添加天然沸石和石灰对土壤镉形态转化的影响

采用土壤培养实验,研究镉污染土壤中添加沸石、石灰及两者配施对土壤pH值和土壤镉形态变化的影响。结果表明,土壤pH值随沸石用量的增加而增加,随培养时间呈现先增加后下降并逐渐趋于稳定的趋势,但均高于对照。高剂量石灰的处理对土壤pH的影响最大,与对照相比土壤pH提高了3.33个单位。在土壤5~50 d培养过程中,石灰处理的土壤交换态镉含量呈现先逐渐降低而后略有升高的趋势,其余处理均呈下降趋势。培养50 d后,高剂量的沸石、石灰及高剂量沸石与石灰配施处理的土壤交换态镉含量从5 d时的67.54、61.95和55.56 mg/kg降低至54.65、49.93和45.96mg/kg。相关分析表明,不同培养时期交换态镉含量与土壤pH值呈负相关关系。在10个处理中,L2Z3(石灰2 g/kg土和沸石60 g/kg土)组合处理效果最好,使土壤交换态镉含量下降了34.68%,碳酸盐结合态镉含量上升了4.30%,铁锰氧化结合态镉含量上升了16.97%,有机结合态镉含量上升了1.31%,残渣态镉含量上升了12.11%。     

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。     

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。     

骨炭和硫化钠联用修复镉-锌污染土壤

以湖南东江湖矿渣堆场土壤为研究对象,利用骨炭-硫化钠组合制剂修复矿区镉锌污染土壤,目的是探讨组合制剂修复重金属镉-锌复合污染土壤效果。采用美国固体废弃物毒性浸出程序(TCLP)评价修复效果,并对最佳处理组采用改进的BCR形态分析法进行分析。结果表明,与对照相比,骨炭-硫化钠使土壤中TCLP浸提态Cd和Zn分别降低了15.88%~58.82%和7.91%~73.60%,同时土壤pH提高了0.26~3.00个单位,且当投加4%骨炭和2%硫化钠时对土壤中镉和锌稳定效果达最佳;最优处理组镉的酸可提取态下降了4.8%~11.5%,锌的酸可提取态下降了4.3%~12.7%。因此,骨炭-硫化钠组合制剂能有效修复镉锌复合污染土壤。     

土壤重金属铅镉形态和有效态的提取方法研究

选择一步提取法(CaCl2法、NaNO3法、NH4NO3法、HCl法)提取土壤铅镉有效态含量,顺序提取法(BCR提取法、Tessier提取法)提取土壤中铅镉各形态含量。结果表明,4种一步提取法对供试土样有效态铅镉的提取效率为HCl法NH4NO3法CaCl2法NaNO3法。当镉质量浓度为0~20、40~90 mg/kg时,BCR法对土壤中镉的总提取率分别为104.9%、105.3%,Tessier法对土壤中镉的总提取率分别为101.7%、98.9%;当镉质量浓度为20~40mg/kg时,两种顺序提取法的提取效果均不佳。BCR法适合铅质量浓度为20 000~45 000 mg/kg时应用,此时BCR法对铅的总提取率为99.8%;Tessier法适合铅质量浓度为0~1 500、9 000~15 000mg/kg时应用,此时Tessier法对土壤铅的总提取率分别为100.7%、90.9%。土壤重金属铅镉各形态的含量受土壤自身pH影响不明显,但在遇到外界酸性环境影响时容易发生重金属铅镉迁移。     

降雨对磷基材料修复镉铅污染土壤稳定性的影响研究

通过模拟加速老化实验和土柱淋溶实验，探究降雨对磷基材料修复镉铅污染土壤效果稳定性的影响。结果表明：模拟降雨加速老化对土壤中有效镉含量的影响不显著，但是加速老化12 a后，土壤中有效铅由(2.74±0.35) mg/kg增加到(3.66±0.39) mg/kg(模拟自然降雨)和(3.59±0.19) mg/kg(模拟酸雨)。在添加磷基材料的土壤中，模拟降雨加速老化后，镉和铅有效性变化不显著。在土柱淋溶实验体系中，模拟4个月降雨当量的酸雨淋溶后，所有处理组的滤出液镉离子和铅离子始终低于0.1μg/L。对照组的表层(0～5 cm)土壤pH显著低于其他剖面层；不同剖面层土壤的镉、铅有效性和赋存形态变化较小，5～10 cm剖面层土壤的酸可溶态镉比例高于表层土壤。在添加磷基材料F、F700的处理组中，土壤pH、镉和铅的有效性与赋存形态在垂向上大多不存在显著差异，但底层(10～15 cm)土壤的酸可溶态镉和铅比例高于其他剖面层。综上所述，磷基材料能够有效固持土壤中镉和铅，削减降雨对重金属的活化-释放作用。     

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.     

铵态氮在非正规垃圾填埋场土壤中的赋存特征

应用连续分级提取法,对重庆市某非正规垃圾填埋场污染土壤中铵态氮的赋存形态进行分级测定,研究了各形态铵的赋存特征及影响因素。结果表明:土壤总铵量在116.32~241.66 mg·kg~(-1)之间,平均值为(164.13±24.98)mg·kg~(-1),水溶态铵、可交换态铵和固定态铵的平均含量分别为(10.93±3.64)、(7.08±3.46)、(146.12±24.11)mg·kg~(-1);3种形态铵占总铵的比重大小为固定态铵水溶态铵可交换态铵。受雨水冲刷及淋滤影响,铵态氮有在下游点位积累的趋势。水溶态铵含量与有机碳含量、氧化还原电位呈极显著相关,与pH、粉粒含量及粘粒含量显著相关。可交换态铵与土壤氧化还原电位在垂直剖面上变化趋势一致,并与土壤粘粒含量呈极显著的负相关。固定态铵含量与土壤中粘粒含量呈极显著的正相关,与砂粒含量呈显著的负相关。     

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。     

pH和有机质对铬渣污染土壤中Cr赋存形态的影响

选用3种不同的铬渣污染土壤作为试验样,通过调节其pH和有机质含量,并采用碱消解-共沉淀法和改良BCR顺序提取法,研究了pH和有机质含量对土壤中铬的价态及形态的影响。结果表明,总体上Cr(Ⅵ)含量随pH降低和有机质投加量增大而减小,Cr(Ⅲ)则增加,但土1各水平间差异均显著(F8.89),土2和土3只有部分水平间差异显著。同时,随pH降低和有机质投加量增大,酸可提取态Cr含量减小,可氧化态Cr增加,可还原态略有增加,表明酸性条件和有机质有利于Cr(Ⅵ)的还原和酸可提取态Cr向可还原态和可氧化态Cr的转化。     

水溶性羧甲基壳聚糖对Cd2+的解吸行为研究

为改善壳聚糖(CTS)的水溶性及对重金属的配位能力,合成水溶性好并能与重金属形成配位作用的水溶性羧甲基壳聚糖(WSCC),研究了WSCC对镉的增溶、解吸行为,考察了pH、离子强度、有机质含量和WSCC初始浓度对镉的解吸影响。结果表明:WSCC对碳酸镉的增溶效果显著,当其质量浓度为2g/L时溶液中Cd2+可达到275mg/L;WSCC对镉解吸能力随着土壤中有机质含量的增加而降低,pH的升高、离子强度的增加和WSCC初始浓度的增加有利于镉的解吸;WSCC对镉污染土壤的解吸更符合准二级动力学方程,该静态解吸研究可以为镉污染土壤的修复提供基础信息及依据。     

Lead contamination in tea garden soils and factors affecting its bioavailability

The consumption of heavy metals is detrimental to human health and most countries restrict the concentration of metals such as lead (Pb) in food and beverages. Recent tests have detected high Pb concentrations in certain commercial brands of tea leaves and this finding has raised concerns for both producers and consumers. To investigate what factors may be contributing to the increase in Pb accumulation in the tea leaves we collected tea leaves and soils from tea producing areas and analyzed them for Pb concentration, pH and organic matter content. The result showed the Pb concentration of 47% investigated tea leaves samples was beyond 2 mg kg(-1), the permissible levels given by China. The total Pb concentration in the surface and subsurface soil layers averaged 36.4 and 32.2 mg kg(-1), respectively which fall below of the 60 mg kg(-1) limit provided for organic tea gardens in China. The pH of the tea garden soils was severely acidic with the lowest pH of 3.37. Soils under older tea gardens tended to have a lower pH and a higher Pb bioavailability which was defined as the amount of lead extracted by CaCl2 solution than those under younger tea gardens. We found that the concentration of bioavailable Pb and the percentage of bioavailable Pb (bioavailable Pb relative to total Pb concentration) were positively correlated with soil H+ activity and soil organic matter content, and the organic matter accumulation contribute more effects on Pb bioavailability in these two factors. We conclude that soil acidification and organic matter accumulation could contribute to increasing Pb bioavailability in soil and that these could increase Pb uptake and accumulation in the tea leaves.     

Sorption of 3,4-dichloroaniline on four contrasting Greek agricultural soils and the effect of liming

Sorption of 3,4-dichloroaniline (3,4-DCA) on four typical Greek agricultural soils, with distinct texture, organic matter content and cation exchange capacities, was compared by using sorption isotherms and the parameters calculated from the fitted Freundlich equations. The sorption process of 3,4-DCA to the soil was completed within 48–72 h. The 3,4-DCA sorption on all soils was well described by the Freundlich equation and all sorption isotherms were of the L-type. The sandy clay loam soil with the highest organic matter content and a slightly acidic pH was the most sorptive, whereas the two other soil types, a high organic matter and neutral pH clay and a low organic matter and acidic loam, had an intermediate sorption capacity. A typical calcareous soil with low organic matter had the lowest sorption capacity which was only slightly higher than that of river sand. The 3,4-DCA sorption correlated best to soil organic matter content and not to clay content or cation exchange capacity, indicating the primary role of organic matter. The distribution coefficient (K _d) decreased with increasing initial 3,4-DCA concentration and the reduction was most pronounced with the highly sorptive sandy clay loam soil, suggesting that the available sorption sites of the soils are not unlimited. Liming of the two acidic soils (the sandy clay loam and the loam) raised their pH (from 6.2 and 5.3, respectively) to 7.8 and reduced their sorption capacity by about 50 %, indicating that soil pH may be the second in importance factor (after organic matter) determining 3,4-DCA sorption.     

Sorption of 3,4-dichloroaniline on four contrasting Greek agricultural soils and the effect of liming

Sorption of 3,4-dichloroaniline (3,4-DCA) on four typical Greek agricultural soils, with distinct texture, organic matter content and cation exchange capacities, was compared by using sorption isotherms and the parameters calculated from the fitted Freundlich equations. The sorption process of 3,4-DCA to the soil was completed within 48-72 h. The 3,4-DCA sorption on all soils was well described by the Freundlich equation and all sorption isotherms were of the L-type. The sandy clay loam soil with the highest organic matter content and a slightly acidic pH was the most sorptive, whereas the two other soil types, a high organic matter and neutral pH clay and a low organic matter and acidic loam, had an intermediate sorption capacity. A typical calcareous soil with low organic matter had the lowest sorption capacity which was only slightly higher than that of river sand. The 3,4-DCA sorption correlated best to soil organic matter content and not to clay content or cation exchange capacity, indicating the primary role of organic matter. The distribution coefficient (K(d)) decreased with increasing initial 3,4-DCA concentration and the reduction was most pronounced with the highly sorptive sandy clay loam soil, suggesting that the available sorption sites of the soils are not unlimited. Liming of the two acidic soils (the sandy clay loam and the loam) raised their pH (from 6.2 and 5.3, respectively) to 7.8 and reduced their sorption capacity by about 50 %, indicating that soil pH may be the second in importance factor (after organic matter) determining 3,4-DCA sorption.     

Evaluation of three common alkaline agents for immobilization of multi-metals in a field-contaminated acidic soil

We investigated three common alkaline agents (NaOH, CaO, and Mg(OH)₂) for immobilization of four heavy metals (Pb, Zn, Cu, and Cd) in a field-contaminated soil and elucidated the underpinning principles. NaOH caused the highest pH spike in the soil, while CaO and Mg(OH)₂ served as a longer-lasting source of OH^-. Amending the soil with CaO or Mg(OH)₂ at ≥0.1 mol as OH^- (kg·soil)^?1 for 24 h was able to immobilize all four metals, while NaOH failed. NaOH leached up to 3 times more organic carbon than CaO and Mg(OH)₂, resulting in elevated leachability of the metals. Column elution tests showed that amendments by CaO and Mg(OH)₂ lowered the leachable Pb²⁺, Zn²⁺, Cu²⁺, and Cd²⁺ by 52–54%, 71–75%, 69–73%, and 68%, respectively, after 1440 pore volumes of elution. Sequential extraction revealed that the soil amendments converted the exchangeable fraction of the metals to the much less available forms. XRD and FTIR analyses indicated that formation of metal oxide precipitates and complexation with soil organic matter were responsible for the metals immobilization. Taken together the chemical cost, technical effectiveness, and environmental impact, CaO is the most suitable alkaline agent for remediation of soil contaminated with heavy metals.

     

Properties of biochars from conventional and alternative feedstocks and their suitability for metal immobilization in industrial soil

In contaminated soils, excessive concentrations of metals and their high mobility pose a serious environmental risk. A suitable soil amendment can minimize the negative effect of metals in soil. This study investigated the effect of different biochars on metal (Cu, Pb, Zn) immobilization in industrial soil. Biochars produced at 300 and 600 °C from conventional (MS, maize silage; WP, wooden pellets) and alternative (SC, sewage sludge compost; DR, digestate residue) feedstocks were used as soil amendments at a dosage of 10 % (w/w). The type of feedstock and pyrolysis temperature affected the properties of the biochars and their ability to immobilize metal in soil. Compared to production at 300 °C, all biochars produced at 600 °C had higher pH (6.2–10.7), content of ash (7.2–69.0 %) and fixed carbon (21.1–56.7 %), but lower content of volatile matter (9.7–37.2 %). All biochars except DR biochar had lower dissolved organic carbon (DOC) content (1.4–2.3 g C/L) when made at 600 °C. Only MS and SC biochars had higher cation exchange capacity (25.2 and 44.7 cmol/kg, respectively) after charring at 600 °C. All biochars contained low concentrations of Cd, Cu, Ni, Pb and Zn; Cd was volatilized to the greatest extent during pyrolysis. Based on FTIR analysis and molar ratios of H/C and O/C, biochars had a greater degree of carbonization and aromaticity after charring at 600 °C. The efficiency of the biochars in metal immobilization depended mainly on their pH, ash content, and concentration of DOC. SC and DR biochars were more effective for Cu and Zn immobilization than MS and WP biochars, which makes them attractive options for large-scale soil amendment.     

Sequential extraction of heavy metals during composting of sewage sludge

The major limitation of soil application of sewage sludge compost is the total heavy metal contents and their bioavailability to the soil-plant system. This study was conducted to determine the heavy metal speciation and the influence of changing the physico-chemical properties of the medium in the course of composting on the concentrations, bioavailability or chemical forms of Cu, Zn, Pb and Ni in sewage sludge. Principal physical and chemical properties and FTIR spectroscopical characterization of sludge compost during treatment show the stability and maturity of end product. The total metal contents in the final compost were much lower than the limit values of composts to be used as good soil fertilizer. Furthermore, it was observed by using a sequential extraction procedure in sludge compost at different steps of treatment, that a large proportion of the heavy metals were associated to the residual fraction (70-80%) and more resistant fractions to extraction X-NaOH, X-EDTA, X-HNO3 (12-29%). Less than 2% of metals bound to bioavailable fractions X-(KNO3+H2O). Heavy metal distribution and bioavailability show some changes during composting depending on the metal itself and the physico-chemical properties of the medium. Bioavailable fractions of all elements tend to decrease except Ni-H2O. Zn and mainly Cu present more affinity to organic and carbonate fractions. In contrast, Pb is usually preferentially bound to sulfide forms X-HNO3. Nickel shows a significant decrease of organic form. Significant degrees of correlation were found between heavy metal fractions and changes of some selected variables (e.g. pH, ash, organic matter, humic substance) during the course of composting. Mobile fractions of metals are poorly predictable from the total content. The R2 value was significantly increased by the inclusion of other variables such as the amount of organic matter (OM) and pH.     

Effects of surface coatings on electrochemical properties and contaminant sorption of clay minerals

Surface charges play a major role in determining the interactions of contaminants with soils. The most important sources of soil charges are clay mineral colloids, whose electrochemical properties are usually modified by metal-oxides and organic matter in natural environments. In this study, effects of coatings of organic matter and Fe- and Al-oxides on a series of electrochemical properties and heavy metal sorption of three clay minerals (kaolinite, montmorillonite and illite) predominant in natural soils were investigated using batch techniques. The results indicate that the coatings increased the specific surface area of the clay minerals, except for the Al-oxide coated montmorillonite and organic matter coated 2:1 clay minerals. The sesquioxide coatings increased amount of positive charges but decreased negative charges. This causes great reduction of the negative potential on the clay surfaces, shift of the zero point of charge to a higher pH, and promotion of fluoride sorption due to presence of more OH- and OH2 on the oxide surfaces than on the clay surfaces. In contrast, the organic coating significantly increased the negativity of surface charges, and thus the zero point of charge and zeta-potential of the clays dropped down. The organic coating also induced a reduction of fluoride sorption on the clays. With respect to the sorption of lead and cadmium, the sesquioxide coatings produced insignificant effects. The experiments of lead/cadmium competitive sorption show that on both the oxide-coated surface and the original clay surface there exist different types of sites, each of which preferentially binds with a heavy metal.     

影响有机污染物在土壤中的迁移、转化行为的因素

本文介绍了有机污染物在土壤中的吸附与解吸附、渗滤、挥发和降解等行为过程。探讨了吸附与解吸附机理、土壤有机质含量和类型、水分含量及温度等对此过程的影响。依据某些典型的化合物行为模型,论述了影响土壤中有机污染物渗滤的因素。有机污染物需要先从土壤深层迁移至地表,然后挥发至大气,在土壤中迁移的速率较慢,控制着整个挥发过程,可用Ｆｉｃｋ 第二定律来描述。有机污染物在土壤中的非生物降解主要包括氧化－ 还原、光解和水解等反应。土壤中的Ｏ２ 含量、土壤有机质成分和含量、辐射强度、光谱分布、土壤水分含量、温度和ｐＨ 值等都会影响非生物降解过程。其中有些因素通过影响微生物的生物活性,还影响有机污染物的生物降解     

Cyprodinil retention on mixtures of soil and solid wastes from wineries. Effects of waste dose and ageing

In spite of its wide-world economic relevance, wine production generates a huge amount of waste that threatens the environment. A batch experiment was designed to assess the effect of the amendment of an agricultural soil with two winery wastes (perlite and bentonite wastes) in the immobilization of cyprodinil. Waste addition (0, 10, 20, 40, and 80 Mg ha^?1) and different times of incubation of soil-waste mixtures (1, 30, and 120 days) were tested. The addition of wastes improved the soil’s ability to immobilize cyprodinil, which was significantly correlated to total C content in soil-waste mixtures. Longer incubation times decreased the cyprodinil sorption possibly due to the mineralization of organic matter but also as a consequence of the high pH values reached after bentonite waste addition (up to 10.0). Cyprodinil desorption increased as the amount of waste added to soil, and the incubation time increased. The use of these winery wastes contributes to a more sustainable agriculture preventing fungicide mobilization to groundwater.