Synthesis and environmental chemistry of silver and iron oxide nanoparticles

Engineered nanoparticles are defined as having a dimension that is between one and one hundred nanometres. With toxicology studies reporting various degrees of toxicity the need to investigate nanoparticle fate and behaviour is vital. Monodispersed engineered nanoparticles were synthesised in-house to produce suitable materials to examine such processes. Iron oxide nanoparticles (5 nm) and citrate coated silver nanoparticles (20 nm) were subjected to different conditions of pH, ionic strength and different types of commercially available natural organic matter. Changes in particle size and aggregation were examined using a multi-method approach. Results showed that the natural organic matter was able to absorb onto nanoparticle surfaces and improve their stability when subjected to changes in pH and ionic strength, where they would normally aggregate. The presence of higher concentrations of NOM in some cases promoted aggregation due to bridging. This work also concluded that silver nanoparticles could be produced in the presence of NOM without additional stabilisers and that they themselves were stable. This work has demonstrated that engineered nanoparticles could remain stable within a range of environmental conditions, and thus raise future pollution concerns

Decommissionable concrete? Adsorption of radionuclides by removable bio-mineralised hydroxyapatite layers

Decomissioning of concrete infrastructure at nuclear sites after years of use can be problematic and dangerous due to high levels of radioactivity, penetration of contamination into concrete and potentially large volumes of contaminated material. The depth of contamination within concrete ranges from mm to cm and contain many radioactive isotopes types such as C, U, Pu, Sr and Cs. Before decommissioning, concrete structures must be surface decontaminated to minimize waste volumes and reduce hazard. Techniques normally applied involve mechanical scabbing/scraping and high pressure blasting of concrete to remove layers of contamination. These techniques are expensive, unsafe for workers, and risk the spread of radioactive contamination. In addressing the above issues, this project aims to develop a novel decommissionable concrete tailored for safe, rapid decommissioning with minimal waste. Previous work in our group has shown that under certain conditions, bacteria can make bio-mineralized hydroxyapatite (HAp) which form layers as surfaces on cement [1]. The Ca from the HAp can substitute for other cations and we hypothesize that this mechanism would be relevant for radioactive isotopes such as Sr2+ and Cs+ and UO22+, by bonding to PO43-. These HAp layers can be engineered for easy removal at the end of life. Our poster presents promising results of the first stage in developing the adsorptive layer of hydroxyapatite (HAp) and show its powerful adsorptive properties for ions such as Sr2+ and Cs+ with promise for UO22+

Hydroxyapatite coatings on cement paste as barriers against radiological contamination

A novel method for precipitating hydroxyapatite (HAp) onto cement paste is investigated for protecting concrete infrastructure from radiological contamination. Legacy nuclear sites contain large volumes of contaminated concrete and are expensive and dangerous to decommission. One solution is to ‘design for decommissioning’ by confining contaminants to a thin layer. Current layering methods, including paints or films, offer poor durability over plant lifespans. Here, we present a mineral-HAp-coated cement, which innovatively serves as a barrier layer to radioactive contaminants (e.g. Sr, U). HAp is shown to directly mineralise onto a cement paste block in a layer several microns thick via a two-step process: first, applying a silica-based scaffold onto a cement paste block; and second, soaking the resulting block in a PO4-enriched Ringer’s solution. Strontium ingression was tested on coated and uncoated cement paste (~ 40 × 40 × 40mm cement, 450 mL, 1000 mg L− 1 Sr) for a period of 1-week. While both coated and uncoated samples reduced the solution concentration of Sr by half, Sr was held within the HAp layer of coated cement paste and was not observed within the cement matrix. In the uncoated samples, Sr had penetrated further into the block. Further studies aim to characterise HAp before and after exposure to a range of radioactive contaminants and to develop a method for mechanical layer separation

Bioavailability of nanoscale metal oxides TiO(2), CeO(2), and ZnO to fish

addresses: The Hatherly Laboratories, University of Exeter, Prince of Wales Road, Exeter EX4 4PS, UK.types: Journal Article; Research Support, Non-U.S. Gov'tCopyright © 2010 American Chemical Society. Post print version of article deposited. The final published version is available from: http://dx.doi.org/10.1021/es901971aNanoparticles (NPs) are reported to be a potential environmental health hazard. For organisms living in the aquatic environment, there is uncertainty on exposure because of a lack of understanding and data regarding the fate, behavior, and bioavailability of the nanomaterials in the water column. This paper reports on a series of integrative biological and physicochemical studies on the uptake of unmodified commercial nanoscale metal oxides, zinc oxide (ZnO), cerium dioxide (CeO(2)), and titanium dioxide (TiO(2)), from the water and diet to determine their potential ecotoxicological impacts on fish as a function of concentration. Particle characterizations were performed and tissue concentrations were measured by a wide range of analytical methods. Definitive uptake from the water column and localization of TiO(2) NPs in gills was demonstrated for the first time by use of coherent anti-Stokes Raman scattering (CARS) microscopy. Significant uptake of nanomaterials was found only for cerium in the liver of zebrafish exposed via the water and ionic titanium in the gut of trout exposed via the diet. For the aqueous exposures undertaken, formation of large NP aggregates (up to 3 mum) occurred and it is likely that this resulted in limited bioavailability of the unmodified metal oxide NPs in fish

Characterisation of uranium-pyrite associations within organic-rich Eocene sediments using EM, XFM-µXANES and µXRD

Sediments that are rich in organic matter (OM) can trap and accumulate metals, including uranium (U), and provide favourable conditions for the formation of minerals such as pyrite. In OM-sediments, pyrite may play an important role in sorption and reduction of U and other metals that are sensitive to redox change. Mulga Rock, located in Western Australia, is an Eocene polymetallic deposit hosting economic uranium within its OM-rich sediments. Our previous work on the Mulga Rock deposits showed that OM may host U(VI) for long periods and suggested that reduction to U(IV) may occur through different pathways. Framboidal-like pyrite, embedded in lignite, displaying U(IV)-rich rims, > 100 µm, were investigated using synchrotron-X-ray fluorescence microscopy-micro-X-ray absorption near edge structure (XFM-µXANES), laboratory micro-X-ray diffraction (µXRD) and electron microscopy. Micro-XRD analyses indicated that the U(IV) phase was mostly coffinite [USiO4] mixed with uraninite [UO2]. Analyses of transects across U-pyrite rims using XFM and XFM-µXANES revealed higher concentrations of U(IV) near the pyrite, and proportionally more U(VI) away from the edge of the pyrite. We infer that within OM environments, pyrite has a local influence on the oxidation state of U, which may be influential when considering U mobility

Real-time detection of faecally contaminated drinking water with tryptophan-like fluorescence: defining threshold values

We assess the use of fluorescent dissolved organic matter at excitation-emission wavelengths of 280 nm and 360 nm, termed tryptophan-like fluorescence (TLF), as an indicator of faecally contaminated drinking water. A significant logistic regression model was developed using TLF as a predictor of thermotolerant coliforms (TTCs) using data from groundwater- and surface water-derived drinking water sources in India, Malawi, South Africa and Zambia. A TLF threshold of 1.3 ppb dissolved tryptophan was selected to classify TTC contamination. Validation of the TLF threshold indicated a false-negative error rate of 15% and a false-positive error rate of 18%. The threshold was unsuccessful at classifying contaminated sources containing 100 TTC cfu per 100 mL). Current commercially available fluorimeters are easy-to-use, suitable for use online and in remote environments, require neither reagents nor consumables, and crucially provide an instantaneous reading. TLF measurements are not appreciably impaired by common intereferents, such as pH, turbidity and temperature, within typical natural ranges. The technology is a viable option for the real-time screening of faecally contaminated drinking water globally

To what extent can portable fluorescence spectroscopy be used in the real-time assessment of microbial water quality?

YesThe intrinsic fluorescence of aquatic organic matter emitted at 350 nm when excited at 280 nm correlates widely with water quality parameters such as biochemical oxygen demand. Hence, in sewage-impacted rivers and groundwater, it might be expected that fluorescence at these wavelengths will also correlate with the microbial water quality. In this paper we use a portable fluorimeter to assess the relationship between fluorescence intensity at this wavelength pair and Escherichia coli enumeration in contrasting river catchments of poor water quality: in KwaZulu-Natal, S. Africa and the West Midlands, UK. Across all catchments we demonstrate a log correlation (r = 0.74) between fluorescence intensity and E. coli over a seven-log range in E. coli enumerations on non-perturbed (unfiltered) samples. Within specific catchments, the relationship between fluorescence intensity and E. coli is more variable, demonstrating the importance of catchment-specific interference. Our research demonstrates the potential of using a portable fluorimeter as an initial screening tool for indicative microbial water quality, and one that is ideally suited to simple pollution scenarios such as assessing the impact of faecal contamination in river or groundwater at specific sites.This research was funded by the UK EPSRC Grant EP/H003061/1

(Hydroxy)apatite on cement: insights into a new surface treatment

(Hydroxy)apatite [Ca10(PO4)6(OH)2], has emerging potential as a cement coating material, with applications in environmental remediation, nuclear waste storage and architectural preservation. In these low temperature environments and when precipitating from aqueous solution on to a porous substrate, the crystal size, nucleation sites and modified surface properties created are key to designing the most effective coating. In this study we show that bacterial (biogenic) or chemical (abiotic) syntheses on to Portland cement alter these critical performance parameters. We identify the most significant difference between these two methods is the rate of pH change of the solution during synthesis, as this alters the surface properties and layer structure of HAp formed on cement. We show that iron present in Portland cement is not incorporated into the HAp structure; that formation of nanoparticulate/nanocrystalline HAp begins in the top 20 – 50 μm of the cement pore structure; and that a pH rise in the deposition solution controlled by bacteria metabolic activity leads to a rougher and more hydrophobic HAp coating compared to the abiotic synthesis. The results present the possibility of tailoring the surface topography and hydrophobicity of (hydroxy)apatite coated cement

Uranium mobility in organic matter-rich sediments: A review of geological and geochemical processes

Uranium (U) is of enormous global importance because of its use in energy generation, albeit with potential environmental legacies. While naturally occurring U is widespread in the Earth's crust at concentrations of ~1 to 3 ppm, higher concentrations can be found, includingwithin organicmatter (OM)-rich sediments, leading to economic extraction opportunities. The primary determinants of U behaviour in ore systems are pH, Eh, U oxidation state (U(IV), U(VI)) and the abundance of CO3 2– ions. The concentration/availability and interrelationships among such determinants vary, and the solubility and mobility of ions (e.g. OH-, CO3 2–, PO4 3-, SiO4 4-, SO4 2-) that compete for U (primarily as U(VI)) will also influence the mobility of U. In addition, the presence of OM can influence U mobility and fate by the degree of OMsorption to mineral surfaces (e.g. Fe- and Si- oxides and hydroxides). Within solid-phase OM, microbes can influence U oxidation state and U stability through direct enzymatic reduction, biosorption, biomineralisation and bioaccumulation. The biogenic UO2 product is, however, reported to be readily susceptible to reoxidation and therefore more likely remobilised over longer time periods. Thus several areas of uncertainty remain with respect to factors contributing to U accumulation, stability and/or (re)mobilisation. To address these uncertainties, this paper reviews U dynamics at both geological and molecular scales. Here we identify U-OMbond values that are in agreement, relatively strong, independent from ionic strength and which may facilitate either U mobilisation or immobilisation, depending on environmental conditions. We also examine knowledge gaps in the literature, with U-OM solubility data generally lacking in comparison to data for U sorption and dissolution, and little information available on multi-component relationships, such as UOM-V (V as vanadate). Furthermore, the capability ofOMto influence the oxidation state of U at near surface conditions remains unclear, as it can be postulated that electron shuttling by OM may contribute to changes in U redox state otherwise mediated by bacteria. Geochemical modelling of the environmental mobility of U will require incorporation of data from multi-corporation studies, as well as from studies of U-OM microbial interactions, all of which are considered in this review

Mortality and pulmonary complications in patients undergoing surgery with perioperative SARS-CoV-2 infection: an international cohort study

Background: The impact of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) on postoperative recovery needs to be understood to inform clinical decision making during and after the COVID-19 pandemic. This study reports 30-day mortality and pulmonary complication rates in patients with perioperative SARS-CoV-2 infection. Methods: This international, multicentre, cohort study at 235 hospitals in 24 countries included all patients undergoing surgery who had SARS-CoV-2 infection confirmed within 7 days before or 30 days after surgery. The primary outcome measure was 30-day postoperative mortality and was assessed in all enrolled patients. The main secondary outcome measure was pulmonary complications, defined as pneumonia, acute respiratory distress syndrome, or unexpected postoperative ventilation. Findings: This analysis includes 1128 patients who had surgery between Jan 1 and March 31, 2020, of whom 835 (74·0%) had emergency surgery and 280 (24·8%) had elective surgery. SARS-CoV-2 infection was confirmed preoperatively in 294 (26·1%) patients. 30-day mortality was 23·8% (268 of 1128). Pulmonary complications occurred in 577 (51·2%) of 1128 patients; 30-day mortality in these patients was 38·0% (219 of 577), accounting for 81·7% (219 of 268) of all deaths. In adjusted analyses, 30-day mortality was associated with male sex (odds ratio 1·75 [95% CI 1·28–2·40], p\textless0·0001), age 70 years or older versus younger than 70 years (2·30 [1·65–3·22], p\textless0·0001), American Society of Anesthesiologists grades 3–5 versus grades 1–2 (2·35 [1·57–3·53], p\textless0·0001), malignant versus benign or obstetric diagnosis (1·55 [1·01–2·39], p=0·046), emergency versus elective surgery (1·67 [1·06–2·63], p=0·026), and major versus minor surgery (1·52 [1·01–2·31], p=0·047). Interpretation: Postoperative pulmonary complications occur in half of patients with perioperative SARS-CoV-2 infection and are associated with high mortality. Thresholds for surgery during the COVID-19 pandemic should be higher than during normal practice, particularly in men aged 70 years and older. Consideration should be given for postponing non-urgent procedures and promoting non-operative treatment to delay or avoid the need for surgery. Funding: National Institute for Health Research (NIHR), Association of Coloproctology of Great Britain and Ireland, Bowel and Cancer Research, Bowel Disease Research Foundation, Association of Upper Gastrointestinal Surgeons, British Association of Surgical Oncology, British Gynaecological Cancer Society, European Society of Coloproctology, NIHR Academy, Sarcoma UK, Vascular Society for Great Britain and Ireland, and Yorkshire Cancer Research