Effect of soil aging on arsenic fractionation and bioaccessibility in inorganic arsenical pesticide contaminated soils

Ingestion of As – contaminated soil by children is a growing concern in former agricultural lands converted to residential or recreational land use areas. The mobility and bioavailability of As is controlled by its reactions with soil particles. The degree and strength of As retention by soil constituents may vary greatly with time. The present authors hypothesize that aging results in reduced mobility of As thereby decreasing As release and its bioavailability. The present study is aimed at evaluating the effect of aging on soil As fractionation and bioaccessibility in a temperature and humidity-controlled greenhouse setting. The design allowed the evaluation of dynamic interactions between soils, pesticides, water, and plants. Therefore, 4 soil types (Immokalee, Millhopper, Pahokee Muck, and Orelia) were selected based on their potential differences in As reactivity. The soils were amended with the pesticide Na arsenate at two rates. Rice was used as the test crop. Soil samples collected after different time periods (0, 6 months, 1 a and 3 a) were extracted for soil-As forms via a sequential extraction technique. Bioaccessible As was extracted via an in vitro gastrointestinal method. At time 0, most of the extractable As in soil was in the soluble form, resulting in high bioaccessibility. As expected, soluble and exchangeable fractions decreased with time for up to 6 months, but remained constant thereafter. After 3 a of soil–pesticide equilibration, As bioaccessibility was still high in all the soils except for the Pahokee Muck. No significant difference in As bioaccessibility was observed between the soils. Arsenic was present predominantly as As(V) with 5–10% of the total dissolved As being present as As(III). Data obtained suggest that although aging had an impact on the geochemical forms, gastric pH was the sole important factor effecting As bioaccessibility.     

Transformation of metal speciation in purple soil as affected by waterlogging

This study was conducted to investigate the effect of waterlogging on copper, lead and cadmium fractionation in Chinese purple soil. Heavy metals were added to purple soil at 80 % field capacity and waterlogging regimes as nitrate salts of 500 mg kg^?1 of copper and lead, and 5 mg kg^?1 of cadmium. Metals in the incubated soil samples were fractionated termly from 1 to 35 days by the sequential extraction procedure. Under both treatments, the heavy metals spiked in the soil were transformed slowly from the exchangeable fractions into more stable fractions, whereas their residual fractions barely changed. The transformation process of exchangeable fraction in soil was estimated by Elovich kinetic equation for the above incubation periods, and the constant B in Elovich equation was applied to reflect the transformation rates of metal speciation. It was found that waterlogging incubation could immobilize heavy metals, resulting in decreased lability and availability of the metals in purple soil. The effect of waterlogging on the redistribution of heavy metals in purple soil might be mainly related to the changes of pH, potential redox and hydrous oxides in varying soil-water systems.     

浙江典型富硒区硒与重金属的形态分析

通过对浙江西部龙游地区富硒土壤中Hg、Cd、Pb、As等重金属含量的研究表明,成土母岩中与硒伴生的重金属含量较高,由于特殊的地形地貌、母岩风化物质搬运条件以及有利的土壤理化性质等,土壤中重金属大为减少。异常地段重金属形态分析结果表明:土壤中仅有Cd的全量、离子交换态、碳酸盐结合态和弱有机态较高,分别为0.6mg/kg、22.1%、26.5%、11.4%;Se全量平均为0.89 mg/kg,离子交换态、弱有机态含量分别为1.12%、26.4%,碳酸盐结合态仅为0.62%。尽管如此,区内莲子、稻米等农产品仍表现出高硒低重金属等特点,居民健康长寿,发硒含量高,从而为龙游县开发富硒农产品提供了有利条件。     

The development of a multi-surface soil speciation model for Cd (II) and Pb (II): Comparison of two approaches for metal adsorption to clay fractions

The mobility of toxic metals in soils or sediments is of great concern to scientists and environmentalists since it directly affects the bioavailability of metals and their movement to surface and ground waters. In this study, a multi-surface soil speciation model for Cd (II) and Pb (II) was developed to predict the partition of metals on various soil solid components (e.g. soil organic matter (SOM), oxide mineral, and clay mineral). In previous study, the sorption of metal cations on SOM and oxide minerals has been evaluated by thermodynamically based surface complexation model. However, metal binding to soil clay fractions was normally treated in a simplistic manner: only cation exchange reactions were considered and exchange coefficient was assumed unity. In this study, the binding of metals onto clays was described by a two-site surface sorption model (a basal surface site and an edge site). The model was checked by predicting the adsorption behavior of Cd (II) and Pb (II) onto three selected Chinese soils as a function of pH and ionic strengths. Results showed that the proposed model more accurately predicted the metal adsorption on soils under studied condition, especially in low ionic strength condition, suggesting that adsorption of metals to soil clay fractions need to be considered more carefully when modeling the partition of trace elements in soils. The developed soil speciation model will be useful when evaluating the movement and bioavailability of toxic metals in soil environment.     

江西赣县清溪地区土壤硒地球化学特征和水稻根系土硒生物有效性影响因素

江西赣南地区是典型的硒缺乏地理分布区,但近年来研究成果表明该地区稻谷富硒率高,土壤与稻谷富硒存在不一致的原因尚不明确,探讨土壤和稻谷硒含量特征和土壤硒的生物有效性,对赣南地区富硒土地资源利用和富硒农产品开发具有重要意义。本文以赣县清溪地区为研究对象,采用电感耦合等离子体质谱/发射光谱(ICP-MS/OES)等方法测定了研究区1734件表层土壤、57组稻谷及配套根系土硒等元素含量及硒形态地球化学指标;系统分析了区内土壤硒含量和分布特征、稻谷硒含量特征,探讨了根系土硒生物有效性的影响因素。结果表明:研究区表层土壤以足硒、富硒区为主,土壤硒含量与成土母岩关系密切,不同成土母岩区土壤硒含量规律为:古生代变质岩中生代花岗岩新元古代变质岩中生代陆源碎屑岩新生代第四系。根系土硒含量均未达到富硒土壤标准,稻谷富硒率为64.91%,稻谷对土壤硒的富集能力强(富集系数20.05%),当根系土硒含量≥0.25mg/kg时,水稻富硒率高达70.83%,能够稳定产出优质富硒水稻。硒的赋存形态是影响土壤硒生物有效性的主要因素,土壤总硒含量较低时,水溶态、离子可交换态、碳酸盐结合态硒的占比高,从而提升了硒的生物有效性;有机质含量低,对硒吸附能力弱,也是硒生物有效性高的重要原因。本研究认为,赣县清溪地区富硒、足硒土壤开发利用时,综合考虑土壤硒含量、土壤理化指标、硒形态对土壤硒生物有效性的影响,有利于科学指导天然富硒土地划定和富硒水稻产业开发。     

茶园土壤不同形态镍的含量及其影响因素

通过自然茶园土壤采样和室内实验分析,探讨浙江、江苏和安徽13个茶园土壤镍的污染状况、形态分布规律以及不同形态镍的含量与土壤镍总量和土壤理化性质的关系。结果表明：部分茶园土壤受到不同程度的镍污染;茶园土壤镍的形态分布有一定差异,按镍的含量多少排序,一般为残渣态＞交换态＞铁锰氧化物结合态＞有机结合态＞碳酸盐结合态;除了交换态以外的所有其他形态的镍含量均随土壤镍含量的增加而显著增加;碳酸盐结合态、铁锰氧化物结合态和残渣态镍含量随土壤pH的升高呈显著增加趋势,而交换态镍则呈减少趋势,但不显著;随土壤有机质含量的增加,铁锰氧化物结合态镍显著减少,而其他形态增加或减少的趋势均不显著;碳酸盐结合态、有机结合态和残渣态的镍含量均随阳离子交换量的增加显著增加;随粘粒含量的增加所有形态中的镍呈增加趋势,但除了残渣态外增加趋势均不显著。     

Solid speciation and availability of chromium in ultramafic soils from Niquelândia, Brazil

The sources and the potential availability of chromium were investigated in ultramafic soils from Niquelândia (Goïas State, Brazil), with chemical extractions associated to mineralogical studies, in order to evaluate its bioavailability and its potential impact on the soil biodiversity. Cr contents are particularly high in the studied soils and its partitioning among the solid phase varies with the position in the landscape and depth. Most of the Cr is associated to Fe-oxides but the amount of exchangeable Cr(VI) is high, particularly in one soil profile. Cr availability is higher than expected, and Cr-tolerant vegetation is probably growing on these soils.     

氨基泡塑的合成及其应用于富集地质样品中的痕量金

采用泡塑(PUF)富集,AAS或ICP-OES测定地质样品中痕量金是常用的分析方法。与活性炭相比,PUF的选择性好,但吸附容量偏低,可将泡塑负载不同的萃取剂或修饰不同的官能团提高吸附容量。本文将聚醚型泡塑经盐酸水解制备成氨基泡塑(PUF-NH_2)。红外光谱和扫描电镜表征显示,PUF-NH_2峰形发生了明显红移(3376.5 cm-1),其中的氨基数量显著增加,另外PUF-NH_2的高分子出现明显断裂,发生水解后裸露出的氨基具有还原性,在吸附金的过程中易与金离子在PUF-NH_2表面发生氧化还原反应,形成金纳米颗粒。改性后的PUF-NH_2吸附容量达到96 mg/g,与PUF相比提高了8倍。将PUF-NH_2应用于富集地质样品中的金,经炭化灼烧、50%王水提取后用ICP-OES测定,金的加标回收率在95.0%~105.0%之间,检出限为0.15μg/g。实验证明用PUF-NH_2处理样品提高了富集倍数和分析灵敏度,有利于低品位矿石的分析。     

Chemical partitioning of trace and major elements in soils contaminated by mining and smelting activities

Soils from historical Pb mining and smelting areas in Derbyshire, England have been analysed by a 5-step sequential extraction procedure, with multielement determination on extraction solutions at each step by ICP-AES. Each of the chemical fractions is operationally defined as: (i) exchangeable; (ii) bound to carbonates or specifically adsorbed; (iii) bound to Fe–Mn oxides; (iv) bound to organic matter and sulphides; (v) residual. The precision was estimated to be about 5%, and the overall recovery rates were between 85 and 110%. The carbonate/specifically adsorbed and Fe–Mn oxide phases are the largest fractions for Pb in soils contaminated by both mining and smelting. Most of the Zn is associated with Fe–Mn oxide and the residual fractions. Cadmium is concentrated in the first 3 extraction steps, particularly in the exchangeable phase. The most marked difference found between soils from the mining and smelting sites is the much higher concentrations and proportions of metals in the exchangeable fraction at the latter sites. This indicates greater mobility and potential bioavailability of Pb, Zn and Cd in soils at the smelting sites than in those in the mining area. The most important fraction for Fe and Al is the residual phase, followed by the Fe–Mn oxide forms. In contrast, the Fe–Mn oxide fraction is the dominant phase for Mn in these soils. In the mining area, most of the Ca is in the carbonate fraction (CaCO₃), while the exchangeable and residual phases are the main fractions for Ca at the smelting sites. Phosphorus is mainly in the residual and organic fractions in both areas. The exchangeable fractions of Pb, Zn and Cd in soils were found to be significantly related to the concentrations of these metals in pasture herbage.     

类芽孢杆菌对铜陵新桥矿区土壤中Cu化学形态的影响

采用Tessier五步连续提取法和红外光谱技术,研究类芽孢杆菌对铜陵新桥矿区重金属污染土壤中Cu化学形态的影响,初步探讨了Cu形态变化的机理。结果表明,不同投入量的类芽孢杆菌接种到土壤培养一周后,土壤溶液pH值降低,土壤中可交换态、有机结合态Cu含量增加,碳酸盐结合态、铁锰氧化物结合态和残渣态Cu的含量降低。土壤中可交换态、铁锰氧化物结合态和残渣态Cu含量的变化主要受土壤溶液的pH值控制;有机结合态升高主要与类芽孢杆菌菌数及其代谢产生的低分子量有机酸有关。类芽孢杆菌可以改变矿区土壤中Cu的化学形态,影响Cu的生物有效性。     

Sorption and distribution of adsorbed metals in three soils of India

The mobility and bioavailability of heavy metals depends on the metal retention capacity of soil and also on the geochemical phases with which metals are associated. Laboratory batch experiments were carried out to study the sorption and distribution of Cd, Ni and Pb in 3 soils differing in their physicochemical properties from India: Oxyaquic Haplustalf (SL1), Typic Haplustalf (SL2) and Typic Haplustert (SL3). The heavy metal adsorption was studied by isotherms and the distribution coefficient (K_D) for each metal was obtained from the linear regressions of the concentration of metal remaining in equilibrium solution and the amount adsorbed. In general, the sorption capacity for all the metals decreased in the order: SL3>SL2>SL1. Among metals, the sorption capacity in all the soils decreased in the order: Pb>>Ni>Cd. Distribution of sorbed metals at various equilibrating concentrations was studied by sequential extraction. Results showed significant differences in the distribution of metals in these soils. At higher additions (such as 200 μM l⁻¹) most of the metals were extracted in their more mobile fractions, exchangeable and/or inorganic in contrast to their original partitioning in soils, where they were preferentially associated with the less mobile residual fraction. Largest percentages of metals extracted in the exchangeable fraction corresponded to those soil–metal systems with smaller K_D values, e.g. Cd, Ni and Pb in SL1 and Cd and Ni in SL2. In neutral and alkaline soils (SL2, pH=7.1, and SL3, pH=8.6) Pb was predominantly extracted from the inorganic fractions and this corresponded to higher K_D values for Pb in these soils. The predominance of metals associated with the exchangeable fraction together with low K_D values indicates higher mobility of metals retained in the acidic soil (SL1, pH=5.2) compared with the others.     

铜陵矿区水系沉积物中重金属存在形态特征研究

通过对铜陵水系沉积物重金属形态分析实验,研究了重金属各种形态在沉积物中分布特征。分析结果显示,矿区水系沉积物中Cu、Pb、Zn、Cd等重金属含量都显著的高于对照样品,水系已经受到重金属的污染。提出了防治和改善铜陵地表水环境污染的措施。     

Mercury, copper and zinc contamination in soils and fluvial sediments from an abandoned gold mining area in southern Minas Gerais State, Brazil

Mercury, zinc and copper contamination was evaluated in soils and fluvial sediments from an abandoned gold mining site at Descoberto Municipality (southern Minas Gerais State, Brazil). Metals bioavailability and potential mobility were studied through physical, chemical and mineralogical characterization, geoaccumulation indexes calculations, mercury speciation and determination of potentially bioavailable contents of zinc and copper. Values of pH were in the neutral range, while organic matter concentrations were very low. Mineralogical characterization, in the total samples, indicated the presence of quartz, kaolinite and gibbsite for all samples. Total mercury, zinc and cooper concentrations were higher than the limits recommended by Brazilian documents. Geoaccumulations indexes revealed that most of the sediment samples were low to moderately polluted by zinc and copper, while just one sample was very strongly polluted by mercury. Mercury speciation revealed the predominance of the elementary form for all samples, and low concentrations for exchangeable, strongly bound and residual fractions. Zinc and copper behavior was strongly controlled by iron and aluminum concentrations, while their bioavailable contents were very low in comparison with the total concentrations.     

基于DGT技术对土壤硒生物有效性及其影响因素的分析

硒是生态环境中重要的微量元素之一,如何准确评估其生物有效性一直存在争议。在四川省广安市邻水县采集了60套农作物及其根系土样品,分析其Se含量和理化性质。同时基于梯度扩散膜技术对土壤有效Se含量进行分析,并对土壤有效Se含量的影响因素进行探究。结果表明,研究区土壤Se含量为0.15~2.42 mg/kg,均值为0.48 mg/kg,不同类型土壤Se含量差异明显,石灰土(1.06 mg/kg)>黄壤(0.78 mg/kg)>紫色土(0.28 mg/kg)>水稻土(0.27 mg/kg)。石灰土和黄壤有机质含量和总铁(TFe₂O₃)含量明显高于其他类型土壤。研究区内不同类型土壤的DGT-Se明显不同,与土壤Se含量分布相反。相关性分析表明土壤DGT-Se与Se含量、TFe₂O₃含量、S含量、有机质含量、pH值、Al₂O₃含量显著相关,受理化性质影响导致不同类型土壤中DGT-Se的差异。水稻根系土壤DGT-Se与水稻籽实Se含量显著正相关,用DGT可以较好地表达水稻-根系土系统中土壤Se的生物有效性。基于DGT技术评估预测区域尺度农业土壤有效Se含量时,需充分考虑土壤类型及其理化性质。     

Influence of temperature decrease and soil drought on the geochemical fractionation of 60Co and 137Cs in fluvisol and cambisol soils

Consideration of the impact of substantial changes in soil temperature or moisture regime on the geochemical forms of radionuclides is important for more accurate assessment of the environmental risk posed by radionuclide migration and potential biological availability, especially in the first months after their release into the environment. This paper presents the results from a study of the influence of cooling, freezing and soil drought on the migration and potential bioavailability of ⁶⁰Co and ¹³⁷Cs in two soils (a fluvisol and a cambisol, according to the World Reference Base for Soil Resources/FAO) from Bulgaria. The changes in the geochemical fractionation of ⁶⁰Co, the exchangeable ¹³⁷Cs and water-soluble forms of both radionuclides were examined under different storage conditions up to 5 months after their introduction into the soils in solution form. Freezing or soil drought resulted in a significant increase of the water-soluble forms of ⁶⁰Co in the fluvisol soil, defining higher mobility and potential bioavailability. No influence of the storing conditions on the water-solubility of ⁶⁰Co in the cambisol soil was established. The cooling, freezing and soil drought caused an increase of the exchangeable ¹³⁷Cs in both soils.     

The distribution of lithium in selected soils and surface waters of the southeastern U.S.A.

The distribution of Li in the environment is not well documented although its geochemistry is thought to influence human health and agriculture. This study examined the distribution of Li in the soils and surface waters of the southeastern U.S.A., contrasting the Piedmont and Coastal Plain regions. Previous studies have been limited to total, and to a lesser extent exchangeable, soil Li, usually at a single soil depth. This study evaluated more carefully the distribution of Li between the soil solution, exchange, and solid phases, and its distribution within soil profiles. Total soil Li was found to correlate strongly with clay content, and ranged from 3.74 to 59.93 mg/kg. Exchangeable Li ranged from 0.1 to 21.8 μmol/kg soil and constituted an insignificant portion of the total exchangeable cations (<0.09%) and total Li present (<1.1%) in the soils studied. Water-soluble Li ranged from 0.08 to 4.62 μg/l. Dissolved Li in 22 surface waters within the Piedmont and Coastal Plain regions of Georgia and South Carolina was also determined and ranged from 0.26 to 4.16 μg/l. The soils and surface waters of the Coastal Plain region were found to be depleted in Li relative to the Piedmont region of the southeastern U.S.A.     

关于土壤中“化学定时炸弹”及其触爆因素的探讨

运用目前环境科学研究中较为流行的“化学定时炸弹”的概念,详细分析了我国土壤中可能的“化学定时炸弹”。认为土壤中存在着地带性和泛地带性的“化学定时炸弹”,地带性的包括土壤盐渍化、土壤酸化等;泛地带性的包括施肥造成的、工业污染造成的及特殊成土作用形成的“化学定时炸弹”。同时,探讨了导致土壤中这些“化学定时炸弹”内在和外在的可能触爆因素。提出了今后开展该领域宏观和微观研究的方向和建议。     

Release kinetics and distribution of boron in different fractions in some calcareous soils

The aim of this study was to evaluate the release kinetics, speciation, and fractionation of boron (B) in some calcareous soils of western Iran. Ten surface soil samples were incubated with 100 mg B kg^?1 for a week at field capacity moisture. After air drying of samples, the trend of B release was experimented using sequential extraction with 10 mM CaCl₂. B speciation in soil solution was calculated for the first and the last steps of extraction by the visual MINTEQ program. The distribution of B among five fractions including exchangeable (F1), specially adsorbed (F2), bound by Fe–Mn oxides (F3), organically bound (F4) and residual (F5), was determined in control and spiked soils. The results indicated that the release rates were initially rapid followed by a slower reaction and the main proportion of the added B was extracted by CaCl₂. The release kinetics of B was described well with Elovich, parabolic diffusion, power function, and first-order equations. The speciation results revealed that the uncharged boric acid (H₃BO ₃ ⁰ ) was the dominant species in soil solutions. In control soils, B concentration in different fractions decreased in the following order: F5 > F1 > F2 > F3 > F4. In spiked soils, however, the largest and the smallest fractions were exchangeable and residual, respectively. This implies that B transformation from soluble to less mobile and non-labile forms is not a rapid process and requires more than a week. The significant relationship observed between kinetic parameters of power and parabolic equations and organically bound B fraction and OM content indicated that organic matter played an important role in B adsorption and release in calcareous soils.     

Speciation,fractionation and plant availability of arsenic as induced by sorbents mixed with soil of Zarshuran (Iran)

The aim of this work was to investigate the effects of sorbent (natural and modified zeolite and bentonite, iron filings and ferric sulfate) on the speciation and bioavailability of arsenic in contaminated soil. The soil used in this experiment was collected from Zarshuran area (Western Azerbaijan province, NW Iran). The sorbents were added to the soil in various rates separately. After a month of incubation, sunflower was planted in pots. After harvest, soil and plant samples of each pot were analyzed. Then various species of arsenic were estimated in soil solutions by MINTEQ software program. Water-soluble arsenate, arsenite and exchangeable arsenic from each pot measured. The results showed that the sorbents had no effect on the speciation of arsenic. Mobility of arsenite in the soil solutions has not changed. Soils treated with natural bentonite and zeolite increased soluble arsenate concentration and decreased exchangeable arsenic concentration. Although Fe-zeolite increased soluble arsenate concentration, Fe-bentonite, iron filings and ferric sulfate decreased soluble arsenate concentration and exchangeable arsenic concentration. Finally, iron filings (containing 354 mmol Fe⁺³) vigorously increases in the plants biomass and decreases in the arsenic concentration in plants tissue, is suggested as the best sorbent for arsenic stabilization in the region.