四种改良剂对铜和镉复合污染土壤的田间原位修复研究

研究了石灰、磷灰石、蒙脱石和凹凸棒石对冶炼厂周边Cu、Cd污染土壤的原位修复效果。以黑麦草(Lolium perenne L.)作为田间修复植物,采用植物重金属吸收性、土壤重金属化学提取性及土壤溶液重金属浓度变化等作指标来评价修复效果,并研究了黑麦草对Cu、Cd的吸收与土壤、土壤溶液中Cu、Cd含量的相关性。结果表明,石灰高添加剂量(石灰占污染土壤耕作层质量的0.4%)处理黑麦草对重金属的富集效果最好,显著降低了重金属毒性,促进了黑麦草的生长及其对重金属的富集;石灰和磷灰石各添加剂量均显著降低了污染土壤交换态Cu含量;石灰、磷灰石和蒙脱石各添加剂量均显著提高了土壤溶液pH并显著降低了其Cu、Cd浓度。黑麦草地上部、根中Cu浓度与土壤交换态Cu及土壤溶液Cu浓度呈显著或极显著正相关关系。     

磷灰石等改良剂对铜污染土壤的修复效果研究——对铜形态分布、土壤酶活性和微生物数量的影响

通过田间小区试验,研究了磷灰石、石灰、木炭、猪粪、铁粉对Cu污染土壤中Cu形态分布、土壤酶活性和微生物数量的影响。结果表明:改良剂的处理减少了离子交换态Cu的百分含量,增加了碳酸盐、铁锰氧化物、有机结合态Cu的百分含量,但对残留态Cu百分含量影响不大。磷灰石、石灰、木炭显著提高了土壤过氧化氢酶、酸性磷酸酶活性和土壤pH,但对脲酶活性影响较小。改良剂不同程度地增加了土壤细菌和真菌数量,且细菌和真菌数量均与土壤pH呈正相关关系,特别是真菌,与pH的相关系数达0.90。pH是影响Cu化学形态、土壤酶活性和微生物数量的主要因素,磷灰石、石灰和木炭显著提高了土壤pH,降低Cu的活性,增加了土壤酶活性和微生物数量,对Cu污染土壤具有较好的修复效果。     

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。     

纳米羟基磷灰石对重金属污染土壤Cu/Cd形态分布及土壤酶活性影响

通过室内培养实验,研究了纳米羟基磷灰石对重金属污染土壤Cu/Cd形态分布及土壤酶活性的影响。结果表明,施加纳米羟基磷灰石显著提高了土壤pH,其中3%和5%添加剂量处理60 d后使土壤pH分别提高了1.23个和1.35个单位;纳米羟基磷灰石显著减少了毒性较强的离子交换态Cu/Cd的含量,增加了毒性中等的碳酸盐结合态、铁锰氧化物结合态、有机结合态及毒性最低的残留态Cu/Cd含量,使Cu/Cd由植物可利用态向潜在可利用态转变;纳米羟基磷灰石不同程度地提高了土壤过氧化氢酶、脲酶和酸性磷酸酶活性。3种酶活性与Cu/Cd形态分布的相关性表明,过氧化氢酶和酸性磷酸酶对土壤重金属Cu/Cd活性变化比较敏感,可以作为重金属Cu/Cd污染土壤的评价指标。     

生物炭对不同酸化水平稻田土壤性质和重金属Cu、Cd有效性影响

针对南方稻田土壤酸化严重,导致养分流失有毒重金属活化,严重影响稻米质量安全的重大现实问题。以水稻秸秆和谷壳等农业废弃物为原料制备生物炭(分别记为RSC和RHC),研究不同原料生物炭对酸化土壤改良及其对重金属有效性的影响。设置3个生物炭用量(0,20,50 g/kg,分别记为CK、C1、C2),4种土壤酸化水平(pH 4.01,4.25,4.33,4.58,分别记为L1、L2、L3、L4),生物炭与重金属污染土壤共同培养60天后测定土壤pH、全氮、有机质、有效磷、速效钾和有效态Cu、Cd含量。结果表明:RSC对酸化土壤pH的改良效果明显优于RHC,且施炭量越高提高幅度越大,RSC的C2处理使4种酸度水平的土壤pH分别提高了0.68,0.97,1.29,1.71个单位。2种生物炭均能提高土壤的全氮、有效磷、速效钾和有机质含量,其中各施炭处理有机质显著提高,尤以速效钾的增幅最为显著,RSC对4种养分的提高均优于RHC。RHC对土壤有效态Cu含量无显著影响;RSC的C2较C1处理更能降低土壤中有效态Cu含量,使4种酸度水平的土壤分别降低了13.62%,6.57%,4.36%,7.88%。RHC处理的L3、L4土壤中有效态Cd含量显著降低,最大分别降低了13.79%,19.23%。RSC使4种酸度土壤有效态Cd含量最大分别降低了20.00%,25.81%,20.69%,19.23%。相关分析表明,土壤pH与有效态重金属含量呈显著负相关关系。水稻秸秆炭用于改良酸化土壤、降低重金属Cu和Cd有效性的效果更佳,且降低污染土壤中Cd的有效性较Cu好;生物炭对酸化程度越低的土壤pH和有效磷含量的提高以及有效态Cd含量的降低效果较好,而有效态Cu含量的降低效果则在酸化程度越高的土壤中表现更佳;土壤pH是生物炭调控重金属Cu、Cd有效性的主要影响因素。     

石灰及其后效对玉米吸收重金属影响的田间实例研究

通过田间试验方法,研究了在铅锌矿废水污染的土壤上施用石灰1 a后,继续施用石灰和石灰后效处理对后续第1、2季低累积玉米（Zea mays）的产量以及重金属Cd、Pb、Zn和Cu含量的影响,并分析了土壤pH、土壤DTPA提取态重金属含量和土壤重金属全量的变化。结果表明,连续施用石灰和石灰后效均显著提高玉米产量,其中连续施用石灰处理效果最佳,第1季籽粒产量是对照（无石灰）的6倍,第2季是对照的3.8倍。与对照相比,连续施用石灰处理显著降低了2季玉米籽粒Cd、Pb、Zn和Cu含量,石灰后效只能降低第2季玉米茎叶Cd、Pb和Cu含量,而籽粒Cd、Pb含量与对照相比略有升高,说明石灰后效能维持一年半左右。对照处理土壤Cd和Zn全量显著低于石灰处理,可能是土壤中Cd和Zn随着雨水的淋洗向下层迁移造成的。施用石灰可防止Cd和Zn对地下水的污染。     

长期肥料试验对土壤和水稻微量元素及重金属含量的影响

长期肥料试验会影响土壤中微量元素和重金属状况以及作物对微量元素和重金属的吸收。本文研究了长期的不同施肥处理对土壤、糙米中微量元素Cu、Zn、Fe、Mn和重金属Pb、Cd含量的影响,结果表明:经17a连续施用猪粪及秸秆还田显著增加了土壤Cu、Zn和Cd全量,而土壤Fe、Mn和Pb全量在不同施肥处理间没有显著差异;施肥增加了土壤有效态Cu、Zn和Fe含量,其中施用猪粪及秸秆还田的3个处理显著增加了土壤有效态Cu、Zn和Cd含量,而土壤有效态Pb含量在不同施肥处理间没有显著差异。不同处理糙米Cu、Zn、Fe、Mn和Pb含量变化较小或没有显著性差异,而在3个施猪粪和秸秆还田处理中,糙米Cd含量均超过国家食品卫生标准(>0.2 mg kg-1)。水稻地上部吸收积累Cu、Zn、Fe、Mn、Pb和Cd总量与其地上部生物量呈正相关,土壤Cu、Zn、Cd有效态与全量含量呈极显著相关关系,而糙米中的镉含量与土壤镉含量有较好的相关关系。长期施用畜粪导致土壤Cd污染问题应引起高度重视。     

连续四年施用规模化猪场猪粪温室土壤重金属积累研究

分别采集连续施用0～4年猪粪的蔬菜温室土壤和蔬菜果实样品，测定土壤和果实中Cu、Zn、Pb、Mn、Cr、Cd、Ni和As全量以及土壤中Cu、Zn、Pb、Mn、Cd和As有效态含量，对测定数据进行了Fisher小样本非参数随机化显著水平检验，研究连续4年施用规模化猪场猪粪的温室土壤重金属积累、重金属有效态含量变化及对蔬菜可食部分的影响。结果表明，连续4年施用猪粪，主要导致土壤中Cu和Zn的积累，As有一定积累，Pb、Cd、Ni和Cr短期积累效应不明显，Mn积累不明显，长期大量施用猪粪，Pb、Cd、Ni和Cr有积累的风险；土壤pH值降低；Cu、Zn有效态与全量呈显著正相关(p<0.05)，与pH值呈极显著负相关(p<0.01)；Pb、Cd和Mn有效态与pH值呈显著负相关(p<0.05)；Cu、Zn、Pb、Cd和Mn有效态含量增加；有效态As与全As含量和pH值相关性不明显，但连年施用猪粪As有效态含量增加；连续4年施用规模化猪场猪粪的温室生产的部分番茄和黄瓜As含量超标。若连续以150 m³/(hm²·a)的猪粪施用量于该研究区蔬菜温室，土壤中全Cu和全Zn含量分别经过10年和15年可能超过国家农田土壤二级标准。该研究可为降低温室土壤重金属污染风险提供依据。     

巨大芽孢杆菌LY02对黑麦草修复重金属污染土壤的影响

采用盆栽试验方法,研究了接种巨大芽孢杆菌LY02对黑麦草修复Cd、Cu污染土壤以及二者复合污染土壤效果的影响。结果表明:在Cd、Cu污染土壤及复合污染土壤中接种巨大芽孢杆菌LY02,可显著提高黑麦草地上部生物量,增幅达65.0%~108.3%;促进了黑麦草在3种污染土壤中对重金属的吸收,其中对Cd污染土壤中黑麦草吸收Cd的影响最为显著,地上部Cd吸收量较对照组增加了45.8%(P0.05);3种污染土壤中黑麦草根际土壤有效磷含量显著升高,较对照组分别增加了18.2%,26.7%,16.2%;黑麦草根际土壤中有效态Fe含量显著提高,Cu单一污染土壤中增幅最大,达到152.5%;3种污染土壤中有效态重金属含量升高,在Cu污染土壤中,有效态Cu增幅达到49.7%(P0.05)。综上所述,巨大芽孢杆菌LY02通过增加污染土壤中生物可利用态P和Fe,促进黑麦草生长;通过提高有效态Cd和Cu的含量,增加黑麦草对其吸收,从而提高了黑麦草对Cu、Cd污染土壤的修复效率。     

磷灰石和石灰稳定化修复对污染土壤铜和镉垂直迁移的影响

大量改良材料被用于重金属污染土壤的稳定化修复,但是不同用量的改良材料长期田间修复后重金属总量和有效态在不同土层的垂直分布特征鲜有研究涉及。本研究采集不同剂量的磷灰石和石灰稳定化修复的0~13、13~30和30~50 cm土层污染土壤,考察铜和镉总量及有效态含量在不同土层的分布特征。结果表明:随着磷灰石和石灰用量的增加,显著降低了0~13 cm土层土壤交换性酸和交换性铝,增加了土壤全钙的含量,且磷灰石处理提高了土壤全磷和速效磷含量。0~13 cm土层土壤pH、总铜和总镉含量均随着磷灰石和石灰用量的增加而逐渐增加,但是降低了13~30和30~50 cm土层土壤总铜和总镉含量。3个土层中铜和镉有效态含量均随着磷灰石和石灰用量的增加而显著降低,其中23.2 g/kg磷灰石处理和4 g/kg石灰处理土壤有效态铜含量降低85.1%和92.0%,有效态镉降低18.8%和23.5%。相关性分析表明,土壤pH和铜镉总量是影响铜镉有效性的主要因素。可见,磷灰石和石灰的应用使铜和镉较好地固定在土壤表层,减少铜和镉向下层土壤的淋溶,降低了铜和镉的有效性。     

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.

     

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.     

改良剂对重金属污染红壤的修复效果及评价

采用盆栽试验,研究了施用改良剂—石灰、有机肥、海泡石对红壤上小油菜生物产量、镉锌吸收量、pH、吸收系数的影响。结果表明,施用改良剂,连续种植3季小油菜 (Brassia campestris L.) 的生物产量都显著提高,石灰、有机肥和海泡石配施的产量是对照的15倍。改良剂能不同程度提高红壤的pH,以石灰的效果最好,土壤pH平均升高了2个单位;而且小油菜对镉锌的吸收也较低。小油菜对镉的吸收系数大于对锌的吸收系数,说明镉容易在土壤-植物体系中迁移,施用改良剂后吸收系数降低。施石灰的小油菜中锌含量达到食品卫生标准。改良剂对提高土壤pH的后效逐渐减弱,对抑制小油菜吸收锌的后效不如抑制镉的后效好。     

土壤改良剂与叶面喷硒联合阻控对小白菜吸收镉的影响

为探究改良剂与叶面喷硒（Se）联合阻控减轻农产品受镉（Cd）毒害的效果,采用土壤培养及盆栽试验的方法,筛选不同用量的牛粪（7.5、15 g kg?1）与石灰（1、2、3、4、5 g kg?1）配施钝化土壤Cd有效性的最优处理,并探讨改良剂与叶面喷Se（1、2、4、8 mg L?1）联合阻控对不同程度Cd污染土壤（0.5、3、6 mg kg?1）中小白菜吸收Cd的影响。结果表明:（1）与未施改良剂处理相比,7.5 g kg?1牛粪与 5 g kg?1石灰配施对土壤Cd的钝化效果最显著,土壤有效Cd含量降低了37.9%。（2）与单施改良剂相比,施用改良剂与叶面喷Se显著抑制了小白菜对Cd的吸收,其中在中轻度污染土壤中（0.5 和 3 mg kg?1 Cd）叶面喷施 4 mg L?1 Se使小白菜Cd含量分别降低了 12.9% 和 78.7%,丙二醛含量分别降低了29.9% 和 60.6%;在重度污染土壤中（6 mg kg?1 Cd）叶面喷施 8 mg L?1 Se使小白菜Cd含量降低了 81.4%,丙二醛含量降低了71.9%;叶面喷Se使小白菜的抗氧化酶活性和谷胱甘肽含量均有不同程度的增加。     

水分和有机物料对镉污染土壤的改良效应

通过室内培养和盆栽试验相结合的方式,系统研究了3种土壤水分含量条件下,添加不同有机物料对镉(Cd)污染土壤的改良效应。研究结果表明:淹水、田间持水量和65%相对含水量条件下添加有机物料均有利于污染土壤中可交换态Cd含量的降低,铁锰氧化物及有机结合态Cd含量的增加。随土壤中水分含量的增加,影响程度增加,即淹水>田间持水量>65%相对含水量。3种水分条件下,添加蚯蚓粪处理Cd活性降低明显,其次为猪粪处理,草炭处理相对较差。淹水条件下,油菜体内Cd的含量最低,田间持水量和65%相对含水量条件下油菜部分发育指标差异不显著。添加不同有机物料各处理促进油菜生长的顺序大致为:蚯蚓粪>草炭>CK>猪粪。     

Influence of Organic Manure and Lime on Cadmium Mobility in Soil and Uptake by Spinach (Spinacia oleracea L.)

Spinach grown in cadmium (Cd)-contaminated soils accumulates Cd compounds in toxic concentration contaminating the food chain leading to the chronic toxic effects on human and animal health. A study was conducted in a Cd-contaminated soil to examine the ameliorative effect of lime and organic manure on the mobility of Cd and its uptake in spinach. Application of lime or organic manure or both decreased the Cd concentration in soil and shoots and increased chlorophyll content of leaves. As compared to the control treatment, combined application of lime and organic manure decreased the level of Cd in soil by 54.7%, in spinach shoot by 61.3%, and the transfer factor of Cd by 35.0% and increased in leaf chlorophyll content by 29.4%. Combined application of lime and organic manure emerged as a viable option in reducing the mobility of Cd in contaminated soil for growing spinach.