Cation distribution and mixing thermodynamics in Fe/Ni thiospinels

The structural analogy between Ni-doped greigite minerals (Fe3S4) and the (Fe,Ni)S clusters present in biological enzymes has led to suggestions that these minerals could have acted as catalysts for the origin of life. However, little is known about the distribution and stability of Ni dopants in the greigite structure. We present here a theoretical investigation of mixed thiospinels (Fe1

Ag(I) and Cu(I) complexes of tetramethyldiphosphinedisulfide: synthesis and structure

Reaction of [M(NCCH3)(4)][PF6] (M = Ag, Cu) with the S2P2Me4 ligand in dichloromethane solution led to substitution of all the nitrile ligands by two molecules of the sulfur ligand, affording the new species [Ag(S2P2Me4)(2)][PF6] (1) and [Cu(S2P2Me4)(2)][PF6] (2). The structures of these complexes were determined by single crystal X-ray diffraction. showing the expected tetrahedral coordination around each metal. Density functional theory (DFT) calculations confirmed the different geometries and energies of the free and coordinated ligand, and provided a very good reproduction of the experimental structures, both for Ag and Cu. The lengths of the S=P bonds are barely affected by coordination, indicating that the pi bond is not important in binding to the metal. (C) 2002 Elsevier Science B.V. All rights reserved.

The water quality of the River Carnon, west Cornwall, November 1992 to March 1994: the impacts of Wheal Jane discharges

In January 1992, there was a major pollutant event for the River Canon and downstream with its confluence to the River Fal and the Fal estuary in the west Cornwall. This incident was associated with the discharge of several million gallons of highly polluted water from the abandoned Wheal Jane tin mine that also extracted Ag, Cu and Zn ore. Later that year, the Centre for Ecology and Hydrology (CBH; then Institute of Hydrology) Wallingford undertook daily monitoring of the River Canon for a range of major, minor and trace elements to assess the nature and the dynamics of the pollutant discharges. These data cover an 18-month period when there remained major water-quality problems after the initial phase of surface water contamination. Here, a summary is provided of the water quality found, as a backdrop to set against subsequent remediation. Two types of water-quality determinant grouping were observed. The first type comprises the determinants B, Cs, Ca, Li, K, Na, SO4, Rb and Sr, and their concentrations are positively correlated with each other but inversely correlated with flow. This type of water-quality determinant shows variations in concentration that broadly link to the normal hydrogeochemical processes within the catchment, with limited confounding issues associated with mine drainage. The second type of water-quality determinant comprises Al, Be, Cd, Ce, Co, Cu, Fe, La, Pb, Pr, Nd, Ni, Si, Sb, U, Y and Zn, and concentrations for all this group are positively correlated. The determinants in this second group all have concentrations that are negatively correlated with pH. This group links primarily to pollutant mine discharge. The water-quality variations in the River Camon are described in relation to these two distinct hydrogeochemical groupings. (C) 2004 Elsevier B.V All rights reserved.

Microwave activation of the electro-oxidation of glucose in alkaline media

The oxidation of glucose is a complex process usually requiring catalytically active electrode surfaces or enzyme modified electrodes. In this study the effect of high intensity microwave radiation on the oxidation of glucose in alkaline solution at Au, Cu, and Ni electrodes is reported. Calibration experiments with the Fe(CN)(6)(3-/4-) redox system in aqueous 0.1 M NaOH indicate that strong thermal effects occur at both 50 and 500 mu m diameter electrodes with temperatures reaching 380 K. Extreme mass transport effects with mass transport coefficients of k(mt) > 0.01 m s(-1) (or k(mt) > 1.0 cm s(-1)) are observed at 50 mu m diameter electrodes in the presence of microwaves. The electrocatalytic oxidation of glucose at 500 mu m diameter Au, Cu, or Ni electrodes immersed in 0.1 M NaOH and in the presence of microwave radiation is shown to be dominated by kinetic control. The magnitude of glucose oxidation currents at Cu electrodes is shown to depend on the thickness of a pre-formed oxide layer. At 50 mu m diameter Au, Cu, or Ni electrodes microwave enhanced current densities are generally higher, but only at Au electrodes is a significantly increased rate for the electrocatalytic oxidation of glucose to gluconolactone observed. This rate enhancement appears to be independent of temperature but microwave intensity dependent, and therefore non-thermal in nature. Voltammetric currents observed at Ni electrodes in the presence of microwaves show the best correlation with glucose concentration and are therefore analytically most useful.

Microwave activation of the electro-oxidation of glucose in alkaline media

The oxidation of glucose is a complex process usually requiring catalytically active electrode surfaces or enzyme-modified electrodes. In this study the effect of high intensity microwave radiation on the oxidation of glucose in alkaline solution at Au, Cu, and Ni electrodes is reported. Calibration experiments with the Fe(CN)63–/4– redox system in aqueous 0.1 M NaOH indicate that strong thermal effects occur at both 50 and 500 µm diameter electrodes with temperatures reaching 380 K. Extreme mass transport effects with mass transport coefficients of kmt > 0.01 m s–1(or kmt > 1.0 cm s–1) are observed at 50 µm diameter electrodes in the presence of microwaves. The electrocatalytic oxidation of glucose at 500 µm diameter Au, Cu, or Ni electrodes immersed in 0.1 M NaOH and in the presence of microwave radiation is shown to be dominated by kinetic control. The magnitude of glucose oxidation currents at Cu electrodes is shown to depend on the thickness of a pre-formed oxide layer. At 50 µm diameter Au, Cu, or Ni electrodes microwave enhanced current densities are generally higher, but only at Au electrodes is a significantly increased rate for the electrocatalytic oxidation of glucose to gluconolactone observed. This rate enhancement appears to be independent of temperature but microwave intensity dependent, and therefore non-thermal in nature. Voltammetric currents observed at Ni electrodes in the presence of microwaves show the best correlation with glucose concentration and are therefore analytically most useful.

Sequential extraction and single-step cold-acid extraction: A feasibility study for use with freshwater-canal sediments

This investigation examines metal release from freshwater sediment using sequential extraction and single-step cold-acid leaching. The concentrations of Cd, Cr, Cu, Fe, Ni, Pb and Zn released using a standard 3-step sequential extraction (Rauret et al., 1999) are compared to those released using a 0.5 M HCl; leach. The results show that the three sediments behave in very different ways when subject to the same leaching experiments: the cold-acid extraction appears to remove higher relative concentrations of metals from the iron-rich sediment than from the other two sediments. Cold-acid extraction appears to be more effective at removing metals from sediments with crystalline iron oxides than the "reducible" step of the sequential extraction. The results show that a single-step acid leach can be just as effective as sequential extractions at removing metals from sediment and are a great deal less time-consuming.

Distribution of selected heavy metals in sediments of the Agueda river (Central Portugal)

The state of river water deterioration in the Agueda hydrographic basin, mostly in the western part, partly reflects the high rate of housing and industrial development in this area in recent years. The streams have acted as a sink for organic and inorganic loads from several origins: domestic and industrial sewage and agricultural waste. The contents of the heavy metals Cr, Cd, Ni, Cu, Pb, and Zn were studied by sequential chemical extraction of the principal geochemical phases of streambed sediments, in the <63 mum fraction, in order to assess their potential availability to the environment, investigating, the metal concentrations, assemblages, and trends. The granulometric and mineralogical characteristics of this sediment fraction were also studied. This study revealed clear pollution by Cr, Cd, Ni, Cu, Zn, and Pb, as a result from both natural and anthropogenic origins. The chemical transport of metals appears to be essentially by the following geochemical phases, in decreasing order of significance: (exchangeable + carbonates) much greater than (organics) much greater than (Mn and Fe oxides and hydroxides). The (exchangeable + carbonate) phase plays an important part in the fixation of Cu, Ni, Zn, and Cd. The organic phase is important in the fixation of Cr, Pb, and also Cu and Ni. Analyzing the metal contents in the residual fraction, we conclude that Zn and Cd are the most mobile, and Cr and Pb are less mobile than Cu and Ni. The proximity of the pollutant sources and the timing of the influx of contaminated material control the distribution of the contaminant-related sediments locally and on the network scale.

Complete filling of zeolite frameworks with polyalkynes formed in situ by transition-metal ion catalysts

We report the use of transition-metal-exchanged zeolites as media for the catalytic formation and encapsulation of both polyethyne and polypropyne, and computer modeling studies on the composites so formed. Alkyne gas was absorbed into the pores of zeolite Y (Faujasite) exchanged with transition-metal cations [Fe(II), Co(II), Cu(II), Ni(II), and Zn(II)]. Ni(II) and Zn(II) were found to be the most efficient for the production of poly-ynes. These cations were also found to be effective in polymer generation when exchanged in zeolites mordenite and beta. The resulting powdered samples were characterized by FTIR, Raman, diffuse reflectance electronic spectroscopy, TEM, and elemental analysis, revealing, nearly complete loading of the zeolite channels for the majority of the samples. Based on the experimental carbon content, we have derived the percentage of channel filling, and the proportion of the channels containing a single polymer chain for mordenite. Experimentally, the channels for Y are close to complete filling for polyethyne (PE) and polypropyne (PP), and this is also true for polyethyne in mordenite. Computer modeling studies using Cerius2 show that the channels of mordenite can only accept a single polymer chain of PP, in which case these channels are also completely filled.

The interplay between geometry, electronic structure, and reactivity of Cu-Ni bimetallic (111) surfaces

The mutual influence of surface geometry (e.g. lattice parameters, morphology) and electronic structure is discussed for Cu-Ni bimetallic (111) surfaces. It is found that on flat surfaces the electronic d-states of the adlayer experience very little influence from the substrate electronic structure which is due to their large separation in binding energies and the close match of Cu and Ni lattice constants. Using carbon monoxide and benzene as probe molecules, it is found that in most cases the reactivity of Cu or Ni adlayers is very similar to the corresponding (111) single crystal surfaces. Exceptions are the adsorption of CO on submonolayers of Cu on Ni(111) and the dissociation of benzene on Ni/Cu(111) which is very different from Ni(111). These differences are related to geometric factors influencing the adsorption on these surfaces.

Nanosized polymetallic resorcinarene-based host assemblies that strongly bind fullerenes

Polymetallic nanodimensional assemblies have been prepared via metal directed assembly of dithiocarbamate functionalized cavitand structural frameworks with late transition metals (Ni, Pd, Cu, Au, Zn, and Cd). The coordination geometry about the metal centers is shown to dictate the architecture adopted. X-ray crystallographic studies confirm that square planar coordination geometries result in "cagelike" octanuclear complexes, whereas square-based pyramidal metal geometries favor hexanuclear "molecular loop" structures. Both classes of complex are sterically and electronically complementary to the fullerenes (C-60 and C-70). The strong binding of these guests occurred via favorable interactions with the sulfur atoms of multiple dithiocarbamate moieties of the hosts. In the case of the tetrameric copper(II) complexes, the lability of the copper(II)-dithiocarbamate bond enabled the fullerene guests to be encapsulated in the electron-rich cavity of the host, over time. The examination of the binding of fullerenes has been undertaken using spectroscopic and electrochemical methods, electrospray mass spectrometry, and molecular modeling.

Soil mobility of sewage sludge-derived dissolved organic matter, copper, nickel and zinc

A soil (sandy loam) column leaching study aimed to determine the extent of mobility and co-mobility of Cu, Ni, Zn and dissolved organic matter (DOM) released from a surface-application (equivalent to 50 t ds ha(-1)) of anaerobically-digested sewage sludge. Leaching of DOM through It the soil column was found to be almost un-retarded. Decidedly similar behaviour was exhibited by Ni suggesting that it migrated as organic complexes. Whilst Cu was also found to be leached, significant retardation was evident. However, the importance of DOM in promoting the mobility of both Cu and Ni was evidenced by their lack of mobility when added to the soil column as inorganic forms. The presence of DOM did not prevent Zn from becoming completely adsorbed by the soil solid phase. In relation to WHO drinking water guidelines, only Ni concentrations showed potential environmental significance. due to the relatively poor retention of Ni by the sludge solid phase. (C) 2003 Elsevier Ltd. All rights reserved.

Influence of dissolved organic matter on the solubility of heavy metals in sewage-sludge-amended soils

Sewage-sludge-amended soils generally contain elevated levels of organic matter and heavy metals compared to control soils. Because organic matter is known to complex with heavy metals, the solubility behavior of the organic matter in such soils may exert a significant influence on the solubility of the metals. Little is known about such a process. Using batch experiments in which the solubility of organic matter in a heavily sludge-amended soil was artificially manipulated, we show that the solubilities of the heavy metals copper (Cu), nickel (Ni), and lead (Pb) show a strong positive relationship to the solubility of organic matter, particularly at high pH. The results suggest that under field conditions, spatiotemporal variations in the solid-solution partitioning of organic matter may have a bearing on the environmental significance (mobility and bioavailability) of these heavy metals.

Comparison of EDTA and EDDS as potential soil amendments for enhanced phytoextraction of heavy metals

Phytoextraction has been proposed as an alternative remediation technology for soils polluted with heavy metals or radionuclides, but is generally conceived as too slow working. Enhancing the accumulation of trace pollutants in harvestable plant tissues is a prerequisite for the technology to be practically applicable. The chelating aminopolycarboxylic acid, ethylene diamine tetraacetate (EDTA), has been found to enhance shoot accumulation of heavy metals. However, the use of EDTA in phytoextraction may not be suitable due to its high environmental persistence, which may lead to groundwater contamination. This paper aims to assess whether ethylene diamine disuccinate (EDDS), a biodegradable chelator, can be used for enhanced phytoextraction purposes. A laboratory experiment was conducted to examine mobilisation of Cd, Cu, Cr, Ni, Pb and Zn into the soil solution upon application of EDTA or EDDS. The longevity of the induced mobilisation was monitored for a period of 40 days after application. Estimated effect half lives ranged between 3.8 and 7.5 days for EDDS, depending on the applied dose. The minimum observed effect half life of EDTA was 36 days, while for the highest applied dose no decrease was observed throughout the 40 day period of the mobilisation experiment. Performance of EDTA and EDDS for phytoextraction was evaluated by application to Helianthus annuus. Two other potential chelators, known for their biodegradability in comparison to EDTA, were tested in the plant experiment: nitrilo acetic acid (NTA) and citric acid. Uptake of heavy metals was higher in EDDS-treated pots than in EDTA-treated pots. The effects were still considered insufficiently high to consider efficient remediation. This may be partly due to the choice of timing for application of the soil amendment. Fixing the time of application at an earlier point before harvest may yield better results. NTA and citric acid induced no significant effects on heavy metal uptake. (C) 2004 Elsevier Ltd. All rights reserved.

Record of natural and anthropogenic changes in reef environments (Barbados West Indies) using laser ablation ICP-MS and sclerochronology on coral cores

Coral growth rate can be affected by environmental parameters such as seawater temperature, depth, and light intensity. The natural reef environment is also disturbed by human influences such as anthropogenic pollutants, which in Barbados are released close to the reefs. Here we describe a relatively new method of assessing the history of pollution and explain how these effects have influenced the coral communities off the west coast of Barbados. We evaluate the relative impact of both anthropogenic pollutants and natural stresses. Sclerochronology documents framework and skeletal growth rate and records pollution history (recorded as reduced growth) for a suite of sampled Montastraea annularis coral cores. X-radiography shows annual growth band patterns of the corals extending back over several decades and indicates significantly lower growth rate in polluted sites. Results using laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) on the whole sample (aragonite, organic matter, trapped particulate matter, etc.), have shown contrasting concentrations of the trace elements (Cu, Sn, Zn, and Pb) between corals at different locations and within a single coral. Deepwater corals 7 km apart, record different levels of Pb and Sn, suggesting that a current transported the metal pollution in the water. In addition, the 1995 hurricanes are associated with anomalous values for Sn and Cu from most sites. These are believed to result from dispersion of nearshore polluted water. We compared the concentrations of trace elements in the coral growth of particular years to those in the relevant contemporaneous seawater. Mean values for the concentration factor in the coral, relative to the water, ranged from 10 for Cu and Ni to 2.4 and 0.7 for Cd and Zn, respectively. Although the uncertainties are large (60-80%), the coral record enabled us to demonstrate the possibility of calculating a history of seawater pollution for these elements from the 1940s to 1997. Our values were much higher than those obtained from analysis of carefully cleaned coral aragonite; they demonstrate the incorporation of more contamination including that from particulate material as well as dissolved metals.

Unprecedented coordination of dithiocarbimate in multinuclear and heteroleptic complexes

An uncommon coordination protocol induced by the p-tolylsulfonyl dithiocarbimate ligand (L) [L = p-CH(3)C(6)H(4)SO(2)N CS(2)(2-)] in conjunction with PPh(3) allowed the formation of novel homodimetallic, Cu(2)(PPh(3))(4)L (1), trinuclear heterometallic Cu(2)Ni(L)(2)(PPh(3))(4) (2) and heteroleptic complexes of general formula cis-[M(PPh(3))(2)L] [M = Pd(II) (3), Pt(II) (4)]. The complexes have been characterized by microanalysis, mass spectrometry, IR, (1)H, (13)C and (31)P NMR and electronic absorption spectra and single-crystal X-ray crystallography. 2 uniquely consists of square planar, trigonal planar and tetrahedral coordination spheres within the same molecule. In both heteroleptic complexes 3 and 4 the orientation of aromatic protons of PPh(3) ligand towards the Pd(II) and Pt(II) center reveals C-H center dot center dot center dot Pd and C-H center dot center dot center dot Pt rare intramolecular anagostic or preagostic interactions. These complexes exhibit photoluminescent properties in solution at room temperature arising mainly from intraligand charge transfer (ILCT) transitions. The assignment of electronic absorption bands has been corroborated by time dependent density functional theory (TD-DFT) calculations. Complexes 1 and 2 with sigma(rt) values similar to 10(-6) S cm(-1) show semi-conductor properties in the temperature range 313-403 K whereas 3 and 4 exhibit insulating behaviour.