The influence of pH and organic matter content in paddy soil on heavy metal availability and their uptake by rice plants

The experiments were done to investigate the effect of soil pH and organic matter content on EDTA-extractable heavy metal contents in soils and heavy metal concentrations in rice straw and grains. EDTA-extractable Cr contents in soils and concentrations in rice tissues were negatively correlated with soil pH, but positively correlated with organic matter content. The combination of soil pH and organic matter content would produce the more precise regression models for estimation of EDTA-Cu, Pb and Zn contents in soils, demonstrating the distinct effect of the two factors on the availability of these heavy metals in soils. Soil pH greatly affected heavy metal concentrations in rice plants. Furthermore, inclusion of other soil properties in the stepwise regression analysis improved the regression models for predicting straw Fe and grain Zn concentrations, indicating that other soil properties should be taken into consideration for precise predicting of heavy metal concentrations in rice plants.     

复配钝化剂对稻田重金属有效性及其水稻吸收的影响

针对红壤稻米中重金属Cd超标的问题,通过筛选钝化剂并将其复配用于大田实验,以研究复配钝化剂对土壤有效态重金属(Cd、Pb和Cu)及水稻吸收重金属的影响及其作用机理。室内筛选实验表明,在11种无机和有机钝化剂中,海泡石、生石灰和聚丙烯酰胺对土壤重金属钝化效果较好,使有效态Cd、Pb和Cu分别降低了32.4% ~ 89.2%、19.5% ~ 99.1%和49.4% ~ 92.4%,并将它们确定为复配钝化剂的成分。大田实验结果表明,生石灰、聚丙烯酰胺和海泡石复配对土壤中重金属钝化效果最佳,使有效态Cd、Pb和Cu分别降低了28.6%、20.2%和23.5%(p<0.05),其钝化机制为离子交换和络合作用。而且,该复配钝化剂对土壤化学性质影响最小。复配钝化剂使稻米中Cd的质量分数降低了21.7% ~ 93.1%(p<0.05)。另外,复配钝化剂对土壤微生物丰度和多样性没有显著影响。考虑到土壤的安全性和稳定性,推荐将生石灰、聚丙烯酰胺和海泡石复配钝化剂用于降低红壤稻米对Cd的吸收以确保粮食安全生产。本研究结果可为重金属污染红壤稻田的安全利用提供参考。     

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。     

含磷材料对矿区铅镉污染土壤重金属形态转化的影响

以湖南郴州东江湖风景区矿区遗留地重金属污染土壤为研究对象,研究了3种含P材料,及其与蒙脱石的组合材料,对矿区土壤铅镉污染的修复效果。实验设6组处理,分别为P1组、P2组、P3组、P1+M组、P2+M组、P3+M组,通过添加5%的稳定剂,稳定2d后,分析土壤中铅镉的形态变化。实验结果表明:添加含P材料,及组合材料后,土壤中铅镉的离子交换态、铁锰结合态、有机结合态大幅度降低,残渣态显著升高。对Pb离子转化效果均在90.00%以上, Cd离子的转化效率相对较差,最优P1处理效果为74.20%。离子交换态的减少,有效地降低了重金属的生物有效性,有效地降低了环境风险。同时,含P材料均增加了土壤有效磷的含量,对矿区土壤的肥力也有一定提升。     

Mitigation effects of silicon rich amendments on heavy metal accumulation in rice (Oryza sativa L.) planted on multi-metal contaminated acidic soil

The mechanisms of stabilization by silicon-rich amendments of cadmium, zinc, copper and lead in a multi-metal contaminated acidic soil and the mitigation of metal accumulation in rice were investigated in this study. The results from a pot experiment indicated that the application of fly ash (20 and 40 g kg⁻¹) and steel slag (3 and 6 g kg⁻¹) increased soil pH from 4.0 to 5.0-6.4, decreased the phytoavailability of heavy metals by at least 60%, and further suppressed metal uptake by rice. Diffusion gradient in thin-film measurement showed the heavy metal diffusion fluxes from soil to solution decreased by greater than 84% after remediation. X-ray diffraction analysis indicated the mobile metals were mainly deposited as their silicates, phosphates and hydroxides in amended treatments. Moreover, it was found metal translocation from stem to leaf was dramatically restrained by adding amendments, which might be due to the increase of silicon concentration and co-precipitation with heavy metals in stem. Finally, a field experiment showed the trace element concentrations in polished rice treated with amendments complied with the food safety standards of China. These results demonstrated fly ash and steel slag could be effective in mitigating heavy metal accumulation in rice grown on multi-metal contaminated acidic soils.     

Isolation and characterization of a heavy metal-resistant Burkholderia sp. from heavy metal-contaminated paddy field soil and its potential in promoting plant growth and heavy metal accumulation in metal-polluted soil

A heavy metal-resistant bacterial strain was isolated from heavy metal-contaminated soils and identified as Burkholderia sp. J62 based on the 16S rDNA gene sequence analysis. The heavy metal- and antibiotic resistance, heavy metal solubilization of the isolate were investigated. The isolate was also evaluated for promoting plant growth and Pb and Cd uptakes of the plants from heavy metal-contaminated soils in pot experiments. The isolate was found to exhibit different multiple heavy metal and antibiotic resistance characteristics. Atomic absorption spectrometer analysis showed increased bacterial solubilization of lead and cadmium in solution culture and in soils. The isolate produced indole acetic acid, siderophore and 1-aminocyclopropane-1-carboxylate deaminase. The isolate also solubilized inorganic phosphate. Inoculation with the isolate was found to significantly (p < 0.05) increase the biomass of maize and tomato plants. Increase in tissue Pb and Cd contents varied from 38% to 192% and from 5% to 191% in inoculated plants growing in heavy metal-contaminated soils compared to the uninoculated control, respectively. These results show that heavy metal-solubilizing and plant growth promoting bacteria are important for plant growth and heavy metal uptake which may provide a new microbial enhanced-phytoremediation of metal-polluted soils.     

Genotypic and environmental variation in chromium, cadmium and lead concentrations in rice

Genotypic and environmental variation in Cr, Cd and Pb concentrations of rice grains and the interaction between these metals were investigated by using 138 rice genotypes grown in three contaminated soils. There were significant genotypic differences in the three heavy metal concentrations of rice grains, with the absolute difference among 138 genotypes in grain Cr, Cd and Pb concentrations being 24.5-, 9.1- and 23.8-folds, respectively, under the slightly contaminated soil (containing 4.61mgkg(-1) Cr, 1.09mgkg(-1) Cd and Pb 28.28mgkg(-1), respectively). A highly significant interaction occurred between genotype and environment (soil type) in the heavy metal concentrations of rice grains. Cr concentration in rice grains was not correlated with Cd and Pb concentration. However, there was a significant correlation between Cd and Pb in slightly and highly contaminated soils. The results suggest the possibility to develop the rice cultivars with low Cd and Pb concentrations in grain.     

重金属污染土壤旋流洗脱设备的设计及性能评估

针对高浓度重金属污染土壤,尤其是污染负荷较高的黏土土壤,传统的物化方法难以实现其高效的洗脱。利用旋流场中土壤颗粒高速自转/公转,实现土壤颗粒污染物的强化快速脱附。土壤旋流洗脱实验分为旋流器的分离性能和单一/复合污染物的脱附性能2部分。在土壤-水体系下,旋流器的最优操作条件为：进口流量0.7 m3·h-1,分流比0.12,固液比为1:20。对于Pb污染物,底流脱附效率均能达到近85%,溢流也能够达到70%。对于Cu污染物,底流和溢流脱附均能达到90%左右。对于Cr(VI)污染物,底流脱附最高能达到60%左右,但溢流洗脱效率极低。复合污染能够在单次通过后脱除Pb、Cu、Cr(VI)等多种重金属污染,且洗脱效果与单一污染洗脱时基本一致。对实际的场地修复具有指导意义。     

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。     

Comparison of EDTA-enhanced phytoextraction and phytostabilisation strategies with Lolium perenne on a heavy metal contaminated soil

Phytoremediation is a promising and cost-effective strategy to manage heavy metal polluted sites. In this experiment, we compared simultaneously phytoextraction and phytostabilisation techniques on a Cd and Zn contaminated soil, through monitoring of plant accumulation and leaching. Lolium perenne plants were cultivated for 2 months under controlled environmental conditions in a 27.6 dm³-pot experiment allowing the collect of leachates. The heavy metal phytoextraction was promoted by adding Na-EDTA (0.5 g kg⁻¹ of soil) in watering solution. Phytostabilisation was assessed by mixing soil with steel shots (1%) before L. perenne sowing. Presence of plants exacerbated heavy metal leaching, by improving soil hydraulic conductivity. Use of EDTA for phytoextraction led to higher concentration of heavy metal in shoots. However, this higher heavy metal extraction was insufficient to satisfactory reduce the heavy metal content in soil, and led to important heavy metal leaching induced by EDTA. On the other hand, addition of steel shots efficiently decreased both Cd and Zn mobility, according to 0.01 M CaCl₂ extraction, and leaching. However, improvement of growth conditions by steel shots led to higher heavy metal mass in shoot tissues. Therefore, soil heavy metal mobility and plant metal uptake are not systematically positively correlated.     

乙酸强化下通电方式对电动修复受重金属污染高岭土的影响

电动修复作为一种绿色的土壤污染修复技术,因具有成本低、操作简单、不易造成二次污染等特点而有巨大的应用前景。以高岭土作为实验材料,研究了不同电场施加方式条件下铜、锌重金属的去除规律。为了进一步提高效率,实验配制pH为3.5的乙酸溶液并加入高岭土中,加入后可以加快土壤酸化并降低重金属沉淀区域的影响。相比于电解液为蒸馏水的情况,pH突变点向阴极靠近,从S3、S4片层移动到了S4、S5片层。加入乙酸后,实验最大电流和反应384 h后的电流相比未加乙酸升高较为明显。在相同条件下,电场强度为0.5 V·cm-1时反应最高电流为60~139 mA,电场强度为1.0 V·cm-1时为108~170 mA,电场强度为1.5 V·cm-1时为152~290 mA。在相同条件下反应384 h后的实验最低电流,电场强度为0.5 V·cm-1时为33~70 mA,电场强度为1.0 V·cm-1时为41~83 mA,电场强度为1.5 V·cm-1时为71~123 mA。高电场强度有利于去除土壤中的低浓度重金属污染物。相比电极室未添加乙酸的实验组,污染物去除率提高15%以上。     

4种茄科植物对矿区污染土壤重金属的吸收和富集

采集了湖南及江苏8个矿区或冶炼厂周边4种茄科(Solanaceae)植物及其根际土壤,分析了植物及土壤样品中Cd、Cu、Pb、Mn和Zn 5种重金属浓度.结果表明:番茄(Lycopersicon esculentum)对5种重金属可能有着较强的耐性,但不具有超积累的潜力;刺天茄(Solanum indicum)对Mn、...     

Accumulation of heavy metals from contaminated soil to plants and evaluation of soil remediation by vermiculite

We evaluated the distribution of 15 metal ions, namely Al, Cd, Cu, Cr, Fe, La, Mn, Ni, Pb, Sc, Ti, V, Y, Zn and Zr, in the soil of a contaminated site in Piedmont (Italy). This area was found to be heavily contaminated with Cu, Cr and Ni. The availability of these metal ions was studied using Tessier’s sequential extraction procedure: the fraction of mobile species, which potentially is the most harmful for the environment, was much higher than that normally present in unpolluted soils. This soil was hence used to evaluate the effectiveness of treatment with vermiculite to reduce the availability of the pollutants to two plants, Lactuca sativa and Spinacia oleracea, by pot experiments. The results indicated that the addition of vermiculite significantly reduces the uptake of metal pollutants by plants, confirming the possibility of using this clay in amendment treatments of metal-contaminated soils. The effect of plant growth on metal fractionation in soils was investigated. Finally, the sum of the metal percentages extracted into the first two fractions of Tessier’s protocol was found to be suitable in predicting the phytoavailability of most of the pollutants present in the investigated soil.     

Effects of 2,4-dichlorophenol,pentachlorophenol and vegetation on microbial characteristics in a heavy metal polluted soil

The aim of this study was to evaluate the soil microbial characteristics in historically heavy-metal polluted soil, which was also affected by organic co-contaminants, 2,4-dichlorophenol or pentachlorophenol, which often occur due to the conventional use of pesticides. It was observed that the normalized microbial biomass (microbial biomass per unit soil organic C) of the contaminated soil was very low, less than 1% in both non-planted and ryegrass planted soil, and showed a decreasing trend with the treatment of organic co-contaminants. The microbial biomass and substrate-induced respiration (SIR) in the ryegrass planted soil were much larger, as compared with the non-planted soil with or without organic pollutants. The different resistant bacterial community and its physiological diversity in the rhizosphere further suggested that the effect of vegetation on microbial activity was not just a general increase in the mass or activity of pre-existing microorganisms, but rather acted selectively on microbial growth so that the relative abundance of different microbial groups in soil was changed. In sum, high concentrations of organic co-contaminants, especially pentachlorophenol (PCP), could strengthen the deterioration of microbial ecology. The adverse effect of heavy metal-organic pollutants on the soil microbial biomass and activity might be the reason for the slow degradation of PCP that has high chlorinated and high toxicity. Vegetation might be the efficient way to assist in improving and restoring the utilization of agricultural ecosystems. The beneficial microbial effect of vegetation could cause the rapid dissipation of 2,4-dichlorophenol (2,4-DCP) that has less chlorinated and less toxicity in the planted soils.     

Effects of phytoextraction on heavy metal concentrations and pH of pore-water of biosolids determined using an in situ sampling technique

Heavy metal concentrations and pH of pore-water in contaminated substrates are important factors in controlling metal uptake by plants. We investigated the effects of phytoextraction on these properties in the solution phase of biosolids and diluted biosolids in a 12-month phytoextraction column experiment. Phytoextraction using Salix and Populus spp. temporarily decreased pore-water pH of the substrates over the experimental period followed by a return to initial pH conditions. Salix × reichardtii and Populus balsamifera effectively extracted Ni, Zn and Cd and actively mobilized these metals from the solid to the solution phase. S. × reichardtii had the stronger effect on mobilization of metals due to its larger root system. Phytoextraction did not affect Cu in the solution phase of the biosolids. Heavy metals were leached down to lower depths of the columns during the phytoextraction process.     

The effects of biochars from rice residue on the formation of iron plaque and the accumulation of Cd, Zn, Pb, As in rice (Oryza sativa L.) seedlings

A historically multi-metal contaminated soil was amended with biochars produced from different parts of rice plants (straw, husk and bran) to investigate how biochar can influence the mobility of Cd, Zn, Pb and As in rice seedlings (Oryza sativa L.). Rice shoot concentrations of Cd, Zn and Pb decreased by up to 98%, 83% and 72%, respectively, due to biochar amendment, though that of As increased by up to 327%. Biochar amendments significantly decreased pore water concentrations (C_pw) of Cd and Zn and increased that of As. For Pb it depended on the amendment. Porewater pH, dissolved organic carbon, dissolved phosphorus, silicon in pore water and iron plaque formation on root surfaces all increased significantly after the amendments. The proportions of Cd and Pb in iron plaque increased by factors 1.8-5.7 and 1.4-2.8, respectively; no increase was observed for As and Zn. Straw-char application significantly and noticeably decreased the plant transfer coefficients of Cd and Pb. This study, the first to investigate changes in metal mobility and iron plaque formation in rice plants due to amending a historically contaminated soil with biochar, indicates that biochar has a potential to decrease Cd, Zn and Pb accumulations in rice shoot but increase that of As. The main cause is likely biochar decreasing the C_pw of Cd and Zn, increasing the C_pw of As, and increasing the iron plaque blocking capacity for Cd and Pb.     

磷肥钝化修复重金属污染土壤及其环境风险

磷肥广泛应用于农田重金属污染土壤钝化修复,但不同类型磷肥对多种重金属复合污染土壤的修复效果及其环境风险尚不明确。通过室内土壤培养和土柱淋溶模拟实验,研究枸溶性磷肥-钙镁磷肥(CMP)和水溶性磷肥-磷酸二氢钾(MPP)对重金属Pb、Cd、Cu、Zn复合污染土壤的钝化效果以及磷在土壤剖面中的淋溶损失特征。结果表明,CMP和MPP施用量(以P₂O₅计)为8 g·kg⁻¹时,Pb、Cd的钝化率分别为35.05%和71.72%、31.76%和40.99%,而Cu、Zn则出现一定程度的活化(最高达29.62%)。MPP对Pb的钝化效果显著优于CMP,但对Cd而言,2者差异不明显,且磷肥用量的成倍增加并不能显著提升钝化效果。土柱中土壤全磷、有效磷和淋溶液总磷的质量分数均随着深度(20~65 cm)递增而显著下降,且在某一深度上随着施磷量(1~8 g·kg⁻¹)的增加而显著升高。MPP在高用量下造成的磷淋溶风险显著大于CMP。采用磷肥钝化修复复合重金属污染土壤应综合重金属类型、钝化效果以及潜在的磷流失风险,选择适当的磷肥种类和用量。本研究结果可为磷肥钝化修复重金属污染土壤提供参考。     

The effect of water flooding at grain-filling stage on the uptake of heavy metal(loid)s by rice in slightly alkaline paddy soil

Environmental Science and Pollution Research - Continuous flooding has been widely used in paddy field to decrease the accumulation of heavy metal(loid)s by rice due to their decreased solubility...     

Reduction in uptake by rice and soybean of aromatic arsenicals from diphenylarsinic acid contaminated soil amended with activated charcoal

Activated charcoal (AC) amendment has been suggested as a promising method to immobilize organic contaminants in soil. We performed pot experiments with rice and soybean grown in agricultural soil polluted by aromatic arsenicals (AAs). The most abundant AA in rice grains and soybean seeds was methylphenylarsinic acid (MPAA). MPAA concentration in rice grains was significantly reduced to 2% and 3% in 0.2% AC treated soil compared to untreated soil in the first year of rice cultivation. In the second year, MPAA concentration in rice grains was significantly reduced to 15% in 0.2% AC treated soil compared to untreated soil. MPAA concentration in soybean seeds was significantly reduced to 44% in 0.2% AC treated soil compared to untreated soil. AC amendment was effective in reducing AAs in rice and soybean.     

Effects of alkaline and bioorganic amendments on cadmium,lead, zinc,and nutrient accumulation in brown rice and grain yield in acidic paddy fields contaminated with a mixture of heavy metals

Paddy soils and rice (Oryza sativa L.) contaminated by mixed heavy metals have given rise to great concern. Field experiments were conducted over two cultivation seasons to study the effects of steel slag (SS), fly ash (FA), limestone (LS), bioorganic fertilizer (BF), and the combination of SS and BF (SSBF) on rice grain yield, Cd, Pb, and Zn and nutrient accumulation in brown rice, bioavailability of Cd, Pb, and Zn in soil as well as soil properties (pH and catalase), at two acidic paddy fields contaminated with mixed heavy metals (Cd, Pb, and Zn). Compared to the controls, SS, LS, and SSBF at both low and high additions significantly elevated soil pH over both cultivation seasons. The high treatments of SS and SSBF markedly increased grain yields, the accumulation of P and Ca in brown rice and soil catalase activities in the first cultivation season. The most striking result was from SS application (4.0 t ha^?1) that consistently and significantly reduced the soil bioavailability of Cd, Pb, and Zn by 38.5–91.2 % and the concentrations of Cd and Pb in brown rice by 20.9–50.9 % in the two soils over both cultivation seasons. LS addition (4.0 t ha^?1) also markedly reduced the bioavailable Cd, Pb, and Zn in soil and the Cd concentrations in brown rice. BF remobilized soil Cd and Pb leading to more accumulation of these metals in brown rice. The results showed that steel slag was most effective in the remediation of acidic paddy soils contaminated with mixed heavy metals.