土壤对砷的缓冲性及平衡时间与污染次数的关系

本文研究了邯郸马头镇土壤对砷的缓冲性及其随平衡时间、污染次数的动态变化规律、土壤对砷的缓冲速率及吸附量与时间的关系。为正确评价，预报预测土壤砷的污染状况提供科学依据。     

四种典型重金属污染对土壤吸附磷的影响

以空白土壤和人工制备的不同浓度铜、砷、镉和铅污染土壤为对象,研究了在不同pH值、温度和柠檬酸浓度条件下重金属污染对土壤吸附磷的影响,并对其进行了相关过程的等温和吸附动力学的机理分析。研究结果表明,空白土壤和As污染土壤吸附磷的等温吸附过程符合Temkin方程,Cu、Pb、Cd污染土壤吸附磷的等温吸附过程符合Freundlich方程,空白土壤和重金属污染土壤吸附磷的动力学过程均符合Elovich方程;重金属污染对土壤吸附磷有一定的抑制作用,抑制程度与污染物浓度呈现显著的正相关,且随外在环境因子的改变而不同。当重金属元素铜、铅、砷、镉的含量分别为200、80、25、0.8 mg kg^-1时:pH值为5时,重金属对土壤吸附磷抑制作用最小,土壤吸附磷量分别降低了30.18%、13.54%、30.74%、37.23%,其抑制作用程度为:Cd> As> Cu> Pb;土壤吸附磷量与温度呈现显著的正相关,温度变化为25~45℃时,土壤对磷的吸附量分别增大了17.14%~28.83%、6.72%~16.05%、8.68%~9.13%、10.30%~23.45%,同一条件下重金属对土壤吸附磷抑制作用程度为Cu> Cd> As> Pb;重金属污染土壤吸附磷量与柠檬酸浓度成负相关,柠檬酸浓度为50 mg L^-1时,土壤吸附磷量分别降低了19.87%、21.94%、23.18%、24.84%,相同柠檬酸浓度下其抑制作用程度为Cd> As> Pb> Cu。     

含铁介质用于修复砷污染土壤研究综述

原位固化/稳定化技术被认为是当前土壤砷污染修复中相对经济、高效的技术之一,含铁介质是土壤固砷的一类上佳材料。从含铁材料修复砷污染土壤的研究现状出发,阐述其固砷机理,主要包括吸附、络合作用以及沉淀/共沉淀作用。介绍了5种常用的固砷效果评价方法,分别为化学形态连续提取法、毒性特征浸滤法、植物指示法、体外消化模拟法以及现代物理学方法。阐述了土壤环境条件,如酸碱条件、氧化还原条件以及土壤中共存离子和有机质的变化对固砷效果的影响。总结了目前含铁材料用于修复砷污染土壤的不足之处,并指出了今后的研究重点。     

超声波活化风化煤对土壤砷形态及土壤酶活性的影响

通过土培盆栽试验研究了不同超声波活化风化煤添加量0g/kg,10g/kg,20g/kg,40g/kg,60g/kg对不同浓度砷污染土壤中砷形态及土壤酶活性的影响,结果表明:活化风化煤添加量40~60g/kg,能够最有效地降低土壤中As的可移动性,增加土壤中的残渣态砷,从而降低了土壤中As的生物毒性;添加活化风化煤60g/kg条件下,污染土壤中土壤蔗糖酶活性最高,风化煤添加量40g/kg时,缓解砷抑制土壤脲酶活性的效果最好。所以活化风化煤能够有效改善砷污染土壤质量,降低生物毒性,减轻对植物的毒害作用。     

不同性质铁铝土对砷酸根吸附特性的比较研究

采用批平衡法研究了8种不同性质铁铝土对砷酸根的吸附特性,分别运用Langmuir单表面方程和Langmuir双表面方程对等温吸附数据进行拟合,以较优拟合方程求出土壤对砷的最大吸附量,并采用简单线性相关分析法探讨土壤性质对砷吸附能力的影响。结果显示,铁铝土对砷吸附强烈,吸附等温线均为非线性。双表面方程对吸附等温线的拟合效果优于单表面方程。采用双表面方程预测的吸附量和实测值的决定系数(0.935～0.978)大于采用单表面方程预测获得的决定系数(0.989～0.998)。土壤的砷吸附能力可采用高能表面和低能表面两种吸附位点进行解释。采集于云南昆明的砂页岩母质发育的红壤具有最强的砷吸附能力,根据Langmuir双表面方程计算的最大吸附量为3 498 mg kg-1。土壤的砷吸附能力受到土壤中游离氧化铁、全铝、全铁、黏粒和全磷含量的显著影响,最大吸附量与这几种土壤组成与性质因子呈显著正相关关系。     

土壤矿物质吸附砷的研究进展

砷是一种有毒的重金属元素,由于自然和人为的原因,世界上的许多国家存在砷污染问题,因此有关砷污染的研究与控制日益受到人们的关注。本文介绍了土壤砷污染的产生原因及污染状况,重点集中在探讨土壤中的各种矿物质对砷吸附行为的作用机理。这些矿物质包括铁铝氧化物和氢氧化物、锰氧化物、黏土矿物和碳酸盐类。关于砷在各类矿物质上的吸附机理,普遍接受的观点认为:砷氧阴离子与矿物质的表面发生了配位体交换过程并通过共价键的作用,形成了表面配位体。表面配位体以内层双齿双核鳌合形式为主,受矿物质的种类、pH值和氧化还原电位等因素的影响,外层吸附和其他鳌合状态可能存在。砷在土壤矿物质上的吸附效果强烈依赖于体系的pH值,这与吸附的理论模型和数学计算结果相一致。矿物质的种类、组成、结晶状态和表面积等影响了砷的吸附过程和吸附效果。土壤中存在的各种阴阳离子通过与砷阴离子竞争吸附位而影响砷在矿物质上的吸附。     

离子强度和磷酸盐对铁铝矿物及土壤吸附As（V）的影响

选用针铁矿、赤铁矿、水铁矿、水铝矿4种铁铝矿物以及性质差异较大的黑土、紫色土和红壤3种土壤,研究离子强度和磷酸盐对其吸附As（V）的影响。结果表明,在0．01、0．1、1mol·L^-13种离子强度下,矿物和土壤对As（V）的吸附量无明显差异或随离子强度增大而增大,其对砷的吸附以专性吸附为主。磷酸盐对矿物和土壤吸附砷的影响与其添加顺序及摩尔浓度比有关。水铝矿和水铁矿在这3种添加顺序下的砷吸附量无明显差异,仅在P／As摩尔比较大时表现出下降趋势;而在针铁矿和赤铁矿两种矿物上,先添加砷时的砷吸附量高于先添加磷时或两者同时添加时,且砷吸附量随WAs摩尔比的增加而逐渐下降。在黑土、紫色土和红壤上,先添加砷比先添加磷或两者同时添加时的砷吸附量均要高,尤其是在紫色土上。随P／As摩尔比升高,土壤对砷的吸附量表现出下降趋势。     

土壤砷污染及其修复技术的研究进展

土壤砷污染已成为严重的环境和公共健康问题,日益受到人们的密切关注。综述了土壤砷污染的现状、来源及其危害,同时探讨了土壤砷污染的物理化学修复和生物修复（特别是植物修复）技术的研究现状;并对今后砷污染修复研究方向进行了展望。     

镉砷复合污染土壤钝化材料研究进展

我国土壤重金属污染严重,尤以镉砷污染最为突出。镉砷复合污染土壤中各元素间表现为拮抗和协同等作用,其有效态含量受土壤pH变化和氧化还原电位等的影响,增加了镉砷复合污染土壤的修复难度,严重威胁我国粮食安全。综述了常见的镉砷复合污染土壤钝化修复材料的优缺点及其对镉砷复合污染土壤钝化修复效果和机理。常见的钝化材料有生物质炭类、磷酸盐类、金属及其氧化物类、含硅类材料、黏土矿物类、有机肥类和新型材料等。有大量研究表明生物质炭材料对镉有良好的吸附效果,为了同时钝化镉砷,通常使用改性生物质炭或与其他材料配合施用,常见的改性/配施材料有金属及其氧化物、黏土矿物、家禽粪便、复合肥等,其钝化反应机制包括离子交换、共沉淀和表面络合等;磷酸盐类主要与铁盐或铁粉配施,通过吸附和同晶替代钝化镉、点位竞争机制钝化砷;金属及其氧化物类多与生物质炭、石灰和黏土矿物等配施,通过专性吸附和共沉淀钝化镉、氧化还原和络合作用等钝化砷;铁硅肥、硅钙肥、硅钾肥等通过共沉淀钝化镉、专性吸附和点位竞争机制钝化砷;黏土矿物中多施用海泡石,主要与金属氧化物和钙镁磷肥等配施,通过离子交换、沉淀和络合反应钝化镉砷;污泥和动物粪便中含有腐殖化程度较高的有机质,主要通过吸附、氧化还原和有机络合以及微生物作用钝化镉砷;此外,富含巯基和氨基、谷聚多以及富含硫和硒的物质也可有效钝化镉砷。本文对镉砷复合污染土壤钝化修复材料进行总结,归纳了镉砷钝化材料特性,以期为镉砷复合污染土壤修复提供一定的指导。     

土壤砷吸附及砷的水稻毒性

在砖红壤、红壤和黄棕壤上的试验结果表明，砖红壤对Ａｓ＾５＋和Ａｓ＾３＋的吸附最强，红壤次之，黄棕壤最弱，但土壤中砷对水稻的毒性却以砖红壤最大，红壤次之，黄棕壤最小，表明土壤砷对植物的毒性，未必受土壤吸附性能所制约。     

土壤吸附砷酸盐动力学的初步研究

本研究目的是了解陕西省的几种土壤吸附和解吸附砷酸盐的速率和过程,以及其吸附能量。Kuo和Lotse导出的双常数速率公式拟合试验资料优于一级、二级、三级反应公式,抛物线扩散和Elovich公式等五个公式。用双常数速率公式(C=k·C₀·t^1/m)分两段拟合能进一步提高拟合优度。根据Arrhenius公式计算出的吸附活化能是0.70—3.40千卡/克分子。低的活化能表明,供试土壤对砷酸盐的吸附作用是一种完全不同于真溶液条件化学反应的物理学过程。土壤吸附和解吸附砷酸盐的速度和容量受作用时间、温度、溶液∶土壤比率,加入的砷量和浓度,以及土壤特性的影响。粘土的吸附反应常数(k),吸附量比沙壤土大。而沙壤土有高的解吸附反应速度常数(k_-1^'),砷酸盐容易被解吸附而释放出来。     

Effect of Water Extract of Compost on the Adsorption of Arsenate by Two Calcareous Soils

The increasing mobility of arsenate will increase its leachingpotential to groundwater and uptake by plants. The mobility ofarsenate in soils is related to the competitive adsorption with other substances. The effect of organic substances on the adsorption of arsenate by soils was evaluated using the water extract of compost (WEC) as a complex anion source in a batch experiment. Two calcareous slate alluvial soils, Chiwulan andShuipientou, with higher arsenic contents of 23.7 and 12.9 mg kg^-1, respectively, were used. The Langmuir equation has been used to describe successfully the As adsorption isotherm for the two soils. The maximum adsorption of As was 6.098 and 4.785 μmol g^-1 for Chiwulan and Shuipientou soils, respectively. There was competitive adsorption for binding siteson the soils between arsenate oxyanions and organic anions derived from the dissolved organic carbon (DOC) of WEC. Differentcritical pH values were for arsenate addition related to arsenateadsorption on both soils in the absence of DOC of WEC but not inthe presence of DOC of WEC. The soil properties related to arsenate adsorption by the two soils may govern the critical pH values.     

THE HIGH- AND LOW-ENERGY PHOSPHATE ADSORBING SURFACES IN CALCAREOUS SOILS

The two-surface Langmuir equation was used to study P adsorption by 24 calcareous soils (pH 7.2-7.6; 0.8-24.2 per cent CaCO₃) from the Sherborne soil series, which are derived from Jurassic limestone. High-energy P adsorption capacities (x″_m) ranged from 140–345 μg P/g and were most closely correlated with dithionite-soluble Fe. Hydrous oxides therefore appear to provide the principal sites, even in calcareous soils, on which P is strongly adsorbed (x″_m 6–51 ml/μg P). The low-energy adsorption capacities (x″_m) ranged from 400–663 μg P/g and were correlated with organic matter contents and the total surface areas of CaCO₃ but not with per cent CaCO₃, pH, or dithionite-soluble Fe. Total surface areas of CaCO₃ in the soils ranged from 4.0 to 8.5 m²/g soil. Low-energy P adsorption capacities agree reasonably with values (100 pg P/m²) for the sorption of phosphate on Jurassic limestones but phosphate was bonded much less strongly by soil carbonates (k″= 0.08–0.45 ml/μg P) than by limestones (k～10.0 ml/μg P). Low-energy P adsorption in these soils is tentatively ascribed to adsorption on sites already occupied by organic anions (and probably also by bicarbonate and silicate ions) which lessen the bonding energy of co-adsorbed P.     

Verification of the prediction technique for the amount of adsorbed linuron on soils

The Freundlich isotherm was used to estimate the adsorption of the herbicide linuron on 39 Japanese soils to confirm the suitability of the prediction technique used in atrazine adsorption. Linuron was adsorbed on the soils according to the Freundlich isotherm. In conjunction with the log K _F prediction equation derived from the soil characteristics, it was possible to predict the linuron adsorption. Comparison of the equations for linuron with those for atrazine, indicated that the difference in the intercept of the 1 / n regression line against log K _F reflected the adsorptive characteristics of the herbicides.     

不同土地利用方式土壤对铜、镉离子的吸附解吸特征

采用一次平衡法对Cu²⁺、Cd²⁺在城市及城郊农田、林地、草地3种土地利用方式土壤中的吸附解吸过程进行比较研究, 结果表明: Cu²⁺、Cd²⁺在3种土地利用方式土壤中的吸附量均随平衡液浓度的增加而增大, Cu²⁺、Cd²⁺在农田土壤上的吸附量均高于林地和草地土壤。分别用Langmuir和Freunlich两种等温吸附方程对吸附过程进行拟合, 3种土壤对Cu²⁺的吸附过程运用Langmuir方程拟合效果好, 而对Cd²⁺的吸附过程运用Freunlich方程拟合效果更好。Cu²⁺在3种土壤的解吸量大小顺序为农田>林地>草地, Cd²⁺在3种土壤的解吸量大小顺序为农田>草地>林地。两种离子在3种土壤中的动态吸附是个快速反应的过程, 随时间延长, 吸附反应趋于平衡。运用双常数函数方程和Elovich方程能较好地拟合重金属在土壤上的吸附动力学过程。Cu²⁺、Cd²⁺的吸附与土壤黏粒含量、有机质含量、CEC和pH均有关。     

One equation to analyse the pH of soil systems

Starting from the basic equations of chemical equilibrium, an analytical mathematical expression is derived that relates pH to base saturation, concentration of acid anions (SO₄^2?, NO₃^?, etc.) and other properties of the soil and soil solution. The equation is particularly valid in acid soils (low base saturation and relatively large, >100 μmol_c dm^?3, concentration of acid anions) in the range in which cation exchange is the buffering mechanism. Values of pH, alkalinity and degassed pH calculated with the aid of this equation compared well to values measured in three forest-floor horizons; calculated pH values also compared well to values measured on a number of acid soils. The equation is also used to derive analytical mathematical expressions for alkalinity, soil leaching sensitivity (a measure of the sensitivity of a soil solution to become dominated by A1³⁺), and other variables of interest in the context of acidification.     

除草剂咪草烟在土壤上吸附-脱附过程及作用机理

本文研究了咪唑啉酮类除草剂咪草烟在不同土壤固－液相间的分配及与土壤组分作用的定量相关性。结论指出：咪草烟在土壤固－液相的分配主要受土壤粘粒,有机质及土壤ｐＨ的影响。它们在土壤上的吸附－脱除均可用Ｆｒｅｕｎｄｌｉｃｈ方程描述;通过运用红外及Ｘ－衍射技术,从分子水平研究了咪草烟与蒙脱石的作用机理,发现咪草烟与蒙脱的作用不仅发生在表面,而且咪草烟还能进入蒙脱石内层与其层间阳离子形成配合物。     

REACTIONS OF AMMONIA WITH SOIL. I

Heats of adsorption and adsorption isotherms of ammonia gas were measured at 300 K (27 °C) on outgassed soil saturated with Na⁺, K⁺, NH₄⁺, Ca²⁺, or Mg²⁺ ions. The Ca and Mg soils adsorbed apparently one more NH₂ molecule per exchangeable ion than the Na and K soils, mostly in the relative pressure range o to 0.005, but not much more than the NH₄ soil. The initial heat of adsorption was c. 75 kJ mol^-1 on the Ca and Mg soils and c. 60 kJ mol^-1 on the other soils. The results suggest that most NH, is sorbed on these soils through reactions not involving exchangeable cations.     

Estimating cation exchange capacity using soil textural data and soil organic matter content: A case study for the south of Iran

Cation exchange capacity (CEC) is an important soil property that is used as an input data in soil and environmental models. Although CEC can be measured directly, its measurement is expensive and time-consuming, therefore pedotransfer functions can be used for estimating it from more readily available soil data. As CEC is highly dependent on soil texture, it may be successfully estimated from the soil textural data. In this study, 20 soils were selected from Fars province, in the south of Iran, and the values of CEC, soil organic matter content, and soil particle size distribution curve of each soil were measured and the geometric mean particle-size diameter (d _g ), and the summation of the number of spherical particles for whole parts of the soil particle-size distribution (N) were determined for each soil. Then, five multiple linear regressions were derived between CEC and mentioned soil properties. The results showed that more applicable equation for the study area was based on the percentages of clay, sand and soil organic matter content.