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Determining past changes in ocean circulation on the Antarctic margin is important for understanding the interactions between climate, circulation, and ice sheet retreat. However, the application of neodymium isotopes (εNd), a well-known proxy of ocean circulation, is limited on the Antarctic margin, due to the lack of carbonate preservation and inconsistency in authigenic εNd leached from bulk sediment. Here we assess the use of the εNd proxy along the continental rise of Wilkes Land, by combining analyses of seawater with phases extracted using a 10-second reductive leach in co-located surface sediments. Dissolved seawater εNd values displayed the following water mass signatures; εNd = −8.8 ± 0.2 (n = 1) for Antarctic Surface Water; εNd = −9.7 ± 0.2 (n = 2) for Winter Water; and εNd = −8.7 ± 0.3 (n = 6) for modified Circumpolar Deep Water. The sediment leachate did not reproduce a bottom water Nd signature and yielded a very variable εNd, ranging from −10.4 to −14.4. In contrast, the bulk detrital sediment εNd fell within a narrow range of −13.1 ± 0.5 (n = 29). Examination of elemental ratios and rare earth element (REE) anomalies indicates that the leaching procedure extracts exclusively authigenic phases. The strong relationship found between phosphorus (P) and REE suggests that a P-associated phase is the main REE host-phase leached, as opposed to ferromanganese oxyhydroxides. The leached europium anomalies and εNd indicate that the extracted Nd signature is influenced by two end members, one with a seawater-like εNd (∼-8) and one more negative than the bulk detritus (εNd ∼−14). Finally, the decoupling between [Nd] and εNd, as well the distinct middle-REE enrichments measured in the leach implies the authigenic εNd is controlled by diagenesis. We thus infer that the Nd signature of the leached phosphates is derived from porewater and influenced by the presence of a reactive detrital component in the sediment. Unradiogenic reactive sedimentary phases which easily dissolve into porewaters are likely sourced from the subglacial erosion of ancient metasediments and crustal remnants on the Wilkes Land coast. These new εNd data contribute to the evaluation of the εNd proxy at complex, dynamic and under-studied interfaces such as the East Antarctic margin. However, further work is still needed to develop reliable proxies of past Antarctic water masses., Geochimica et Cosmochimica Acta, 344, ISSN:0016-7037, ISSN:1872-9533

Manganese (Mn) is an abundant element in the Earth's crust. However, its concentrations in open ocean seawater are low, where external inputs are scarce. In this study, we report the dissolved Mn and particulate Mn distributions in the Southern Ocean, measured along the GEOTRACES—SR3 transect, from Tasmania (Australia) to Antarctica in the Southern Ocean, during the austral summer 2018. Both dissolved Mn and particulate Mn concentrations were generally low away from localized sources (−1 and −1, respectively) along the transect. Our observations of a lower labile particulate fraction than previously measured suggest the Southern Ocean has a unique particulate Mn composition. Low surface dissolved Mn concentrations were attributed to biological uptake and few external sources. Our results suggest biological control of the Mn cycle was higher above the Antarctic continental slope, compared to the rest of the section, and our particulate Mn : P ratios indicated the presence of iron‐stressed diatoms south of the Sub‐Antarctic Front. We suggest low dissolved Mn surface concentrations may (co‐)limit phytoplankton growth in this region. Localized higher dissolved Mn concentrations were observed due to external sources, such as sedimentary and hydrothermal inputs. The presence of an eddy at the same latitude as a hydrothermal plume induced an upwelling of hydrothermally enriched waters up to 1000 m; however, no dissolved Mn inputs to the surface waters were observed. We suggest previous dissolved Mn inputs to the surface layer may be obscured by biological uptake.

The Southern Ocean is a key regulator of global climate, and it’s responsible for about one-quarter of the global carbon export. Part of this export is fuelled by phytoplankton, however, in some areas of the ocean, phytoplankton activity remains to a minimum despite the abundance of nutrients. These areas, known as high nutrient low chlorophyll (HNLC), from which the Southern Ocean is the largest one, exist due to the absence of the micro-nutrient iron (Fe). The Kerguelen Plateau located in the Indian sector of the SO hosts one of the largest phytoplankton blooms in the SO during spring and summer. This study focused on the role of Heard and McDonald Islands, located in the southern part of the Kerguelen Plateau, on the Fe fertilization of the whole region, and their role in overcoming HNLC conditions. For this, we combined thorium, rare earth element concentrations and Nd isotopic composition to trace the lithogenic supply of Fe. Our results highlight the importance of Heard and Mc Donald Islands, surrounding shallow areas and probably the melting of glaciers from Heard Island on the supply of Fe that fuels the bloom in the region. We used thorium isotopes (230Th and 232Th) to estimate the flux of Fe produced by the dissolution of lithogenic particles. These results suggest that thorium isotopes can be used to calculate the fluxes of other elements not only in the remote open ocean but also near continental margins. Cerium and europium anomalies, together with the neodymium isotopic composition data seem to indicate that Heard and McDonald Islands are the main contributors to the natural Fe fertilization of the region. This study highlights the need for more systematic studies to obtain a better understanding of the functioning of the Southern Ocean carbon pump and its relationship with global climate.

Iron (Fe) is an essential micronutrient to oceanic microalgae, and its dissolved fraction (DFe) is retained in surface waters by Fe-binding ligands. Previous work has suggested that ligands may also bind Fe within sea ice, although supporting data are limited. This study investigates distribution, concentration, and potential drivers of Fe-binding ligands in Antarctic sea ice, considering the ice type, location and season. Results suggest that the concentration of ligands (CL) varies throughout the year, both spatially and seasonally. The lowest CL (3.3–8.0 nM) and DFe concentrations (0.7–3.5 nM) were recorded in newly formed winter sea ice in the Weddell Sea, likely due to the early stage of sea-ice growth and low biological activity. The highest CL (1.7–74.6 nM), which follows the distribution of DFe (1.0–75.5 nM), was observed during springtime, in the Eastern Antarctic Sector. There, consistently higher values for CL in bottom ice depths were likely associated with enhanced algal biomass, while aeolian deposition may have acted as an additional source of DFe and ligands near Davis station. In summer, the senescence of ice algae and advanced sea-ice melting led to intermediate CL (1.0–21.9 nM) and DFe concentrations (0.6–13.3 nM) both on and off the East Antarctic coast. Regardless of time and location, >99% of DFe was complexed, suggesting that CL controls the distribution of DFe in sea ice. This study represents a first attempt at a year-round investigation of CL in sea ice, providing results that support the premise that sea ice acts as a potential biogeochemical bridge between autumn and spring phytoplankton blooms.

Antarctic sea ice is an important temporal reservoir of iron which can boost primary production in the marginal ice zone during the seasonal melt. While studies have reported that Antarctic fast ice bears high concentrations of iron due to the proximity to coastal sources, less clear is the biogeochemical changes this iron pool undergoes during late spring. Here we describe a 3-weeks? time series of physical and biogeochemical data, including iron, from first-year coastal fast ice sampled near Davis Station (Prydz Bay, East Antarctica) during late austral spring 2015. Our study shows that dissolved and particulate iron concentrations in sea ice were up to two orders of magnitude higher than in under-ice seawater. Furthermore, our results indicate a significant contribution of lithogenic iron from the Vestfold Hills (as deduced from the comparison with crustal element ratios) to the particulate iron pool in fast ice after a blizzard event halfway through the time series. Windblown dust represented approximately 75% of the particulate iron found in the ice and is a potential candidate for keeping concentrations of soluble iron stable during our observations. These results suggest that iron entrapped during ice formation, likely from sediments, as well as local input of coastal dust, support primary productivity in Davis fast ice. As ice-free land areas are likely to expand over the course of the century, this work highlights the need to quantify iron inputs from continental Antarctic dust and its bioavailability for ice algae and phytoplankton. Plain summary Oceanic single-celled algae are the base of the ocean food web and play an important role in the Earth climate. In the Southern Ocean, the growth of these microorganisms is limited by the naturally low concentration of iron in the seawater. Microalgae benefits from the presence of the Antarctic sea ice since iron there are many times concentrated relative to the seawater. Less clear though, is the contribution of the potential sources of iron to the sea ice. We collected and analyzed sea ice cores for a series of parameters, including iron, from first-year coastal sea ice sampled near Davis Station (Prydz Bay, East Antarctica) during late austral spring 2015. Our results suggest that iron entrapped during ice formation, likely from seafloor sediments, as well as dust blown by winds from the neighboring Vestfold Hills, are the main sources of iron to Davis coastal sea ice. Since we can expect the expansion of ice-free areas and exposed grounds over the course of this century, our results highlight the need to quantify the amount of iron coming from continental Antarctic dust and to access if sea algae can access this form of iron for their basic physiological needs.

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

As salmon aquaculture continues to grow, understanding aquafeed conversion is imperative for making informed strategic growth planning and management decisions. Accurately measuring the apparent digestibility (AD) of commercial aquafeeds on farms requires greater understanding and method development, including the validation of one or more inert endogenous AD markers. Laboratory and commercial experiments assessed the potential of elements that naturally occur in aquafeeds as potential endogenous AD markers. Two commonly used and validated AD markers, acid insoluble ash (an endogenous marker) and ytterbium oxide (an exogenous marker) were compared using protein AD calculated from a range of endogenous elements. Using a Percentage Similarity Analysis, comparison of protein digestibility calculated with recognised AD markers demonstrated lutetium (Lu) was the most accurate endogenous AD marker. Identification of Lu as an effective endogenous AD marker in commercial salmon aquafeeds will facilitate straightforward measurement of AD under commercial conditions. This work has important application in salmon aquaculture where protein AD is fundamental to growth efficiency.

Iron (Fe) has been shown to limit growth of marine phytoplankton in the Southern Ocean, regulating phytoplankton productivity and species composition, yet does not seem to limit primary productivity in Antarctic sea ice. Little is known, however, about the potential impact of other metals in controlling sea-ice algae growth. Here, we report on the distribution of dissolved and particulate cadmium (Cd), cobalt (Co), copper (Cu), manganese (Mn), nickel (Ni), and zinc (Zn) concentrations in sea-ice cores collected during 3 Antarctic expeditions off East Antarctica spanning the winter, spring, and summer seasons. Bulk sea ice was generally enriched in particulate metals but dissolved concentrations were similar to the underlying seawater. These results point toward an environment controlled by a subtle balance between thermodynamic and biological processes, where metal availability does not appear to limit sea-ice algal growth. Yet the high concentrations of dissolved Cu and Zn found in our sea-ice samples raise concern about their potential toxicity if unchelated by organic ligands. Finally, the particulate metal-to-phosphorus (P) ratios of Cu, Mn, Ni, and Zn calculated from our pack ice samples are higher than values previously reported for pelagic marine particles. However, these values were all consistently lower than the sea-ice Fe:P ratios calculated from the available literature, indicating a large accumulation of Fe relative to other metals in sea ice. We report for the first time a P-normalized sea-ice particulate metal abundance ranking of Fe >> Zn ≈ Ni ≈ Cu ≈ Mn > Co ≈ Cd. We encourage future sea-ice work to assess cellular metal quotas through existing and new approaches. Such work, together with a better understanding of the nature of ligand complexation to different metals in the sea-ice environment, would improve the evaluation of metal bioavailability, limitation, and potential toxicity to sea-ice algae.

Antarctic sea ice can incorporate high levels of iron (Fe) during its formation and has been suggested as an important source of this essential micronutrient to Southern Ocean surface waters during the melt season. Over the last decade, a limited number of studies have quantified the Fe pool in Antarctic sea ice, with a focus on late winter and spring. Here we study the distribution of operationally defined dissolved and particulate Fe from nine sites sampled between Wilkes Land and King George V Land during austral summer 2016/2017. Results point toward a net heterotrophic sea‐ice community, consistent with the observed nitrate limitation (−1) which can serve as a hotspot for bacterial activity. Finally, results indicate a potential relationship between glacial meltwater discharged from the Moscow University Ice Shelf and the occurrence of Fe‐rich (∼4.3 μM) platelet ice in its vicinity. As climate change is expected to result in enhanced Fe‐rich glacial discharge and changes in summer sea‐ice extent and quality, the processes influencing Fe distribution in sea ice that persists into summer need to be better constrained.

The Southern Ocean is the largest region in which iron limits the growth of phytoplankton. However, a phytoplankton bloom thousands of square kilometres in area forms each spring‐summer in the Indian sector of the Southern Ocean, both above and to the east of the Kerguelen Plateau. The central region of the Kerguelen Plateau hosts the volcanically active islands, Heard and McDonald (HIMI), the former of which is largely covered by glaciers. The sources and processes governing supply of iron from HIMI to the region are relatively unknown. In the austral summer of 2016, the first voyage to focus on biogeochemical cycling in the HIMI region was undertaken (GEOTRACES process study GIpr05). Using dissolved iron (II) (DFe (II)) and hydrogen peroxide (H2O2) measurements, we are able to resolve iron sources and show that each of the adjacent islands are strong sources of reduced iron, though controlled by different supply mechanisms. At Heard Island, the greatest DFe (II) concentrations (0.57 nmol L‐1) were detected north of the island. An inverse correlation of DFe (II) concentrations with salinity suggests the origin is from a sea‐terminating glacier on the island. At McDonald Islands, the greatest DFe (II) concentrations (1.01 nmol L‐1) were detected east of the islands which, based on DFe (II) profiles from five targeted stations, appears likely to originate from shallow diffuse hydrothermalism. Elevated DFe (II) around HIMI may increase Fe availability for biota and has implications for transport of Fe away from the islands to the broader northern Kerguelen Plateau where the annual plankton bloom is strongest.

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 of5.4% 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.

Although the supply of iron generally limits phytoplankton productivity in the Southern Ocean, substantial seasonal blooms are observed over and downstream of the Kerguelen plateau in the Indian sector of the Southern Ocean. Surprisingly, of the oceanic blooms, those associated with the deeper southern plateau last much longer (~3 months) than the northern bloom (~1‐month downstream of northern plateau). In this study, iron supply mechanisms around the southern plateau were investigated, obtaining profiles of dissolved iron (

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.

It is widely accepted that iron (Fe)-binding organic ligands play a crucial role in Fe distribution in the marine environment and thus in Fe biogeochemistry. Although Competitive Ligand Equilibration – Adsorptive Cathodic Stripping Voltammetry (CLE-AdCSV) is a well-established technique to investigate Fe chemical speciation in marine samples, several impediments still need to be addressed. These include the extrapolation of laboratory measurements to in-situ conditions, the harmonization of the analytical procedures used, and the applicability of the methods over salinity ranges wider than seawater (e.g., sea ice). This work focusses on the calibration of 2-(2-thiazolylazo)-p-cresol (TAC), salicylaldoxime (SA) and 1-nitroso-2-naphthol (NN), along the salinity range 1–90, and titration of natural samples at two different temperatures (4 °C and 20 °C). The artificial ligand concentration was 10 μM for TAC and 5 μM for SA and NN. Calibrations showed that increasing salinity caused a decrease in the conditional stability constants (logK'Fe’AL) for NN and SA (although different behaviours were noted for the two species FeSA and FeSA2). Less accuracy was noted using TAC, which behaved inconsistently outside the 21 < S < 35 range, and its use is therefore discouraged in fresh and highly saline waters. Titrations of natural samples showed that only SA covered the salinity range selected, up to 78, and its use is therefore recommended in sea-ice studies. The side reaction coefficient (logα'Fe’AL) of each artificial ligand was found to be influenced by temperature differently: logα'Fe’SA was higher at lower temperature (4 °C), whereas logα'Fe’SA2 and logα'Fe’NN3 increased with increasing temperature (to 20 °C). Although titrations performed at 4 °C highlighted that the uncomplexed Fe fraction was 14% lower than at 20 °C, with potential consequences on primary productivity, the percentage of natural Fe complexed was >99%. Future investigations should consider the analysis of the samples at a temperature as close as possible to in-situ conditions to reduce the potential temperature effects.

Primary productivity in large areas of the Southern Ocean is limited by the availability of a key micronutrient—iron (Fe). Recently it has been suggested that marine animals could play an important role in recycling Fe through their diet and subsequent defecation, however there is no information on the relative bioavailability of faecal Fe for uptake. The bioavailability of Fe in seawater is controlled by a number of complex interactions. The physical separation between the dissolved ( 0.2 μm) and particulate (> 0.2 μm) fractions is one common measure used to determine element bioavailability. Here, the size fractionation of Fe from 3 whale faecal samples in 4 different size classes ( 0.2 μm, 0.2–10 μm, 10–60 μm and > 60 μm) was investigated, along with the leaching of particulate Fe over time. Although the total particulate fraction (> 0.2 μm, 5026–22,526 nmol L− 1) dominated the total Fe pool, the concentrations of dissolved Fe in whale faecal samples (186–754 nmol L− 1 ) were three order of magnitude higher than published Southern Ocean surface seawater concentrations. Furthermore, results from the leaching experiment suggest that Fe is continually leached from faecal particles over an initial 12-hour period, thus increasing the concentration of bioavailable Fe in surface seawater. Although the concentrations measured here are some of the highest reported in the literature, the true supply of Fe back to surface seawater will be controlled by processes such as organic complexation , scavenging and sinking by particles, remineralisation , and vertical transport, not measured in this study.

Increased export production (EP) in the Subantarctic Zone (SAZ) of the Southern Ocean due to iron fertilisation has been proposed as a key mechanism for explaining carbon drawdown during the last glacial maximum (LGM). This work reconstructs marine EP since the LGM at four sites around New Zealand. For the first time in this region, 230-Thorium-normalised fluxes of biogenic opal, carbonate, excess barium, and organic carbon are presented. In Subtropical Waters and the SAZ, these flux variations show that EP has not changed markedly since the LGM. The only exception is a site currently north of the subtropical front. Here we suggest the subtropical front shifted over the core site between 18 and 12ka, driving increased EP. To understand why EP remained mostly low and constant elsewhere, lithogenic fluxes at the four sites were measured to investigate changes in dust deposition. At all sites, lithogenic fluxes were greater during the LGM compared to the Holocene. The positive temporal correlation between the Antarctic dust record and lithogenic flux at a site in the Tasman Sea shows that regionally, increased dust deposition contributed to the high glacial lithogenic fluxes. Additionally, it is inferred that lithogenic material from erosion and glacier melting deposited on the Campbell Plateau during the deglaciation (18–12ka). From these observations, it is proposed that even though increased glacial dust deposition may have relieved iron limitation within the SAZ around New Zealand, the availability of silicic acid limited diatom growth and thus any resultant increase in carbon export during the LGM. Therefore, silicic acid concentrations have remained low since the LGM. This result suggests that both silicic acid and iron co-limit EP in the SAZ around New Zealand, consistent with modern process studies.

The most common mineral employed in the management of fruit cracking is calcium (Ca). Ca is a xylem mobile mineral, and as fruit xylem connections and pathways are thought to be reduced during maturation, so early accumulation is vital. Ca has been implicated in building resilience to cracking into fruit, with many studies exploring the impact of late season calcium chloride (CaCl2) spray applications on cracking. These trials have produced inconsistent results but early and repeated spray patterns for calcium uptake are supported by studies in apples. Enhanced Ca uptake rates have been recorded in the sweet cherry cultivar 'Van' with the use of thickeners and surfactants. A major limitation of using direct Ca application to prevent cracking is the unsightly residue left on the fruit, therefore the benefits must outweigh this disadvantage. To assess from where Ca was incorporated into fruit (vascular supply, or directly across the fruit skin) trials were undertaken in southern Tasmania, Australia which included Ca applications supplied via fertigation and/or foliar spray applications. Foliar sprays commenced either before or after Stage II (pit-hardening) of fruit development to assess when any uptake occurred. Ca levels were assessed using ICP-MS at both Stage II and at harvest maturity. It was expected that increased calcium would strengthen fruit tissue and reduce cracking resulting from rain. Relationships between fruit Ca and fruit quality (firmness) were explored, and the potential for continued use of Ca in mediating fruit cracking after rainfall discussed.

Iron (Fe) is an essential micronutrient that controls phytoplankton growth in the Southern Ocean. Dissolved Fe (0.4 μm) is far more abundant and may also become bioavailable through biogeochemical processing. To assess natural Fe fertilisation from the particulate fraction, we surveyed suspended particles in the water column at 11 stations in the vicinity of Heard and McDonald Islands (HIMI), in the Indian sector of the Southern Ocean and compared these to downstream plateau and reference stations. We quantified the labile (potentially bioavailable) fraction using a chemical leach. Suspended particles sourced from glacial erosion and fluvial outflow, including nanoparticulate Fe oxides near Heard Island, contained a significantly higher fraction of labile Fe (18 ± 2.8% of total Fe, or 115 ± 34 nM, n = 9) than all other coastal areas surveyed. In contrast, waters around McDonald Island, proximal to diffuse gasohydrothermal sites, contained poorly labile, highly refractory titanium and Fe bearing minerals such as ilmenite. We conclude that glacial erosion of Heard Island in combination with a unique elemental signature of the source rock, is an important mechanism of Fe supply to downstream waters. Our calculations show that the labile Fe supplied from primarily glacial erosion on Heard Island is sufficient to satisfy previously unmet estimates of phytoplankton demand for the region, and therefore critical to the area’s productivity. As we move into a world facing major ecosystem shifts under a changing climate, it is important to understand those ecosystem services that may change into the future. At the current rate of glacier retreat, this ecosystem service of glacial erosion and Fe supply to coastal waters will cease with the eventual loss of glacial cover with direct impacts for this historically highly productive region.

WOS:000460710200086; International audience; A seawater preconcentration system (sPAFAST) 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 PAl 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 (similar to 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 +/- 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 +/- 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 (R-2 = 0.95, n = 244 (Fe) and 0.92, n = 85 (Mn), paired t-test, p \textless\textless 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 PAl column (\textgreater 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.

We test for trace element proxies in the high-magnesium calcite fraction of bamboo coral internodes by comparing environmental conditions and growth rates to the specimen-mean compositions of 73 corals that were live-caught at depths ranging from 3 to 3950 m and collected from habitats ranging from tropical coral reefs to the Antarctic slope. Comparisons were done at a large geographic scale (LGS) and for a well sampled area south of Australia, across depths at a single site, in order to help separate the effects of environmental variables that co-vary at one spatial scale, but not the other. Thirty-seven trace elements were measured using solution-based Sector Field ICP-MS, of which seventeen were significantly detected in more than a third of the specimens. Only eight element/calcium ratios correlated significantly with any environmental variable at the large geographic scale, and only four did so at the local level. At the LGS, the highest correlation was between ambient temperature and Mg/Ca, which accounted for 89% of the variance across specimens, spanned all four Isidid sub-families and was independently significant in the two best sampled sub-families. The predictive (geometric mean) relationship is T ( ° C ) = - 23.9 ( ± 2.46 ) + 0.34 ( ± 0.25 ) Mg / Ca ( mmol / mol ) spanning a temperature range of −1.9 to 26.8 °C, Mg/Ca ratios from 58.6 to 155.1 mmol/mol, and an uncertainty (RMS) of 2.78 °C. The numbers in parentheses are 95% CIs. The slope of the regression does not differ significantly from that of abiotic high-Mg calcites, which suggests that the temperature-dependent incorporation of Mg into the carbonate results from kinetic reactions at the crystal surface. Analysis at the SH scale for the sub-set of specimens for which we had data suggests is also affected by growth rates. There were no obvious trace element correlates at either spatial scale of salinity or oxygen levels that could not be accounted for by covariance between these environmental parameters and, in most cases, temperature. Single and multiple correlation analyses also confirm previous suggestions that Ba/Ca in bamboo coral calcite is a proxy for seawater barium and hence refractory nutrients, suggest that Sr/Ca is influenced by specimen-mean Mg/Ca ratios and water temperature as well as possibly seawater Sr/Ca, and falsify for bamboo corals P/Ca (as well as P/Cd and Cd/Ca) as a proxy for seawater phosphate levels. The predictive relationship between Isidid skeletal-mean Ba/Ca and seawater silicate concentrations appears to be linear, and is given by silicate ( μ mol kg - 1 ) = - 56.7 ( ± 20.8 ) + 9217 ( ± 1632 ) Ba / Ca ( mmol / mol ) spanning a silicate range of 0.5 to 120 μmol kg−1, a Ba/Ca range of 0.0042 to 0.0195 mmol/mol, and with an uncertainty (RMS) of 33.1 μmol kg−1. Mn/Ca differences among specimens and sites are highly significant and appear to reflect seawater Mn, suggesting a proxy for this micronutrient. The compilation of growth rate data across 34 specimens indicates a wide range of growth rates even among con-familial specimens from within a single habitat, and suggests both ambient temperature and food availability underlie at least part of this variability.

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 7400 μg/L respectively in non-renewal tests at 5.5 °C (ambient subtidal temperature) over 14 days. Under renewed exposures over the same temperature and time period the LC50 for copper was 2204 μg/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.

Antarctic krill may play a significant role in the Southern Ocean iron cycle. However, understanding the control on iron budgets by Antarctic krill is hampered by the large range in the reported iron concentration of krill. The aim of this study was to investigate the causes of the large range of iron concentrations in krill reported in the literature (6–190 mg kg−1). Antarctic krill samples were collected from three research voyages to Pyrdz Bay, Antarctica, and analysed individually. Iron concentrations were measured using sector field inductively coupled plasma mass spectrometry in whole krill specimens and in the isolated stomach, digestive gland, muscle, body (whole krill excluding stomach and digestive gland), exoskeleton and faecal pellets. Iron concentrations in stomach (6–98 mg/kg), digestive gland (14–82 mg kg−1), and faecal pellet (683–1039 mg kg−1) were higher compared to muscle (4–7 mg kg−1), exoskeleton (6–15 mg kg−1), and body (4–18 mg kg−1) indicating that krill may ingest more iron than they require for physiological processes. Iron concentrations in whole krill from March 2012 (10 ± 3 mg kg−1) were significantly lower compared to February 2003 (19 ± 7 mg kg−1) and February 2015 (18 ± 12 mg kg−1). Overall, the iron concentrations in krill from this study were consistently at the lower end of the published range. We propose that the large range in reported whole iron concentrations of krill can be accounted for by a combination of seasonal and regional differences in sampling, reflecting differences in the quantity and quality of their diet.

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.

WOS:000467669600001; International audience; At the southern part of the northern Kerguelen Plateau (Southern Ocean) is an active volcanic hotspot, hosting volcanically active Heard Island and McDonald Islands (HIMI), the former of which is largely covered by glaciers. While offshore waters are persistently Fe limited, typical of the broader Southern Ocean, near shore waters over the Kerguelen plateau show variability in Fe distributions and support a high biomass of phytoplankton during austral spring-summer. This study investigates dissolved iron (DFe) and macronutrient distributions in waters surrounding HIMI during the Heard Earth-Ocean-Biosphere Interactions (HEOBI) voyage in January-February 2016. Comparison of surface DFe with macronutrient concentrations shows that the majority of the plateau is Fe limited in late summer and, based on comparison with previous voyages, also Fe limited in different years and earlier in the bloom season. The distribution of DFe drawdown from estimated winter inventories to observed late summer inventories shows that DFe availability drives macronutrient uptake on the plateau. The drawdown of silicic acid decreases relative to nitrate drawdown in proximity to HIMI, in agreement with classical diatom nutrient uptake behaviour under iron replete conditions. Comparison of Fe: nitrate and Fe: phosphate drawdown ratios with expected uptake stoichiometry suggest that recycling of Fe increases with distance from Fe sources on the plateau. Lastly, comparison with data from previous voyages shows that DFe distribution varies inter-annually due to complex oceanographic conditions on the plateau, with greatest variability observed over the rough bathymetry and strongly tidally influenced region closest to HIMI. Together these data highlight the central role of Fe in driving nutrient uptake and stoichiometry in the HIMI region of the Kerguelen Plateau.

The GEOTRACES Intermediate Data Product 2017 (IDP2017) is the second publicly available data product of the international GEOTRACES programme, and contains data measured and quality controlled before the end of 2016. The IDP2017 includes data from the Atlantic, Pacific, Arctic, Southern and Indian oceans, with about twice the data volume of the previous IDP2014. For the first time, the IDP2017 contains data for a large suite of biogeochemical parameters as well as aerosol and rain data characterising atmospheric trace element and isotope (TEI) sources. The TEI data in the IDP2017 are quality controlled by careful assessment of intercalibration results and multi-laboratory data comparisons at crossover stations. The IDP2017 consists of two parts: (1) a compilation of digital data for more than 450 TEIs as well as standard hydrographic parameters, and (2) the eGEOTRACES Electronic Atlas providing an on-line atlas that includes more than 590 section plots and 130 animated 3D scenes. The digital data are provided in several formats, including ASCII, Excel spreadsheet, netCDF, and Ocean Data View collection. Users can download the full data packages or make their own custom selections with a new on-line data extraction service. In addition to the actual data values, the IDP2017 also contains data quality flags and 1-σ data error values where available. Quality flags and error values are useful for data filtering and for statistical analysis. Metadata about data originators, analytical methods and original publications related to the data are linked in an easily accessible way. The eGEOTRACES Electronic Atlas is the visual representation of the IDP2017 as section plots and rotating 3D scenes. The basin-wide 3D scenes combine data from many cruises and provide quick overviews of large-scale tracer distributions. These 3D scenes provide geographical and bathymetric context that is crucial for the interpretation and assessment of tracer plumes near ocean margins or along ridges. The IDP2017 is the result of a truly international effort involving 326 researchers from 25 countries. This publication provides the critical reference for unpublished data, as well as for studies that make use of a large cross-section of data from the IDP2017. This article is part of a special issue entitled: Conway GEOTRACES - edited by Tim M. Conway, Tristan Horner, Yves Plancherel, and Aridane G. González., National Science Foundation (U.S.) (Grant OCE-0608600), National Science Foundation (U.S.) (Grant OCE0938349), National Science Foundation (U.S.) (Grant OCE-1243377), National Science Foundation (U.S.) (Grant OCE-1546580)

Microwave-assisted digestion permits a rapid and total dissolution of sediments and various other sample types, allowing easier and more accurate multi-element determinations. In this study, we present an optimised microwave digestion method for the complete digestion of 200 mg of carbonate-rich sediments. The optimised method prevents the formation of precipitates and assures a complete dissolution of the material. The optimised method involves treatment with concentrated hydrochloric acid (HCl) prior to microwave digestion, which prevents the formation of an insoluble calcium fluoride precipitate associated with the use of hydrofluoric acid (HF). Three different certified reference samples along with a pure calcium carbonate standard and a carbonate-rich in-house marine sediment sample were considered. Sediments were found to only be partially digested if insufficient HF was present, while a noticeable fluoride-based precipitate was found if excess HF was present. Twenty elements were analysed u...

The functionalisation of nanodiamond is a key step in furthering its application in areas such as surface coatings, drug delivery, bio imaging and other biomedical avenues. Accordingly, analytical methods for the detailed characterisation of functionalised nano-material are of great importance. This work presents an alternative approach for the elemental analysis of zero-dimensional nanocarbons, specifically detonation nanodiamond (DND) following purification and functionalisation procedures. There is a particular emphasis on the presence of silicon, both for the purified DND and after its functionalisation with silanes. Five different silylation procedures for purified DND were explored and assessed quantitatively using inductively coupled plasma-mass spectrometry (ICP-MS) for analysis of dilute suspensions. A maximum Si loading of 29,300 μg g−1 on the DND was achieved through a combination of silylating reagents. The presence of 28 other elements in the DND materials was also quantified by ICP-MS. The characterisation of Si-bond formation was supported by FTIR and XPS evaluation of relevant functional groups. The thermal stability of the silylated DND was examined by thermogravimetric analysis. Improved particle size distribution and dispersion stability resulted from the silylation procedure, as confirmed by dynamic light scattering and capillary zone electrophoresis.

Deposition of iron (Fe) bearing aerosols to Fe deficient waters of the Southern Ocean may drive rapid changes in primary productivity, trophic structure and the biological uptake of carbon dioxide. The fractional solubility (i.e., the ratio of water leachable Fe to total Fe) of aerosol Fe is an important variable determining its availability for biological uptake, and is a function of both particle type and the experimental conditions used to leach the particles. There have been few studies of fractional Fe solubility over the Southern Ocean where the aerosol loading is the lowest in the world. To investigate Southern Ocean aerosol Fe solubility, the fractional solubility of Fe was determined in cryogenically archived Southern Ocean aerosols. Samples were collected at the Cape Grim Baseline Air Pollution Station (CGBAPS), Tasmania, Australia from February 1999 to April 2000. Fractions determined included water soluble Fe ( 0.45 μm; acetic acid and hydroxylamine hydrochloride leachable Fe) and refractory Fe (> 0.45 μm; total digestion using nitric and hydrofluoric acids). Extremely low Fe mass concentrations were observed for baseline Southern Ocean air during the study period. An inverse hyperbolic relationship was observed between fractional Fe solubility (0.5 to 56%) and total Fe mass concentration (0.04 to 5.8 ng m3; excluding an anomalously high sample). A peak of 4.6 ng m3 of labile Fe occurred during May/June 1999 and was linked to atmospheric transport from South Western Australia over the Southern Ocean. Bioavailable Fe was estimated by summing the water soluble and labile Fe fractions, and this likely represents the upper bound of long range transport aerosol over the Southern Ocean. The results confirm previous reports of a range of fractional Fe solubility within all atmospheric particles measured and also suggest that a large fraction of the Fe from Australian mineral aerosols is labile and potentially bioavailable.

International audience; Dissolved Fe (dFe) concentrations were measured in the upper 1300 m of the water column in the vicinity of the Kerguelen Islands as part of the second KErguelen Ocean Plateau compared Study (KEOPS2). Concentrations ranged from 0.06 nmol L−1 in offshore, Southern Ocean waters to 3.82 nmol L−1 within Hillsborough Bay, on the north-eastern coast of the Kerguelen Islands. Direct island runoff, glacial melting and resuspended sediments were identified as important inputs of dFe that could potentially fertilise the northern part of the plateau. A significant deep dFe enrichment was observed over the plateau with dFe concentrations increasing up to 1.30 nmol L−1 close to the seafloor, probably due to sediment resuspension and pore water release. Biological uptake was shown to induce a significant decrease in dFe concentrations between two visits (28 days apart) at a station above the plateau. Our work also considered other processes and sources, such as lateral advection of enriched seawater, remineralisation processes, and the influence of the polar front (PF) as a vector for Fe transport. Overall, heterogeneous sources of Fe over and off the Kerguelen Plateau, in addition to strong variability in Fe supply by vertical or horizontal transport, may explain the high variability in dFe concentrations observed during this study.

Iron, phosphate and nitrate are essential nutrients for phytoplankton growth and hence their supply into the surface ocean controls oceanic primary production. Here, we present a GEOTRACES zonal section (GP13; 30-33oS, 153oE-150oW) extending eastwards from Australia to the oligotrophic South Pacific Ocean gyre outlining the concentrations of these key nutrients. Surface dissolved iron concentrations are elevated at >0.4 nmol L-1 near continental Australia (west of 165°E) and decreased eastward to ≤0.2 nmol L-1 (170oW-150oW). The supply of dissolved iron into the upper ocean (

In the present work microwave-assisted purification approaches for detonation nanodiamond (DND) are considered, and the resultant impurity content of purified DND revealed by direct ICP-MS and elemental analysis. A significant reduction in noncarbon contaminants as compared with detonation soot was achieved with resulting purity of 99.95%. Surface characterisation including scanning electronic microscopy, low temperature adsorption of nitrogen, acid–base potentiometric titration, zeta potential measurements and particle size distribution of the DND in suspensions revealed distinctive surface properties for each purified DND sample. Results highlight the suitability of the microwave purification approach using acid reagents, allowing nanodiamonds with different and reproducible surface properties to be produced or modified. Contamination effects from laboratory glassware used to store samples were carefully considered. Refined DND with impurity levels over two orders of magnitude lower than commercially available samples was prepared. The profile and concentration levels of residual impurities in purified samples of nanodiamond are discussed with identification of possible reasons for contamination.

Melting sea ice represents a large seasonal source of iron (Fe) for planktonic growth in the marginal ice zone, but no data currently show how accessible this Fe is for biological uptake. We investigated the size fractionation in East Antarctic fast ice of Fe, manganese (Mn) and aluminium (Al) in the soluble ( 10 μm) particulate fractions during a time-series carried out in late spring/early summer 2009. Concentrations of all metals in fast ice were 2 to 3 orders of magnitude more concentrated than in ice-free polar waters, across all sizes combined. Dissolved Fe, Mn and Al were coupled in fast ice, and decreased with time, indicating some loss due to spring melting and/or biological uptake. Fractional solubilities (FS = dissolved-to-total metal ratio) demonstrate that particles dominated the total metal pool (97% in the case of Fe, 83% for Al and 57% for Mn). The low FS-Fe values also suggest that Fe is far less bio-available in fast ice than in Antarctic pack ice and surface waters, with soluble and colloidal Fe respectively representing only

The quantitation of 55 elemental impurities in 15 commercial samples of detonation nanodiamond (DND), micron-sized diamond of high pressure/high temperature synthesis and detonation synthesis soot (DS) was achieved using a direct sector field ICP-MS analytical method. A set of 23 elements contributing more than 99.8 mass % of all impurities was selected and used as markers for the evaluation of DND purity. Obtained data were evaluated to identify important information on possible sources of nanodiamond contamination during purification, disaggregation, solubilisation or stabilisation of suspensions. Distinctive groups of elements (including Cr, Mn and S; Mo, W, V and Ti; Na, B and Si; Ca and Mg) occurring at elevated levels in DND can be readily visualised using radar plots, and can be related to the detonation synthesis (construction materials of explosion chamber, admixture in coolant, detonator type) and/or purification processes (type of oxidation process and reagents). The contaminant profile for each respective DND can be also considered as a fingerprint, characteristic for every producer and technology used. Results obtained also highlight how DND can be considered as effective collectors of various inorganic impurities from chemical reagents, glassware, sonotrode and other materials used during processing, including disaggregation and stabilisation of suspensions.

A simple, rapid, sensitive and accurate method for the determination of metal impurities in detonation nanodiamond (DND), based upon the direct aspiration of aqueous suspensions of nanodiamond into a sector field inductively coupled plasma mass spectrometer (ICP-MS) is proposed. Quantitative release, atomisation and ionisation of the nanodiamond coated and encased elements, within the plasma, and their detection free from spectral interference, was confirmed by comparing results obtained from the direct ICP-MS analysis of aqueous suspensions with results from the ICP-MS analysis of the acidic digests of pre-ashed DND, obtained through DND combustion in air at 723 K for 48 h. The developed direct method was capable of the quantification of more than 30 elements at concentration levels of 10−8 wt.%, with acceptable levels of precision and accuracy, from an aqueous suspension of just 0.1 mg mL−1 DND.

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.

Sediment profiles for pH, Eh, 28 elements, water and organic content are presented here for human impacted and reference locations in the Windmill Islands, East Antarctica. Variations in element concentrations are observed with increasing depth, especially at Brown Bay where the impact of past human activities is most pronounced in the top 10 cm. Spatial differences were observed between sediment profiles at reference and impacted locations and were largely explained by Pb variability in the top 5 cm. Median element concentrations from surface, middle and bottom regions of the sediment profile were compared to composite sample medians (no depth stratigraphy) for 11 elements at O'Brien Bay (reference) and Brown Bay (impacted). Pronounced differences were observed for Brown Bay, particularly surface and middle sections, implying that composite samples dilute the near surface anthropogenic signal by mixing with deeper uncontaminated sediment.

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-μg L −1 for polycarbonate filters and 1–2 μg 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.

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.

An extensive Pb isotope ratio survey of approximately 100 marine sediment samples from near Casey Station, East Antarctica has been undertaken. Sediment surface grabs and cores were collected over nine years between 1997-2006 and, following HF total digestion, were analysed by magnetic sector ICP-MS. Fifty-two reference samples ([Pb] range 5-26 mg kg(-1)) from 6 non-impacted locations displayed a broad range of Pb isotope ratios representative of the natural background geology of the region ((208)Pb/(204)Pb ratios of 37.5-40; (206)Pb/(204)Pb ratios of 17-19). Potentially impacted sediments from Brown Bay (n=27, [Pb] range 18-215 mg kg(-1)), adjacent to the current and former Australian Stations at Casey (and the associated Thala Valley tip site) showed contamination by Pb characteristic of Broken Hill and Mt Isa Australian deposits ((208)Pb/(204)Pb and (206)Pb/(204)Pb values of 35.5-36 and 16.0-16.1, respectively). The nearby abandoned Wilkes Station was previously manned by both US (1957-59) and Australian (1959-69) expeditioners. Adjacent marine sediment samples (n=24, [Pb] range 13-40 mg kg(-1)) displayed Pb isotopic signatures suggesting anthropogenic input from multiple sources. On a three-isotope diagram Wilkes sediments were found to display Pb ratios lying intermediate between Missouri (US), Broken Hill/Mt Isa (Australia)/Idaho (US), and natural geogenic Pb end members. Discarded Pb batteries, paint samples and fuel spills were all considered in this work as possible point sources of Pb contamination to the local environment. Batteries are thought to be the dominant source.

To assess the selenium status of Southern Tasmanians. Cross-sectional. One thousand and five hundred adults randomly selected from the electoral roll living in the Greater Hobart region of Southern Tasmania, Australia, were invited to participate. The overall response rate was 22% (335/1500). A venous blood sample was collected and a questionnaire administered (consisting of brief demographic details and health questions) to subjects who granted informed consent. A previously validated assay using magnetic sector ICP-MS was employed for plasma analysis. Total plasma selenium levels for this sample population were normally distributed with a mean level of 110 μg/l (range 67–268 μg/l) indicating that the majority of the subjects were not selenium-depleted (71% with levels greater than 100 μg/l). Adjustment for differential age/gender response rates produced similar values. More women under 50 (42%) and men over 50 (32%) had selenium levels