冻融循环及有机肥配施对黑土中镉形态的影响

以黑龙江黑土为对象,研究了冻融循环及有机肥配施量对黑土中镉形态分布的影响。对配施不同有机肥的土壤样品进行5次冻融循环,采用电感耦合等离子质谱仪(ICP-MS)分析土壤样品中镉的赋存形态。结果表明,冻融循环数及有机肥的配施有助于降低黑土中的总镉量;冻融循环会促使黑土中的镉由交换态、碳酸盐结合态、有机结合态向铁锰氧化物结合态和残渣态转化,而增加有机肥配施量会使黑土中的镉由交换态向其他形态转化。因此,冻融循环及有机肥配施有助于降低土壤中镉的生物有效性,进而降低其环境风险。     

硫化钠对土壤中铅镉的固定效果简

研究了硫化钠用于固定土壤中铅镉的可行性，考察了硫化钠用量及土壤pH、有机质对固定过程中土壤铅、镉赋存形态及固定效果的影响。结果表明，添加硫化钠可改变土壤中铅镉的形态分布，明显降低可交换态铅镉的含量。条件适当时，铅镉可交换态下降值分别为63%和73%。硫化钠在固定铅的过程中，固定效率对土壤pH、有机质含量的变化较为敏感，在有机质含量较低或酸性土壤中，硫化钠对铅固定效率较高；相对于铅，有机质含量和pH变化对镉的固定效率影响不是很大。     

几种典型土壤对电动修复镉污染效果的影响

选择5种典型土壤进行了镉污染的电动修复研究。结果表明,经12 d电动修复后,黑土、潮土、红壤、水稻土和黄棕壤中镉的去除率依次为16.7%、21.0%、47.1%、10.7%和12.6%。红壤靠阳极附近Cd含量由初期435 mg·kg-1降至32.4 mg·kg-1,迁移率高达92.5%。黑土、红壤和潮土都维持了较高的电流强度和电渗流量,但由于红壤对碱的缓冲能力较强,修复效果最好。水稻土中电渗流量高,但由于电流低,镉的去除率不高,说明电动修复中电迁移作用强于电渗析。修复后,土壤中可交换态镉、碳酸盐结合态镉、铁锰氧化物结合态镉总量减少,残渣态镉总量增加,有机结合态在阳极附近总量减少、阴极附近总量增加。上述结论揭示了电动修复的土壤镉污染的主要机制,通过镉的运动轨迹和形态分布,可预测不同土壤的电动修复效果,同时能改变不同土壤的电动修复策略,为场地修复提供参考。     

淹水条件下蚕沙复配材料对酸性水稻土中镉铅钝化的影响

通过室内淹水土培实验,研究蚕沙配施蚕沙炭、膨润土、腐殖质钾和泥炭对酸性水稻土中镉(Cd)、铅(Pb)的钝化效果,从土壤pH、有机质、有效态Fe、Mn含量变化初步探析蚕沙复配材料对镉、铅的钝化机制。结果表明,蚕沙复配材料均不同程度地提高了土壤pH和有机质含量,有效态Cd、Pb的含量随着淹水时间的延长都有不同程度的降低。培养28d后,与对照相比,添加了蚕沙+蚕沙炭(CB)、蚕沙+腐殖质钾(CF)、蚕沙+蚕沙炭+腐殖质钾(CBF)、蚕沙+泥炭(CN)处理的土壤有效态Cd分别降低了16.07%、15.51%、11.08%、7.76%,有效态Pb则降低了32.54%、27.12%、37.72%、42.31%。其中蚕沙+蚕沙炭(CB)对镉的钝化效果最好,蚕沙+泥炭(CN)处理对铅的钝化效果最好,综合来看,CB和CN处理同时对镉铅有很好的钝化效果,可以作为镉铅复合污染土壤的修复材料。相关分析结果显示,土壤的pH、有机质与有效态Cd、Pb含量均呈显著负相关关系,表明蚕沙复配材料对土壤中镉、铅的钝化作用可以通过提高土壤的pH、有机质含量来实现。     

撒施阻控材料快速去除上覆水Cd对的室内模拟研究

湘中矿区塘、水库等灌溉水体及其底泥重金属超标问题日益凸显,研究选取石灰、水稻秸秆生物炭和人造沸石等3种环境友好型土壤重金属阻控材料,通过室内玻璃柱模拟静止水体实验探讨水面缓慢撒施阻控材料对上覆水重金属Cd去除与底泥Cd有效性影响。为期60 d的实验结果显示,1%(0~20 cm表层底泥质量分数)的单一石灰、生物炭、沸石与石灰+生物炭+人造沸石配方(质量比1∶1∶1)4种处理均可明显快速去除上覆水中水溶态Cd质量浓度,其中石灰效果最佳,沸石效果最差,石灰与3种阻控剂组配处理均可使上覆水中水溶态Cd质量浓度由20μg·L~(-1)以上降至10μg·L~(-1),符合我国灌溉水Cd的限定标准。阻控材料自然沉积在底泥表面后对5 cm处底泥水溶液Cd质量浓度具有一定的消减效应,沸石效果优于石灰、生物炭处理,其中"石灰+生物炭+沸石"的不同粒径阻控材料组配方式效果最佳。石灰、生物炭、沸石及3种阻控剂组配处理60 d后底泥pH值依然略高于对照,差异不显著,但可交换态Cd含量明显低于对照。结果可为塘库型水体上覆水及底泥Cd等重金属污染的生态风险降低及控制措施研究提供科学参考与方法指导。     

改性沸石对土壤铅、锌赋存形态的影响简

通过室内土壤培养实验，研究改性沸石对污染土壤中Pb、Zn赋存形态的影响。结果表明，土壤中的Pb主要是以Fe-Mn氧化物结合态存在，土壤Zn主要以残渣态存在。添加天然沸石和改性沸石不同程度地降低土壤酸提取态Pb、Zn的含量，提高土壤残渣态Pb、Zn的含量。与CK处理相比，添加4种沸石导致土壤酸提取态Pb含量降低8.7%~40.3%，土壤酸提取态Zn含量降低10.5%~49.8%（培养1个月）。硝酸钾改性沸石比天然沸石更能显著地降低土壤酸提取态Pb、Zn的含量，而氢氧化钠改性沸石和硝酸钾改性沸石比天然沸石更能显著地降低土壤酸提取态的Zn含量。培养1、2和3月后，不同沸石处理导致土壤残渣态Zn比率分别比CK处理提高14.4%~23.5%、19.6%~23.7%和1.9%~11.1%。研究结果表明，天然沸石经过一定方法改性后，是固定污染土壤Pb、Zn的潜在改良剂。     

金矿区高浓度砷污染土壤的稳定化处理

以粉煤灰、干化污泥、粉碎花生壳、硫酸亚铁(Fe_2SO_4)和磷酸二氢钾(KH_2PO_4)为稳定剂对矿区高浓度As污染土壤进行处理,通过土壤理化性质、重金属形态和浸出浓度变化等综合评估稳定剂对高浓度砷污染土壤的稳定化处理效果。结果表明,添加稳定剂可以提高土壤pH值、有机质含量和阳离子交换量。粉煤灰、干化污泥、粉碎花生壳、硫酸亚铁对土壤中的As有较好的稳定化作用,其中硫酸亚铁对土壤中As的稳定效果最好。同时添加10%粉煤灰、10%干化污泥和1%硫酸亚铁后,土壤中可交换态As、碳酸盐结合态As、铁锰氧化物结合态As、有机结合态As含量显著降低,降幅分别为62.3%、55.2%、29.6%、58.2%,残渣态As含量增加8.1%。添加粉煤灰、干化污泥、硫酸亚铁能显著降低土壤中As的浸出浓度,而添加KH_2PO_4会使土壤中As浸出浓度增加,移动性增强。当同时添加10%粉煤灰、10%干化污泥、1%粉碎花生壳和1%硫酸亚铁后,As浸出浓度最低(0.93 mg·L~(-1)),稳定效果最好,稳定化效率达到了74.8%。土壤中As的浸出浓度与可交换态As和碳酸盐结合态As呈显著正相关,与残渣态As呈显著负相关,可交换态As、碳酸盐结合态As和残渣态-As含量是影响土壤中As浸出浓度变化的主要因素。     

生物炭基调理剂对水稻镉吸收的影响

以木质生物炭为基础,与沸石、石灰石、磷酸钙等混配制生物炭基调理剂,并用于镉污染稻田。通过田间水稻栽培实验,探讨该生物炭基调理剂的合适配比及应用效果。按照DTPA浸提法分析土壤中有效态镉含量,按HNO_3-HCLO_4消化法测定水稻植株中镉的含量。结果表明:随木炭用量增加,土壤中有效态镉减少,施用0.48 kg·m~(-2)木炭时降幅高达23.87%。施用不同配比炭基调理剂实验中,木炭:石灰石:沸石:磷酸钙=4:1:1:1时对土壤中有效态镉的钝化效果最好,达到36.42%。水稻根、茎累积镉量高于叶、壳、糙米,并且稻米中镉含量与栽培后期50 d土壤中有效态镉含量高度相关,相关系数为0.921 6(P0.05)。     

黔中地区不同污染风险等级黄壤镉形态分布特征

为探究喀斯特地区地带性黄壤的镉形态分布特征,在中国南方喀斯特中心区域——黔中地区进行了农田黄壤样品采集,并对其化学成分进行了定量分析,通过对土壤镉形态及pH、钙、镁的分析测定,探究了喀斯特背景对黄壤中镉形态分布的影响。结果表明,黔中地区黄壤全镉为0.184～3.316mg/kg,具有较大的空间差异,各形态镉含量随污染风险等级的提高而显著增加(p0.01)。黄壤中的镉主要以残渣态及可还原态存在,可交换态镉占全镉的17.52%(质量分数,下同)～22.83%,且随着风险等级的提高,可交换态镉向更为稳定的形态转变。可交换态镉与全镁、可交换态镁均显著负相关(p0.05),镁组分可在一定程度上降低黄壤中可交换态镉含量,对镉的生物有效性具有一定的调控作用。     

氮肥对污染农田土壤中铅的调控效应

用铅污染农田土壤做盆栽试验,研究了氮肥品种和施用量对小白菜吸收铅及土壤中铅形态的影响.结果表明,在氮肥施用量相同的条件下,施用不同形态氮肥对小白菜地上部及根系吸收铅有显著影响;适量的NH4NO3不会对小白菜地上部造成显著影响,增施Ca(NO3)2也不会造成小白菜地上部含铅量的继续增加;各施氮处理的土壤pH较不施氮处理的土壤pH均有不同程度的降低,且以(NH4)2SO4处理的土壤pH下降幅度最大,施用Ca(NO3)2的处理的土壤pH变化不显著;氮肥在一定程度上会影响土壤中各形态含铅量,其中对交换态、碳酸盐结合态、无定形氧化锰结合态,无定形氧化铁结合态及有机结合态含铅量影响较大,但并未改变各形态铅的分布顺序;小白菜吸收的铅主要来源于土壤中的交换态铅,但也可吸收部分碳酸盐结合态铅、铁锰氧化物结合态铅及有机结合态铅,甚至可吸收部分残渣态铅.     

过磷酸钙与石灰混施对污染农田低累积玉米生长和重金属含量的影响

通过田间实验,研究了过磷酸钙和石灰混施对重金属污染农田上低累积玉米产量以及籽粒、茎叶重金属含量的影响,并分析了施用过磷酸钙和石灰后土壤pH和有效重金属含量的变化。结果表明,与单施过磷酸钙和单施石灰相比,过磷酸钙和石灰混施更能显著提高玉米生物产量,且过磷酸钙和石灰均有一定的后效。单施石灰处理、石灰与过磷酸钙混施处理都均显著降低玉米籽粒Cd、Zn和Cu含量,其中以中量(0.4 kg/m2)、高量石灰(0.6 kg/m2)+中量过磷酸钙(0.2kg/m2)处理效果最佳,其玉米籽粒Cd、Zn和Cu含量降低到了国家食品卫生标准允许的含量水平。石灰处理均不同程度地提高了玉米籽粒Pb含量,配施过磷酸钙也不能明显降低玉米籽粒Pb含量,但仍低于饲料卫生标准允许的含量水平。另外,单施石灰处理和石灰与过磷酸钙混施处理均显著降低了玉米茎叶Cd、Pb、Zn和Cu含量,可以安全用作有机肥。     

Silicon-mediated enhancement of cadmium tolerance in maize (Zea mays L.) grown in cadmium contaminated soil

Pot experiments were performed to study the alleviative effects of exogenous silicon (Si) on cadmium (Cd) phytotoxicity in maize grown in an acid soil experimentally contaminated with Cd. Five treatments were investigated in the first trial consisting of a control (neither Cd nor Si added), Cd added at 20 or 40 mg kg(-1) Cd without or with Si added at 400 mg kg(-1) Si. A following-up trial was conducted with almost the same treatments as in the first trial except that Si was incorporated at 50 mg kg(-1) Si. The results showed that Cd treatment significantly decreased shoot and root dry weight, while addition of Si at both levels significantly enhanced biomass. Addition of Si at 400 mg kg(-1) Si significantly increased soil pH but decreased soil Cd availability, thus reducing Cd concentration in the shoots and roots and total Cd in the shoots. Moreover, more Cd was found to be in the form of specific adsorbed or Fe-Mn oxides-bound fraction in the Si-amended soil. In contrast, soil pH, available Cd and Cd forms were unaffected by addition of Si at 50 mg kg(-1) Si, but shoot Cd concentration in the Si-amended Cd treatments significantly decreased at both Cd levels used compared to the non-Si-amended Cd treatments. Total Cd in the shoots and roots was considerably and significantly higher in the Si-amended Cd treatments than in the non-Si-amended Cd treatments. The xylem sap significantly increased but Cd concentration in the xylem sap significantly decreased in the Si-amended Cd treatments compared with the non-Si-amended Cd treatments irrespective of Cd and Si levels used. The results suggest that Si-enhanced tolerance to Cd can be attributed not only to Cd immobilization caused by silicate-induced pH rise in the soils but also to Si-mediated detoxification of Cd in the plants.     

Cadmium uptake by tobacco as affected by liming, N form, and year of cultivation

Tobacco is able to accumulate cadmium and reduction of cadmium content can reduce health hazards to smokers. Soil pH and form of N fertilizers are among the factors affecting Cd uptake by tobacco. This hypothesis was tested in an acid soil in northern Greece by a four year field experiment. The variability of Cd uptake by tobacco was attributed to the variation of soil Cd availability as affected by soil pH. Liming with 3000 kg Ca(OH)(2) ha(-1) increased soil pH by 0.8 units and decreased extractable with DTPA soil and leaf Cd by 40% and 35%, respectively. The ammonium fertilizer caused the opposite, but weaker, effects. Liming reduced soil Cd more in the ammonium treatment than in nitrate or combined N treatments. The year of cultivation strongly affected soil and leaf Cd. Four years after tobacco cultivation, soil pH was reduced by 0.5 units, whereas soil and leaf Cd reduction was more than 60% in the limed treatments. Liming affected Cd uptake only in the first three years of cultivation.     

柠檬酸对褐土中DTPA提取态铜、镉含量及对紫花苜蓿吸收铜、镉的影响

为了阐述有机酸对土壤中重金属生物有效性的影响,通过盆栽实验,研究了Cu、Cd复合污染下柠檬酸对褐土中二乙基三胺五乙酸(DTPA)提取态铜和镉含量的影响,并探讨了柠檬酸对植物吸收铜、镉的影响。结果表明,土壤中DT-PA-Cu含量随柠檬酸添加量的增加而减小,添加高浓度铜(Cu 1 000)处理中,DTPA-Cu含量减小更明显。在添加低铜浓度(Cu600)处理下,柠檬酸添加量为2和12 mmol/kg时,土壤DTPA-Cu含量随土壤镉含量的增加而增加,而柠檬酸含量为5mmol/kg时,DTPA-Cu含量在低镉处理(Cd 1)时含量最低。紫花苜蓿中铜含量随柠檬酸添加量的增加明显降低。土壤中DTPA-Cd含量随柠檬酸添加量的增加而减小,且随铜添加量的增加而降低。紫花苜蓿中的镉含量随柠檬酸添加量的增加先增加后减小;在相同柠檬酸添加量处理时,紫花苜蓿中镉的含量随镉含量的增加而增加;在低镉处理下,铜的加入对较低柠檬酸浓度时紫花苜蓿镉含量影响不明显,但柠檬酸浓度为12 mmol/kg时,紫花苜蓿中镉含量随铜添加量的增加而明显增加。     

微生物矿化修复重金属污染土壤

以选矿厂附近土壤为研究对象,分析了土壤中交换态重金属含量,As、Pb、Cd、Zn和Cu的交换态浓度为14.01、4.95、0.64、33.46和12.95 mg/kg。基于生物矿化原理,利用碳酸盐矿化菌生长代谢过程产生的脲酶来分解底物尿素,产生碳酸根离子,固结重金属离子,使得土壤中活泼的重金属离子转变为碳酸盐矿物态,降低其危险。研究了温度、pH和重金属离子对酶活性的影响,发现环境30℃温度有利于促进酶活性;在弱酸性条件下,底物分解量减少15%;重金属离子在低浓度时对脲酶活性影响不大,浓度提高后对酶活性抑制作用没有加剧。将制备好的微生物矿化修复制剂喷洒于1 000 m2的污染土壤中,实验结果发现,土壤中交换态重金属离子含量在0～20 cm范围内明显减少,As、Pb、Cd、Zn和Cu的交换态浓度分别减少至2.37、1.25、0.31、16.67和3.42 mg/kg。     

An inter-laboratory study to test the ability of amendments to reduce the availability of Cd, Pb, and Zn in situ

An international inter-laboratory research program investigated the effectiveness of in situ remediation of soils contaminated by cadmium, lead and zinc, measuring changes in soil and soil solution chemistry, plants and soil microbiota. A common soil, from mine wastes in Jasper County MO, was used. The soil was pH 5.9, had low organic matter (1.2 g kg(-1) C) and total Cd, Pb, and Zn concentrations of 92, 5022, and 18 532 mg kg(-1), respectively. Amendments included lime, phosphorus (P), red mud (RM), cyclonic ashes (CA), biosolids (BIO), and water treatment residuals (WTR). Both soil solution and NH4NO3 extractable metals were decreased by all treatments. Phytotoxicity of metals was reduced, with plants grown in P treatments having the highest yields and lowest metal concentration (0.5, 7.2 and 406 mg kg(-1) Cd, Pb, and Zn). Response of soil micro-organisms was similar to plant responses. Phosphorus addition reduced the physiologically based extraction test Pb from 84% of total Pb extracted in the untreated soil to 34.1%.     

Promotion effect of graphene on phytoremediation of Cd-contaminated soil

Echinacea purpurea (L.) Moench was selected as a remediation plant in this study, and different concentrations of graphene oxide (GO) were added to Cd-contaminated soil. Through pot experiments, the effect of E. purpurea on Cd-contaminated soil was determined at 60 days, 120 days, and 150 days. A preliminary study on the remediation mechanism of GO was explored through changes in the forms of Cd in the rhizosphere soil, soil pH, and soil functional groups. Results showed that the optimal concentration of GO was 0.4 g/kg, and under the condition, the accumulation of Cd in the roots of E. purpurea was as high as 113.69 ± 23.86 mg/kg, and the maximum EF reached 5.87 ± 1.34. Compared with those of the control group, accumulated Cd concentration and EF in the roots increased by 60.34% and 2.32, respectively. Correlation analysis showed that the absorption and accumulation of Cd was negatively correlated with the exchangeable Cd content at 120 days, and the exchangeable Cd was negatively correlated with the relative content of functional groups in the soil with 0.4 g/kg GO (E2). The artificial application of GO to the soil can be used as an effective way to improve the effect of E. purpurea in the remediation of Cd soil pollution, and it has great application potential in the stabilization of plants and vegetations and restoration of high-concentration Cd-contaminated soil.

Graphical abstract

     

Changes in speciation and leaching behaviors of heavy metals in dredged sediment solidified/stabilized with various materials

Solidification/stabilization (S/S) of sediments is frequently used to treat contaminants in dredged sediments. In this study, sediment collected from the Pearl River Delta (China) was solidified/stabilized with three different kinds of functional materials: cement, lime and bentonite. Lime primarily acted via induced increases in pH, while cements stabilization occurred through their silicate-based systems and the main function of bentonite was adsorption. The speciation and leaching behaviors of specific heavy metals before and after S/S were analyzed and the results showed that the residual speciation of Cd, Cr, Ni, Pb and Zn increased in all treatments except for Cu, as the exchangeable speciation, carbonate-bound speciation and Fe-Mn-oxide-bound speciation of Cu (all of which could be stabilized) were less than 2 % of the total amount. Pb leaching only decreased when pH increased, while the mobility of Cr and Ni only decreased in response to the silicate-based systems. The leached portion of the Fe-Mn-oxide-bound speciation followed the order Zn?>?Cu?>?Ni/Cd?>?Pb?>?Cr. The leached portion of organic-matter-bound species was less than 4 % for Cd, Cr, Ni and Pb, but 35.1 % and 20.6 % for Cu and Zn, respectively.     

矿区炼金废渣的固化/稳定化处理

通过对金矿矿区炼金废渣的酸中和能力、净产酸量及浸出毒性实验，测定了废渣的产酸潜力及重金属砷、镉、铅、锌的总量和它们的浸出量。为了合理处置矿区炼金废渣，并为矿区重金属污染土壤的修复提供技术支持，采用石灰、粉煤灰、堆肥化污泥作为添加剂对废渣进行固化/稳定化处理；通过浸出毒性实验对固化/稳定化处理效果进行综合分析，试图寻求一种最佳的稳定剂。结果表明，无论是单独添加石灰、粉煤灰或者堆肥化污泥还是两两组合混合添加，样品浸出液的pH都有升高，As、Cd的浸出浓度都有明显下降，而且两两组合添加比单独添加的固化/稳定化处理效果更好。在两两组合添加中，粉煤灰混合堆肥化污泥的处理效果最好，浸出液的pH值达到7.82，As、Cd的浸出率分别下降72.0%和72.2%。说明粉煤灰混合堆肥化污泥处理炼金废渣效果最佳，同时具有以废治污的资源化生态效能。     

土壤中无机钠盐对不同形态Cu含量的影响

采用TESSIER连续提取法研究了不同种类、不同加入量的无机钠盐对土壤中不同形态Cu含量的影响。结果表明,对于可交换态Cu,3种无机钠盐的加入均使其含量减少,其中NaCl的影响最大,4、8g/kg的NaCl分别使其减少了28.13%(质量分数,下同)和50.59%;对于碳酸盐结合态Cu,3种无机钠盐的加入均使其含量增加,其中Na2CO3(8g/kg)对其影响最大;对于铁锰氧化态Cu,Na2SO4和Na2CO3的加入使其含量先升高后降低,NaCl则使其含量降低;有机结合态Cu受Na2SO4和Na2CO3的影响较大,在它们的影响下含量均增加;残渣态Cu在3种无机钠盐的影响下变化幅度均很大,其中4、8g/kg的Na2SO4分别使其含量减少了47.47%和62.21%。