Zn, Cd and Pb accumulation and arbuscular mycorrhizal colonisation of pennycress Thlaspi praecox Wulf. (Brassicaceae) from the vicinity of a lead mine and smelter in Slovenia

Significant hyperaccumulation of Zn, Cd and Pb in field samples of Thlaspi praecox Wulf. collected from a heavy metal polluted area in Slovenia was found, with maximal shoot concentrations of 14,590 mg kg(-1) Zn, 5960 mg kg(-1) Cd and 3500 mg kg(-1) Pb. Shoot/root ratios of 9.6 for Zn and 5.6 for Cd show that the metals were preferentially transported to the shoots. Shoot bioaccumulation factors exceeded total soil Cd levels 75-fold and total soil Zn levels 20-fold, further supporting the hyperaccumulation of Cd and Zn. Eighty percent of Pb was retained in roots, thus indicating exclusion as a tolerance strategy for Pb. Low level colonisation with arbuscular mycorrhizal fungi (AMF) of a Paris type was observed at the polluted site, whereas at the non-polluted site Arum type colonisation was more common. To our knowledge this is the first report of Cd hyperaccumulation and AMF colonisation in metal hyperaccumulating T. praecox.     

Evaluation of a biomarker of Cd(II) exposure on Limnoperna fortunei

The use of organisms to monitor contamination allows the access to information that cannot be acquired by chemical methods. Limnoperna fortunei, mussel frequently found in Río de la Plata estuary, fulfils the requirements to be used as a biomonitoring organism. In this work we report that a polypeptide of 22 kDa of molecular weight (LF22) is induced when L. fortunei is exposed to Cd (II), Cu(II) and Hg(II) sublethal levels. To characterize LF22, mussels were sampled from a non-polluted region and whole soft tissue was homogenized, with and without previous exposure to 100 microg/L of Cd(II). The cytosolic proteins were evaluated by mono and bidimensional SDS-PAGE, and size exclusion chromatography. All the methods showed that LF22 triples its concentration in presence of Cd(II). Purification of LF22 was achieved by fractioned precipitation, salting-out, ionic exchange and size exclusion chromatography. We conclude that LF22 is a useful biomarker of heavy metal exposure.     

Activation of cadmium under simulated solar illumination and its impact on the mobility of Cd in flooded soils

In waterlogged paddy soils, cadmium (Cd) can be precipitated as cadmium sulfide (CdS) under reductive environment, thereby limiting the absorption of Cd by plants. Multiple environmental factors (such as water, pH, and Eh) played a role in the control of Cd mobility and bioavailability. In this study, we investigated the influence of the solar irradiation on the photodissolution of synthetic CdS-montmorillonite composites (CdS-M) in solution and the stability of Cd in natural soil. The release kinetic of Cd²⁺ showed that after the irradiation of simulated sunlight, CdS-M composites became less stable compared to the dark control. The solar irradiation seemed to enhance the release of Cd²⁺ from CdS significantly and continuously. Electron paramagnetic resonance (EPR) and quenching experiments confirmed that the photogenerated holes, ?O₂^? and ?OH, were possibly involved in the photo-induced release of Cd²⁺, while the holes was primarily responsible for the reaction. Irradiation under alkaline solution or the presence of DOM, PO₄^3?, CO₃^2?, and urea markedly inhibited the photodissolution process of CdS. The photo-mediated activation of Cd was further confirmed in paddy soil under natural sunlight, with a nearly threefold increase in concentration of extractable Cd during the 15 days of irradiation. This study highlights the importance of photochemical transformation of Cd in the environmental water and soil.

     

Effect of arsenate on adsorption of Cd(II) by two variable charge soils

The effect of arsenate on Cd(II) adsorption in two variable charge soils and the desorption of Cd(II) pre-adsorbed in the presence of arsenate were studied. The batch type experiments showed, the presence of arsenate led to increase in Cd(II) adsorption and the desorption of pre-adsorbed Cd(II). Further it was observed that the extent of adsorption and desorption of Cd(II) was greatly influenced by the initial concentrations of arsenate and Cd(II), the solution pH, and the nature of the soils. In general the increase in arsenate concentration and pH favored the uptake of Cd(II). Moreover, the arsenate concentration influenced more in Hyper-Rhodic Ferralsol than Rhodic Ferralsol at least for the Cd(II) adsorption/desorption. This may be due to the content of Fe/Al oxides in these soils. The larger the content of Fe/Al oxides, the more the adsorption of arsenate by the soil, hence greater the uptake of Cd(II). It can be assumed that the enhanced Cd(II) adsorption was mainly due to the increase in net negative surface charge of the soil induced by the adsorption of arsenate, because the presence of arsenate led to the decrease in zeta potential of these soil suspensions. The increase of electrostatically adsorbed Cd(II) was responsible for the increase in the desorption of Cd(II) pre-adsorbed in the presence of arsenate.     

Column dynamic studies and breakthrough curve analysis for Cd(II) and Cu(II) ions adsorption onto palm oil boiler mill fly ash (POFA)

This paper investigates the adsorption characteristics of palm oil boiler mill fly ash (POFA) derived from an agricultural waste material in removing Cd(II) and Cu(II) from aqueous solution via column studies. The performance of the study is described through the breakthrough curves concept under relevant operating conditions such as column bed depths (1, 1.5, and 2 cm) and influent metal concentrations (5, 10, and 20 mg/L). The Cd(II) and Cu(II) uptake mechanism is particularly bed depth- and concentration-dependant, favoring higher bed depth and lower influent metal concentration. The highest bed capacity of 34.91 mg Cd(II)/g and 21.93 mg Cu(II)/g of POFA was achieved at 20 mg/L of influent metal concentrations, column bed depth of 2 cm, and flow rate of 5 mL/min. The whole breakthrough curve simulation for both metal ions were best described using the Thomas and Yoon–Nelson models, but it is apparent that the initial region of the breakthrough for Cd(II) was better described using the BDST model. The results illustrate that POFA could be utilized effectively for the removal of Cd(II) and Cu(II) ions from aqueous solution in a fixed-bed column system.     

Resuspension of contaminated field and formulated reference sediments Part I: Evaluation of metal release under controlled laboratory conditions

In aquatic systems where metal contaminated sediments are present, the potential exists for metals to be released to the water column when sediment resuspension occurs. The release and partitioning behavior of sediment-bound heavy metals is not well understood during resuspension events. In this study, the release of Cd, Cu, Hg, Ni, Pb and Zn from sediments during resuspension was evaluated using reference sediments with known physical and chemical properties. Sediment treatments with varying quantities of acid volatile sulfide (AVS), total organic carbon (TOC), and different grain size distributions were resuspended under controlled conditions to evaluate their respective effects on dissolved metal concentrations. AVS had the greatest effect on limiting release of dissolved metals, followed by grain size and TOC. Predictions of dissolved concentrations of Cd, Ni, Pb and Zn were developed based on the formulated sediment Σ_metal/AVS ratios with Σ_metal being the total sediment metal concentration. Predicted values were compared to measured dissolved metal concentrations in contaminated field sediments resuspended under identical operating conditions. Metal concentrations released from the field sediments were low overall, in most cases lower than predicted values, reflecting the importance of other binding phases. Overall, results indicate that for sulfidic sediments, low levels of the study metals are released to the dissolved phase during short-term resuspension.     

Role of extracellular compounds in Cd-sequestration relative to Cd uptake by bacterium Sinorhizobium meliloti

The role of bacterially derived compounds in Cd(II) complexation and uptake by bacterium Sinorhizobium meliloti wild type (WT) and genetically modified ExoY-mutant, deficient in exopolysaccharide production, was explored combining chemical speciation measurements and assays with living bacteria. Obtained results demonstrated that WT- and ExoY-strains excreted siderophores in comparable amounts, while WT-strain produced much higher amount of exopolysaccharides and less exoproteins. An evaluation of Cd(II) distribution in bacterial suspensions under short term exposure conditions, showed that most of the Cd is bound to bacterial surface envelope, including Cd bound to the cell wall and to the attached extracellular polymeric substances. However, the amount of Cd bound to the dissolved extracellular compounds increases at high Cd(II) concentrations. The implications of these findings to more general understanding of the Cd(II) fate and cycling in the environment is discussed.     

硝基苯酚类的快速吸附与降解

以对硝基苯酚(PNP)和邻硝基苯酚(ONP)为主要研究对象,采用粉末活性炭和Fenton试剂快速吸附与降解PNP和ONP溶液,使其浓度降至生活饮用水准许浓度(分别为0.02 mg/L和0.06 mg/L)以下,并比较2种物质的处理效果,为硝基苯酚的水体污染治理和废水处理中的深度降解提供依据。结果表明,用粉末活性炭吸附浓度为1 mg/L和4 mg/L的PNP溶液60 min后,浓度低于0.02 mg/L,长时间跟踪监测,污染物浓度仍控制在0.02 mg/L以下,在pH<6时,粉末活性炭吸附PNP的效果较好;用Fenton试剂处理浓度为10 mg/L的PNP溶液70 min后,可完全降解PNP。粉末活性炭吸附12 mg/L的ONP溶液时,效率高于吸附PNP;Fenton试剂处理浓度为12 mg/L的ONP时,与PNP的处理效果相当。     

Vertical Profile of Acid Volatile Sulfide (AVS) and Risk Assessment of Sediments from Baihua Lake,China

Acid volatile sulfide (AVS), simultaneously extracted metals (SEMs), and total concentrations of trace elements (Cu, Cd, Pb, Zn, Ni, Hg, As, and Cr) were studied in sediment cores from Baihua Lake in southwest China. The molar ratios of SEMs to AVS for all samples were lower than 1.0 except for the 25- to 30-cm layer of the sample collected at location YPZ, indicating that the heavy metals were currently not significantly bioavailable as a whole to benthic organisms. Based on the sediment quality guidelines and the potential ecological risk assessment, Hg presented a high ecological risk for the water body.     

Heavy metal uptake by two edible Amaranthus herbs grown on soils contaminated with lead, mercury, cadmium, and nickel

The uptake of an element by a plant is primarily dependent on the plant species, its inherent controls, and the soil quality. Amaranthus hybridus (green herbs) and Amaranthus dubius (red herbs) were chosen to investigate their response and ability to accumulate and tolerate varying levels of elements in their roots and shoots. Red herbs and green herbs were grown in soil pots contaminated with three mixtures of Cd(II), Ni(II), Pb(II), and Hg(II). Plants in the control treatment were grown in the absence of the heavy metals mixture. The distribution of Cd, Ni, Pb, and Hg in the plants (in roots, stems, and leaves) was determined in two stages. Stage 1, after 5 weeks of plant growth and stage 2, full grown after 10 weeks of growth. In the red herbs the Cd concentration in the leaves at stage 2 was 150 ppm and was present in higher concentrations than Ni, Hg, and Pb. At the highest contamination level, in the green herbs plant, Hg was present in the highest concentration in the root, i.e., 336 ppm at stage 1, while the level in the leaves was 7.12 ppm. Both the green and red herbs species showed an affinity for Ni and Cd with moderate to high levels detected in the leaves, respectively.     

pH对污水污泥中污染物浸出的影响

研究pH对污泥中污染物浸出的影响可以为投海过程中海洋水体酸碱性变化对污泥中污染物浸出的影响及其变化规律提供理论依据。为了得出不同pH值对污泥中污染物浸出的影响，采用CEN/TS 14429：2005浸出实验对上海5个污水处理厂脱水污泥中重金属、溶解性有机碳、溶解性硫化物和主要离子的浸出情况进行了研究，同时分别以超纯水和海水为浸提剂研究在相应pH范围内盐度对上述指标浸出的影响。结果表明，Zn、Cd、Pb和As在酸性和碱性条件下浸出量较高，在中性或接近中性条件下浸出量则最低，且海水中Zn和Cd的浸出量比超纯水中高；Cu在碱性条件下的浸出量明显比酸性条件高；在所研究的pH范围内，5个污泥样品中溶解性有机碳的浸出量均随pH的升高而增高；仅酸挥发性硫含量最高的S5在海水中有较明显的溶解性硫化物浸出；部分污泥样品中的氮在酸性纯水中有较高的浸出量，海水中浸出量较少；而无论海水或纯水中，磷在强酸和强碱条件下均有明显浸出。     

Biomass-derived materials in the remediation of heavy-metal contaminated water: removal of Cadmium(II) and copper(II) from aqueous solutions

Manganese-coated activated carbon (MCAC) and activated carbon were used in batch experiments for the removal of cadmium(II) and copper(II). Results showed that uptake of Cd(II) and Cu(II) was unaffected by increases in pH (3.0 to 8.5) or concentration (1 to 20 mg/L). Increased ionic strength (from 0.001 to 1 M NaNO3), however, significantly affected the uptake of Cd(II); adsorption of Cu(II) was not affected. Freundlich adsorption isotherm results indicated that MCAC possessed higher sorption capacity than activated carbon. Second-order rate constants were found to be 0.0386 for activated carbon and 0.0633 g/mg x min for MCAC for Cd(II) and 0.0774 for AC and 0.1223 g/mg x min for MCAC for Cu(II). Column experiments showed that maximum sorption capacity of MCAC was 39.48 mg/g for Cu(II) and 12.21 mg/g for Cd(II).     

棘孢曲霉（Aspergillus aculeatus）对Pb2＋和Cd2＋的吸附特征

为了研究棘孢曲霉（Aspergillus aculeatus）对溶液中Pb^2＋和Cd^2＋吸附过程的特征，分别从动力学、热力学和吸附等温线三方面进行了实验，同时还研究了pH、温度、时间、重金属离子起始浓度和吸附剂用量对吸附过程的影响。等温吸附过程可以用Langmuir方程来描述。在实验设定条件下，棘孢曲霉对Pb^2＋和Cd^2＋最大吸附量分别为71.2 mg/g和59.8 mg/g；动力学实验数据很好的符合二级     

Heavy Metal Uptake by Two Edible Amaranthus Herbs Grown on Soils Contaminated with Lead,Mercury, Cadmium,and Nickel

The uptake of an element by a plant is primarily dependent on the plant species, its inherent controls, and the soil quality. Amaranthus hybridus (green herbs) and Amaranthus dubius (red herbs) were chosen to investigate their response and ability to accumulate and tolerate varying levels of elements in their roots and shoots. Red herbs and green herbs were grown in soil pots contaminated with three mixtures of Cd(II), Ni(II), Pb(II), and Hg(II). Plants in the control treatment were grown in the absence of the heavy metals mixture. The distribution of Cd, Ni, Pb, and Hg in the plants (in roots, stems, and leaves) was determined in two stages. Stage 1, after 5 weeks of plant growth and stage 2, full grown after 10 weeks of growth. In the red herbs the Cd concentration in the leaves at stage 2 was 150 ppm and was present in higher concentrations than Ni, Hg, and Pb. At the highest contamination level, in the green herbs plant, Hg was present in the highest concentration in the root, i.e., 336 ppm at stage 1, while the level in the leaves was 7.12 ppm. Both the green and red herbs species showed an affinity for Ni and Cd with moderate to high levels detected in the leaves, respectively.     

Sorption of Zn(II) in aqueous solutions by scoria

We conducted kinetic and equilibrium sorption experiments on removal of Zn(II) from aqueous solutions by scoria (a vesicular pyroclastic rock with basaltic composition) from Jeju Island, Korea, in order to examine its potential use as an efficient sorbent. The batch-type kinetic sorption tests under variable conditions indicated that the percentage of Zn(II) removal by scoria increases with decreasing initial Zn(II) concentration, particle size, and sorbate/sorbent ratio. However, the sorption capacity decreases with the decrease of the initial Zn(II) concentration and sorbate/sorbent ratio. Equilibrium sorption tests show that Jeju scoria has a larger capacity and affinity for Zn(II) sorption than commercial powdered activated carbon (PAC); at initial Zn(II) concentrations of more than 10mM, the sorption capacity of Jeju scoria is about 1.5 times higher than that of PAC. The acquired sorption data are better fitted to the Langmuir isotherm than the Freundlich isotherm. Careful examination of ionic concentrations in sorption batches suggests that the sorption behavior is mainly controlled by cation exchange and typically displays characteristics of 'cation sorption'. The Zn(II) removal capacity decreases when solution pH decreases because of the competition with hydrogen ions for sorption sites, while the Zn(II) removal capacity increases under higher pH conditions, likely due to hydroxide precipitation. At an initial Zn(II) concentration of 5.0mM, the removal increases from 70% to 96% with the increase of initial pH from 3.0 to 7.0. We recommend Jeju scoria as an economic and efficient sorbent for Zn(II) in contaminated water.     

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.     

Compressed air-assisted solvent extraction (CASX) for metal removal

A novel process, compressed air-assisted solvent extraction (CASX), was developed to generate micro-sized solvent-coated air bubbles (MSAB) for metal extraction. Through pressurization of solvent with compressed air followed by releasing air-oversaturated solvent into metal-containing wastewater, MSAB were generated instantaneously. The enormous surface area of MSAB makes extraction process extremely fast and achieves very high aqueous/solvent weight ratio (A/S ratio). CASX process completely removed Cr(VI) from acidic electroplating wastewater under A/S ratio of 115 and extraction time of less than 10s. When synthetic wastewater containing Cd(II) of 50mgl(-1) was treated, A/S ratios of higher than 714 and 1190 could be achieved using solvent with extractant/diluent weight ratio of 1:1 and 5:1, respectively. Also, MSAB have very different physical properties, such as size and density, compared to the emulsified solvent droplets, making separation and recovery of solvent from treated effluent very easy.     

Biosorption of heavy metals using rice milling by-products. Characterisation and application for removal of metals from aqueous effluents

The morphological characteristics as well as chemical composition of rice husks were evaluated by different techniques such as spectroscopy and thermogravimetry. The material, which is considered a by-product obtained from rice milling, was then investigated as a potential decontaminant of toxic heavy metals present in laboratory effluents. Studies using glass columns were carried out at room temperature employing 100 ml of synthetic solutions containing Cd(II) and Pb(II) at 100 mg l(-1) in order to study the effects of pH, flow rate and particle size on Cd(II) and Pb(II) adsorption. After establishing the optimised conditions, the potentiality of rice husks for removing Cd(II) and Pb(II) ions from 100 ml of laboratory effluent, presenting concentrations before treatment of 22 and 12 mg l(-1), respectively, was evaluated. The ability to take up other metals species, such as Al(III), Cu(II) and Zn(II), present in this effluent was also studied. According to the data obtained, under the optimised conditions (pH=4.0, flow rate of 8.0 ml min(-1) and < or =355 microm rice husk particle size), 30 g of husks were necessary to attain the permissible limits for effluent release, as recommend by the EPA, for those species evolved in this work (Al, Cd, Cu, Pb and Zn).     

Stability of core/shell quantum dots—role of pH and small organic ligands

The improvement of knowledge about the toxicity and even processability, and stability of quantum dots (QD) requires the understanding of the relationship between the QD binding head group, surface structure, and interligand interaction. The scanned stripping chronopotentiometry and absence of gradients and Nernstian equilibrium stripping techniques were used to determine the concentration of Cd dissolved from a polyacrylate-stabilized CdTe/CdS QD. The effects of various concentrations of small organic ligands such as citric acid, glycine, and histidine and the roles of pH (4.5–8.5) and exposure time (0–48 h) were evaluated. The highest QD dissolution was obtained at the more acidic pH in absence of the ligands (52 %) a result of the CdS shell solubility. At pH 8.5 the largest PAA ability to complex the dissolved Cd leads to a further QD solubility until the equilibrium is reached (24 % of dissolved Cd vs. 4 % at pH 6.0). The citric acid presence resulted in greater QD dissolution, whereas glycine, an amino acid, acts against QD dissolution. Surprisingly, the presence of histidine, an amino acid with an imidazole functional group, leads to the formation of much strong Cd complexes over time, which may be non-labile, inducing variations in the local environment of the QD surface.     

Sequential removal of heavy metals ions and organic pollutants using an algal-bacterial consortium

The residual algal-bacterial biomass from photosynthetically supported, organic pollutant biodegradation processes, in enclosed photobioreactors, was tested for its ability to accumulate Cu(II), Ni(II), Cd(II), and Zn(II). Salicylate was chosen as a model contaminant. The algal-bacterial biomass combined the high adsorption capacity of microalgae with the low cost of the residual biomass, which makes it an attractive biosorbent for environmental applications. Cu(II) was preferentially taken-up from the medium when the metals were present both separately and in combination. There was no observed competition for adsorption sites, which suggested that Cu(II), Ni(II), Cd(II), and Zn(II) bind to different sites and that active Ni(II), Cd(II) and Zn(II) binding groups were present at very low concentrations. Therefore, special focus was given to Cu(II) biosorption. Cu(II) biosorption by the algal-bacterial biomass was characterized by an initial fast cell surface adsorption followed by a slower metabolically driven uptake. pH, Cu(II), and algal-bacterial concentration significantly affected the biosorption capacity for Cu(II). Maximum Cu(II) adsorption capacities of 8.5+/-0.4 mg g-1 were achieved at an initial Cu(II) concentration of 20 mg l-1 and at pH 5 for the tested algal-bacterial biomass. These are consistent with values reported for other microbial sorbents under similar conditions. The desorption of Cu(II) from saturated biomass was feasible by elution with a 0.0125 M HCl solution. Simultaneous Cu(II) and salicylate removal in a continuous stirred tank photobioreactor was not feasible due to the high toxicity of Cu(II) towards the microbial culture. The introduction of an adsorption column, packed with the algal-bacterial biomass, prior to the photobioreactor reduced Cu(II) concentration, thereby allowing the subsequent salicylate biodegradation in the photobioreactor.