Contamination of the marine environment by Antarctic research stations: Monitoring marine pollution at Casey station from 1997 to 2015.

The contamination of the marine environment surrounding coastal Antarctic research stations remains insufficiently understood in terms of its extent, persistence, and characteristics. We investigated the presence of contaminants in marine sediments near Casey Station, located in the Windmill Islands of East Antarctica, during the period spanning from 1997 to 2015. Metals, hydrocarbons, PBDEs, PCBs, and nutrients were measured in sediments at anthropogenically disturbed sites, including the wastewater outfall, the wharf area, two former waste disposal sites, and various control locations. Sampling was carried out at three spatial scales: Locations, which were generally kilometres apart and formed the primary scale for comparison; Sites, which were 100 meters apart within each location; and Plots, which were 10 meters apart within each site. Consistently higher concentrations of most contaminants, and in some cases nutrients, were observed at disturbed locations. Some locations also exhibited an increase in contaminant concentrations over time. The spatial distribution of sediment properties (such as grain size and organic matter) and contaminants displayed intricate patterns of variation. Variation in grain size depended on the size category, with fine grains (e.g., <63 µm) showing the greatest variation at the Location scale, while coarse grains exhibited minimal variation at this scale. Contaminant levels demonstrated significant differences between Locations, accounting for approximately 55% of the overall variation for metals, while the variation within the 10-meter scale generally exceeded that within the 100-meter scale. Residual variation among replicate samples was also very high, demonstrating the need for adequate replication in studies of sediments and contaminants around stations. Some contaminants exceeded international guidelines for sediment quality, including metals, hydrocarbons, and PCBs. We conclude that Antarctic research stations such as Casey are likely to pose a moderate level of long-term ecological risk to local marine ecosystems through marine pollution. However, contamination is expected to be confined to areas in close proximity to the stations, although its extent and concentration are anticipated to increase with time. Raising awareness of the contamination risks associated with Antarctic stations and implementing monitoring programs for marine environments adjacent to these stations can contribute to informed decision-making and the improvement of environmental management practices in Antarctica.

Inexpensive portable capillary electrophoresis instrument for Monitoring Zinc(II) in remote areas.

A compact, inexpensive capillary electrophoresis instrument was developed for monitoring metal ions and evaluated for Zn(II) in remote contaminated locations in western Tasmania, Australia. The portable instrument, measuring 21 cm x 10 cm x 7 cm, was powered from the USB port of a laptop computer and built from off-the-shelf components costing ∼$1200 USD. Electrophoretic separations were conducted using a fused silica capillary (10-50 µm I.D.), applying 8.5 kV over capillaries ranging from 25 cm to 40 cm in length. The capillary inlet was connected with an electrically grounded cross-piece as flow-through injection interface. Automated fluidic management was achieved by controlling four mini peristaltic pumps and a solenoid valve. Detection was realised using a purpose-built visible LED absorption detector, optimised for the detection of Co(II), Cu(II) and Zn(II) after complexation with 4-(2-Pyridylazo) resorcinol (PAR). Limits of detection of sub-µM were obtained. The instrument was tested for continuous operation in the laboratory for up to 3 months, and relative standard deviations of <5.4% were found over 945 consecutive injections. In the field, the system was able to measure 106 samples within 11 h, the time it can be powered from the laptop computer. As Field measurement of Zn(II) in western Tasmania was demonstrated to show capability for on-site metal testing.

Protein sources influence both apparent digestibility and gastrointestinal evacuation rate in juvenile slipper lobster (Thenus australiensis).

Apparent digestibility and gastrointestinal evacuation rate were measured to assess the potential of five commercially available protein sources for their inclusion in feeds for juvenile slipper lobster, Thenus australiensis. Protein sources tested were fishmeal, krill meal, lupin meal, soybean meal and squid by-product meal. Apparent digestibility of crude protein ranged from 79.6% to 95.3%, with fishmeal protein significantly less digestible than lupin meal, squid by-product meal and soybean meal. Gastrointestinal evacuation rate was estimated from marker replacement, where yttrium oxide replaced ytterbium oxide. Faeces were collected every 3 h for 48 h, and a kinetic model was used to calculate the rate and time for the second marker to replace the first marker. Gastrointestinal evacuation (≥ 95%) was completed between 4 and 6 h with no significant differences among protein sources. Faeces consisted of both markers in equal parts 2.7 to 5.0 h after the feed switch, with lupin meal reaching the midpoint significantly faster than squid by-product meal and reference feed. The present study is the first in crustaceans to examine the relationship between apparent digestibility and gastrointestinal evacuation, showing more digestible protein sources had slower evacuation rates. The combined approach provides deeper insight into crustaceans' digestive physiology and helps understand their ability to digest specific ingredients. Further research is recommended to understand protein requirements in a broader context to verify highly digestible protein sources meet all nutritional requirements.

Scalable 3D printing method for the manufacture of single-material fluidic devices with integrated filter for point of collection colourimetric analysis.

Assembly and bonding are major obstacles in manufacturing of functionally integrated fluidic devices. Here we demonstrate a single-material 3D printed device with an integrated porous structure capable of filtering particulate matter for the colourimetric detection of iron from soil and natural waters. Selecting a PolyJet 3D printer for its throughput, integrated filters were created exploiting a phenomenon occurring at the interface between the commercially available build material (Veroclear-RGD810) and water-soluble support material (SUP707). The porous properties were tuneable by varying the orientation of the print head relative to the channel and by varying the width of the build material. Porous structures ranging from 100 to 200 µm in thickness separated the sample and reagent chambers, filtering particles larger than 15 µm in diameter. Maintaining the manufacturing throughput of the Polyjet printer, 221 devices could be printed in 1.5 h (∼25 s per device). Including the 12 h post-processing soak in sodium hydroxide to remove the solid support material, the total time to print and process 221 devices was 13.5 h (3.6 min per device), with a material cost of $2.50 each. The applicability of the fluidic device for point of collection analysis was evaluated using colourimetric determination of iron from soil slurry and environmental samples. Following the reduction of Fe3+ to Fe2+ using hydroxylammonium chloride, samples were introduced to the fluidic device where particulate matter was retained by the filter, allowing for particulate-free imaging of the red complex formed with 1,10-phenanthroline using a smartphone camera. The calibration curve ranged from of 1-100 mg L-1 Fe2+ and good agreement (95%) was obtained between the point of collection device and Sector Field ICP-MS.

Pre-concentration of thorium and neodymium isotopes using Nobias chelating resin: Method development and application to chromatographic separation.

The isotopes of thorium (Th) and neodymium (Nd) are used as tracers in oceanography, and are key parameters in the international GEOTRACES program. The very low concentrations of Th and Nd as well as the reactive nature of Th isotopes makes the analysis of seawater samples a complex process. Analysis requires time-consuming pre-concentration from over 5 L of seawater. We describe a method to simultaneously pre-concentrate dissolved Th and Nd from acidified seawater samples using the Nobias® PA1L chelating resin. Prior to pre-concentration, hydrofluoric acid is added to the sample to stabilise Th, ammonium acetate buffer added (0.05 M), pH adjusted to 4.75, and then finally the prepared sample is pumped through the Nobias resin at a rate of 15 ml min-1. Up to 6 samples can be processed simultaneously. Following elution in 3 M HNO3, both elements are chromatographically separated and determined using Inductively Coupled Plasma Mass Spectrometry. Oxidation of the sample between all column separation steps, including after the initial Nobias resin, is important for obtaining maximum elemental recoveries. The method has >90% recovery with blank levels typically <10 pg for 232Th and <70 pg for Nd. Accuracy is excellent, as our reported values generally agree within 1% of the GEOTRACES intercalibration standards. The long-term analysis of these materials also indicates excellent reproducibility. The pre-concentration of Th and Nd using the Nobias resin is a time saving option compared to the widely used iron co-precipitation technique. Sample handling is also reduced, decreasing the risk of sample contamination. The simplicity of our suggested pre-concentration procedure makes it possible to be applied at sea.

Critical evaluation of a seaFAST system for the analysis of trace metals in marine samples.

A seawater preconcentration system (seaFAST) with offline sector-field inductively coupled plasma mass spectrometry (SF-ICP-MS) detection was critically evaluated for ultra-low trace elemental analysis of Southern Ocean samples over a four-year period (2015-2018). The commercially available system employs two Nobias PA1 resin columns for buffer cleaning and sample preconcentration, allowing salt matrix removal with simultaneous extraction of a range of trace elements. With a primary focus on method simplicity and practicality, a range of experimental parameters relevant to oceanographic analysis were considered, including reduction of blank levels (over weeks and years), instrument conditioning, extraction efficiencies over different pH ranges (5.8-6.4), and preconcentration factors (~10-70 times). Conditions were optimised for the analysis of ten important trace elements (Cd, Co, Cu, Fe, Ga, Mn, Ni, Pb, Ti and Zn) in open ocean seawater samples, and included initial pre-cleaning and conditioning of the seaFAST unit for one week before each separate analytical sequence; a controlled narrow buffer pH of 6.20 ±â€¯0.02 used for extraction; and a sample preconcentration factor of 10 for (relatively) concentrated rainwater or sea ice, 40 for typical seawater samples, and up to 67 times for seawater samples collected in the remote open ocean such as the Southern Ocean. Method accuracy (both short - days to weeks - and long term - months to years) were evaluated through extensive analysis of a range of oceanographic standard reference samples including SAFe D1 (n = 20), D2 (n = 3), S (n = 15), GEOTRACES GD (n = 6), GSC (n = 42) and GSP (n = 42), as well as NASS-6 (n = 6). Measured values for oceanographic samples were found to agree with consensus values to within ±â€¯6% for Cd, Cu, Fe, Ni, Pb and Zn. Offsets were noted for Co (labile fraction only; no UV oxidation), Mn (difference also noted in other recent studies) and Ti (limited reference values). No consensus values currently exist for Ga. Iron and Mn in Southern Ocean samples were also independently verified via flow injection analysis methods (R2 = 0.95, n = 244 (Fe) and 0.92, n = 85 (Mn), paired t-test, p ≪0.05). Precisions over four years were evaluated through analysis of community seawater samples as well as a range of bulk in-house seawaters (3 sources, each n~100) and acid blanks (n = 250), and were typically found to be within 5-8%, depending on analyte and concentration. Values presented here represent one of the largest independent data sets for these reference samples, as well as the most documented comprehensive suite of GSP and GSC values currently available (consensus values have not yet been released). Samples covering a range of salinities (0-60) were investigated to demonstrate method versatility, with excellent recoveries noted using the seaFAST Nobias PA1 column (>98% for most elements, with 70-80% for Ga and Ti). By way of example, data is presented showing the application of the method to samples collected on the Kerguelen plateau in the Indian sector of the Southern Ocean (HEOBI voyage, January-February 2016) and in land-fast ice and brine collected near Davis station, Antarctica, in austral summer 2015 (with a salinity range from 0 to 73 g kg-1). Finally, a range of recommendations for successful implementation of a seaFAST system are provided, along with considerations for future investigation.

Seawater temperature effect on metal accumulation and toxicity in the subantarctic Macquarie Island isopod, Exosphaeroma gigas.

Very little is currently known of subantarctic nearshore invertebrates' sensitivity to environmental metals and the role of temperature in this relationship. This study investigated Cu and Zn toxicity in the common subantarctic intertidal isopod, Exosphaeroma gigas, and the influence of temperature on Cu toxicity and bioaccumulation kinetics. Adult E. gigas are insensitive to Cu and Zn at concentrations of 3200 and 7400µg/L respectively in non-renewal tests at 5.5°C (ambient subtidal temperature) over 14days. Under renewed exposures over the same temperature and time period the LC50 for copper was 2204µg/L. A 10-fold increase in Cu body burden occurred relative to zinc, indicating E. gigas has different strategies for regulating the two metals. Copper toxicity and time to mortality both increased with elevated temperature. However, temperature did not significantly affect Cu uptake rate and efflux rate constants derived from biodynamic modelling at lower Cu concentrations. These results may be attributable to E. gigas being an intertidal species with physiological mechanisms adapted to fluctuating environmental conditions. Cu concentrations required to elicit a toxicity response indicates that E. gigas would not be directly threatened by current levels of Cu or Zn present in Macquarie Island intertidal habitats, with the associated elevated temperature fluctuations. This study provides evidence that the sensitivity of this subantarctic intertidal species to metal contaminants is not as high as expected, and which has significance for the derivation of relevant guidelines specific to this distinct subpolar region of the world.

Direct electrokinetic injection of inorganic cations from whole fruits and vegetables for capillary electrophoresis analysis.

A novel approach for the direct injection from plant tissues without any sample pre-treatment has been developed by simply placing a small piece of the tissue into a capillary electrophoresis vial followed by application of a voltage for electrokinetic injection. Separations of sodium, potassium, calcium and magnesium were achieved using a BGE comprising 10mM imidazole and 2.5mM 18-crown-6-ether at pH 4.5. The addition of 2% (m/v) hydroxypropylmethyl cellulose to the separation buffer allowed for precise and accurate electrokinetic injection of ions from the plant material by halting the movement of tissue fluid into the capillary. This method provides both qualitative and quantitative data of inorganic cations, with quantitation in zucchini, mushroom and apple samples in agreement with Sector Field Inductively Coupled Plasma Mass Spectrometric analysis (r(2)=0.98, n=9). This method provides a new way for rapid, quantitative analysis by eliminating sample preparation procedures, and has great potential for a range of applications in plant science and food chemistry.

Microbial life at -13 °C in the brine of an ice-sealed Antarctic lake.

The permanent ice cover of Lake Vida (Antarctica) encapsulates an extreme cryogenic brine ecosystem (-13 °C; salinity, 200). This aphotic ecosystem is anoxic and consists of a slightly acidic (pH 6.2) sodium chloride-dominated brine. Expeditions in 2005 and 2010 were conducted to investigate the biogeochemistry of Lake Vida's brine system. A phylogenetically diverse and metabolically active Bacteria dominated microbial assemblage was observed in the brine. These bacteria live under very high levels of reduced metals, ammonia, molecular hydrogen (H(2)), and dissolved organic carbon, as well as high concentrations of oxidized species of nitrogen (i.e., supersaturated nitrous oxide and ∼1 mmol⋅L(-1) nitrate) and sulfur (as sulfate). The existence of this system, with active biota, and a suite of reduced as well as oxidized compounds, is unusual given the millennial scale of its isolation from external sources of energy. The geochemistry of the brine suggests that abiotic brine-rock reactions may occur in this system and that the rich sources of dissolved electron acceptors prevent sulfate reduction and methanogenesis from being energetically favorable. The discovery of this ecosystem and the in situ biotic and abiotic processes occurring at low temperature provides a tractable system to study habitability of isolated terrestrial cryoenvironments (e.g., permafrost cryopegs and subglacial ecosystems), and is a potential analog for habitats on other icy worlds where water-rock reactions may cooccur with saline deposits and subsurface oceans.

Historical lead isotope record of a sediment core from the Derwent River (Tasmania, Australia): a multiple source environment.

A 105 cm sediment core from the Derwent River (Tasmania, Australia) was collected in 2004 and was characterised considering both physical (loss on ignition at 550 °C and grain size) and chemical (Fe, Cu, Zn, Cd and Pb concentrations, Pb isotope ratios and (210)Pb dating) properties. The core was analysed to (i) investigate the historical profiles of some important elements associated with the Risdon zinc refinery adjacent to the Derwent River, (ii) determine Pb isotopic signatures of sediment samples, and (iii) assess the veracity of Pb isotope ratios as indicators of contaminant Pb input. Extractable metal concentrations were (all values as mgkg(-1), non-normalised for grain size) Fe: 20,000-35,000, Zn: 42-4500, Pb: 5-1090, Cu: 13-141, and Cd: 1-31; with a close correlation between Cu, Zn, Cd and Pb. Metal enrichment factors (normalised to Al) were Pb: 0.9-144, Zn: 0.8-93, Cd: 0.8-30, Cu: 0.8-8.9 and Fe: 0.9-1.3, confirming anthropogenic contributions of Cu, Zn, Pb and Cd to the sediments. The onset of metal contamination above background levels occurred at a depth between 43 and 49 cm, with maximum concentrations noted near 20 cm for Cu, Zn, Cd and Pb. Lead isotope ratios were determined in sediments using sector field ICP-MS, and were found to be 36.5-38.8, 16.5-18.7 and 1.07-1.20 for (208)Pb/(204)Pb, (206)Pb/(204)Pb and (206)Pb/(207)Pb ratios, respectively. Major Australian ores processed at the refinery over the previous ~90 years include those from Broken Hill, Rosebery, Mt Isa, Elura, Hellyer and Century deposits. Anthropogenic impact by Pb with Broken Hill type isotopic ratio was initially evident in the core at 43-49 cm. The introduction of Rosebery and Elura ores to the refinery was also clearly noted. Pb isotope ratios further highlight that the Derwent River has been exposed to a greater impact by anthropogenic Pb in comparison to other major Tasmanian rivers, namely the Huon and Tamar.

Modern sampling and analytical methods for the determination of trace elements in marine particulate material using magnetic sector inductively coupled plasma-mass spectrometry.

Trace elements often limit phytoplankton growth in the ocean, and the quantification of particulate forms is essential to fully understand their biogeochemical cycling. There is presently a lack of reliable measurements on the trace elemental content of marine particles, in part due to the inadequacies of the sampling and analytical methods employed. Here we report on the development of a series of state-of-the-art trace metal clean methods to collect and process oceanic particulate material in open-ocean and sea ice environments, including sampling, size-fractionated filtration, particle digestions and analysis by magnetic sector inductively coupled plasma-mass spectrometry (ICP-MS). Particular attention was paid to the analysis of certified reference materials (CRMs) and field blanks, which are typically the limiting factor for the accurate analysis of low concentrations of trace metals in marine particulate samples. Theoretical detection limits (3 s of the blank) were low for all 17 elements considered, and varied according to filter material and porosity (sub-microg L(-1) for polycarbonate filters and 1-2 microg L(-1) for quartz and polyester filters). Analytical accuracy was verified using fresh water CRMs, with excellent recoveries noted (93-103%). Digestion efficiencies for various acid combinations were assessed using sediment and plankton CRMs. Using nitric acid only, good recoveries (79-90%) were achieved for Mo, Cd, Ba, Pb, Mn, Fe, Co, Ni, Cu, Zn and Ga. The addition of HF was necessary for the quantitative recovery of the more refractory trace elements such as U, Al, V and Cr. Bioactive elements such as P can also be analysed and used as a biomass normaliser. Our developed sampling and analytical methods proved reliable when applied during two major field programs in both the open Southern Ocean and Antarctic sea ice environments during the International Polar Year in 2007. Trace elemental data are presented for particulate samples collected in both suspended and sinking marine material, and also within sea ice cores.

The application of lead isotope ratios in the Antarctic macroalga Iridaea cordata as a contaminant monitoring tool.

Lead (Pb) isotope ratios were measured in the marine macroalga Iridaea cordata collected from four locations in the Windmill Islands, East Antarctica. Based on the masses of thalli collected, samples analysed in this study were likely to be a mixture of one and two year old thalli. For a sample of thalli of various ages (<12 months to 2 years old) from the same site there was no apparent variation in Pb concentration or Pb isotope ratio with thallus mass/age, indicating that contaminant sources had been constant over the lifetime of the thalli sampled. I.cordata samples close to the Thala Valley waste disposal site (Brown Bay Inner) near the Australian Station, Casey, displayed isotopic signatures ((208)Pb/(204)Pb 35.99; (206)Pb/(207)Pb 1.066; n=3; average values shown) trending towards that possessed by major Australian Pb sources (Broken Hill and Mt Isa, (208)Pb/(204)Pb 35.60; (206)Pb/(207)Pb 1.041) suggesting that these samples had been exposed to anthropogenic Pb originating from the Thala Valley waste disposal site. Material collected hundreds of metres from the tip location at Brown Bay Outer had isotopic values ((208)Pb/(204)Pb 36.32; (206)Pb/(207)Pb 1.088; n=10) intermediate between Brown Bay Inner and sites further from the contaminant source at Sparkes Bay and Wilkes ((208)Pb/(204)Pb 36.46; (206)Pb/(207)Pb 1.094; n=4) showing that contaminant transport was predominantly restricted to Brown Bay Inner. This study demonstrates that the isotope ratios of Pb in marine macroalgae can provide valuable information as to the origin and extent of heavy metal flux in a marine environment.

A comparison of an optimised sequential extraction procedure and dilute acid leaching of elements in anoxic sediments, including the effects of oxidation on sediment metal partitioning.

The effect of oxidation of anoxic sediment upon the extraction of 13 elements (Cd, Sn, Sb, Pb, Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, As) using the optimised Community Bureau of Reference of the European Commission (BCR) sequential extraction procedure and a dilute acid partial extraction procedure (4h, 1 molL(-1) HCl) was investigated. Elements commonly associated with the sulfidic phase, Cd, Cu, Pb, Zn and Fe exhibited the most significant changes under the BCR sequential extraction procedure. Cd, Cu, Zn, and to a lesser extent Pb, were redistributed into the weak acid extractable fraction upon oxidation of the anoxic sediment and Fe was redistributed into the reducible fraction as expected, but an increase was also observed in the residual Fe. For the HCl partial extraction, sediments with moderate acid volatile sulfide (AVS) levels (1-100 micromolg(-1)) showed no significant difference in element partitioning following oxidation, whilst sediments containing high AVS levels (>100 micromolg(-1)) were significantly different with elevated concentrations of Cu and Sn noted in the partial extract following oxidation of the sediment. Comparison of the labile metals released using the BCR sequential extraction procedure (SigmaSteps 1-3) to labile metals extracted using the dilute HCl partial extraction showed that no method was consistently more aggressive than the other, with the HCl partial extraction extracting more Sn and Sb from the anoxic sediment than the BCR procedure, whilst the BCR procedure extracted more Cr, Co, Cu and As than the HCl extraction.

Baseline metal concentrations in Paramoera walkeri from East Antarctica.

Remediation of the Thala Valley waste disposal site near Casey Station, East Antarctica was conducted in the austral summer of 2003/2004. Biomonitoring of the adjacent marine environment was undertaken using the gammaridean amphipod Paramoera walkeri as a sentinel species [Stark, J.S., Johnstone, G.J., Palmer, A.S., Snape, I., Larner, B.L., Riddle, M.J., in press, . Monitoring the remediation of a near shore waste disposal site in Antarctica using the amphipod Paramoera walkeri and diffusive gradients in thin films (DGTs). Marine Pollution Bulletin and references therein]. Determination of uptake of metals and hypothesis testing for differences that could be attributed to contamination required the establishment of baseline metal concentrations in P. walkeri. Baseline metal concentrations from two reference locations in the Windmill Islands are presented here. P. walkeri was a found to be a sensitive bioaccumulating organism that recorded spatial and temporal variability at the reference sites. Measurement of metals in P. walkeri required the development of a simple digestion procedure that used concentrated nitric acid. For the first time, rare earth metals were determined with additional clean procedures required to measure ultra low concentrations using magnetic sector ICP-MS. Certified and in-house reference materials were employed to ensure method reliability.

Selenoprotein P analysis in human plasma: a discrepancy between HPLC fractionation of human plasma with heparin-affinity chromatography and SDS-PAGE with immunoblot analysis.

Several recent analytical methods for determination of Se and selenoprotein P have involved high-performance liquid chromatography (HPLC) using heparin-affinity columns coupled to inductively coupled plasma-mass spectrometry (ICP-MS) for Se detection. HPLC-ICP-MS chromatography using tandem HPLC columns with ICP-MS detection was used to detect the major selenium-containing proteins in plasma (glutathione peroxidase, albumin, and selenoprotein P). The efficiency of HPLC separation of plasma selenoprotein P was investigated by analyzing HPLC fractions using sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) with immunoblot analysis. The HPLC fraction corresponding to selenoprotein P contained 25.1% of total selenoprotein P as measured by immunoblot analysis. The majority (74.9%) of total selenoprotein P found by immunoblot analysis was contained in the early HPLC fractions, consistent with either poor heparin affinity, which was not evident based on the HPLC-ICP-MS technique alone or nonspecific binding of the antibody. Immunoblot analysis of selenoprotein relies on antibodies binding to a selenoprotein P epitope, which might be preserved when selenoprotein P is broken down to release selenocysteine residues. Immunoblot methods overestimate selenoprotein P and are not suitable for determinations of intact selenoprotein P.

Mechanisms of arsenic attenuation in acid mine drainage from Mount Bischoff, western Tasmania.

There is a dearth of research concerning the geochemistry of arsenic in acid mine drainage (AMD) in western Tasmania. To help address this, the controls on the mobility and fate of arsenic in AMD and its associated sediment at the Mount Bischoff mine site in western Tasmania were investigated. AMD issuing from the adit mouth contained dissolved arsenic and iron concentrations of 2.5 and 800 mg L(-1), respectively. The aqueous concentration of both arsenic and iron decreased markedly over a 150-m stretch from the adit mouth due to precipitation of hydrous ferric oxides (HFO) and jarosite, both of which are effective scavengers of arsenic. Microwave-assisted digestion of the sediment collected at the adit mouth revealed that the arsenic concentration exceeded 1%. Sequential extraction of this sediment showed that the bulk of arsenic was associated with amorphous and crystalline hydrous oxides of Al and/or Fe. Extended X-ray absorption fine structure (EXAFS) analysis indicated that the solid phase arsenic exists as As(V). EXAFS data were consistent with arsenate tetrahedra substituting for sulphate in jarosite and with corner-sharing complexes adsorbed on ferric oxyhydroxide octahedra. Erosional transport of AMD sediment downstream to higher pH waters may increase the mobility (and hence bioavailablity) of arsenic through dissolution of As-rich jarosite.

Determination of vanadium as 4-(2-pyridylazo)resorcinol-hydrogen peroxide ternary complexes by ion-interaction reversed-phase liquid chromatography.

The separation and determination of the vanadium(V) ternary complex formed with 4-(2-pyridylazo)resorcinol (PAR) and hydrogen peroxide using ion-interaction reversed-phase high-performance liquid chromatography on a C18 column has been investigated. The optimal mobile phase was a methanol-water solution (32:68, v/v) containing 3 mM tetrabutylammonium bromide, 5 mM acetic acid and 5 mM citrate buffer at pH 7, with absorbance detection at 540 nm. The stoichiometry of the ternary complex of vanadium at pH 6 in 10 mM acetate buffer using the mole ratio and Job's method by HPLC indicated that the mole ratio of V(V):PAR:H2O2 was 1:1:1. The optimal conditions for precolumn formation of the ternary complex were 10 mM acetate, 7 mM H2O2, 0.3 mM PAR, and pH 6. The method gave relative standard deviations of retention time, peak area and peak height for the ternary complex of 0.187, 0.45 and 0.57%, respectively. The detection limit (at a signal-to-noise ratio of 3) for V(V) was 0.09 ng/ml in the digested sample using a 100-microl injection loop (or 0.09 microg/g in the solid fertiliser sample). The method was applied to the analysis of fertilisers (phosphate rocks and nitrogen, phosphorus and potassium fertiliser). The results for vanadium obtained by the HPLC method agreed well with those from magnetic sector inductively coupled plasma MS analysis.