The importance of the bacterial cell wall in uranium(VI) biosorption.

The bacterial cell envelope, in particular the cell wall, is considered the main controlling factor in the biosorption of aqueous uranium(vi) by microorganisms. However, the specific roles of the cell wall, associated biomolecules, and other components of the cell envelope are not well defined. Here we report findings on the biosorption of uranium by isolated cell envelope components and associated biomolecules, with P. putida 33015 and B. subtilis 168 investigated as representative strains for the differences in Gram-negative and Gram-positive cell envelope architecture, respectively. The cell wall and cell surface membrane were isolated from intact cells and characterised by X-ray Photoelectron Spectroscopy (XPS) and Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FT-IR) spectroscopy; revealing variations in the abundance of functional moieties and biomolecules associated with components of the cell envelope. Uranium biosorption was investigated as a function of cell envelope component and pH, comparing with intact cells. The isolated cell wall from both strains exhibited the greatest uranium biosorption capacity. Deprotonation of favourable functional groups on the biomass as the pH increased from 3 to 5.5 increased their uranium biosorption capacity by approximately 3 fold. The results from ATR-FT-IR indicated that uranium(vi) biosorption was mediated by phosphate and carboxyl groups associated with proteins and phosphorylated biopolymers of the cell envelope. This includes outer membrane phospholipids and LPS of Gram-negative bacteria and teichoic acids, surface proteins and peptidoglycan from Gram-positive bacteria. As a result, the biosorption process of uranium(vi) to microorganisms is controlled by surface interactions, resulting in higher accumulation of uranium in the cell envelope. This demonstrates the importance of bacterial cell wall as the key mediator of uranium biosorption with microorganisms.

Improved rice cooking approach to maximise arsenic removal while preserving nutrient elements.

Inorganic arsenic (iAs) is a group 1 carcinogen, and consumption of rice can be a significant pathway of iAs exposure in the food chain. Although there are regulations in place to control iAs for marketed rice in some countries, additional measures are explored to remove arsenic from rice. Due to the surface-bound and soluble nature of iAs, previous studies have shown that it can be removed to a significant extent using different cooking methods. Towards this goal we modified and tested the absorption method in combination with four home-friendly cooking treatments (UA = unwashed and absorbed, WA = washed and absorbed, PSA = pre-soaked and absorbed, and PBA = parboiled and absorbed) using both brown and white rice (3 types each). The nutrient elements were measured using ICP-MS and arsenic speciation was carried out using LC-ICP-MS. Overall, our results show that PBA was the optimum approach assessed, removing 54% and 73% of inorganic arsenic (iAs) for brown and white rice respectively, raising the margin of exposure (MOE) by 3.7 for white rice and 2.2 times for brown rice, thus allowing the consumption of rice more safely for infants, children and adults. Other cooking treatments were effective in reducing the iAs concentration from white rice only. Here we also report changes in selected nutrient elements (P, K, Mg, Zn and Mn) which are relatively abundant in rice. In general, the treatments retained more nutrients in brown rice than white rice. No significant loss of Zn was observed from both rice types and the loss of other nutrients was similar or less than in comparison to reported losses from rice cooked in excess water in the literature. We conclude that PBA is a promising technique and further research is needed by including different regional rice types and water quality levels.

Do arsenic levels in rice pose a health risk to the UK population?

Consumption of rice and rice products can be a significant exposure pathway to inorganic arsenic (iAs), which is a group 1 carcinogen to humans. The UK follows the current European Commission regulations so that iAs concentrations must be < 0.20 mg kg-1 in white (polished) rice and <0.25 mg kg-1 in brown (unpolished) rice. However, iAs concentration in rice used for infant food production or direct consumption has been set at a maximum of 0.1 mg kg-1. In this context, this study aimed to evaluate iAs concentrations in different types of rice sold in the UK and to quantify the health risks to the UK population. Here, we evaluated 55 different types of rice purchased from a range of retail outlets. First, we analysed all rice types for total As (tAs) concentration from which 42 rice samples with tAs > 0.1 mg kg-1 were selected for As speciation using HPLC-ICP-MS. Based on the average concentration of iAs of our samples, we calculated values for the Lifetime Cancer Risk (LCR), Target Hazard Quotient (THQ) and Margin of Exposure (MoE). We found a statistically significant difference between organically and non-organically grown rice. We also found that brown rice contained a significantly higher concentration of iAs compared to white or wild rice. Notably, 28 rice samples exceeded the iAs maximum limit stipulated by the EU (0.1 mg kg-1) with an average iAs concentration of 0.13 mg kg-1; therefore consumption of these rice types could be riskier for infants than adults. Based on the MoE, it was found that infants up to 1 year must be restricted to a maximum of 20 g per day for the 28 rice types to avoid carcinogenic risks. We believe that consumers could be better informed whether the marketed product is fit for infants and young children, via appropriate product labelling containing information about iAs concentration.

The role of extracellular DNA in uranium precipitation and biomineralisation.

Bacterial extra polymeric substances (EPS) have been associated with the extracellular precipitation of uranium. Here we report findings on the biomineralisation of uranium, with extracellular DNA (eDNA) used as a model biomolecule representative of EPS. The complexation and precipitation of eDNA with uranium were investigated as a function of pH, ionic strength and varying concentrations of reactants. The role of phosphate moieties in the biomineralisation mechanism was studied by enzymatically releasing phosphate (ePO4) from eDNA compared to abiotic phosphate (aPO4). The eDNA-uranium precipitates and uranium minerals obtained were characterised by Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FT-IR) spectroscopy, Scanning Electron Microscopy-Energy Dispersive X-Ray analysis (SEM-EDX), X-Ray Powder Diffraction (XRD) and X-Ray Photoelectron Spectroscopy (XPS). ATR-FT-IR showed that at pH 5, the eDNA-uranium precipitation mechanism was predominantly mediated by interactions with phosphate moieties from eDNA. At pH 2, the uranium interactions with eDNA occur mainly through phosphate. The solubility equilibrium was dependent on pH with the formation of precipitate reduced as the pH increased. The XRD data confirmed the formation of a uranium phosphate precipitate when synthesised using ePO4. XPS and SEM-EDX studies showed the incorporation of carbon and nitrogen groups from the enzymatic orthophosphate hydrolysis on the obtained precipitated. These results suggested that the removal of uranium from solution occurs via two mechanisms: complexation by eDNA molecules and precipitation of a uranium phosphate mineral of the type (UO2HPO4)·xH2O by enzymatic orthophosphate hydrolysis. This demonstrated that eDNA from bacterial EPS is a key contributor to uranium biomineralisation.