TCLP underestimates leaching of arsenic from solid residuals under landfill conditions

Recent revision of the arsenic in drinking water standard will cause many utilities to implement removal technologies. Most of the affected utilities are expected to use adsorption onto solid media for arsenic removal. The arsenic-bearing solid residuals (ABSR) from adsorption processes are to be disposed of in nonhazardous landfills. The Toxicity Characteristic Leaching Procedure (TCLP) tests whether a waste is hazardous or nonhazardous; most solid residuals pass the TCLP. However, the TCLP poorly simulates the alkaline pH, low redox potential, biological activity, long retention time, and organic composition of mature landfills. These same conditions are likely to favor mobilization of arsenic from metal oxide sorbents. This study quantifies leaching of arsenic from Activated Alumina (AA) and Granular Ferric Hydroxide (GFH), two sorbents expected to be widely used for arsenic removal. The sorbents were subjected to the TCLP, the Waste Extraction Test (WET), an actual landfill leachate, and two synthetic leachate solutions. Up to tenfold greater arsenic concentration is extracted by an actual landfill leachate than by the TCLP. Equilibrium leachate concentrations are not achieved within 18 h (the TCLP duration) and an N2 headspace and end-over-end tumbling increase the rate of arsenic mobilization. However, tests with actual landfill leachate indicate the WET may also underestimate arsenic mobilization in landfills.     

MSWI fly ash particle analysis by scanning electron microscopy-energy dispersive X-ray spectroscopy

Municipal solid waste incinerator (MSWI) fly ash was investigated to study metal distribution on the particle surface. A detailed investigation into the distribution of chlorine, copper, iron, and zinc was carried out by electron microscopy coupled with X-ray fluorescence spectroscopy. Compositional and leaching test data were used to identify the correlation of significant variables and to formulate a hypothesis about metals speciation. The presence of copper chloride, iron, and zinc oxides was inferred. The iron and zinc accumulation in the submicron nuclei indicates that these metals came from the condensation of volatile species. As far as concerns copper, morphological data together with the element correlation study suggest that this element accumulates on particles involved in heterogeneous condensation processes. Furthermore, during such processes, particles of small size containing copper are formed.     

Leaching of lead from computer printed wire boards and cathode ray tubes by municipal solid waste landfill leachates

The proper management of discarded electronic devices (E-waste) is an important issue for solid waste professionals because of the magnitude of the waste stream and because these devices often contain a variety of toxic metals (e.g., lead). While recycling of E-waste is developing, much of this waste stream is disposed in landfills. Leaching tests are frequently used to characterize the potential of a solid waste to leach when disposed in a landfill. In the United States, the Toxicity Characteristic Leaching Procedure (TCLP) is used to determine whether a solid waste is a hazardous waste by the toxicity characteristic. The TCLP is designed to simulate worse-case leaching in a landfill environment where the waste is co-disposed with municipal solid waste (MSW). While the TCLP is a required analysis from a regulatory perspective, the leachate concentrations measured may not accurately reflect the concentrations observed under typical landfill conditions. Another method that can be performed to assess the degree a pollutant might leach from a waste in a landfill is to use actual landfill leachate as the leaching solution. In this study, two lead-containing components found in electronic devices (printed wire boards from computers and cathode ray tubes from computers and televisions) were leached using the TCLP and leachates from 11 Florida landfills. California's Waste Extraction Test (WET) and the Synthetic Precipitation Leaching Procedure were also performed. The results indicated that the extractions using MSW landfill leachates resulted in lower lead concentrations than those by the TCLP. The pH of the leaching solution and the ability of the organic acids in the TCLP and WET to complex with the lead are factors that regulate the amount of lead leached.     

X-ray absorption and micro X-ray fluorescence spectroscopy investigation of copper and zinc speciation in biosolids

Despite its pivotal role in determining the risks and time frames associated with contaminant release, metal speciation remains a poorly understood aspect of biosolids chemistry. The work reported here used synchrotron-based spectroscopy techniques to investigate the speciation of copper and zinc in a range of Australian biosolids. High resolution element mapping of biosolids samples using micro X-ray fluorescence spectroscopy revealed considerable heterogeneity in key element associations, and a combination of both organic and inorganic copper and zinc binding environments. Linear combination fitting of K-edge X-ray absorption spectra indicated consistent differences in metal speciation between freshly produced and stockpiled biosolids. While sulfide minerals play a dominant role in metal binding in freshly dewatered biosolids, they are of lesser importance in dried biosolids that have been stockpiled. A degree of metal binding with iron oxide minerals was apparent but the results did not support the hypothesis that biosolids metals are chiefly associated with iron minerals. This work has potential implications for the long-term stability of metals in biosolids and their eventual fate following land application.     

Comparison between acetic acid and landfill leachates for the leaching of Pb(II), Cd(II), As(V), and Cr(VI) from cementitious wastes

The Toxicity Characteristic Leaching Procedure (TCLP) has been widely used to characterize the suitability of solid wastes for disposal in landfills. However, the widespread application of this test for the assessment of wastes disposed in different landfill types is often questionable. This paper investigates the leaching profiles of cement-stabilized heavy metal ions, namely, Pb (II), Cd (II), As(V), and Cr(VI), using acetic acid and leachates from municipal and nonputrescible Australian landfill sites. The leaching profiles of Pb, Cd, As, and Cr using acetic acid were found to be similar to the nonputrescible landfill leachate and differed markedly from the municipal solid waste (MSW) leachate. The additional presence of high amounts of organic and inorganic compounds in the municipal landfill leachate influenced the leaching profiles of these metal ions as compared to the acetic acid and the nonputrescible systems. It is postulated that the organic compounds present in the municipal landfill leachate formed complexes with the Pb and Cd, increasing the mobility of these ions. Moreover, the organic compounds in the municipal landfill leachate induced a reducing environment in the leachate, causing the reduction of Cr(VI) to Cr(III). It was also found that the presence of carbonates in the municipal landfill leachate affected the stability of calcium arsenate, with the carbonate competing with arsenate for calcium at high pH, forcing arsenate into the solution.     

Solubility of hematite revisited: effects of hydration

Measured pH and dissolved ferric iron concentration ([Fe(III)diss]) in contact with well-characterized hematite indicated an equilibrium with hematite immediately after synthesis, but [Fe(III)diss] increased with hydration time to be consistent with the predicted solubility of goethite or hydrous ferric oxide (HFO), hydrated analogues of hematite. X-ray diffraction did not detect structural modification of hematite after 190 days of hydration, but M?ssbauer spectroscopy detected hydration that penetrated several crystalline layers. When the hematite suspension was diluted with water, solids were invariably identified as hematite, but [Fe(III)diss] and pH indicated an equilibrium with goethite or HFO. This is the first experimental confirmation that the interfacial hydration of anhydrous hematite results in higher solubility than predicted by bulk thermodynamic properties of hematite. Correspondence of the results with previously published measurements and implications for environmental chemistry of ferric oxides are also discussed.     

Relative leaching and aquatic toxicity of pressure-treated wood products using batch leaching tests

Size-reduced samples of southern yellow pine dimensional lumber, each treated with one of five different waterborne chemical preservatives, were leached using 18-h batch leaching tests. The wood preservatives included chromated copper arsenate (CCA), alkaline copper quaternary, copper boron azole, copper citrate, and copper dimethyldithiocarbamate. An unpreserved wood sample was tested as well. The batch leaching tests followed methodology prescribed in the U.S. Environmental Protection Agency toxicity characteristic leaching procedure (TCLP). The wood samples were first size-reduced and then leached using four different leaching solutions (synthetic landfill leachate, synthetic rainwater, deionized water, and synthetic seawater). CCA-treated wood leached greater concentrations of arsenic and copper relative to chromium, with copper leaching more with the TCLP and synthetic seawater. Copper leached at greater concentrations from the arsenic-free preservatives relative to CCA. Arsenic leached from CCA-treated wood at concentrations above the U.S. federal toxicity characteristic limit (5 mg/L). All of the arsenic-free alternatives displayed a greater degree of aquatic toxicity compared to CCA. Invertebrate and algal assays were more sensitive than Microtox. Examination of the relative leaching of the preservative compounds indicated that the arsenic-free preservatives were advantageous over CCA with respect to waste disposal and soil contamination issues but potentially posed a greater risk to aquatic ecosystems.     

Mechanisms of selenate adsorption on iron oxides and hydroxides

Selenate (SeO4(2-)) is an oxyanion of environmental importance because of its toxicity to animals and its mobility in the soil environment. It is known that iron(III) oxides and hydroxides are important sorbents for SeO4(2-) in soils and sediments, but the mechanism of selenate adsorption on iron oxides has been the subject of intense debate. Our research employed Extended X-ray absorption fine structure and attenuated total reflectance-Fourier transform infrared spectroscopies to determine SeO4(2-) bonding mechanisms on hematite, goethite, and hydrous ferric oxide (HFO). It was learned that selenate forms only inner-sphere surface complexes on hematite but forms a mixture of outer- and inner-sphere surface complexes on goethite and HFO. This continuum of adsorption mechanisms is strongly affected by both pH and ionic strength. These results suggest that adsorption experiments should be conducted on several different iron oxides and over a wide range of reaction conditions to accurately assess the reactivity of oxyanions on iron oxides.     

The dietary significance of adventitious iron, zinc, copper and lead in domestically prepared food

The uptake of iron, zinc, copper and lead by food cooked under domestic conditions in utensils made of different metals (cast iron, aluminium, plain and tinned copper) was investigated. It was found that the metal content of the food was generally related to the metal in immediate contact with the food during cooking. Daily dietary intake could vary from 11 to 6 mg of iron, 11 to 9 mg of zinc, 2 to 1 mg of copper and 0.4 to 0.1 mg of lead, depending on the cooking utensils used. Dietary intake of the metals was also related to sources and domestic practices regarding water supply. Consistent use of municipal water from a domestic hot water system could contribute a daily intake of 32 mg iron, 29 mg zinc and 12 mg copper. Rainwater stored in a galvanized iron tank could provide 23 mg of zinc per day when used for domestic purposes. The nutritional and toxicological significance of such adventitious sources of metals in the diet are discussed. The need to consider them when investigating the metal intake of individuals is stressed.     

Enhanced coagulation for satisfying the arsenic maximum contaminant level under variable and uncertain conditions

This study evaluated the effects of influent variability and model parameter uncertainty when utilizing enhanced coagulation modification to bring existing treatment plants into compliance with a stricter arsenic regulation. Enhanced coagulation modification options include: (1) increased ferric chloride dose, (2) addition of an acid dose, and (3) a combination of the individual options. Arsenic removal is described by adsorption to hydrous ferric oxide with a surface complexation model and subsequent removal through sedimentation and filtration. The least-cost modification for reliably satisfying the arsenic regulation is determined using an optimization algorithm that explicitly includes variability and uncertainty. The ferric chloride only modification is always the least-cost treatment modification. The ferric chloride and acid modification could be the least-cost option when considering waste handling processes due to a tradeoff between modification cost and sludge production. By inclusion of variability and uncertainty, the relative importance of individual parameter distributions for determining whether the arsenic regulation is reliably satisfied is assessed. Influent arsenic concentration variability is always critical, while variability in the influent pH and sulfate concentrations and uncertainty in the filter removal efficiency and equilibrium adsorption constant for the triple bond Fe(s)OHCa2+ surface species are critical or important, depending on influent conditions.     

Leaching of arsenic from granular ferric hydroxide residuals under mature landfill conditions

Most arsenic bearing solid residuals (ABSR) from water treatment will be disposed in nonhazardous landfills. The lack of an appropriate leaching test to predict arsenic mobilization from ABSR creates a need to evaluate the magnitude and mechanisms of arsenic release under landfill conditions. This work studies the leaching of arsenic and iron from a common ABSR, granular ferric hydroxide, in a laboratory-scale column that simulates the biological and physicochemical conditions of a mature, mixed solid waste landfill. The column operated for approximately 900 days and the mode of transport as well as chemical speciation of iron and arsenic changed with column age. Both iron and arsenic were readily mobilized under the anaerobic, reducing conditions. During the early stages of operation, most arsenic and iron leaching (80% and 65%, respectively) was associated with suspended particulate matter, and iron was lost proportionately faster than arsenic. In later stages, while the rate of iron leaching declined, the arsenic leaching rate increased greater than 7-fold. The final phase was characterized by dissolved species leaching. Future work on the development of standard batch leaching tests should take into account the dominant mobilization mechanisms identified in this work: solid associated transport, reductive sorbent dissolution, and microbially mediated arsenic reduction.     

The reaction between water-soluble tree leaf constituents and ferric oxide in relation to podzolisatlon

Sterile aqueous extracts of tree leaves dissolve ferric oxide, and the reaction products are sorbed on residual ferric oxide. Extracts of autumn-fallen leaves and needles of oak, beech and larch, and picked Scots pine needles, were allowed to react with ferric oxide under conditions in which both the solution and sorption processes may be assumed to go to completion, and the effect on the composition of the extracts was determined. Under these conditions the net excess of solution of iron over sorption was quite small, and polyphenols, sugars, α-amino acids and carboxylic acids were retained on the ferric oxide.     

RCRA toxicity characterization of discarded electronic devices

The potential for discarded electronic devices to be classified as toxicity characteristic (TC) hazardous waste under provisions of the Resource Conservation and Recovery Act (RCRA) using the toxicity characteristic leaching procedure (TCLP) was examined. The regulatory TCLP method and two modified TCLP methods (in which devices were disassembled and leached in or near entirety) were utilized. Lead was the only element found to leach at concentrations greater than its TC limit (5 mg/L). Thirteen different types of electronic devices were tested using either the standard TCLP or modified versions. Every device type leached lead above 5 mg/L in at least one test and most devices leached lead above the TC limit in a majority of cases. Smaller devices that contained larger amounts of plastic and smaller amounts of ferrous metal (e.g., cellular phones, remote controls) tended to leach lead above the TC limit at a greater frequency than devices with more ferrous metal (e.g., computer CPUs, printers).     

Preloading hydrous ferric oxide into granular activated carbon for arsenic removal

Arsenic is of concern in water treatment because of its health effects. This research focused on incorporating hydrous ferric oxide (HFO) into granular activated carbon (GAC) for the purpose of arsenic removal. Iron was incorporated into GAC via incipient wetness impregnation and cured at temperatures ranging from 60 to 90 degrees C. X-ray diffractions and arsenic sorption as a function of pH were conducted to investigate the effect of temperature on final iron oxide (hydroxide) and their arsenic removal capabilities. Results revealed that when curing at 60 degrees C, the procedure successfully created HFO in the pores of GAC, whereas at temperatures of 80 and 90 degrees C, the impregnated iron oxide manifested a more crystalline form. In the column tests using synthetic water, the HFO-loaded GAC prepared at 60 degrees C also showed higher sorption capacities than media cured at higher temperatures. These results indicated that the adsorption capacity for arsenic was closely related to the form of iron (hydr)oxide for a given iron content For the column test using a natural groundwater, HFO-loaded GAC (Fe, 11.7%) showed an arsenic sorption capacity of 26 mg As/g when the influent contained 300 microg/L As. Thus, the preloading of HFO into a stable GAC media offered the opportunity to employ fixed carbon bed reactors in water treatment plants or point-of-use filters for arsenic removal.     

Removal of heavy metals from mine waters by natural zeolites

In this study, we investigated the removal of Fe, Pb, Cd, and Zn from synthetic mine waters by a natural zeolite. The emphasis was given to the zeolite's behavior toward a few cations in competition with each other. Pb was removed efficiently from neutral as well as from acidic solutions, whereas the uptake of Zn and Cd decreased with low pH and high iron concentrations. With increasing Ca concentrations in solution, elimination of Zn and Cd became poorer while removal of Pb remained virtually unchanged. The zeolite was stable in acidic solutions. Disintegration was only observed below pH 2.0. Forward- and back-titration of synthetic acidic mine water were carried out in the presence and absence of zeolite to simulate the effects of a pH increase by addition of neutralizing agents and a re-acidification which can be caused by subsequent mixing with acidic water. The pH increase during neutralization causes precipitation of hydrous ferric oxides and decreased dissolved metal concentrations. Zeolite addition further diminished Pb concentrations but did not have an effect on Zn and Cd concentrations in solution. During re-acidification of the solution, remobilization of Pb was weaker in the presence than in the absence of zeolite. No substantial differences were observed for Fe, Cd, and Zn immobilization. The immobilization of the metals during pH increase and the subsequent remobilization caused by re-acidification can be well described by a geochemical equilibrium speciation model that accounts for metal complexation at hydrous ferric oxides, for ion exchange on the zeolite surfaces, as well as for dissolution and precipitation processes.     

pH调控在钢帘线废水处理中的应用

钢帘线生产过程中产生的废水含有大量的铅、铜、锌、铁等重金属离子,在污水处理过程中,理论计算最佳沉淀pH、完全沉淀pH和实际值均有差距,两性金属返溶现象和理论值有一定差异,碱性物质的投加量具有不确定性.以电镀车间排放的酸性废水为试验对象,利用氢氧化钠溶液调控酸性废水的pH,分析化学沉淀法处理电镀废水时,pH调控与杂质残余...     

Redox transformations of arsenic and iron in water treatment sludge during aging and TCLP extraction

Laboratory experiments and modeling studies were performed to investigate the redox transformations of arsenic and iron in water treatment sludge during aging, and to evaluate the impact of those transformations on the leachability of arsenic determined with the U.S. EPA toxicity characteristic leaching procedure (TCLP). When the backwash suspension samples collected from a California surface water treatment plant were aged in closed containers for a few weeks, soluble arsenic increased from less than 5 microg/L to as high as 700 microg/L and then decreased dramatically because of biotic reduction of arsenate [As(V)], ferric oxyhydroxide, and sulfate. The experimental results and the thermodynamic models showed that arsenic mobility can be divided into three redox zones: (a) an adsorption zone at pe > 0, which is characterized by strong adsorption of As(V) on ferric oxyhydroxide; (b) a mobilization (transition) zone at -4.0 < pe < 0, where arsenic is released because of reduction of ferric oxyhydroxide to ferrous iron and As(V) to arsenite [As(III)]; and (c) a reductive fixation zone at pe < -4.0, where arsenic is immobilized by pyrite and other reduced solid phases. The TCLP substantially underestimated the leachability of arsenic in the anoxic sludge collected from sludge ponds because of the oxidation of Fe(II) and As(III) by oxygen. The leaching test should be performed in zero-headspace vessels or under nitrogen to minimize the transformations of the redox-sensitive chemical species.     

Evaluation of particulate zinc and copper as wood preservatives for termite control

Subterranean termites are a major factor in the biodegradation of wood construction products. In this study the efficacy of wood treated with micronized copper, zinc oxide and their mixture was compared to that of wood treated with soluble amine copper oxide against subterranean termites in a laboratory test. All of the formulations tested were effective in controlling wood degradation by the termites, with copper being slightly more effective than zinc and micronized copper being slightly more effective than amine copper.     

葡萄园土壤中铜、铁、锌、锰四种金属元素的分析与研究

采用湿法消解处理样品,火焰原子吸收光谱法检测河北昌黎葡萄酒产区5 个葡萄园土壤中的铜、铁、锌、锰4 种金属元素。并对比研究3 种葡萄、葡萄酒与葡萄园土壤中铜、铁、锌、锰4 种金属元素含量的关系。对不同葡萄园和同一葡萄园种植不同品种葡萄,其土壤中金属元素含量进行差异性分析。结果显示：葡萄园地理位置和微环境及所栽培的葡萄品种、树龄和架势不同,土壤中4 种金属元素含量不同,差异性显著。铁、锌、锰3 种元素在土壤中的含量与葡萄中的含量有一定关系。赤霞珠、美乐和西拉3 种葡萄的土壤中铜、铁、锌的含量与葡萄及其葡萄酒中相对含量规律相同,而锰不同。     

Role of zinc in MSW fly ash during formation of chlorinated aromatics

In this study, we determined the thermochemical role of zinc in municipal solid waste (MSW) fly ash. Zinc's role depended on its chemical form and the presence of other metal catalysts. When only zinc was present or it dominated other metal elements, chlorinated aromatic compound (aromatic-Cl) formation was promoted by zinc chloride but blocked by zinc oxide. When only zinc was present, such as in zinc metallurgical plants, some aromatic-Cls were generated and contaminated the environment. When zinc coexisted with other metal promoters in a thermal postcombustion solid phase, such as MSW incineration, Fourier-transform Zn K-edge extended X-ray absorption fine structure (EXAFS) analysis showed that the chemical forms of zinc were primarily chloride and/or oxide, and zinc chloride (ZnCl(2)) was thermally stable in the solid phase. Thus, we used ZnCl(2) in coexistence experiments as a promoter to generate aromatic-Cls. Zinc chloride acted as a coexistent inhibitor of metal catalysis and precursor dimerization to generate aromatic-Cls. There were two coexistent inhibition mechanisms. First, a low-temperature transition of chlorine to the gas phase (low-Cl(g)) occurred with metal catalysts such as CuCl(2) and FeCl(3), confirmed by Cl K-edge near-edge X-ray absorption fine structure (NEXAFS) analysis. Second, X-ray photoelectron spectroscopy (XPS) analysis of the surface or near-surface concentration of ZnCl(2) indicated weak reactivity between the catalysts and the carbon matrix.