CHROMIUM(II)-MEDIATED CONVERSION OF ALPHA,BETA-UNSATURATED ALDEHYDES TO CYCLOPROPANOLS

Chromium(II) chloride converts alpha,beta-unsaturated aldehydes to the corresponding cyclopropanols.

Simultaneous biosorption of methylene blue and trivalent chromium onto olive stone

In this work, olive stone (OS) was utilized to investigate its capacity as biosorbent for methylene blue (MB) and Cr(III), which are usually present in textile industry effluents. Equilibrium and kinetic experiments were performed in batch experiments. The biosorption process followed pseudo-second-order kinetics. The equilibrium data were fitted with several models, but Langmuir and Sips models best reproduced the experimental results. Maximum biosorption capacities were 3.296 mg/g (0.0116 mmol/g) and 4.990 mg/g (0.0960 mmol/g) for MB and Cr(III), respectively. Several operation variables, such as
biosorbent mass, flow rate, and initial concentration on the removal of dye and metal, were evaluated in column system. The removal efficiency improved as OS mass increased and decreased when flow rate and initial concentration increased. Also, MB uptake was substantially decreased by increasing the initial concentration of Cr(III), ranging from 6.09 to 2.75 mg/g. These results show that the presence of Cr(III) significantly modifies the biosorption capacity of MB by the OS. These results suggest that OS is a potential low-cost food industry waste for textile industry wastewater treatment.

Abatement technologies for road surface run-off

Heavy metals, primarily zinc, copper, lead, and chromium, and Polycyclic Aromatic Hydrocarbons (PAHs) are the main hazardous constituents of road runoff. The main sources of these contaminants are vehicle emission, mostly through wear and leakage, although erosion of the road surface and de-icing salts are also recognised pollution sources. The bioavailability of these toxic compounds, and more importantly their potential biomagnification along food chains, could affect aquatic communities persistently exposed to road runoff. Several internationally approved abatement technologies are available for the management of road runoff on new motorway schemes. Recent studies conducted in Cork and Dublin, Ireland demonstrated the efficacy of infiltration trenches as abatement technologies in the removal of both heavy metals and PAHs prior to discharge; the technology was however inefficient in mitigating first flush events. Gully traps with sedimentation chambers, another technology investigated, demonstrated to have a substantially lower removal potential but appeared to be more effective in attenuating surges of contaminants attributed to first flush events. Consequently the employment of combined abatement techniques could efficiently minimise deviations from required effluent concentrations. The studies determined a relatively stationary accumulation of heavy metals and PAHs in sediments close to the point of discharge with a rapid decline in concentration in nearby downstream sediments (<50m). Further, Microtox® Solid Phase testing reported a negligible impact on assemblages exposed to contaminated sediments for all sites investigated. This paper describes pollutant loading from road runoff and mitigation measures from a freshwater deterioration in a water quality perspective. The results and analysis of field samples collected adjacent to a number of roads and motorways in Ireland is also presented. Finally sustainable drainage systems, abatement techniques and technologies available for onsite treatment of runoff are presented to improve and mitigate impacts of vehicular transport on the environment.

Toenail trace element status and risk of Barrett's oesophagus and oesophageal adenocarcinoma. Results from the FINBAR study

Trace elements have been cited as both inhibitory and causative agents of cancer but importantly exposure to them is potentially modifiable. Our study aimed to examine toenail trace element status and risk of Barrett's oesophagus (BO) and oesophageal adenocarcinoma (OAC). Toenail clippings from each hallux were obtained from 638 participants of the FINBAR (Factors Influencing the Barrett's Adenocarcinoma Relationship) study comprising 221 healthy controls, 98 reflux oesophagitis, 182 BO and 137 OAC cases. The concentrations of eight toenail trace elements were determined using instrumental neutron activation analysis. Using multivariable adjusted logistic regression analysis, odds ratios (OR) and 95% confidence intervals (CIs) were calculated within tertiles of trace element concentrations. A twofold increased risk of BO was observed, but not OAC, among individuals in the highest tertile of toenail zinc status OR 2.21 (95% CI, 1.11-4.40). A higher toenail selenium status was not associated with risk of OAC OR 0.94 (95% CI, 0.44-2.04) or BO OR 0.89 (95% CI, 0.37-2.12). A borderline significant increased risk of BO was detected with a higher toenail cobalt concentration, OR 1.97 (95% CI, 1.01-3.85). No association was found between toenail levels of chromium, cerium, mercury and OAC or BO risk. This is the first case-control study to investigate a variety of trace elements in relation to OAC and BO risk. Despite antioxidant and proapoptotic properties, no associations were found with selenium. Higher concentrations of toenail zinc and cobalt were associated with an increased BO risk, but not OAC. These findings need confirmation in prospective analysis.

Risk assessment of potentially toxic elements in agricultural soils and maize tissues from selected districts in Tanzania

A field survey was conducted to investigate the contamination of potentially toxic elements (PTEs) arsenic (As), lead (Pb), chromium (Cr), and nickel (Ni) in Tanzanian agricultural soils and to evaluate their uptake and translocation in maize as proxy to the safety of maize used for human and animal consumption. Soils and maize tissues were sampled from 40 farms in Tanzania and analyzed using inductively coupled plasma-mass spectrometry in the United Kingdom. The results showed high levels of PTEs in both soils and maize tissues above the recommended limits. Nickel levels of up to 34.4 and 56.9mgkg(-1) respectively were found in some maize shoots and grains from several districts. Also, high Pb levels >0.2mgkg(-1) were found in some grains. The grains and shoots with high levels of Ni and Pb are unfit for human and animal consumption. Concentrations of individual elements in maize tissues and soils did not correlate and showed differences in uptake and translocation. However, Ni showed a more efficient transfer from soils to shoots than As, Pb and Cr. Transfer of Cr and Ni from shoots to grains was higher than other elements, implying that whatever amount is assimilated in maize shoots is efficiently mobilized and transferred to grains. Thus, the study recommended to the public to stop consuming and feeding their animals maize with high levels of PTEs for their safety.

Ecotoxicological screening of Kenyan tannery dust using a luminescent-based bacterial biosensor

Ecotoxicological screening of dust sampled throughout a Kenyan tannery was conducted using a luminescence (lux)-based bacterial biosensor for both solid and liquid assays. This was complemented by chemical analysis in an attempt to identify possible causative toxic components. The biosensor results showed a highly significant (p <0.001) difference in both solid and liquid phase toxicity in samples collected from various identified sampling points in the tannery. A positive correlation was observed between results of the solid and liquid phase techniques, for most of the sampling points indicating that the toxic contaminants were bioavailable both in the solid and liquid state. However, the results generally indicated toxicity associated with liquid phase except certain areas in solid phase such as chemical handling, buffing area and weighing. The most toxic tannery area identified was the weighing area (p <0.001), showing the lowest bioluminescence for both the solid (0.38 +/- 2.21) and liquid phases (0.01 +/- 0.001). Chromium was the metal present in the highest concentration indicating levels higher than the stipulated regulatory requirement of 0.5 mg Cr/m3 for total Cr (highest Cr concentration was at chemical handling at 209.24 mg l(-1)) in all dust samples. The weighing area had the highest Ni concentration (1.87 mg l(-1)) and the chemical handling area showed the highest Zn concentration (31.9 mg l(-1)). These results raise environmental health concerns, as occupational exposure to dust samples from this site has been shown to give rise to elevated concentrations (above the stipulated levels) of chromium in blood, urine and some body tissues, with inhalation being the main route. Health and Safety Executive (HSE), UK, and American Conference of Governmental Industrial Hygienist (ACGIH) and National Institute for Occupational Safety and Health (NIOSH), USA stipulates an occupational exposure limit of 0.5 mg Cr/m3 (8 h TWA) for total chromium. However, schedule 1 of Controls of substances hazardous to health (COSHH) regulations developed by HSE, indicate 0.05 mg m3 (8 h TWA reference periods) to be the limit for Cr (VI) exposure. The exposure limit for individual (e.g., Cr, Zn, Ni etc.) contaminants (homogeneity) was not exceeded, but potential impact of heterogeneity (multi-element synergistic effect) on toxicity requires application of the precautionary principle.

An ecotoxicological approach to assessing the impact of tanning industry effluent on river health

A study was conducted to investigate the sediment health and water quality of the River Sagana, Kenya, as impacted by the local tanning industry. Chemical analysis identified the main chemical pollutants (pentachlorophenols and chromium) while a bioassay addressed pollutant bioavailability. The bioassay, exploiting the luminescence response of a lux marked bacterial biosensor, was coupled to a dehydrogenase and Dapnia magna test to determine toxicity effects on sediments. Results highlighted the toxicity of the tannery effluent to the sediments at the point of discharge (64% of control bioluminescence) with gradual improvement downstream. There was a significant increase in dehydrogenase downstream, with the enzyme activity attaining a peak at 600 m, also indicating a gradual reduction of toxicity. Biological oxygen demand (19.56 mg L(-1)) dissolved oxygen (3.97 mg L(-1)) and high lethal dose value (85%) of D. magna also confirmed an initial stress at the point of discharge and recovery downstream. Optical density of surface water demonstrated an increase in suspended particulates and colour after the discharge point, eventually decreasing beyond 400 m. In conclusion, the study highlighted the importance of understanding the biogeochemistry of river systems impacted by industries discharging effluent into them and the invaluable role of a biosensor-based ecotoxicological approach to address effluent hazards, particularly in relation to river sediments.

Downstream changes in the transport and storage of sediment-associated contaminants (P, Cr and PCBs) in agricultural and industrialized drainage basins

Samples of suspended, floodplain and channel bed sediment have been used to examine downstream changes in ediment-associated contaminant transport and storage in contrasting rivers in Yorkshire, UK. The concentrations of hosphorus, chromium and selected PCBs associated with sediment in the River Aire and its main tributary, the River Calder, which drain an urbanized and industrialized catchment, are considerably higher than those in the relatively unpolluted River Swale, which drains an agricultural catchment. Concentrations of sediment-associated contaminants in the Aire/Calder system increase downstream, reflecting the location of urban and industrial areas in the middle and lower reaches, and the location of point source inputs, such as sewage treatment works. The ontaminant concentrations associated with floodplain and channel bed sediment in the Rivers Aire and Calder are high, particularly in the lower reaches. This, combined with measurements of sediment storage on the floodplain and channel bed, indicate that significant storage of sediment-associated contaminants occurs in the Rivers Aire and Calder.

On the Mechanism of Lewis Acid Catalyzed Glucose Transformations in Ionic Liquids

A complementary computational and experimental study of the reactivity of Lewis acidic CrCl2, CuCl2 and FeCl2 catalysts towards glucose activation in dialkylimidazolium chloride ionic liquids is performed. The selective dehydration of glucose to 5-hydroxymethylfurfural (HMF) proceeds through the intermediate formation of fructose. Although chromium(II) and copper(II) chlorides are able to dehydrate fructose with high HMF selectivity, reasonable HMF yields from glucose are only obtained with CrCl2 as the catalyst. Glucose conversion by CuCl2 is not selective, while FeCl2 catalyst does not activate sugar molecules. These differences in reactivity are rationalized on the basis of in situ X-ray absorption spectroscopy measurements and the results of density functional theory calculations. The reactivity in glucose dehydration and HMF selectivity are determined by the behavior of the ionic liquid-mediated Lewis acid catalysts towards the initial activation of the sugar molecules. The formation of a coordination complex between the Lewis acidic Cr2+ center and glucose directs glucose transformation into fructose. For Cu2+ the direct coordination of sugar to the copper(II) chloride complex is unfavorable. Glucose deprotonation by a mobile Cl- ligand in the CuCl42- complex initiates the nonselective conversion. In the course of the reaction the Cu2+ ions are reduced to Cu+. Both paths are prohibited for the FeCl2 catalyst.

Phosphotungstic Acid Encapsulated in Metal-Organic Framework as Catalysts for Carbohydrate Dehydration to 5-Hydroxymethylfurfural

MIL-101, a chromium-based metal-organic framework, is known for its very large pore size, large surface area and good stability. However, applications of this material in catalysis are still limited. 5-Hydroxymethylfurfural (HMF) has been considered a renewable chemical platform for the production of liquid fuels and fine chemicals. Phosphotungstic acid, H3PW12O40 (PTA), encapsulated in MIL-101 is evaluated as a potential catalyst for the selective dehydration of fructose and glucose to 5-hydroxymethylfurfural. The results demonstrate that PTA/MIL-101 is effective for HMF production from fructose in DMSO and can be reused. This is the first example of the application of a metal-organic framework in carbohydrate dehydration.

Microwave Irradiation for the Facile Synthesis of Transition-Metal Nanoparticles (NPs) in Ionic Liquids (ILs) from Metal-Carbonyl Precursors and Ru-, Rh-, and Ir-NP/IL Dispersions as Biphasic Liquid-Liquid Hydrogenation Nanocatalysts for Cyclohexene

Stable chromium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, and iridium metal nanoparticles (MNPs) have been reproducibly obtained by facile, rapid (3 min), and energysaving 10 W microwave irradiation (MWI) under an argon atmosphere from their metal–carbonyl precursors [Mx(CO)y] in the ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]). This MWI synthesis is compared to UV-photolytic (1000 W, 15 min) or conventional thermal decomposition (180–2508C, 6–12 h) of [Mx(CO)y] in ILs. The MWIobtained nanoparticles have a very small (<5 nm) and uniform size and are prepared without any additional stabilizers or capping molecules as long-term stable M-NP/IL dispersions (characterization by transmission electron microscopy (TEM), transmission electron diffraction (TED), and dynamic light scattering (DLS)). The ruthenium, rhodium, or iridium nanoparticle/IL dispersions are highly active
and easily recyclable catalysts for the biphasic liquid–liquid hydrogenation of cyclohexene to cyclohexane with activities of up to 522 (mol product)(mol Ru)1h1 and 884 (mol product)(molRh)1h1 and give almost quantitative conversion within 2 h at 10 bar H2 and 908C. Catalyst poisoning experiments with CS2 (0.05 equiv per Ru) suggest a heterogeneous surface catalysis of RuNPs.

The importance of solid-phase distribution on the oral bioaccessibility of Ni and Cr in soils overlying Palaeogene basalt lavas, Northern Ireland

Potentially toxic elements (PTEs) including nickel and chromium are often present in soils overlying basalt at concentrations above regulatory guidance values due to the presence of these elements in underlying geology. Oral bioaccessibility testing allows the risk posed by PTEs to human health to be assessed; however, bioaccessibility is controlled by factors including mineralogy, particle size, solid-phase speciation and encapsulation. X-ray diffraction was used to characterise the mineralogy of 12 soil samples overlying Palaeogene basalt lavas in Northern Ireland, and non-specific sequential extraction coupled with chemometric analysis was used to determine the distribution of elements amongst soil components in 3 of these samples. The data obtained were related to total concentration and oral bioaccessible concentration to determine whether a relationship exists between the overall concentrations of PTEs, their bioaccessibility and the soils mineralogy and geochemistry. Gastric phase bioaccessible fraction (BAF %) ranged from 0.4 to 5.4 % for chromium in soils overlying basalt and bioaccessible and total chromium concentrations are positively correlated. In contrast, the range of gastric phase BAF for nickel was greater (1.4–43.8 %), while no significant correlation was observed between bioaccessible and total nickel concentrations. However, nickel BAF was inversely correlated with total concentration. Solid-phase fractionation information showed that bioaccessible nickel was associated with calcium carbonate, aluminium oxide, iron oxide and clay-related components, while bioaccessible chromium was associated with clay-related components. This suggests that weathering significantly affects nickel bioaccessibility, but does not have the same effect on the bioaccessibility of chromium.

Investigating local relationships between trace elements in soils and cancer data

Medical geology research has recognised a number of potentially toxic elements (PTEs), such as arsenic, cobalt, chromium, copper, nickel, lead, vanadium, uranium and zinc, known to influence human disease by their respective deficiency or toxicity. As the impact of infectious diseases has decreased and the population ages, so cancer has become the most common cause of death in developed countries including Northern Ireland. This research explores the relationship between environmental exposure to potentially toxic elements in soil and cancer disease data across Northern Ireland. The incidence of twelve different cancer types (lung, stomach, leukaemia, oesophagus, colorectal, bladder, kidney, breast, mesothelioma, melanoma and non melanoma(NM) both basal and squamous, were examined in the form of twenty-five coded datasets comprising aggregates over the 12 year period from 1993 to 2006. A local modelling technique,geographically weighted regression (GWR) is usedto explore the relationship between environmental exposure and cancer disease data. The results show comparisons of the geographical incidence of certain cancers (stomach and NM squamous skin cancer) in relation to concentrations of certain PTEs (arsenic levels in soils and radon were identified). Findings from the research have implications for regional human health risk assessments.

Double-detonation sub-Chandrasekhar supernovae: Synthetic observables for minimum helium shell mass models

In the double-detonation scenario for Type Ia supernovae, it is suggested that a detonation initiates in a shell of helium-rich material accreted from a companion star by a sub-Chandrasekhar-mass white dwarf. This shell detonation drives a shock front into the carbon-oxygen white dwarf that triggers a secondary detonation in the core. The core detonation results in a complete disruption of the white dwarf. Earlier studies concluded that this scenario has difficulties in accounting for the observed properties of Type Ia supernovae since the explosion ejecta are surrounded by the products of explosive helium burning in the shell. Recently, however, it was proposed that detonations might be possible for much less massive helium shells than previously assumed (Bildsten et al.). Moreover, it was shown that even detonations of these minimum helium shell masses robustly trigger detonations of the carbon-oxygen core (Fink et al.). Therefore, it is possible that the impact of the helium layer on observables is less than previously thought. Here, we present time-dependent multi-wavelength radiative transfer calculations for models with minimum helium shell mass and derive synthetic observables for both the optical and ? -ray spectral regions. These differ strongly from those found in earlier simulations of sub-Chandrasekhar-mass explosions in which more massive helium shells were considered. Our models predict light curves that cover both the range of brightnesses and the rise and decline times of observed Type Ia supernovae. However, their colors and spectra do not match the observations. In particular, their B - V colors are generally too red. We show that this discrepancy is mainly due to the composition of the burning products of the helium shell of the Fink et al. models which contain significant amounts of titanium and chromium. Using a toy model, we also show that the burning products of the helium shell depend crucially on its initial composition. This leads us to conclude that good agreement between sub-Chandrasekhar-mass explosions and observed Type Ia supernovae may still be feasible but further study of the shell properties is required.

Influence of solution chemistry on Cr(VI) reduction and complexation onto date-pits/tea-waste biomaterials

Tea waste (TW) and Date pits (DP) were investigated for their potential to remove toxic Cr(VI) ions from aqueous solution. Investigations showed that the majority of the bound Cr(VI) ions were reduced to Cr(III) after biosorption at acidic conditions. The electrons for the reduction of Cr(VI) may have been donated from the TW and DP biomasses. The experimental data obtained for Cr(VI)-TW and Cr(VI)-DP at different solution temperatures indicate a multilayer type biosorption, which explains why the Sips isotherm accurately represents the experimental data obtained in this study. The Sips maximum biosorption capacities of Cr(VI) onto TW and DP were 5.768 and 3.199 mmol/g at 333 K, respectively, which is comparatively superior to most other low-cost biomaterials. Fourier transform infrared spectroscopic analysis of the metal loaded biosorbents confirmed the participation of -COOH, -NH and O-CH groups in the reduction and complexation of chromium. Thermodynamic parameters demonstrated that the biosorption of Cr(VI) onto TW and DP biomass was endothermic, spontaneous and feasible at 303-333 K. The results evidently indicated that tea waste and date pits would be suitable biosorbents for Cr(VI) in wastewater under specific conditions.