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.

The biogeochemical role of baleen whales and krill in Southern Ocean nutrient cycling.

The availability of micronutrients is a key factor that affects primary productivity in High Nutrient Low Chlorophyll (HNLC) regions of the Southern Ocean. Nutrient supply is governed by a range of physical, chemical and biological processes, and there are significant feedbacks within the ecosystem. It has been suggested that baleen whales form a crucial part of biogeochemical cycling processes through the consumption of nutrient-rich krill and subsequent defecation, but data on their contribution are scarce. We analysed the concentration of iron, cadmium, manganese, cobalt, copper, zinc, phosphorus and carbon in baleen whale faeces and muscle, and krill tissue using inductively coupled plasma mass spectrometry. Metal concentrations in krill tissue were between 20 thousand and 4.8 million times higher than typical Southern Ocean HNLC seawater concentrations, while whale faecal matter was between 276 thousand and 10 million times higher. These findings suggest that krill act as a mechanism for concentrating and retaining elements in the surface layer, which are subsequently released back into the ocean, once eaten by whales, through defecation. Trace metal to carbon ratios were also higher in whale faeces compared to whale muscle indicating that whales are concentrating carbon and actively defecating trace elements. Consequently, recovery of the great whales may facilitate the recycling of nutrients via defecation, which may affect productivity in HNLC areas.

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.

High-accuracy determination of iron in seawater by isotope dilution multiple collector inductively coupled plasma mass spectrometry (ID-MC-ICP-MS) using nitrilotriacetic acid chelating resin for pre-concentration and matrix separation.

In the present paper we describe a robust and simple method to measure dissolved iron (DFe) concentrations in seawater down to <0.1 nmol L(-1) level, by isotope dilution multiple collector inductively coupled plasma mass spectrometry (ID-MC-ICP-MS) using a (54)Fe spike and measuring the (57)Fe/(54)Fe ratio. The method provides for a pre-concentration step (100:1) by micro-columns filled with the resin NTA Superflow of 50 mL seawater samples acidified to pH 1.9. NTA Superflow is demonstrated to quantitatively extract Fe from acidified seawater samples at this pH. Blanks are kept low (grand mean 0.045+/-0.020 nmol L(-1), n=21, 3 x S.D. limit of detection per session 0.020-0.069 nmol L(-1) range), as no buffer is required to adjust the sample pH for optimal extraction, and no other reagents are needed than ultrapure nitric acid, 12 mM H(2)O(2), and acidified (pH 1.9) ultra-high purity (UHP) water. We measured SAFe (sampling and analysis of Fe) reference seawater samples Surface-1 (0.097+/-0.043 nmol L(-1)) and Deep-2 (0.91+/-0.17 nmol L(-1)) and obtained results that were in excellent agreement with their DFe consensus values: 0.118+/-0.028 nmol L(-1) (n=7) for Surface-1 and 0.932+/-0.059 nmol L(-1) (n=9) for Deep-2. We also present a vertical DFe profile from the western Weddell Sea collected during the Ice Station Polarstern (ISPOL) ice drift experiment (ANT XXII-2, RV Polarstern) in November 2004-January 2005. The profile shows near-surface DFe concentrations of approximately 0.6 nmol L(-1) and bottom water enrichment up to 23 nmol L(-1) DFe.

Dissolved and particulate metals (Fe, Zn, Cu, Cd, Pb) in two habitats from an active hydrothermal field on the EPR at 13 degrees N.

The distribution of Fe, Cu, Zn, Pb, Cd between the dissolved (<2 microm) and the particulate (>2 microm) fractions was measured after in-situ filtration in two hydrothermal habitats. The total metal concentration ranges exhibit a clear enrichment compared with the seawater concentration, accounting for the hydrothermal input for all the metals considered. Iron is the predominant metal (5-50 microM) followed by Zn and Cu. Cd and Pb are present at the nM level. At the scale studied, the behavior of temperature, pH and dissolved iron is semi-conservative whereas the other dissolved and particulate metals are characterized by non-conservative patterns. The metal enrichment of the >2 microm fraction results from the settlement and accumulation of particulate matter close to the organisms, acting as a secondary metal source. The enrichment observed in the dissolved fraction can be related to the dissolution or oxidation of particles (mainly polymetallic sulfide) or to the presence of small particles and large colloids not retained on the 2 microm frit. SEM observations indicate that the bulk particulate observed is characteristic of crystalline particles settling rapidly from the high temperature smoker (sphalerite, wurtzite and pyrite), amorphous structures and eroded particles formed in the external zone of the chimney. Precipitation of Zn, Cu, Cd and Pb with Fe as wurtzite, sphalerite and pyrite is the main process taking place within the area studied and is semi-quantitative. The distribution of the dominant observed fauna has been related to the gradient resulting from the dilution process, with the alvinellids worms colonizing the hotter and more variable part of the mixing zone, but also to the metallic load of the mixing zone. Dissolved and particulate metal concentrations are therefore necessary abiotic factors to be studied in a multiparametric approach to understand the faunal distribution in hydrothermal ecosystems.

Precise measurement of Fe isotopes in marine samples by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS).

A novel analytical technique for isotopic analysis of dissolved and particulate iron (Fe) from various marine environments is presented in this paper. It combines coprecipitation of dissolved Fe (DFe) samples with Mg(OH)(2), and acid digestion of particulate Fe (PFe) samples with double pass chromatographic separation. Isotopic data were obtained using a Nu Plasma MC-ICP-MS in dry plasma mode, applying a combination of standard-sample bracketing and external normalization by Cu doping. Argon interferences were determined prior to each analysis and automatically subtracted during analysis. Sample size can be varied between 200 and 600 ng of Fe per measurement and total procedural blanks are better than 10 ng of Fe. Typical external precision of replicate analyses (1S.D.) is +/-0.07 per thousand on delta(56)Fe and +/-0.09 per thousand on delta(57)Fe while typical internal precision of a measurement (1S.E.) is +/-0.03 per thousand on delta(56)Fe and +/-0.04 per thousand on delta(57)Fe. Accuracy and precision were assured by the analysis of reference material IRMM-014, an in-house pure Fe standard, an in-house rock standard, as well as by inter-laboratory comparison using a hematite standard from ETH (Zürich). The lowest amount of Fe (200 ng) at which a reliable isotopic measurement could still be performed corresponds to a DFe or PFe concentration of approximately 2 nmol L(-1) for a 2 L sample size. To show the versatility of the method, results are presented from contrasting environments characterized by a wide range of Fe concentrations as well as varying salt content: the Scheldt estuary, the North Sea, and Antarctic pack ice. The range of DFe and PFe concentrations encountered in this investigation falls between 2 and 2000 nmol L(-1) Fe. The distinct isotopic compositions detected in these environments cover the whole range reported in previous studies of natural Fe isotopic fractionation in the marine environment, i.e. delta(56)Fe varies between -3.5 per thousand and +1.5 per thousand. The largest fractionations were observed in environments characterized by redox changes and/or strong Fe cycling. This demonstrates the potential use of Fe isotopes as a tool to trace marine biogeochemical processes involving Fe.