Soil attenuation of As(III,V) and Se(IV,VI) seepage potential at ash disposal facilities

Leachate from ash landfills is frequently enriched with As and Se but their off-site movement is not well understood. The attenuation potential of As and Se by soils surrounding selected landfills during leachate seepage was investigated in laboratory column studies using simulated ash leachate. As(III, V) and Se(IV, VI) concentrations as well as pH, flow rate, and a tracer were monitored in influent and effluent for up to 800 pore volumes followed by sequential desorption, extraction, and digestion of column segments. Column breakthrough curves (BTCs) were compared to predictions based on previously measured sorption isotherms. Early As(V) breakthrough and retarded As(III) breakthrough relative to predicted BTCs are indicative of oxidative transformation during seepage. For Se(VI), which exhibits linear sorption and the lowest sorption propensity, measured BTCs were predicted fairly well by equilibrium sorption isotherms, except for the early arrival of Se(IV) in one site soil, which in part, may be due to higher column pH values compared to batch isotherms. Most of the As and Se retained by soils during leaching was found to be strongly sorbed (60–90%) or irreversibly bound (10–40%) with <5% readily desorbable. Redox potential favoring transformation to the more sorptive valence states of As(V) and Se(IV) will invoke additional attenuation beyond equilibrium sorption-based predictions. With the exception of Se(IV) on one site soil, results indicate that attenuation by down-gradient soils of As and Se in ash landfill seepage will often be no less than what is predicted by equilibrium sorption capacity with further attenuation expected due to favorable redox transformation processes, thus mitigating contaminant plumes and associated risks.     

Influences of redox transformation, metal complexation and aggregation of fulvic acid and humic acid on Cr(VI) and As(V) removal by zero-valent iron

This study investigated the removal kinetics and mechanisms of Cr(VI) and As(V) by Fe(0) in the presence of fulvic acid (FA) and humic acid (HA) by means of batch experiments. The focus was on the involvements of FA and HA in redox reactions, metal complexation, and iron corrosion product aggregation in the removal of Cr(VI) and As(V) removal by Fe(0). Synthetic groundwater was used as the background electrolyte to simulate typical groundwater. The results showed faster Cr(VI) removal in the presence of HA compared to FA. Fluorescence spectroscopy revealed that no redox reaction occurred in the FA and HA. The results of the speciation modeling indicate that the free Fe(II) concentration was higher in the presence of HA, resulting in a higher removal rate of Cr(VI). However, the removal of As(V) was inhibited in the HA solution. Speciation modeling showed that the concentration of dissolved metal-natural organic matter (metal-NOM) complexes significantly affected the aggregation of the iron corrosion products which in turn affected the removal of As(V). The aggregation was found to be induced by gel-bridging of metal-NOM with the iron corrosion products. The effects of metal-NOM on the aggregation of the iron corrosion products were further confirmed by TEM studies. Larger sizes of iron corrosion products were formed in the FA solution compared to HA solution. This study can shed light on understanding the relationships between the properties of NOM (especially the content of metal-binding sites) and the removal of Cr(VI) and As(V) by Fe(0).     

Neptunium(V) adsorption to calcite

The migration behavior of the actinyl ions U(VI)O₂²⁺, Np(V)O₂⁺ and Pu(V,VI)O₂^(+,2+) in the geosphere is to a large extend controlled by sorption reactions (inner- or outer-sphere adsorption, ion-exchange, coprecipitation/structural incorporation) with minerals. Here NpO₂⁺ adsorption onto calcite is studied in batch type experiments over a wide range of pH (6.0–9.4) and concentration (0.4 μM–40 μM) conditions. pH is adjusted by variation of CO₂ partial pressure. Adsorption is found to be pH dependent with maximal adsorption at pH 8.3 decreasing with increasing and decreasing pH. pH dependence of adsorption decreases with increasing Np(V) concentration. EXAFS data of neptunyl adsorbed to calcite and neptunyl in the supernatant shows differences in the Np(V)-O-yl distance, 1.85 ± 0.01 Å for the adsorbed and 1.82 ± 0.01 Å for the solution species. The equatorial environment of the neptunyl in solution shows about 5 oxygen neighbours at 2.45 ± 0.02 Å. For adsorbed neptunyl there are also about 5 oxygen neighbours at 2.46 ± 0.01 Å. An additional feature in the adsorbed species' R-space spectrum can be related to carbonate neighbours, 3 to 6 carbon backscatterers (C-eq) at 3.05 ± 0.03 Å and 3 to 6 oxygen backscatterers (O-eq2) at 3.31 ± 0.02 Å. The differences in the Np(V)-O-yl distance and the C-eq and O-eq2 backscatterers which are only present for the adsorbed species indicate inner-sphere bonding of the adsorbed neptunyl species to the calcite surface. Experiments on adsorption kinetics indicate that after a fast surface adsorption process a continuous slow uptake occurs which may be explained by incorporation via surface dissolution and reprecipitation processes. This is also indicated by the part irreversibility of the adsorption as shown by increased K_D values after desorption compared to adsorption.     

Adsorption of As(III) versus As(V) from aqueous solutions by cerium-loaded volcanic rocks

Environmental Science and Pollution Research - Contamination of drinking water with arsenic causes severe health problems in various world regions. Arsenic exists predominantly as As(III) and As(V)...     

氨基复合铁氧化物对As（V）的吸附性能与机理

用氯化十六烷基三甲铵（Cetyltrimethylammonium chloride,CTAC）修饰铁氧化物Fe2O3,得到氨基复合的铁氧化物纳米材料（Fe2O3@CTAC）并研究了其对As（V）的吸附去除性能及机理。CTAC修饰不会改变Fe2O3的物理化学结构,而形成的Fe2O3@CTAC不仅可以通过铁氧化物表面络合作用吸附As（V）,复合材料表面的氨基也可以通过静电作用吸附As（V）。因而复合材料对As（V）的吸附去除效果显著提升,饱和吸附容量可以达到23.13 mg·g-1。Fe2O3@CTAC 吸附As（V）可以在2 min内达到平衡,符合拟二级动力学模型和two-site Langmuir模型。在pH为3~9的范围内,Fe2O3@CTAC均能有效吸附去除As（V）,去除率均能达到90%以上。天然有机质和硫酸根、碳酸氢根、硅酸根对As（V）在Fe2O3@CTAC上的吸附没有明显的抑制作用。磷酸根由于与As（V）存在竞争吸附作用而抑制As（V）的吸附,然而在通常水体磷酸根浓度条件下,Fe2O3@CTAC对As（V）的去除率依然达到90%以上。此外,Fe2O3@CTAC可以再生并重复利用,经过5次循环利用后As（V）的去除率能够保持在85%以上。     

Adsorption of As(III) on chitosan-Fe-crosslinked complex (Ch-Fe)

It was reported the adsorption of As(III) on the surface of the chitosan-Fe-crosslinked complex. Theoretical correlation of the experimental equilibrium adsorption data for As(III)/Ch-Fe system is best explained by the non-linearized form Langmuir-Freundlich isotherm model. At optimum conditions, pH 9.0, the maximum adsorption capacity, calculated using the Langmuir-Freundlich isotherm model was 13.4 mg g⁻¹. The adsorption kinetics of As(III) onto Ch-Fe are described by the pseudo-first-order kinetic equation. The results of the Mössbauer spectroscopy showed that there is no redox process on the surface of the adsorbent.     

Impacts of pH and ammonia on the leaching of Cu(II) and Cd(II) from coal fly ash

Many coal-fired power plants are implementing ammonia-based technologies to reduce NO(x) emissions. Excess ammonia in the flue gas often deposits on the coal fly ash. Ammonia can form complexes with many heavy metals and change the leaching characteristics of these metals. This research tends to develop a fundamental understanding of the ammonia impact on the leaching of some heavy metals, exemplified by Cu(II) and Cd(II), under different pH conditions. Batch results indicated that the adsorption is the main mechanism controlling Cu(II) and Cd(II) leaching, and high concentrations of ammonia (>5,000 mg/l) can increase the release of Cu(II) and Cd(II) in the alkaline pH range. Based on the chemical reactions among fly ash, ammonia, and heavy metal ion, a mathematical model was developed to quantify effects of pH and ammonia on metal adsorption. The adsorption constants (logK) of Cu(2+), Cu(OH)(+), Cu(OH)(2), and Cu(NH(3))(m)(2+) for the fly ash under investigation were respectively 6.0, 7.7, 9.6, and 2.9. For Cd(II), these constants were respectively 4.3, 6.9, 8.8, and 2.6. Metal speciation calculations indicated that the formation of less adsorbable metal-ammonia complexes decreased metal adsorption, therefore enhanced metal leaching.     

Natural attenuation of xenobiotic organic compounds in a landfill leachate plume (Vejen,Denmark)

Demonstration of natural attenuation of xenobiotic organic compounds (XOCs) in landfill leachate plumes is a difficult task and still an emerging discipline within groundwater remediation. One of the early studies was made at the Vejen Landfill in Denmark in the late 1980s, which suggested that natural attenuation of XOCs took place under strongly anaerobic conditions within the first 150 m of the leachate plume. This paper reports on a revisit to the same plume 10 years later. Within the strongly anaerobic part of the plume, 49 groundwater samples were characterized with respect to redox-sensitive species and XOCs. The analytical procedures have been developed further and more compounds and lower detection limits were observed this time. In addition, the samples were screened for degradation intermediates and for toxicity. The plume showed fairly stationary features over the 10-year period except that the XOC level as well as the level of chloride and nonvolatile organic carbon (NVOC) in the plume had decreased somewhat. Most of the compounds studied were subject to degradation in addition to dilution. Exceptions were benzene, the herbicide Mecoprop (MCPP), and NVOC. In the early study, NVOC seemed to degrade in the first part of the plume, but this was no longer the case. Benzyl succinic acid (BSA) was for the first time identified in a leachate plume as a direct indicator, and as the only intermediate of toluene degradation. Toxicity measurements on solid phase-extracted (SPE) samples revealed that toxic compounds not analytically identified were still present in the plume, suggesting that toxicity measurements could be helpful in assessing natural attenuation in leachate plumes.     

Removal of As(III) and As(V) from water by chitosan and chitosan derivatives: a review

As arsenic removal becomes a global concern, the development of removal processes for arsenic treatment is still a major challenge. With regard to environmental compatibility and cheapness, chitosan and chitosan derivatives are considered as a promising removal technology for arsenic. Chitosan and chitosan derivatives possess the properties of low cost and good sorption on the arsenic removal. The present review is concerned about the present understanding of the mechanisms involved in sorption processes. Further on, detailed discussions are given of the effects of various factors on the performance of chitosan and chitosan derivatives in arsenic treatment processes. Finally, special attention is paid to the future challenges of chitosan and chitosan derivatives utilized for industrial arsenic treatment.     

硫酸钛混凝去除无机砷(III)的效能

使用硫酸钛作为混凝剂,研究了混凝去除As(III)过程中溶液pH值、混凝剂投加量、砷的初始浓度以及阴离子对除砷效果的影响.硫酸钛的水解沉淀物颗粒等电点为pH=5;当pH=6时,水解沉淀物的粒径最大.在pH=5~8范围内,As(III)的去除率高且基本稳定;而沉淀物颗粒Zeta电位降低较大.说明水解沉淀物Zeta电位对As(III)的去除影响不大.混凝剂投加量为2.5~10 mg/L时,As(III)的去除率随投加量的增加而显著增加;混凝剂投加量大于15 mg/L时,As(III)去除率随混凝剂投加量的增加变化趋于平缓.水中阴离子(硅酸根和磷酸根离子)的存在会降低混凝对As(III)的去除效率.     

Evaluation of the multiple-ion competition in the adsorption of As(V) onto reclaimed iron-oxide coated sands by fractional factorial design

This study describes the competitive effects of selected ions and natural organic matter on As(V) removal using reclaimed iron-oxide coated sands (RIOCS) in the single- and multi-ion systems. A 2(7-3) factional factorial experimental design (FFD) was employed for screening main competitive factors in this adsorption process. As a result, the inhibitive competition effects of the anions on As(V) removal in the single ion system were in the following sequence: PO(4)(3-)>SiO(3)(2-)>HCO(3)(-)>humic acid (HA)>SO(4)(2-)>Cl(-), whereas the cation Ca(2+) was observed to enhance the As(V) removal. In addition, the optimum initial pH for As(V) removal in single-ion system was 5. Based on the estimates of major effects and interactions from the FFD, PO(4)(3-), SiO(3)(2-), Ca(2+) and HA were important factors on As(V) removal in the multi-ion system. The promoters for the As(V) removal were found to be Ca(2+) and, to a lesser extent, SO(4)(2-). The competitive effects of these ions on As(V) removal were in the order of PO(4)(3-), SiO(3)(2-), HA, HCO(3)(-), and Cl(-). In the single ion system, the efficiencies of As(V) removal range from 75% to 96%, much higher than those in the multi-ion system (44%) at the initial pH 5. Clearly, there were some complex anion interactions in the multi-ion system. To promote the removal of As(V) by RIOCS, it is proposed to lower the pH in the single-ion system, while in the multi-ion system, the increase of the Ca(2+) concentration, or decreases of PO(4)(3-), SiO(3)(2-) and HA concentrations is suggested.     

Evaluation and standardisation of a simple HG-AAS method for rapid speciation of As(III) and As(V) in some contaminated groundwater samples of West Bengal, India

A simple HG-AAS technique has been evaluated and standardised for rapid speciation of As(III) and As(V) in a number of contaminated groundwater samples of West Bengal, India. Citric acid has been used for selective hydride formation of As(III). The sensitivity of the evaluated HG-AAS method is 7.91 mg(-1)l, standard deviation, 0.001 and detection limit, 0.4 microg l(-1). As(III) sensitivity remains constant in the sample pH range of 2.3-10.6. Concomitant mineral matrix of the water samples did not interfere with arsenic determination. Eight out of ten groundwater samples analysed for As(IlI)and As(V) contain more As(III), which lies in the range of 54-350 ppb. As(III) estimation in drinking water along with total arsenic should be invoked as a policy for a realistic risk assessment of the contaminated water.     

Polycyclic aromatic hydrocarbons (PAHs) and their oxygen-containing derivatives (OPAHs) in soils from the Angren industrial area, Uzbekistan

We measured the concentrations and depth distribution (0-10, 10-20 cm) of 31 PAHs and 12 OPAHs in soils at eleven equidistant sampling points along a 20-km transect in the Angren industrial region (coal mine, power plant, rubber factory, gold mine), Uzbekistan to gain an insight into their concentrations, sources, and fate. Concentrations of all compounds were mostly much higher in the 0-10 cm than in the 10-20 cm layer except in disturbed soil close to the coal mine. Proximity to one of the industrial emitters was the main determinant of PAH and OPAH concentrations. The ∑31PAHs concentrations correlated positively with the ∑7 carbonyl-OPAH (r = 0.98, p < 0.01), ∑5 hydroxyl-OPAH (r = 0.72, p < 0.05), and with industrially emitted trace metals in the topsoil, identifying industrial emissions as their common source. Concentrations of several OPAHs were higher than their parent PAHs, but their vertical distribution in soil suggested only little higher mobility of OPAHs than their corresponding parent PAHs.     

城市生活垃圾焚烧飞灰水泥固化技术研究

用硫铝酸盐水泥对城市垃圾焚烧飞灰(简称飞灰)进行固化实验,研究了飞灰重金属浸出特性,分析了飞灰掺量、浸提剂pH值对重金属浸出特性以及飞灰掺量对不同龄期(3、7、28 d)飞灰固化体抗压强度的影响,并对飞灰及其固化体进行XRD分析。结果表明,在HJ/T 299-2007和HJ/T 300-2007两种不同浸出体系下,飞灰中Cu、Zn、Cd、Pb、Cr和Mn等重金属浸出浓度差别较大,建议应根据评价目标合理选择重金属浸出测量方法。其中,飞灰中Pb的浸出浓度超过《危险废物鉴别标准浸出毒性鉴别》(GB 5085.3-2007)限值的3.35倍,因此被列为危险废物,应妥善处理。除飞灰掺量小于40%时的固化体Cd符合标准,其余飞灰固化体Pb和Cd的浸出浓度仍超过《生活垃圾填埋场污染控制标准》(GB 16889-2008)限值,故达不到卫生填埋的要求。固化体抗压强度随飞灰掺量增大而降低,重金属浸出浓度与之相反。飞灰掺量为40%时,固化体中重金属浸出浓度随浸提剂pH值降低而增大,但pH值大于5时,未测出重金属浸出。XRD结果表明:飞灰中可溶性盐参与水泥水化反应,重金属Cr以CrO42-的形式固化于钙矾石中。     

Influence of fly ash aided phytostabilisation of Pb, Cd and Zn highly contaminated soils on Lolium perenne and Trifolium repens metal transfer and physiological stress

Due to anthropogenic activities, large extends of soils are highly contaminated by Metal Trace Element (MTE). Aided phytostabilisation aims to establish a vegetation cover in order to promote in situ immobilisation of trace elements by combining the use of metal-tolerant plants and inexpensive mineral or organic soil amendments. Eight years after Coal Fly Ash (CFA) soil amendment, MTE bioavailability and uptake by two plants, Lolium perenne and Trifolium repens, were evaluated, as some biological markers reflecting physiological stress. Results showed that the two plant species under study were suitable to reduce the mobility and the availability of these elements. Moreover, the plant growth was better on CFA amended MTE-contaminated soils, and the plant sensitivity to MTE-induced physiological stress, as studied through photosynthetic pigment contents and oxidative damage was lower or similar. In conclusion, these results supported the usefulness of aided phytostabilisation of MTE-highly contaminated soils.     

Influence of extracellular polymeric substances (EPS) on Cd adsorption by bacteria

The role of extracellular polymeric substances (EPS) in Cd adsorption by Bacillus subtilis and Pseudomonas putida was investigated using a combination of batch adsorption experiments, potentiometric titrations, Fourier transform infrared spectroscopy (FTIR). An increased adsorption capacity of Cd was observed for untreated bacteria relative to that for EPS-free bacteria. Surface complexation modeling of titration data showed the similar pK_a values of functional groups (carboxyl, phosphate and hydroxyl) between untreated and EPS-free bacteria. However, site concentrations on the untreated bacteria were found to be higher than those on the EPS-free bacteria. FTIR spectra also showed that no significant difference in peak positions was observed between untreated and EPS-free bacteria and carboxyl and phosphate groups were responsible for Cd adsorption on bacterial cells. The information obtained in this study is of fundamental significance for understanding the interaction mechanisms between heavy metals and biofilms in natural environments.     

模拟酸雨对氧化锰吸附砷(Ⅲ)的解吸行为研究

以合成的氧化锰为吸附剂研究了酸雨pH值、酸雨离子强度、解吸时间和解吸次数等因素对模拟酸雨解吸砷(Ⅲ)的影响。实验结果表明:氧化锰对砷(Ⅲ)吸附容量较大,等温平衡吸附量为:48.38 mg/g。模拟酸雨的pH值与离子强度对砷(Ⅲ)的解吸影响不大;解吸反应在90 min后基本达到平衡,平衡解吸量为2.69×10-2mg/g;随解吸次数的增加解吸量变化不大。氧化锰对砷(Ⅲ)的吸附主要是专性的配位吸附,吸附砷(Ⅲ)后难以被模拟酸雨解吸。     

Proteomic analysis in Daphnia magna exposed to As(III), As(V) and Cd heavy metals and their binary mixtures for screening potential biomarkers

In this study, the effects of three widespread heavy metals, As(III), As(V) and Cd, and their binary mixtures on the proteomic profile in D. magna were examined to screen novel protein biomarkers using the two-dimensional gel electrophoresis method (2DE). Ten 20d daphnia were exposed to the LC20 concentrations for each of a total of 8 treatments, including the control, As(III), As(V), Cd, [As(III)+As(V)], [As(III)+Cd], [As(V)+Cd], and [As(III), As(V), Cd], for 24 h before protein isolation. Three replicates were performed for each treatment. These protein samples were employed for 2DE experiments with a pH gradient gel strip from pH 3 to pH 10. The protein spots were detected by a silver staining process and their intensities were analyzed by Progenesis software to discover the differentially expressed proteins (DEPs) in response to each heavy metal. A total of 117 differentially expressed proteins (DEPs) were found in daphnia responding to the 8 treatments and mapped onto a 2D proteome map, which provides some information of the molecular weight (MW) and pI value for each protein. All of these DEPs are considered as potential candidates for protein biomarkers in D. magna for detecting heavy metals in the aquatic ecosystem. Comparing the proteomic results among these treatments suggested that exposing D. magna to binary mixtures of heavy metals may result in some complex interactive molecular responses within them, rather than just the simple sum of the proteomic profiles of the individual chemicals, (As(III), As(V), and Cd).     

Arsenic(III) and iron(II) co-oxidation by oxygen and hydrogen peroxide: Divergent reactions in the presence of organic ligands

Iron-catalyzed oxidation of As(III) to As(V) can be highly effective for toxic arsenic removal via Fenton reaction and Fe(II) oxygenation. However, the contribution of ubiquitous organic ligands is poorly understood, despite its significant role in redox chemistry of arsenic in natural and engineered systems. In this work, selected naturally occurring organic ligands and synthetic ligands in co-oxidation of Fe(II) and As(III) were examined as a function of pH, Fe(II), H₂O₂, and radical scavengers (methanol and 2-propanol) concentration. As(III) was not measurably oxidised in the presence of excess ethylenediaminetetraacetic acid (EDTA) (i.e. Fe(II):EDTA < 1:1), contrasting with the rapid oxidation of Fe(II) by O₂ and H₂O₂ at neutral pH under the same conditions. However, partial oxidation of As(III) was observed at a 2:1 ratio of Fe(II):EDTA. Rapid Fe(II) oxidation in the presence of organic ligands did not necessarily result in the coupled As(III) oxidation. Organic ligands act as both iron speciation regulators and radicals scavengers. Further quenching experiments suggested both hydroxyl radicals and high-valent Fe species contributed to As(III) oxidation. The present findings are significant for the better understanding of aquatic redox chemistry of iron and arsenic in the environment and for optimization of iron-catalyzed arsenic remediation technology.