石灰组配土壤改良剂抑制污染农田水稻镉吸收

为达有效地调控污染稻田水稻糙米对Cd吸收,该研究选取湖南省长株潭地区的湘潭、醴陵和株洲3处不同Cd污染程度田块,研究石灰配施海泡石、钙镁磷肥、有机肥对水稻Cd吸收和累积的影响。结果表明,施用石灰及其组配改良剂均可明显提高土壤pH值,有效降低土壤中酸提取态Cd含量和水稻中Cd含量。与不施用改良剂相比,石灰配施海泡石或有机肥、配施海泡石和有机肥,Cd污染稻田土壤pH值平均升高1.08,0.96和0.93个单位,酸提取态Cd质量分数分别平均降低20.6%,15.6%和21.2%。石灰配施海泡石、有机肥或钙镁磷肥处理下在轻度Cd污染田块中糙米Cd含量较对照分别显著降低了48.3%,46.7%和34.2%,石灰配施有机肥、钙镁磷肥或钙镁磷肥和有机肥处理下在中度Cd污染田块中糙米Cd含量较对照分别显著降低了52.8%,47.8%和37.5%,石灰配施钙镁磷肥和有机肥、有机肥或海泡石处理下在重度Cd污染田块中糙米Cd含量较对照分别显著降低了51.2%,44.6%和42.5%,均低于食品安全国家标准中糙米限量值0.2 mg/kg(GB2762-2017)。相关分析表明,土壤中酸提取态Cd含量与水稻根、茎叶和糙米中Cd含量呈显著正相关关系(P0.05),说明土壤酸提取态Cd含量是影响糙米对Cd吸收的关键因素之一。上述结果说明,石灰配施海泡石、有机肥或钙镁磷肥+有机肥可有效调控污染稻田土壤中Cd进入水稻,实现水稻安全生产。     

不同改良剂对镉污染土壤中小白菜吸收镉的影响

采用盆栽试验, 研究了施用石灰、钙镁磷肥、泥炭、碱渣4种土壤改良剂对外加镉污染的赤红壤上小白菜产量、镉吸收量、土壤有效态镉及pH的影响。结果表明: 外加1 mg·kg^-1和5 mg·kg^-1镉对小白菜生物量无显著影响, 且1 mg·kg^-1镉对小白菜生长有一定的促进作用; 施用改良剂对镉污染土壤上小白菜无显著增产效果。施用4种改良剂均能降低小白菜地上部镉含量, 作用效果为石灰≈泥炭>碱渣>钙镁磷肥。不同改良剂对小白菜根部镉含量影响不同, 泥炭和石灰在所有镉浓度下、钙镁磷肥在0和1 mg·kg^-1镉浓度下可显著降低根部镉含量, 而碱渣无明显作用, 种植两茬规律一致。土壤有效态镉含量与pH呈显著负相关; 施用石灰、碱渣、钙镁磷肥使土壤pH显著升高, 有效态镉含量显著降低, 从而降低小白菜对镉的吸收; 泥炭可显著提高土壤pH, 虽降低土壤有效态镉作用效果不显著, 但显著降低小白菜体内镉含量, 这可能与土壤中形成难以被植物吸收的镉有机结合物有关。两茬蔬菜种植结果显示, 施用后期改良剂对镉污染的抑制效果也较明显。     

湖南某铅锌矿污染土壤稳定化修复研究

使用海泡石、磷酸二氢钙、钙镁磷肥、氧化钙和氧化镁等土壤改良剂及其组合,对湖南省某铅锌矿冶炼厂附近的重金属污染土壤进行了稳定化修复试验,利用BCR连续提取法进行形态分析,并进行稳定化效果的评价。结果表明,各改良剂组合均能够有效改变土壤中Zn、Cd和Pb的形态分布,弱酸提取态含量的减少率分别为Zn:17.03%~83.13%,Cd:45.03%~99.17%,Pb:54.05%~99.44%,降低重金属的不稳定形态和生物可利用性,稳定化效果显著。改良剂对Zn元素的稳定化效果影响程度为:钙镁磷肥+氧化钙钙镁磷肥+氧化镁钙镁磷肥海泡石+磷酸二氢钙海泡石;对Cd元素的稳定化效果影响程度为:钙镁磷肥+氧化钙钙镁磷肥+氧化镁钙镁磷肥海泡石+磷酸二氢钙海泡石;对Pb元素的稳定化效果影响程度为:海泡石+磷酸二氢钙钙镁磷肥+氧化镁钙镁磷肥+氧化钙钙镁磷肥海泡石。该复合污染土壤中,Zn、Cd、Pb稳定效果最优处理为10%钙镁磷肥+5%氧化钙组合。     

石灰化水稻土的形成

石灰化水稻土在我国约有400多万亩。CaCO₃含量10—20%,CaCO₃/MgCO₃之比10—30不等。土壤板结,有石灰结核,有时形成石灰盘。土壤缺磷,少钾,有效态硼、锌、钼、锰也不足。是华南的一种中低产水稻土。石灰化水稻土中的钙主要来自年复一年的施用石灰和引灌含钙高的石灰岩溶洞水;石灰积聚的条件是土壤pH高,土壤CO₂分压低和通透性不良;根据土壤中石灰含量和¹⁴C测定估算,石灰化水稻土的形成至少有360年以上的历史。石灰化水稻土施用石灰不起中和酸性的作用。所以,必须停施石灰,增施有机肥以根本上改良这种土壤,在未改良前应对症施肥以提高产量。     

钝化剂对酸性高镉土壤钝化效果及水稻镉吸收的影响

以海泡石、磷酸二氢钾、钙镁磷肥、钢渣、生石灰及生物炭为重金属镉钝化材料,研究钝化剂对湖南省酸性高镉(Cd)稻田土壤及水稻中Cd含量的影响。以土壤pH值和有效态镉作为评价指标,筛选出三种效果较优的钝化剂,通过正交试验进行复配,选择最优的钝化剂配方进行田间验证。结果表明,海泡石、钙镁磷肥、钢渣在施用比例为1%时均可显著提高土壤pH,pH的提升效果排序为钢渣钙镁磷肥海泡石;除钢渣外,其余钝化剂在施用比例为1%时均可不同程度降低土壤有效态Cd含量,钝化效果排序为磷酸二氢钾钙镁磷肥生物炭海泡石生石灰。选取海泡石、钙镁磷肥和磷酸二氢钾复配钝化剂,依据正交试验结果并综合考虑钝化效果、成本及材料易得性,确定钝化剂的最优施用量组合为海泡石500 mg kg-1、钙镁磷肥500 mg kg-1、磷酸二氢钾170 mg kg-1。大田试验结果表明,施用钝化剂后,土壤pH值提高0.5个单位,土壤有效Cd含量降低34.00%,糙米中Cd含量降低19.44%,水稻各器官Cd的富集与迁移系数明显降低,水稻产量明显升高。     

4种不同原料生物炭对镉污染土壤的钝化效果与稳定性比较

生物炭的性质与老化作用是影响生物炭钝化修复Cd污染土壤效果的重要因素。比较研究4种不同原料生物炭(污泥类、秸秆类、动禽粪便类和木本类)对Cd²⁺吸附作用和Cd污染土壤的钝化修复效果的差异。结果表明:施用生物炭显著提升土壤孔隙水pH(棕榈丝生物炭除外),降低孔隙水DOC和Cd浓度,从而减少水稻根系对孔隙水中Cd的吸收。同时,4种生物炭提高土壤pH,降低土壤有效态Cd、水稻根系和籽粒Cd含量。老化作用减弱稻秆生物炭的钝化效果,显著增强棕榈丝生物炭对土壤Cd的钝化作用,然而,老化作用对富含灰分的猪粪生物炭和污泥生物炭的影响较小。因此,选择生物炭钝化修复Cd污染稻田土壤时,必须考虑生物炭的原料及其老化作用。     

不同施用量石灰和生物炭对稻田镉污染钝化的延续效应

为筛选适用于西南地区稻田土壤及农作物Cd污染的修复技术,采用田间小区试验比较了单施石灰、生物炭以及复合施用石灰+生物炭及其不同用量对Cd污染稻田的土壤基本理化性质、稻米Cd含量及其水稻各部位富集转运的影响。结果表明:第1年修复试验中,单施石灰和生物炭以及复合施用均可降低稻米Cd含量以及水稻各部位富集和转运系数,且随着施加量的增加稻米Cd含量呈降低趋势,土壤至水稻根系Cd富集系数呈先降低后增加趋势,复合施用(石灰(1.5 t/hm^2)+生物炭)效果优于单施石灰和生物炭,与对照相比,稻米Cd含量降低57.14%~88.57%,土壤至水稻根系富集系数降低22.06%~32.96%;施用石灰可显著提高土壤pH和降低土壤有效态Cd含量。第2年修复剂施用延续效应试验中,石灰在短时间内降低土壤有效Cd和稻米Cd的效果较好,但其长效性和稳定性不及生物炭,与对照相比,单施石灰和生物炭以及复合施用土壤有效Cd分别降低2.97%~25.19%,13.94%~23.41%,1.93%~21.41%,稻米Cd含量分别降低0.72%~34.87%,12.11%~49.14%,36.55%~51.71%。总体来看,设定试验条件下,复合施用(石灰(1.5 t/hm^2)+生物炭(3.0 t/hm^2)),效果最优。     

不同改良剂降低矿区土壤水溶态重金属的效果及其长效性

为了解施用不同种类改良剂对降低矿区土壤重金属移动性的长期效果,进行为期6年的模拟试验,用化学提取方法评价磷灰石、农用石灰、坡缕石、钙镁磷肥、沸石、猪粪和水稻秸秆7种常用改良剂对降低土壤重金属溶解性的影响。结果表明,农用石灰、钙镁磷肥、磷灰石、坡缕石和沸石对降低矿区土壤水溶态重金属均有良好的效果,但猪粪和水稻秸秆有机物改良剂的效果较差。降低土壤水溶态Cd的效果以钙镁磷肥为最佳(平均可降至29%),降低土壤水溶态Cu的效果以坡缕石为最佳(平均可降至65%),降低土壤水溶态Pb的效果以磷灰石、石灰和钙镁磷肥3种改良剂为佳(平均可降至27%左右);降低土壤水溶态Zn的效果以钙镁磷肥为最佳(平均可降至48%)。磷灰石和沸石对土壤重金属的稳定性有较长的作用效果,坡缕石、石灰和钙镁磷肥对土壤重金属稳定性随试验时间增加有明显的下降;有机物类改良剂对土壤重金属的稳定效果较差,且随有机物质的降解,其稳定效果显著下降。     

石灰和海泡石对镉污染土壤的修复效应与机理研究

研究了稻作和旱作两种种植制度下,施用石灰、海泡石及两种改良剂配施对镉污染土壤pH值、土壤镉形态变化及作物对镉的吸收等的影响.结果表明,施用改良剂使稻作条件下的土壤pH提高0.3～1.8个单位,旱作条件下土壤pH提高幅度为0.3～2.0个单位:两种种植制度下,作物有效性较高的酸提取态镉含量显著减少,而作物有效性较低的可还原态和残渣态镉含量显著增加,进而引起了水稻和萝卜对镉的吸收量降低.其中以石灰和海泡石配施的效果最好,单施海泡石次之,单施石灰效果最差,且各处理均随改良剂用量的增加效果增强,虽然,施用改良剂可以有效降低土壤中镉的作物有效性,但对水稻产量和生物量及镉在水稻和萝卜两种作物地上部分的分配规律均没有明显的影响.     

改良剂配合水分管理减少水稻吸收土壤中镉的研究

为研究减少水稻籽粒中镉的积累,选择一中度重金属污染农田,进行了4种改良剂处理(不施改良剂、生物质炭、钙镁磷肥—坡缕石—硫磺粉(比例为100∶50∶1)和石灰—沸石—硫磺粉(比例为100∶50∶1))和2种水分管理模式(深灌和浅灌)的不同组合处理,田间试验研究了改良剂配合水分管理减少水稻吸收土壤镉的效果,改良剂用量为3 t/hm~2。结果表明,施用改良剂和采取深灌均可显著减少水稻从土壤中吸收镉,并以二者配合的效果最佳。与浅灌/不施改良剂处理比较,钙镁磷肥—坡缕石—硫磺粉和石灰—沸石—硫磺粉2种复合改良剂配合深灌可分别降低籽粒中镉含量56.53%和55.53%,但施用生物质炭降低水稻吸收土壤中镉的效果相对较差。施用复合改良剂促使土壤中交换态镉转化为碳酸盐结合态、氧化物结合态及残余态镉等较为稳定的镉形态,降低了土壤中生物有效态和水溶态镉,减少了水稻吸收土壤镉;深灌有利于硫化镉的形成,并通过"稀释"作用降低水稻吸收土壤镉。研究认为改良剂配合深灌是一种较为方便、有效的技术,适用于农田土壤镉污染的控制。     

Sustainability of in situ remediation of Cu- and Cd-contaminated soils with one-time application of amendments in Guixi,China

Purpose

In situ immobilization of heavy metal-contaminated soils with the repeated incorporation of amendments can effectively reduce the bioavailability of soil heavy metals. However, the long-term application of amendments would lead to the destruction of soil structure and accumulation of soil toxic elements, ultimately affecting food security and quality. Thus, the sustainability of the amendments in a heavy metal-contaminated soil was evaluated from 2010 to 2012.

Materials and methods

Batch field experiments were conducted in the soils, which were amended with apatite (22.3 t ha^?1), lime (4.45 t ha^?1), and charcoal (66.8 t ha^?1), respectively. The amendments were applied only one time in 2009, and ryegrass was sown each year. Ryegrass and setaria glauca (a kind of weed) were harvested each year. Concentrations of copper (Cu) and cadmium (Cd) were determined by batch experiments. Five fractions of Cu and Cd were evaluated by a sequential extraction procedure.

Results and discussion

Ryegrass grew well in the amended soils in the first year, but it failed to grow in all the soils in the third year. However, setaria glauca could grow with higher biomass in all the amended soils. The treatment of apatite combined with plants was more effective than lime and charcoal treatments in removing Cu and Cd from the contaminated soils by taking biomass into account. Apatite had the best sustainable effect on alleviating soil acidification. The Cu and Cd concentrations of CaCl₂-extractable and exchangeable fractions decreased with the application of amendments. Moreover, apatite and lime could effectively maintain the bioavailability of Cu and Cd low.

Conclusions

Apatite had a better sustainable effect on the remediation of heavy metal-contaminated soils than lime and charcoal. Although all the amendment treated soils did not reduce soil total concentrations of Cu and Cd, they could effectively reduce the environmental risk of the contaminated soils. The findings could be effectively used for in situ remediation of heavy metal-contaminated soils.

     

协助自然修复微量元素污染酸性土壤研究：8年田间试验

There are many remediation techniques for organic contaminated soils,but relatively few of them are applicable to trace elementcontaminated soils.A field experiment was carried out to investigate assisted natural remediation（ANR） of an acid soil contaminated by As,Cd,Cu,Zn and Pb using one inorganic amendment,sugar beet lime（SL）,and two organic amendments,biosolid compost（BC）and leonardeite（LE）.The experiment was arranged in a completely randomized block design with four treatments in three replicates:1) a non-amended control（NA）;2) SL amended at 30 Mg ha^-1 year^-1;3) BC amended at 30 Mg ha^-1 year^-1 and 4) LE amended at 20 Mg ha^-1 year^-1 plus SL amended at 10 Mg ha^-1 year^-1（LESL）.The amended plots received two doses of each amendment（DO2）:one in October 2002 and another in October 2003.The plots were then divided in half into two subpolts and one subplot received another two doses of the same amendments（DO4） in October 2005 and October 2006.In 2011,the pH values of the amended soils were greater than that of the NA soil,with the SL-amended soil showing the highest pH.Total organic carbon（TOC） was also greater in the amended soil,and greater with DO4 than with DO2.Amendments reduced the concentrations of 0.01 mol L^-1 CaCl₂-extractable Cd,Cu and Zn,especially in the SL-amended soil.Plant cover of colonizing vegetation was enhanced by amendments,but was independent of amendment doses.Changes in soil properties from 2003 to 2011 showed that the first amendment application of DO2 caused a high differentiation between all the amendment treatments and the NA treatment.After the second application of DO2,soil pH and TOC continued increasing slowly.Further two applications of amendments（DO4） caused differences only in the organic treatments.Plant cover increased over time in all the treatments including NA.It could be concluded that the slow and steady natural remediation of this soil could be enhanced by amendment application（ANR）.     

不同改良剂对土壤-叶菜系统Cd迁移累积的调控作用

为筛选适合在中轻度镉污染土壤上有效降低叶菜吸收镉的改良剂及用量,采用镉污染菜地土壤进行盆栽试验,研究不同用量的石灰、泥炭和碱渣对小白菜（Brassica chinensis L.）生物量、镉吸收量,土壤pH及有效态镉含量的影响。结果表明,3种改良剂对小白菜生长均无显著的抑制作用;与不施改良剂的处理相比,石灰、泥炭显著抑制小白菜对镉的吸收,地上部镉含量与石灰和泥炭用量均呈显著负相关关系（R=-0.668、-0.785,P〈0.05）,碱渣对小白菜地上部镉含量的影响不显著,但显著增加根系镉含量;改良剂均显著提高土壤pH,但对DTPA-Cd影响不同,石灰显著降低DTPA-Cd,泥炭、碱渣均有增加DTPA-Cd含量的趋势;泥炭对土壤-小白菜系统Cd迁移的调控效果最佳,其最佳用量为20 g.kg-1土,石灰次之,碱渣不适合。     

我国稻田土壤镉污染现状及安全生产新措施

水稻是我国重要的粮食作物,由于受重金属污染威胁日益增大,其安全生产问题备受关注。通过综述我国稻田土壤及稻米镉污染现状、镉污染土壤改良剂研究进展以及稻米对镉富集的品种间差异,认为在土壤中镉的去除修复技术无法在短时间内实现的前提下,镉排异型水稻品种的筛选与利用是实现其安全生产的一个新的有效措施。在此基础上,配合一些污染土壤改良剂的使用,会进一步增强其安全生产水平。     

Immobilization of Cu and Cd in a contaminated soil: one- and four-year field effects

Purpose

Many amendments have been applied to immobilize heavy metals in soil. However, little information is available on the changes of immobilization efficiencies of heavy metals in contaminated soils over time. This work investigated the immobilization efficiencies of copper (Cu) and cadmium (Cd) in contaminated soils in situ remediated with one-time application of three amendments for 1 year and 4 years.

Materials and methods

Apatite, lime, and charcoal were mixed with the topsoil of each plot with the amounts of 22.3, 4.45, and 66.8 t/ha, respectively. Soil chemical properties and fractions of Cu and Cd were examined after in situ remediation for 1 year and 4 years. Soil sorption and retention capacities and desorption proportions for Cu and Cd were investigated by batch experiments.

Results and discussion

The addition of amendments significantly increased soil pH, but decreased exchange acid and aluminum (Al). The amendments significantly decreased the CaCl₂ extractable Cu and Cd and transformed them from active to inactive fractions. After the application of amendments for 1 year, the maximum sorption capacities ranged from 35.6 to 38.8 mmol/kg for Cu and from 14.4 to 17.0 mmol/kg for Cd, which were markedly higher than those of the application of amendments for 4 years (Cu, 29.6–34.7 mmol/kg; Cd, 10.9–16.4 mmol/kg). Desorption proportions (D) of Cu and Cd using three extractants followed the order of \( {D}_{{\mathrm{NaNO}}_3}<{D}_{{\mathrm{CaCI}}_2}<{D}_{{\mathrm{MgCI}}_2} \) . Moreover, the retention capacities (R) of Cu and Cd both increased and followed the order of R _apatite?>?R _lime?>?R _charcoal, resulting in higher Cu and Cd in the amended soils than the untreated soil.

Conclusions

Apatite, lime, and charcoal increased the soil sorption and retention capacities of Cu and Cd and resulted in higher immobilization efficiencies in the amended soils than the untreated soil. However, the immobilization efficiencies of Cu and Cd decreased with the decrease of sorption capacities after 4 years. It was concluded that apatite had the best effect on the long-term stability of immobilized Cu and Cd and can be applied to immobilize heavy metals in contaminated soils.     

石灰石和海泡石组配对水稻糙米重金属积累的影响

为了研究组配改良剂(石灰石+海泡石,LS)对于重金属Pb、Cd、Cu和Zn复合污染稻田的修复效果,在湘南某矿区附近稻田中进行了组配改良剂的田间试验。结果表明:施用0~1.8 kg m-2的组配改良剂LS使土壤pH和CEC显著增加,使土壤中Pb、Cd、Cu和Zn交换态含量显著降低。土壤Pb、Cd、Cu和Zn交换态含量的降低是pH升高,土壤胶体的CEC增加及土壤吸附能力增强的共同作用。施用组配改良剂LS显著降低了3个水稻品种(黄华占、丰优9号、Ⅱ优93)糙米中Pb、Cd和Cu的累积量,最大降幅分别为55.8%、66.9%、37.4%,而对糙米中Zn的含量没有明显影响。当LS施用量为1.8 kg m-2时,能使丰优9号糙米中Cd含量(0.195 mg kg-1)达到国家食品中污染物限量标准(0.20 mg kg-1)以下。土壤中交换态Pb、Cd和Cu含量的降低是糙米中重金属累积量减少的原因。土壤交换态Pb、Cd和Cu含量的对数值(lnC交换态)与其糙米中含量(lnC糙米)的对数值之间存在显著的线性相关关系。     

铅镉高污染土壤的钝化材料筛选及其修复效果初探

本研究以重金属高污染农田土壤(全Pb含量为1 277 mg/kg,全Cd含量为39.0 mg/kg)为研究对象,通过土培试验和玉米苗期盆栽试验,探讨海泡石、石灰、腐植酸、钙镁磷肥、磷矿粉、生物质炭等常用稳定材料不同剂量及复配组合对高污染土壤重金属的钝化修复效应。土培试验结果表明,石灰对Pb和Cd钝化效果最好,其次是海泡石,但两者表现为较高添加量处理间没有显著差异;而低剂量生物质炭和腐植酸显著增加土壤有效态Pb和Cd含量,高剂量生物质炭具有较好的钝化效果。盆栽试验表明,海泡石与石灰配施钝化效果较好,与对照相比,土壤氯化钙提取态Pb、Cd含量分别降低了97.5%、81.4%;玉米根和地上部Cd含量分别降低48.5%、34.0%,Pb含量分别降低35.6%、29.6%;但海泡石与磷材料配施显著增加玉米根Pb含量,对玉米Cd吸收没有显著影响。以上结果表明,重金属高污染农田土壤添加合适的改良剂,可较大幅度降低土壤重金属有效性和植物重金属吸收性。     

Flooding-enhanced immobilization effect of sepiolite on cadmium in paddy soil

Purpose  

Little is known of the effect of sepiolite on the transformation of Cd in anthropogenically contaminated paddy soil under different moisture conditions; therefore, we studied the effects of sepiolite and flooding on the extractability and fractionation of Cd in paddy soils.     

Efficiency of KOH-modified rice straw-derived biochar for reducing cadmium mobility, bioaccessibility and bioavailability risk index in red soil

Cadmium (Cd) pollution in agricultural soils has exerted a serious threat due to continuous application of pesticides, fertilizers, and wastewater irrigation. The present study aimed to test the efficiency of KOH-modified and non-modified rice straw-derived biochar (KBC and BC, respectively) for reducing Cd solubility and bioavailability in Cd-contaminated soil. Cadmium-contaminated soil was incubated for 60 d with 15 and 30 g kg^-1 BC and KBC. At the end of incubation, Cd mobility was estimated by the European Community Bureau of Reference sequential extraction and toxicity characteristic leaching procedure (TCLP), while bioavailability was determined using 1 mol L^-1 NH₄NO₃ extraction. The bioavailability risk index and bioaccessibility, assessed by a simple bioaccessibility extraction test, of Cd were used to examine the potential effects of Cd on living organisms. The results indicated that application of both KBC and BC significantly increased soil pH, cation exchange capacity, nutrients, and organic carbon. The soluble fraction of Cd was significantly decreased by 30.3% and 27.4%, respectively, with the addition of KBC and BC at 30 g kg^-1 compared to the control (without biochar addition). Similarly, the bioaccessible Cd was significantly decreased by 32.4% and 25.2%, respectively, with the addition of KBC and BC at 30 g kg^-1 compared to the control. In addition, both KBC and BC significantly reduced Cd leaching in the TCLP and NH₄NO₃-extractable Cd in the amended soil compared to the control. The reduction in Cd solubility and bioaccessibility by KBC and BC may be due to significant increases in soil pH and surface complexation. Overall, KBC at an application rate of 30 g kg^-1 demonstrated positive results as soil amendment for Cd immobilization, and reduced bioaccessible Cd in contaminated soil.