流动注射分析在环境水质重金属检测中的应用进展

重金属具有毒性大、不易被代谢、易被生物富集并有生物放大效应等特点,不但污染水环境,也严重威胁人类和水生生物的存在。近年来各类水环境中重金属污染日趋加剧,重金属的检测及处理方法有多种,而流动注射分析技术以其自动化程度高、分析速度快、精密度高、分析成本低等优点在水环境监测方面占有重要地位。介绍了流动注射在重金属检测方面的应用。     

Comprehensive evaluation of the effluents eluted from different processes of the textile industry and its immobilization to trim down the environmental pollution

Due to the significance of industrial waste water pollution, which creates severe health hazards in humans, this study concentrates over the reduction and determination of the amounts of toxic metals/pollution parameters in the effluents leached from different processes of the textile industry. The concentrations of metal ions were measured by using neutron activation analysis (NAA) technique. The values of toxic metals such as As (49.1 ± 1.8 mg/L), Cu (42.7 ± 1.5 mg/L), Ni (41.1 ± 3.3 mg/L), Mn (51.1 ± 0.7 mg/L), Sb (1.89 ± 0.04 mg/L), Se (0.41 ± 0.01 mg/L), Co (7.5 ± 0.3 mg/L), Cr (8.5 ± 0.5 mg/L) and Cd (1.21 ± 0.08 mg/L) were found very high in crude textile??s effluents as compared to their standard recommended limits. The immense variation observed among the injurious pollutants of the effluents i.e. pH, temperature, electrical conductivity, turbidity, biological oxygen demands, chemical oxygen demands, total suspended solids, total dissolved solids, total solids etc. The toxic metals and injurious pollutants in the unprocessed effluents have been reduced in the post filtration effluents up to 98% and 96% respectively with the help of an ultra-filtration membrane therapy unit.     

Self-immobilization of Recombinant Caulobacter crescentus and Its Application in Removal of Cadmium from Water

Microbial biofilms can be valuable in many biotechnological applications, including bioremediation. We have previously constructed a recombinant strain of Caulobacter crescentus JS4022/p723-6H by inserting a hexahistidine peptide to a permissive site of the host surface layer (S-layer) protein RsaA. This engineered strain is highly effective in removal of cadmium from water as free cells. In this communication, we examined the biofilms formed by self-immobilized JS4022/p723-6H and evaluated their ability to retrieve cadmium from contaminated water samples. According to light and electron microscopic observations, JS4022/p723-6H cells developed a uniform monolayer biofilm on borosilicate surfaces through their intrinsic appendage, a stalk with an adhesive holdfast. The density of the biofilms reached a maximum after 48 h of incubation and was not affected by exposure to at least 1 ppm cadmium. When 0.4 ppm Cd(II) was added to the growth medium, immobilized JS4022/p723-6H removed 76.9% of the total metal, whereas the control strain only removed 13.5%. When a water sample collected from Lake Erie was spiked with various amounts of CdCl₂, immobilized JS4022/p723-6H was able to sequester 44～51% of the total metal, compared to 37～42% accumulated by the control strain. By combining two powerful techniques, cell surface display and self-immobilization, we achieved complete separation of dissolved heavy metals from contaminated water in a single step. This study laid down the foundation to cost-effectively construct large-scale bioreactors with high efficiency and specificity to retrieve environmental contaminants from water.     

Ultrasensitive immunoassay of microcystins-LR using G-quadruplex DNAzyme as an electrocatalyst

An electrochemical immunoassay for microcystin-LR (MC-LR) detection was developed using multi-labeled horseradish peroxidase-mimicking DNAzyme on carbon nanotubes (CNTs) as electrocatalyst for signal amplification. CNTs were covalently conjugated to multiple DNAzyme along with MC-LR for a competitive immunoassay. The as-prepared DNAzyme/CNTs/MC-LR biolabel was specifically captured on the electrode surface, and current responses were obtained upon the electro-catalytic reduction of hydrogen peroxide by the captured biolabels. Under optimal conditions, the electro-catalytic current decreased linearly with the increase amount of MC-LR in the range from 0.01 to 7.0 µg L^?1. The linear regression equation was I (µA) = 12.96 ? 1.48 X _[MC–LR] (µg L^?1), with a correlation coefficient of 0.989. The limit of detection of MC-LR was 2.31 ng L^?1. Application of the immunoassay method and LC/MS/MS method for MC-LR determination on spiked reservoir water gave recovery range of 91.7–105.2% and 94.0–105.0%, respectively. The resulting versatile immunoassay exhibited high sensitivity, good precision and satisfactory reproducibility, which could have vast potential in routine water quality monitoring for various environmental toxins.     

土壤重金属污染评价指标的研究进展

土壤重金属污染评价指标主要有：土壤重金属总含量，有效含量，土壤酶活性以及植物中毒临界含量等。由于受重金属污染的土壤中往往伴有多种重金属元素以及元素之间的交互作用，使得临界值的确定更为复杂，目前评价土壤重金属复合污染的方法主要是综合指数法。     

金属离子的光催化去除研究进展

利用光催化剂表面的光生电子或空穴等活性物种，通过还原或氧化反应去除水相中的金属离子，是与环境保护、贵金属回收或金属担载催化剂制备相关的重要过程。笔者结合半导体的结构特征，综述了利用光催化还原反应或氧化反应，对铬、汞、铜、镍、银及铂、钯等贵金属和锰、铀等的光催化去除效果，介绍了该技术在处理金属离子混合体系实现金属分离过程的应用。结合有关实验数据，对一些可能反应机制进行了探讨。对与环境保护及其它相关工艺过程的应用进行了介绍。     

Remediation of metalliferous soils through the heavy metal resistant plant growth promoting bacteria: Paradigms and prospects

Various industrial, agricultural and military operations have released huge amounts of toxic heavy metals into the environment with deleterious effects on soils, water and air. Under metal stress, soil microorganisms including plant growth promoting bacteria (PGPB) have developed many strategies to evade the toxicity generated by the various heavy metals. Such metal resistant PGPB, when used as bioinoculant or biofertilizers, significantly improved the growth of plants in heavy metal contaminated/stressed soils. Application of bacteria possessing metal detoxifying traits along with plant-beneficial properties is a cost effective and environmental friendly metal bioremediation approach. This review highlights the different mechanisms of metal resistance and plant growth promotion of metal resistant PGPB as well as the recent development in exploitation of these bacteria in bioremediation of heavy metals in different agroecosystems.     

Assessment of Heavy Metal Pollution and Ecological Risk of Roadside Soils in Tlemcen (Algeria) Using Flame-Atomic Absorption Spectrometry

In Algeria, few studies have been conducted on the evaluation of roadside soil pollution. A total of 34 soil samples (28 roadside and 6 off-road) was obtained at 0–20?cm depth along the RN 35 national road. Heavy metal (Cd, Cr, Cu, Fe, Ni, Pb, and Zn) contents were extracted using aqua regia digestion and determined using atomic absorption spectrometry. Background values of heavy metal contents were determined using the robust statistical method of median plus two times the median absolute deviation. Single- and multi-element pollution and ecological risk indices were calculated. The results showed that background values were 2.5?±?0.3, 64.9?±?8.1, 28.0?±?4.1, 29371.5?±?4403.0, 32.9?±?4.4, 72.2?±?12.8, and 445.1?±?62.9?mg/kg for Cd, Cr, Cu, Fe, Ni, Pb, and Zn, respectively. The results were all higher than their corresponding median values. Single-element pollution indices (enrichment factor and geoaccumulation index) showed that the pollution is primarily due to Pb and Zn. Multi-element pollution index (Nemerow index) indicated that only 3% of the soil samples are strongly contaminated, whereas 23% are seriously contaminated. The potential ecological risk index showed that Cd is the most harmful element, followed by Pb and Zn. 65% of the soil samples had moderate potential ecological risk, while only 3% had considerable potential ecological risk. This study may be used as a baseline for future monitoring and as a tool for decision-making regarding environmental protection policies and sustainability of this semiarid agroecosystem.     

Metal–Organic Framework‐Activated Carbon Composite Materials for the Removal of Ammonia from Contaminated Airstreams

Metal–organic frameworks (MOFs) are a class of porous materials that show promise in the removal of toxic industrial chemicals (TICs) from contaminated airstreams, though their development for this application has so far been hindered by issues of water stability and the wide availability and low cost of traditionally used activated carbons. Here a series of three MOF‐activated carbon composite materials with different MOF to carbon ratios are prepared by growing STAM‐17‐OEt crystals inside the commercially available BPL activated carbon. The composite materials display excellent water stability and increased uptake of ammonia gas when compared to unimpregnated carbon. Such properties make these composites very promising in the fields of air purification and personal protective equipment.     

Ultrasensitive voltammetric detection of trace heavy metal ions using carbon nanotube nanoelectrode array

We describe an ultrasensitive voltammetric detection of trace heavy metal ions using nanoelectrode arrays (NEAs) that are based on low-site density carbon nanotubes (CNTs). The NEAs were prepared by sealing the side-walls of CNTs with an epoxy passive layer that reduces the current leakage and eliminates the electrode capacitance, leading to a low background current. This provides a high signal-to-noise ratio. The CNTs-NEAs coated with a bismuth film were used successfully for voltammetric detection of trace cadmium(II) and lead(II) at the sub-ppb level. The detection limit of 0.04 microg L(-1) was obtained under optimum experimental conditions. The attractive behavior of the new carbon NEA sensing platform holds great promise for onsite environmental monitoring and biomonitoring of toxic metals.     

金属有机骨架材料MIL-101及其改性材料去除环境污染物的研究进展

目前我国水环境以及空气面临着严峻的污染形势,许多危害人身体健康的污染物亟待治理。 金属有机骨架作为目前新兴的多孔材料,具有高孔隙率、高比表面积、结构可调性以及不饱和金属位点等特点。 这使得金属有机骨架材料具有一定的环境污染物去除能力。 围绕对苯二甲酸铬金属有机骨架材料(MIL-101)及其功能化修饰的改性材料的结构信息展开,总结了材料的主要合成方法,对功能化修饰的方法和原理进行分析,重点分析了这种材料在环境污染物去除等方面的应用研究进展,包括它在重金属离子、农药、抗生素、有机染料、碘离子等污染物的吸附处理领域的应用, 以及在污染物的监测和环境风险预警方面的应用潜力。 指出了材料在制备成本、反复利用次数、污染物后续处理等方面仍然存在的问题。     

Speciation analysis of thallium using electrothermal AAS following on-line pre-concentration in a microcolumn filled with multiwalled carbon nanotubes

The enrichment ability of carbon nanotubes (CNTs) was investigated and a new method established for the determination of trace thallium species in environmental samples using electrothermal atomization-atomic absorption spectrometry (ETAAS). The CNTs were employed as sorbent substrate in a continuous flow system coupled to ETAAS. Parameters influencing the recoveries of thallium were optimized. Under optimal conditions, the detection limit and precision of the method were 0.009 µg L^?1 and 3.9%, respectively. The method was applied to the determination of thallium in real environmental samples and the recoveries were in the range from 96 to 100%. This system was able to separate thallium (I) from the matrix, which allowed its selective determination. The total thallium content was then determined by reducing Tl(III) with hydroxylamine. All these experimental results indicated that this new procedure can be applied to the determination of trace thallium in drinking water samples.     

Evaluation of toxic metals in the industrial effluents and their segregation through peanut husk fence for pollution abatement

The industrial pollution is exponentially growing in the developing countries due to the discharge of untreated effluents from the industries in the open atmosphere. This may cause severe health hazards in the general public. To reduce this effect, it is essential to remove the toxic and heavy metals from the effluents before their disposal into the biosphere. In this context, samples of the effluents were collected from the textile/yarn, ceramics and pulp/paper industries and the concentrations of the toxic metal ions were determined using neutron activation analysis (NAA) technique. The observed concentration values of the As, Cr and Fe ions, in the unprocessed industrial effluents, were 4.91 ± 0.8, 9.67 ± 0.7 and 9.71 ± 0.8 mg/L, respectively which was well above the standard recommended limits (i.e. 1.0, 1.0 and 2.0 mg/L, respectively). In order to remove the toxic metal ions from the effluents, the samples were treated with pea nut husk fence. After this treatment, 91.5% arsenic, 81.9% chromium and 66.5% iron metal ions were successfully removed from the effluents. Then the treated effluents contained concerned toxic metal ions concentrations within the permissible limits as recommended by the national environmental quality standards (NEQS).     

Separation and quantification of quantum dots and dissolved metal cations by size exclusion chromatography–ICP-MS

The prevalence of engineered metallic nanoparticles within electronic products has evoked a need to assess their occurrence and fate within environmental systems upon potential release of these nanoparticles. Quantum dots (QDs) are mixed-metal nanocrystals with the smallest of particle sizes (2–10 nm) that readily leach heavy metal cations in water, potentially creating a co-occurrence of nanoparticulate and dissolved metal pollutants. In this report, we develop a size exclusion chromatography–inductively coupled plasma–mass spectrometry method (SEC-ICP-MS) for the rapid separation and quantification of ~5-nm-sized CdSe/ZnS QDs and dissolved Cd²⁺ and Zn²⁺ cations in water. The SEC-ICP-MS method provided a wide chromatographic separation of CdSe/ZnS QDs and dissolved Cd²⁺ and Zn²⁺ cations only when using the smallest SEC column pore size available and an eluent composition that prevented loss of metals to column polymer surfaces by using a surfactant to ensure elution of QDs (ammonium lauryl sulfate) and a complexing ligand to ensure elution of metal cations (ethylenediaminetetraacetate). Detection limits were between 0.2 and 2 µg L^–1 for Cd²⁺ and Zn²⁺ among dissolved cation and QD phases, and ranges of linearity covered two to three orders of magnitude. Gold nanoparticles of sizes 5, 10, 20 and 50 nm were also effectively separated from dissolved Au³⁺ cations, illustrating the method applicability to a wide range of nanoparticle sizes and compositions. QD and dissolved metal concentrations measured by SEC-ICP-MS were comparable to those measured using the more conventional method of centrifuge ultrafiltration on split samples for dissolved and total metals. The applicability of the SEC-ICP-MS method to environmental systems was verified by measuring QDs and dissolved metals added to samples of natural waters. The method was also applied to monitoring CdSe/ZnS dissolution kinetics in an urban river water. The SEC-ICP-MS developed here may offer improved automation for characterising heterogeneous suspensions containing >1 µg L^–1 heavy metals.     

Removal of toxic metal ions using chitosan coated carbon nanotube composites for supercapacitors

Environmental pollution and energy crisis are two major global challenges to human beings.Recovering energy from wastewater is considered to be one of the effective approaches to address these two issues synchronously.As the main pollutants in wastewater,toxic heavy metal ions are the potential candidates for energy storage devices with pseudocapacitive behaviors.In this study,toxic metal ions of Cr(VI)and Cu(II)are removed efficiently by chitosan coated oxygen-containing functional carbon nanotubes,and the corresponding equilibrium adsorption capacity is 142.1 and 123.7 mg g~(-1).Followed by carbonization of metal ions-adsorbed adsorbents,Cu-and Cr N-loaded carbon composites can be obtained.Electrochemical measurements show that the supercapacitor electrodes based on Cu-and Cr N-loaded carbon composites have specific capacitance of 144.9 and 114.9 F g~(-1)at2 m V s~(-1),with superior electrochemical properties to pure chitosan coated carbon nanotubes after carbonization.This work demonstrates a new strategy for the resource-utilization of other heavy metal ions for energy devices,and also provides a new way to turn environmental pollutants into clean energy.     

Bioremediation of Cd by Microbially Induced Calcite Precipitation

Contamination by Cd is a significant environmental problem. Therefore, we examined Cd removal from an environmental perspective. Ureolysis-driven calcium carbonate precipitation has been proposed for use in geotechnical engineering for soil remediation applications. In this study, 55 calcite-forming bacterial strains were newly isolated from various environments. Biomineralization of Cd by calcite-forming bacteria was investigated in laboratory-scale experiments. A simple method was developed to determine the effectiveness of microbially induced calcite precipitation (MICP). Using this method, we determined the effectiveness of biomineralization for retarding the flow of crystal violet through a 25-mL column. When the selected bacteria were analyzed using an inductively coupled plasma optical emission spectrometer, high removal rates (99.95 %) of Cd were observed following incubation for 48 h. Samples of solids that formed in the reaction vessels were examined using a scanning electron microscope. The CdCO₃ compounds primarily showed a spherical shape. The results of this study demonstrate that MICP-based sequestration of soluble heavy metals via coprecipitation with calcite may be useful for toxic heavy metal bioremediation.     

Bioremediation of Cd by Microbially Induced Calcite Precipitation

Contamination by Cd is a significant environmental problem. Therefore, we examined Cd removal from an environmental perspective. Ureolysis-driven calcium carbonate precipitation has been proposed for use in geotechnical engineering for soil remediation applications. In this study, 55 calcite-forming bacterial strains were newly isolated from various environments. Biomineralization of Cd by calcite-forming bacteria was investigated in laboratory-scale experiments. A simple method was developed to determine the effectiveness of microbially induced calcite precipitation (MICP). Using this method, we determined the effectiveness of biomineralization for retarding the flow of crystal violet through a 25-mL column. When the selected bacteria were analyzed using an inductively coupled plasma optical emission spectrometer, high removal rates (99.95 %) of Cd were observed following incubation for 48 h. Samples of solids that formed in the reaction vessels were examined using a scanning electron microscope. The CdCO₃ compounds primarily showed a spherical shape. The results of this study demonstrate that MICP-based sequestration of soluble heavy metals via coprecipitation with calcite may be useful for toxic heavy metal bioremediation.     

Studying the enhanced phytoremediation of lead contaminated soils via laser induced breakdown spectroscopy

Phytoremediation popularly known as 'green clean technology' is a new promising technology used for toxic contaminants removal from the environment such as heavy metals (HMs), adopting suitable plants. This concept is increasingly being adopted as it is a cost effective and environmentally friendly alternative to traditional methods of treatment. This study was focused on using scented geranium, Pelargonium zonale, as accumulator or hyperaccumulator plant for natural lead extraction from artificially contaminated soil with different Pb concentrations (0, 2000, 5000, 7000 ppm). Utilization of EDTA as a chelator, that would permit higher metal availability and uptake by the tested plants roots, was also tested.     

Stability and Mobility of Metal-Humic Complexes Isolated from Different Soils

The contamination of potable water aquifers by heavy metals is one of the most severe environmental threats. For the transport of heavy metals from various types of contaminated sites into the ground water and also into surface water aquifers, humic substances (HS) are recognized to be of main importance. Dissolved in natural waters humic substances are readily complexed with a variety of metal ions. Therefore, humic substances are of cardinal importance for the migration and, consequently, the pollution of ground waters with heavy metals. Our paper presents the results of a comprehensive comparison of several isolated humic acids of soils of different origin (different geochemical milieu) and their metal complexes. Two polluted sites in Germany, which differ in their geochemical milieu (pH-value) were selected. The aim of our experiments was to describe the properties of terrestrial humic substances depending on their origin and genesis as well as the effects of the transport of humic substance-bound metals into the water-unsaturated soil zone. After determination of heavy metals in the soils by photon activation analysis the activated soil was used as an inherent tracer in batch experiments with the isolated humic acid. After adsorption of the loaded humic acid on an XAD-8 resin column, the partition of metals mobilized by humic acids could be quantified. There are correlations of the formation of metal-humic complexes with the soil pedogenes, with the pH-value as well as with the humic acid concentration.     

Treatment of the solution extracted from metal contaminated soils by reverse osmosis and chemical precipitation

In this study a process for the remediation of soils contaminated by lead or copper is proposed, consisting of the operations in sequence: soil flushing, membrane treatment, acidification, and metal precipitation. Pb(II) and Cu(II) extraction from a synthetically contaminated soil using a 0.05 M EDTA aqueous solution were investigated in column. The metal removal efficiencies and the final soil metal concentration were 98.2% and 37.96 mg/g respectively for lead and 95.4% and 59.20 mg/kg for copper. The extracted solutions were concentrated through a membrane treatment to reduce the water content up to the 75% and to obtain a permeate metal concentration in compliance with the Italian Environmental Regulation. The recovery of the used EDTA from the retentate solution, with recovery yield of at least 85.4%, was also obtained through acidification. Metal precipitation from the filtered solution was then performed according two different methods, achieving metal removal yield of more than 99.4%.