h and 24-h incubation periods, respectively.     

含Cr（Ⅵ）废水生物处理技术及其影响因素

本文综述了微生物还原处理含价铬的废水的研究进展。讨论了影响微生物还原Cr(Ⅵ）因素包括生物体密度、初始Cr（Ⅵ）的浓度、碳源、pH、温度、溶解氧、氧化还原电位、含氧阴离子和金属离子。微生物还原Cr（Ⅵ）技术作为一种富有创新的研究应用于Cr（Ⅵ）污染的环境恢复。     

Utilisation of steel slags as neutralising agents in biooxidation of a refractory gold concentrate and their influence on the subsequent cyanidation

A study on the possibilities to utilise steel slag as neutralising agent in biooxidation of a refractory gold concentrate has been done with reference to commercial grade slaked lime. The idea has been to reduce the operating costs for neutralisation in the biooxidation plant, which is known to be the second largest operating cost. Other benefits would be savings in cost for landfilling of slag, possibilities to recycle elements present in the slag and savings of virgin limestone deposits. The slags used were an EAF slag and a slag from ladle refining; both originating from Swedish scrap based steel-making. Continuous biooxidation of the refractory gold concentrate was conducted in a single-stage 5 L reactor at a retention time of 56 h. The neutralisation capacity was determined by comparing the amount needed, per ton of feed concentrate added, to maintain the desired pH of 1.5 during steady state operation. Slaked lime had the highest neutralisation capacity with 110 kg/ton feed followed by ladle slag and EAF slag with values of 152 and 267 kg/ton feed, respectively. Sulphide mineral oxidation was similar and high in all cases although the ladle slag results were slightly better. Gold recoveries after cyanide leaching on the residues obtained were also similar and were in the range of 86-89%. However, the cyanide consumption expressed as kilogram cyanide per ton of concentrate fed to biooxidation, was double in the case of ladle slag and three times as much for the EAF slag compared to the slaked lime experiment. The increased cyanide consumption could not be explained only by the increased amount of elemental sulphur obtained in the slag experiments. The elemental sulphur formed had different reactivities as seen from the thiocyanate formation and cyanide losses due to thiocyanate formation were 16%, 32% and 40% for EAF slag, slaked lime and ladle slag, respectively. It is concluded that the ladle slag could be a possible replacement for limestone if they are mixed in proper proportions so that the microbial carbon dioxide demand is met whereas the EAF slag is less suitable due to the very fine reaction products obtained which gave operational problems with filtration and washing. To come further, experiments with the normal multi-stage biooxidation set-up with total retention time of 120 h should be performed which would increase the sulphur oxidation and eventually also reduce the cyanide consumption.     

Soil,water and plants contamination by total chrome and chrome VI

The chrome (Cr) is a metal utilized in various industrial sectors and its investigation in the environment is necessary, for the Cr (III) contain aessential micronutrients in the human nourishment and the Cr (VI), on the other hand, is toxic. In the present work soil contamination with Cr was realized in drainagelysimetersset in concentrations of 0, 200, 400, 600, 800 and 1000 mg kg⁻¹ of total Cr, with the intuition to determine the total Cr and Cr (VI) flux in leached water, in soil and in plants of lettuce (Lactuca sativa L.). In the lysimeters were cultivated four plants, in three cultivation circles. In the end of the cultivations was observed, that the total applied Cr leached in the soil, evidencing the Cr mobility in latossoil with simulant characteristics to the ones utilized in this paper. The Cr (VI) concentrations in the soil increased soon after the treatment applications, but tend to decrees in the time elapse, the same tendences were observed for the total Cr concentrations in the leached water. The Cr absorption by plants was related to the Cr disponibility in the soil, for the soil concentration and the plants decreased with time passing. The Cr mobility in the soil possibilitated the groundwater contamination presenting risks to the water quality and, consequently to public health.     

Evaluation of hexavalent chromium removal in a continuous biological filter with the use of central composite design (CCD)

Hexavalent chromium is frequently found in industrial effluents as a result of the industrial applications of this compound and its anti-corrosive features. However, hexavalent chromium is extremely toxic, and its discharge in water is regulated, with a maximum limit of 0.1 mg/L in accordance with legislation established by CONAMA-Brazil (no. 397, April 3, 2008). To achieve lower discharge values, it is necessary to reduce from Cr(VI) to Cr(III), which is less toxic, and an economic alternative involves biological removal of this compound. Residence time distributions (RTDs) were measured to evaluate the behavior of actual biofilter operation conditions in a biofilter flow. The medium residence time distributions used were 8 and 24 h (recommended by the legislation). To optimize this process, a central composite design was used, considering the initial chromium concentration and pH as the independent variables and the removal of hexavalent chromium as the response. The boundary curves and surface response showed optimal behavior at 3.94 mg/L [Cr(0)] and a pH of 6.2. The removal process of hexavalent chromium is mathematically described by the Michaelis-Menten kinetic model. This model appropriately represents the variation of chromium concentration along the bioreactor.     

Soil microbial community response to hexavalent chromium in planted and unplanted soil

Theories suggest that rapid microbial growth rates lead to quicker development of metal resistance. We tested these theories by adding hexavalent chromium [Cr(VI)] to soil, sowing Indian mustard (Brassica juncea), and comparing rhizosphere and bulk soil microbial community responses. Four weeks after the initial Cr(VI) application we measured Cr concentration, microbial biomass by fumigation extraction and soil extract ATP, tolerance to Cr and growth rates with tritiated thymidine incorporation, and performed community substrate use analysis with BIOLOG GN plates. Exchangeable Cr(VI) levels were very low, and therefore we assumed the Cr(VI) impact was transient. Microbial biomass was reduced by Cr(VI) addition. Microbial tolerance to Cr(VI) tended to be higher in the Cr-treated rhizosphere soil relative to the non-treated systems, while microorganisms in the Cr-treated bulk soil were less sensitive to Cr(VI) than microorganisms in the non-treated bulk soil. Microbial diversity as measured by population evenness increased with Cr(VI) addition based on a Gini coefficient derived from BIOLOG substrate use patterns. Principal component analysis revealed separation between Cr(VI) treatments, and between rhizosphere and bulk soil treatments. We hypothesize that because of Cr(VI) addition there was indirect selection for fast-growing organisms, alleviation of competition among microbial communities, and increase in Cr tolerance in the rhizosphere due to the faster turnover rates in that environment.     

Technological behaviour and recycling potential of spent foundry sands in clay bricks

The feasibility of recycling spent foundry sand in clay bricks was assessed in laboratory, pilot line and industrial trials, using naturally occurring sand as a reference. Raw materials were analyzed by X-ray fluorescence, X-ray diffraction, particle size distribution, and leaching and combined to produce bodies containing up to 35% wt. sand. The extrusion, drying and firing behaviour (plasticity, drying sensitivity, mechanical strength, bulk density, water absorption, and shrinkage) were determined. The microstructure, phase composition, durability and leaching (EN 12457, granular materials, end-life step, European Waste Landfill Directive; NEN 7345, monolithic materials, use-life step, Dutch Building Material Decree) were evaluated for bricks manufactured at optimal firing temperature. These results demonstrate that spent foundry sand can be recycled in clay bricks. There are no relevant technological drawbacks, but the feasibility strongly depends on the properties of the raw materials. Spent foundry sand may be introduced into bricks up to 30% wt. Most of the hazardous elements from the spent foundry sand are inertized during firing and the concentrations of hazardous components in the leachates are below the standard threshold for inert waste category landfill excepting for chromium and lead; however, their environmental risk during their use-life step can be considered negligible.