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。     

砂姜黑土中重金属Cu、Cd、Zn形态分布与土壤酶活性研究

采用小麦农田取样,对土壤中的重金属运用连续提取方法,研究了皖北砂姜黑土中Cu、Cd、Zn的化学形态特征及其与四种土壤酶(过氧化氢酶、脲酶、蔗糖酶、中性磷酸酶)活性间的关系。结果表明:在砂姜黑土中,残留态Cu、Cd、Zn在总量中所占比例很高,交换态、有机态、碳酸盐结合态含量明显低于残留态。在三种元素中,Zn的化学形态变化趋势最为一致,表现为残留态>碳酸盐结合态>铁锰结合态>有机态>交换态;砂姜黑土中交换态Cu、Cd、Zn对脲酶活性有显著抑制作用,有机态Cu、Cd、Zn对过氧化氢酶表现为一定程度的促进作用。因此,在砂姜黑土壤中,把交换态Cu、Cd、Zn和脲酶以及中性磷酸酶的活性共同作为评价土壤Cu、Cd、Zn污染程度的主要生化指标是可行的。     

磷灰石联合黑麦修复铜污染土壤研究

通过田间试验研究了不同剂量磷灰石(10、20、30、50 g/kg,编号分别为LH1、LH2、LH3和LH4)与黑麦联合作用对Cu污染土壤的修复效果,重点考察了磷灰石对黑麦生物量及Cu吸收、土壤pH及Cu形态转化、土壤酶活性、植物生理指标等的影响。试验结果表明,磷灰石显著提高了土壤pH、黑麦生物量及其Cu吸收量,显著降低了黑麦地上部分及根系Cu含量,其中LH3处理黑麦Cu吸收量最高,达到对照处理的33.38倍;与对照相比,LH1、LH2、LH3和LH4处理土壤可交换态Cu含量显著降低了37.0%、58.9%、89.0%和83.3%,碳酸盐结合态Cu含量显著增加了46.6%、63.1%、78.0%和93.3%;与对照相比,LH2、LH3和LH4处理显著提高了土壤磷酸酶、过氧化氢酶和脲酶活性,显著提高了黑麦SOD和POD酶活性,显著降低了黑麦MDA含量。综合而言,施用30 g/kg的磷灰石并种植黑麦能够很好地修复Cu污染土壤。     

不同改良剂对矿区土壤重金属有效性及土壤酶活性的影响

通过分析不同改良剂对矿区污染土壤理化性状、有效态重金属含量及土壤酶活性的影响,比较了氨基酸生态肥、饼肥、鸡粪肥、钙镁磷肥对矿区土壤的改良效果。结果表明:各处理均能不同程度的改善土壤理化性状,钙镁磷肥对土壤pH提高最为明显,氨基酸生态肥、饼肥与鸡粪肥能显著提高土壤有机质;钙镁磷肥对有效态重金属含量的降低最为显著,其次为氨基酸生态肥、饼肥与鸡粪肥;氨基酸生态肥、饼肥与鸡粪肥处理明显提高土壤酶活性;饼肥处理的土壤酶活性最高;饼肥处理150d后,土壤脲酶活性较对照提高17.67倍,土壤酸性磷酸酶较对照提高36.99倍,土壤蔗糖酶较对照提高17.59倍,土壤脱氢酶较对照提高3.59倍。统计分析表明,土壤pH值与土壤有效Cd、Cu含量呈显著负相关,土壤脲酶活性与有效Cd、Cu呈显著负相关,酸性磷酸酶活性与有效Cu含量呈显著负相关。     

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。     

磷灰石等改良剂对重金属铜镉污染土壤的田间修复研究

通过田间小区试验,研究了磷灰石、石灰、木炭、猪粪、铁粉5种改良剂对Cu、Cd复合污染土壤的改良效果。结果表明,石灰、磷灰石、木炭、猪粪降低了土壤溶液中重金属Cu、Cd的含量,提高了土壤溶液的pH,但改良效果随着时间的推移不断降低。磷灰石、石灰、木炭的加入显著降低了有效态Cu含量,但对有效态Cd含量影响较小。与猪粪相比,磷灰石、石灰、木炭显著增加了黑麦草生物量,提高了对重金属Cu、Cd的吸收能力,对该污染土壤的修复具有实践应用价值。     

基于TCLP法研究纳米羟基磷灰石对污染土壤重金属的固定

通过室内培养试验,研究了纳米羟基磷灰石对土壤重金属的固定和修复,并通过毒性溶出试验TCLP（Toxicity Characteristic Leaching Procedure）对同定效果进行了评价。结果表明,纳米羟基磷灰石的施入显著降低了土壤中Cu和Zn的生物有效性,而且土壤中Cu和Zn有效态的含量与纳米羟基磷灰石的施用量呈显著负相关。其主要原因为纳米羟基磷灰石的水解释放大量OH^-离子,导致土壤pH增加;此外纳米羟基磷灰石吸附固定重金属进而降低了土壤中重金属的有效性。包施不如同等材料用量混施的钝化效果好,且所用时间较长,但包施具有将所施材料和被吸附重金属移出土壤体系的优点。     

铬铜复合污染下铬形态分布及与土壤酶活性的关系

采用土培盆栽实验和室内分析相结合的方法,研究了Cr单一和Cu-Cr复合污染条件下,外源施加的Cr在土壤中的形态变化及其对土壤酶活性的影响。结果表明：随外源Cr浓度的增加,土壤交换态Cr含量增多,残渣态占总量的百分比减少,铁锰氧化物结合态与有机结合态变化不大（碳酸盐结合态未检出）。Cu-Cr复合污染条件下,≤400mg·kg-1Cu能促进Cr从有机结合态向交换态及铁锰氧化物结合态转化（P〈0.05）,而高浓度Cu（800mg·kg-1）却抑制了这种转化的发生。与对照（CK）相比,重金属Cu、Cr单一及复合污染均对土壤脲酶、碱性磷酸酶和过氧化氢酶活性产生一定的抑制作用,且酶活性抑制率随外源金属浓度的增加而增大;3种供试酶相比较,Cr、Cu对土壤脲酶和碱性磷酸酶活性影响较大,对除C（r5mg·kg-1）处理的过氧化氢酶活性影响较小;低浓度C（r5mg·kg-1）对土壤过氧化氢酶活性有一定激活作用。土壤脲酶活性受土壤交换态Cr含量的影响较大;碱性磷酸酶活性与铁锰氧化物结合态Cr含量有关;铁锰氧化物结合态和有机物结合态Cr对土壤过氧化氢酶活性产生一定的影响。残渣态Cr含量与3种供试的土壤酶活性间无显著相关。     

喀斯特林地土壤重金属形态特征及其评价

通过野外调查与室内分析,对喀斯特林地土壤重金属全量及形态构成进行了调查,对土壤重金属污染及其生物有效性进行了评价,并探讨分析了土壤重金属与土壤pH值的相关性。结果表明:中性土壤As,Cd,Cu,Ni,Pb,Zn及Cr全量均大于酸性土壤的全量;As以酸溶态为主,Cd,Cu,Ni,Pb,Zn及Cr以残渣态为主,残渣态土壤重金属比例为中性高于酸性土壤;酸性和中性土壤重金属Pb全量、中性土壤的As和Cu全量均高于贵州土壤背景值;中性和酸性土壤重金属As,Cd和Ni全量及酸性土壤重金属Cu全量超过土壤环境质量二级标准值;酸性土壤为轻度污染,中性土壤为中度污染;重金属生物有效性表现为AsCdCrNiPbZnCu,酸性土壤As生物有效性指数最高,与中性土壤相比,酸性土壤重金属生物有效性高;Cu全量、可氧化态Pb、残渣态Cu与pH值呈极显著正相关,酸溶态Zn与pH值呈极显著负相关,酸溶态Cr与pH值呈显著负相关,残渣态As与pH值呈显著正相关。喀斯特林地土壤主要受到As,Cd,Cu,Ni这4种重金属的影响,除As外,其余3种元素属于"高背境,低活性"状态。     

羟基磷灰石–植物联合修复对Cu/Cd污染植物根际 土壤微生物群落的影响

针对江西贵溪Cu、Cd重金属污染土壤,通过田间试验,比较无机生物材料羟基磷灰石及3种植物(海州香薷、巨菌草、伴矿景天)与羟基磷灰石联合修复对土壤总Cu、Cd的吸收及对活性Cu、Cd的钝化吸收能力差异。采用磷脂脂肪酸(PLFA)分析法,比较不同修复模式对土壤微生物群落结构的影响,以评估土壤微生态环境对不同修复措施的响应。研究结果表明:羟基磷灰石的施加可显著提高土壤pH,并有效钝化土壤活性Cu、Cd含量,但对土壤总Cu、Cd的含量影响较小。植物与羟基磷灰石的联合修复在显著降低土壤活性Cu、Cd(P0.05)的同时,减少了植物根际土壤总Cu、Cd的含量(P0.05)。不同修复措施对土壤微生物群落组成影响差异明显。单独施加羟基磷灰石与土壤真菌群落呈显著正相关,使土壤真菌生物量提高,从而引起真菌/细菌(F/B)的升高。植物与羟基磷灰石的联合修复可有效缓解土壤真菌化的趋势,其中巨菌草与羟基磷灰石的联合修复可有效提高土壤革兰氏阳性、革兰氏阴性细菌生物量及多样性,降低F/B值,从而降低土壤真菌病害的风险。不同植物根系活性代谢引起有机质的积累促进植物与羟基磷灰石处理中根际有机碳含量显著提高。聚类增强树(Aggregated boosted tree,ABT)分析结果表明:不同修复模式是影响土壤微生物群落的重要因素,其次土壤pH和Cu的含量及活性也是改变重金属污染区域微生物群落的因子。该研究从微生物群落结构角度解释了植物与羟基磷灰石联合修复对土壤微生态体系的作用,为开展Cu、Cd等重金属污染地植物与无机生物材料的联合修复方式的筛选及实施提供可靠的理论依据。     

Cd Pb污染土壤中蛋白酶酸性磷酸酶脱氢酶活性的变化

通过现场采样及室内分析方法,研究了Cd、Pb严重污染的土壤中蛋白酶、酸性磷酸酶和脱氢酶活性的变化及其与土壤Cd、Cu、Pb、Zn含量和土壤基本性质之间的关系。通径分析表明,影响蛋白酶活性主要直接因素为土壤有效Cd、土壤有效Zn、砂粒和黏粒,其中土壤有效Zn刺激了酶活性而土壤有效Cd抑制了酶活性;影响酸性磷酸酶活性主要直接因素为碱解氮、速效磷、pH值,土壤有效Cu、土壤有效Cd、土壤有效Pb、土壤有效Zn对酸性磷酸酶的直接影响较小;影响脱氢酶活性主要直接因素为土壤有效Cd、土壤有效Zn、土壤速效钾,其中土壤有效Cd抑制了酶活性而土壤有效Zn刺激了酶活性。总体而言,4种重金属有效态对酶活性毒性大小依次为：Cd〉Cu〉Pb〉Zn。综合简单相关分析结果可知,总体上Cu、Cd、Pb、Zn复合污染刺激了蛋白酶活性,抑制了脱氢酶活性,对酸性磷酸酶活性影响不大,脱氢酶可作为上述土壤重金属复合污染的指标。3种土壤酶活性变化是重金属与土壤理化性质综合作用的结果。     

Additive effects of copper and zinc on cadmium toxicity on phosphatase activities and ATP content of soil as estimated by the ecological dose (ED50)

The ecological dose (ED₅₀) of Cd on alkaline and acid phosphatase activity and the ATP content of three contrasting forest soils was measured with or without Cu and Zn to assess the additive toxic effects of these two metals. Soils polluted with Cu and/or Zn were treated with increasing Cd concentrations to give the following metal combinations: Cd, Cd+Cu, Cd+Zn and Cd+Cu+Zn. Alkaline and acid phosphatase activities and ATP content of the three soils were analysed 4 h, 7 and 28 days after the metal additions. The ED₅₀ values were obtained by interpolating the enzyme activities or ATP data with a kinetic model and the goodness of fit was satisfactory.Generally, the ED₅₀ values of both acid and alkaline phosphatase activities for Cd were lower (higher toxicity) with than without Cu and Zn and the effect of Cu and Zn was particularly adverse when these two metals were both added to soils. The alkaline phosphatase was more sensitive in the acid and neutral soil whereas the acid phosphatase was more sensitive in the alkaline soil. Both phosphatase activities and the ATP content were more sensitive in the sandy than in the finer textured soils. The ATP content was less sensitive to the additive effects. Increasing toxicity was observed during the incubation.Analysis of 1 M NH₄NO₃-extractable Cd, Cu and Zn revealed that Cd competed with Zn for the adsorption sites but not with Cu. However, the lower ED₅₀ values for Cd of the two phosphatase activities and of the ATP content in the presence of heavy metal combinations could be not explained by the heavy metal solubility data. It is concluded that the ED₅₀ may be a sensitive tool for assessing additve toxic effects to soil biochemical parameters.     

大棚菜田种植年限对土壤重金属含量及酶活性的影响

为了探讨大棚种植年限对大棚菜田土壤重金属累积、土壤酶活性的影响以及二者的关系,采集不同种植年限(0、5、10、15、20、25、30 a)大棚菜田土壤样品共140份,测定土壤样品中重金属的含量以及土壤酶活性。结果表明:大棚菜田土壤中重金属Zn、Pb、Cu的含量和种植年限极显著相关;重金属Cd、Ni、Mn的含量和种植年限显著相关;重金属Cr的含量和种植年限不相关。大棚菜田土壤中过氧化物酶、多酚氧化酶、淀粉酶活性和种植年限极显著相关,磷酸酶、蔗糖酶活性和种植年限显著相关,过氧化氢酶、脲酶、蛋白酶活性和种植年限相关性不显著。随着种植年限的延长重金属Zn、Cu含量对多酚氧化酶、过氧化物酶活性有抑制作用,其敏感性顺序为:过氧化物酶对Zn敏感性>多酚氧化酶对Zn敏感性>过氧化物酶对Cu敏感性>多酚氧化酶对Cu敏感性。土壤中过氧化物酶、多酚氧化酶可以作为重金属Zn污染的指示酶,过氧化物酶可以作为重金属Cu污染的指示酶。该文为设施污染土壤环境质量评价提供依据。     

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。     

Fractions of Cu, Cd, and enzyme activities in a contaminated soil as affected by applications of micro- and nanohydroxyapatite

Purpose

With the rapid development of nanotechnology, hydroxyapatite-based nanoparticles have been applied in wastewater and soil remediation. However, limited studies have been conducted on the remediation of heavy metal-contaminated soils by microhydroxyapatite (MHA) and nanohydroxyapatite (NHA). Thus, we investigated the effects of MHA and NHA on soil pH values and fractions of copper (Cu) and cadmium (Cd). The changes of soil enzymes with application of MHA and NHA were also evaluated.

Materials and methods

Pots contained 200 g of the soil with MHA and NHA ranging from 1 % to 5 % incubated for 60 days under greenhouse condition, and maintained at 60 % of soil water holding capacity by adding deionized water. Soil pH, catalase, urease, and acid phosphatase were analyzed at incubation times of 7, 14, 30, and 60 days by chemical assays. The fractions of Cu and Cd were analyzed after 60 days by a sequential extraction procedure.

Results and discussion

Application of MHA and NHA significantly increased soil pH values. Especially, we found for the first time that soil pH values with 3 % (pH?>?7.90) and 5 % (pH?>?8.83) application rates of MHA were larger than that of MHA itself (pH?=?7.71). MHA was more effective than NHA in immobilizing Cu and Cd by significantly decreasing exchangeable fractions of Cu and Cd and transforming them from active to inactive fractions. Soil catalase and urease significantly increased, but acid phosphatase apparently decreased with increasing application rates of MHA. However, three enzymes activities changed slightly for NHA treatments.

Conclusions

MHA was more effective than NHA in immobilizing Cu and Cd. MHA had a more positive effect on soil catalase and urease activities than NHA. Furthermore, Pearson’s correlation coefficients showed that soil pH value was a key factor to influence the bioavailability of Cu and Cd and the activity of soil enzymes. The results of this study provided an efficient method for the remediation of heavy metal-contaminated soils.     

不同有机肥中Cu、 Zn在农田土壤中的有效性与形态归趋

【目的】畜禽粪便有机肥的施用是造成我国农田土壤重金属污染的重要原因之一。本文选用两种典型规模化养殖场畜禽粪便有机肥,研究其在石灰性土壤和酸性土壤上施用1年后Cu、 Zn的有效性和形态归趋,为客观评价畜禽粪便有机肥中重金属进入土壤后的环境行为和生态风险提供理论依据。【方法】采用温室土壤培养试验,在石灰性土壤和酸性土壤上分别设对照(CK)、 施2%鸡粪(CM2%)、 施5%鸡粪(CM5%)、 施与CM2%、 CM5%含等量Cu、 Zn的重金属无机盐溶液(CS2%、 CS5%)、 施2%猪粪(PM2%)、 施5%猪粪(PM5%)、 施与PM2%、 PM5%含等量Cu、 Zn的重金属无机盐溶液(PS2%、 PS5%)9个处理,每个处理设3次重复,在温室条件下培养1年。测定土壤pH值, EDTA提取有效态Cu、 Zn以及采用改进Tessier连续提取法提取的各形态Cu、 Zn的含量,分析鸡粪、 猪粪及等量无机盐溶液中Cu、 Zn进入土壤后的有效性和形态归趋。【结果】施用鸡粪和猪粪1年后,石灰性土壤的pH值降低,酸性土壤的pH值升高,施用5%猪粪时石灰性土壤pH值降低了0.23个单位,酸性土壤pH值升高了0.87个单位。施入鸡粪、 猪粪1年后,石灰性土壤中有效态Zn和酸性土壤中有效态Cu、 Zn含量显著增加,施用5%猪粪时酸性土壤中有效态Cu含量增加了1.95倍,施用5%鸡粪时2种土壤中有效态Cu的含量均显著低于等量无机盐。施用鸡粪和等量无机盐后,2种土壤中交换态和有机结合态Cu的含量显著增加,交换态、 碳酸盐结合态、 有机结合态和铁锰氧化物结合态Zn的含量显著增加; 施用猪粪和等量无机盐后,2种土壤中交换态、 铁锰氧化物结合态和有机结合态Cu的含量显著增加,碳酸盐结合态和铁锰氧化物结合态Zn的含量显著增加。【结论】施用鸡粪、 猪粪提高了石灰性土壤中Zn和酸性土壤中Cu、 Zn的有效性,高用量条件下鸡粪中Cu的有效性低于等量无机盐。1年后, 通过畜禽粪便有机肥带入2种土壤中的Cu 主要以交换态和有机结合态的形式存在,Zn则主要以碳酸盐结合态、 铁锰氧化物结合态和有机结合态的形式存在。2种土壤上有机肥带入的Cu、 Zn转化为铁锰氧化物结合态的比例低于等量无机盐,2种有机肥带入2种土壤中的Cu转化为交换态和有机结合态的比例高于等量无机盐。鸡粪带入的Zn转化为交换态的比例在酸性土壤中低于等量无机盐,但在石灰性土壤中则高于等量无机盐。     

Microbiological rates and enzyme activities as indicators of functionality in soils affected by the Aznalcóllar toxic spill

This study focused on the potential of using soil enzyme activities and general microbiological rates (respiration, N-mineralisation, nitrification) to evaluate the quality of soils affected by a pyrite mud spill which contained high concentrations of heavy metals. The quality of soils after restoration was estimated by comparing enzyme activities and general microbiological rates in three different types of experimental field plots: (i) non-polluted, (ii) polluted but restored, and (iii) polluted but un-restored soils. Non-polluted soils showed the highest levels of enzyme activity. Significant differences were detected for acid phosphatase, β-glucosidase and urease activities between all types of plots. However, arylsulfatase and alkaline phosphatase activities showed no significant differences between the restored plots and polluted but un-restored plots. Geometric mean statistics were used as an index of soil quality in terms of overall: (i) bioavailable heavy metal concentrations, (ii) assayed enzyme activities, and (iii) general microbiological rates, in order to compare plots differing in the degree of pyritic mud pollution. The results indicate that it is important to consider these three criteria in to estimate the soil quality of heavy-metal contaminated soils. Typically, enzyme activities were negatively correlated with bioavailable Cd, Cu and Zn concentrations, but positively with soil pH values. In contrast, pH values were negatively correlated with bioavailable concentrations of Cd, Cu and Zn. It is unclear if the generalised lower enzyme activities found in restored soils, compared to non-polluted soils, is promoted by pH or bioavailable heavy metals concentrations, or a combination of both.