Impact of sample preparation on mineralogical analysis of zero-valent iron reactive barrier materials

Permeable reactive barriers (PRBs) of zero-valent iron (Fe⁰) are increasingly being used to remediate contaminated ground water. Corrosion of Fe⁰ filings and tbe formation of precipitates can occur when the PRB material comes in contact with ground water and may reduce the lifespan and effectiveness of the barrier. At present, there are no routine procedures for preparing and analyzing the mineral precipitates from Fe⁰ PRB material. These procedures are needed because mineralogical composition of corrosion products used to interpret the barrier processes can change with iron oxidation and sample preparation. The objectives of this study were (i) to investigate a method of preparing Fe⁰ reactive barrier material for mineralogical analysis by X-ray diffraction (XRD), and (ii) to identify Fe mineral phases and rates of transformations induced by different mineralogical preparation techniques. Materials from an in situ Fe⁰ PRB were collected by undisturbed coring and processed for XRD analysis after different times since sampling for three size fractions and by various drying treatments. We found that whole-sample preparation for analysis was necessary because mineral precipitates occurred within the PRB material in different size fractions of the samples. Green rusts quickly disappeared from acetone-dried samples and were not present in air-dried and oven-dried samples Maghemite/magnetite content increased over time and in oven-dried samples, especially after heating to 105°C. We conclude that care must be taken during sample preparation of Fe⁰ PRB material, especially for detection of green rusts, to ensure accurate identification of minerals present within the barrier system.

Two-dimensional images of dissolved sulfide and metals in anoxic sediments by a novel diffusive gradients in thin film probe and optical scanning techniques

A novel diffusive gradients in thin film probe developed comprises diffusive gel layer of silver iodide (AgI) and a back-up Microchelex resin gel layer. 2D high-resolution images of sulfide and trace metals were determined respectively on the AgI gel by densitometric analysis and on the Microchelex resin layer with laser-ablation-inductively-coupled plasma mass spectrometry (LA-ICP-MS).We investigated the validity of the analytical procedures used for the determination of sulfide and trace metals. We found low relative standard deviations on replicate measurements, linear trace-metal calibration curves between the LA-ICP-MS signal and the true trace-metal concentration in the resin gel, and a good agreement of the sulfide results obtained with the AgI resin gel and with other analytical methods. The method was applied on anoxic sediment pore waters in an estuarine and marine system. Simultaneous remobilization of sulfide and trace metals was observed in the marine sediment.

Identification of vegetable oil botanical speciation in refined vegetable oil blends using an innovative combination of chromatographic and spectroscopic techniques

European Regulation 1169/2011 requires producers of foods that contain refined vegetable oils to label the oil types. A novel rapid and staged methodology has been developed for the first time to identify common oil species in oil blends. The qualitative method consists of a combination of a Fourier Transform Infrared (FTIR) spectroscopy to profile the oils and fatty acid chromatographic analysis to confirm the composition of the oils when required. Calibration models and specific classification criteria were developed and all data were fused into a simple decision-making system. The single lab validation of the method demonstrated the very good performance (96% correct classification, 100% specificity, 4% false positive rate). Only a small fraction of the samples needed to be confirmed with the majority of oils identified rapidly using only the spectroscopic procedure. The results demonstrate the huge potential of the methodology for a wide range of oil authenticity work.

Whey proteins have beneficial effects on intestinal enteroendocrine cells stimulating cell growth and increasing the production and secretion of incretin hormones

Whey protein has been indicated to curb diet-induced obesity, glucose intolerance and delay the onset of type 2 diabetes mellitus. Here the effects of intact crude whey, intact individual whey proteins and beta-lactoglobulin hydrolysates on an enteroendocrine (EE) cell model were examined. STC-1 pGIP/neo cells were incubated with several concentrations of yogurt whey (YW), cheese whey (CW), beta-lactoglobulin (BLG), alpha-lactalbumin (ALA) and bovine serum albumin (BSA). The findings demonstrate that BLG stimulates EE cell proliferation, and also GLP-1 secretion (an effect which is lost following hydrolysis with chymotrypsin or trypsin). ALA is a highly potent GLP-1 secretagogue which also increases the intracellular levels of GLP-1. Conversely, whey proteins and hydrolysates had little impact on GIP secretion. This appears to be the first investigation of the effects of the three major proteins of YW and CW on EE cells. The anti-diabetic potential of whey proteins should be further investigated.

Development of a doped titania immobilised thin film multi tubular photoreactor

This paper describes a novel doped titania immobilised thin film multi tubular photoreactor which has been developed for use with liquid, vapour or gas phase media. In designing photocatalytic reactors measuring active surface area of photocatalyst within the unit is one of the critical design parameters. This dictate greatly limits the applicability of any semi-conductor photocatalyst in industrial applications, as a large surface area equates to a powder catalyst. This demonstration of a thin film coating, doped with a rare earth element, novel photoreactor design produces a photocatalytic degradation of a model pollutant (methyl orange) which displayed a comparable degradation achieved with P25 TiO2. The use of lanthanide doping is reported here in the titania sol gel as it is thought to increase the electron hole separation therefore widening the potential useful wavelengths within the electromagnetic spectrum. Increasing doping from 0.5% to 1.0% increased photocatalytic degradation by ∼17% under visible irradiation. A linear relationship has been seen between increasing reactor volume and degradation which would not normally be observed in a typical suspended reactor system. © 2012 Elsevier B.V.

Hand-held voltammetric analyser for real-time monitoring of heavy metals in situ

This paper presents a novel hand-held instrument capable of real-time in situ detection and identification of heavy metals. The proposed system provides the facilities found in a traditional lab-based instrument in a hand held a design. In contrast to existing commercial systems, it can stand alone without the need of an associated computer. The electrochemical instrument uses anodic stripping voltammetry which is a precise and sensitive analytical method with excellent limits of detection. The sensors comprise disposable screen-printed (solid working) electrodes rather than the more common hanging mercury drop electrodes. The system is reliable, easy to use, safe, avoids expensive and time-consuming procedures and may be used in a variety of situations to help in the fields of environmental assessment and control.

A study of the kinetic solvent isotope effect on the destruction of microcystin-LR and geosmin using TiO2 photocatalysis

We have previously reported the effectiveness of TiO₂ photocatalysis in the destruction of species generated by cyanobacteria, specifically geosmin and microcystin-LR. In this paper we report an investigation of factors which influence the rate of the toxin destruction at the catalyst surface. A primary kinetic solvent isotope effect of approximately 1.5 was observed when the destruction was performed in a heavy water solvent. This is in contrast to previous reports of a solvent isotope effect of approximately 3, however, these studies were undertaken with a different photocatalyst material. The solvent isotope effect therefore appears to be dependent on the photocatalyst material used. The results of the study support the theory that the photocatalytic decomposition occurs on the catalyst surface rather than in the bulk of the solution. Furthermore it appears that the rate determining step is not oxygen reduction as previously reported. 

Photosensitized destruction of Chlorella vulgaris by methylene blue or nuclear fast red combined with hydrogen peroxide under visible light irradiation

A considerable number of investigations have started to elucidate the essential roles biological agents play in the biodeterioration of stone. Chemical biocides are becoming increasingly banned because of the environmental and health hazards associated with these toxic substances. The present study reports the photodynamic effect of Methylene Blue (MB) and Nuclear Fast Red (NFR) in the presence of hydrogen peroxide (H₂O₂) on the destruction of the algae Chlorella vulgaris (C. vulgaris) under irradiation with visible light. Illumination of C. vulgaris in the presence of MB or NFR combined with H₂O₂ results in the decomposition of both the algal species and the photosensitizer. The photodynamic effect was investigated under aerobic and anaerobic conditions. Differences in mechanism type are reported and are dependent on both the presence and the absence of oxygen. The behavior of each photosensitizer leads to a Type II mechanism and a Type I/Type II combination for MB and NFR, respectively, being concluded. This novel combination could be effective for the remediation of biofilm-colonized stone surfaces.

Mechanistic studies of the photocatalytic oxidation of microcystin-LR: An investigation of byproducts of the decomposition process

Microcystins (cyclic heptapeptides) are produced by a number of freshwater cyanobacteria and cause concern in potable water supplies due to their acute and chronic toxicity. The present study reports the structural characterization of the degradation products of the photocatalytic oxidation of microcystin-LR, so aiding the mechanistic understanding of this process. TiO₂ photocatalysis is a promising technology for removal of these toxins from drinking water. However, before it can be adopted in any practical application it is necessary to have a sufficient knowledge of degradation byproducts and their potential toxicity. Liquid chromatography-mass spectrometry analysis demonstrated that the major destruction pathway of microcystin appears to be initiated via three mechanisms: UV irradiation, hydroxyl radical attack, and oxidation. UV irradiation caused geometrical isomerization of microcystin converting the (4E), (6E) of the Adda configuration to (4E), 6(Z) or 4(Z), 6(E). Hydroxyl radical attack on the conjugated diene structure of Adda moiety produced dihyroxylated products. Further oxidation cleaved the hydroxylated 4-5 and/or 6-7 bond of Adda to form aldehyde or ketone peptide residues, which then were oxidized into the corresponding carboxylic acids. Photocatalysis also hydrolyzed the peptide bond on the ring structure of microcystin to form linear structures although this appeared to be a minor pathway.

Detoxification of microcystins (cyanobacterial hepatotoxins) using TiO2 photocatalytic oxidation

TiO₂ photocatalysis has been used to destroy microcystin-LR in aqueous solution. The destruction of this toxin was monitored by HPLC, and the disappearance was accompanied by the appearance of seven UV detectable compounds. Spectral analysis revealed that some of these compounds retained spectra similar to the parent compound suggesting that the Adda moiety, thought to be responsible for the characteristic spectrum, remained intact whereas the spectra of some of the other products was more radically altered. Six of the seven observed reaction products did not appear to undergo further degradation during prolonged photocatalysis (100 min). The degree to which microcystin-LR was mineralized by photocatalytic oxidation was determined. Results indicated that less than 10% mineralization occurred. Mass spectral analysis of the photocatalyzed microcystin-LR allowed tentative characterization of the reaction process and products. Reduction in toxicity due to the photocatalytic oxidation was evaluated using an invertebrate bioassay, which demonstrated that the disappearance of microcystin-LR was paralleled by a reduction in toxicity. These findings suggest that photocatalytic destruction of microcystins may be a suitable method for the removal of these potentially hazardous compounds from drinking water.

The Environmental Fate of polybrominated diphenyl ethers in western Taiwan and coastal waters: evaluation with a fugacity based model

The environmental fate of polybrominated diphenyl ethers (PBDEs), a group of flame retardants that are considered to be persistent organic pollutants (POPs), around the Zhuoshui River and Changhua County regions of Taiwan was assessed. An investigation into emissions, partitioning, and fate of selected PBDEs was conducted based on the equilibrium constant (EQC) fugacity model developed at Trent University, Canada. Emissions for congeners PBDE 47, PBDE 99, and PBDE 209 to air (4.9–92 × 10−3 kg/h), soil (0.91–17.4 × 10−3 kg/h), and water (0.21–4.04 × 10−3 kg/h), were estimated by modifying previous models on PBDE emission rates by considering both industrial and domestic rates. It was found that fugacity modeling can give a reasonable estimation of the behavior, partitioning, and concentrations of PBDE congeners in and around Taiwan. Results indicate that PBDE congeners have a high affinity for partitioning into sediments then soils. As congener number decreases, the PBDEs then partition more readily into air. As the degree of bromination increases, congeners more readily partition to sediments. Sediments may then act as a long-term source of PBDEs which can be released back into the water column due to resuspension during storm events.

Effects of arsenic-contaminated irrigation water on growth, yield, and nutrient concentration in rice

A study was undertaken to determine the effects of different concentrations of arsenic (As) in irrigation water on Boro (dry-season) rice (Oryza sativa) and their residual effects on the following Aman (wet-season) rice. There were six treatments, with 0, 0.1, 0.25, 0.5, 1, and 2 mg As L-1 applied as disodium hydrogen arsenate. All the growth and yield parameters of Boro rice responded positively at lower concentrations of up to 0.25 mg As L-1 in irrigation water but decreased sharply at concentrations more than 0.5 mg As L-1. Arsenic concentrations in grain and straw of Boro rice increased significantly with increasing concentration of As in irrigation water. The grain As concentration was in the range of 0.25 to 0.97 μg g-1 and its concentration in rice straw varied from 2.4 to 9.6 μg g-1 over the treatments. Residual As from previous Boro rice showed a very similar pattern in the following Aman rice, although As concentration in Aman rice grain and straw over the treatments was almost half of the As levels in Boro rice grain. Arsenic concentrations in both grain and straw of Boro and Aman rice were found to correlate with iron and be antagonistic with phosphorus. Copyright © Taylor & Francis Group, LLC.

Bioavailability of 2,4-dichlorophenol associated with soil water-soluble humic material

Interaction of organic xenobiotics with soil water-soluble humic material (WSHM) may influence their environmental fate and bioavailability. We utilized bacterial assays (lux-based toxicity and mineralization by Burkholderia sp. RASC) to assess temporal changes in the bioavailability of [¹⁴C]-2,4-dichlorophenol (2,4-DCP) in soil water extracts (29.5 μg mL^-1 2,4-DCP; 840.2 μg mL^-1 organic carbon). HPLC determined and bioavailable concentrations were compared. Gel permeation chromatography (GPC) was used to confirm the association of a fraction (>50%) of [¹⁴C]-2,4-DCP with WSHM. Subtle differences in parameters describing 2,4-DCP mineralization curves were recorded for different soil-2,4-DCP contact times. Problems regarding the interpretation of mineralization data when assessing the bioavailability of toxic compounds are discussed. The lux-bioassay revealed a time-dependent reduction in 2,4-DCP bioavailability: after 7 d, less than 20% was bioavailable. However, GPC showed no quantitative difference in the amount of WSHM-associated 2,4-DCP over this time. These data suggest qualitative changes in the nature of the 2,4-DCP-WSHM association and that associated 2,4-DCP may exert a toxic effect. Although GPC distinguished between free- and WSHM-associated 2,4-DCP, it did not resolve the temporal shift in bioavailability revealed by the lux biosensor. These results stress that assessment of risk posed by chemicals must be considered using appropriate biological assays.

Interactions between soil, toxicant, and a lux-marked bacterium during solid phase-contact toxicity testing

Bioluminescence-based, solid-contact toxicity assays allow test bacterium and toxicant to interact at the solid-solution interface. A lux- marked bacterium, Burkholderia sp. RASC, and 2,4-dichlorophenol (2,4-DCP) were used to characterize these interactions. In the basic bioassay, cells were added to soil slurries containing 2,4-DCP (0-120 μg ml^-1). After 15 min, soil was removed by centrifugation, and bioluminescence in the supernatant was determined. Investigation of 2,4-DCP adsorption to soil revealed that sorption was linear and not significantly (p > 0.1) affected by the presence of Burkholderia cells. The numbers of culturable Burkholderia cells in the assay supernatant were 48.2 to 64.8% of the inoculum and independent of the soil weight. The effect of soil on 2,4-DCP toxicity was investigated by comparing soil aqueous extract and contact assays. The percentage bioluminescence for the contact assay was consistently higher than the extract assay at all test concentrations, and counts of viable Burkholderia cells were enhanced by the presence of 2,4-DCP in the contact assay. Expressing results as specific bioluminescence decreased the variability in response and the discrepancy in results between the two protocols. We suggest that solid-contact assays need improvement to ensure defined contact between cells and solid phase, and that the reporting of specific activity should be emphasized.

Spatial and temporal regulation of the pesticide dieldrin within industrial catchments

The river catchments of south Yorkshire support a very high density of wool processing industries. Dieldrin was once used as a moth proofing agent, as a sheep dip, and as a pesticide to protect wool fleeces during storage and transport, all of which caused pollution of these catchments due to textile processing. Weekly sampling of four of these rivers revealed two classes of dieldrin contamination: the Aire and Calder (the rivers which support very high concentrations of wool processing industries) had higher concentrations (averaging ~3 ng/l) than the Don and Trent (~1 ng/l). The average flux of dieldrin from these rivers into the Humber estuary was 9.8 g/day, with the Aire (of which the Calder is a tributary) and the Trent contributing almost equally, with a smaller contribution from the Don. The Trent has the highest average flow, explaining its large contribution to dieldrin flux. Less detailed sampling of rivers from the north Humber catchment which drain predominantly rural areas had dieldrin concentrations similar to the heavily industrialized southern catchment rivers. This suggests that dieldrin from agronomic and domestic usage may be more persistent than the pollution caused by textile processing industries. Evidence is presented to suggest that the principle dieldrin sources to the Humber catchments are sewage treatment plants, and that the dieldrin sources are in rapid equilibrium with the water column. (C) 2000 Elsevier Science B.V.