Strong evidence for the continued contribution of lead deposited during the 20th century to the atmospheric environment in London of today.

Although leaded gasoline was banned at the end of the last century, lead (Pb) remains significantly enriched in airborne particles in large cities. The remobilization of historical Pb deposited in soils from atmospheric removal has been suggested as an important source providing evidence for the hypothetical long-term persistency of lead, and possibly other pollutants, in the urban environment. Here, we present data on Pb isotopic composition in airborne particles collected in London (2014 to 2018), which provide strong support that lead deposited via gasoline combustion still contributes significantly to the lead burden in present-day London. Lead concentration and isotopic signature of airborne particles collected at a heavily trafficked site did not vary significantly over the last decade, suggesting that sources remained unchanged. Lead isotopic composition of airborne particles matches that of road dust and topsoils and can only be explained with a significant contribution (estimate of 32 ± 10 to 43 ± 9% based on a binary mixing model) of Pb from leaded gasoline. The lead isotopes furthermore suggest significant contributions from nonexhaust traffic emissions, even though isotopic signatures of anthropogenic sources are increasingly overlapping. Lead isotopic composition of airborne particles collected at building height shows a similar signature to that collected at street level, suggesting effective mixing of lead within the urban street canyon. Our results have important implications on the persistence of Pb in urban environments and suggest that atmospheric Pb reached a baseline in London that is difficult to decrease further with present policy measures.

Parasitic Light Absorption, Rate Laws and Heterojunctions in the Photocatalytic Oxidation of Arsenic(III) Using Composite TiO2 /Fe2 O3.

Composite photocatalyst-adsorbents such as TiO2 /Fe2 O3 are promising materials for the one-step treatment of arsenite contaminated water. However, no previous study has investigated how coupling TiO2 with Fe2 O3 influences the photocatalytic oxidation of arsenic(III). Herein, we develop new hybrid experiment/modelling approaches to study light absorption, charge carrier behaviour and changes in the rate law of the TiO2 /Fe2 O3 system, using UV-Vis spectroscopy, transient absorption spectroscopy (TAS), and kinetic analysis. Whilst coupling TiO2 with Fe2 O3 improves total arsenic removal by adsorption, oxidation rates significantly decrease (up to a factor of 60), primarily due to the parasitic absorption of light by Fe2 O3 (88 % of photons at 368 nm) and secondly due to changes in the rate law from disguised zero-order kinetics to first-order kinetics. Charge transfer across this TiO2 -Fe2 O3 heterojunction is not observed. Our study demonstrates the first application of a multi-adsorbate surface complexation model (SCM) towards describing As(III) oxidation kinetics which, unlike Langmuir-Hinshelwood kinetics, includes the competitive adsorption of As(V). We further highlight the importance of parasitic light absorption and catalyst fouling when designing heterogeneous photocatalysts for As(III) remediation.

Unravelling the modus operandi of phytosiderophores during zinc uptake in rice: the importance of geochemical gradients and accurate stability constants.

Micronutrient deficiencies threaten global food production. Attempts to biofortify crops rely on a clear understanding of micronutrient uptake processes. Zinc deficiency in rice is a serious problem. One of the pathways proposed for the transfer of zinc from soils into rice plants involves deoxymugineic acid (DMA), a phytosiderophore. The idea that phytosiderophores play a wider role in nutrition of Poaceae beyond iron is well established. However, key mechanistic details of the DMA-assisted zinc uptake pathway in rice remain uncertain. In particular, questions surround the form in which zinc from DMA is taken up [i.e. as free aqueous Zn(II) or as Zn(II)-DMA complexes] and the role of competitive behaviour of other metals with DMA. We propose that an accurate description of the effect of changes in pH, ligand concentration, and ionic strength on the stability of Zn(II)-DMA complexes in the presence of other metals in the microenvironment around root cells is critical for understanding the modus operandi of DMA during zinc uptake. To that end, we reveal the importance of geochemical changes in the microenvironment around root cells and demonstrate the effect of inaccurate stability constants on speciation models.

A Revised Pseudo-Second-Order Kinetic Model for Adsorption, Sensitive to Changes in Adsorbate and Adsorbent Concentrations.

The development of new adsorbent materials for the removal of toxic contaminants from drinking water is crucial toward achieving the United Nations Sustainable Development Goal 6 (clean water and sanitation). The characterization of these materials includes fitting models of adsorption kinetics to experimental data, most commonly the pseudo-second-order (PSO) model. The PSO model, however, is not sensitive to parameters such as adsorbate and adsorbent concentrations (C0 and Cs) and consequently is not able to predict changes in performance as a function of operating conditions. Furthermore, the experimental conditionality of the PSO rate constant, k2, can lead to erroneous conclusions when comparing literature results. In this study, we analyze 103 kinetic experiments from 47 literature sources to develop a relatively simple modification of the PSO rate equation, yielding dqtdt=k'Ct(1-qtqe)2. Unlike the original PSO model, this revised rate equation (rPSO) provides the first-order and zero-order dependencies upon C0 and Cs that we observe empirically. Our new model reduces the residual sum of squares by 66% when using a single rate constant to model multiple adsorption experiments with varying initial conditions. Furthermore, we demonstrate how the rPSO rate constant k' is more appropriate for comparing literature studies, highlighting faster kinetics in the adsorption of arsenic onto alumina versus iron oxides. This revised rate equation should find applications in engineering studies, especially since the rPSO rate constant k' does not show a counter-intuitive inverse relationship with increasing reaction rates when C0 is increased, unlike the PSO rate constant k2.

Cu isotopes in marine black shales record the Great Oxidation Event.

The oxygenation of the atmosphere ∼2.45-2.32 billion years ago (Ga) is one of the most significant geological events to have affected Earth's redox history. Our understanding of the timing and processes surrounding this key transition is largely dependent on the development of redox-sensitive proxies, many of which remain unexplored. Here we report a shift from negative to positive copper isotopic compositions (δ(65)CuERM-AE633) in organic carbon-rich shales spanning the period 2.66-2.08 Ga. We suggest that, before 2.3 Ga, a muted oxidative supply of weathering-derived copper enriched in (65)Cu, along with the preferential removal of (65)Cu by iron oxides, left seawater and marine biomass depleted in (65)Cu but enriched in (63)Cu. As banded iron formation deposition waned and continentally sourced Cu became more important, biomass sampled a dissolved Cu reservoir that was progressively less fractionated relative to the continental pool. This evolution toward heavy δ(65)Cu values coincides with a shift to negative sedimentary δ(56)Fe values and increased marine sulfate after the Great Oxidation Event (GOE), and is traceable through Phanerozoic shales to modern marine settings, where marine dissolved and sedimentary δ(65)Cu values are universally positive. Our finding of an important shift in sedimentary Cu isotope compositions across the GOE provides new insights into the Precambrian marine cycling of this critical micronutrient, and demonstrates the proxy potential for sedimentary Cu isotope compositions in the study of biogeochemical cycles and oceanic redox balance in the past.

Computational Tools for Calculating log ß Values of Geochemically Relevant Uranium Organometallic Complexes.

Uranium (UVI) interacts with organic ligands, subsequently controlling its aqueous chemistry. It is therefore imperative to assess the binding ability of natural organic molecules. We evidence that density functional theory (DFT) can be used as a practical protocol for predicting the stability of UVI organic ligand complexes, allowing for the development of a relative stability series for organic complexes with limited experimental data. Solvation methods and DFT settings were benchmarked to suggest a suitable off-the-shelf solution. The results indicate that the IEFPCM solvation method should be employed. A mixed solvation approach improves the accuracy of the calculated stability constant (log ß); however, the calculated log ß are approximately five times more favorable than experimental data. Different basis sets, functionals, and effective core potentials were tested to check that there were no major changes in molecular geometries and Δr G. The recommended method employed is the B3LYP functional, aug-cc-pVDZ basis set for ligands, MDF60 ECP and basis set for UVI, and the IEFPCM solvation model. Using the fitting approach employed in the literature with these updated DFT settings allows fitting of 1:1 UVI complexes with root-mean-square deviation of 1.38 log ß units. Fitting multiple bound carboxylate ligands indicates a second, separate fitting for 1:2 and 1:3 complexes.

Soil CO2 venting as one of the mechanisms for tolerance of Zn deficiency by rice in flooded soils.

We sought to explain rice (Oryza sativa) genotype differences in tolerance of zinc (Zn) deficiency in flooded paddy soils and the counter-intuitive observation, made in earlier field experiments, that Zn uptake per plant increases with increasing planting density. We grew tolerant and intolerant genotypes in a Zn-deficient flooded soil at high and low planting densities and found (a) plant Zn concentrations and growth increased with planting density and more so in the tolerant genotype, whereas the concentrations of other nutrients decreased, indicating a specific effect on Zn uptake; (b) the effects of planting density and genotype on Zn uptake could only be explained if the plants induced changes in the soil to make Zn more soluble; and (c) the genotype and planting density effects were both associated with decreases in dissolved CO2 in the rhizosphere soil solution and resulting increases in pH. We suggest that the increases in pH caused solubilization of soil Zn by dissolution of alkali-soluble, Zn-complexing organic ligands from soil organic matter. We conclude that differences in venting of soil CO2 through root aerenchyma were responsible for the genotype and planting density effects.

Experimental Determination of Zinc Isotope Fractionation in Complexes with the Phytosiderophore 2'-Deoxymugeneic Acid (DMA) and Its Structural Analogues, and Implications for Plant Uptake Mechanisms.

The stable isotope signatures of zinc and other metals are increasingly used to study plant and soil processes. Complexation with phytosiderophores is a key reaction and understanding the controls of isotope fractionation is central to such studies. Here, we investigated isotope fractionation during complexation of Zn2+ with the phytosiderophore 2'-deoxymugeneic acid (DMA), and with three commercially available structural analogues of DMA: EDTA, TmDTA, and CyDTA. We used ion exchange chromatography to separate free and complexed zinc, and identified appropriate cation exchange resins for the individual systems. These were Chelex-100 for EDTA and CyDTA, Amberlite CG50 for TmDTA and Amberlite IR120 for DMA. With all the ligands we found preferential partitioning of isotopically heavy zinc in the complexed form, and the extent of fractionation was independent of the Zn:ligand ratio used, indicating isotopic equilibrium and that the results were not significantly affected by artifacts during separation. The fractionations (in ‰) were +0.33 ± 0.07 (1σ, n = 3), + 0.45 ± 0.02 (1σ, n = 2), + 0.62 ± 0.05 (1σ, n = 3) and +0.30 ± 0.07 (1σ, n = 4) for EDTA, TmDTA, CyDTA, and DMA, respectively. Despite the similarity in Zn-coordinating donor groups, the fractionation factors are significantly different and extent of fractionation seems proportional to the complexation stability constant. The extent of fractionation with DMA agreed with observed fractionations in zinc uptake by paddy rice in field experiments, supporting the possible involvement of DMA in zinc uptake by rice.

Molecular recognition and scavenging of arsenate from aqueous solution using dimetallic receptors.

A series of copper(II), nickel(II) and zinc(II) dimetallic complexes were prepared and their affinities towards arsenate investigated. Indicator displacement assays (IDAs) were carried out to establish the complexes with best affinities towards arsenate. A di-zinc complex (3) was selected and its arsenate-binding abilities investigated by isothermal titration calorimetry (ITC). The X-ray crystal structure of this metallo-receptor bound to arsenate is also reported, which allowed us to establish the binding mode between 3 and this oxyanion. Immobilising 3 onto HypoGel resin yielded a novel adsorbent (Zn-HypoGel) with high affinity for arsenate. Adsorption of arsenate from competitive solutions and natural groundwater was greater than that of the commercially used iron oxide Bayoxide E33. Zn-HypoGel could be efficiently and simply regenerated by washing with sodium acetate solution.

Identification of atmospheric particulate matter derived from coal and biomass burning and from non-exhaust traffic emissions using zinc isotope signatures.

Improving urban air quality is a global challenge. To implement successful abatement measures that reduce atmospheric particulate matter (APM) and associated metal concentrations, precise source apportionment is needed. For this, apportioning contributions from coal and biomass burning and differentiating these from non-exhaust traffic emissions in urban APM is critical. Recent studies characterising the metal isotope composition of urban APM, and potential source materials suggested that non-traditional isotope systems could prove unique fingerprinting tools. Zinc isotopes should be able to separate APM derived from uncontrolled combustion (fly ash, isotopically heavy) from non-exhaust traffic sources (tyre and brake wear, intermediate) and from controlled industrial emissions (flue gas, light). To test this hypothesis, we determined zinc isotope ratios of APM (TSP, PM2.5, PM1) in Beijing (coal combustion for residential heating) and Varanasi (biomass burning in pre-monsoon periods). In Beijing, δ66ZnLyon values of PM2.5 ranged from -0.41 to +1.01‰ in 2015 (avg = +0.25 ± 0.50‰, n = 19). Aerosols (including TSP, PM2.5 and PM1 samples) from the heating period were significantly (t-test, p < 0.001) heavier (avg = +0.90 ± 0.12‰, n = 7) than those from the non-heating period (avg = +0.14 ± 0.36‰, n = 23). Average δ66ZnLyon values of PM2.5 in Varanasi in spring 2015 were +0.82 ± 0.11‰ (n = 4). Extent and direction of isotope fractionation is in line with that expected from theoretical models and the isotope signatures observed agree with previously determined ratios of source materials. Our study links for the first time comprehensively the heavy zinc isotope compositions in APM to coal and biomass burning and shows that zinc isotope compositions of aerosols can discriminate between non-exhaust traffic and combustion sources.

Uranium surface processes with sandstone and volcanic rocks in acidic and alkaline solutions.

Understanding the behaviour of uranium waste, for disposal purposes, is crucial due to the correlation between pH values and the disposal of distinct types of waste, with low level waste typically associated with acidic pH values, and higher and intermediate level waste commonly related to alkaline pH values. We studied the adsorption of U(VI) on sandstone and volcanic rock surfaces at pH 5.5 and 11.5 in aqueous solutions with and without bicarbonate (2 mM HCO3-) using XAS and FTIR. In the sandstone system, U(VI) adsorbs as a bidentate complex to Si at pH 5.5 without bicarbonate and as uranyl carbonate species with bicarbonate. At pH 11.5 without bicarbonate, U(VI) adsorbs as monodentate complexes to Si and precipitates as uranophane. With bicarbonate at pH 11.5, U(VI) precipitated as a Na-clarkeite mineral or remained as a uranyl carbonate surface species. In the volcanic rock system, U(VI) adsorbed to Si as an outer sphere complex at pH 5.5, regardless of the presence of bicarbonate. At pH 11.5 without bicarbonate, U(VI) adsorbed as a monodentate complex to one Si atom and precipitated as a Na-clarkeite mineral. With bicarbonate at pH 11.5, U(VI) sorbed as a bidentate carbonate complex to one Si atom. These results provide insight into the behaviour of U(VI) in heterogeneous, real-world systems related to the disposal of radioactive waste.

Decline of anthropogenic lead in South Atlantic Ocean surface waters from 1990 to 2011: New constraints from concentration and isotope data.

Anthropogenic emissions have severely perturbed the marine biogeochemical cycle of lead (Pb). Here, we present new Pb concentration and isotope data for surface seawater from GEOTRACES section GA02, sampled in the western South Atlantic in 2011. The South Atlantic is divided into three hydrographic zones: equatorial (0-20°S), subtropical (20-40°S), and subantarctic (40-60°S). The equatorial zone is dominated by previously deposited Pb transported by surface currents. The subtropical zone largely reflects anthropogenic Pb emissions from South America, whilst the subantarctic zone presents a mixture of South American anthropogenic Pb and natural Pb from Patagonian dust. The mean Pb concentration of 16.7 ± 3.8 pmol/kg is 34 % lower than in the 1990s, mostly driven by changes in the subtropical zone, with the fraction of natural Pb increasing from 24 % to 36 % between 1996 and 2011. Although anthropogenic Pb remains predominant, these findings demonstrate the effectiveness of policies that banned leaded gasoline.

Tracing bioavailability of ZnO nanoparticles using stable isotope labeling.

Zinc oxide nanoparticles (ZnO NPs) are widely used in commercial products and knowledge of their environmental fate is a priority for ecological protection. Here we synthesized model ZnO NPs that were made from and thus labeled with the stable isotope (68)Zn and this enables highly sensitive and selective detection of labeled components against high natural Zn background levels. We combine high precision stable isotope measurements and novel bioimaging techniques to characterize parallel water-borne exposures of the common mudshrimp Corophium volutator to (68)ZnO NPs, bulk (68)ZnO, and soluble (68)ZnCl(2) in the presence of sediment. C. volutator is an important component of coastal ecosystems where river-borne NPs will accumulate and is used on a routine basis for toxicity assessments. Our results demonstrate that ionic Zn from ZnO NPs is bioavailable to C. volutator and that Zn uptake is active. Bioavailability appears to be governed primarily by the dissolved Zn content of the water, whereby Zn uptake occurs via the aqueous phase and/or the ingestion of sediment particles with adsorbed Zn from dissolution of ZnO particles. The high sorption capacity of sediments for Zn thus enhances the potential for trophic transfer of Zn derived from readily soluble ZnO NPs. The uncertainties of our isotopic data are too large, however, to conclusively rule out any additional direct uptake route of ZnO NPs by C. volutator.

Synergistic use of siderophores and weak organic ligands during zinc transport in the rhizosphere controlled by pH and ion strength gradients.

Citrate (Cit) and Deferoxamine B (DFOB) are two important organic ligands coexisting in soils with distinct different affinities for metal ions. It has been theorized that siderophores and weak organic ligands play a synergistic role during the transport of micronutrients in the rhizosphere, but the geochemical controls of this process remain unknown. Here we test the hypothesis that gradients in pH and ion strength regulate and enable the cooperation. To this end, first we use potentiometric titrations to identify the dominant Zn(II)-Cit and Zn(II)-DFOB complexes and to determine their ionic strength dependent stability constants between 0 and 1 mol dm-3. We parametrise the Extended Debye-Hückel (EDH) equation and determine accurate intrinsic association constants (logß0) for the formation of the complexes present. The speciation model developed confirms the presence of [Zn(Cit)]-, [Zn(HCit)], [Zn2(Cit)2(OH)2]4-, and [Zn(Cit)2]4-, with [Zn(Cit)]- and [Zn2(Cit)2(OH)2]4- the dominant species in the pH range relevant to rhizosphere. We propose the existence of a new [Zn(Cit)(OH)3]4- complex above pH 10. We also verify the existence of two hexadentate Zn(II)-DFOB species, i.e., [Zn(DFOB)]- and [Zn(HDFOB)], and of one tetradentate species [Zn(H2DFOB)]+. Second, we identify the pH and ionic strength dependent ligand exchange points (LEP) of Zn with citrate and DFOB and the stability windows for Zn(II)-Cit and Zn(II)-DFOB complexes in NaCl and rice soil solutions. We find that the LEPs fall within the pH and ionic strength gradients expected in rhizospheres and that the stability windows for Zn(II)-citrate and Zn(II)-DFOB, i.e., low and high affinity ligands, can be distinctly set off. This suggests that pH and ion strength gradients allow for Zn(II) complexes with citrate and DFOB to dominate in different parts of the rhizosphere and this explains why mixtures of low and high affinity ligands increase leaching of micronutrients in soils. Speciation models of soil solutions using newly determined association constants demonstrate that the presence of dissolved organic matter and inorganic ligands (i.e., bicarbonate, phosphate, sulphate, or chlorides) do neither affect the position of the LEP nor the width of the stability windows significantly. In conclusion, we demonstrate that cooperative and synergistic ligand interaction between low and high affinity ligands is a valid mechanism for controlling zinc transport in the rhizosphere and possibly in other environmental reservoirs such as in the phycosphere. Multiple production of weak and strong ligands is therefore a valid strategy of plants and other soil organisms to improve access to micronutrients.

Effect of salinity on the zinc(II) binding efficiency of siderophore functional groups and implications for salinity tolerance mechanisms in barley.

Bacteria, fungi and grasses use siderophores to access micronutrients. Hence, the metal binding efficiency of siderophores is directly related to ecosystem productivity. Salinization of natural solutions, linked to climate change induced sea level rise and changing precipitation patterns, is a serious ecological threat. In this study, we investigate the impact of salinization on the zinc(II) binding efficiency of the major siderophore functional groups, namely the catecholate (for bacterial siderophores), α-hydroxycarboxylate (for plant siderophores; phytosiderophores) and hydroxamate (for fungal siderophores) bidentate motifs. Our analysis suggests that the order of increasing susceptibility of siderophore classes to salinity in terms of their zinc(II) chelating ability is: hydroxamate < catecholate < α-hydroxycarboxylate. Based on this ordering, we predict that plant productivity is more sensitive to salinization than either bacterial or fungal productivity. Finally, we show that previously observed increases in phytosiderophore release by barley plants grown under salt stress in a medium without initial micronutrient deficiencies, are in line with the reduced zinc(II) binding efficiency of the α-hydroxycarboxylate ligand and hence important for the salinity tolerance of whole-plant zinc(II) status.

Possible application of stable isotope compositions for the identification of metal sources in soil.

Metals in soil are potentially harmful to humans and ecosystems. Stable isotope measurement may provide "fingerprint" information on the sources of metals. In light of the rapid progress in this emerging field, we present a state-of-the-art overview of how useful stable isotopes are in soil metal source identification. Distinct isotope signals in different sources are the key prerequisites for source apportionment. In this context, Zn and Cd isotopes are particularly helpful for the identification of combustion-related industrial sources, since high-temperature evaporation-condensation would largely fractionate the isotopes of both elements. The mass-independent fractionation of Hg isotopes during photochemical reactions allows for the identification of atmospheric sources. However, compared with traditionally used Sr and Pb isotopes for source tracking whose variations are due to the radiogenic processes, the biogeochemical low-temperature fractionation of Cr, Cu, Zn, Cd, Hg and Tl isotopes renders much uncertainty, since large intra-source variations may overlap the distinct signatures of inter-source variations (i.e., blur the source signals). Stable isotope signatures of non-metallic elements can also aid in source identification in an indirect way. In fact, the soils are often contaminated with different elements. In this case, a combination of stable isotope analysis with mineralogical or statistical approaches would provide more accurate results. Furthermore, isotope-based source identification will also be helpful for comprehending the temporal changes of metal accumulation in soil systems.

Evidence for the mechanisms of zinc uptake by rice using isotope fractionation.

In an earlier study, we found that rice (Oryza sativa) grown in nutrient solution well-supplied with Zn preferentially took up light (64)Zn over (66)Zn, probably as a result of kinetic fractionation in membrane transport processes. Here, we measure isotope fractionation by rice in a submerged Zn-deficient soil with and without Zn fertilizer. We grew the same genotype as in the nutrient solution study plus low-Zn tolerant and intolerant lines from a recombinant inbred population. In contrast to the nutrient solution, in soil with Zn fertilizer we found little or heavy isotopic enrichment in the plants relative to plant-available Zn in the soil, and in soil without Zn fertilizer we found consistently heavy enrichment, particularly in the low-Zn tolerant line. These observations are only explicable by complexation of Zn by a complexing agent released from the roots and uptake of the complexed Zn by specific root transporters. We show with a mathematical model that, for realistic rates of secretion of the phytosiderophore deoxymugineic acid (DMA) by rice, and realistic parameters for the Zn-solubilizing effect of DMA in soil, solubilization and uptake by this mechanism is necessary and sufficient to account for the measured Zn uptake and the differences between genotypes.

Measurement of zinc stable isotope ratios in biogeochemical matrices by double-spike MC-ICPMS and determination of the isotope ratio pool available for plants from soil.

Analysis of naturally occurring isotopic variations is a promising tool for investigating Zn transport and cycling in geological and biological settings. Here, we present the recently installed double-spike (DS) technique at the MAGIC laboratories at Imperial College London. The procedure improves on previous published DS methods in terms of ease of measurement and precisions obtained. The analytical method involves addition of a (64)Zn-(67)Zn double-spike to the samples prior to digestion, separation of Zn from the sample matrix by ion exchange chromatography, and isotopic analysis by multiple-collector inductively coupled plasma mass spectrometry. The accuracy and reproducibility of the method were validated by analyses of several in-house and international elemental reference materials. Multiple analyses of pure Zn standard solutions consistently yielded a reproducibility of about ±0.05‰ (2 SD) for δ(66)Zn, and comparable precisions were obtained for analyses of geological and biological materials. Highly fractionated Zn standards analyzed by DS and standard sample bracketing yield slightly varying results, which probably originate from repetitive fractionation events during manufacture of the standards. However, the δ(66)Zn values (all reported relative to JMC Lyon Zn) for two less fractionated in-house Zn standard solutions, Imperial Zn (0.10 ± 0.08‰: 2 SD) and London Zn (0.08 ± 0.04‰), are within uncertainties to data reported with different mass spectrometric techniques and instruments. Two standard reference materials, blend ore BCR 027 and ryegrass BCR 281, were also measured, and the δ(66)Zn were found to be 0.25 ± 0.06‰ (2 SD) and 0.40 ± 0.09‰, respectively. Taken together, these standard measurements ascertain that the double-spike methodology is suitable for accurate and precise Zn isotope analyses of a wide range of natural samples. The newly installed technique was consequently applied to soil samples and soil leachates to investigate the isotopic signature of plant available Zn. We find that the isotopic composition is heavier than the residual, indicating the presence of loosely bound Zn deposited by atmospheric pollution, which is readily available to plants.

Improved accuracy in multicomponent surface complexation models using surface-sensitive analytical techniques: Adsorption of arsenic onto a TiO2/Fe2O3 multifunctional sorbent.

Novel composite materials are increasingly developed for water treatment applications with the aim of achieving multifunctional behaviour, e.g. combining adsorption with light-driven remediation. The application of surface complexation models (SCM) is important to understand how adsorption changes as a function of pH, ionic strength and the presence of competitor ions. Component additive (CA) models describe composite sorbents using a combination of single-phase reference materials. However, predictive adsorption modelling using the CA-SCM approach remains unreliable, due to challenges in the quantitative determination of surface composition. In this study, we test the hypothesis that characterisation of the outermost surface using low energy ion scattering (LEIS) improves CA-SCM accuracy. We consider the TiO2/Fe2O3 photocatalyst-sorbents that are increasingly investigated for arsenic remediation. Due to an iron oxide surface coating that was not captured by bulk analysis, LEIS significantly improves the accuracy of our component additive predictions for monolayer surface processes: adsorption of arsenic(V) and surface acidity. We also demonstrate non-component additivity in multilayer arsenic(III) adsorption, due to changes in surface morphology/porosity. Our results demonstrate how surface-sensitive analytical techniques will improve adsorption models for the next generation of composite sorbents.

Portable and rapid arsenic speciation in synthetic and natural waters by an As(V)-selective chemisorbent, validated against anodic stripping voltammetry.

Inorganic arsenic speciation, i.e. the differentiation between arsenite and arsenate, is an important step for any program aiming to address the global issue of arsenic contaminated groundwater, whether for monitoring purposes or the development of new water treatment regimes. Reliable speciation by easy-to-use, portable and cost-effective analytical techniques is still challenging for both synthetic and natural waters. Here we demonstrate the first application of an As(V)-selective chemisorbent material for simple and portable speciation of arsenic using handheld syringes, enabling high sample throughput with minimal set-up costs. We first show that ImpAs efficiently removes As(V) from a variety of synthetic groundwaters with a single treatment, whilst As(III) is not retained. We then exemplify the potential of ImpAs for simple and fast speciation by determining rate constants for the photooxidation of As(III) in the presence of a TiO2 photocatalyst. Finally, we successfully speciate natural waters spiked with a mix of As(III) and As(V) in both Indian and UK groundwaters with less than 5 mg L-1 dissolved iron. Experimental results using ImpAs agreed with anodic stripping voltammetry (ASV), a benchmark portable technique, with analysis conditions optimised here for the groundwaters of South Asia. This new analytical tool is simple, portable and fast, and should find applications within the overall multi-disciplinary remediation effort that is taking place to tackle this worldwide arsenic problem.