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- Grasse, Patricia, et al.
(författare)
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GEOTRACES inter-calibration of the stable silicon isotope composition of dissolved silicic acid in seawater
- 2017
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Ingår i: Journal of Analytical Atomic Spectrometry. - : Royal Society of Chemistry (RSC). - 0267-9477 .- 1364-5544. ; 32:3, s. 562-578
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Tidskriftsartikel (refereegranskat)abstract
- The first inter-calibration study of the stable silicon isotope composition of dissolved silicic acid in seawater, delta Si-30(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 mmol L-1, 300 m) and a relatively high (113 mmol L-1, 1000 m) silicic acid concentration as sample preparation differs for low- and highconcentration samples. Data for the 1000 m water sample were not normally distributed so the median is used to represent the central tendency for the two samples. Median delta Si-30(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 inter-laboratory differences in chemical preparation including pre-concentration and purification methods together with different volumes of seawater analyzed, and the use of different mass spectrometers including the Neptune MC-ICP-MS (Thermo Fisher (TM), Germany), the Nu Plasma MC-ICP-MS (Nu Instruments (TM), Wrexham, UK), and the Finnigan (TM) (now Thermo Fisher (TM), Germany) MAT 252 IRMS. Future studies analyzing delta Si-30(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.
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| 2. |
- Gäng, Frederik, et al.
(författare)
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Critical assessment of U, Ba and Ni as redox and productivity proxies in organic-rich sediments underneath dynamic, highly productive waters
- 2023
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Ingår i: Geochimica et Cosmochimica Acta. - : Elsevier BV. - 0016-7037 .- 1872-9533. ; 348, s. 206-220
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Tidskriftsartikel (refereegranskat)abstract
- Sediments of the continental shelf anoxic zones of the Benguela upwelling system (BUS) and the Peruvian upwelling system are present-day hotspots of trace element accumulation. However, contribution of the lithogenic trace element fraction and early diagenetic transformation processes are poorly constrained. The identification of source and accumulation mechanisms is necessary for the validation of trace elements as proxies for productivity and redox cycling, notably in highly dynamic upwelling systems such as the BUS. Here, we analyzed redox- and biosensitive elements (U, Ba, Ni), lithogenic tracers (Al, Ti, Zr), total organic carbon (TOC) and P in eleven short sediment cores from the Namibian shelf (ca. 22–25°S) as well as grain size fractionated hinterland samples from the Tsauchab Valley at Sossusvlei (∼25°S). These samples help to constrain the lithogenic trace element contributions, a prerequisite for a realistic interpretation of marine authigenic trace element data. Our findings corroborate previous findings that Zr is a sensitive tracer of the coarse fraction in marine sediment for dust input and/or sediment reworking. Hence, the combined analysis of the coarse fraction (Zr), organic matter, and P enrichments (TOC/P) differentiates between a calm, organic matter-rich central shelf environment and a more energetic phosphorite-rich southern shelf environment. A significant correlation of U with P in cores from the southern shelf corroborates previous findings of U incorporation into apatite, the initial formation of which requires oscillating oxic to sulfidic redox conditions. Non-apatite associated U dominates in the cores from the central shelf, where it is only enriched in the buried, anoxic parts of the sediment. This also supports oscillating oxic to sulfidic redox conditions in surface sediment, where U may be recycled. Hence, U accumulates either (i) in apatite under oscillating oxic to sulfidic conditions or (ii) in buried anoxic sediment sections. This strongly questions the use of U as indicator of suboxic conditions but rather anoxic conditions. While lithogenic fractions of U were negligible, the lithogenic fractions of Ba and Ni were found to be elevated. The calculation of authigenic Ba when accounting for lithogenic Ba from the Sossusvlei fine fractions gives more realistic authigenic Ba values. The high Ba enrichment in the BUS is interpreted as uptake of Ba by diatoms and/or nucleation of barite in P-rich diatom remains, as suggested previously. Given the shallow water depth of the cores, barite formation must already take place in subsurface waters (<50 m water depth) as opposed to previous suggesting greater water depths. The lithogenic background of Ni strongly varies from 23°S to 25°S based on Sossusvlei data and the literature. When authigenic Ni contents are calculated accordingly and plotted versus TOC, more systematic trends are seen (compared to total Ni versus TOC). Essentially all cores show an increase in the authigenic Ni/TOC ratio with sediment depth suggesting better preservation and retention of Ni as compared to TOC consistent with previous observations in sediments from the Peruvian upwelling system. This trend corroborates the use of Ni as a productivity indicator for upwelling sediments.
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