Utilisation of Supernatants of Pure Cultures of Streptomyces thermocarboxydus NH50 to Reduce Chromium Toxicity and Mobility in Contaminated Soils

Chromium is a heavy metal used in various industrial sectors. Improper handling and storage of chromium-laden effluents or wastes can lead to the pollution of the environment. The most toxic form is the more mobile one: hexavalent chromium Cr(VI). The reduction of Cr(VI) results in the immobilisation of chromium into its less toxic trivalent form Cr(III). This phenomenon may prevent the contamination of groundwater when the soil in the vadose zone is contaminated. Many bacteria have been isolated from contaminated soils and described to reduce Cr(VI) into Cr(III). A new Cr(VI)-reducing strain, identified as a Streptomyces thermocarboxydus,has been isolated and studied in our laboratories for its ability to reduce Cr(VI). This aerobic bacterium, in contrast to other genera described which mediate reduction via enzymes, produces reducing agents into the culture supernatants. Cr(VI) reduction by these substances is accelerated by the presence of small concentration of cupric ions (Cu²⁺). The reducing agent(s) can be easily recovered from the bacterial cultures and used as cell-free solution to treat contaminated soils by an in situ or ex situ processes.     

Composites Produced from Natural Rubber and Chrome-Tanned Leather Wastes: Evaluation of their In Vitro Toxicological Effects for Application in Footwear and Textile Industries

A new composite has been developed from natural rubber and chrome-tanned leather waste for use in footwear and textile industries. The contribution of this material to environmental quality and sustained development should be highligh because chrome tanned leather wastes, a major environmental problem, can be recycled. However, the safety of this new material for human use is questionable, as it is already well reported in the literature that chromium, particularly in its hexavalent oxidation state, can be genotoxic and carcinogenic to living beings. Thus, the aim of this study was to evaluate in vitro biocompatibility of this composite material for possible use in the footwear and textile industries, through cytotoxicity, cell adhesion, and genotoxicity tests. Inductively coupled plasma optical emission spectrometry (ICP-OES) was used to measure both concentrations of total and hexavalent chromium. Based on the findings, it was concluded that the composite exhibits low levels of cytotoxicity and genotoxicity, and possesses favorable properties for initial cell adhesion. Furthermore, it was verified that the composites released low concentrations of chromium and that the predominant species released would be trivalent chromium. The results of the present study open the possibility of the incorporation of solid residues of tanned leather into chromium without necessarily the chromium contained in these residues influences the toxicity and genotoxicity of this new material.     

Optimum Dose Of Lime And Fly Ash For Treatment Of Hexavalent Chromium–Contaminated Soil

The presence of hexavalent chromium, Cr(VI), in soil is an environmental concern due to its effect on human health. The concern arises from the leaching and the seepage of Cr(VI) from soil to groundwater. In this paper, a stabilization technology to prevent this problem was simulated on an artificial soil contaminated with hexavalent chromium. The process is a physico-chemical treatment in which the toxic pollutant is physically entrapped within a solid matrix formed by the pozzolanic reactions of lime and fly ash to reduce its leachability and, therefore, its toxicity. This paper presents the optimum ratio of fly ash and lime in order to stabilize artificial soils contaminated with 0.4 wt.% of Cr (VI) in a brief term process. The degree of chromium released from the soil was evaluated using a modified Toxicity Characteristic Leaching Procedure (TCLP) by US Environmental Protection Agency (EPA). Overall, experimental results showed reduced leachability of total and hexavalent chromium from soils treated with both fly ash and quicklime, and that leachability reduction was more effective with increasing amount of fly ash and quicklime. Stabilization percentages between 97.3% and 99.7% of the initial chromium content were achieved, with Cr(VI) concentration in the TCLP leachates below the US EPA limit for chromium of 5 mg/l. Adequate treatment was obtained after 1 day of curing with just 25% fly ash and 10% quicklime.     

Remedial Process Optimization and Ozone Sparging for Petroleum Hydrocarbon‐Impacted Groundwater

A former natural gas processing station is impacted with total petroleum hydrocarbons (TPH) and benzene. Remedial process optimization (RPO) was conducted to evaluate the effectiveness of the historical air sparging/soil vapor extraction (AS/SVE) system and the current groundwater extraction and treatment system. The RPO indicated that both remedial activities offered no further benefit in meeting remediation goals. Instead, an in situ chemical oxidation (ISCO) system was recommended. Ozone was selected, and the results of a bench test indicated that the ozone demand was 8 to 12 mg ozone/mg TPH and that secondary by‐products would include hexavalent chromium and bromate. A capture zone analysis was conducted through groundwater flow modeling (MODFLOW) to ensure containment of the injected oxidant using the existing groundwater extraction system. Results of a pilot study indicated that the optimum frequency of ozone sparging is 60 minutes in order to reach a maximum radius of influence of 20 feet. TPH concentrations within the treatment zone decreased by 97 percent over two months of ozone sparging. Concentrations of hexavalent chromium and bromate increased from nondetect to 44 and 110 mg/L, respectively, during the ozone sparging but attenuated to nondetectable concentrations within three months of system shut down. ©2016 Wiley Periodicals, Inc.     

Biochemical Treatment of Hydraulically Complex Hexavalent Chromium and Chlorinated Volatile Organic Plumes

Groundwater contaminated with hexavalent chromium (Cr⁺⁶) and chlorinated volatile organic compounds (cVOCs) presents unique in situ remedial challenges in an oxygen‐rich environment. On one hand, chemical oxidation would be effective in treating the cVOCs; however, it would not be appropriate to treat Cr⁺⁶. Biological treatment may be appropriate to treat the Cr⁺⁶; however, the cVOC degradation pathway within these mixed plumes is currently following an abiotic pathway with little to no daughter‐product production. Thus, a blended approach was needed to treat both constituents in situ in an effort to avoid a long‐term, costly pump‐and‐treat solution. This article evaluates an in situ biogeochemical stabilization/reduction strategy by injecting an inorganic carbon‐based remedial additive into the geologic and hydrogeologic environment to decrease concentrations within the commingled Cr⁺⁶ and cVOC plume. The concept involves creating favorable redox reducing conditions to shift the groundwater geochemical equilibrium from the more toxic Cr⁺⁶ to the less toxic trivalent chromium (Cr⁺³), with the final outcome being a conversion to chrome oxide that molecularly fixes to the soil grains. In addition, reducing conditions developed for chromium reduction should result in an increase in the available natural formation iron that should further enhance the natural abiotic reduction of cVOCs. © 2013 Wiley Periodicals, Inc.     

Effects of the type of sintering atmosphere on the chromium leachability of thermal-treated municipal solid waste incinerator fly ash

The sintering process offers an opportunity to combine detoxification and resource recovery for the treatment of municipal solid waste (MSW) incinerator fly ash. However, the chromium (Cr) in the sintered fly ash becomes more readily leachable with increasing sintering time and temperature, thus posing severe threats to the environment and human health when the sintered ash is recycled or reused. This study investigated the enhanced leachability of fly ash containing Cr, by heating the chromium (III) oxide (Cr2O3)-spiked fly ash to 800 degrees C in atmospheres containing air, nitrogen gas (N2), and 5% H2 + 95% N2, respectively. The results indicated that trivalent chromium was converted to its soluble hexavalent form during sintering in the air atmosphere; whereas sintering in a nitrogen atmosphere significantly reduced the leachability of Cr due to lack of oxygen (O2) to oxidize. The effects of the sintering temperature on the total chromium content and the leaching concentration in the toxicity characteristic leaching procedure (TCLP) extract are also discussed.     

Rapid-extraction oxidation process to recover and reuse copper chromium and arsenic from industrial wood preservative sludge

Chromated copper arsenate (CCA) wood preservative can form insoluble sludges when the hexavalent chromium component is reduced by wood extractives, wood particles and preservative additives in the solution. This sludge accumulates in treating solution work tanks, sumps and in-line filters and must be disposed of as hazardous wastes by waste disposal companies at high costs. A number of commercial sludges were investigated and found to contain 18-94% copper, chromium and arsenic as oxides combined with sand, oil, wood particles, additives and wood extractives. We have developed a multi-stage recycling process whereby approximately 97% of the CCA components are recovered from the sludge. It involves extraction with sodium hypochlorite to remove and oxidize chromium (more than 90%) and extract most of the arsenic (approx. 80%) followed by extraction of the copper and remaining arsenic and chromium with phosphoric acid. The phosphoric acid extract contains some trivalent chromium, which is subsequently oxidized by sodium hypochlorite. The combined oxidized extract containing CrVI, CuII and AsV was compatible with CCA treating solutions and could be re-used commercially for treating wood without having a significant effect on the preservative fixation rate or the leach resistance of the treated wood. A cost analysis showed that the economic savings from recovery of CCA chemicals and reduced landfill costs exceeded the variable costs for materials and energy for the process by as much as Can $966 per tonne of sludge if sodium sulfite can be acquired in bulk quantities for the process.     

Innovative applications of subgrade biogeochemical reactors: Three case studies

Subgrade biogeochemical reactors (SBGRs) are an in situ remediation technology shown to be effective in treating contaminant source areas and groundwater hot spots, while being sustainable and economical. This technology has been applied for over a decade to treat chlorinated volatile organic compound source areas where groundwater is shallow (e.g., less than approximately 30 feet below ground surface [ft bgs]). However, this article provides three case studies describing innovative SBGR configurations recently developed and tested that are outside of this norm, which enable use of this technology under more challenging site conditions or for treatment of alternative contaminant classes. The first SBGR case study addresses a site with groundwater deeper than 30 ft bgs and limited space for construction, where an SBGR column configuration reduced the maximum trichloroethene (TCE) groundwater concentration from 9,900 micrograms per liter (μg/L) to <1 μg/L (nondetect) within approximately 15 months. The second SBGR is a recirculating trench configuration that is supporting remediation of a 5.7‐acre TCE plume, which has significant surface footprint constraints due to the presence of endangered species habitat. The third SBGR was constructed with a new amendment mixture and reduced groundwater contaminant concentrations in a petroleum hydrocarbon source area by over 97% within approximately 1 year. Additionally, a summary is provided for new SBGR configurations that are planned for treatment of additional classes of contaminants (e.g., hexavalent chromium, 1,4‐dioxane, dissolved explosives constituents, etc.). A discussion is also provided describing research being conducted to further understand and optimize treatment mechanisms within SBGRs, including a recently developed sampling approach called the aquifer matrix probe.     

Factors affecting sodium hypochlorite extraction of CCA from treated wood

Significant amounts of chromated copper arsenate (CCA) treated wood products, such as utility poles and residential construction wood, remain in service. There is increasing public concern about environmental contamination from CCA-treated wood when it is removed from service for reuse or recycling, placed in landfills or burned in commercial incinerators. In this paper, we investigated the effects of time, temperature and sodium hypochlorite concentration on chromium oxidation and extraction of chromated copper arsenate from CCA-treated wood (Type C) removed from service. Of the conditions evaluated, reaction of milled wood with sodium hypochlorite for one hour at room temperature followed by heating at 75 °C for two hours gave the highest extraction efficiency. An average of 95% Cr, 99% Cu and 96% As could be removed from CCA-treated, milled wood by this process. Most of the extracted chromium was oxidized to the hexavalent state and could therefore be recycled in a CCA treating solution. Sodium hypochlorite extracting solutions could be reused several times to extract CCA components from additional treated wood samples.     

Mineralogy and pore water chemistry of a boiler ash from a MSW fluidized-bed incinerator

This paper presents an investigation of the mineralogy and pore water chemistry of a boiler ash sampled from a municipal solid waste fluidized-bed incinerator, subject to 18 months of dynamic leaching in a large percolation column experiment. A particular focus is on the redox behaviour of Cr(VI) in relation to metal aluminium Al⁰, as chromium may represent an environmental or health hazard. The leaching behaviour and interaction between Cr(VI) and Al⁰ are interpreted on the basis of mineralogical evolutions observed over the 18-month period and of saturation indices calculated with the geochemical code PhreeqC and reviewed thermodynamic data. Results of mineralogical analyses show in particular the alteration of mineral phases during leaching (e.g. quartz and metal aluminium grains), while geochemical calculations suggest equilibria of percolating fluids with respect to specific mineral phases (e.g. monohydrocalcite and aluminium hydroxide). The combination of leaching data on a large scale and mineralogical analyses document the coupled leaching behaviour of aluminium and chromium, with chromium appearing in the pore fluids in its hexavalent and mobile state once metal aluminium is no longer available for chromium reduction.     

Uptake of chromium by Aspergillus foetidus

Aspergillus foetidus has the ability to take up chromium during the stationary phase of growth and under growth-nonsupportive conditions. We observed a 97% decrease in hexavalent chromium (initial concentration 5 µg/g) at the end of 92 h of growth, which may be due to its reduction to Cr (III) and/or complexation with organic compounds released due to the metabolic activity of the fungus. Replacement culture studies under growth-nonsupportive conditions revealed that the maximum uptake of Cr (VI) at pH 7.0 is 2 mg/g of dry biomass. At low or high pH values, Cr (VI) uptake is significantly reduced. In addition, the initial rate of total chromium uptake is also enhanced by higher biomass concentrations and the presence of glucose. The results obtained through this investigation indicate the possibility of treating waste effluents containing hexavalent chromium using Aspergillus foetidus.     

Thermal treatment and non-thermal technologies for remediation of manufactured gas plant sites

More than 1500 manufactured gas plant (MGP) sites exist throughout the U.S. Many are contaminated with coal tar from coal-fueled gas works which produced ‘town gas’ from the mid-1800s through the 1950s.^1,2 Virtually all old U.S. cities have such sites. Most are in downtown areas as they were installed for central distribution of manufactured gas. While a few sites are CERCLA/Superfund, most are not. However, the contaminants and methods used for remediation are similar to those used for Superfund clean-ups of coal tar contamination from wood-treating and coke oven facilities. Clean-up of sites is triggered by regulatory pressure, property transfers and re-development as well as releases to the environment — in particular, via groundwater migration. Due to utility de-regulation, site clean-ups may also be triggered by sale of a utility or of a specific utility site to other utilities. Utilities have used two approaches in dealing with their MGP sites. The first is ‘do nothing and hope for the best’. History suggests that, sooner or later, these sites become a bigger problem via a release, citizen lawsuit or regulatory/public service commission intervention. The second, far better approach is to define the problem now and make plans for waste treatment or immobilization. This paper describes recent experience with a high capacity/low cost thermal desorption process for this waste and reviews non-thermal technology, such as bio-treatment, capping, recycling, and dig and haul. Cost data is provided for all technologies, and a case study for thermal treatment is also presented.     

Effect of microbial activity on the mobility of chromium in soils

The effect of microbial activity on the chemical state of chromium, in a contaminated soil located in the Rh?ne-Alpes region (France), has been investigated. This soil contained 4,700 mg kg(-1) Cr, with about 40% present in the soluble hexavalent form. Indigenous microbial activity was found to significantly reduce Cr(VI) to the less mobile form (III) when the soil was incubated at 30 degrees C in an aqueous medium containing glucose and nutrients. A Cr(VI)-reducing strain of Streptomyces thermocarboxydus was isolated from the contaminated soil. The strain was found to metabolize Cr(VI) in a similar manner as an exogenous inoculum of Pseudomonas fluorescens LB300, and to precipitate chromium as a Cr oxyhydroxide with a gammaCrOOH-like local structure. The Cr(VI)-reducing activity of S. thermocarboxydus was induced, or significantly accelerated, by the aggregation of bacterial cells or their adhesion to suspended solid particles, and was stimulated in pure culture by glycerol and chromate.     

Look at groundwater quality to set VOC cleanup levels

In 1981, the Arizona Department of Health Services (ADHS) discovered groundwater contamination by solvents and chromium at the Phoenix Goodyear Airport (PGA), just outside the city of Phoenix. ADHS and the U.S. EPA sampled the site for the next two years, finding that eighteen of their wells were contaminated with trichloroethene (TCE), six exceeding ADHS's action level of five micrograms per liter (μg/l). In 1983, the PGA site was added to the National Priorities List, and, in 1984, EPA began a $3 million remedial investigation, focusing on soils and groundwater. This article discusses how that investigation inspired the authors to develop a stream-lined evaluation method for PGA's volatile organic compounds (VOCs), the process for establishing VOC cleanup levels, and the $26 million of remediation work needed to be done at the site. The heart of this effort is a computer program called VLEACH, loosely standing for VOC-LEACHing, which anticipates the influence of VOCs on PGA's groundwater, even as remediation proceeds.     

Chromium removal from groundwater using simple physical/chemical treatment

Groundwater at a Superfund site in west Texas has been found to contain chromium at concentrations exceeding EPA's drinking water standard of .05 mg/l. Alternative treatment methods for this site were investigated; this article presents the evaluation of a physicochemical treatment system, in which removal of total chromium to levels below the drinking water standard was achieved through reduction of hexavalent chromium and subsequent removal by coprecipitation with iron. Costs for the construction of the pilot and full-scale systems are also discussed.     

Stabilization of As, Cr, Cu, Pb and Zn in soil using amendments--a review

The spread of contaminants in soil can be hindered by the soil stabilization technique. Contaminant immobilizing amendments decrease trace element leaching and their bioavailability by inducing various sorption processes: adsorption to mineral surfaces, formation of stable complexes with organic ligands, surface precipitation and ion exchange. Precipitation as salts and co-precipitation can also contribute to reducing contaminant mobility. The technique can be used in in situ and ex situ applications to reclaim and re-vegetate industrially devastated areas and mine-spoils, improve soil quality and reduce contaminant mobility by stabilizing agents and a beneficial use of industrial by-products. This study is an overview of data published during the last five years on the immobilization of one metalloid, As, and four heavy metals, Cr, Cu, Pb and Zn, in soils. The most extensively studied amendments for As immobilization are Fe containing materials. The immobilization of As occurs through adsorption on Fe oxides by replacing the surface hydroxyl groups with the As ions, as well as by the formation of amorphous Fe(III) arsenates and/or insoluble secondary oxidation minerals. Cr stabilization mainly deals with Cr reduction from its toxic and mobile hexavalent form Cr(VI) to stable in natural environments Cr(III). The reduction is accelerated in soil by the presence of organic matter and divalent iron. Clays, carbonates, phosphates and Fe oxides were the common amendments tested for Cu immobilization. The suggested mechanisms of Cu retention were precipitation of Cu carbonates and oxy-hydroxides, ion exchange and formation of ternary cation-anion complexes on the surface of Fe and Al oxy-hydroxides. Most of the studies on Pb stabilization were performed using various phosphorus-containing amendments, which reduce the Pb mobility by ionic exchange and precipitation of pyromorphite-type minerals. Zn can be successfully immobilized in soil by phosphorus amendments and clays.     

Removal of Cr(VI) from contaminated soil by electrokinetic remediation

A new process for the removal of hexavalent chromium [Cr(VI)] contaminated soil is described. The process provides for an efficient removal of anionic chemicals from contaminated soils. Chromate anions were removed from the soil to the anodic reservoir by the moving force of electromigration. In this process, the chromate anions that accumulate in the anodic reservoir are simultaneously eliminated by using a column packed adsorbent. The adsorbent (immobilized tannin) used was chemically incorporated into cellulose. Cr(VI) was found to be adsorbed to this adsorbent efficiently. In the electrokinetic process, the pH of the aqueous solution in the anodic reservoir was decreased by the electrolysis of water. In the present study, the pH of the solution in the anodic reservoir is maintained at pH 6 by the addition of an aqueous alkaline solution during the electrokinetic process. The advantage of pH control is that it promotes the release of Cr(VI) from the soil by electromigration, thus permitting the maximum adsorption of Cr(VI) on the immobilized tannin. Simultaneous collection of Cr(VI) from the anodic reservoir leads to the protection from secondary contamination with Cr(VI).     

Using wind to power a groundwater circulation well—preliminary results

In areas of the country where the U.S. Department of Energy has classified the available wind resources as Class 3 or greater, the use of wind turbines to provide power to relatively small remediation systems such as groundwater circulation wells may be technically and economically feasible. Groundwater circulation wells are a good candidate technology to couple with renewable energy, because the remediation system removes contamination from the subject aquifer with no net loss of the groundwater resource, while the wind turbine does not create potentially harmful air emissions. Wind data collected in the vicinity of the former Nebraska Ordnance Plant Superfund site were used to select a wind turbine system to provide a portion of the energy necessary to power a groundwater circulation well located in an area of high trichloroethylene groundwater contamination. Because utility power was already installed at the remediation system, a 10 kW grid inter‐tie wind turbine system supplements the utility system without requiring batteries for energy storage. The historical data from the site indicate that the quantity of energy purchased correlates poorly with the quantity of groundwater treated. Preliminary data from the wind turbine system indicate that the wind turbine provides more energy than the remediation system treatment components and the well submersible pump require on a monthly average. The preliminary results indicate that the coupling of wind turbines and groundwater circulation wells may be an attractive alternative in terms of the system operation time, cost savings, and contaminant mass removal. © 2004 Wiley Periodicals, Inc.     

Pollutant source identification and allocation: Advances in hydrocarbon fingerprinting

Often liability for environmental damage and cleanup of contaminated sites is made difficult, especially with chemically complex environments containing different pollutants, by the inability to differentiate potential sources (or “owners”) of pollutants from each other. As a result, unnecessary costs may be associated with having to assume financial responsibility for alleged contamination of a site. This article reviews the advances in chemical fingerprinting as a tool in identifying and differentiating sources of hydrocarbon pollutants in chemically complex environments. Appropriate hydrocarbon target analytes and required analytical methods for hydrocarbon fingerprinting are discussed, and new interpretative tools are presented that may be applied to contaminated soil, sediment, and groundwater environmental situations. With these analytical and interpretative techniques, an appropriate allocation of chemical contamination and costs at a site can be made.     

When the Going Gets Tough,Communities Believe It's Time to Optimize and Adapt

The people who live in the communities where complex groundwater sites are located are as diverse as the country itself, but those who fight for the cleanup of our groundwater recognize that total cleanup may be difficult, if not impossible, in our lifetimes. Still, as explained in a December 2013 joint letter to US EPA, we want those who are responsible for environmental protection, be they polluters, developers, or regulatory agencies, to try harder before admitting defeat. In Mountain View, California, community activists have developed criteria for the adaptive cleanup of the Moffett‐MEW Regional Plume of TCE groundwater contamination that emphasizes areas with high contaminant mass, source areas, locations that reduce the need for long‐term vapor intrusion mitigation, properties where the detectable plume encroaches on residential areas, schools, and other sensitive uses, and areas planned for reuse. In many other communities, trust is the key to developing community support for remedial strategies. Communities that are listened to tend to feel more empowered. Empowered communities tend to offer more constructive advice. Decision makers tend to listen to communities that offer constructive advice. In summary, when the cleanup going gets tough, empowered communities believe that it is time to optimize and adapt, not to give up. © 2014 Wiley Periodicals, Inc.