Mineral phosphorus drives glacier algal blooms on the Greenland Ice Sheet.

Melting of the Greenland Ice Sheet is a leading cause of land-ice mass loss and cryosphere-attributed sea level rise. Blooms of pigmented glacier ice algae lower ice albedo and accelerate surface melting in the ice sheet's southwest sector. Although glacier ice algae cause up to 13% of the surface melting in this region, the controls on bloom development remain poorly understood. Here we show a direct link between mineral phosphorus in surface ice and glacier ice algae biomass through the quantification of solid and fluid phase phosphorus reservoirs in surface habitats across the southwest ablation zone of the ice sheet. We demonstrate that nutrients from mineral dust likely drive glacier ice algal growth, and thereby identify mineral dust as a secondary control on ice sheet melting.

Determination and Prediction of Zinc Speciation in Estuaries.

Lowering of the estuarine Environmental Quality Standard for zinc in the UK to 121 nM reflects rising concern regarding zinc in ecosystems and is driving the need to better understand its fate and behavior and to develop and parametrize speciation models to predict the metal species present. For the first time, an extensive data set has been gathered for the speciation of zinc within an estuarine system with supporting physicochemical characterization, in particular dissolved organic carbon. WHAM/Model VII and Visual MINTEQ speciation models were used to simulate zinc speciation, using a combination of measured complexation variables and available defaults. Data for the five estuarine transects from freshwater to seawater endmembers showed very variable patterns of zinc speciation depending on river flows, seasons, and potential variations in metal and ligand inputs from in situ and ex situ sources. There were no clear relationships between free zinc ion concentration [Zn2+] and measured variables such as DOC concentration, humic and biological indices. Simulations of [Zn2+] carried out with both models at high salinities or by inputting site specific complexation capacities were successful, but overestimated [Zn2+] in low salinity waters, probably owing to an underestimation of the complexation strength of the ligands present. Uncertainties in predicted [Zn2+] are consistently smaller than standard deviations of the measured values, suggesting that the accuracy of the measurements is more critical than model uncertainty in evaluating the predictions.

Evaluating water quality and ecotoxicology assessment techniques using data from a lead and zinc effected upland limestone catchment.

Point and diffuse sources associated with historical metal ore mining are major causes of metal pollution. The understanding of metal behaviour and fate has been improved by the integration of water chemistry, metal availability and toxicity. Efforts have been devoted to the development of efficient methods of assessing and managing the risk posed by metals to aquatic life and meeting national water quality standards. This study focuses on the evaluation of current water quality and ecotoxicology techniques for the metal assessment of an upland limestone catchment located within a historical metal (lead ore) mining area in northern England. Within this catchment, metal toxicity occurs at circumneutral pH (6.2-7.5). Environmental Quality Standards (EQSs) based on a simple single concentration approach like hardness based EQS (EQS-H) are more overprotective, and from sixteen sites monitored in this study more than twelve sites (>75%) failed the EQSs for Zn and Pb. By increasing the complexity of assessment tools (e.g. bioavailability-based (EQS-B) and WHAM-FTOX), less conservative limits were provided, decreasing the number of sites with predicted ecological risk to seven (44%). Thus, this research supports the use of bioavailability-based approaches and their applicability for future metal risk assessments.

Understanding the mobilisation of metal pollution associated with historical mining in a carboniferous upland catchment.

Point and diffuse pollution from metal mining has led to severe environmental damage worldwide. Mine drainage is a significant problem for riverine ecosystems, it is commonly acidic (AMD), but neutral mine drainage (NMD) can also occur. A representative environment for studying metal pollution from NMD is provided by carboniferous catchments characterised by a circumneutral pH and high concentrations of carbonates, supporting the formation of secondary metal-minerals as potential sinks of metals. The present study focuses on understanding the mobility of metal pollution associated with historical mining in a carboniferous upland catchment. In the uplands of the UK, river water, sediments and spoil wastes were collected over a period of fourteen months, samples were chemically analysed to identify the main metal sources and their relationships with geological and hydrological factors. Correlation tests and principal component analysis suggest that the underlying limestone bedrock controls pH and weathering reactions. Significant metal concentrations from mining activities were measured for zinc (4.3 mg l-1), and lead (0.3 mg l-1), attributed to processes such as oxidation of mined ores (e.g. sphalerite, galena) or dissolution of precipitated secondary metal-minerals (e.g. cerussite, smithsonite). Zinc and lead mobility indicated strong dependence on biogeochemistry and hydrological conditions (e.g. pH and flow) at specific locations in the catchment. Annual loads of zinc and lead (2.9 and 0.2 tonnes per year) demonstrate a significant source of both metals to downstream river reaches. Metal pollution results in a large area of catchment having a depleted chemical status with likely effects on the aquatic ecology. This study provides an improved understanding of geological and hydrological processes controlling water chemistry, which is critical to assessing metal sources and mobilization, especially in neutral mine drainage areas.

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

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).

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.

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.

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).

Application of DGT to high pH environments: uptake efficiency of radionuclides of different oxidation states onto Chelex binding gel.

The DGT Chelex binding phase has not been tested for binding efficiency over the extreme high pH range (i.e., 10 to 13). Here, we examined the uptake efficiency of the gel-encapsulated Chelex cation exchange resin binding phase when in direct contact with solutions of radionuclides of different oxidation states over the circumneutral to high pH range (∼7 to 13). Results show that the Chelex binding gel is suitable for Eu(3+) for circumneutral pH, for UO2(2+) up to at least pH 10.7 and for NpO2(+) up to at least pH 11.7. Application may be appropriate at higher pH values but testing of complete solution deployment units will be required. This work provides the framework to use DGT as a tool for the study of high pH radionuclide systems.

Estimation of Model VII humic binding constants for Pd2+, Sn2+, U4+, NpO2(2+), Pu4+ and PuO2(2+).

Using previously established procedures that utilise linear free energy relationships, we estimated binding constants for the Windermere Humic Aqueous Model VII (WHAM/Model VII) for several radionuclide cations (Pd(2+), Sn(2+), U(4+), NpO(2)(2+), Pu(4+) and PuO(2)(2+)). This extends the number of cations that can be calculated with the model above the 40 included in the original Model VII work. When combined with equilibrium constants for inorganic species this allows the calculation of equilibrium distributions of chemical species under a wide range of conditions.

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.

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.