Cd、Pb复合污染下柠檬酸对龙葵修复效率及抗氧化酶的影响

植物修复土壤重金属被普遍认为是清洁、经济的生物修复方法。为了提高生物修复土壤重金属污染的效率,在室内盆栽实验中添加柠檬酸作为螯合剂促进龙葵对重金属的吸收,并研究其生理活性的变化。结果表明:当添加柠檬酸浓度为10 nmol/kg时,龙葵生物量显著提高(P<0.05),各部分生物量表现为:茎>叶>根;随着柠檬酸浓度的增加,龙葵对重金属Cd的吸收量显著(P<0.05)增加,在10 nmol时总吸收量最大,为229.85μg/g DW;龙葵对Cd、Pb的富集系数均在柠檬酸浓度为5 nmol/kg时达到最大;Pb吸收量随柠檬酸浓度增加表现出先增大后减小的趋势;添加柠檬酸促进了龙葵对Cd的吸收,增强了抗氧化酶活性,而对Pb的吸收效果不明显。     

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%。     

铜、镉对水螅的急性和联合毒性作用

试验研究重金属铜(Cu2 )、镉(Cd2 )对水螅的急性毒性和联合毒性作用,探索水螅(Hydra sp.)对Cu2 、Cd2 以及两者混合的毒性效应,为水产动物病害的防治中合理使用消毒、杀虫剂以及水体污染评价提供一些参考信息.结果表明,Cu2 对水螅的24 h半致死浓度(LC50)、48 hLC50、72 hLC50、96 hLC50分别为0.072、0.054、0.042、0.037 mg/L;Cd2 对水螅的24 hLC50、48hLC50、72 hLC50、96 hLC50分别为0.001 70、0.000 63、0.000 36、0.000 36 mg/L;Cu2 、Cd2 对水螅的安全浓度分别为3.7×10-4、3.6×10-6mg/L.水螅对两种重金属的毒性反应既快速又敏感,其中Cu2 对水螅的毒性较Cd2 快,但Cd2 的毒性比Cu2 的强.等毒性配比的两种重金属混合液对水螅的毒性大于单一毒性,为协同作用.两种重金属对水螅的LC50随试验时间的延长而减小,它们对水螅的安全浓度远低于渔业水质标准.     

乙二胺二琥珀酸和柠檬酸对黑土中外源重金属的活化效应

通过解吸实验和小麦盆栽实验,研究了生物可降解有机配体乙二胺二琥珀酸(EDDS)、柠檬酸(CIT)对黑土中外源Cu、Cd、Zn和Pb的活化效应.不同浓度EDDS﹑CIT对黑土中外源重金属解吸实验表明,EDDS对黑土中外源Cu、Cd、Zn和Pb的解吸远高于CIT.重金属/EDDS摩尔比为1∶1时,4种重金属的解吸率在50.8%～69.2%.小麦盆栽实验表明,EDDS为5 mmol/kg时,对小麦幼苗茎叶和根系中重金属含量影响较大,明显导致小麦幼苗茎叶和根系中Cd、Cu、Pb和Zn的富集量增加.EDDS处理组Cd、Cu、Pb和Zn的茎叶富集系数远高于对照组和CIT处理组.随时间的增加,EDDS处理组和CIT处理组重金属的根系富集量均增加,但对照组和CIT处理组大部分重金属14 d茎叶富集量略低于7 d茎叶富集量.因此,EDDS对黑土中外源重金属有较强的解吸和活化能力,可以较大程度地强化小麦幼苗根系对黑土中外源Cd、Cu、Pb和Zn的吸收并诱导这些重金属由根系向茎叶迁移.     

铜、镉复合污染红壤对黑麦草生长和土壤酶活性的影响

采用石灰石调节红壤酸性后,利用对铜、镉具有一定耐性的高产牧草黑麦草修复铜、镉复合污染土壤。分析黑麦草的生长、生理生化指标以及土壤中酶活性的变化,探索在修复铜、镉复合污染红壤的同时又满足饲料作物安全种植的土地利用方式。结果表明,对于弱酸性红壤（pH 6.0左右）,土壤铜全量较低时（〈50 mg/kg）,黑麦草的生物量、叶...     

土壤铜形态和生物有效性对施用生物质炭的响应

采用改进的Tessier方法对土壤Cu形态进行分级,研究了添加生物质炭对土壤重金属Cu形态、生物有效性和小麦生长及生理指标的影响。结果表明,石灰性土壤中Cu主要以碳酸盐结合态、氧化态和残渣态形式存在,三者占土壤Cu的90%以上。添加生物质炭后,土壤中的碳酸盐结合态铜、氧化态铜含量有所减少,但不显著;有机物结合态铜含量增加了131.25%,达到极显著水平,其中主要增加了紧有机结合态。添加生物质炭在培养一定时间后(30 d后)土壤有效态铜含量降低,120天时最大降低幅度达50.66%,添加生物质炭提高了冬小麦的根系重、茎秆干重、籽粒干重和灌浆期旗叶叶绿素含量,降低了根系、茎秆和籽粒的含铜量以及超氧化物歧化酶(SOD)活性,并随着生物质炭施用量的增加有显著性差异。综合看来,生物质炭对土壤铜污染具有钝化作用。     

草炭对Cd~(2+)的吸附及其用于Cd污染土壤修复的实验研究

通过室内模拟实验研究了草炭对Cd2+的典型吸附特征,以及添加草炭对Cd污染土壤中其浸出毒性和存在形态的影响。结果表明,溶液pH为3~6时,草炭对Cd2+的吸附量随着pH升高而增加,pH为6~8时草炭对Cd2+的吸附量趋于平稳;当溶液体系Cd2+初始质量浓度不超过800mg/L时,草炭对Cd2+的吸附未达到平衡,其吸附率随Cd2+初始浓度的增大而由98.60%降低至88.53%;草炭对Cd2+的等温吸附行为可用Langmuir、Freundlich方程拟合,r均达到极显著水平;添加草炭能降低轻污染(总Cd为3.0mg/kg)土样中Cd2+浸出量,Cd2+钝化率随草炭添加量增加而增加;相对较低(1%~2%,质量分数,下同)的草炭添加量对重污染(总Cd为6.0mg/kg)土样中的Cd2+表现出活化效果,导致Cd2+浸出量增加;但较高(4%)的草炭添加量下,重污染土样中Cd2+的钝化率要明显大于轻污染土样;添加草炭能影响土样中Cd的存在形态。在2种污染程度的土样中添加草炭后,有效态、无机结合态和残留态Cd所占比例均降低,而有机结合态Cd所占比例均增加。     

丁草胺与镉复合污染对土壤呼吸强度的影响

研究了除草剂丁草胺和重金属镉(Cd)复合污染对两种土壤呼吸强度的影响及其随时间的动态变化.结果表明,单一污染中,丁草胺和Cd对土壤呼吸强度的影响,随土样不同而异,随农药浓度及培养时间的变化而变化;复合污染中,两种土样的复合污染对土壤呼吸强度的影响存在明显的交互作用,与单一污染相比,对土壤呼吸强度的影响依次表现为:丁草胺＞Cd与丁草胺复合污染＞Cd.建立了丁草胺和Cd在不同浓度配比下对土壤呼吸强度影响的多元回归分析模型.     

菜籽饼施加对镉-铜污染土壤中重金属形态转化及其植物有效性的影响

选择菜籽饼作为有机物料,模拟水田条件,研究菜籽饼施用后重金属污染土壤中镉-铜的赋存形态的变化及其有效性的影响。结果表明,菜籽饼施加后,土壤pH波动在0.5内,变化较小。但在一定程度促进土壤中镉、铜由弱酸提取态向可还原态转化,残渣态占比变化均较小。经培养一定时间,植物有效态DTPA-Cd由1.26±0.03下降至0.69±0.03,下降幅度约为45.2%,DTPA-Cu由82.9±0.09下降至48.7±0.09,最大下降幅度约为41.3%,下降较为明显。同时,土壤溶液中可溶性碳(DOC)和可溶性氮(DON)的含量显著增加,分别增加约4.14倍和6.48倍,因此,菜籽饼应用于重金属污染水稻土改良,可以间接降低水稻中重金属的含量。     

多种有机酸对土壤中碳酸镉的活化效应

采用振荡活化方法,探究44种有机酸对碳酸镉的活化差异及其机理,评价活化能力较强的5种有机酸对低浓度Cd污灌菜园土的活化效应。结果表明:低分子有机酸、酚酸及氨基酸对碳酸镉的活化能力存在明显差异;低分子有机酸活化能力总体较强,其中草酸、柠檬酸活化率达7.48%、7.06%。等摩尔浓度有机酸活化效果计算表明:柠檬酸的活化效果最大,活化量为22.73 mg·L~(-1),其次是苹果酸和顺乌头酸,分别为14.55和12.75 mg·L~(-1),酚酸的活化效果不明显,氨基酸中除天冬氨酸、组氨酸和谷氨酸活化效果较强,其余无明显效果。研究表明在等摩尔浓度时,柠檬酸活化碳酸镉主要机制为官能团的螯合作用,而草酸主要为酸溶作用;活化碳酸镉能力较强的柠檬酸对污灌菜园土低浓度Cd的活化最强,对镉的活化量达到食品安全风险水平。     

Enhanced phytoextraction of Cu, Pb, Zn and Cd with EDTA and EDDS

Chemically enhanced phytoextraction has been proposed as an effective approach to removing heavy metals from contaminated soil through the use of high biomass plants. Using pot experiments, the effects of the application of EDTA, EDDS and citric acid on the uptake of Cu, Pb, Zn and Cd by corn (Zea mays L. cv. Nongda 108) and bean (Phaseolus vulgaris L. white bean) plants were studied. The results showed that EDDS was more effective than EDTA at increasing the concentration of Cu in corn and beans. The application of 5 mmol kg-1 soil EDDS to soil significantly increased concentrations of Cu in shoots, with maximum levels of 2060 and 5130 mg kg-1 DW in corn and beans, respectively, which were 45- and 135-fold higher than that in the corresponding control plants to which chelate had not been applied. Concentrations of Zn in shoots were also higher in the plants treated with EDDS than in those treated with EDTA. For Pb and Cd, EDDS was less effective than EDTA. The maximum Cu phytoextraction was found with the EDDS treatment. The application of EDTA and EDDS also significantly increased the shoot-to-root ratios of the concentrations of Cu, Pb, Zn and Cd in both plant species. The results of metal extraction with chelates showed that EDDS was more efficient at solubilizing Cu and Zn than EDTA, and that EDTA was better at solubilizing Pb and Cd than EDDS.     

Effect of o-phenylenediamine on Cu adsorption and desorption in red soil and its uptake by paddy rice (Oryza sativa)

A study was carried out of Cu adsorption and desorption processes in red soil as affected by o-phenylenediamine (o-PD) in the range 0-80 mg/l. The results indicated that the presence of o-PD enhanced Cu adsorption in red soil in weakly acid media, meanwhile, desorption percentage of Cu from soil, extracted by 1.0 M MgCl(2), also increased when Cu adsorption in soil occurred in the presence of o-PD. The response of paddy rice to Cu in red soil shows that Cu toxicity was mitigated in the presence of o-PD and that the Cu concentration in rice straw decreased with increasing concentration of o-PD from 0 to 4.0 mmol/kg in soil. The fractions of background Cu in soil did not change noticeably in the presence of o-PD, whereas the effect of o-PD on the fractions of added Cu was significant. It was found that the exchangeable and carbonate bound Cu fractions decreased and the fraction of Cu bound to Fe-Mn oxides and organic matter increased with increasing o-PD concentration in soil when Cu was added at the same rate. Copper concentration in rice straw was significantly correlated with exchangeable Cu (r=0.961) and carbonate bound Cu (r=0.959) in soil. This result implicates that the behavior of Cu in soil is likely to be affected by organic pollutants containing amino groups.     

Chelator induced phytoextraction and in situ soil washing of Cu

In a soil column experiment, we investigated the effect of 5 mmol kg(-1) soil addition of citric acid, ethylenediamine tetraacetate (EDTA), diethylenetriamine-pentaacetate (DTPA) and [S,S]-stereoisomer of ethylenediamine-disuccinate (EDDS) on phytoextraction of Cu from a vineyard soil with 162.6 mg kg(-1) Cu, into the test plant Brassica rapa var. pekinensis. We also examined the use of a horizontal permeable barrier, composed of layers of nutrient enriched sawdust and apatite, for reduction of chelator induced Cu leaching. The addition of all chelators, except citric acid, enhanced Cu mobility and caused leaching of 19.5-23% of initial total Cu from the soil column. However, Cu plant uptake did not increase accordingly; the most effective was the EDDS treatment, in which plant Cu concentration reached 37.8 +/-1.3 mg kg(-1) Cu and increased by 3.3-times over the control treatment. The addition of none of the chelators in the concentration range from 5 to 15 mmol kg(-1) exerted any toxic effect on respiratory soil microorganisms. When EDDS was applied into the columns with horizontal permeable barriers, only 0.53 +/- 0.32% of the initial total Cu was leached. Cu (36.7%) was washed from the 18 cm soil layer above the barrier and accumulated in the barrier. Our results indicate that rather than for a reduction of Cu leaching during rather ineffective chelate induced Cu phytoextraction, horizontal permeable barriers could be more effective in a new remediation technique of controlled in situ soil washing of Cu with biodegradable chelates.     

Effects of EDTA and low molecular weight organic acids on soil solution properties of a heavy metal polluted soil

A pot experiment was conducted to study the effects of EDTA and low molecular weight organic acids (LMWOA) on the pH, total organic carbon (TOC) and heavy metals in the soil solution in the rhizosphere of Brassica juncea grown in a paddy soil contaminated with Cu, Zn, Pb and Cd. The results show that EDTA and LMWOA have no effect on the soil solution pH. EDTA addition significantly increased the TOC concentrations in the soil solution. The TOC concentrations in treatments with EDTA were significantly higher than those in treatments with LMWOA. Adding 3 mmol kg(-1) EDTA to the soil markedly increased the total concentrations of Cu, Zn, Pb and Cd in the soil solution. Compared to EDTA, LMWOA had a very small effect on the metal concentrations. Total concentrations in the soil solution followed the sequence: EDTA > citric acid (CA) approximately oxalic acid (OA) approximately malic acid (MA) for Cu and Pb; EDTA > MA > CA approximately OA for Zn; and EDTA > MA > CA > OA for Cd. The labile concentrations of Cu, Zn, Pb and Cd showed similar trends to the total concentrations.     

Nitrilotriacetate- and citric acid-assisted phytoextraction of cadmium by Indian mustard (Brassica juncea (L.) Czernj, Brassicaceae)

In a pot experiment the effects of nitrilotriacetate (NTA) and citric acid applications on Cd extractibility from soil as well as on its uptake and accumulation by Indian mustard (Brassica juncea) were investigated. Plants were grown in a sandy soil with added CdS at four levels ranging from 50 to 200 mg Cd kg(-1) soil. After 30 days of growth, pots were amended with NTA or citric acid at 10 and 20 mmol kg(-1). Control pots were not treated with chelates. Harvest of plants was performed immediately before and one week after chelate addition. Soil water-, NH(4)NO(3)- and EDTA-extractable Cd fractions increased constantly with both increasing soil metal application and chelate concentration. Shoot dry weights did not suffer significant reductions with increasing Cd addition to the soil except for both NTA treatments in which at 200 mg Cd kg(-1) a 30% decrease in dry matter was observed. Generally, following NTA and citric acid amendments, Cd concentration in shoots increased with soil Cd level. However, due to Cd toxicity, at the highest metal application rate both NTA treatments lowered Cd concentration in the above-ground parts. Compared to the control, at 10 mmol kg(-1) citric acid did not change Cd concentration in shoots, whereas NTA-treated plants showed an about 2-fold increase. The addition of chelates at 20 mmol kg(-1) further enhanced Cd concentration in shoots up to 718 and 560 microg g(-1) dry weight in the NTA and citrate treatments, respectively.     

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.     

Soil Cd availability to Indian mustard and environmental risk following EDTA addition to Cd-contaminated soil

A pot experiment was conducted to investigate the influence of EDTA on the extractability of Cd in the soil and uptake of Cd by Indian mustard (Brassica juncea). Twenty levels of soil Cd concentration ranging from 10 to 200 mg kg(-1) were produced by spiking aliquots of a clay loam paddy soil with Cd(NO3)2. One week before the plants were harvested EDTA was applied to pots in which the soil had been spiked with 20, 40, 60...200 mg Cd kg(-1). The EDTA was added at the rate calculated to complex with all of the Cd added at the 200 mg kg(-1) level. Control pots spiked with 10, 30, 50... 190 mg Cd kg(-1) received no EDTA. The plants were harvested after 42 days' growth. Soil water- and NH4NO3-extractable Cd fractions increased rapidly following EDTA application. Root Cd concentrations decreased after EDTA application, but shoot concentrations increased when the soil Cd levels were >130 mg kg(-1) and Cd toxicity symptoms were observed. The increases in soil solution Cd induced by EDTA did not increase plant total Cd uptake but appeared to stimulate the translocation of the metal from roots to shoots when the plants appeared to be under Cd toxicity stress. The results are discussed in relation to the possible mechanisms by which EDTA may change the solubility and bioavailability of Cd in the soil and the potential for plant uptake and environmental risk due to leaching losses to groundwater.     

Assessing copper thresholds for phytotoxicity and potential dietary toxicity in selected vegetable crops

Copper pollution in soils is widespread, and its accumulation in crop products could pose a risk on human health. In this paper, bioavailability of added copper (Cu) and critical Cu concentrations in a vegetable garden soil was evaluated for Chinese cabbage (Brassica chinensis L.), pakchoi (Brassica chinensis L.), and celery (Apiumg graveolens L. var. dulce DC) based on human dietary toxicity. The availability of added Cu in the soil decreased with incubation time, and had minimal change after 10-12 weeks. After incubated for 12 weeks, about 60% of added Cu was not extractable by DTPA. The same crops were also grown in sand culture to determine their responses to solution Cu. Shoot growth was significantly inhibited at Cu concentrations above 10 mg kg(-1) in the solution or above 150 mg kg(-1) (DTPA-Cu) in the soil. The sensitivity of the crops to Cu toxicity differed among the three vegetable crops. Copper concentration in shoots and edible parts varied with Cu supply levels and type of the vegetables. Negative correlations (r=-0.90-0.99**) were noted between Cu concentration in shoots and fresh matter yields, but Cu concentrations in the edible parts were positively correlated with available and total Cu in the soil (r=0.91-0.99**). The critical tissue Cu concentrations at 10% shoot DM reduction were 19.4, 5.5, 30.9 mg kg(-1) for Chinese cabbage, pakchoi, and celery, respectively. Based on the threshold of human dietary toxicity for Cu (10 mg kg(-1)), the critical concentrations of total and available Cu in the soil were 430 and 269 mg kg(-1) for pakchoi, 608 and 313 mg kg(-1) for celery, and 835 and 339 mg kg(-1) for Chinese cabbage, respectively.     

Effects of organic acids on the photosynthetic and antioxidant properties and accumulations of heavy metals of <Emphasis Type="Italic">Melilotus officinalis</Emphasis> grown in Cu tailing

The effect of citric acid (CA), acetic acid (Ac), and ethylene diamine tetraacetic acid (EDTA) on the photosynthetic and antioxidant properties and the accumulation of some heavy metals (HMs) of Melilotus officinalis seedling growing in Cu mine tailings for 25 days were studied. Results showed that the formation of photosynthesizing cells of M. officinalis was inhibited by EDTA at 2 mmol/kg. Photosynthetic pigment contents under EDTA of 2 mmol/kg were reduced by 26, 40, and 19 %, respectively, compared to the control. The proline contents in aboveground and underground parts increased as the level of EDTA was enhanced. CA and Ac enhanced the activities of superoxide dismutase (SOD) and peroxidase (POD) in the aboveground parts and EDTA inhibited the activity of POD in the underground parts. The addition of CA promoted significantly the growth of M. officinalis, while the biomass decreased significantly under 2 mmol/kg EDTA. Cu contents in the aboveground parts treated with 0.5 and 2.0 mmol/kg EDTA reached 175.50 and 265.17 μg/g dry weight, respectively. Ac and EDTA treatments promoted Cd to translocate from root to aboveground parts. The result indicated that M. officinalis was a tolerant species of Cu tailing and can be used to remediate Cu contaminated environment, and rationally utilization of organic acids, especially EDTA, in the phytoremediation can improve the growth and metals accumulation of M. officinalis.     

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%.