钝化剂在烟草植物修复铅镉污染土壤中的作用简

重金属钝化剂可以改变土壤中重金属的形态，降低其在土壤中的有效浓度、植物毒性及生物有效性，影响污染土壤中植物的生长及其对重金属的吸收。在温室盆栽条件下研究了施加羟基磷灰石（HA）、纳米羟基磷灰石（nHA）、纳米零价铁（nFe⁰）和纳米TiO₂（nTiO₂）对烟草植物修复铅镉污染土壤的作用。结果表明，HA降低土壤中Pb、Cd的有效性、促进烟草生长、增加了烟草叶、茎、根中Cd的吸收量和根系中Pb的吸收量，有利于Pb、Cd的钝化和植物修复。nHA也可以降低土壤中Pb、Cd的有效性，增加了烟草叶中Cd的吸收量，有利于Pb、Cd的钝化和Cd的植物提取。nFe⁰和nTiO₂对于土壤Pb和Cd的钝化作用和植物修复均没有显著影响。综合来看，HA最适合应用于烟草植物修复铅镉污染土壤。     

EDTA/纳米羟基磷灰石联合修复重金属污染土壤

土壤淋洗可能导致残留重金属活化,采用淋洗/钝化联合修复重金属污染土壤可在一定程度上减少这一影响。研究了EDTA淋洗、纳米羟基磷灰石钝化及两者联合修复对土壤重金属洗脱率、TCLP浸出浓度、化学形态分布的影响,构建了涵盖土壤重金属残留量、生物有效性和生理毒性的环境风险评价方法,对淋洗、钝化及其联合修复进行了评价。结果发现,EDTA淋洗对Pb和Cu的洗脱效果较好,对Zn浸出浓度的削减率较高。当EDTA投加量为2 g·L~(-1)时,Zn的浸出浓度降低了70.40%。纳米羟基磷灰石对Pb和Zn具有较好的钝化效果,对Cu和Cd的钝化作用相对较弱。当纳米羟基磷灰石投加量为2%时,Pb浸出浓度削减率高达89.65%。淋洗/钝化联合修复大幅度降低了Pb和Cd的浸出浓度,降低了可还原态Cu残留量、可还原态和残渣态Cd残留量,以及弱酸提取态和可还原态Zn、Pb残留量。当EDTA和纳米羟基磷灰石投加量分别为1 g·L~(-1)和1%时,土壤重金属总环境风险削减率达到74.12%。EDTA对土壤中Cu和Cd的洗脱效果较好,后续钝化修复作用有限,Pb和Zn则可通过淋洗/钝化联合修复大幅度提高削减环境风险削减率。     

EDTA对污染土壤中金属解吸的影响

重金属污染是当今土壤污染中的污染面积最广、危害最大的环境问题之一，有关污染土壤的修复研究正日益受到重视。现以黄土体土壤为对象，以铜、铅为代表，研究有机配体EDTA（乙二胺四乙酸）对土壤被重金属污染的解吸的影响。并分别讨论土壤中的单元素金属污染以及复合金属污染的解吸过程。结果表明，EDTA的加入，对Cu或Pb的单一污染土壤，可以大幅度增加金属的解吸量，但在Cu—Ph复合污染土壤中，由于两种金属离子同时存在，却出现Cu、Pb对EDTA的竞争性反应，彼此互为影响。     

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。     

生物炭复配磷酸盐对Pb-Cd污染土壤原位钝化修复的研究

采用小区试验方法,选取生物炭、磷酸盐及两者复配材料作为钝化剂原位修复工业遗留场地Pb-Cd污染土壤,通过毒性浸出方法(TCLP)以及欧共体标准物质局(BCR)连续提取法分析钝化修复效果,以期获取最优化的钝化修复方法。结果表明,生物炭、磷酸盐及两者复配材料均能够有效降低土壤Pb、Cd的生物有效性和迁移能力。生物炭能提高土壤pH,使TCLP提取态Pb、Cd分别降低56.26%和83.54%,生物炭能促进重金属沉淀的形成进而提升残渣态Pb、Cd比例;磷酸盐主要通过矿物沉淀作用促使重金属由弱结合态向强结合态方向的转化,使TCLP提取态Pb、Cd分别降低70.66%、89.94%,残渣态Pb、Cd比例显著提升,进而有效降低Pb、Cd的生物有效性和迁移能力。生物炭和磷酸盐复配材料相比单一钝化剂材料未表现出协同作用,但复配材料在保证钝化修复效果的前提下,能补偿酸性磷酸盐造成的土壤酸化,在修复实践中更具应用优势。     

组合式水生植物净化系统对Cu、Pb和Cd的去除与生物富集特征

选取再力花、美人蕉、水烛、旱伞草、梭鱼草、慈姑、菖蒲、水葫芦和大藻9种植物作为实验植物，构建成以高效净化重金属污染水体为主要功能的组合式水生植物高效净化系统（人工湿地＋生态浮床＋水生植物塘3个处理单元串联而成），研究不同处理单元中水生植物对重金属Cu、Pb和cd的去除能力及富集特征。结果表明，该净化系统经过为期60d的连续运行，对Cu、Pb和Cd的去除率较为稳定，可分别达到Cu93．5％～96．1％、Ph94．5％～95．2％和Cd95．6％～97．4％，3种重金属出水浓度均可达到GB3838-2002Ⅲ类水排放要求；其中人工湿地单元对重金属去除贡献率最高，Cu、Pb和Cd分别为54．15％、33．61％和44．84％，其次为生态浮床处理单元，Cu、Pb和Cd的去除贡献率分别为38．61％、51．42％和38．56％，而水生植物塘主要起到深度处理作用，对Cu、Pb和cd的去除贡献率分别为7．24％、14．97％和16．6％。9种植物在系统运行期间，生长状况良好，且重金属累积量较高，尤其是生物塘系统中的水葫芦和大藻，实验期间其重金属生物富集系数（BCF）均在200以上。所选植物不同部位对3种重金属的吸收富集能力均表现为根最强。     

胡敏素钝化修复重金属Cu(Ⅱ)、Pb(Ⅱ)污染土壤

通过土壤培养实验,研究了添加胡敏素对污染土壤中Cu、Pb生物有效性和化学形态的影响。结果表明,添加胡敏素可显著降低重金属的浸出浓度。当投加2%的胡敏素5 d后,土壤中重金属Cu~(2+)和Pb~(2+)的浸出浓度分别下降45.16%和56.97%,并且投加胡敏素10 d后对重金属的钝化基本达到稳定。尿素、硫酸铵、磷酸二氢钾可显著提高胡敏酸对Pb的钝化效果,浸出浓度分别下降了29.36%、23.57%和28.69%,但对Cu的影响不明显。进一步的研究表明,投加2%的胡敏素钝化处理30 d后土壤中交换态铜和铅的所占的比例由原来的15.68%和15.79%下降到了0.48%和1.22%,而有机态铜和铅的比例则由5.35%和10.93%上升到了13.24%和27.32%。因此,采用胡敏素作为重金属污染土壤的钝化剂具有广阔的应用前景。     

含磷材料在铅污染土壤修复中的应用

铅不是生物体必需的元素,具有很强的生物毒性,低剂量铅就会对人体健康产生严重威胁。铅的生物有效性与其生物毒性密切相关,降低土壤铅生物有效性是铅污染土壤修复的重要手段之一。含磷材料可作为铅的稳定修复剂的特性被广泛地接受。含磷材料通过吸附、沉淀、离子交换等作用与铅离子形成稳定的磷氯铅矿类物质[Pb_5(PO_4)_3X;X=F,Cl,Br or OH]。通过概述国内外关于含磷材料原位钝化修复铅污染土壤的分子机理,列举了几种应用较为广泛的含磷材料(如磷酸、磷酸盐、羟基磷灰石、磷矿石等)的最新研究进展,总结了温度、p H值、磷铅摩尔分子比等影响因子及其修复效果方面的研究进展,并讨论含磷材料原位修复铅污染土壤的工程适用性及其长期稳定性。     

重金属污染废弃地修复植物种类的筛选与评价

基于修复被重金属污染土壤的优良植物的特征，并结合前人的研究成果，对修复被Cd、Pb、Zn、Cu、Mn污染土壤的植物进行了罗列与分析，筛选出了一些可以应用于修复因重金属污染而废弃土地的、且生态恢复生长快、生物量大、抗逆性强、富集重金属多的植物。     

观赏植物与驯化污泥联合修复垃圾渗滤液污染土壤

垃圾填埋场渗滤液污染土壤具有重金属-有机物复合污染的特性。研究了观赏植物广东万年青、白掌、孔雀竹芋和经垃圾渗滤液驯化的污泥对该污染土壤的修复效果,结果表明:采用单一植物修复时,广东万年青较白掌和孔雀竹芋对土壤污染物具有更强耐性,能在污染土壤中生长良好,对重金属Cd和Pb的富集能力也更强;驯化污泥能明显提高污染土壤中有机污染物的降解率,并使重金属Cd和Pb稳定态比例分别提高了34.7%和36.6%,降低了重金属的生物有效性。当采用广东万年青和驯化污泥联合修复时,污泥能促进植物的生长,且当污泥添加量为480 mg·kg~(-1)时,联合修复对土壤中Cd、Pb及有机污染物的去除率分别较不加污泥的对照提高了51.7%、25.5%和40.2%。     

Chemical methods and phytoremediation of soil contaminated with heavy metals

The effects of chemical amendments (calcium carbonate (CC), steel sludge (SS) and furnace slag (FS)) on the growth and uptake of cadmium (Cd) by wetland rice, Chinese cabbage and wheat grown in a red soil contaminated with Cd were investigated using a pot experiment. The phytoremediation of heavy metal contaminated soil with vetiver grass was also studied in a field plot experiment. Results showed that treatments with CC, SS and FS decreased Cd uptake by wetland rice, Chinese cabbage and wheat by 23-95% compared with the unamended control. Among the three amendments, FS was the most efficient at suppressing Cd uptake by the plants, probably due to its higher content of available silicon (Si). The concentrations of zinc (Zn), lead (Pb) and Cd in the shoots of vetiver grass were 42-67%, 500-1200% and 120-260% higher in contaminated plots than in control, respectively. Cadmium accumulation by vetiver shoots was 218 g Cd/ha at a soil Cd concentration of 0.33 mg Cd/kg. It is suggested that heavy metal-contaminated soil could be remediated with a combination of chemical treatments and plants.     

Heavy metal immobilization by chemical amendments in a polluted soil and influence on white lupin growth

The effects of chemical amendments (zeolite, compost and calcium hydroxide) on the solubility of Pb, Cd and Zn in a contaminated soil were determined. The polluted soil was from the Southwest Sardinia, Italy. It showed very high total concentrations of Pb (19663 mgkg(-1) d.m.), Cd (196 mgkg(-1) d.m.) and Zn (14667 mgkg(-1) d.m.). The growth and uptake of heavy metals by white lupin (Lupinus albus L., cv. Multitalia) in amended soils were also studied in a pot experiment under greenhouse conditions. Results showed that the amendments increased the residual fraction of heavy metals in the soils, and decreased the heavy metals uptake by white lupin compared with the unamended control. Among the three amendments, compost and Ca(OH)2 were the most efficient at reducing Pb and Zn uptake, while zeolite was the most efficient at reducing Cd uptake by the plants. White lupin growth was better in amended soils than in unamended control. The above ground biomass increased with a factor 1.8 (soil amended with zeolite), 3.6 (soil amended with compost) and 3.1 (soil amended with Ca(OH)2) with respect to unamended soil. The roots biomass increased with a factor 1.4 (soil amended with zeolite), 5.6 (soil amended with compost) and 4.8 (soil amended with Ca(OH)2). Results obtained suggest that the soil chemical treatment improved the performance of crops by reducing bioavailability of metals in the soils. However it would be therefore interesting to find a suitable mixture of these amendments to contemporarily immobilize the three main pollutants in the polluted soils.     

Evaluation of the effectiveness of phosphate treatment for the remediation of mine waste soils contaminated with Cd, Cu, Pb, and Zn

The effectiveness of phosphate treatment for Cd, Cu, Pb, and Zn immobilization in mine waste soils was examined using batch conditions. Application of synthetic hydroxyapatite (HA) and natural phosphate rock (FAP) effectively reduced the heavy metal water solubility generally by about 84-99%. The results showed that HA was slightly superior to FAP for immobilizing heavy metals. The possible mechanisms for heavy metal immobilization in the soil involve both surface complexation of the metal ions on the phosphate grains and partial dissolution of the phosphate amendments and precipitation of heavy metal-containing phosphates. HA and FAP could significantly reduce Cd, Cu, Pb, and Zn availability in terms of water solubility in contaminated soils while minimizing soil acidification and potential risk of eutrophication associated with the application of highly soluble phosphate sources.     

Evaluation of metal mobility, plant availability and immobilization by chemical agents in a limed-silty soil

Metal-contaminated soils in the vicinity of industrial sites become of ever-increasing concern. Diagnostic criteria and ecological technologies for soil remediation should be calibrated for various soil conditions; actually, our knowledge of calcareous soil is poor. Silty soils near smelters at Evin (Pas de Calais, France) have been contaminated by non-ferrous metal fallout and regularly limed using foams. Therefore, the mobility, bioavailability, and potential phytotoxicity of Cd, Pb and Zn, were investigated using single soil extractions (i.e. water, 0.1 n Ca(NO(3))(2), and EDTA pH 7), and vegetation experiments, in parallel with a biological test based on (iso)-enzymes in leaves and roots, before and following soil treatment with chemical agents, i.e. Thomas basic slags (TBS), hydrous manganese oxide (HMO), steel shots (ST) and beringite. No visible toxicity symptoms developed on the above-ground parts of ryegrass, tobacco and bean plants grown in potted soil under controlled environmental conditions. Cd, Zn and Pb uptake resulted in high concentrations in the above-ground plant parts, but the enzyme capacities in leaves and roots, and the peroxidase pattern indicated that these metal concentrations were not phytotoxic for beans as test plants. The addition of chemical agents to the soil did not increase biomass production, but treatment with either HMO, ST or beringite markedly decreased the mobility of Cd, Zn and Pb. These agents were proven to be effective in mitigating the Cd uptake by plants. HMO and ST decreased either Pb or Zn uptake by ryegrass. TBS was effective in lowering Pb uptake by the same species. Beringite decreased Cd uptake by beans. If fallout could be restricted, the metal content of food crops in this area should be lowered by soil treatment. However, the differences in Cd uptake between plant species were not suppressed, regardless of the type of agents applied to the soil.     

Potential availability of heavy metals to phytoextraction from contaminated soils induced by exogenous humic substances

Effective phytoremediation of soils contaminated by heavy metals depends on their availability to plant uptake that, in turn, may be influenced by either the existing soil humus or an exogenous humic matter. We amended an organic and a mineral soil with an exogenous humic acid (HA) in order to enhance the soil organic carbon (SOC) content by 1% and 2%. The treated soils were further enriched with heavy metals (Cu, Pb, Cd, Zn, Ni) to a concentration of 0, 10, 20, and 40 microg/g for each metal and allowed to age at room temperature for 1 and 2 months. After each period, they were extracted for readily soluble and exchangeable (2.5% acetic acid), plant-available (DTPA, Diethylentriaminepentaacetic acid), and occluded (1 N HNO(3)) metal species. Addition of HA generally reduced the extractability of the soluble and exchangeable forms of metals. This effect was directly related to the amount of added HA and increased with ageing time. Conversely, the potentially plant-available metals extracted with DTPA were generally larger with increasing additions of exogenous HA solutions. This was attributed to the formation of metal-humic complexes, which ensured a temporary bioavailability of metals and prevented their rapid transformation into insoluble species. Extractions with 1 N HNO(3) further indicated that the added metals were present in complexes with HA. The observed effects appeared to also depend on the amount of native SOC and its structural changes with ageing. The results suggest that soil amendments with exogenous humic matter may accelerate the phytoremediation of heavy metals from contaminated soil, while concomitantly prevent their environmental mobility.     

Effects of sewage sludge amendment on heavy metal accumulation and consequent responses of Beta vulgaris plants

Use of sewage sludge, a biological residue produced from sewage treatment processes in agriculture is an alternative disposal technique of waste. To study the usefulness of sewage sludge amendment for palak (Beta vulgaris var. Allgreen H-1), a leafy vegetable and consequent heavy metal contamination, a pot experiment was conducted by mixing sewage sludge at 20% and 40% (w/w) amendment ratios to the agricultural soil. Soil pH decreased whereas electrical conductance, organic carbon, total N, available P and exchangeable Na, K and Ca increased in soil amended with sewage sludge in comparison to unamended soil. Sewage sludge amendment led to significant increase in Pb, Cr, Cd, Cu, Zn and Ni concentrations of soil. Cd concentration in soil was found above the Indian permissible limit in soil at both the amendment ratios.

The increased concentration of heavy metals in soil due to sewage sludge amendment led to increases in heavy metal uptake and shoot and root concentrations of Ni, Cd, Cu, Cr, Pb and Zn in plants as compared to those grown on unamended soil. Accumulation was more in roots than shoots for most of the heavy metals. Concentrations of Cd, Ni and Zn were more than the permissible limits of Indian standard in the edible portion of palak grown on different sewage sludge amendments ratios. Sewage sludge amendment in soil decreased root length, leaf area and root biomass of palak at both the amendment ratios, whereas shoot biomass and yield decreased significantly at 40% sludge amendment. Rate of photosynthesis, stomatal conductance and chlorophyll content decreased whereas lipid peroxidation, peroxidase activity and protein and proline contents, increased in plants grown in sewage sludge-amended soil as compared to those grown in unamended soil.

The study clearly shows that increase in heavy metal concentration in foliage of plants grown in sewage sludge-amended soil caused unfavorable changes in physiological and biochemical characteristics of plants leading to reductions in morphological characteristics, biomass accumulation and yield. The study concludes that sewage sludge amendment in soil for growing palak may not be a good option due to risk of contamination of Cd, Ni and Zn and also due to lowering of yield at higher mixing ratio.     

Allocation and source attribution of lead and cadmium in maize (Zea mays L.) impacted by smelting emissions

Plants grown in contaminated areas may accumulate trace metals to a toxic level via their roots and/or leaves. In the present study, we investigated the distribution and sources of Pb and Cd in maize plants (Zea mays L.) grown in a typical zinc smelting impacted area of southwestern China. Results showed that the smelting activities caused significantly elevated concentrations of Pb and Cd in the surrounding soils and maize plants. Pb isotope data revealed that the foliar uptake of atmospheric Pb was the dominant pathway for Pb to the leaf and grain tissues of maize, while Pb in the stalk and root tissues was mainly derived from root uptake. The ratio of Pb to Cd concentrations in the plants indicated that Cd had a different behavior from Pb, with most Cd in the maize plants coming from the soil via root uptake.     

Drought-tolerant <Emphasis Type="Italic">Streptomyces pactum</Emphasis> Act12 assist phytoremediation of cadmium-contaminated soil by <Emphasis Type="Italic">Amaranthus hypochondriacus</Emphasis>: great potential application in arid/semi-arid areas

Microbe-assisted phytoremediation provides an effective approach to clean up heavy metal-contaminated soils. However, severe drought may affect the function of microbes in arid/semi-arid areas. Streptomyces pactum Act12 is a drought-tolerant soil actinomycete strain isolated from an extreme environment on the Qinghai-Tibet Plateau, China. In this study, pot experiments were conducted to assess the effect of Act12 on Cd tolerance, uptake, and accumulation in amaranth (Amaranthus hypochondriacus) under water deficit. Inoculated plants had higher Cd concentrations (root 8.7–33.9 %; shoot 53.2–102.1 %) and uptake (root 19.9–95.3 %; shoot 110.6–170.1 %) than non-inoculated controls in Cd-treated soil. The translocation factor of Cd from roots to shoots was increased by 14.2–75 % in inoculated plants, while the bioconcentration factor of Cd in roots and shoots was increased by 10.2–64.4 and 53.9–114.8 %, respectively. Moreover, inoculation with Act12 increased plant height, root length, and shoot biomass of amaranth in Cd-treated soil compared to non-inoculated controls. Physiochemical analysis revealed that Act12 enhanced Cd tolerance in the plants by increasing glutathione, elevating superoxide dismutase and catalase activities, as well as reducing malondialdehyde content in the leaves. The drought-tolerant actinomycete strain Act12 can enhance the phytoremediation efficiency of amaranth for Cd-contaminated soils under water deficit, exhibiting potential for application in arid and semi-arid areas.     

Ascorbic acid, β-carotene,sugars, phenols,and heavy metals in sweet potatoes grown in soil fertilized with municipal sewage sludge

Municipal sewage sludge (MSS) used for land farming typically contains heavy metals that might impact crop quality and human health. A completely randomized experimental design with three treatments (six replicates each) was used to monitor the impact of mixing native soil with MSS or yard waste (YW) mixed with MSS (YW +MSS) on: i) sweet potato yield and quality; ii) concentration of seven heavy metals (Cd, Cr, Mo, Cu, Zn, Pb, and Ni) in sweet potato plant parts (edible roots, leaves, stem, and feeder roots); and iii) concentrations of ascorbic acid, total phenols, free sugars, and β-carotene in sweet potato edible roots at harvest. Soil samples were collected and analyzed for total and extractable metals using two extraction procedures, concentrated nitric acid (to extract total metals from soil) as well as CaCl₂ solution (to extract soluble metals in soil that are available to plants), respectively. Elemental analyses were performed using inductively coupled plasma mass spectrometry (ICP-MS). Overall, plant available metals were greater in soils amended with MSS compared to control plots. Concentration of Pb was greater in YW than MSS amendments. Total concentrations of Pb, Ni, and Cr were greater in plants grown in MSS+YW treatments compared to control plants. MSS+YW treatments increased sweet potato yield, ascorbic acid, soluble sugars, and phenols in edible roots by 53, 28, 27, and 48%, respectively compared to plants grown in native soil. B-carotene concentration (157.5 μg g^?1 fresh weight) was greater in the roots of plants grown in MSS compared to roots of plants grown in MSS+YW treatments (99.9 μg g^?1 fresh weight). Concentration of heavy metals in MSS-amended soil and in sweet potato roots were below their respective permissible limits.