Patricia Grasse

Online preconcentration ICP-MS analysis of rare earth elements in seawater

The rare earth elements (REEs) with their systematically varying properties are powerful tracers of continental inputs, particle scavenging intensity and the oxidation state of seawater. However, their generally low (∼pmol/kg) concentrations in seawater and fractionation potential during chemical treatment makes them difficult to measure. Here we report a technique using an automated preconcentration system, which efficiently separates seawater matrix elements and elutes the preconcentrated sample directly into the spray chamber of an ICP-MS instrument. The commercially available “seaFAST” system (Elemental Scientific Inc.) makes use of a resin with ethylenediaminetriacetic acid and iminodiacetic acid functional groups to preconcentrate REEs and other metals while anions and alkali and alkaline earth cations are washed out. Repeated measurements of seawater from 2000 m water depth in the Southern Ocean allows the external precision (2σ) of the technique to be estimated at <23% for all REEs and <15% for most. Comparison of Nd concentrations with isotope dilution measurements for 69 samples demonstrates that the two techniques generally agree within 15%. Accuracy was found to be good for all REEs by using a five point standard addition analysis of one sample and comparing measurements of mine water reference materials diluted with a NaCl matrix with recommended values in the literature. This makes the online preconcentration ICP-MS technique advantageous for the minimal sample preparation required and the relatively small sample volume consumed (7 mL) thus enabling large data sets for the REEs in seawater to be rapidly acquired.

GEOTRACES Intercalibration of the Stable Silicon Isotope Composition of Dissolved Silicic Acid in Seawater

The first inter-calibration study of the stable silicon isotope composition of dissolved silicic acid in seawater, δ30Si(OH)4, is presented as a contribution to the international GEOTRACES program. Eleven laboratories from seven countries analyzed two seawater samples from the north Pacific subtropical gyre (Station ALOHA) collected at 300 m and at 1000 m water depth. Sampling depths were chosen to obtain samples with a relatively low (9 μmol L-1, 300 m) and a relatively high (113 μmol L-1, 1000 m) silicic acid concentration as sample preparation differs for low- and high- concentration samples. Data for the 1000m water sample were not normally distributed so the median is used to represent the central tendency for the two samples. Median δ30Si(OH)4 values of +1.66 ‰ for the low-concentration sample and +1.25 ‰ for the high-concentration sample were obtained. Agreement among laboratories is overall considered very good; however, small but statistically significant differences among the mean isotope values obtained by different laboratories were detected likely reflecting interlaboratory differences in chemical preparation including pre-concentration and purification methods together with different volumes of seawater volume analyzed, and the use of different mass spectrometers including the Neptune MC-ICP-MS (Thermo Fisher™, Germany), the Nu Plasma MC-ICP-MS (Nu Instruments™, Wrexham, UK), and the Finnigan™ (now Thermo Fisher™, Germany) MAT 252 IRMS. Future studies analyzing δ30Si(OH)4 in seawater should also analyze and report values for these same two reference waters in order to facilitate comparison of data generated among and within laboratories over time.

A review of the stable isotope bio-geochemistry of the global silicon cycle and its associated trace elements

Silicon (Si) is the second most abundant element in the Earth’s crust and is an important nutrient in the ocean. The global Si cycle plays a critical role in regulating primary productivity and carbon cycling on the continents and in the oceans. Development of the analytical tools used to study the sources, sinks, and fluxes of the global Si cycle (e.g., elemental and stable isotope ratio data for Ge, Si, Zn, etc.) have recently led to major advances in our understanding of the mechanisms and processes that constrain the cycling of Si in the modern environment and in the past. Here, we provide background on the geochemical tools that are available for studying the Si cycle and highlight our current understanding of the marine, freshwater and terrestrial systems. We place emphasis on the geochemistry (e.g., Al/Si, Ge/Si, Zn/Si, δ13 C, δ15 N, δ18 O, δ30 Si) of dissolved and biogenic Si, present case studies, such as the Silicic Acid Leakage Hypothesis, and discuss challenges associated with the development of these environmental proxies for the global Si cycle. We also discuss how each system within the global Si cycle might change over time (i.e., sources, sinks, and processes) and the potential technical and conceptual limitations that need to be considered for future studies.