Spatial distribution of metal(loid)s in groundwater of a mining dominated area: recognising metal(loid) sources and assessing carcinogenic and non-carcinogenic human health risk

The study represents the first systematic risk assessment study in East Singhbhum district, Jharkhand, India for the safety of groundwater for drinking purpose with respect to metal(loid)s. The district is known for its mining and related activities. The results demonstrated that concentrations of the metal(loid)s showed significant spatial variation with Al, Mn, Fe, Ni and Zn exceeding the drinking water standards. Principal component analysis resulted in extraction of four factors explaining 76.3% of the data variability. The extracted principal components pointed towards both geogenic and anthropogenic activities governing the groundwater quality. Risk assessment was quantified by the hazard quotient (HQ) and cancer risk for both adult and child. The risk on human health posed by the metal(loid)s was found to be adverse for Mn with HQ > 1 for child. The chronic risks to the local population were largely contributed by Mn, Co and As. However, the carcinogenic risk for As was within the acceptable cancer risk value of 1 × 10^?4. Considering the geometric mean of the metal(loid)s in the study area, the hazard index (HI) for adult was above unity. Considering all the locations, the HI varied from 0.23 to 13.03 and 0.20 to 11.15 for adult and child, respectively, suggesting that the groundwater is unsuitable for drinking without treatment at most of the locations.     

Development of a robust technique for sampling volatile metal(loid)s in wetlands

The formation of volatile organic and inorganic metals and metalloids in aquatic environments is a known, but not very intensively investigated, process. Several techniques have been developed over the past 10 years to determine these trace components. These techniques are of limited use in wetland environments, where samples have to be taken from the soil-water interface, and require an immediate sample analysis due to thermodynamic instabilities of the volatile metal(loid)s. This paper presents an innovative sampling technique for total concentrations of volatile metal(loid)s in wetlands, based on an in situ gas-water separation via a porous PTFE membrane and stabilising the volatile metal(loid)s in a liquid sorbent (NaOCl solution). Samples may thus be collected even at remote sites, where longer storage times have to be accounted for. The sampling system was tested by means of a laboratory facility simulating the generation of arsine and dimethyl arsine under abiotic conditions as well as under field conditions. Results for sampling efficiency, reproducibility, and long-term storage are presented. Application of the sampling system in the field is shown.     

Artefacts and facts about metal(loid)s and their species from analytical procedures in environmental biomonitoring

Critical components of the total analytical process for the trace determination of metals, metalloids and their species in environmental biological specimens are highlighted. Examples are given of phenomena that may accompany “established” monitoring techniques but cause problems in the transformation of the original chemical composition of the bioindicators into scientifically sound analytical data and environmental information. It turns out that more problem-specific analytical developments are necessary in the field of environmental biomonitoring, in particular for the introduction of rigorously validated procedures of speciation analysis.     

Quantification of phytochelatins and their metal(loid) complexes: critical assessment of current analytical methodology

Whilst there are a variety of methods available for the quantification of biothiols in sample extracts, each has their own inherent advantages and limitations. The ease with which thiols readily oxidise not only hinders their quantification but also alters the speciation profile. The challenge faced by the analyst is not only to preserve the speciation of the sample, but also to select a method which allows the retrieval of the desired information. Given that sulfur is not a chromophore and that it cannot easily be monitored by ICP-MS, a number of direct and indirect methods have been developed for this purpose. In order to assess these methods, they are compared in the context of the measurement of arsenic–phytochelatin complexes in plant extracts. The inherent instability of such complexes, along with the instabilities of reduced glutathione and phytochelatin species,necessitates a rapid and sensitive analytical protocol. Whilst being a specific example, the points raised and discussed in this review will also be applicable to the quantification of biothiols and thiol–metal(loid) species in a wide range of systems other than just the analysis of arsenic–phytochelatin species in plant extracts.     

Application of X-ray fluorescence analytical techniques in phytoremediation and plant biology studies

Phytoremediation is an emerging technology that employs the use of higher plants for the clean-up of contaminated environments. Progress in the field is however handicapped by limited knowledge of the biological processes involved in plant metal uptake, translocation, tolerance and plant–microbe–soil interactions; therefore a better understanding of the basic biological mechanisms involved in plant/microbe/soil/contaminant interactions would allow further optimization of phytoremediation technologies. In view of the needs of global environmental protection, it is important that in phytoremediation and plant biology studies the analytical procedures for elemental determination in plant tissues and soil should be fast and cheap, with simple sample preparation, and of adequate accuracy and reproducibility. The aim of this study was therefore to present the main characteristics, sample preparation protocols and applications of X-ray fluorescence-based analytical techniques (energy dispersive X-ray fluorescence spectrometry—EDXRF, total reflection X-ray fluorescence spectrometry—TXRF and micro-proton induced X-ray emission—micro-PIXE). Element concentrations in plant leaves from metal polluted and non-polluted sites, as well as standard reference materials, were analyzed by the mentioned techniques, and additionally by instrumental neutron activation analysis (INAA) and atomic absorption spectrometry (AAS). The results were compared and critically evaluated in order to assess the performance and capability of X-ray fluorescence-based techniques in phytoremediation and plant biology studies. It is the EDXRF, which is recommended as suitable to be used in the analyses of a large number of samples, because it is multi-elemental, requires only simple preparation of sample material, and it is analytically comparable to the most frequently used instrumental chemical techniques. The TXRF is compatible to FAAS in sample preparation, but relative to AAS it is fast, sensitive and multi-elemental. The micro-PIXE technique requires rather expensive instrumentation, but offers multi-elemental analysis on the tissue and cellular level.     

Speciation of metal(loid)s in environmental samples by X-ray absorption spectroscopy: A critical review

Element specificity is one of the key factors underlying the widespread use and acceptance of X-ray absorption spectroscopy (XAS) as a research tool in the environmental and geo-sciences. Independent of physical state (solid, liquid, gas), XAS analyses of metal(loid)s in complex environmental matrices over the past two decades have provided important information about speciation at environmentally relevant interfaces (e.g. solid–liquid) as well as in different media: plant tissues, rhizosphere, soils, sediments, ores, mineral process tailings, etc. Limited sample preparation requirements, the concomitant ability to preserve original physical and chemical states, and independence from crystallinity add to the advantages of using XAS in environmental investigations. Interpretations of XAS data are founded on sound physical and statistical models that can be applied to spectra of reference materials and mixed phases, respectively. For spectra collected directly from environmental matrices, abstract factor analysis and linear combination fitting provide the means to ascertain chemical, bonding, and crystalline states, and to extract quantitative information about their distribution within the data set. Through advances in optics, detectors, and data processing, X-ray fluorescence microprobes capable of focusing X-rays to micro- and nano-meter size have become competitive research venues for resolving the complexity of environmental samples at their inherent scale. The application of μ-XANES imaging, a new combinatorial approach of X-ray fluorescence spectrometry and XANES spectroscopy at the micron scale, is one of the latest technological advances allowing for lateral resolution of chemical states over wide areas due to vastly improved data processing and detector technology.     

HG/LT-GC/ICP-MS coupling for identification of metal(loid) species in human urine after fish consumption

Human urine samples after fish consumption have been investigated by low-temperature gas chromatography with inductively coupled plasma mass spectrometric detection after sample derivatization by hydride generation (HG/LT-GC/ICP-MS). This analytical technique enabled the identification of organometal(loid) compounds in human urine; species of the six elements germanium, arsenic, selenium, tin, antimony, and mercury were determined. Three different organic selenium species, two germanium species, seven arsenic species, four tin species, five antimony species, and one species of mercury were found; 18 of the 22 species detected could be identified. The relative detection limits ranged between 2 and 12 pg x L(-1) (x=element). These organometal(loid) compounds probably build up in the human body under the influence of micro-organisms, in the presence of hydrogen sulfide and methane, in the human intestine.     

Speciation of Np(V) uptake by Opalinus Clay using synchrotron microbeam techniques

Synchrotron-based X-ray absorption spectroscopy has been used to determine the chemical speciation of Np sorbed on Opalinus Clay (OPA, Mont Terri, Switzerland), a natural argillaceous rock revealing a micro-scale heterogeneity. Different sorption and diffusion samples with Np(V) were prepared for spatially resolved molecular-level investigations. Thin sections of OPA contacted with Np(V) solution under aerobic and anaerobic conditions as well as a diffusion sample were analysed spatially resolved. Micro-X-ray fluorescence (μ-XRF) mapping has been used to determine the elemental distributions of Np, Fe and Ca. Regions of high Np concentration were subsequently investigated by micro-X-ray absorption fine structure spectroscopy to determine the oxidation state of Np. Further, micro-X-ray diffraction (μ-XRD) was employed to gain knowledge about reactive crystalline mineral phases in the vicinity of Np enrichments. One thin section was also analysed by electron microprobe to determine the elemental distributions of the lighter elements (especially Si and Al), which represent the main elements of OPA. The results show that in most samples, Np spots with considerable amounts of Np(IV) could be found even when the experiments were carried out in air. In some cases, almost pure Np(IV) L(III)-edge X-ray absorption near-edge structure spectra were recorded. In the case of the anaerobic sample, the μ-XRF mapping showed a clear correlation between Np and Fe, indicating that the reduction of Np(V) is caused by an iron(II)-containing mineral which could be identified by μ-XRD as pyrite. These spatially resolved investigations were complemented by extended X-ray absorption fine structure measurements of powder samples from batch experiments under aerobic and anaerobic conditions to determine the structural parameters of the near-neighbour environment of sorbed Np.     

Mechanism of multi‐metal(loid) methylation and hydride generation by methylcobalamin and cob(I)alamin: a side reaction of methanogenesis

Metal(loid)s are subject to many transformation processes in the environment, such as oxidation, reduction, methylation and hydride generation, predominantly accomplished by prokaryotes. Since these widespread processes affect the bioavailability and toxicity of metal(loid)s to a large extent, the investigation of their formation is of high relevance. Methanogenic Archaea are capable of methylating and hydrogenating Group 15 and 16 metal(loid)s arsenic, selenium, antimony, tellurium, and bismuth due to side reactions between central methanogenic cofactors, methylcobalamin (CH₃Cob(III)) and cob(I)alamin (Cob(I)). Here, we present systematic mechanistic studies on methylation and hydride generation of Group 15 and 16 metal(loid)s by CH₃Cob(III) and Cob(I). Pentavalent arsenical species showed neither methylation nor reduction as determined by using a newly developed oxidation state specific hydride generation technique, which allows direct determination of tri‐ and pentavalent arsenic species in a single batch. In contrast, efficient methylation of trivalent species without a change in oxidation state indicated that the methyl transfer does not proceed via a Challenger‐like oxidative methylation, but via a non‐oxidative methylation. Our findings also point towards a similar mechanism for antimony, bismuth, selenium, and tellurium. Overall, we suggest that the transfer of a methyl group does not involve a free reactive species, such as a radical, but instead is transferred either in a concerted nucleophilic substitution or in a caged radical mechanism. For hydride generation, we propose the intermediate formation of hydridocobalamin, transferring a hydride ion to the metal(loid)s. Copyright © 2012 John Wiley & Sons, Ltd.     

Noble metal nanoparticles meet molecular cages: A tale of integration and synergy

Noble metal nanoparticles attract growing interest owing to their high surface-to-volume ratio and unique optical, electric and catalytic properties. Fine-tuning these properties and broadening potential applications can be envisaged if nanoparticles are coupled to supramolecular cages that afford a highly tailorable inner environment as well as rich endo-/exo-functionalization. Due to rich chemical/physical properties of cages, integration of multiple host-guest interactions in confined cavities through endo-molecular design has been achieved. Such cages provide ideal confined templates for size-controlled synthesis of ultrafine nanoparticles with superior catalytic activities. Moreover, exo-functionalization of cages offers huge opportunities to couple with nanoparticles, generating cage-nanoparticle hybrids or hierarchical assemblies that combine merits of both. The present review provides recent advances in cage-mediated nanoparticle systems with synergistic effects and integrated functions, and demonstrates their applications in catalysis, sensing, chiral amplification, plasmonic switches, imaging and cell therapy. Finally, we highlight key challenges and identify emerging directions in the coming years.     

Synthesis and structural characterisation of novel linked bis(beta-diketiminato) rare earth metal complexes

Rare earth metal complexes based on novel linked bis(beta-diketiminato) ligands have been prepared via amine elimination and their structural characterisation revealed that the linker unit has significant influence on the geometry and coordination mode of the ancillary ligand.     

金属和非金属元素的甲基化行为其在环境化学研究中的意义

甲基化过程是许多金属元素与生物地球化学循环的重要途径,目前已知多种金属,非金属元素在自然界中均匀甲在化反应过程,在前人工作的基础上,本文对甲基化供体以及甲化反应的机理进行了论述,并对其在环境化学研究中的意义进行了讨论。     

Characterization of molecular transport in poly(dimethylsiloxane) microchannels for electrophoresis fabricated with synchrotron radiation-lithography and UV-photolithography

In the present paper, a study was undertaken of molecular transport in ploy(dimethylsiloxane) microchannels that were fabricated by ultraviolet (UV)-photolithography and synchrotron radiation (SR)-lithography characterized and compared for microchip capillary electrophoresis by evaluating in-channel molecular dispersion. A fluorescent tag, sulforhodamine B was used as the probing molecule. It was found that microchannels made by SR-lithography fabrication were superior to those made by UV-photolithography fabrication in terms of molecular transport performance. A deep insight into surface conditions characterized by scanning electron microscopy suggested it was related to the difference in surface roughness. Chromatographic retention in electropherograms further supported such a conclusion, which depended on the phase ratio of the channel surface. The results revealed for PDMS microchannels in this work were in good agreement with the phenomenon found for glass microchannels in the literature.     

Radiochemical characterisation,heavy metal determination and morphologic evolution of coastal sediments in the Ravenna area (Italy)

The basic aim of this work was to achieve a preliminary but integrated characterisation of an area of the Ravenna littoral coastline. The use of suitable computerised procedures has allowed the reconstruction of the morphological evolution of this area by means of historical and recent cartography. Coastal sediments were characterised by sampling 3 cores at about 2 km offshore. The following aspects were studied: 1) Mineralogical characterisation of both the total and the fine fraction of sediments by X-ray Diffraction. 2) Characteristion of sedimentary horizons by radiodating. 3)Magnetic susceptibility profiling. 4) Determination of some heavy metals (Cu, Pb, Zn, Cd) by anodic stripping voltammetry.     

Synthesis and characterisation of transition metal halide complexes of the xylyl-distibine, 1,2-bis(dimethylstibanylmethyl)benzene

Complexes of the title ligand with Cu(I), Ag(I), Au(I), Pd(II), Pt(II), Rh(III), and rare examples with Ni(II) and Co(III) have been prepared and characterised by analysis, IR, UV-vis, 1H, 63Cu and 59Co NMR spectroscopy and ES+ mass spectrometry as appropriate. The structures of [Cu[1,2-C6H4(CH2SbMe2)2]2]BF4, [PtCl2[1,2-C6H4(CH2SbMe2)2]], [M[1,2-C6H4(CH2SbMe2)2]2][PF6]2 (M = Pd or Pt), and [NiI[1,2-C6H4(CH2SbMe2)2]2]ClO4 have been determined, and the varying chelate bite and conformations of the xylyl backbone in these structures are discussed. Despite the unfavourable seven-membered chelate ring and the large soft antimony donors, 1,2-C6H4(CH2SbMe2)2 proves to be a surprisingly good ligand for late transition metals in medium oxidation states.     

A chirality-induced alpha phase and a novel molecular magnetic metal in the BEDT-TTF/tris(croconate)ferrate(III) hybrid molecular system

The novel paramagnetic and chiral anion [Fe(C5O5)3]3- has been combined with the organic donor BEDT-TTF (= ET = bis(ethylenedithio)tetrathiafulvalene) to yield the first chirality-induced alpha phase and a paramagnetic metal.     

Functional mesoporous carbon nanotubes and their integration in situ with metal nanocrystals for enhanced electrochemical performances

Functional mesoporous carbon nanotubes (MCNTs) and their integration in situ with Pt nanocrystals (Pt/MCNTs) have been designed and successfully developed via a facile route, which exhibited enhanced performances in energy storage and conversion applications.     

Effect of interligand repulsion of the molecular structures of bis-(dithiocarbamato) metal(II) complexes

A survey of the structural data on M(R₂dtc)₂, where R₂dtc⁻ is R₂NCS₂⁻ and M^II  Fe, Ni, Cu, Se, Te, Zn, Cd, Hg and Pb, has revealed that the ligand is essentially uncharged upon coordination to the metal ion and consequently should be considered as stereochemically rigid. A correlation between b (normalized bite distance) and r_M (ionic radios of M) has been found and explained in terms of constant ∡SCS and variable r_M. Both R(MS) and ∡SMS in this model are defined by the approach of M to the rigid CS₂ group. The interligand repulsion was found to depend heavily on the ligand's bite angle. The distortion of the molecular structures of M(R₂dtc)₂ in the crystal state from the regular pseudotetrahedral or planar arrangements was explained as a means of reducing the interligand repulsion energy when an additional (intermolecular) contact is formed in the crystal due to crystal packing requirements.     

Synthesis and characterisation of complexes of Group 13 metal amidinate heterocycles with the CpFe(CO)2 fragment

The first examples of complexes between a 4-membered amidinato-Group 13 metal(III) heterocycle and a transition metal fragment are formed in salt elimination reactions between Na[CpFe(CO)2] and [MX2(amid)], M=Al, Ga or In; X=Cl or Br; amid-=[(RN)2CBut]-; R=Pri or cyclohexyl (Cy). The formed complexes, [CpFe(CO)2M(X)(amid)] (4 examples) have been crystallographically characterised and subject to halide abstraction reactions. In one case, the cationic complex, [CpFe(CO)2Ga(OEt2){(CyN)2CBut}][BArf4], was isolated and crystallographically characterised. A hydrolysis product of this complex, [{CpFe(CO)2Ga[(CyN)2CBut]}2(micro-OH)][BArf4], was also isolated in low yield from this reaction and structurally characterised.     

Derivatization of organometal(loid) species by sodium borohydride problems and solutions.

Like other derivatization techniques, hydride generation is a chemical reaction that produces side-reactions leading to analytical problems. Demethylation of dimethylarsinic acid was observed to be dependent upon the pH level of the hydride generation reaction mixture. If the reaction mixture was acidic, then in addition to (CH3)2AsH, the monomethyl arsenic hydride [(CH3)AsH2] could be detected. Demethylation and also the formation of an unidentified arsenic species were noted when trimethyl arsonic oxide was used as derivatization educt. All of these effects depend on the pH level of the hydride generation mixture. We observed significant levels of organometal(loid) species of elements such as Ge, As, Sn, Sb, Hg and Bi in blank hydride generation mixtures. The organometal(loid) contamination was irreproducible even during I day using a single solution of sodium borohydride in deionized water. We concluded that the organometal(loid) contamination arises directly from the derivatization agent, sodium borohydride, itself. Use of helium purging and various adsorptive materials to decontaminate the sodium borohydride solution prior to analysis did not result in a significant decrease in organometal(loid) contamination levels. Use of a palladium-cluster stabilised with 1,10-phenanthrolin as alternative hydride generation derivatization agent was not found to be suitable, since reaction yields were poor and transmethylation reactions were noted.