Direct and indirect methods for chromium identification in industrial wastes

The examinations of selected wastes and stream sediments from the vicinity of a chemical plant by sequential extraction procedures and direct methods, SEM/EDX and XRD, were carried out in order to identify the different forms of chromium, particularly as they are released to potential mobility. The results show that the top and bottom waste samples contain 37,756 and 53,650 μg g¹ Cr, respectively, but about 7% and 2% of the total chromium type Cr(VI). The chemical extraction results show that the mobility of Cr in the upper part of the waste pile is significantly higher than in the bottom section; the exchangeable form of Cr accounts for 25% and < 1%, respectively, the last one irrespective of redox conditions. About 50% of Cr is associated with the reducible fraction of the top waste, and similar with the residual fraction in the bottom waste. Oxidation of the bottom waste shift some portion of Cr from residual to the moderately reducible fraction. The major Cr-forms in the river sediments are compounded with Fe-oxides. The < 2 μm size fraction of the selected sediment sample, particular enriched in chromium contained up to 73,000 μg g¹ Cr with about 95% of this in the moderately reducible fraction, predominantly bound with oxyhydroxides. SEM/EDX and XRD analysis of wastes and river sediment indicate that the main insoluble Cr-phase is ferroan — (Mg, Fe) (Cr, Al)²O⁴ which would be dissolved mainly in the residual fraction.     

Stabilization of Heavy Metal Containing Hazardous Wastes with Byproducts from Advanced Clean Coal Technology Systems

ABSTRACT

The purpose of this investigation was to evaluate the success of residues from advanced Clean Coal Technology (CCT) systems as stabilization agents for heavy metal containing hazardous wastes. In the context examined here, stabilization refers to techniques that reduce the toxicity of a waste by converting the hazardous constituents to a less soluble, mobile, or toxic form.¹ Three advanced CCT byproducts were used: coal waste-fired circulating fluidized bed combustor residue, pressurized fluidized bed combustor residue, and spray drier residue. Seven metal-laden hazardous wastes were treated: three contaminated soils, two air pollution control dusts, wastewater treatment plant sludge, and sandblast waste. Each of the seven hazardous wastes was treated with each of the three CCT byproducts at dosages of 10, 30, and 50% by weight (byproduct:waste). The treatment effectiveness of each mixture was evaluated by the Toxicity Characteristic Leaching Procedure. Of the 63 mixtures evaluated, 21 produced non-hazardous residues. Treatment effectiveness can likely be attributed to mechanisms such as precipitation and encapsulation due to the formation of hydrated calcium silicates and calcium sulfo-alu-minates. Results indicate that these residues have potential beneficial uses to the hazardous waste treatment community, possibly substituting for costly treatment chemicals.     

Burning Chemical Wastes as Fuels in Cement Kilns

Hazardous wastes in the environment represent one of our most serious problems. Ever increasing quantities of toxic wastes have contaminated our land, air, and water. Lack of adequate hazardous waste disposal facilities is a critical problem. Landfilling toxic wastes is no longer considered safe. The tragedy of the Love Canal has demonstrated the need for proper hazardous waste disposal facilities. The best organic chemical waste disposal method is process incineration. Cement kilns have been used for burning toxic chemical industrial wastes in Canada, Michigan, New York, Sweden, etc. Existing cement kilns, when properly operated, can destroy most organic chemical wastes. Even the most complex chlorinated hydrocarbons, including PCB can be completely destroyed during normal cement kiln operations, with minimal emissions to the environment. Burning toxic chemical wastes in cement kilns, and other mineral industries, is mutually beneficial to both industry, who generates such wastes, and to society and government, who want to dispose properly of such wastes in a safe, environmentally acceptable manner. The added benefit of energy conservation is important, since large quantities of valuable fuel can be saved in the manufacture of cement when such techniques are employed.     

典型危险废物的工程力学特性

掌握填埋废物的工程力学特性是确保危险废物填埋堆体稳定性的重要前提条件,因此,针对6种典型危险废物的工程力学特性开展了调查研究.研究结果表明,污泥类危险废物的含水率和有机质含量远高于非污泥类危险废物,而前者的比重则显著低于后者.污泥类危险废物的渗透系数相对较小,比污染土壤和飞灰炉渣混合物的渗透系数小1个数量级,比滤池填料的渗透系数小2个数量级.不同危险废物的无侧限抗压强度排序为:飞灰炉渣混合物(314.3 kPa)和滤池填料(278.9 kPa)＞污染土壤(124.9 kPa)＞杭州氧气厂污泥(68.6 kPa)、锌铬污泥(71.4 kPa)、油泥(58.4 kPa).不同危险废物的粘聚力排序为:飞灰炉渣混合物(40.8 kPa)、滤池填料(31.1 kPa)＞污染土壤(20.9 kPa)＞杭州氧气厂污泥(1.94kPa)、锌铬污泥(3.10 kPa)、油泥(1.81 kPa).此外,不同危险废物的内摩擦角差异相对较小,其变化范围在18.8°～35.0°之间.综合分析可知,飞灰炉渣混合物和滤池填料的工程力学特性较好,而污泥类危险废物的工程力学特性则较差.     

Treatment Technologies For Hazardous Wastes: Part IV A Review of Alternative Treatment Processes for Metal Bearing Hazardous Waste Streams

The U.S. Congress and the U.S. Environmental Protection Agency believe that treatment and recovery techniques should be given maximum priority when considering methods for managing the nation's generated hazardous waste. A prohibition for the disposal of certain categories of hazardous wastes either directly onto or into the land without being treated to an accepted degree prior to such disposal practice has been promulgated.¹ Wastes containing toxic metals and cyanide complexes have been selected as a group to be restricted. Due to the high generation rate associated with this category, a large capacity of waste treatment processing will be required. Existing and emerging treatment alternatives which are or have the potential to be employed for waste treatment of metal bearing wastes are presented in this paper.     

Vermicomposting as an advanced biological treatment for industrial waste from the leather industry

The leather industry (tanneries) generates high amounts of toxic wastes, including solid and liquid effluents that are rich in organic matter and mineral content. Vermicomposting was studied as an alternative method of treating the wastes from tanneries. Vermicompost was produced from the following tannery residues: tanned chips of wet-blue leather, sludge from a liquid residue treatment station, and a mixture of both. Five hundred earthworms (Eisenia fetida) were added to each barrel. During the following 135 days the following parameters were evaluated: pH, total organic carbon (TOC), organic matter (OM), cation exchange capacity (CEC), C:N ratio, and chromium content as Cr (III) and Cr (VI). The results for pH, TOC and OM contents showed decreases in their values during the composting process, whereas values for CEC and total nitrogen rose, indicating that the vermicompost reached maturity. For chromium, at 135 days, all values of Cr (VI) were below the detectable level. Therefore, the Cr (VI) content had probably been biologically transformed into Cr (III), confirming the use of this technique as an advanced biological treatment. The study reinforces the idea that vermicomposting could be introduced as an effective technology for the treatment of industrial tannery waste and the production of agricultural inputs.     

Removal of chromium from synthetic plating waste by zero-valent iron and sulfate-reducing bacteria.

Experiments were conducted to evaluate the potential of zero-valent iron and sulfate-reducing bacteria (SRB) for reduction and removal of chromium from synthetic electroplating waste. The zero-valent iron shows promising results as a reductant of hexavalent chromium (Cr+6) to trivalent chromium (Cr+3), capable of 100% reduction. The required iron concentration was a function of chromium concentration in the waste stream. Removal of Cr+3 by adsorption or precipitation on iron leads to complete removal of chromium from the waste and was a slower process than the reduction of Cr+6. Presence SRB in a completely mixed batch reactor inhibited the reduction of Cr+6. In a fixed-bed column reactor, SRB enhanced chromium removal and showed promising results for the treatment of wastes with low chromium concentrations. It is proposed that, for waste with high chromium concentration, zero-valent iron is an efficient reductant and can be used for reduction of Cr+6. For low chromium concentrations, a SRB augmented zero-valent iron and sand column is capable of removing chromium completely.     

1985 Directory of Governmental Air Pollution Control Agencies

Abstract

Clay that contains kaolinite has been used extensively as a raw material for manufacturing of bricks and china at 900–1100 °C. This study used clay to stabilize the contaminant chromium(VI) [Cr(VI)] through a heating process at 500–1100 °C. X-ray absorption spectroscopic results indicated that the 500–900 °C heating process transformed hazardous Cr(VI) to nontoxic Cr(III); Cr₂O₃ was the species detected as most abundant. The 1100 °C heating process caused the formation of Cr₂SiO₅, which was not detected in the samples heated at 500–900 °C. Fourier transformed extended X-ray absorption fine structure spectra were fitted by use of WinXAS software. Phase shifts and backscatter(ing) amplitudes for specific atom pairs, based on the crystallographic data for CrO₃ and Cr₂O₃, were theoretically calculated with the FEFF software. The processed XAS data show that the first shell coordination numbers were similar to each other as the temperature was increased from 500 to 900 °C and 1100 °C, implying that their Cr(III) crystallite size was relatively similar. The interatomic distance between the target center element and the first shell for the 500– 1100 °C samples was 1.98Å. The Debye-Waller factor for the 1100 °C sample was increased compared with the 500 and 900 °C samples and probably indicates the formation of Cr₂SiO₅.     

Thermal Encapsulation of Metals in Superfund Soils

Abstract

Superfund sites frequently contain both heavy metals and organic hazardous waste. If not properly controlled, the metals may be changed to a more leachable form and may also be emitted to the atmosphere via the exhaust stack. This paper documents a batch kiln R&D test program to solve these metal-related problems. It was performed under the U.S. EPA’s SITE (Superfund Innovative Technology Evaluation) Emerging Technology Program. Allis Mineral Systems has developed the Thermal Encapsulation Process. Metals with limits set by EPA’s TCLP (Toxicity Characteristic Leaching Procedure) test and BIF (boiler and industrial furnace) stack emission regulations, such as cadmium, chromium, and lead, are the initial target of this process. This process, while unproven in these areas, may also apply to mixed waste (EPA hazardous waste/low-level radioactive wastes) and may also benefit commercial hazardous waste or Superfund thermal treatment systems. The results of the SITE tests were positive: strong, durable nodules were produced with excellent crush strength and improved resistance to leaching. Feed preparation, particularly control of moisture content, was found to be a key element in initiation of agglomeration. A good correlation was found between decreasing TCLP metals leachate levels and increasing crush strength.     

Hazardous Waste Minimization: Part VI Waste Minimization in the Foundry Industry

The foundry industry is a major consumer of waste materials (scrap). Unfortunately, the recycling of these waste materials can result in the generation of hazardous wastes that must be properly managed at a significant cost. This article focuses on two waste streams in the foundry industry; calcium carbide desulfurization slag and melt emission control residuals. The author presents an overview of how foundries have evaluated different waste management options with the ultimate goal of minimizing the generation of hazardous waste.     

Remediation of Cr(VI) from chromium slag by biocementation

Here we demonstrate a calcifying ureolytic bacterium Bacillus sp. CS8 for the bioremediation of chromate (Cr(VI)) from chromium slag based on microbially induced calcite precipitation (MICP). A consolidated structure like bricks was prepared from chromium slags using bacterial cells, and five stage Cr(VI) sequential extraction was carried out to know their distribution pattern. Cr(VI) mobility was found to significantly be decreased in the exchangeable fraction of Cr slag and subsequently, the Cr(VI) concentration was markedly increased in carbonated fraction after bioremediation. It was found that such Cr slag bricks developed high compressive strength with low permeability. Further, leaching behavior of Cr(VI) in the Cr slag was studied by column tests and remarkable decrease in Cr(VI) concentration was noticed after bioremediation. Cr slags from columns were characterized by SEM–EDS confirming MICP process in bioremediation. The incorporation of Cr(VI) into the calcite surface forms a strong complex that leads to obstruction in Cr(VI) release into the environment. As China is facing chromium slag accidents at the regular time intervals, the technology discussed in the present study promises to provide effective and economical treatment of such sites across the country, however, it can be used globally.     

Advantages and risks of using steel slag in preparing composts from raw organic waste

It had been reported that iron and manganese oxides in steel slag enhanced the production of humic acid (HA) from low-molecular-weight compounds, such as phenolic acids, amino acids, and saccharides. In the present study, this function of steel slag was applied to the composting of raw organic wastes (ROWs). The degree of humification of HAs is an important factor in evaluating compost quality. Thus, HAs were extracted from the prepared composts and the humification parameters were determined, in terms of elemental compositions, acidic functional group contents, molecular weights, spectroscopic parameters from UV–vis absorption and ¹³C NMR spectra. The timing for adding steel slag affected the degree of humification of HAs in the composts. The weight average molecular weight of a HA when slag was added initially (29 kDa) was significantly higher than when slag was added after elevating the temperature of the compost pile (17–18 kDa). These results show that ROWs are decomposed to low-molecular-weight compounds after the pile temperature is elevated and the presence of slag enhances the polycondensation of these compounds to produce HAs with a higher degree of humification. Because the slag used in the present study contained several-tens ng g^?1 to several μg g^?1 of toxic elements (B, Cu, Cr, and Zn), leaching tests for these elements from the prepared composts were carried out. Levels for leaching boron from composts prepared by adding slag (0.2–0.4 mg L^?1) were obviously higher than the corresponding levels without slag (0.05 mg L^?1).     

Mercury Measurement and Its Control: What We Know,Have Learned,and Need to Further Investigate

Disposal of mercury waste has always provided unique challenges due to its high degree of complexity and volatility. This study evaluated the feasibility of using waste LF slag to form a cementitious matrix capable of providing an effective stabilization/solidification solution for the treatment of mercury wastes. The new matrix was synthesized and simulated through a combination of alkali activation and autoclaving process and doped with mercury nitrate at increasing dosage while monitoring the final form of the mercury and its effects on the mineral stability and structure of the new matrix. Compressive strength of up to 20 N/mm² was achievable for the original matrix. Promising results were obtained in terms of reduced leachability of the mercury when compared to ordinary Portland cement systems at low doping concentration of around 0.5% by weight. A series of precipitation reactions was found to be the main cause responsible for this successful stabilization, especially the metal sulfide precipitation that occurred with the sulfur present in the original waste LF slag.

Implications: Using waste to treat waste as a concept is a new approach that not only solves waste disposal problems but also minimizes the toxicity and the potential hazard of leaching of heavy metals. This study evaluated the feasibility of using waste ladle furnace slag generated from steel-making industries to form a cementitious matrix capable of providing an effective stabilization/solidification solution for the treatment of mercury-containing wastes. Promising results were obtained, and it clearly showed this approach is feasible, which could be a one-stone-kills-two-birds solution for mercury stabilization as well as an industrial waste disposal problem.     

Nopalea cochenillifera, a potential chromium (VI) hyperaccumulator plant

Hexavalant chromium [Cr(VI)] tolerance and accumulation in in vitro grown Nopalea cochenillifera Salm. Dyck. plants was investigated. A micropropagation protocol was establish for a rapid multiplication of N. cochenillifera and [Cr(VI)] tolerance and accumulation was studied in in vitro grown cultures. Cr concentration was estimated by atomic absorption spectroscopy in roots and shoots to confirm plant’s hyperaccumulation capacity. Plants showed tolerance up to 100 μM K₂Cr₂O₇ without any significant changes in root growth after 16 days treatment; whereas, chlorophyll content in plants treated with 1 and 10 μM K₂Cr₂O₇ were not so different than the control plant. The levels of lipid peroxidation and protein oxidation increased significantly (p?<?0.01) with increasing concentration of chromium. Exposures of N. cochenillifera to lower concentrations of K₂Cr₂O₇ (≤10 μM) induced catalase (CAT) and superoxide dismutase (SOD) significantly (p?<?0.001) but higher concentrations of K₂Cr₂O₇ (>100 μM) inhibited the activities of CAT and SOD. Roots accumulated a maximum of 25,263.396?±?1,722.672 mg?Cr?Kg^?1 dry weight (DW); while the highest concentration of Cr in N. cochenillifera shoots was 705.714?±?32.324 mg?Cr?Kg^?1?DW. N. cochenillifera could be a prospective hyperaccumulator plant of Cr(VI) and a promising candidate for phytoremediation purposes.     

Bioadsorption and bioaccumulation of chromium trivalent in Cr(III)-tolerant microalgae: A mechanisms for chromium resistance

Anthropogenic activity constantly releases heavy metals into the environment. The heavy metal chromium has a wide industrial use and exists in two stable oxidation states: trivalent and hexavalent. While hexavalent chromium uptake in plant cells has been reported that an active process by carrying essential anions, the cation Cr(III) appears to be taken up inactively. Dictyosphaerium chlorelloides (Dc1M), an unicellular green alga is a well-studied cell biological model organism. The present study was carried out to investigate the toxic effect of chromium exposures on wild-type Cr(III)-sensitive (Dc1M^wt) and Cr(III)-tolerant (Dc1M^Cr(III)R30) strains of these green algae, and to determine the potential mechanism of chromium resistance. Using cell growth as endpoint to determine Cr(III)-sensitivity, the IC₅₀₍₇₂₎ values obtained show significant differences of sensitivity between wild type and Cr(III)-tolerant cells. Scanning electron microscopy (SEM) showed significant morphological differences between both strains, such as decrease in cell size or reducing the coefficient of form; and transmission electron microscopy (TEM) revealed ultrastructural changes such as increased vacuolization and cell wall thickening in the Cr(III)-tolerant strain with respect to the wild-type strain. Energy dispersive X-ray analysis (SEM/XEDS) revealed that Cr(III)-tolerant D. chlorelloides cells are able to accumulate considerable amounts of chromium distributed in cell wall (bioadsorption) as well as in cytoplasm, vacuoles, and chloroplast (bio-accumulation). Morphological changes of Cr(III)-tolerant D. chlorelloides cells and the presence of these electron-dense bodies in their cell structures can be understood as a Cr(III) detoxification mechanism.     

Treatment of Nonhazardous Petroleum-Contaminated Soils by Thermal Desorption Technologies

Spills, leaks, and accidental discharges of petroleum products have contaminated soil at thousands of sites in the United States. One remedial action technique for treating petroleum contaminated soil is the use of thermal desorption technologies.

This paper describes key elements of the U.S. Environmental Protection Agency report titled “Thermal Desorption Applications Manual for Treating Nonhazardous Petroleum Contaminated Soils.”¹ The applications manual describes the types, mechanical and operating characteristics of thermal desorption technologies that are commercially available to treat petroleum-contaminated soils. It also provides step-by-step procedures to rate the critical success factors influencing the general applicability of thermal desorption at a particular site. These factors include site, waste and soil characteristics, regulatory requirements, and process equipment design and operating characteristics. Procedures are provided to determine the types of thermal desorption systems that are most technically suitable for a given application and to determine whether on-site or off-site treatment is likely to be the most cost-effective alternative. Key factors that determine process economics are identified, and estimated cost ranges for treating petroleum-contaminated soils are presented. Spreadsheets are provided that can be used for performing cost analyses for specific applications.

The aforementioned report is applicable only to the treatment of petroleum-contaminated soils that are exempt from being classified as hazardous wastes under the Resource Conservation and Recovery Act (RCRA) or as toxic materials under the Toxic Substances Control Act (TSCA). Although much of the technical discussion in this paper is applicable to the treatment of both nonhazardous and hazardous ortoxic materials, permitting requirements and treatment costs are significantly different forthe individual categories of waste materials.     

Simultaneous reduction of Cr(VI) and oxidation of As(III) by Bacillus firmus TE7 isolated from tannery effluent

Hexavalent chromium [Cr(VI)] and arsenite [As(III)] are the most toxic forms of chromium and arsenic respectively, and reduction of Cr(VI) to Cr(III) and oxidation of As(III) to As(V) has great environmental implications as they affect toxicity and mobility of these toxic species. Bacillus firmus strain TE7, resistant to chromium and arsenic was isolated from tannery effluent. The strain exhibited ability to reduce Cr(VI) and oxidize As(III). It reduced 100 mg L^?1 Cr(VI) within 60 h in nutrient broth and oxidized 150 mg L^?1 As(III) within 10 h in minimal medium. It also completely reduced 15 mg L^?1 Cr(VI) and oxidized 50 mg L^?1 of As(III) simultaneously in minimal medium. To the best of our knowledge, this is the first bacterial strain showing simultaneous reduction of Cr(VI) and oxidation of As(III) and is a potential candidate for bioremediation of environments contaminated with these toxic metal species.     

Wind Tunnel Testing of Open Top Field Chambers for Plant Effects Assessment

ABSTRACT

This study reports the first field measurements of airborne exavalent chromium (Cr(vi)) in southwestern Ontario. Hexavalent chromium was identified as an inhalation carcinogen and an air toxic of concern during the 1991-93 Windsor Air Quality Study. The results of that study indicated that approximately 20% of the routinely monitored ambient airborne chromium (Cr) was in the hexavalent form. In addition, the range of carcinogenic health risks attributable to airborne Cr(vi) was determined to be between 1.4 x IO⁶ and 3.0 x 10^-4 for people living in the Windsor area. During the summer of 1993, analyses of concurrent indoor and outdoor 24-hour air quality samples taken at 33 residences in Hamilton resulted in geometric mean Cr(vi) concentrations of 0.20 r|g/m³ and 0.55 r|g/m³, respectively, and little or no relationship between the indoor and outdoor sample sets. During the summer of 1994, an airborne Cr(vi) size-fractionation study was conducted in Hamilton, the results of which suggested that the majority of the Cr(vi) was in the inhalable fraction.     

Hazardous waste disposal in Germany: a case study of the site in Billigheim, Baden-Wurttemberg

The disposal of hazardous waste is a very critical issue. It is associated with many risks. Efforts are made to minimise these by consistent legislation and by proper treatment of the waste. The goal of a hazardous waste disposal site, as described in this paper, is to ensure that hazardous waste is treated and disposed of in a way that does not harm human beings or the environment. To assure this it is necessary to observe the handling of the hazardous waste from its producer up to the disposal site, and to identify possible inherent risks.