Influence of Indian mustard （Brassicajuncea） on rhizosphere soil solution chemistry in long-term contaminated soils： A rhizobox study

This study investigated the influence of Indian mustard (Brassica juncea) root exudation on soil solution properties (pH, dissolved organic carbon (DOC), metal solubility) in the rhizosphere using a rhizobox. Measurement was conducted following the cultivation of Indian mustard in the rhizobox filled four di erent types of heavy metal contaminated soils (two alkaline soils and two acidic soils). The growth of Indian mustard resulted in a significant increase (by 0.6 pH units) in rhizosphere soil solution pH of acidic soils and only a slight increase (< 0.1 pH units) in alkaline soils. Furthermore, the DOC concentration increased by 17–156 mg/L in the rhizosphere regardless of soil type and the extent of contamination, demonstrating the exudation of DOC from root. Ion chromatographic determination showed a marked increase in the total dissolved organic acids (OAs) in rhizosphere. While root exudates were observed in all soils, the amount of DOC and OAs in soil solution varied considerably amongst di erent soils, resulting in significant changes to soil solution metals in the rhizosphere. For example, the soil solution Cd, Cu, Pb, and Zn concentrations increased in the rhizosphere of alkaline soils compared to bulk soil following plant cultivation. In contrast, the soluble concentrations of Cd, Pb, and Zn in acidic soils decreased in rhizosphere soil when compared to bulk soils. Besides the influence of pH and DOC on metal solubility, the increase of heavy metal concentration having high stability constant such as Cu and Pb resulted in a release of Cd and Zn from solid phase to liquid phase.     

Free cupric ions in contaminated agricultural soils around a copper mine in eastern Nanjing City, China

To determine the environmental free metal ion activity was a recent hot issue. A method to measure low-level free cupric ion activity in soil solution extracted with 0.01 mol/L KNO3 was developed by using cupric ion-selective electrode （ISE） and calibrating with Cu-buffer solution. Three copper buffers including iminodiacetic acid （IDA）, ethylenediamine （EN）, and glycine （Gly） were compared for calibrating the Cu-ISE curves in the range of free cupric ions （pCu^2＋） 7-13. The Cu-EN buffer showed the best electrode response and thus was applied as the calibration buffer. The pCu^2＋ of 39 contaminated agricultural soils around a copper mine was measured, ranging from 5.03 to 9.20. Most Cu in the soil solutions was found to be complexed with dissolved soil organic matters, averaging 98.1%. The proportion of free Cu^2＋ ions in the soil solutions decreased with the increasing of solution pH. Soluble Cu and free Cu^2＋ ions concentrations were analyzed by multiple linear regressions to evaluate the effects of soil properties on metal levels and speciation. The results showed that soil solution pH was the most significant factor influencing pCu^2＋ （with R^2 value of 0.76）, while not important for the soluble Cu concentration.     

Catchment soils as a factor of trace metal accumulation in sediments of the reservoir Klingenberg (eastern Ore Mountains, Germany)

The release and accumulation dynamics of trace metals in soils and aquatic sediments were exemplarily investigated in the catchment area of the Reservoir Klingenberg(Germany). Catchment soils were examined for mobilizable and total concentrations of arsenic(As), cadmium(Cd), chrome(Cr), iron(Fe), manganese(Mn), nickel(Ni), lead(Pb),and zinc(Zn) and compared with trace metal quantities accumulated in riverbed and reservoir sediments. The comparison of all samples showed relatively small variations of Cr(7.96–46.0 mg/kg), Fe(7.79–40.4 g/kg), and Ni(6.06–56.5 mg/kg), while stronger differences were found for As(11.2–164 mg/kg), Cd(0.14–30.5 mg/kg), Mn(0.08–1.84 g/kg), Pb(20.7–183 mg/kg), and Zn(69.1–916 mg/kg). The catchment soils were slightly enriched by Cd, Pb, and Zn. Especially Cd and Zn were characterized by large mobilizable proportions.The mean trace metal concentrations in riverbed sediments were higher than in catchment soils, while reservoir sediments accumulated the highest amounts of the analyzed elements. The enrichment of trace metals in reservoir sediments was generally determined by the sedimentation of fine particles, while the distribution of As, Fe, and Mn was additionally impacted by redox conditions. For Cd and Zn, which in comparison were most enriched in riverbed and reservoir sediments, a significant release from soils by leaching processes was observed. The accumulation of As and Pb in reservoir sediments was influenced to a greater extent by soil erosion and by anthropogenic or chalcogen sources in the catchment.     

Effect of incubation temperature and wet-dry cycle on the availabilities of Cd, Pb and Zn in soil

The effect of incubation temperature and wet-dry cycle on the availabilities of Cd, Pb and Zn was studied. Three soils with pH ranging from 3.8 to 7.3, organic carbon （OC） from 0.7% to 2.4%, and clay from 12.3% to 35.6% were selected. Soils were spiked with reagent grade Cd（NO3）2, Pb（NO3）2, and Zn（NO3）2 at concentrations of 30 mg Cd/kg soil, 300 mg Zn/kg soil and 2000 mg Pb/kg soil. The soils were incubated at 35, 60, 105℃, respectively and went through four wet-dry cycles. Metal availability in soils was estimated by soil extraction with 0.1 mol/L Ca（NO3）2. According to this study, the effect of the spiking temperature on the metal availabilities was different among the metals, soils and wet-dry cycles. Mostly, 35 ~C was the first recommended spiking temperature for Cd and Pb while no spiking temperature was obviously better than others for Zn. Three wet-dry cycles was recommended regardless of the type of metals and incubation temperature.     

Risk assessment of heavy metal contaminated soil in the vicinity of a lead/zinc mine

Heavy metal contamination of soils through anthropogenic activities is a widespread and serious problem confronting scientists and regulators throughout the world. In this study we investigated the distribution, chemical species and availability of lead, zinc, cadmium and copper in nine surface（0 to 20 cm） soils from near an abandoned lead/zinc mine tailings located in Shaoxing, Zhejiang, China. Total heavy metal contents ranged from 5271 to 16369 mg/kg for Pb, 387 to 1221 mg/kg for Zn, 3.0 to 9.3 mg/kg for Cd and 65 to 206 mg/kg for Cu. In general, all heavy metals exceeded China National Standards for Soil Environmental Quality of Heavy Metals by a factor of 3-65 times. Comparison of the heavy metal concentrations（Pb, Zn, Cd and Cu） with clay content revealed a strongly significant relationship while significant relationship（ P 〈 0.001 ） was also obtained between Cd ＋ Zn and Pb ＋ Cu. Solid phase speciation of the soils using Tessier procedure showed that the heavy metals were distributed in the order： residual 〉〉 organically complexed-Fe-Mn oxides occluded 〉 carbonate bound 〉 exchangeable 〉 water soluble. In the organic matter fraction, the ratio of Pb（29.1% ） to its total concentration in the soils was higher than those of Zn（4.70% ）, Cd（3.16% ） and Cu（9.50% ）. The percentages of the water soluble and the exchangeable fractions of Pb（1.80% ） and Cd（2.74% ） were markedly greater than those of Zn（0.10% ） and Cu（0.15% ）, suggesting that Pb and Cd are relatively more mobile and hence more toxic in the contaminated soils. Strongly significant relationships between H20-Pb, H20-Zn and H20-Cu, strong positive correlations between H20-Pb, H20-Zn, H20-Cu and organic matter in soil were found. The content of H20-Pb, H20-Zn, H20-Cu was negatively correlated with pH values. The similar negative relationships between pH values and exchangeable heavy metals were also recorded. It is suggested that increasing soil pH or liming the soil could decrease bioavailability of heavy metals in the soil.     

Removal of heavy metals from a contaminated soil using tartaric acid

This study reports the feasibility of remediation of a heavy metal （HM） contaminated soil using tartaric acid, an environmentally-friendly extractant. Batch experiments were performed to test the factors influencing remediation of the HM contaminated soil. An empirical model was employed to describe the kinetics of riM dissolution/desorption and to predict equilibrium concentrations of HMs in soil leachate. The changes of HMs in different fractions before and after tartaric acid treatment were also investigated. Tartaric acid solution containing HMs was regenerated by chestnut shells. Results show that utilization of tartaric acid was effective for removal of riMs from the contaminated soil, attaining 50%-60% of Cd, 40%-50% of Pb, 40%-50% of Cu and 20%-30% of Zn in the pH range of 3.5-4.0 within 24 h. Mass transfer coefficients for cadmium （Cd） and lead （Pb） were much higher than those for copper （Cu） and zinc （Zn）. Sequential fractionations of treated and untreated soil samples showed that tartaric acid was effective in removing the exchangeable, carbonate fractions of Cd, Zn and Cu from the contaminated soil. The contents of Pb and Cu in Fe-Mn oxide fraciton were also significantly decreased by tartaric acid treatment. One hundred milliliters of tartaric acid solution containing HMs could be regenerated by 10 g chestnut shells in a batch reactor. Such a remediation procedure indicated that tartaric acid is a promising agent for remediation of HM contaminated soils. However, further research is needed before the method can be practically used for in situ remediation of contaminated sites.     

Removal of heavy metals and arsenic from a co-contaminated soil by sieving combined with washing process

Batch experiments were conducted with a heavy metals and arsenic co-contaminated soil from an abandoned mine to evaluate the feasibility of a remediation technology that combines sieving with soil washing.Leaching of the arsenic and heavy metals from the different particle size fractions was found to decrease in the order: 0.1,2–0.1,and 2 mm.With increased contact time,the concentration of heavy metals in the leachate was significantly decreased for small particles,probably because of adsorption by the clay soil component.For the different particle sizes,the removal efficiencies for Pb and Cd were75%–87%,and 61%–77% for Zn and Cu,although the extent of removal was decreased for As and Cr at 45%.The highest efficiency by washing for Pb,Cd,Zn,and As was from the soil particles 2 mm,although good metal removal efficiencies were also achieved in the small particle size fractions.Through SEM-EDS observations and correlation analysis,the leaching regularity of the heavy metals and arsenic was found to be closely related to Fe,Mn,and Ca contents of the soil fractions.The remediation of heavy metal-contaminated soil by sieving combined with soil washing was proven to be efficient,and practical remediation parameters were also recommended.     

Factors influencing the contents of metals and As in soils around the watershed of Guanting Reservoir, China

Topsoil samples from 61 sites around the Guanting Reservoir,China,were measured for Cu,Zn,Cr,Ni,Cd,Pb and As concentrations.The mean concentrations of Cu,Zn,Cr,Ni,Cd,Pb and As were 16.8,59.4,37.8,18.3,0.32,20.1 and 8.67 mg/kg dry weight,respectively.Factors that influence the dynamics of these metals in soils around the watersheds of Beijing reservoirs were examined.The influence of atmospheric deposition,land use,soil texture,soil type and soil chemical parameters on metal contents in soils was investigated.Atmospheric deposition,land use and soil texture were the important factors affecting heavy metal residues.Soil type and soil chemical parameters were also involved in heavy metal retention in soils.The data provided in this study are considered crucial for reservoir remediation,especially since the Guanting Reservoir will serve as one of the main drinking water sources for Beijing in the foreseeable future.     

Heavy metal concentrations in redeveloping soil of mine spoil under plantations of certain native woody species in dry tropical environment, India

Total concentration of heavy metals(Cd, Cr, Cu, Fe, Pb, Ni, Mn and Zn) was estimated in the redeveloping soil of mine spoil under 5-yr old plantations of four woody species namely: Albizia lebbeck, Albizia procera, Tectona grandis and Dendrocalamus strictus.The data recorded in the present study were compared with other unplanted coal mine spoil colliery, which was around to the study site and adjoining area of dry tropical forest. Among all the heavy metals, the maximum concentration was found for Fe and minimum for Cd.However, among all four species, total concentrations of these heavy metals were recorded maximally in the plantation plots of T. grandis except for Fe, while minimally in A. lebbeck except for Zn, whereas, the maximum concentration of Fe and Zn was in the plantation plots of D. strictus and A. procera. Statistical analysis revealed significant differences due to species for all the heavy metals except Cu.Among four species, A. lebbeck, A. procera and D. strictus showed more efficient for reducing heavy metal concentrations whereas T. grandis was not more effective to reduce heavy metal concentrations in redeveloping soil of mine spoil.     

Heavy metal （Pb,Zn） uptake and chemical changes in rhizosphere soils of four wetland plants with different radial oxygen loss

Lead and Zn uptake and chemical changes in rhizosphere soils of four emergent-rooted wetland plants; Aneilema bracteatum, Cyperus alternifolius, Ludwigia hyssopifolia and Veronica serpyllifolia were investigated by two experiments: (1) rhizobag filled with “clean” or metal-contaminated soil for analysis of Pb and Zn in plants and rhizosphere soils; and (2) applied deoxygenated solution for analyzing their rates of radial oxygen loss (ROL). The results showed that the wetland plants with di erent ROL rates had significant e ects on the mobility and chemical forms of Pb and Zn in rhizosphere under flooded conditions. These e ects were varied with di erent metal elements and metal concentrations in the soils. Lead mobility in rhizosphere of the four plants both in the “clean” and contaminated soils was decreased, while Zn mobility was increased in the rhizosphere of the “clean” soil, but decreased in the contaminated soil. Among the four plants, V. serpyllifolia, with the highest ROL, formed the highest degree of Fe plaque on the root surface, immobilized more Zn in Fe plaque, and has the highest e ects on the changes of Zn form (EXC-Zn) in rhizosphere under both “clean” and contaminated soil conditions. These results suggested that ROL of wetland plants could play an important role in Fe plaque formation and mobility and chemical changes of metals in rhizosphere soil under flood conditions.     

重金属在松花江沉积物中的竞争吸附行为及pH的影响

研究了复合污染的重金属体系(多元体系)中松花江沉积物吸附Hg2+,Cu2+,Pb2+,Zn2+和Cd2+的热力学和动力学特征,以及pH对重金属吸附量的影响. 结果表明:Langmuir吸附等温线可以很好地描述多元体系中沉积物吸附重金属的热力学过程,沉积物吸附5种重金属离子能力的顺序为Hg2+>Cu2+>Pb2+>>Zn2+> Cd2+. 在相同的条件下,与单一体系相比,多元体系中Pb2+,Zn2+和Cd2+吸附量减小的程度远远大于Hg2+和Cu2+,Pb2+,Zn2+和Cd2+的吸附量分别减少了31.9%,32.1%和68.1%. 一级动力学方程和Langmuir动力学方程可以较好地描述沉积物吸附Hg2+,Cu2+,Pb2+,Zn2+和Cd2+的动力学过程. 沉积物对5种重金属的吸附速率为Cd2+>Zn2+>Pb2+>Cu2+>Hg2+. 沉积物对Cu2+,Pb2+,Zn2+和Cd2+的吸附能力随pH的降低而减小,pH的降低造成锰氧化物的溶解,可能在一定程度上影响沉积物对重金属的吸附能力.      

Heavy metals removal from aqueous solution using carbonaceous K_2S-impregnated adsorbent

A novel carbonaceous adsorbent for heavy metal removal was prepared from raw coal by one-step simple sulfur impregnation using K_2S. Raw coal was mixed with K_2S powder and then heated at 800℃ for 30 min in nitrogen to produce K_2S char. The sulfur content and form in K_2S char were determined, and the ability of K_2S char to adsorb Zn~(2+), Cd~(2+) and Pb~(2+) was examined. The K_2S impregnation was effective at impregnating sulfur into coal, especially in the form of elemental, thiophenic and sulfatic sulfur. The sulfur content of K_2S char was higher than those of raw coal and pyrolysis char. The Zn~(2+) removal in 2.4 mmol/L of Zn~(2+) solution by K_2S char was higher than raw coal with the removal rate of 100%. K_2S char adsorbed Pb~(2+) and Cd~(2+) in 24 mmol/L of Pb~(2+) and Cd~(2+) solution with the removal rate of 97 % and 35 %, respectively. The elution extents of adsorbed Pb~(2+) and Cd~(2+) were zero in distilled water and 27% in 0.1 mol/L HCl solution. These results indicated that an effective adsorbent for heavy metal ions was prepared from coal using K_2S sulfur impregnation, and that the adsorbed metals were strongly retained in K_2S char.     

电炉钢渣对水中Cu2+、Cd2+和Pb2+的去除作用

以宝钢电炉钢渣为研究对象,考察了钢渣对溶液中重金属离子Cu2+、Cd2+、Pb2+的吸附动力学、吸附等温线、吸附热力学特征,借助多种分析手段(XRD、BET比表面分析、SEM/EDS等)对钢渣进行了理化性能测试和表征.结果表明,电炉钢渣对重金属离子的吸附速率较快,吸附速率顺序为Cd2+>Pb2+>Cu2+,吸附过程符合一级动力学模型(R2>0.99).吸附等温实验结果表明,Langmuir模型较为适合重金属离子在钢渣上的吸附,实验条件下对Cu2+、Cd2+、Pb2+离子的最大吸附容量分别为0.101、0.058、0.120 mmol.g-1.3种重金属离子在钢渣上的吸附是一个吸热(ΔH0<0)、熵值增大(ΔS0>0)的自发反应过程(ΔG0<0),熵效应是吸附反应自发进行的主要驱动力.SEM/EDS分析结果揭示了吸附前后钢渣表面形貌和化学成分的变化.电炉钢渣以其低价、高效性在重金属废水处理中具有广阔的应用前景.     

固定化活性污泥吸附重金属离子的试验研究

讨论了固定化活性污泥对重金属离子的吸附。在实验条件下 ,温度对固定化活性吸附金属的影响并不显著 ,而体系pH值和底物浓度的影响较为重要 ,固定化活性污泥对Cu2 + 的吸附符合Langmuir模型。研究了固定化细胞填充柱对各种金属离子的吸附特性和选择性 ,固定化活性污泥对Cu2 + 离子的吸附性能明显高于Cd2 + 和Zn2 + 。     

重金属离子对生物污泥活性的抑制

研究了工业废水中常见的Cd~(2+)、Ni~(2+)、Cr~(6+)、Zn~(2+)、Cu~(2+)、Al~(3+)和Fe~(3+)七种重金属离子对生物污泥的抑制作用。发现其抑制的机理各不相同,前五种为不可逆抑制,污泥经过洗涤,活性不易恢复,而后二种为可逆抑制,污泥洗涤后,活性能基本恢复。试验还发现,几种金属离子同时存在时,抑制性比单一金属离子强。金属离子会在污泥中积聚,因此,即使废水中浓度很低,长期接触也会使生物污泥活性降低。     

单一重金属污染对水稻叶片光合特性的影响

以杂交稻协优818为材料，研究了Cu^2＋、Hg^2＋、Cd^2＋ 3种重金属离子对水稻叶片光合特性的影响。试验结果表明：（1）Cu^2＋在低浓度时BI起叶片叶绿素含量降低。而Hg^2＋、Cd^2＋在低浓度时。则导致叶绿素含量增加：高浓度时，3种重金属均BI起叶绿素含量降低。同时，低浓度时3种重金属离子均导致叶绿素a／b值升高：高浓度时则均引起叶绿素a／b值下降。（2）Cu^2＋、Hg^2＋、Cd^2＋对水稻叶片叶绿素的吸收光谱均无明显影响，在活体条件下并未发生卟啉环中Mg^2＋的置换。（3）Cu^2＋、Hg^2＋、Cd^2＋均引起叶片希尔反应活力降低，即重金属污染明显影响光合作用。     

十二烷基磺酸钠(SDS)改性蒙脱石对Cu~(2+)、Cd~(2+)的吸附研究

以阴离子表面活性剂(十二烷基磺酸钠,SDS)为改性剂制备了有机蒙脱石,研究其对Cu2+、Cd2+的吸附行为,并用XRD、FTIR、SEM、XPS对有机蒙脱石进行表征.实验结果表明,有机蒙脱石对Cu2+、Cd2+的吸附基本上在20min内达到平衡,并随pH增大(1.0～7.0),吸附量增加,最佳pH约为6.0.有机蒙脱石对Cu2+、Cd2+的吸附等温线更符合Langmuir等温吸附方程,SDS改性蒙脱石对Cu2+、Cd2+的最大吸附量较纯蒙脱石分别增加15.7%、15.5%.XRD、FTIR、SEM、XPS及碳含量分析结果显示,SDS主要分布在蒙脱石表面且相对稳定,少量嵌入层间,有机蒙脱石对Cu2+、Cd2+的吸附机制为配位吸附和离子交换.     

Cu~(2+)和Zn~(2+)对日本新糠虾生长、蛋白含量和体内磷酸酶活性的影响

观察了不同浓度(10、20、40和80 μg/L)重金属离子Cu~(2+)和Zn~(2+)对日本新糠虾存活、蜕皮、蛋白含量和体内磷酸酶(碱性磷酸酶和酸性磷酸酶)活性的慢性(30 d)影响.结果显示:(1)Cu~(2+)和Zn~(2+)能明显降低糠虾存活率,金属离子浓度增高,存活率降低,其中Cu~(2+)引起的存活率降低更为明显,在最高浓度(80 μg/ L)Cu~(2+)组中糠虾的存活率仅为同浓度Zn~(2+)组的1/3,两组均明显低于对照组(P<0.05);Cu~(2+)和Zn~(2+)能明显降低糠虾蜕皮次数,最高浓度(80 μg/ L)Cu~(2+)和Zn~(2+)中糠虾的蜕皮数分别为11.00±1.73(次)和11.33±0.58(次),分别约为对照组的55.92%和57.6%.(2)Cu~(2+)和Zn~(2+)均能明显影响糠虾蛋白含量,其中Cu~(2+)的影响力更强,最高浓度(80 μg/ L)Cu~(2+)组糠虾体内蛋白白含量占湿重比为9.78%,仅约为对照组的1/2.(3)Cu~(2+)和Zn~(2+)能明显抑制糠虾体内两种磷酸酶的活力,碱性磷酸酶和酸性磷酸酶活力能作为糠虾监测环境重金属污染(Cu~(2+)和Zn~(2+))的检测指标.     

垃圾渗滤液水溶性有机物对土壤吸附重金属Cd2+、Pb2+的影响

采用序批次吸附试验,研究了不同填埋年限(0、4～5、12a)垃圾渗滤液中的DOM对土壤吸持重金属Cd2 、Pb2 的影响.结果表明,垃圾渗滤液中的DOM能促进土壤对重金属Cd2 、Pb2 的吸附.在有垃圾渗滤液DOM存在的条件下,Cd2 、Pb2 的吸附等温线可用Freundlich方程拟合(R2＞0.94),土壤对Cd2 、Pb2 的吸附量比对照处理(无垃圾渗滤液DOM)分别高1.13～1.42倍和1.09～1.84倍,填埋年限长的垃圾渗滤液较之填埋年限短的渗滤液对土壤吸附Cd2 、Pb2 的影响强烈.在Cd2 、Pb2 初始浓度相同时,潮土较红壤具有更高的吸持能力,并且随体系pH的增高,其吸持量增加.     

离子交换树脂吸附Cd(Ⅱ)和Pb(Ⅱ)的研究

采用静态法和动态法对阳离子交换树脂吸附Cd(Ⅱ)、Pb(Ⅱ)的行为进行了研究。考察了pH值、流速、吸附时间等条件对吸附效果的影响,优化了树脂洗脱再生的最佳条件。实验结果表明,732型强酸阳离子交换树脂能够有效地吸附废水中的Cd(Ⅱ)和Pb(Ⅱ)。对比两种交换方式,动态法具有操作简单、效率高、可连续运行等特点,具有较高的实用价值。