低分子有机酸对土壤中重金属的解吸及影响因素

研究了柠檬酸、草酸、酒石酸和苹果酸对矿区土壤中重金属Pb、Cd、Cu和Zn的解吸行为,并探讨了介质pH值对其解吸土中重金属的影响。振荡解吸试验结果表明四种低分子有机酸对供试污染土壤中Pb、Cd、Cu和Zn都具有一定的解吸能力。由于土壤中重金属有效态含量较低,各重金属的解吸率都不高。在对Pb和Cd的解吸中,各低分子有机酸能力大小顺序为柠檬酸>酒石酸≈苹果酸>草酸;Cu的解吸顺序为柠檬酸>草酸>酒石酸≈苹果酸;Zn的解吸顺序为酒石酸>柠檬酸≈苹果酸>草酸。低分子有机酸随浓度的增加,其解吸能力提高。低分子有机酸对重金属的解吸量随pH值的降低而增加。     

pH和有机酸对酸性紫色土吸附-解吸镉的影响

选择酸性紫色土,研究pH和有机酸对紫色土吸附镉的影响。结果表明,pH在1.0~5.0的范围内,Cd2 的解吸率从接近100%急剧降低到20.0%。当pH>5.0,Cd2 的解吸率缓慢下降。相对较低的有机酸浓度(≤10-3mol/L)限制了Cd2 解吸,而较高的有机酸浓度则增加了Cd2 的解吸。柠檬酸和醋酸在较高浓度(>10-3mol/L)时极大地促进了Cd2 的解吸,其次是苹果酸,最小的是酒石酸。     

pH和有机酸对酸性紫色土吸附-解吸镉的影响

选择酸性紫色土,研究pH和有机酸对紫色土吸附镉的影响。结果表明,pH在1.0～5.0的范围内,Cd^2＋的解吸率从接近100%急剧降低到20.0%。当pH〉5.0,Cd^2＋的解吸率缓慢下降。相对较低的有机酸浓度（≤10^-3mol/L）限制了Cd^2＋解吸,而较高的有机酸浓度则增加了Cd^2＋的解吸。柠檬酸和醋酸在较高浓度（〉10^-3mol/L）时极大地促进了Cd^2＋的解吸,其次是苹果酸,最小的是酒石酸。     

低分子有机酸对贵州黄壤中镉释放及形态的影响

以贵州典型黄壤为研究对象,采用不同浓度的柠檬酸、苹果酸及酒石酸作为浸提剂,通过振荡浸提法及BCR连续提取法,研究了低分子有机酸对黄壤中Cd的浸提作用及黄壤中Cd的形态变化。同时,分析了低分子有机酸对黄壤中Cd活化的环境风险。结果表明:3种低分子有机酸均可促进土壤Cd的浸出,且随有机酸浓度的增加而增加,浸提效果大小为柠檬酸苹果酸≈酒石酸。苹果酸、酒石酸分别与柠檬酸复合添加的浸提率,均高于单一添加苹果酸、酒石酸,小于单一柠檬酸。在有机酸作用下,土壤中弱酸可溶态Cd比例增加,增幅在21.11%～64.25%之间;可还原态Cd减少,降幅为7.88%～24.03%之间。可氧化态和残渣态Cd变化不大。有机酸的复合添加后,可进一步增加土壤中弱酸可溶态Cd,降低可还原态Cd,其中复合方式N5+P5效果最明显,但会增加土壤中Cd活化的环境风险。环境风险分析表明,柠檬酸对土壤中Cd活化的环境风险要远大于苹果酸和酒石酸,且随有机酸浓度的增加有增加趋势。     

低分子有机酸去除土壤中重金属条件的研究

采用化学萃取实验,以湖南郴州柿竹园和湖南衡阳水口山矿区的重金属污染农田土壤为研究对象,采用柠檬酸、草酸、酒石酸作为低分子有机酸萃取剂,在一定的条件下对污染土壤中重金属进行萃取实验,确定各个单因素的适宜条件。结果表明,对于湖南郴州和衡阳两个污染地区土壤运用化学萃取技术萃取重金属来进行土壤修复是实际可行的;柠檬酸、酒石酸、草酸对各种土壤中的重金属都表现出了良好的萃取能力,是高效的土壤重金属萃取剂;单因素的适宜萃取条件为100mmol·L^-1有机酸溶液,固液比1∶5,恒定温度35℃,pH为3,反应时间24h,且萃取率随着电解质浓度的增大而提高;土壤中重金属存在形态与萃取效果有一定的相关性,稳定态（残渣态、硫化物和有机结合态、铁-锰氧化物结合态）金属含量高,表现为较低的萃取率;反之,萃取率高;柠檬酸、草酸、酒石酸3种萃取剂均能有效地降低衡阳污染土壤中的重金属浓度,3种萃取剂的萃取效率依次为酒石酸〉草酸〉柠檬酸。     

不同pH下有机酸对针铁矿和膨润土吸附Cd2+、Pb2+的影响

用平衡吸附法研究了不同pH下,三种有机酸(乙酸、酒石酸和柠檬酸)对针铁矿和膨润土等温吸附Cd2 、Pb2 的影响。结果表明:在加入的Cd2 、Pb2 浓度分别小于0.2 mmol L-1和4.0 mmol L-1时,针铁矿和膨润土吸附平衡体系的pH随加入重金属浓度的增加而降低,膨润土体系的pH降低更明显。在有机酸作用下,pH对针铁矿和膨润土吸附Cd2 、Pb2 的影响差异显著。3酒石酸>乙酸,其对膨润土吸附的影响差异不明显。     

有机酸根与铝氧化物表面吸附磷的解吸

研究了有机酸根离子与合成铝氧化物表面吸附磷解吸的相互关系。结果表明:（1）有有机酸时比无有机酸时吸附的磷具有更高的解吸率,无草酸且加磷pH为4时,0.01molL-1KCI对磷的解吸率最低,草酸与磷共存且pH为6时磷的解吸率最高;（2）高浓度有机酸可解吸低浓度有机酸难解吸的磷,草酸难解吸的磷可为等浓度的柠檬酸极解吸;（3）不同浓度草酸和柠檬酸对铝-草酸复合物吸附磷的解吸率比对Al（OH)x的低,而对铝-柠檬酸复合物吸附磷的解吸率则比对Al（OH）x的高;（4）柠檬酸对铝-磷复合物中磷的解吸量随柠檬酸浓度升高而增大。这些结果证明,有机酸对铝氧化物吸附磷的解吸机理包括配位交换和溶解,有机酸可促进磷的解吸,提高磷的有效性。     

有机酸对几种土壤胶体吸附解吸镉离子的影响

用平衡法研究了有机酸对土壤胶体吸附 解吸Cd2 的影响。结果表明 ,黄棕壤、红壤、砖红壤胶体Cd2 最大吸附容量 (Qm)分别为 4 3 7、16 8、1 5 8mmolkg-1。在加入Cd2 浓度相同的条件下 ,土壤胶体Cd2 吸附量随有机酸浓度的升高呈峰形曲线变化。当有机酸与Cd2 共存时 (竞争吸附 ) ,低浓度的草酸 (小于0 5～ 2mmolL-1)或柠檬酸 (小于 0 0 2 5～ 0 2mmolL-1)提高Cd2 吸附量 ,高浓度的草酸或柠檬酸能降低Cd2 吸附量。吸附有机酸后的土壤胶体 (次级吸附 )对Cd2 次级吸附量的影响与竞争吸附一致 ,但两者的Cd2 吸附量变化幅度不一样。这是由于两种吸附体系液相中有机酸残留浓度不同所致。土壤胶体吸附态Cd2 的解吸结果表明 ,草酸浓度不仅影响Cd2 的总解吸量、总解吸率 ,还影响土壤胶体表面KNO3 解吸态与DTPA解吸态Cd2 的分配比例     

低分子量有机酸强化烟草修复镉污染土壤的适用性研究

采用盆栽试验,以0.125mmol/kg EDTA为对照,研究3种低分子量有机酸(酒石酸、柠檬酸和草酸)在强化烟草修复镉污染土壤中应用的可行性。3种低分子量有机酸(LMWOA)均可显著降低土壤pH,提高镉的有效含量,酒石酸和草酸对镉在烟草中转运有抑制作用,柠檬酸在酸性土壤中促进镉在烟草中转运,在中性土壤中则起抑制作用。31.25mmol/kg LMWOA对烟草地上部的生长有一定的促进作用,该浓度的柠檬酸和草酸使酸性土壤中烟草地上部镉累积量分别提高42.95%和28.67%,柠檬酸还使中性土壤中烟草地上部镉的累积量提高40.91%,所有酒石酸处理镉在烟草地上部的累积量均降低,EDTA使酸性土壤中烟草地上部镉的累积量提高24.56%,对中性土壤中烟草地上部镉累积量的影响不显著。表明柠檬酸和草酸具有强化烟草地上部对镉的吸收、提高烟草提取土壤镉效率的作用,但要获得与EDTA相当的效果,需大大提高其用量,这必然导致修复成本大大提高,故不宜用于强化烟草修复镉污染土壤。     

有机酸淋洗对土壤Cd纵向迁移及有效性的影响

针对保定市污灌区土壤重金属污染现状,采用土柱模拟淋洗试验,以自然Cd污染土壤为对象,研究了EDTA、柠檬酸、草酸3种淋洗剂对污染土壤中镉纵向迁移的影响,以及有效态镉在表层污染土壤中(0-20cm)的变化规律。结果表明:淋洗后表层污染土壤中Cd含量均随着有机酸添加量的增加而降低,随着EDTA添加量增加各处理较对照分别降低了4.72%,8.96%,19.38%,30.46%;不同柠檬酸添加量处理较对照分别降低了0.42%,1.14%,16.9%,27.9%;不同草酸处理较对照分别降低了4.23%,5.70%,14.01%,17.75%。随着有机酸添加量的增加,底层全镉(20-50cm)迁移深度增加,最大迁移深度可达到40cm,含量随着深度的增加而减少,3种有机酸对污染土壤镉迁移能力顺序为EDTA>柠檬酸>草酸。除低柠檬酸添加量处理下(<75kg/667m2)表层污染土壤有效镉含量较对照略有降低外,土壤有效态镉的含量均随着各有机酸添加量的增加而增加,且两者之间呈显著的线性正相关。     

几种有机酸对可变电荷和恒电荷土壤吸附镉的影响

The objectives of this study were to illustrate the reaction processes, to identify and quantify the precipitates formed, and to estimate the porosity losses in order to eliminate drawbacks during remediating monochlorobenzene （MCB） and trichloroethylene （TCE）-contaminated aquifers using the ORC-GAC-Fe^0-CaCO3 system. The system consisted of four columns （112 cm long and 10 cm in diameter） with oxygen-releasing compound （ORC）, granular activated carbon （GAC）, zero-valent iron （Fe^0）, and calcite used sequentially as the reactive media. The concentrations of MCB in the GAC column effluent and TCE in the Fe^0 column effluent were below the detection limit. However, the concentrations of MCB and TCE in the final calcite column exceeded the maximum contaminant level （MCL） under the Safe Drinking Water Act of the US Environmental Protection Agency （US EPA） that protects human health and environment. These results suggested that partitioning of MCB and TCE into the gas phase could occur, and also that transportation of volatile organic pollutants in the gas phase was important. Three main precipitates formed in the ORC-GAC-Fe^0-CaCO3 system： CaCO3 in the ORC column along with Fe（OH）2 and FeCO3 in the Fe^0 column. The total porosity losses caused by mineral precipitation corresponded to about 0.24% porosity in the ORC column, and 1% in the Fe^0 column. The most important cause of porosity losses was anaerobic corrosion of iron. The porosity losses caused by gas because of the production and entrapment of oxygen in the ORC column and hydrogen in the Fe^0 column should not be ignored. Volatilization, precipitation and porosity losses were considered to be the main drawbacks of the ORC-GAC-Fe^0-CaCO3 system in remediating the MCB and TCE-contaminated aquifers. Thus, measurements such as using a suitable oxygen-releasing compound, weakening the increase in pH using a buffer material such as soil, stimulating biodegradation rates and minimizing the plugging caused by the relatively high dissolved oxygen levels should be taken to eliminate the drawbacks and to improve the efficiency of the ORC-GAC-Fe^0-CaCO3 system.     

七种钾释放动力学方程的比较和动力学参数的应用

Batch equilibrium experiments were conducted to investigate cadmium （Cd） sorption by two permanent-charge soils, a yellow-cinnamon soil and a yellow-brown soil, and two variable-charge soils, a red soil and a latosol, with addition of selected organic acids （acetate, tartrate, and citrate）. Results showed that with an increase in acetate concentrations from 0 to 3.0 mmol L^-1, Cd sorption percentage by the yellow-cinnamon soil, the yellow-brown soil, and the latosol decreased. The sorption percentage of Cd by the yellow-clnnamon soil and generally the yellow-brown soil （permanent-charge soils） decreased with an increase in tartrate concentration, but increased at low tartrate concentrations for the red soil and the latosol. Curves of percentage of Cd sorption for citrate were similar to those for tartrate. For the variable-charge soils with tartrate and citrate, there were obvious peaks in Cd sorption percentage. These peaks, where organic acids had maximum influence, changed with soil type, and were at a higher organic acid concentration for the variable-charge soils than for the permanent charge soils. Addition of cadmium after tartrate adsorption resulted in higher sorption increase for the varlable-charge soils than permanent-charge soils. When tartrate and Cd solution were added together, sorption of Cd decreased with tartrate concentration for the yellow-brown soil, but increased at low tartrate concentrations and then decreased with tartrate concentration for the red soil and the latosol.     

Effects of Organic Anions on Phosphate Adsorption and Desorption from Variable—Charge Clay Minerals and Soil

Effects of citrate and tartrate on phosphate adsorption and desorption from kaolinite,goethite,amorphous Al-oxide and Ultisol were studied.P adsorption was significantly decreased as the concentration of the organic anions increased from 10^-5 to 10^-1 M.At 0.1 M and pH 7.0,tartrate decreased P adsorption by 27.6%-50.6% and citrate by 37.9-80.4%,depending on the kinds of adsorbent.Little Al and/or Fe were detected in the equilibrium solutions,even at the highest concentration of the organic anions.Effects of the organic anions on phosphate adsorption follow essentially the competitive adsorption mechanism.The selectivity coefficients for competitive adsorption can be used to compare the effectiveness of different organic anions in reducing P adsorption under given gonditions. Phosphate desorption was increased by 3 to 100 times in the presence of 0.001 M citrate or tartrate compared to that in 0.02 M KCl solution alone.However,for all the soil and clay minerals studied the amount of P desorbed by citrate or tartrate was generally lower than or close to that of isotopically exchangeable P.The effect of organic anions on phosphate desorption arises primarily from ligand exchange.     

有机酸对高岭石, 针铁矿和水铝英石吸附镉的影响

Effects of organic acids （oxalic, acetic, and citric） on adsorption characteristics of Cadmium （Cd） on soil clay minerals （kaolinite, goethite, and bayerite） were studied under different concentrations and different pH values. Although the types of organic acids and minerals were different, the effects of the organic acids on the adsorption of Cd on the minerals were similar, i.e., the amount of adsorbed Cd with an initial solution pH of 5.0 and initial Cd concentration of 35 mg L^-1 increased with increasing concentration of the organic acid in solution at lower concentrations, and decreased at higher concentrations. The percentage of Cd adsorbed on the minerals in the presence of the organic acids increased considerably with increasing pH of the solution. Meanwhile, different Cd adsorption in the presence of the organic acids, due to different properties on both organic acids and clay minerals, on kaolinite, goethite, or bayerite for different pHs or organic acid concentrations was found.     

可变电荷土壤中铜离子的解吸

研究了我国四种可变电荷土壤红壤、赤红壤、砖红壤和铁质砖红壤以及二种恒电荷土壤黄棕壤和黑土中吸附性铜离子的解吸特征。研究结果表明 ,可变电荷土壤吸附的一部分铜离子可以被去离子水解吸 ,而且在pH～解吸率曲线上在一定pH值时出现解吸率最大值。在最大值时不同土壤中铜离子解吸率的大小与土壤中氧化铁的含量有关。氧化铁的含量越高 ,在最大值时铜离子的解吸率越大。当用中性电解质解吸可变电荷土壤吸附的铜离子时 ,电解质的浓度越大 ,解吸率越低。与此相反 ,恒电荷土壤吸附的铜离子不能被去离子水解吸 ,只能被中性电解质解吸 ,且电解质的浓度越高 ,解吸率越大。这表明 ,可变电荷土壤中吸附性铜离子的解吸规律 ,完全不同于恒电荷土壤中者。本文初步讨论了其原因     

Solubility,sorption and desorption of native and added cadmium in relation to properties of soils in New Zealand

Solution cadmium (Cd) concentrations and sorption and desorption of native and added Cd were studied in a range of New Zealand soils. The concentration of Cd in solution and the concentrations and patterns of native soil Cd desorbed and added Cd sorbed and desorbed varied greatly between the 29 soils studied. Correlation analysis revealed that pH was the most dominant soil variable affecting solution Cd concentration and sorption and desorption of native and added Cd in these soils. However, organic matter, cation exchange capacity (CEC) and total soil Cd were also found to be important. Multiple regression analysis showed that the log concentration of Cd in solution was strongly related to soil pH, organic matter and total Cd, which in combination explained 76% of the variation between soils. When data from the present study were combined into a single multiple regression with soil data from a previously published study, the equation generated could explain 81% of the variation in log Cd solution concentration. This reinforces the importance of pH, organic matter and total Cd in controlling solution Cd concentrations. Simple linear regression analysis could at best explain 53% of the total variation in Cd sorption or desorption for the soils studied. Multiple regression analysis showed that native Cd desorption was related to pH, organic matter and total Cd, which in combination explained 85% of the variation between soils. For sorption of Cd (from 2 μg Cd g^–1 soil added), pH and organic matter in combination explained 75% of the variation between soils. However, for added Cd desorption (%), pH and CEC explained 77%. It is clear that the combined effects of a range of soil properties control the concentration of Cd in solution, and of sorption and desorption of Cd in soils. The fraction of potentially desorbable added Cd in soils could also be predicted from a soil’s K_d value. This could have value for assessing both the mobility of Cd in soil and its likely availability to plants.     

外源低分子量有机酸对碳酸钙预处理的酸性土壤中活性铝钙镁影响的研究

通过在所研究的第四纪红黏土发育的红壤中混入CaCO3,研究在pH缓冲体系中外加低分子量有机酸对土壤中Al、Ca和Mg的影响。结果表明:无论加CaCO3与否,在pH 4.5的条件下外源草酸、柠檬酸、苹果酸的加入均使土壤可溶性Al显著提高,交换性Al显著下降和交换性Ca显著升高;加入CaCO3的情况下,3种有机酸处理的交换性Mg均显著提高。3种有机酸促进Al溶解能力的大小顺序为:柠檬酸>草酸>苹果酸,这一结果与有机酸和Al形成络合物的稳定常数大小一致。另一方面,3种有机酸处理下,CaCO3预处理均引起可溶性Al的显著升高和交换性Al的下降。双因素方差分析表明,有机酸通过络合作用或沉淀作用对可溶性和交换性Al、Ca和Mg均具有绝对的影响优势,CaCO3仅对可溶性和交换性Al、交换性Ca有显著影响,由于实验中pH缓冲体系的控制,这种影响主要通过Al与Ca、Mg的竞争交换作用实现。总体来说,外源低分子量有机酸的加入使土壤活性Al显著升高,活性Ca、Mg略有升高,有机酸在酸性土壤中的作用需从有机酸溶解阳离子的角度进一步评价。