Heavy metal immobilization in soil near abandoned mines using eggshell waste and rapeseed residue

Heavy metal contamination of agricultural soils has received great concern due to potential risk to human health. Cadmium and Pb are largely released from abandoned or closed mines in Korea, resulting in soil contamination. The objective of this study was to evaluate the effects of eggshell waste in combination with the conventional nitrogen, phosphorous, and potassium fertilizer (also known as NPK fertilizer) or the rapeseed residue on immobilization of Cd and Pb in the rice paddy soil. Cadmium and Pb extractabilities were tested using two methods of (1) the toxicity characteristics leaching procedure (TCLP) and (2) the 0.1 M HCl extraction. With 5 % eggshell addition, the values of soil pH were increased from 6.33 and 6.51 to 8.15 and 8.04 in combination with NPK fertilizer and rapeseed residue, respectively, compared to no eggshell addition. The increase in soil pH may contribute to heavy metal immobilization by altering heavy metals into more stable in soils. Concentrations of TCLP-extracted Cd and Pb were reduced by up to 67.9 and 93.2 % by addition of 5 % eggshell compared to control. For 0.1 M HCl extraction method, the concentration of 0.1 M HCl-Cd in soils treated with NPK fertilizer and rapeseed residue was significantly reduced by up to 34.01 and 46.1 %, respectively, with 5 % eggshell addition compared to control. A decrease in acid phosphatase activity and an increase in alkaline phosphatase activity at high soil pH were also observed. Combined application of eggshell waste and rapeseed residue can be cost-effective and beneficial way to remediate the soil contaminated with heavy metals.     

废弃铬盐厂土壤中铬的赋存特征及异位淋洗修复可行性研究

土壤理化性质、污染物的分布及赋存特征是土壤异位淋洗技术是否可行的关键依据。以西北某废弃铬盐厂铬污染场地土壤作为研究对象,测定了土壤基本理化参数及各粒径污染物的浓度,探究总铬和六价铬在不同粒径土壤中的分布特征,并通过铬的赋存形态分析确定清水作为淋洗剂,开展异位清水淋洗实验。结果表明：供试土壤粗颗粒物料（粒径分别为：>9.50 mm、2.00~9.50 mm、0.841~2.00 mm及0.25~0.841 mm）占土壤总质量的比例达到93.36%,总铬和六价铬污染物富集于土壤细颗粒（粒径-1,达到修复标准要求。     

Dodonaea viscosa (Sapindaceae) as a phytoremediator for soils contaminated by heavy metals in abandoned mines

Environmental Science and Pollution Research - Dodonaea viscosa (L.) Jacq. is a plant with a wide distribution that expands throughout almost all Mexican territory and is used in traditional...     

Biodegradation and speciation of residual SS-ethylenediaminedisuccinic acid (EDDS) in soil solution left after soil washing

This paper aims to investigate the degradation and speciation of EDDS-complexes (SS-ethylenediaminedisuccinic acid) in soil following soil washing. The changes in soil solution metal and EDDS concentrations were investigated for three polluted soils. EDDS was degraded after a lag phase of 7-11 days with a half-life of 4.18-5.60 days. No influence of EDDS-speciation on the reaction was observed. The decrease in EDDS resulted in a corresponding decrease in solubilized metals. Changes in EDDS speciation can be related to (1) initial composition of the soil, (2) temporarily anoxic conditions in the soil slurry after soil washing, (3) exchange of EDDS complexes with Cu even in soils without elevated Cu and (4) formation of NiEDDS. Dissolved organic matter is important for metal speciation at low EDDS concentrations. Our results show that even in polluted soils EDDS is degraded from a level of several hundred micromoles to below 1 microM within 50 days.     

Particle-facilitated lead and arsenic transport in abandoned mine sites soil influenced by simulated acid rain

The role of acid rain in affecting Pb and As transport from mine tailings was investigated by pumping simulated acid rain at a infiltration rate of 10.2 cm/h through soil columns. Simulated acid rain with pH of 3.0, 4.5 and 5.6 were used as leaching solutions. Results showed that 86.9–95.9% of Pb and 90–91.8% of As eluted from the columns were adsorbed by particles in the leachates. Scanning electron microscopy (SEM) analysis showed that particles released from the columns were mainly composed of flocculated aggregates and plate or rod shaped discrete grains. Transmission electron microscopy (TEM) coupled with energy dispersive X-ray analysis (EDX) showed that these particles were predominantly silicate minerals. Results from our experiments demonstrated that when rapid infiltration conditions or a rainstorm exist, particle-facilitated transport of contaminants is likely to the dominant metal transport pathway influenced by acid rain.     

Optimization of uranium soil decontamination in alkaline washing using mechanical stirring and ultrasound field

Environmental Science and Pollution Research - The ex situ decontamination of uranium polluted soils was performed by alkaline washing using mechanical agitation and ultrasound field. Two types of...     

某废弃硫酸厂场地土壤重金属污染特征及健康风险评估

以某废弃硫酸厂场地为研究对象,对该场地土壤中As、Cd、Cu、Pb、Zn的污染特征进行分析,并对该场地进行健康风险评估。采用单因子污染指数法、主成分分析和相关性分析对场地重金属污染特征及污染来源进行分析,并评价目标污染物的健康风险。结果表明,Zn、Cd、As、Pb、Cu最大超标倍数分别为18.86、320.25、466.00、132.50、12.42倍。污染比较严重的区域主要分布在厂区的原堆渣场、磷石膏、硫酸以及锌锭的生产车间,随着土壤深度的增加,污染物都发生了不同程度的垂向迁移。As、Pb具有同源性,来源于工业废渣的裸露堆放;Zn、Cd来源于硫酸以及锌锭生产车间,Cu与其他重金属具有相似的污染途径,受废渣堆放、硫酸生产、锌锭制造的共同影响。根据健康风险评价结果,土壤中As、Cd、Pb均超出可接受风险水平,是后续场地修复的目标污染物。     

Determination of chemical availability of cadmium and zinc in soils using inert soil moisture samplers

A rapid method for extracting soil solutions using porous plastic soil-moisture samplers was combined with a cation resin equilibration based speciation technique to look at the chemical availability of metals in soil. Industrially polluted, metal sulphate amended and sewage sludge treated soils were used in our study. Cadmium sulphate amended and industrially contaminated soils all had > 65% of the total soil solution Cd present as free Cd2+. However, increasing total soil Cd concentrations by adding CdSO4 resulted in smaller total soil solution Cd. Consequently, the free Cd2+ concentrations in soil solutions extracted from these soils were smaller than in the same soil contaminated by sewage sludge addition. Amendment with ZnSO4 gave much greater concentrations of free Zn2+ in soil solutions compared with the same soil after long-term Zn contamination via sewage sludge additions. Our results demonstrate the difficulty in comparing total soil solution and free metal ion concentrations for soils from different areas with different physiochemical properties and sources of contamination. However, when comparing the same Woburn soil, Cd was much less available as Cd2+ in soil solution from the CdSO4 amended soils compared with soil contaminated by about 36 years of sewage sludge additions. In contrast, much more Zn was available in soil solution as free Zn2+ in the ZnSO4 amended soils compared with the sewage sludge treated soils.     

Mobility of aniline, benzoic acid, and toluene in four soils and correlation with soil properties

Soil properties and retention mechanisms affecting the relative mobility of aniline, benzoic acid, and toluene in Cecil sandy loam (clayey, kaolinitic, thermic Typic Hapludults), Holdredge silt loam (fine-silty, mixed, mesic Typic Argiustolls), Sharpsburg silty clay loam (fine, montmorillonitic, mesic Typic Argiudolls), and Valentine fine sand (mixed, mesic Typic Ustipsamments) were delineated in laboratory studies. The effect of the synthetic organic compounds (SOCs) was also determined on effective organic campounds (SOCs) was also determined on effective cation exchange capacity (ECEC) of the soils. Benzoic acid was most mobile of the SOCs but was retained in the Cecil soil by hydrogen bonds to Fe oxides. Toluene was least mobile and probably was hydrophobically sorbed to all soils. Aniline was electrostatically retained in protonated form to organic and inorganic exchange sites of the soils and reduced the ECEC of aniline-treated Holdredge and Sharpsburg soils.     

Degradability of ethylenediaminedisuccinic acid (EDDS) in metal contaminated soils: implications for its use soil remediation

Previous research has identified ethylenediaminedisuccinate (EDDS) as a promising biodegradable alternative for persistent compounds such as EDTA for application in soil washing or enhanced phytoextraction of heavy metals. This study examines heavy metal mobilization in three polluted soils varying in soil composition, with specific attention for competitive behaviour for complexation between the various metals and major elements, such as Al, Fe, Mn, Ca and Mg. In addition, amendment biodegradability was compared between the different soil types. The selected soils included a moderately contaminated calcareous clayey soil, a dredged sediment derived surface soil with similar soil characteristics yet more heavily polluted with Cd, Cr and Zn, and a sandy soil moderately contaminated by historical smelter activity (atmospheric deposition). Biodegradability of EDDS in the three soils varied distinctly. This was mainly expressed in the duration of the lag phase prior to metal complex degradation, and not so much in the half life when degradation effectively did set in. Differences in the lag phase were attributed to differences in soil pollution. However, EDDS was fully degraded within a period of 54 d in all soils regardless of initial delay. Assessment of the cation mobilisation patterns in the three soils under study revealed that mainly Ca, Fe and Al can reduce effectiveness of heavy metal mobilisation by competition for complexation.     

Speciation and distribution of copper in a mining soil using multiple synchrotron-based bulk and microscopic techniques

Molecular-level understanding of soil Cu speciation and distribution assists in management of Cu contamination in mining sites. In this study, one soil sample, collected from a mining site contaminated since 1950s, was characterized complementarily by multiple synchrotron-based bulk and spatially resolved techniques for the speciation and distribution of Cu as well as other related elements (Fe, Ca, Mn, K, Al, and Si). Bulk X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy revealed that soil Cu was predominantly associated with Fe oxides instead of soil organic matter. This agreed with the closest association of Cu to Fe by microscopic X-ray fluorescence (U-XRF) and scanning transmission X-ray microscopy (STXM) nanoanalysis, along with the non-occurrence of photoreduction of soil Cu(II) by quick Cu L_3,2-edge XANES spectroscopy (Q-XANES) which often occurs when Cu organic complexes are present. Furthermore, bulk-EXAFS and STXM-coupled Fe L_3,2-edge nano-XANES analysis revealed soil Cu adsorbed primarily to Fe(III) oxides by inner-sphere complexation. Additionally, Cu K-edge μ-XANES, L_3,2-edge bulk-XANES, and successive Q-XANES results identified the presence of Cu₂S rather than radiation-damage artifacts dominant in certain microsites of the mining soil. This study demonstrates the great benefits in use of multiple combined synchrotron-based techniques for comprehensive understanding of Cu speciation in heterogeneous soil matrix, which facilitates our prediction of Cu reactivity and environmental fate in the mining site.     

异喹啉季铵盐在盐酸中对A3钢的吸附及其缓蚀作用

采用失重、电化学法研究了异喹啉季铵盐在 1mol/L盐酸溶液中对A3钢的缓蚀行为及吸附规律。实验表明 ,异喹啉季铵盐是一种阴、阳极混合型缓蚀剂 ,其缓蚀性能优良 ,在A3钢表面产生化学吸附 ,吸附过程为放热反应。     

An investigation of inorganic antimony species and antimony associated with soil humic acid molar mass fractions in contaminated soils

The presence of antimony compounds is often suspected in the soil of apple orchards contaminated with lead arsenate pesticide and in the soil of shooting ranges. Nitric acid (1M) extractable Sb from the shooting range (8300 microg kg(-1)) and the apple orchard (69 microg kg(-1)) had considerably higher surface Sb levels than the control site (<1.5 microg kg(-1)), and Sb was confined to the top approximately 30 cm soil layer. Sb(V) was the principal species in the shooting range and the apple orchard surface soils. Size exclusion chromatography-inductively coupled plasma-mass spectrometry (SEC-ICP-MS) analysis of humic acids isolated from the two contaminated soils demonstrated that Sb has complexed to humic acid molar mass fractions. The results also indicate that humic acids have the ability to arrest the mobility of Sb through soils and would be beneficial in converting Sb(III) to a less toxic species, Sb(V), in contaminated areas.     

重金属污染土壤淋洗技术的基础研究与工程应用进展

随着城市结构调整,工业企业易地搬迁后遗留下大量污染场地,严重威胁人居环境,亟待开展土壤修复.土壤淋洗技术具有工艺简单、处理范围广、修复效率高和治理费用相对低廉等优点,是目前修复重金属污染土壤最有效的技术之一,同时对于有机物污染土壤也具有显著修复效果.经过大量资料、文献调研,系统梳理土壤淋洗技术在国内的研究现状,结合实际...     

马来酸酐-丙烯酸共聚物的合成及在石灰浆液吸收SO2废气中的应用

以水作溶剂、过氧化物作引发剂合成马来酸酐与丙烯酸共聚物,详细探讨了共聚物组成、引发剂浓度、反应温度和时间等因素对共聚物稳定分散Ca(OH)2碱性悬浮液吸收SO2废气的影响.结果表明,该生物降解性无磷、无氮型水质稳定剂对碱液吸收SO2的效率可提高50%以上.     

Experimental approaches and analytical techniques for determining organic compound bound residues in soil and sediment

Research has shown that many chemicals form persistent and permanently bound residues in soils and sediments that play an important role in soil and sediment detoxification processes, long-term compound partitioning behaviour and compound bioavailability and toxicity in soil and sediment. This article reviews the methodological approaches that have been applied to determine the nature of bound residues in soil and sediment, the application of specific analytical techniques, the type of information they generate, and their relative advantages and disadvantages. It begins by defining bound residues and discussing soil-compound interactions. The application of model compound studies for elucidating specific binding interactions is reviewed along with long-term laboratory and field soil incubation experiments. The use of radiolabelled compounds, isotopically labelled compounds and combinations of both in these experiments are outlined by examples from the literature, along with sequential extraction schemes for releasing bound residues from soil, sediment and humic materials. The importance of spectroscopic methods, and particularly nuclear magnetic resonance techniques for characterising the structure of bound residues in soil and sedimentary humic substances is discussed and illustrated by examples from the literature on the subject. The process of bound residue formation is highly complex and requires further research to establish the mechanisms of bound residue formation and their subsequent environmental and toxicological fate. Much of the uncertainty regarding the elucidation of bound residue formation arises from our poor understanding of the structure of soil and sedimentary organic matter. Significant advances in our understanding of the formation and fate of bound residues will be made when we develop a deeper insight into the complex and heterogeneous structure of soil and sedimentary organic matter.     

Soil identification and chemometrics for direct determination of nitrate in soils using FTIR-ATR mid-infrared spectroscopy

The use of mid-infrared attenuated total reflectance (ATR) spectroscopy enables direct measurement of nitrate concentration in soil pastes, but strong interfering absorbance bands due to water and soil constituents limit the accuracy of straightforward determination. Accurate subtraction of the water spectrum improves the correlation between nitrate concentration and its nu3 vibration band around 1350 cm(-1). However, this correlation is soil-dependent, due mostly to varying contents of carbonate, whose absorbance band overlaps the nitrate band. In the present work, a two-stage method is developed: First, the soil type is identified by comparing the "fingerprint" region of the spectrum (800-1200 cm(-1)) to a reference spectral library. In the second stage, nitrate concentration is estimated using the spectrum interval that includes the nitrate band, together with the soil type previously identified. Three methods are compared for estimating nitrate concentration: integration of the nitrate absorbance band, cross-correlation with a reference spectrum, and principal component analysis (PCA) followed by a neural network. When using simple band integration, the use of soil specific calibration curves leads to determination errors ranging from 5.5 to 24 mg[N]/kg[dry soil] for the mineral soils tested. The cross-correlation technique leads to similar results. The combination of soil identification with PCA and neural network modeling improves the predictions, especially for soils containing calcium carbonate. Typical prediction errors for light non-calcareous soils are about 4 mg[N]/kg[dry soil], whereas for soils containing calcium carbonate they range from 6 to 20 mg[N]/kg[dry soil], which is less than four percent of the concentration range investigated.     

Survival, Pb-uptake and behaviour of three species of earthworm in Pb treated soils determined using an OECD-style toxicity test and a soil avoidance test

Mature (clitellate) Eisenia andrei Bouché (ultra epigeic), Lumbricus rubellus Hoffmeister (epigeic), and Aporrectodea caliginosa (Savigny) (endogeic) earthworms were placed in soils treated with Pb(NO(3))(2) to have concentrations in the range 1,000 to 10,000 mg Pb kg(-1). After 28 days LC50(-95%confidence limit)(+95%confidence limit) values were E. andrei 5824(-361)(+898) mg Pb kg(-1), L. rubellus 2867(-193)(+145) mg Pb kg(-1) and A. caliginosa2747(-304)(+239) mg Pb kg(-1) and EC50s for weight change were E. andrei2841(-68)(+150) mg Pb kg(-1), L. rubellus1303(-201)(+240) mg Pb kg(-1) and A. caliginosa1208(-206)(+212) mg Pb kg(-1). At any given soil Pb concentration, Pb tissue concentrations after 28 days were the same for all three earthworm species. In a soil avoidance test there was no difference between the behaviour of the different species. The lower sensitivity to Pb exhibited by E. andrei is most likely due to physiological adaptations associated with the modes of life of the earthworms, and could have serious implications for the use of this earthworm as the species of choice in standard toxicological testing.     

Influence of flooding and metal immobilising soil amendments on availability of metals for willows and earthworms in calcareous dredged sediment-derived soils

Soil amendments previously shown to be effective in reducing metal bioavailability and/or mobility in calcareous metal-polluted soils were tested on a calcareous dredged sediment-derived soil with 26 mg Cd/kg dry soil, 2200 mg Cr/kg dry soil, 220 mg Pb/kg dry soil, and 3000 mg Zn/kg dry soil. The amendments were 5% modified aluminosilicate (AS), 10% w/w lignin, 1% w/w diammonium phosphate (DAP, (NH₄)₂HPO₄), 1% w/w MnO, and 5% w/w CaSO₄. In an additional treatment, the contaminated soil was submerged. Endpoints were metal uptake in Salix cinerea and Lumbricus terrestris, and effect on oxidation-reduction potential (ORP) in submerged soils. Results illustrated that the selected soil amendments were not effective in reducing ecological risk to vegetation or soil inhabiting invertebrates, as metal uptake in willows and earthworms did not significantly decrease following their application. Flooding the polluted soil resulted in metal uptake in S. cinerea comparable with concentrations for an uncontaminated soil.     

A comparison of filter,denuder, and real-time chemiluminescence techniques for nitric acid determination in ambient air

Measurements of gas-phase nitric acid were made by four separate techniques during a 7-day summertime period at a near-coastal site on Long Island, NY. Results from methods intercomparison data for HNO₃, and their relationship to particulate NO₃⁻ and other odd N and oxidant species show the following: (a) high-volume filter pack HNO₃ concentrations are well correlated with diffusion denuder difference (DD) results, except for small absolute losses with the former; (b) daytime real-time two-channel chemiluminescence HNO₃ levels correlated well with DD results, but were higher during night-time periods; (c) results by a new Al₂(SO₄)₃ denuder/thermal evolution technique were not in agreement with other techniques. Based on HNO₃ and paniculate NO₃ results reported herein, it appears that negative errors in HNO₃filter-sampling techniques resulting from HNO₃ loss by sorption generally exceed positive errors NH₄NO₃ volatilization at this site.