Evaluating cadmium bioavailability in contaminated rice paddy soils and assessing potential for contaminant immobilisation with biochar.

Cadmium (Cd) contaminated soils from the Mae Sot district in northwest Thailand, a region in which rice Cd concentrations often exceed health limits (0.4 mg/kg) set by the World Health Organisation, were examined for isotopically exchangeable Cd (Cd E values using a 111Cd spike) to determine how this rates as a predictor of rice grain Cd in comparison with soil total Cd and solution extractable Cd (using the commonly applied BCR scheme and, in an attempt to distinguish carbonate bound forms, the Tessier soil sequential extraction scheme reagents). Step 1 of the BCR scheme (0.11 M CH3COOH) and step 1 of the Tessier scheme (1M MgCl2) showed the highest R2 values in regressions with rice Cd (91% and 90%, respectively), but all predictors were strongly linked to rice Cd (p < 0.001) and could be used for prediction purposes. One soil, of the six tested, was an exception to this, where all predictors over-estimated grain Cd by a factor of 2.5-5.7, suggesting that rice grain Cd had been restricted here by the differing flooding regime and subsequent changes to redox conditions. E values and Tessier step 1 extractions were closely related, indicating that these measurements access similar pools of soil Cd. Separately, the isotopic exchangeability (representing bioavailability) of Cd was also assessed in two soils amended with rice husk and miscanthus biochars (0, 1, 5, 10, 15 and 20% w/w) in order to assess the utility of the biochars as a soil amendment for immobilising Cd in situ. One soil showed significant reductions in Cd E value at 5% rice husk biochar addition and at 15% miscanthus biochar addition however, based on the E value-rice grain Cd regression relationship previously established, the E values in the amended soils still predicted for a rice Cd concentration above the health limit. In the second soil, neither of the biochars successfully reduced the Cd E value. This indicates that further work is needed to customise biochar properties to suit specific soil and contaminant situations if they are to be used successfully for remediation of metal contaminated soils.

Laser Desorption/Ionization Coupled to FTICR Mass Spectrometry for Studies of Natural Organic Matter.

Laser desorption/ionization (LDI) was investigated as an ionization method for Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) studies of natural organic matter (NOM). Using International Humic Substances Society standards, Suwannee River fulvic acid (SRFA) and Suwannee River natural organic matter (SRNOM), LDI was found to ionize a very similar set of compounds (>90% of molecular formulas identity) to the matrix assisted laser desorption/ionization (MALDI), while producing higher quality spectra. A comparison of electrospray ionization (ESI) and LDI spectra showed that different types of compounds are ionized by these methods with only 9.9% of molecular formulas common to both. The compounds ionized by LDI/MALDI belong to low oxygen classes (maximum number of species for O7-O9), while ESI compounds belong to higher oxygen classes (maximum number of species for O14-O16). Compounds ionized by LDI can be classified as aliphatic, aromatic, and condensed aromatics in approximately equal measure, while aliphatic compounds dominated the ESI spectra of SRFA. In order to maximize the coverage of molecular species, LDI, as a particularly convenient and readily deployable ionization method, should be used routinely in combination with other ionization methods, such as ESI, for FTICR MS studies of NOM.

Effect of pH and Pressure on Uranium Removal from Drinking Water Using NF/RO Membranes.

Groundwater is becoming an increasingly important drinking water source. However, the use of groundwater for potable purposes can lead to chronic human exposure to geogenic contaminants, for example, uranium. Nanofiltration (NF) and reverse osmosis (RO) processes are used for drinking water purification, and it is important to understand how contaminants interact with membranes since accumulation of contaminants to the membrane surface can lead to fouling, performance decline and possible breakthrough of contaminants. During the current study laboratory experiments were conducted using NF (TFC-SR2) and RO (BW30) membranes to establish the behavior of uranium across pH (3-10) and pressure (5-15 bar) ranges. The results showed that important determinants of uranium-membrane sorption interactions were (i) the uranium speciation (uranium species valence and size in relation to membrane surface charge and pore size) and (ii) concentration polarization, depending on the pH values. The results show that it is important to monitor sorption of uranium to membranes, which is controlled by pH and concentration polarization, and, if necessary, adjust those parameters controlling uranium sorption.

Relationships of PROP Taste Phenotype, Taste Receptor Genotype, and Oral Nicotine Replacement Use.

INTRODUCTION: Recommended dosage of oral nicotine replacement therapy (NRT) product is often not achieved in smoking cessation attempts. n-6-propylthiouracil (PROP) bitter taste phenotype may be a potential risk factor for non-adherence to oral NRT products due to their bitter taste. There is limited literature on this phenotype in the context of smoking and none in relation to oral NRT pharmacotherapy. METHODS: The association of PROP taste phenotype with NRT usage and sensory response to products was examined. In a cross-over experimental design, 120 participants received a 1 week supply of nicotine inhalers and 1 week of nicotine lozenges with random assignment to order. Mixed effects linear model analyses were conducted. RESULTS: PROP taste phenotype and taste receptor genotype were not associated with NRT usage or sensory response to NRT, after adjusting for other factors. However, PROP non-tasters used a higher number of lozenges per day (continuous exposure) than nicotine cartridges (intermittent exposure). Unexpectedly, half of baseline PROP non-tasters shifted to taster phenotype 2 weeks after smoking cessation or reduction. Menthol cigarette smokers identified higher NRT strength of sensation scores than nonmenthol smokers. Taste receptor genotype was related to PROP taste phenotype (Kendall τ = .591, p = .0001). CONCLUSIONS: A nonsignificant relationship of PROP phenotype and NRT usage may be associated with NRT under-dosing and limited variance in the outcome variable. PROP non-tasters' greater use of lozenges is consistent with nicotine exposure being less aversive to non-tasters. Further research of this and other factors impacting NRT usage are warranted to effectively inform smoking cessation pharmacotherapy.

Isotope-Filtered 4D NMR Spectroscopy for Structure Determination of Humic Substances.

Humic substances, the main component of soil organic matter, could form an integral part of green and sustainable solutions to the soil fertility problem. However, their global-scale application is hindered from both scientific and regulatory perspectives by the lack of understanding of the molecular make-up of these chromatographically inseparable mixtures containing thousands of molecules. Here we show how multidimensional NMR spectroscopy of isotopically tagged molecules enables structure characterization of humic compounds. We illustrate this approach by identifying major substitution patterns of phenolic aromatic moieties of a peat soil fulvic acid, an operational fraction of humic substances. Our methodology represents a paradigm shift in the use of NMR active tags in structure determination of small molecules in complex mixtures. Unlike previous tagging methodologies that focused on the signals of the tags, we utilize tags to directly probe the identity of the molecules they are attached to.

Composition of PAHs in Biochar and Implications for Biochar Production.

The content of polycyclic aromatic hydrocarbons (PAHs) in biochar has been studied extensively; however, the links between biomass feedstock, production process parameters, and the speciation of PAHs in biochar are understudied. Such an understanding is crucial, as the health effects of individual PAHs vary greatly. Naphthalene (NAP) is the least toxic of the 16 US EPA PAHs but comprises the highest proportion of PAHs in biochar. Therefore, we investigate which parameters favor high levels of non-NAP PAHs (∑16 US EPA PAHs without NAP) in a set of 73 biochars. On average, the content of non-NAP PAHs was 9 ± 29 mg kg-1 (median 0.9 mg kg-1). Importantly, during the production of the biochars with the highest non-NAP PAH contents, the conditions in the post-pyrolysis area, where pyrolysis vapors and biochar are separated, favored condensation and deposition of PAHs on biochar. Under these conditions, NAP condensed to a lower degree because of its high vapor pressure. In biochars not contaminated through this process, the average non-NAP content was only 2 ± 3 mg kg-1 (median 0.5 mg kg-1). Uneven heat distribution and vapor trapping during pyrolysis and cool zones in the post-pyrolysis area need to be avoided. This demonstrates that the most important factor yielding high contents of toxic PAHs in biochar was neither a specific pyrolysis parameter nor the feedstock but the pyrolysis unit design, which can be modified to produce clean and safe biochar.

Investigating the hydration of C3A in the presence of the potentially toxic element chromium-a route to remediation?

Pollution by hexavalent chromium is a growing, global problem. Its presence in public water systems is often the result of industrial activities, both past and present. In this study, tricalcium aluminate (C3A, Ca3Al2O6) is added to solutions of varying concentrations of potassium chromate (K2CrO4) and samples of both the solid and liquid are taken at various time intervals to monitor the removal of chromium from the solutions. Solution concentrations of 0.2 M, 0.1 M, 0.02 M, and 0.01 M are used, and the chromium concentration is found to reduce in all cases. For the 0.02 M solution the chromium concentration is reduced from 1040 ppm to 3.1 ppm in 1 week, and the chromium concentration of the 0.01 M solution is reduced from 520 ppm to 0.26 ppm in only one day of reaction with the C3A. The chromium removed from solution is identified in the solid products, which were fully characterised as being a mixture of ettringite (Ca6[Al(OH)6]2(CrO4)3·26H2O) and monochromate (Ca4[Al(OH)6]2CrO4·8H2O) phases from analysis of Powder X-ray Diffraction and Fourier Transform Infrared Spectroscopy data. The work presented here is a proof of concept study to investigate C3A as a potential material for the removal of hexavalent chromium from solution. The results from this study are initial steps towards development of this as a technology for hexavalent chromium remediation.

Efficacy of a language-concordant health coaching intervention for latinx with diabetes.

OBJECTIVE: To describe the effect of a language-concordant health coaching intervention for Spanish-speaking patients with limited English proficiency (LEP) and uncontrolled Type 2 Diabetes (T2D) on glycemic control, anxiety, depression, and diabetes self-efficacy. METHODS: 64 patients with T2D were randomly assigned to a control or intervention group. Outcomes were assessed by blood work and surveys pre and post intervention. RESULTS: The mean sample age was 47.8 years (SD=11.3) and 81% were female. HbA1c was not significantly different between groups at baseline. The intervention group's HbA1c was significantly lower at times 2 and 3 than in the control arm (p < .01 and p < .001). There were significant reductions in the intervention group's mean HbA1c levels from baseline 10.37 to midpoint 9.20, p < .001; and from baseline 10.42 to study end 8.14, p < .001. Depression and anxiety scores significantly decreased (p < .05 and p < .001), and diabetes self-efficacy significantly increased (p < .001). CONCLUSION: Health coaching led to statistically significant and clinically meaningful decreases in HbA1c, depression, and anxiety scores among LEP Latinx adults with uncontrolled T2D. PRACTICE IMPLICATIONS: Heath coaching can be conducted in primary care clinics by nurses or advanced practice nurses. The short-term intervention tested here could be adapted to the clinical setting.

Scottish peat bog records of atmospheric vanadium deposition over the past 150 years: comparison with other records and emission trends.

Cores from four Scottish ombrotrophic peat bogs were used to reconstruct the historical record of atmospheric vanadium (V) deposition in Scotland over the last 150 years. The general similarity of V and Pb concentration profile trends in (210)Pb-dated cores from each of the sites strongly suggested that V, like Pb, is essentially immobile in ombrotrophic peat. After allowance via use of the conservative element Ti for the contribution of soil dust V, the deposition of anthropogenic V was found to be greatest (∼ 1.3 to 2.0 mg m(-2) y(-1)) in the mid-20(th) century before decreasing to 0.1-0.3 mg m(-2) y(-1) in the early years of the 21(st) century. The latter values were in good agreement with directly measured atmospheric V fluxes at nearby sites, a finding also observed in the case of Pb. The decline in peat-core-derived fluxes for both V and Pb from 1970 to 2004, however, was not as large as the decline in official UK emission estimates for the two metals during this period. This, along with an order of magnitude discrepancy between the anthropogenic V/Pb ratios at the peat core surface and the higher values of the ratio for UK emissions in the early 2000s, suggests that the recently revised UK emissions data for V may perhaps still be overestimated and/or that some previously deposited Pb is being resuspended in the atmosphere.

Locating hydrogen positions in the autunite mineral metatorbernite [Cu(UO2)2(PO4)2·8H2O]: a combined approach using neutron powder diffraction and computational modelling.

Metatorbernite [Cu(UO2)2(PO4)2·8H2O] is a promising remediation material for environmental uranium contamination. Previous X-ray diffraction studies have been unable to definitively locate hydrogen positions within metatorbernite, which are key to determining the hydrogen-bond network that helps to stabilize the structure. Here, hydrogen positions have been determined using a combination of neutron powder diffraction and the computational modelling technique ab initio random structure searching (AIRSS). Atomic coordinates determined through Rietveld analysis of neutron powder diffraction data are in excellent agreement with the minimum energy configuration predicted by AIRSS; thus, simulations confirm that our proposed model likely represents the global minimum configuration. Two groups of water molecules exist within the metatorbernite structure: free water and copper-coordinating water. Free water molecules are held within the structure by hydrogen bonding only, whilst the coordinating water molecules bond to copper in the equatorial positions to produce a 4 + 2 Jahn-Teller octahedra. The successful agreement between neutron powder diffraction data and AIRSS suggests that this combined approach has excellent potential for the study of other (trans)uranium materials in which hydrogen bonding plays a key role in phase stability.

Organic complexation of U(VI) in reducing soils at a natural analogue site: Implications for uranium transport.

Understanding the long-term fate, stability, and bioavailability of uranium (U) in the environment is important for the management of nuclear legacy sites and radioactive wastes. Analysis of U behavior at natural analogue sites permits evaluation of U biogeochemistry under conditions more representative of long-term equilibrium. Here, we have used bulk geochemical and microbial community analysis of soils, coupled with X-ray absorption spectroscopy and µ-focus X-ray fluorescence mapping, to gain a mechanistic understanding of the fate of U transported into an organic-rich soil from a pitchblende vein at the UK Needle's Eye Natural Analogue site. U is highly enriched in the Needle's Eye soils (∼1600 mg kg-1). We show that this enrichment is largely controlled by U(VI) complexation with soil organic matter and not U(VI) bioreduction. Instead, organic-associated U(VI) seems to remain stable under microbially-mediated Fe(III)-reducing conditions. U(IV) (as non-crystalline U(IV)) was only observed at greater depths at the site (>25 cm); the soil here was comparatively mineral-rich, organic-poor, and sulfate-reducing/methanogenic. Furthermore, nanocrystalline UO2, an alternative product of U(VI) reduction in soils, was not observed at the site, and U did not appear to be associated with Fe-bearing minerals. Organic-rich soils appear to have the potential to impede U groundwater transport, irrespective of ambient redox conditions.

An integrated colloid fractionation approach applied to the characterisation of porewater uranium-humic interactions at a depleted uranium contaminated site.

Methods for the fractionation of aquatic colloids require careful application to ensure efficient, accurate and reproducible separations. This paper describes the novel combination of mild colloidal fractionation and characterisation methods, namely centrifugal ultrafiltration, gel electrophoresis and gel filtration along with spectroscopic (UV-visible) and elemental (Inductively Coupled Plasma-Optical Emission Spectroscopy, Inductively Coupled Plasma-Mass Spectrometry) analysis, an approach which produced highly consistent results, providing improved confidence in these methods. Application to the study of the colloidal and dissolved components of soil porewaters from one soil at a depleted uranium (DU)-contaminated site revealed uranium (U) associations with both large (100 kDa-0.2 microm) and small (3-30 kDa) humic colloids. For a nearby soil with lower organic matter content, however, association with large (100 kDa-0.2 microm) iron (Fe)-aluminium (Al) colloids in addition to an association with small (3-30 kDa) humic colloids was observed. The integrated colloid fractionation approach presented herein can now be applied with confidence to investigate U and indeed other trace metal migration in soil and aquatic systems.

Distribution and partitioning of depleted uranium (DU) in soils at weapons test ranges - investigations combining the BCR extraction scheme and isotopic analysis.

Depleted uranium (DU) has become a soil contaminant of considerable concern in many combat zones and weapons-testing sites around the world, including locations in Europe, the Middle East and the USA, arising from its dispersion via the application of DU-bearing munitions. Once DU is released into the environment its mobility and bioavailability will, like that of other contaminants, largely depend on the type of associations it forms in soil and on the nature of the soil components to which it binds. In this study we used the BCR sequential extraction scheme to determine the partitioning of DU amongst soil fractions of texturally varying soils from locations affected by weapons-testing activities. Isotopic analyses (MC-ICP-MS and alpha-spectrometry) were performed to verify the presence of DU in whole soils and soil fractions and to determine any preferential partitioning of the contaminant. Results identified soil organic matter as being consistently the most important component in terms of DU retention, accounting for 30-100% of DU observed in the soils examined. However, at greater distances from known contamination points, DU was also found to be largely associated with the exchangeable fraction, suggesting that DU can be mobilised and transported by surface and near-surface water and does remain in an exchangeable (and thus potentially bioavailable) form in soils.

Impacts of glyphosate-based herbicides on disease resistance and health of crops: a review.

Based on experimental data from laboratory and field, numerous authors have raised concern that exposure to glyphosate-based herbicides (GBHs) may pre-dispose crops to damage by microbial pathogens. In this review, we distinguish and evaluate two principal pathways by which GBHs may affect the susceptibility of crops to disease: pathway 1-via disruptions to rhizosphere microbial ecology, and pathway 2-via restriction of nutrients to crops. We conclude that GBHs have the potential to undermine crop health in a number of ways, including: (i) impairment of the innate physiological defences of glyphosate-sensitive (GS) cultivars by interruption of the shikimic acid pathway; (ii) impairment of physiological disease defences has also been shown to occur in some glyphosate-resistant (GR) cultivars, despite their engineered resistance to glyphosate's primary mode of action; (iii) interference with rhizosphere microbial ecology (in particular, GBHs have the potential to enhance the population and/or virulence of some phytopathogenic microbial species in the crop rhizosphere); and finally, (iv) the as yet incompletely elucidated reduction in the uptake and utilisation of nutrient metals by crops. Future progress will best be achieved when growers, regulators and industry collaborate to develop products, practices and policies that minimise the use of herbicides as far as possible and maximise their effectiveness when used, while facilitating optimised food production and security.

Sequential extraction combined with isotope analysis as a tool for the investigation of lead mobilisation in soils: application to organic-rich soils in an upland catchment in Scotland.

Sequential extraction (modified BCR procedure) combined with isotope analysis has been investigated as a tool for assessing mobilisation of lead into streams at an upland catchment in NE Scotland. The maximum lead concentrations (up to 110 mg kg(-1) in air-dried soil) occurred not at the surface but at about 10 cm depth. The lowest (206)Pb/(207)Pb ratios in any profile occurred, with one exception, at 2.5-5 cm depth. In the one exception, closest to the only road in the area, significantly lower (206)Pb/(207)Pb ratios in the surface soil together with much increased chloride concentrations (in comparison to other surface waters) indicated the possible mobilisation of roadside lead and transfer to the stream. The (206)Pb/(207)Pb ratios in extractable fractions tended at depth towards the ratio measured in the residual phase but the ratios in the oxidizable fraction increased to a value higher than that of the residual phase.

Calcium polysulfide remediation of hexavalent chromium contamination from chromite ore processing residue.

Past disposal of high-lime chromite ore processing residue (COPR) from a chemical works in S.E. Glasgow, UK, has led to continuing release of toxic and carcinogenic hexavalent chromium (Cr(VI)) to groundwaters which are highly contaminated with Cr(VI)O4(2-). Traditional methods of remediating Cr(VI)-contaminated land, e.g. using ferrous sulfate and organic matter, have had limited success in converting Cr(VI) to less harmful and insoluble Cr(III). This paper describes the first application of calcium polysulfide (CaS(x)) to the remediation of contaminated groundwater and high-lime COPR in a series of laboratory experiments, which have demonstrated the effectiveness of the treatment in quantitatively and rapidly reducing Cr(VI) to Cr(III) over the pH range (8-12.5) typically found at the sites. Cr(III)-organic complexes, present in groundwater at one location, were also effectively precipitated upon treatment with CaS(x). The potential for large-scale use of CaS(x) in the remediation of Cr(VI) from COPR is also discussed.

Risks and benefits of marginal biomass-derived biochars for plant growth.

In this study, 19 biochars from marginal biomass, representing all major biomass groups (woody materials, grass, an aquatic plant, anthropogenic wastes) were investigated regarding their content of available potentially toxic elements (PTEs) and nutrients (determined by NH4NO3-extractions) and their effects on cress (Lepidium sativum) seedling growth. The objective was to assess the potential and actual effects of biochar with increased PTE content on plant growth in the context of use in soil amendments and growing media. It showed that the percentage of available PTEs was highest for biochars produced at the highest treatment temperature (HTT) of 750°C. On average, however, for all 19 biochars, the percentage availability of Cu, Cr, Ni and Zn (<1.5% for all) was similar to the percentage availability reported in the literature for the same elements in soils at similar pH values which is a highly important finding. Most biochars exceeded German soil threshold values for NH4NO3-extractable PTEs, such as Zn (by up to 25-fold), As and Cd. Despite this, cress seedling growth tests with 5% biochar in sand did not show any correlations between inhibitory effects (observed in 5 of the 19 biochars) and the available PTE concentrations. Instead, the available K concentration and biochar pH were highly significantly, negatively correlated with seedling growth (K: p<0.001, pH: p=0.004). K had the highest available concentration of all elements and the highest percentage availability (47.7±19.7% of the total K was available). Consequently, available K contributed most to the osmotic pressure and high pH which negatively affected the seedlings. Although a potential risk if some of these marginal biomass-derived biochar were applied at high concentrations, e.g. 5% (>100tha(-1)), when applied at agriculturally realistic application rates (1-10tha(-1)), the resulting smaller increases in pH and available K concentration may actually be beneficial for plant growth.

Suitability of marginal biomass-derived biochars for soil amendment.

The term "marginal biomass" is used here to describe materials of little or no economic value, e.g. plants grown on contaminated land, food waste or demolition wood. In this study 10 marginal biomass-derived feedstocks were converted into 19 biochars at different highest treatment temperatures (HTT) using a continuous screw-pyrolysis unit. The aim was to investigate suitability of the resulting biochars for land application, judged on the basis of potentially toxic element (PTE) concentration, nutrient content and basic biochar properties (pH, EC, ash, fixed carbon). It was shown that under typical biochar production conditions the percentage content of several PTEs (As, Al, Zn) and nutrients (Ca, Mg) were reduced to some extent, but also that biochar can be contaminated by Cr and Ni during the pyrolysis process due to erosion of stainless steel reactor parts (average+82.8% Cr, +226.0% Ni). This can occur to such an extent that the resulting biochar is rendered unsuitable for soil application (maximum addition +22.5 mg Cr kg(-1) biochar and +44.4 mg Ni kg(-1) biochar). Biomass grown on land heavily contaminated with PTEs yielded biochars with PTE concentrations above recommended threshold values for soil amendments. Cd and Zn were of particular concern, exceeding the lowest threshold values by 31-fold and 7-fold respectively, despite some losses into the gas phase. However, thermal conversion of plants from less severely contaminated soils, demolition wood and food waste anaerobic digestate (AD) into biochar proved to be promising for land application. In particular, food waste AD biochar contained very high nutrient concentrations, making it interesting for use as fertiliser.