Cu/Pb/Zn/Cd在石英砂中的迁移实验及模拟

通过稳定流混合置换实验,研究了孔隙水流速和pH变化对Cu/Pb/Zn/Cd在石英砂中迁移行为的影响,获得了示踪剂Br-和Cu/Pb/Zn/Cd的穿透曲线(BTCs);并通过室内批量平衡实验获得吸附系数,进而计算出阻滞因子Rd。基于这些实验结果,借助CXTFIT2.1软件,用平衡CDE模型拟合了Br-的BTCs,得到了弥散系数D;在此基础上应用CDE非平衡模型拟合Cu/Pb/Zn/Cd在不同流速和pH条件下的BTCs,并预测了平行实验和不同埋深处Cu/Pb/Zn/Cd浓度的动态变化。结果表明,Cu/Pb/Zn/Cd的迁移能力随流速的增大而增强,而随pH的增大而降低;化学非平衡的两点模型能较好地模拟本文实验条件下Cu/Pb/Zn/Cd的迁移过程。     

不同pH值和离子强度下土壤Zn2+/Cd2+/NH4+的运移特征

为探究锌、镉及铵态氮在土壤中的运移特征,该文通过室内土柱混合置换试验,分析了不同 pH 值和离子强度对锌、镉、铵态氮（Zn2+、Cd2+、NH4+）在土壤中运移的影响;获得了示踪剂Br和Zn2+/Cd2+/NH4+的穿透曲线（breakthrough curves,BTCs）,并对试验结果进行了模拟。研究表明：Zn2+/Cd2+/NH4+在土壤中运移时,运移速度：NH4+＞Zn2+＞Cd2+,pH 值越高,Zn2+/Cd2+/NH4+的出流时间越晚,峰值越低;离子强度越大,出流时间越早,峰值越高。描述溶质运移的非平衡两点模型（two-site model,TSM）能够较好地模拟 Zn2+/Cd2+/NH4+在土壤中的运移,pH值越高,模拟得到的分配系数Kd值越大（以Zn2+为例,由3.853增大到4.386）,f值越小（以Zn2+为例,由0.231减小到0.006）,分形系数β值很小且无明显变化规律;离子强度越大,模拟得到的分配系数Kd值越小（以Zn2+为例,由4.023减小到到3.381）,f值及分形系数β值均很小且无明显变化规律。该研究对深入了解Zn2+/Cd2+/NH4+在土壤中的运移机理、提出污染土壤修复措施提供科学依据。     

中国自然土壤、旱作土壤、水稻土的氧化还原状况和特点

以原位测定资料作基础,首次系统地总结了我国主要自然土壤、旱作土壤和水稻土的氧化还原状况。自然土壤、旱作土壤同属于氧化性土壤,Eh为440～730mV,还原性物质量相当于Mn2+0.00～4.01×10-5molL-1,一年内基本上处于氧化状态,物质转化迁移微弱;水稻土的Eh为670～-70mV,还原性物质量相当于Mn2+0.01～17.8×10-5molL-1,变动范围从氧化性到还原性,氧化还原状况随水分条件而周期性变化,物质转化迁移的强度和速度远甚于前两者;依据水稻土的氧化还原状况,可将其划分为氧化性、氧化还原性、还原性三种类型;土壤氧化还原状况的特点为:Eh与还原性物质量之间相关性良好、具水平带谱和垂直带谱分异、不均一性显著、变动的范围宽和变化的可逆性强。     

不同pH/离子强度时Cu/Cd复合污染土壤解吸和迁移特征

重金属污染土壤在用固化/稳定化技术修复后,若外部环境发生变化,失去活性的重金属会否再次释放出来并在土壤中迁移,造成污染风险,是一个值得探讨的重要科学问题。为揭示不同化学因素对污染土壤中重金属活化及迁移过程的影响,通过室内土柱实验,研究了不同离子强度、pH及阳离子类型（Ca2+、Na+）下Cu2+、Cd2+在土壤中的解吸及迁移行为。结果表明：总体而言,离子强度增大,Cu2+、Cd2+淋出浓度峰值也随之增大;此外,在CaCl2淋溶阶段,0.005、0.01、0.05、0.1 mol·L-1 CaCl2时,Cu2+、Cd2+解吸量依次增加,且Cd2+的解吸量高于Cu2+,而0.5 mol·L-1 CaCl2时抑制了Cd2+的解吸,且Cu2+的解吸量高于Cd2+。pH减小时,Cu2+、Cd2+解吸量增大,即偏酸性的环境有利于Cu2+、Cd2+的解吸;但从Cu2+、Cd2+浓度峰值来看,pH为3时的Cu2+、Cd2+浓度峰值反而小于pH为4、5时。Ca2+较Na+更有利于Cu2+、Cd2+的解吸,但在0.005 mol·L-1时,NaCl溶液更有利于Cu2+的解吸,并且去离子水淋溶阶段Cu2+浓度要高于CaCl2淋溶阶段;此外,离子强度为0.005、0.05和0.5 mol·L-1 NaCl的三种情况下均出现了土壤颗粒的出流,且0.05和0.5 mol·L-1 NaCl时,存在流速下降的现象。     

鼎湖山、尖峰岭和那大地区某些土壤的氧化还原状况

用电化学方法测定了鼎湖山、尖峰岭和那大地区某些土壤的氧化还原电位(强度因素)和还原性物质数量(容量因素)。自然林下土壤的氧化还原状况随植物群落的垂直带(谱)而呈规律性变化。其表层的Eh为400—560mV,较以下土层低80—220mV,还原性物质含量相当于0.5—3.6×10^-3mol/L亚锰。经济林下土壤表层的Eh为490—570mV,较下层低50-100mV,还原性物质含量为0.1—1.36×10^-3mol/L。水稻土表层的还原性物质含量达6.6×10^-3mol/L,Eh为330mV,较下层低100mV。在还原性物质含量的对数值和Eh之间存在着良好的相关性,相关系数为-0.734^**。本文对用电化学方法原位测定弱还原性土壤的氧化还原状况给予了评价,对氧化还原过程在红壤形成中的作用进行了讨论。     

不同土壤的还原状况对铁镉形态转化和水稻吸收的影响

采用土壤-蛭石联合培养,以填充蛭石的网袋模拟根际,置于红壤、水稻土、盐土中后淹水栽培水稻13 d.试验结果表明,水稻栽培期问,红壤、水稻土、盐土pH变化范围分别为6.05 ～6.78、6.47 ～7.33、6.42 ～7.44;有机质处理下,除红壤根际pH明显升高外,其余土壤根际和非根际pH均有所下降.各土壤对照根际Eh保持在233 ～ 385 mV;有机质处理使根际Eh下降,同时也导致除盐土外的非根际Eh上升.土壤还原溶解Fe与蛭石吸附Fe的90％以上均米自铁锰氧化物结合态铁(Oxide-Fe)组分,与溶液Eh、pe+ pH均有显著相关性,表明两表面同为Fe的氧化还原反应,但方向相反.水稻根表Fe膜的形成与根际氧化还原状况有关,在对照根际(高Eh)环境下,根表Fe含量随pH升高而降低,在有机质处理根际(低Eh)环境下则随pH升高而升高;在红壤中,根表Fe膜阻碍Fe的吸收,在水稻土和盐土中,根表Fe膜促进Fe吸收.根表Cd含量与根内Cd、地上部Cd有显著正相关;在红壤中,根表Fe膜阻碍了水稻Cd的吸附和吸收;水稻土和盐土中,根表Fe膜促进了水稻Cd的吸附和吸收.     

外源秸秆对污染土壤氧化还原过程水分散性胶体态重金属的影响

土壤胶体尤其是水分散性胶体，作为一种重要的污染物载体，在重金属吸附、迁移以及生物吸收过程起着重要作用。通过土壤培养试验探讨了外源添加水稻秸秆在氧化还原波动条件下如何影响土壤液相中及水分散性胶体中重金属的分布。结果表明，外源秸秆增加厌氧过程液相中溶解性有机碳(DOC)、砷(As)、铁(Fe)、锰(Mn)、钙(Ca)、钾(K)、硅(Si)、铝(Al)、镁(Mg)等浓度，降低了厌氧过程氧化还原电位(Eh)及铜(Cu)、铅(Pb)等浓度，提高了好氧过程Pb浓度。利用非对称流场流分馏-紫外可见-电感耦合等离子体-质谱联用技术(AF4-UV-ICP-MS)，测得水分散性胶体颗粒主要分布在0.3~3 kDa、3~40 kDa和130 kDa~450 nm三个粒径范围，各粒径颗粒的组成有所差异，主要含有机质、无机黏土矿物和铁矿物等。外源秸秆促进液相中Fe和As由胶体态向溶解态转化，促进镉(Cd)和Cu由溶解态向胶体态转化。本研究有助于揭示农业活动影响重金属迁移转化及有效性的界面机制。     

重金属的土水分配行为研究——根际土壤溶液采样器的应用

采用根际土壤溶液采样器(Rhizon-SMS)原位采集河南平原耕地土壤溶液.用土壤溶液中重金属浓度对数作为因变量、土壤溶液理化性质作为自变量,进行多元线性逐步回归,结果表明:只有有机碳进入Cu的相关方程,pH进入Cd的相关方程.土壤溶液pH和土壤中的Zn都作为自变量进入Zn的相关方程.土壤溶液中的Cu与pH没有线性关系,而Cd和Zn与土壤溶液pH有显著的线性关系(p＜0.01).计算了土壤中Cu、Cd、Zn在土壤与土壤溶液中的分配系数Kd.本研究中,3种重金属的Kd大小顺序为:Cu＞Zn＞Cd.根据Freeze 和Cherry模型,联合log(Kd-Cd)、log(Kd-Zn)与pH的线性关系,估计了Cd和Zn在土壤中的迁移速度.     

农田土壤重金属淋洗剂筛选与效应分析

为分析不同淋洗剂在不同淋洗条件下对重金属淋洗效果的影响,采用振荡淋洗法对比研究4种淋洗剂(柠檬酸(CA)、酒石酸(TA)、乙二胺四乙酸二钠盐(EDTA)和氨三乙酸三钠盐(NTA))不同浓度、淋洗时间、pH和固液比对重金属复合污染农田土壤中Pb、Cd、Cu和Zn的淋洗效果及单因素最佳淋洗条件下土壤淋洗前后重金属不同形态含量的变化。结果表明,CA和TA的最佳淋洗浓度为0.3mol/L,EDTA和NTA为0.05mol/L;CA和NTA的最佳淋洗时间为480min,EDTA和TA为720min;4种淋洗剂的最佳淋洗pH均为3,最佳固液比均为1∶20。单因素最佳淋洗条件下,EDTA对土壤重金属去除效果最佳,对Pb、Cd、Zn和Cu的去除率分别为67.4%,61.0%,13.8%和76.0%;NTA效果次之,去除率分别为41.6%,42.4%,9.9%和54.3%。土壤重金属去除率随淋洗剂pH的降低而升高,随固液比的增加而增加,随淋洗剂CA与TA浓度增大而增大。淋洗剂对土壤重金属的解吸动力学曲线符合准二级动力学模型,解吸过程为化学解吸,且解吸反应速率受土壤重金属含量与淋洗剂浓度控制。土壤重金属在淋洗剂作用下的解吸速率为Cd>Pb≈Zn≈Cu。EDTA和NTA淋洗显著降低土壤中Pb、Cd、Zn和Cu铁锰氧化态和有机结合态的含量,CA和TA显著降低Pb、Cd、Zn和Cu铁锰氧化态的含量。淋洗剂对重金属的去除效率为EDTA>NTA>CA>TA。     

施污土壤与污泥中Cu、Pb、Cd、Zn的形态分布

污泥中的重金属元素是限制其大规模农田利用的重要因素。施污土壤和污泥中重金属的形态研究可以用来评价土壤中重金属的生物有效性以及它们在土壤中的移动性。用修正BCR三步连续提取法进行分步提取研究了污水污泥和施污后的西红柿地土壤中Cu、Pb、Cd、Zn的形态分布状况。施用污泥堆肥10t hm-2后的土壤中Cu、Pb、Cd、Zn的全量与各种形态含量无明显增加,Cu、Pb、Zn含量远低于国家土壤环境质量标准。土壤中Cu的各种形态分布关系是:残渣态>可还原态=可氧化态>可交换态和弱酸溶解态,Cu在土壤中的存在是以最稳定的残渣态为主。堆肥污泥与干化污泥相比,残渣态Cu的比例明显增加。土壤中Pb的各种形态分布关系是以残渣态和可还原态为主,但可氧化态的分布比例最小。土壤中Cd的可交换态、可还原态和残渣态各占据相等的含量,但可氧化态Cd的含量几乎为零。Zn在土壤中的各种形态分布关系是:可交换态和弱酸溶解态>可氧化态>可还原态>残渣态,Zn在土壤中的存在是以最易迁移的可交换态和弱酸溶解态为主。这些金属元素在土壤中的相对稳定性顺序为:Cu>Pb>Cd>Zn。Zn在土壤中的移动性要远高于Cu。     

影响土壤中镉的植物有效性的因素及镉污染土壤的植物修复

阐述了镉的来源及其对人类的危害,并对影响土壤中镉的植物有效性的土壤因素中的pH、氧化还原电位(Eh)、有机物质、营养物质浓度对镉的植物有效性的作用作了详细的阐述。此外对其它如EDTA、淤泥等对土壤中镉的植物有效性的影响和镉污染土壤的植物修复等方面也进行了综述,并对镉污染土壤的修复治理与趋势进行了展望。     

Einfluß von Bodenreaktion,Redoxbedingungen und organischer Substanz auf die Phosphatgehalte der Bodenlösung

Influence of soil reaction, redox conditions and organic matter on the phosphate content of soil solutions Samples of seven agriculturally used soils of different composition (A_p-horizons), one marine underwater soil and two garbage composts were adjusted in suspensions (soil-water-ratio 1:3) to different pH values between 3 and 8 by additions of NaOH or HCl. By a different degree of aeration the redox potential was kept constant at selected values between +600 and ?300 mV. After an incubation period of 22–24 days under controlled E_h-pH-conditions the content of total phosphate and orthophosphate was measured in the equilibrium solutions. At oxidizing conditions all soil and compost samples show the lowest phosphate content in solution at pH S6. At higher and lower pH values the phosphate content increases. The results indicate that the phosphate concentration is determined by adsorption/desorption processes – mainly connected with iron oxides – and not by dissolution or precipitation of definite phosphorus compounds. Under reducing conditions the phosphate content increases in the equilibrium solutions of all samples. Especially in samples with high content of sulphides a considerable increase of the phosphate concentration could be measured at Eh values below +300 mV at pH 5, +200 mV at pH 6, and ± 0 mV at pH7 and 8. Below these values phosphate containing iron(II1) oxides were reduced and – with further decreasing redox potentials – transformed to iron sulphides. In samples without sulphide formation the phosphate mobilization is much lower. With increasing amount of soluble organic matter the phosphate content of the solutions also increases because of phosphate desorption by organic anions or complexation of aluminium and iron from phosphate adsorbing compounds. But also the content of soluble organically bound phosphate increases and may amount to 70 % of the total phosphate content in solution.     

Influence of nitrate on methane production and oxidation in flooded soil

Abstract

Methane (CH₄) production in paddy soils and sediments as influenced by nitrate (NO₃) addition was studied under a closely controlled soil pH and oxidation‐reduction (redox) potential (Eh) conditions. CH₄ production was affected by soil pH and NO₃ ^‐. Added NO₃ ^‐ reduced the amount of CH₄ produced of each pH level studied. Nitrate addition primary effect in reducing CH₄ production was through the resultant increase in soil redox potential (Eh). Using Methyl Fluoride (MF), a CH₄ oxidation inhibitor we found that added NO₃ ^‐ was not used in CH₄ oxidation by methanotrophic bacteria.     

Iodine desorption from rice paddy soil

Laboratory experiments on the desorption phenomena of iodine from rice paddy soil under waterlogged conditions, with a special reference to soil redox potential (Eh) and pH, have been conducted. Radioiodine tracer (1251), added to the soil, was readily sorbed on it. At the beginning of the waterlogging, the iodine desorption was low. However, iodine was desorbed into soil solution with time. The iodine desorption was enhanced markedly by the addition of organic substances such as straw pieces and glucose to the soil. Cultivation of rice plants in soil also affected the iodine desorption, suggesting root exudates and/or root autolysis might be participating in the desorption process. Eh dropped considerably after soil was waterlogged due to microbial metabolisms. Particularly low Eh values were observed in soils with plants and also with added organic substances. A negative correlation was seen between the desorption and soil Eh. High desorption was frequently observed when the Eh dropped to about -100 mV or below. Due to the reducing conditions (low Eh) by waterlogging, iodine in soil was leached into the soil solution; consequently total iodine concentration in paddy soil was considerably lower than forest and upland field soils. These iodine desorption phenomena under anaerobic conditions should be considered in assessing transfer of the long-lived radioiodine (129I) in the environment, especially in rice fields and marshland.     

Solubility of heavy metals in a contaminated soil: Effects of redox potential and pH

To assess the mobilities of Pb, Cd, and Zn from a contaminated soil, the effects of redox potential and pH value on metal solubilities were investigated. Both redox potential and pH were found to greatly affect heavy metal solubility in the soil. Results showed that the soil suspension under continuous oxygen aeration for 21 days resulted in increases of redox potential from 290 to 440 mV and pH value from 6.9 to 7.0, respectively. Soluble concentrations of Pb, Cd, and Zn varied with time, and were all lower than 1 mg kg^?1. When the soil suspension was aerated with nitrogen, final redox potential was ?140 mV and pH value of 7.1. The soluble metal concentrations were slightly higher than those aerated with oxygen. The equilibrium solubility experiments were conducted under three different pH values (3.3, 5.0, 8.0) and three redox potential (325, 0, ?100 mV). Results showed that metals were sparingly soluble under alkaline conditions (pH = 8.0). Metal solubilities were higher when under slightly acidic conditions (pH = 5.0), and increased drastically when pH was kept at 3.3. When solubilities were compared under same pH values, it was observed that metal solubilities increased as redox potential decreased. Generally speaking, acidic and reducing conditions were most favorable for metal solubilization, and the effect of pH was more significant than that of redox potential. It was proposed that heavy metals were mostly adsorbed onto Fe-Mn oxyhydroxides. The pH-dependent metal adsorption reaction and the dissolution of Fe-Mn oxyhydroxides under reducing conditions was the mechanism controlling the release of heavy metals from soils.     

Changes of Redox and pH Conditions in a Flooded Soil Amended with Glucose and Nitrate under Laboratory Conditions

The changes of soil Eh and pH during decomposition of nitrates at different levels of glucose (0%; 0, 5% and 1.0%) and nitrates (0%; 0,5%; 1% and 2% KNO₃) in water saturated soil samples (Ah horizon of a Mollic Gleysol) were examined. It was found that in the presence of 0–2% nitrates and 0,5–1% glucose in the soil with 1–2 days anaerobiosis at 20°C resulted in the increase of reduction processes and a decrease of redox potential up to 500 mV (Eh). Soil pH increased in the range of 2.5 units. The results from the model experiment - implying Eh > 200 mV and pH < 6.5 as range of nitrate stability in the soil studied - can be useful for field conditions both to predict the stability of nitrates in the soil environment and to create proper conditions for the effective use of carbon sources as a main factor of redox transformations.     

Saccharidic compounds as soil redox effectors and their influence on potential N2O production

Cellulose, xylan, and glucose were compared in waterlogged soil as modifying factors of the redox potential (Eh), of the quantity of reducing equivalents, and of the soil capacity to produce N₂O and CO₂. During the study period (168 h) soils supplied with glucose and xylan showed a higher Eh decrease than the control soil and the soil treated with cellulose. In samples taken after 0, 24, 48, and 168 h, the soils supplied with C showed a higher number of reducing equivalents than the control soil did. These quantities were not correlated with Eh values, nor with N₂O production. N₂O production was increased compared with the control soil over the entire experimental period in the glucose-amended soils but only after 48 h in the xylan-amended soils and not until 168 h in the cellulose-treated soils. The CO₂:N₂O ratio was consistently higher than the theoretical value of 2, suggesting that denitrification and CO₂ production via fermentation occurred simultaneously. Moreover, this ratio was highly correlated with the Eh values. We conclude that more research is needed to explain the role of soil redox intensity (Eh) and capacity (quantity of redox species undergoing reduction) in the expression of soil denitrification-fermentation pathways.     

Restoring the capacity of spent mushroom compost to treat coal mine drainage by reducing the inflow rate: A microcosm experiment

Four volumes of spent mushroom compost were exposed to synthetic coal mine drainage (pH 3.5, 48 mg L^?1 Fe, 22 mg L^?1 Mn) under oxidizing conditions (Eh 300 to 400 mV) at a relatively high rate of flow. After 15 days, the compost lost its ability to elevate pH, to lower the redox potential, to lower outlet iron concentrations, and to lower manganese concentrations, with larger volumes retaining more Fe and H⁺, but less Mn. Estimated retention maxima per liter of spent mushroom compost were 281 μeq H⁺, 5.56 g Fe, and 0.15 g Mn. These values are similar to those reported elsewhere for peat. The ‘saturated’ compost was then mixed and exposed to mine water in order to eliminate ‘dead zones’ in the compost. Subsequently, the compost was re-exposed to synthetic mine water (pH 4.0, 60 mg L^?1 Fe, O mg L^?1 Mn) under a much lower flow rate and less oxidizing regime for a period of 114 days. Under the low flow regime, iron was first exported from the compost as reducing conditions were established, and then retained on a stable basis. In addition, Eh was lowered and pH was elevated by the compost. On a net basis, the capacity of the compost to retain iron was increased and apparently stable under the decreased flow conditions.     

Effect of addition of various carbon substrates on denitrification in a vertic Mollisol

Summary Glucose, acetate, malate, and citrate were added to an agricultural soil. The pe values (-log e^-; calculated from the redox potential) obtained 30 min after the addition of C were not correlated with the theoretical reducing power nor with the theoretical total energy of the C compounds. By contrast the number of electron (e^-) equivalents was correlated with pe⁷, indicating that the proton number affected the redox potential (Eh) measurement. After 24 h of incubation, denitrification rates followed the order citrate>malate>glucose and control. No N₂O production was detected with acetate. Denitrification was not correlated with the theoretical reducing power of the added C compounds but was correlated with pe+pH. Similar numbers of e^- equivalents were measured with all treatments. After 72 h of incubation, the order of the denitrification rates was malate>citrate >acetate>glucose and control. The Eh values (lower than after 24h) did not differ with treatment while the number of e^- equivalents was influenced by the quality of the C source. This also demonstrates that the proton number affected the measured Eh. Our results suggest that the different C substrates did not directly influence the soil physicochemical and biological conditions through their degree of oxidation. Any effects appeared to be indirect, arising from the ability of the substrates to generate new metabolites, and consequently initiate different metabolic pathways that modified the soil physicochemical conditions, reducing power and microbial activity.     

Methane and water soluble iron production under controlled soil pH and redox conditions

Abstract

When a soil is flooded, iron (Fe) reduction and methane (CH₄) production occurred in sequence as predicted by thermodynamics. The dissolution and precipitation of Fe reflected both soil pH and soil redox potential (Eh). The objective of our experiment was to determine both CH₄ production and Fe reduction as measured by Fe in solution in a flooded paddy soil over a wide range of closely controlled pH and Eh conditions. The greatest release of CH₄ gas occurred at neutral soil pH in combination with low soil redox potential (‐250 mV). Production of CH₄ decreased when soil pH was lowered in combination with an increase in the soil redox potential above ‐250 mV. Highest concentration of ferrous‐iron (Fe²⁺) under reducing conditions occurred when soil pH was lowered. Thus Fe reduction influenced CH4 formation in the flooded paddy soil. Results indicated that CH₄ production was inhibited by the process of ferric‐iron (Fe³⁺) reduction.