The synthesis, structure, and electrochemical properties of Fe(C CC N)(dppe)Cp and related compounds

The cyanoacetylide complex Fe(CCCN)(dppe)Cp (3) is readily obtained from sequential reaction of Fe(CCSiMe3)(dppe)Cp with methyllithium and phenyl cyanate. Complex 3 is a good metalloligand, and coordination to the metal fragments [RhCl(CO)(2)], [Ru(PPh3)(2)Cp](+), and [Ru(dppe)Cp*](+) affords the corresponding cyanoaceylide-bridged heterobimetallic complexes. In the case of the 36-electron complexes [Cp(dppe)Fe-CCCN-MLn](n+), spectroscopic and structural data are consistent with a degree of charge transfer from the iron centre to the rhodium or ruthenium centre via the C3N bridge, giving rise to a polarized ground state. Electrochemical and spectroelectrochemical methods reveal significant interactions between the metal centres in the oxidized (35 electron) derivatives, [Cp(dppe)Fe-CCCN-MLn]((n+1)+).

Synthesis and properties of new trinuclear Mo(II) complexes containing imidazole and benzimidazole ferrocene units

The reaction of FcCOC1 (Fc = (C5H5) Fe(C5H4)) with benzimidazole or imidazole in 1: 1 ratio gives the ferrocenyl derivatives FcCO(benzim) (L1) or FcCO(im) (L2), respectively. Two molecules of L1 or L2 can replace two nitrile ligands in [Mo(eta(3)-C3H5)( CO)(2)(CH3CN)(2)Br] or [Mo(eta(3)-C5H5O)(CO)(2)(CH3CN)(2)Br] leading to the new trinuclear complexes [Mo(eta(3)-C3H5)(CO)(2)(L)(2)Br] (C1 for L = L1; C3 for L = L2) and [Mo(eta(3)-C5H5O)(CO)(2)(L)(2)Br] (C-2 for L = L1; C4 for L = L2) with L1 and L2 acting as N-monodentade ligands. L1, L2 and C2 were characterized by X-ray diffraction studies. [Mo(eta(3)-C5H5O)(CO) 2(L1)(2)Br] was shown to be a trinuclear species, with the two L1 molecules occupying one equatorial and one axial position in the coordination sphere of Mo(II). Cyclic voltammetric studies were performed for the two ligands L1 and L2, as well as for their molybdenum complexes, and kinetic and thermodynamic data for the corresponding redox processes obtained. In agreement with the nature of the frontier orbitals obtained from DFT calculations, L1 and L2 exhibit one oxidation process at the Fe(II) center, while C1, C3, and C4 display another oxidation wave at lower potentials, associated with the oxidation of Mo(II). (C) 2007 Elsevier B. V. All rights reserved.

Mono- and binuclear bipyridyl derivatives of the Mo(eta(3)-C3H5)(CO)(2) fragment: structural studies and fluxionality in solution

New mono- and binuclear complexes of the Mo(eta(3)-C3H5)(CO)(2) fragment, containing bipyridyl ligands (2,2'-bpy, 4,4'-Me-2-2,2'-bpy) as chelates, and mono- (4-CNpy, 4-Mepy, NCMe, Br) or bidentate nitrogen ligands (4,4'-bpy, bipyridylethylene, pyrazine) as terminal or bridging ligands, respectively, were prepared. The binuclear complex [{Mo(eta(3)-C3H5)(CO)(2)(2,2'-bpy)}(2)(mu-4,4'-bpy)][PF6](2) (2) was shown by X-ray diffraction to assemble in the crystal forming large channels with a rectangular section. A longer bridge, such as bipyridylethylene, led to a different structure (3). 4-CNpy behaved as monodentate ligand (4), coordinating through the pyridine nitrogen as a terminal ligand. NMR spectroscopy studies showed that the complexes exhibited a fluxional behavior in solution, the endo and exo forms of the more symmetrical equatorial isomers being usually present and interconverting in solution. The solid state structures of the complexes revealed a preference for the more symmetrical equatorial isomer, with the two chelate ligands in trans positions in the binuclear species. The rings tended to become parallel in the organized crystal. (C) 2003 Elsevier B.V. All rights reserved.

A new cyano-bridged one-dimensional (GdFeIII)-Fe-III coordination polymer with o-phenanthroline as the blocking ligand: synthesis, structure, and magnetic properties

Synthesis, structural characterization, and magnetic properties of a new cyano-bridged one-dimensional iron (III)-gadolinium (III) compound, trans-[Gd(o-phen)(2)(H2O)(2)(mu-CN)(2)Fe(CN)(4)], - 2no-phen (o-phen = 1,10-phenanthroline), have been described. The compound crystallizes in the triclinic P (1) over bar space group with the following unit cell parameters: a = 10.538(14) angstrom, b = 12.004(14) angstrom, c = 20.61(2) angstrom, alpha = 92.41(1)degrees, beta = 92.76(1)degrees, gamma = 11 2.72(1)degrees, and Z = 2. In this complex, each gadolinium (III) is coordinated to two nitrile nitrogens of the CN groups coming from two different ferricyanides, the mutually trans cyanides of each of which links another different Gd-III to create -NC-Fe(CN)(4)-CN-Gd-NC- type 1-D chain structure. The one-dimensional chains are self-assembled in two-dimensions via weak C-H center dot center dot center dot N hydrogen bonds. Both the variable-temperature (2-300 K, 0.01 T and 0.8 T) and variable-field (0-50 000 Gauss, 2 K) magnetic measurements reveal the existence of very weak interaction in this molecule. The temperature dependence of the susceptibilities has been analyzed using a model for a chain of alternating classic (7/2) and quantum (1/2) spins. (c) 2005 Elsevier B.V. All rights reserved.

Characteristics of silica-rich pedofeatures in a buried paleosol

Whitish and whitish-light brown milky-like textural pedofeatures and impregnations were found in the voids and the matrix of buried paleosols older than 2.7 million years in a site in Sardinia, Italy. The pedofeatures were described and analysed using micromorphology, X-ray diffraction and microprobe techniques, and their spatial distribution correlated with field evidence. The suite of analyses showed that the main components of the pedofeatures were more or less ordered silica phases. As well as forming a matrix cement, these pedofeatures also occurred as coatings and infillings in pores. Significant amounts of alumina and, less, Mg, Ca and Fe were also present in the pedofeatures, possibly in the form of silicate coatings and inclusions/impurities, or alumino-silicates of the adjacent soil matrix. A number of hypotheses are drawn on the possible mechanisms of formation of these silica-rich pedofeatures, including the possibility of prolonged weathering of volcanic materials and the resulting formation of colloids and more or less ordered silica phases, with successive dehydration and progressive ordering of phases during the at least 2.5 million years. (C) 2003 Elsevier B.V. All rights reserved.

Spectral properties, iron oxide content and provenance of Namib dune sands

This paper applies multispectral remote sensing techniques to map the Fe-oxide content over the entire Namib sand sea. Spectrometric analysis is applied to field samples to identify the reflectance properties of the dune sands which enable remotely sensed Fe-oxide mapping. The results indicate that the pattern of dune colour in the Namib sand sea arises from the mixing of at least two distinct sources of sand; a red component of high Fe-oxide content (present as a coating on the sand grains) which derives from the inland regions, particularly from major embayments into the Southern African escarpment; and a yellow coastal component of low Fe-oxide content which is brought into the area by northward-moving aeolian transport processes. These major provenances are separated by a mixing zone between 20 kin and 90 kin from the coast throughout the entire length of the sand sea. Previous workers have also recognised a third, fluvial, provenance, but the methodology applied here is not able to map this source as a distinct spectral component. (c) 2006 Elsevier B.V. All rights reserved.

Microbial perchlorate reduction: A precise laboratory determination of the chlorine isotope fractionation and its possible biochemical basis

Perchlorate-reducing bacteria fractionate chlorine stable isotopes giving a powerful approach to monitor the extent of microbial consumption of perchlorate in contaminated sites undergoing remediation or natural perchlorate containing sites. This study reports the full experimental data and methodology used to re-evaluate the chlorine isotope fractionation of perchlorate reduction in duplicate culture experiments of Azospira suillum strain PS at 37 degrees C (Delta Cl-37(Cr)--ClO4-) previously reported, without a supporting data set by Coleman et al. [Coleman, M.L., Ader, M., Chaudhuri, S., Coates,J.D., 2003. Microbial Isotopic Fractionation of Perchlorate Chlorine. Appl. Environ. Microbiol. 69, 4997-5000] in a reconnaissance study, with the goal of increasing the accuracy and precision of the isotopic fractionation determination. The method fully described here for the first time, allows the determination of a higher precision Delta Cl-37(Cl)--ClO4- value, either from accumulated chloride content and isotopic composition or from the residual perchlorate content and isotopic composition. The result sets agree perfectly, within error, giving average Delta Cl-37(Cl)--ClO4- = -14.94 +/- 0.15%omicron. Complementary use of chloride and perchlorate data allowed the identification and rejection of poor quality data by applying mass and isotopic balance checks. This precise Delta Cl-37(Cl)--ClO4-, value can serve as a reference point for comparison with future in situ or microcosm studies but we also note its similarity to the theoretical equilibrium isotopic fractionation between a hypothetical chlorine species of redox state +6 and perchlorate at 37 degrees C and suggest that the first electron transfer during perchlorate reduction may occur at isotopic equilibrium between art enzyme-bound chlorine and perchlorate. (C) 2008 Elsevier B.V. All rights reserved.

Evaluating the century C model using long-term fertilizer trials in the Indo-Gangetic Plains, India

The GEFSOC Project developed a system for estimating soil carbon (C) stocks and changes at the national and sub-national scale. As part of the development of the system, the Century ecosystem model was evaluated for its ability to simulate soil organic C (SOC) changes in environmental conditions in the Indo-Gangetic Plains, India (IGP). Two long-term fertilizer trials (LTFT), with all necessary parameters needed to run Century, were used for this purpose: a jute (Corchorus capsularis L.), rice (Oryza sativa L.) and wheat (Triticum aestivum L.) trial at Barrackpore, West Bengal, and a rice-wheat trial at Ludhiana, Punjab. The trials represent two contrasting climates of the IGP, viz. semi-arid, dry with mean annual rainfall (MAR) of < 800 mm and humid with > 1600 turn. Both trials involved several different treatments with different organic and inorganic fertilizer inputs. In general, the model tended to overestimate treatment effects by approximately 15%. At the semi-arid site, modelled data simulated actual data reasonably well for all treatments, with the control and chemical N + farm yard manure showing the best agreement (RMSE = 7). At the humid site, Century performed less well. This could have been due to a range of factors including site history. During the study, Century was calibrated to simulate crop yields for the two sites considered using data from across the Indian IGP. However, further adjustments may improve model performance at these sites and others in the IGP. The availability of more longterm experimental data sets (especially those involving flooded lowland rice and triple cropping systems from the IGP) for testing and validation is critical to the application of the model's predictive capabilities for this area of the Indian sub-continent. (C) 2007 Elsevier B.V. All rights reserved.

Hydrochemical variations and contaminant load in the Rio Tinto (Spain) during flood events

The aim of this work is to study the hydrochemical variations during flood events in the Rio Tinto, SW Spain. Three separate rainfall/flood events were monitored in October 2004 following the dry season. In general, concentrations markedly increased following the first event (Fe from 99 to 1130 mg/L; Q(max) = 0.78 m(3)/s) while dissolved loads peaked in the second event (Fe = 7.5 kg/s, Cu = 0.83 kg/s, Zn = 0.82 kg/s; Q(max) = 77 m(3)/s) and discharge in the third event (Q(max) = 127 m(3)/s). This pattern reflects a progressive depletion of metals and sulphate stored in the dry summer as soluble evaporitic salt minerals and concentrated pore fluids, with dilution by freshwater becoming increasingly dominant as the month progressed. Variations in relative concentrations were attributed to oxyhydroxysulphate Fe precipitation, to relative changes in the sources of acid mine drainage (e.g. salt minerals, mine tunnels, spoil heaps etc.) and to differences in the rainfall distributions along the catchment. The contaminant load carried by the river during October 2004 was enormous, totalling some 770 t of Fe, 420 t of Al, 100 t of Cu, 100 t of Zn and 71 t of Mn. This represents the largest recorded example of this flush-out process in an acid mine drainage setting. Approximately 1000 times more water and 1408 200 times more dissolved elements were carried by the river during October 2004 than during the dry, low-flow conditions of September 2004, highlighting the key role of flood Events in the annual pollutant transport budget of semi-arid and and systems and the need to monitor these events in detail in order to accurately quantify pollutant transport. (c) 2007 Elsevier B.V. All rights reserved.

Trace element partitioning and soil particle characterisation around mining and smelting areas at Tharsis, Riotinto and Huelva, SW Spain

Trace elements may present an environmental hazard in the vicinity of mining and smelting activities. However, the factors controlling trace element distribution in soils around ancient and modem mining and smelting areas are not always clear. Tharsis, Riotinto and Huelva are located in the Iberian Pyrite Belt in SW Spain. Tharsis and Riotinto mines have been exploited since 2500 B.C., with intensive smelting taking place. Huelva, established in 1970 and using the Flash Furnace Outokumpu process, is currently one of the largest smelter in the world. Pyrite and chalcopyrite ore have been intensively smelted for Cu. However, unusually for smelters and mines of a similar size, the elevated trace element concentrations in soils were found to be restricted to the immediate vicinity of the mines and smelters, being found up to a maximum of 2 kin from the mines and smelters at Tharsis, Riotinto and Huelva. Trace element partitioning (over 2/3 of trace elements found in the residual immobile fraction of soils at Tharsis) and soil particles examination by SEM-EDX showed that trace elements were not adsorbed onto soil particles, but were included within the matrix of large trace element-rich Fe silicate slag particles (i.e. 1 min circle divide at least 1 wt.% As, Cu and Zn, and 2 wt.% Pb). Slag particle large size (I mm 0) was found to control the geographically restricted trace element distribution in soils at Tharsis, Riotinto and Huelva, since large heavy particles could not have been transported long distances. Distribution and partitioning indicated that impacts to the environment as a result of mining and smelting should remain minimal in the region. (c) 2006 Elsevier B.V. All rights reserved.

Aqueous geochemistry and oxygen isotope compositions of acid mine drainage from the Río Tinto, SW Spain, highlight inconsistencies in current models

The Rio Tinto river in SW Spain is a classic example of acid mine drainage and the focus of an increasing amount of research including environmental geochemistry, extremophile microbiology and Mars-analogue studies. Its 5000-year mining legacy has resulted in a wide range of point inputs including spoil heaps and tunnels draining underground workings. The variety of inputs and importance of the river as a research site make it an ideal location for investigating sulphide oxidation mechanisms at the field scale. Mass balance calculations showed that pyrite oxidation accounts for over 93% of the dissolved sulphate derived from sulphide oxidation in the Rio Tinto point inputs. Oxygen isotopes in water and sulphate were analysed from a variety of drainage sources and displayed delta O-18((SO4-H2O)) values from 3.9 to 13.6 parts per thousand, indicating that different oxidation pathways occurred at different sites within the catchment. The most commonly used approach to interpreting field oxygen isotope data applies water and oxygen fractionation factors derived from laboratory experiments. We demonstrate that this approach cannot explain high delta O-18((SO4-H2O)) values in a manner that is consistent with recent models of pyrite and sulphoxyanion oxidation. In the Rio Tinto, high delta O-18((SO4-H2O)) values (11.2-13.6 parts per thousand) occur in concentrated (Fe = 172-829 mM), low pH (0.88-1.4), ferrous iron (68-91% of total Fe) waters and are most simply explained by a mechanism involving a dissolved sulphite intermediate, sulphite-water oxygen equilibrium exchange and finally sulphite oxidation to sulphate with O-2. In contrast, drainage from large waste blocks of acid volcanic tuff with pyritiferous veins also had low pH (1.7). but had a low delta O-18((SO4-H2O)) value of 4.0 parts per thousand and high concentrations of ferric iron (Fe(III) = 185 mM, total Fe = 186 mM), suggesting a pathway where ferric iron is the primary oxidant, water is the primary source of oxygen in the sulphate and where sulphate is released directly from the pyrite surface. However, problems remain with the sulphite-water oxygen exchange model and recommendations are therefore made for future experiments to refine our understanding of oxygen isotopes in pyrite oxidation. (C) 2009 Elsevier 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.

An inventory of heavy metals inputs to agricultural soils in England and Wales

An inventory of heavy metal inputs (Zn, Cu, Ni, Pb, Cd, Cr, As and Hg) to agricultural soils in England and Wales in 2000 is presented, accounting for major sources including atmospheric deposition, sewage sludge, livestock manures, inorganic fertilisers and lime, agrochemicals, irrigation water, industrial by-product 'wastes' and composts. Across the whole agricultural land area, atmospheric deposition was the main source of most metals, ranging from 25 to 85% of total inputs. Livestock manures and sewage sludge were also important sources, responsible for an estimated 37-40 and 8-17% of total Zn and Cu inputs, respectively. However, at the individual field scale sewage sludge, livestock manures and industrial wastes could be the major source of many metals where these materials are applied. This work will assist in developing strategies for reducing heavy metal inputs to agricultural land and effectively targeting policies to protect soils from long-term heavy metal accumulation. (C) 2003 Elsevier Science B.V. All rights reserved.

Hydrological controls on soil redox dynamics in a peat-based, restored wetland

Increasing areas of altered wetland are being restored by re-flooding the soil. Evidence in the literature indicates that this practice can induce the redox-mediated release of soil nutrients, thereby increasing the risk of diffuse water pollution. However, for the sake of improving wedand management decisions, there is a need for more detailed studies of the underlying relationship between the hydrological and redox dynamics that explain this risk; this is particularly the case in agricultural peatlands that are commonly targeted for the creation of lowland wet grassland. A 12-month field study was conducted to evaluate the relationship between hydrological fluctuations and soil redox potential (Eh) in a nutrient-rich peat field (32 g N kg(-1) and 1100 mg P kg(-1) in the surface 0-30 cm soil) that had been restored as lowland wet grassland from intensive arable production. Field tensiometers were installed at the 30-, 60- and 90-cm soil depths, and Pt electrodes at the 10-, 30-, 60- and 90-cm depths, for daily logging of soil water tension and Eh, respectively. The values for soil water tension displayed a strong negative relationship (P < 0.001) with monthly dip well observations of water table height. Calculations of soil water potential from the logged tension values were used, therefore, to provide a detailed profile of field water level and, together with precipitation data, explained some of the variation in Eh. For example, during the summer, alternating periods of aerobism (Eh > 330 mV) in the surface, 0-10 cm layer of peat coincided with intense precipitation events. Redox potential throughout the 30-100 cm profile also fluctuated seasonally; indeed, at all depths Eh displayed a strong, negative relationship (P < 0.001) with water table height over the 12-month study period. However, Eh throughout the 30-100 cm profile remained relatively low (< 230 mV), indicating permanently reduced conditions that are associated with denitrification and reductive dissolution of Fe-bound P. The implications of these processes in the N- and P-rich peat for wetland plant diversity and water quality are discussed. (c) 2006 Elsevier B.V. All rights reserved.

Mineral and geochemical characterization of a leptic aluandic soil and a thapto aluandic-ferralsol developed on trachytes in Mount Bambouto (Cameroon volcanic line)

Mineral and geochemical investigations were carried out on soil samples and fresh rock (trachytes) from two selected soil profiles (TM profile on leptic aluandic soils and TL profile on thapto aluandic-ferralsols) from Mount Bambouto to better understand geochemical processes and mineral paragenesis involved in the development of soils in this environment. In TM profile, the hydrated halloysites and goethite occur in the weathered saprolite boulders of BC horizon while dehydrated halloysite, gibbsite and goethite dominate the soils matrices of BC and A horizons. In TL profile, the dehydrated halloysites and goethite are the most abundant secondary minerals in the weathered saprolites of C and BC horizons while gibbsite, hematite and kaolinite occur in the soil matrices of BC, B and A horizons. The highest gibbsite content is in the platy nodules of B horizon. In both soil profiles, organo-metal complexes (most likely of AI and Fe) are present in the surface A horizon. Geochemically, between the fresh rock and the weathered saprolites in both soils, SiO2, K2O, CaO, Na2O and MgO contents decrease strongly while Fe2O3 and Al2O3 tend to accumulate. The molar ratio of SiO2/Al2O3 (Ki) and the sum of Ca, Mg, K and Na ions (TRB) also decreases abruptly between fresh rocks and the weathered saprolites, but increases significantly at the soil surface. The TM profile shows intense Al enrichment whereas the TL profile highlights enrichment in both AI and Fe as the weathering progresses upwards. Both soil profiles are enriched in Ni, Cu, Ba and Co and depleted in U, Th, Ta, Hf, Y, Sr, Pb, Zr and Zn relative to fresh rock. They also show a relatively low fractionation of the rare earth elements (REE: La, Nd, Sm, Eu, Tb, Yb and Lu), except for Ce which tends to be enriched in soils compared to CI chondrite. All these results give evidence of intense hydrolysis at soil deep in Mount Bambouto resulting in the formation of halloysite which progressively transforms into gibbsite and/or dehydrated halloysite. At the soil surface, the prominent pedogenetic process refers to andosolization with formation of organo-metal complexes. In TL profile, the presence of kaolinite in soil matrices BC and B horizons is consistent with ferralitization at soil deep. In conclusion, soil forming processes in Mount Bambouto are strongly influenced by local climate: (i) in the upper mountain (>2000 m), the fresh, misty and humid climate favors andosolization; whereas (ii) in the middle lands (1700-2000 m) with a relatively dry climate, both andosolization at the soil surface and ferralitization at soil deep act together. (C) 2009 Elsevier B.V. All rights reserved.