底泥生长基质中重金属的迁移特征及生物有效性

河道底泥中重金属含量较高,重金属的迁移性及生物有效性是限制疏浚底泥土地施用或用作废弃场地修复基质资源化利用途径的主要因素。以沈阳细河待疏浚底泥为材料,通过盆栽实验的方法研究了河道底泥与碱性粉煤灰、炉渣和锯木屑配比基质中重金属在紫花苜蓿体内累积、迁移及生物有效性的变化。结果发现,配比底泥基质上紫花苜蓿生物量、株高及株径均好于纯底泥处理,其中底泥、粉煤灰、炉渣、锯木屑以2：0．5：0．5：0．5配比的s2处理中紫花苜蓿生物量是纯底泥处理的11．7倍。与底泥对照相比,配比底泥基质上植株体内重金属含量极显著降低,而且地上部重金属含量显著低于根部含量;底泥基质中紫花苜蓿地上部和根部对Cd、Cu、Pb、Zn的富集系数（BCF）显著低于底泥处理,但转移系数（TF）无显著变化,富集系数（BCF）和转移系数（TF）均小于1．0。紫花苜蓿种植后底泥基质中重金属含量显著低于农用污泥重金属控制标准,除Cd含量略高外,Cu、Pb和Zn含量低于土壤环境质量三级标准。这些结果表明,城市重污染河道底泥经过合理处置后,重金属浓度、活性及生物有效性降低,在其土地施用或废弃地修复中可以用作一些耐性植物的生长基质。     

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 phosphate on the adsorption of Cu and Cd on natural hematite

Interactions between anions and cations are important to understand the chemical processes of pollutants in environment. In this study, batch experiments were carried out to investigate the simultaneous adsorption of Cu and Cd on hematite as affected by phosphate. Phosphate pretreatment suppressed the maximum adsorption of Cu and Cd on hematite and moved the adsorption pH edges to a higher pH range. Phosphate application time had a marked impact on Cu and Cd adsorption and longer contact time resulted in more reduction of Cu and Cd adsorption. Results of back-titration, Fourier transform infrared (FTIR) spectroscopy study and ionic strength effect on the adsorption revealed that Cu and Cd were adsorbed on hematite mainly through the inner-sphere complex formation mechanism and phosphate treatment reduced the inner-sphere adsorption sites, thus decreasing Cu and Cd adsorption on hematite.     

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。     

Relation between extracellular polymers' composition and its ability to complex Cd,Cu and Pb

Activated sludges originated from wastewater treatment plants (WWTPs) play an important role in heavy metal removal from effluents. Extracellular polymers (ECP) form a major part of the activated sludge and are heavily involved in biosorption of heavy metals. The complexation of three heavy metals (Cd, Cu and Pb) with ECP extracted from six activated sludges, originated from different WWTPs, was investigated at pH 7.

ECP in the study were shown to be mainly composed of proteins, humic acids, uronic acids and polysaccharides along with smaller amounts of lipids and nucleic acids. IR spectra confirmed the presence of the functional groups usually found in the ECP and the content in each fraction was determined using colorimetric methods. The determination of surface charge was carried out on each ECP sample and allowed two pK_a values characteristic of two distinctive functional groups to be determined. At the pH used in the study, the value of these constants indicates that only one functional group is under protonated form.

A polarographic method was used to determine the complexation parameters (number of binding sites and complexation constant) of ECP solutions towards metals. The following orders were established for the number of binding sites: Cu > Pb  Cd and for the stability of the ECP–metal complex: Cd > Pb  Cu.

A matrix of correlation between the composition of the polymers and the complexation parameters showed that the number of binding sites and the complexation constant were strongly linked to proteins, polysaccharides and humic substances content.     

Uptake and distribution of Zn, Cu, Cd, and Pb in an aquatic plant Potamogeton natans

A better understanding of metal uptake and translocation by aquatic plants can be used to enhance the performance of constructed wetland systems for stormwater treatment. Specifically, this study examines whether the uptake of Zn, Cu, Cd, and Pb by Potamogeton natans is via the leaves, stems, or roots, and whether there is translocation from organs of uptake to other plant parts. Competition between the metals at uptake and at the level of the cell wall-bound part of the metals accumulated in stem and leaf tissue was also examined. The results show that Zn, Cu, Cd, and Pb were taken up by the leaves, stems, and roots, with the highest accumulation found in the roots. At the elevated metal concentrations common in stormwater the uptake of Cu, but not of Zn, Cd, or Pb, by the roots was somewhat limited at uptake due to competition with other metals. Between 24% and 59% of the metal content was bound to the cell walls of the plant. Except in the case of Pb, the cell wall-bound fraction was generally smaller in stems than in leaves. No translocation of the metals to other parts of the plant was found, except for Cd which was translocated from leaf to stem and vice versa. Dispersion of metals from sediment to water through P. natans is therefore unlikely.     

Leaching behaviour of Cd, Cu, Pb and Zn in surface soils derived from dredged sediments

Leaching of heavy metals from land-disposed dredged sediment spoils is a potential environmental hazard. The leaching behavior of Cd, Cu, Pb and Zn in surface soils sampled from abandoned dredged sediment disposal sites was assessed. Using simple mass-balance calculations, the significance of the leaching test results with respect to metal migration into underlying clean soil was appraised. The potential leachability, defined as the amounts released at constant pH 4, decreased in the order (% of total contents): Zn (58%) approximately equal to Cd (49%)>Cu (5%) approximately equal to Pb (2%). The kinetics of metal release were determined in a cascade shaking test using de-mineralized water acidified to pH 4 (HNO(3)). Metal concentrations in the leachates were low and metal migration was, assuming uniform convective flow, predicted to be of no environmental concern. It is emphasized that any long-term prediction of metal migration is uncertain.     

矿区土壤中重金属元素含量异常的调查

对某金矿区下游土壤重金属元素含量异常区进行了调查,研究了异常元素的空间分布和相态组成.通过对土壤、水、农产品、大气沉降物等的采样分析表明,土壤中重金属元素含量异常是由于矿山开采,废水排放,下游引水灌溉造成的.对异常元素的环境影响进行了分析评价,并提出了土壤治理建议.     

Dynamic modelling of atmospherically-deposited Ni, Cu, Zn, Cd and Pb in Pennine catchments (northern England)

Simulation modelling with CHUM-AM was carried out to investigate the accumulation and release of atmospherically-deposited heavy metals (Ni, Cu, Zn, Cd and Pb) in six moorland catchments, five with organic-rich soils, one with calcareous brown earths, in the Pennine chain of northern England. The model considers two soil layers and a third layer of weathering mineral matter, and operates on a yearly timestep, driven by deposition scenarios covering the period 1400-2010. The principal processes controlling heavy metals are competitive solid-solution partitioning of solutes, chemical interactions in solution, and chemical weathering. Agreement between observed and simulated soil metal pools and surface water concentrations for recent years was generally satisfactory, the results confirming that most contemporary soil metal is from atmospheric pollution. Metals in catchments with organic-rich soils show some mobility, especially under more acid conditions, but the calcareous mineral soils have retained nearly all anthropogenic metal inputs. Complexation by dissolved organic matter and co-transport accounts for up to 80% of the Cu in surface waters.     

Genotypic variations in the accumulation of Cd, Cu, Pb and Zn exhibited by six commonly grown vegetables

Metal contaminants in garden and allotment soils could possibly affect human health through a variety of pathways. This study focused on the potential pathway of consumption of vegetables grown on contaminated soil. Five cultivars each of six common vegetables were grown in a control and in a soil spiked with Cd, Cu, Pb and Zn. Highly significant differences in metal content were evident between cultivars of a number of vegetables for several of the contaminants. Carrot and pea cultivars exhibited significant differences in accumulated concentrations of Cd and Cu with carrot cultivars also exhibiting significant differences in Zn. Distinctive differences were also identified when comparing one vegetable to another, legumes (Leguminosae) tending to be low accumulators, root vegetables (Umbelliferae and Liliaceae) tending to be moderate accumulators and leafy vegetables (Compositae and Chenopodiaceae) being high accumulators.     

Heavy metal (Cu,Cd, Pb,Cr) washing from river sediment using biosurfactant rhamnolipid

Heavy metal-contaminated sediments posed a serious threat to both human beings and environment. A biosurfactant, rhamnolipid, was employed as the washing agent to remove heavy metals in river sediment. Batch experiments were conducted to test the removal capability. The effects of rhamnolipid concentration, washing time, solution pH, and liquid/solid ratio were investigated. The speciation of heavy metals before and after washing in sediment was also analyzed. Heavy metal washing was favored at high concentration, long washing time, and high pH. In addition, the efficiency of washing was closely related to the original speciation of heavy metals in sediment. Rhamnolipid mainly targeted metals in exchangeable, carbonate-bound or Fe-Mn oxide-bound fractions. Overall, rhamnolipid biosurfactant as a washing agent could effectively remove heavy metals from sediment.

     

Effect of biochars on adsorption of Cu(II), Pb(II) and Cd(II) by three variable charge soils from southern China

The purpose of this study is to compare the relative contribution of different mechanisms to the enhanced adsorption of Cu(II), Pb(II) and Cd(II) by variable charge soils due to incorporation of biochars derived from crop straws. The biochars were prepared from the straws of canola and peanut using an oxygen-limited pyrolysis method at 350 °C. The effect of biochars on adsorption and desorption of Cu(II), Pb(II) and Cd(II) by and from three variable charge soils from southern China was investigated with batch experiments. Based on the desorption of pre-adsorbed heavy metals, the electrostatic and non-electrostatic adsorptions were separated. EDTA was used to replace the heavy metals complexed with biochars and to evaluate the complexing ability of the biochars with the metals. The incorporation of biochars increased the adsorption of Cu(II), Pb(II) and Cd(II) by the soil; peanut straw char induced a greater increase in the adsorption of the three metals. The increased percentage of Cd(II) adsorption induced by biochars was much greater than that for the adsorption of Cu(II) and Pb(II). Cu(II) adsorption on three variable charge soils was enhanced by the two biochars mainly through a non-electrostatic mechanism, while both electrostatic and non-electrostatic mechanisms contributed to the enhanced adsorption of Pb(II) and Cd(II) due to the biochars. Peanut straw char had a greater specific adsorption capacity than canola straw char and thus induced more non-electrostatic adsorption of Cu(II), Pb(II) and Cd(II) by the soils than did the canola straw char. The complexing ability of the biochars with Cu(II) and Pb(II) was much stronger than that with Cd(II) and thus induced more specific adsorption of Cu(II) and Pb(II) by the soils than that of Cd(II). Biochars increased heavy metal adsorption by the variable charge soils through electrostatic and non-electrostatic mechanisms, and the relative contribution of the two mechanisms varied with metals and biochars.     

Role of microbial inoculation and chitosan in phytoextraction of Cu, Zn, Pb and Cd by Elsholtzia splendens--a field case

A field experiment was carried out to study the effect of microbial inoculation on heavy metal phytoextraction by Elsholtzia splendens and whether chitosan could have a synergistic effect with the microbial inocula. The microbial inocula consisted of a consortium of arbuscular mycorrhizal fungi and two Penicillium fungi. Three treatments were included: the control, inoculation with microbial inocula, and the inoculation combined with chitosan. Microbial inoculation increased plant biomass especially shoot dry weight, enhanced shoot Cu, Zn and Pb concentrations but did not affect Cd, leading to higher shoot Cu, Zn, Pb and Cd uptake. Compared with microbial inoculation alone, chitosan application did not affect plant growth but increased shoot Zn, Pb and Cd concentrations except Cu, which led to higher phytoextraction efficiencies and partitioning to shoots of Zn, Pb and Cd. These results indicated synergistic effects between microbial inocula and chitosan on Zn, Pb and Cd phytoextraction.     

Leaching of Cu,Cd, Pb,and phosphorus and their availability in the phosphate-amended contaminated soils under simulated acid rain

Environmental Science and Pollution Research - Phosphate amendments have been used to immobilize heavy metal-contaminated soils. However, phosphate amendments contain large amounts of phosphorus,...     

Modelling equilibrium adsorption of single,binary, and ternary combinations of Cu,Pb, and Zn onto granular activated carbon

Environmental Science and Pollution Research - Elevated concentrations of heavy metals in water can be toxic to humans, animals, and aquatic organisms. A study was conducted on the removal of Cu,...     

The solid-solution partitioning of heavy metals (Cu,Zn, Cd,Pb) in upland soils of England and Wales

Ninety-eight surface soils were sampled from the uplands of England and Wales, and analysed for loss-on-ignition (LOI), and total and dissolved base cations, Al, Fe, and trace heavy metals (Cu, Zn, Cd, Pb). The samples covered wide ranges of pH (3.4-8.3) and LOI (9-98%). Soil metal contents measured by extraction with 0.43 mol l-1 HNO3 and 0.1 mol l-1 EDTA were very similar, and generally lower than values obtained by extraction with a mixture of concentrated nitric and perchloric acids. Total heavy metal concentrations in soil solution depend positively upon soil metal content and [DOC], and negatively upon pH and LOI, values of r2 ranging from 0.39 (Cu) to 0.81 (Pb). Stronger correlations (r2=0.76-0.95) were obtained by multiple regression analysis involving free metal ion (Cu2+, Zn2+, Cd2+, Pb2+) concentrations calculated with the equilibrium speciation model WHAM/Model VI. The free metal ion concentrations depend positively upon MHNO3 and negatively upon pH and LOI. The data were also analysed by using WHAM/Model VI to describe solid-solution interactions as well as solution speciation; this involved calibrating each soil sample by adjusting the content of "active" humic matter to match the observed soil pH. The calibrated model provided fair predictions of total heavy metal concentrations in soil solution, and predicted free metal ion concentrations were in reasonable agreement with the values obtained from solution-only speciation calculations.     

Distribution of Pb, V, Cr, Ni, Cd, Cu and Fe in particles formed from the combustion of waste oils

The determination of Pb, V, Cr, Ni, Cd, Cu and Fe in particles of different size obtained from the combustion of waste oils has been carried out. The study consists of the separation of several fractions according to the size of particles, the wet digestion and the individual analysis by graphite furnace atomic absorption spectrometry of the mentioned metals. Taking into account the volatilization temperature of different compounds containing the metals and their distribution on the size fractions, the mineral speciation of metals is proposed.     

Kinetic extractions to assess mobilization of Zn, Pb, Cu, and Cd in a metal-contaminated soil: EDTA vs. citrate

Kinetic EDTA and citrate extractions were used to mimic metal mobilization in a soil contaminated by metallurgical fallout. Modeling of metal removal rates vs. time distinguished two metal pools: readily labile (QM1) and less labile (QM2). In citrate extractions, total extractability (QM1+QM2) of Zn and Cd was proportionally higher than for Pb and Cu. Proportions of Pb and Cu extracted with EDTA were three times higher than when using citrate. We observed similar QM1/QM2 ratios for Zn and Cu regardless of the extractant, suggesting comparable binding energies to soil constituents. However, for Pb and Cd, more heterogeneous binding energies were hypothesized to explain different kinetic extraction behaviors. Proportions of citrate-labile metals were found consistent with their short-term, in-situ mobility assessed in the studied soil, i.e., metal amount released in the soil solution or extracted by cultivated plants. Kinetic EDTA extractions were hypothesized to be more predictive for long-term metal migration with depth.     

苯酚和间甲酚的竞争吸附研究

研究了水中苯酚和间甲酚在大孔树脂上的吸附,结果表明,ＩＡＳ及ＬＣＡ模型都能较好地反映这一吸附系统的竞争吸附规律。