Anthony Stockdale

Toxicity of proton-metal mixtures in the field: Linking stream macroinvertebrate species diversity to chemical speciation and bioavailability

Understanding metal and proton toxicity under field conditions requires consideration of the complex nature of chemicals in mixtures. Here, we demonstrate a novel method that relates streamwater concentrations of cationic metallic species and protons to a field ecological index of biodiversity. The model WHAM-F(TOX) postulates that cation binding sites of aquatic macroinvertebrates can be represented by the functional groups of natural organic matter (humic acid), as described by the Windermere Humic Aqueous Model (WHAM6), and supporting field evidence is presented. We define a toxicity function (F(TOX)) by summing the products: (amount of invertebrate-bound cation) x (cation-specific toxicity coefficient, α(i)). Species richness data for Ephemeroptera, Plecoptera and Trichoptera (EPT), are then described with a lower threshold of F(TOX), below which all organisms are present and toxic effects are absent, and an upper threshold above which organisms are absent. Between the thresholds the number of species declines linearly with F(TOX). We parameterised the model with chemistry and EPT data for low-order streamwaters affected by acid deposition and/or abandoned mines, representing a total of 412 sites across three continents. The fitting made use of quantile regression, to take into account reduced species richness caused by (unknown) factors other than cation toxicity. Parameters were derived for the four most common or abundant cations, with values of α(i) following the sequence (increasing toxicity) H+ < Al < Zn < Cu. For waters affected mainly by H+ and Al, F(TOX) shows a steady decline with increasing pH, crossing the lower threshold near to pH 7. Competition effects among cations mean that toxicity due to Cu and Zn is rare at lower pH values, and occurs mostly between pH 6 and 8.

High-resolution two-dimensional quantitative analysis of phosphorus, vanadium and arsenic, and qualitative analysis of sulphide, in a freshwater sediment.

Environmental context. Chemical characterisation of sediment microniches can reveal diagenetic processes that may not be detected by larger-scale analysis. With the development of a new preparation method for a binding phase gel, the technique of diffusive gradients in thin films has been used to demonstrate links between the diagenesis of sulfide, phosphorus, vanadium and arsenic at microniches. Knowledge of these processes may improve predictions of past deposition climates where trace elements are considered as paleoredox proxies. Abstract. Recently introduced techniques that can provide two-dimensional images of solution concentrations in sediments for multiple analytes have revealed discrete sites of geochemical behaviour different from the average for that depth (microniches). We have developed a new preparation method for a binding phase, incorporated in a hydrogel, for the diffusive gradients in thin films (DGT) technique. It allows co-analysis of sulfide and the reactive forms of phosphorus, vanadium and arsenic in the porewaters at the surface of the device. This gel, when dried and analysed using laser ablation mass spectrometry, allows the acquisition of high-resolution sub-millimetre-scale data. The binding phase was deployed within a DGT device in a sediment core collected from a productive lake, Esthwaite Water (UK). Localised removal of phosphate and vanadium from the porewaters has been demonstrated at a microniche of local sulfide production. The possible removal processes, including bacterial uptake and reduction of vanadate to insoluble VIII by sulfide, are discussed. Understanding processes occurring at this scale may allow improved prediction of pollutant fate and better prediction of past climates where trace metals are used as paleoredox proxies.

Effect of Ocean Acidification on Organic and Inorganic Speciation of Trace Metals

Rising concentrations of atmospheric carbon dioxide are causing acidification of the oceans. This results in changes to the concentrations of key chemical species such as hydroxide, carbonate and bicarbonate ions. These changes will affect the distribution of different forms of trace metals. Using IPCC data for pCO2 and pH under four future emissions scenarios (to the year 2100) we use a chemical speciation model to predict changes in the distribution of organic and inorganic forms of trace metals. Under a scenario where emissions peak after the year 2100, predicted free ion Al, Fe, Cu, and Pb concentrations increase by factors of up to approximately 21, 2.4, 1.5, and 2.0 respectively. Concentrations of organically complexed metal typically have a lower sensitivity to ocean acidification induced changes. Concentrations of organically complexed Mn, Cu, Zn, and Cd fall by up to 10%, while those of organically complexed Fe, Co, and Ni rise by up to 14%. Although modest, these changes may have significance for the biological availability of metals given the close adaptation of marine microorganisms to their environment.

2D simultaneous measurement of the oxyanions of P, V, As, Mo, Sb, W and U

Previous work used the sampling technique diffusive gradients in thin films analysed by laser ablation mass spectrometry to measure sulfide, P, V and As at a microniche of reactive organic carbon in a freshwater sediment. Here we present new developments of this technique. The number of analytes has been extended and we demonstrate the technique for depth profiling of analytes in both one and two dimensions. The physical dimensions of the cell in the laser ablation unit restrict the maximum length of gel that can be analysed. We address this problem by proposing a method for obtaining better data continuity when analysing multiple segments of gel from the same probe. (13)C is used as the internal standard for each gel segment. For the cross-standardisation of different gel segments (58)Fe signals are obtained from ablation of a small piece of standard ferrihydrite gel analysed during the same run as the sample gel. As the ferrihydrite gel is a subsection of a much larger gel (i.e. the Fe concentration is consistent for all subsections), any difference in signal can be attributed to changes in detector sensitivity, allowing consistent standardisation of gels analysed in different runs and on different days.

The Potential Impact of Saharan Dust and Polluted Aerosols on Microbial Populations in the East Mediterranean Sea, an Overview of a Mesocosm Experimental Approach

Recent estimates of nutrient budgets for the Eastern Mediterranean Sea (EMS) indicate that atmospheric aerosols play a significant role as suppliers of macro- and micro- nutrients to its Low Nutrient Low Chlorophyll water. Here we present the first mesocosm experimental study that examines the overall response of the oligotrophic EMS surface mixed layer (Cretan Sea, May 2012) to two different types of natural aerosol additions, “pure” Saharan dust (SD, 1.6 mg l-1) and mixed aerosols (A - polluted and desert origin, 1 mg l-1). We describe the rationale, the experimental set-up, the chemical characteristics of the ambient water and aerosols and the relative maximal biological impacts that resulted from the added aerosols. The two treatments, run in triplicates (3 m3 each), were compared to control-unamended runs. Leaching of approximately 2.1-2.8 and 2.2-3.7 nmol PO4 and 20-26 and 53-55 nmol NOx was measured per each milligram of SD and A, respectively, representing an addition of approximately 30% of the ambient phosphate concentrations. The nitrate/phosphate ratios added in the A treatment were twice than those added in the SD treatment. Both types of dry aerosols triggered a positive change (25-600% normalized per 1 mg l-1 addition) in most of the rate and state variables that were measured: bacterial abundance (BA), bacterial production (BP), Synechococcus (Syn) abundance, chlorophyll-a (chl-a), primary production (PP) and dinitrogen fixation (N2-fix), with relative changes among them following the sequence BP>PP≈N2-fix>chl-a≈BA≈Syn. Our results show that the ‘polluted’ aerosols triggered a relatively larger biological change compared to the SD amendments (per a similar amount of mass addition), especially regarding BP and PP. We speculate that despite the co-limitation of P and N in the EMS, the additional N released by the A treatment may have triggered the relatively larger response in most of the rate and state variables as compared to SD. An implication of our study is that a warmer atmosphere in the future may increase dust emissions and influence the intensity and length of the already well stratified water column in the EMS and hence the impact of the aerosols as a significant external source of new nutrients.

Metal and proton toxicity to lake zooplankton: A chemical speciation based modelling approach

The WHAM-FTOX model quantifies the combined toxic effects of protons and metal cations towards aquatic organisms through the toxicity function (FTOX), a linear combination of the products of organism-bound cation and a toxic potency coefficient for each cation. We describe the application of the model to predict an observable ecological field variable, species richness of pelagic lake crustacean zooplankton, studied with respect to either acidification or the impacts of metals from smelters. The fitted results give toxic potencies increasing in the order H(+) < Al < Cu < Zn < Ni. In general, observed species richness is lower than predicted, but in some instances agreement is close, and is rarely higher than predictions. The model predicts recovery in agreement with observations for three regions, namely Sudbury (Canada), Bohemian Forest (Czech Republic) and a subset of lakes across Norway, but fails to predict observed recovery from acidification in Adirondack lakes (USA).

Trace metals in the open oceans: speciation modelling based on humic-type ligands

The speciation of trace metals in the oceans is typically explained by invoking the concept of metal binding to specific organic ligands, but a lack of detailed knowledge about the ligands has impeded the formulation of comprehensive models to predict speciation chemistry. The aim of our study was to shed further light on the possible role of humic-type ligands in trace metal complexation in the oceans by comparing published seawater (open ocean) speciation measurements with predictions obtained using a speciation model typically used for freshwater and soil systems (Windermere Humic Aqueous Model; WHAM). We show that in some cases, speciation of trace metals in seawater environments may be reasonably predicted using this model with its default parameter set, without any model fitting. The results support the idea that humic-type ligands may account for much of the observed organic binding at least in the cases of Fe, Cu and Pb. Although the model does not consistently provide agreement with the measured values, it provides a useful benchmark to compare different datasets and to examine variation in speciation as a result of varying levels of competing metal ion concentration and fulvic acid activity.

A three-dimensional reactive transport model for sediments, incorporating microniches

Environmental context. Modelling of discrete sites of diagenesis in sediments (microniches) has typically been performed in 1-D and has involved a limited set of components. Here we present a new 3-D model for microniches within a traditional vertical sequence of redox reactions, and show example modelled niches of a range of sizes, close to the sediment–water interface. Microniche processes may have implications for understanding trace metal diagenesis, via formation of sulfides. The model provides a quantitative framework for examining microniche data and concepts. Abstract. Most reactive transport models have represented sediments as one-dimensional (1-D) systems and have solely considered the development of vertical concentration gradients. However, application of recently developed microscale and 2-D measurement techniques have demonstrated more complicated solute structures in some sediments, including discrete localised sites of depleted oxygen, and elevated trace metals and sulfide, referred to as microniches. A model of transport and reaction in sediments that can simulate the dynamic development of concentration gradients occurring in 3-D was developed. Its graphical user interface allows easy input of user-specified reactions and provides flexible schemes that prioritise their execution. The 3-D capability was demonstrated by quantitative modelling of hypothetical solute behaviour at organic matter microniches covering a range of sizes. Significant effects of microniches on the profiles of oxygen and nitrate are demonstrated. Sulfide is shown to be readily generated in microniches within 1 cm of the sediment surface, provided the diameter of the reactive organic material is greater than 1 mm. These modelling results illustrate the geochemical complexities that arise when processes occur in 3-D and demonstrate the need for such a model. Future use of high-resolution measurement techniques should include the collection of data for relevant major components, such as reactive iron and manganese oxides, to allow full, multicomponent modelling of microniche processes.

Dissolved trace metal speciation in estuarine and coastal waters: Comparison of WHAM/Model VII predictions with analytical results

The authors apply the chemical speciation model WHAM/Model VII to investigate the distribution of metal species of Fe(III) and the divalent cations of Ni, Cu, Zn, Cd, Hg, and Pb, in the water column of estuaries and coastal areas. The authors compare, for the same locations, measured and modeled free ion and organically bound metal concentrations. The modeled free ion calculations show varying levels of agreement with experimental measurements. Where only natural organic matter is considered as the organic ligand, for Ni, Cd, and Pb, agreement within 1 order of magnitude is found in 122 of 128 comparisons. For Fe and Zn comparisons 12 of 34 (Fe) and 10 of 18 (Zn) agree to within 1 order of magnitude, the remaining modeled values being over 1 order of magnitude higher than measurements. Copper measurements agree within 1 order of magnitude of modeled values in 314 of 533 (59%) cases and are more than 1 order of magnitude lower than modeled values in 202 cases. There is a general tendency for agreement between modeled and measured values to improve with increasing total metal concentrations. There are substantial variations among different analysis techniques but no systematic bias from the model is observed across techniques. It would be beneficial to cross-validate the different analytical methods, in combination with further modeling. The authors also assessed the effect of including an anthropogenic organic ligand (ethylenediamine tetraacetic acid (EDTA)) in the modeling, given its known presence in some coastal environments. Except for Cd, all metals were sensitive to the presence of EDTA, even at a low concentration of 50 nM.

Understanding the nature of atmospheric acid processing of mineral dusts in supplying bioavailable phosphorus to the oceans

Significance Mineral dust is the most important external source of phosphorus (P), a key nutrient controlling phytoplankton productivity and carbon uptake, to the offshore ocean. The bioavailable P in dust exhibits considerable and poorly understood variability. Detailed laboratory experiments elucidate and quantify the major processes controlling P dissolution in the atmosphere. Dust exposure to acids is the main driver of P mineral transformations, and a simple direct proportionality is found between the amount of bioavailable P dissolved from the dust and acid exposure. Simulations suggest that dust acidification increases leachable P over large areas of the globe and explains much of its variability in important oceanic areas where primary productivity is limited by this nutrient (e.g., North Central Atlantic, Mediterranean). Acidification of airborne dust particles can dramatically increase the amount of bioavailable phosphorus (P) deposited on the surface ocean. Experiments were conducted to simulate atmospheric processes and determine the dissolution behavior of P compounds in dust and dust precursor soils. Acid dissolution occurs rapidly (seconds to minutes) and is controlled by the amount of H+ ions present. For H+ < 10−4 mol/g of dust, 1–10% of the total P is dissolved, largely as a result of dissolution of surface-bound forms. At H+ > 10−4 mol/g of dust, the amount of P (and calcium) released has a direct proportionality to the amount of H+ consumed until all inorganic P minerals are exhausted and the final pH remains acidic. Once dissolved, P will stay in solution due to slow precipitation kinetics. Dissolution of apatite-P (Ap-P), the major mineral phase in dust (79–96%), occurs whether calcium carbonate (calcite) is present or not, although the increase in dissolved P is greater if calcite is absent or if the particles are externally mixed. The system was modeled adequately as a simple mixture of Ap-P and calcite. P dissolves readily by acid processes in the atmosphere in contrast to iron, which dissolves more slowly and is subject to reprecipitation at cloud water pH. We show that acidification can increase bioavailable P deposition over large areas of the globe, and may explain much of the previously observed patterns of variability in leachable P in oceanic areas where primary productivity is limited by this nutrient (e.g., Mediterranean).