Description: In this study we present an initial dataset of Mn/Ca and Fe/Ca ratios in tests of benthic foraminifera from the Peruvian oxygen minimum zone (OMZ) determined with SIMS. These results are a contribution to a better understanding of the proxy potential of these elemental ratios for ambient redox conditions. Foraminiferal tests are often contaminated by diagenetic coatings, like Mn rich carbonate- or Fe and Mn rich (oxyhydr)oxide coatings. Thus, it is substantial to assure that the cleaning protocols are efficient or that spots chosen for microanalyses are free of contaminants. Prior to the determination of the element/Ca ratios, the distributions of several elements (Ca, Mn, Fe, Mg, Ba, Al, Si, P and S) in tests of the shallow infaunal species Uvigerina peregrina and Bolivina spissa were mapped with an electron microprobe (EMP). To visualize the effects of cleaning protocols uncleaned and cleaned specimens were compared. The cleaning protocol included an oxidative cleaning step. An Fe rich phase was found on the inner test surface of uncleaned U. peregrina specimens. This phase was also enriched in Al, Si, P and S. A similar Fe rich phase was found at the inner test surface of B. spissa. Specimens of both species treated with oxidative cleaning show the absence of this phase. Neither in B. spissa nor in U. peregrina were any hints found for diagenetic (oxyhydr)oxide or carbonate coatings. Mn/Ca and Fe/Ca ratios of single specimens of B. spissa from different locations have been determined by secondary ion mass spectrometry (SIMS). Bulk analyses using solution ICP-MS of several samples were compared to the SIMS data. The difference between SIMS analyses and ICP-MS bulk analyses from the same sampling sites was 14.0-134.8 µmol mol-1 for the Fe/Ca and 1.68(±0.41) µmol mol-1 for the Mn/Ca ratios. This is in the same order of magnitude as the variability inside single specimens determined with SIMS at these sampling sites (1sigma[Mn/Ca] = 0.35-2.07 µmol mol-1; 1sigma[Fe/Ca] = 93.9-188.4 µmol mol-1). The Mn/Ca ratios in the calcite were generally relatively low (2.21-9.93 µmol mol-1) but in the same magnitude and proportional to the surrounding pore waters (1.37-6.67 µmol mol-1). However, the Fe/Ca ratios in B. spissa show a negative correlation to the concentrations in the surrounding pore waters. Lowest foraminiferal Fe/Ca ratios (87.0-101.0 µmol mol-1) were found at 465 m water depth, a location with a strong sharp Fe peak in the pore water next to the sediment surface and respectively, high Fe concentrations in the surrounding pore waters. Previous studies found no living specimens of B. spissa at this location. All these facts hint that the analysed specimens already were dead before the Fe flux started and the sampling site just recently turned anoxic due to fluctuations of the lower boundary of the OMZ near the sampling site (465 m water depth). Summarized Mn/Ca and Fe/Ca ratios are potential proxies for redox conditions, if cleaning protocols are carefully applied. The data presented here may be rated as base for the still pending detailed calibration.

Description: In this study we present an initial dataset of Mn/Ca and Fe/Ca ratios in tests of benthic foraminifera from the Peruvian oxygen minimum zone (OMZ) determined with SIMS. These results are a contribution to a better understanding of the proxy potential of these elemental ratios for ambient redox conditions. Foraminiferal tests are often contaminated by diagenetic coatings, like Mn rich carbonate- or Fe and Mn rich (oxyhydr)oxide coatings. Thus, it is substantial to assure that the cleaning protocols are efficient or that spots chosen for microanalyses are free of contaminants. Prior to the determination of the element/Ca ratios, the distributions of several elements (Ca, Mn, Fe, Mg, Ba, Al, Si, P and S) in tests of the shallow infaunal species Uvigerina peregrina and Bolivina spissa were mapped with an electron microprobe (EMP). To visualize the effects of cleaning protocols uncleaned and cleaned specimens were compared. The cleaning protocol included an oxidative cleaning step. An Fe rich phase was found on the inner test surface of uncleaned U. peregrina specimens. This phase was also enriched in Al, Si, P and S. A similar Fe rich phase was found at the inner test surface of B. spissa. Specimens of both species treated with oxidative cleaning show the absence of this phase. Neither in B. spissa nor in U. peregrina were any hints found for diagenetic (oxyhydr)oxide or carbonate coatings. Mn/Ca and Fe/Ca ratios of single specimens of B. spissa from different locations have been determined by secondary ion mass spectrometry (SIMS). Bulk analyses using solution ICP-MS of several samples were compared to the SIMS data. The difference between SIMS analyses and ICP-MS bulk analyses from the same sampling sites was 14.0–134.8 μmol mol−1 for the Fe/Ca and 1.68(±0.41) μmol mol−1 for the Mn/Ca ratios. This is in the same order of magnitude as the variability inside single specimens determined with SIMS at these sampling sites (1σ[Mn/Ca] = 0.35–2.07 μmol mol−1; 1σ[Fe/Ca] = 93.9–188.4 μmol mol−1). The Mn/Ca ratios in the calcite were generally relatively low (2.21–9.93 μmol mol−1) but in the same magnitude and proportional to the surrounding pore waters (1.37–6.67 μmol mol−1). However, the Fe/Ca ratios in B. spissa show a negative correlation to the concentrations in the surrounding pore waters. Lowest foraminiferal Fe/Ca ratios (87.0–101.0 μmol mol−1) were found at 465 m water depth, a location with a strong sharp Fe peak in the pore water next to the sediment surface and respectively, high Fe concentrations in the surrounding pore waters. Previous studies found no living specimens of B. spissa at this location. All these facts hint that the analysed specimens already were dead before the Fe flux started and the sampling site just recently turned anoxic due to fluctuations of the lower boundary of the OMZ near the sampling site (465 m water depth). Summarized Mn/Ca and Fe/Ca ratios are potential proxies for redox conditions, if cleaning protocols are carefully applied. The data presented here may be rated as base for the still pending detailed calibration.

Description: The volatile contents of olivine‐hosted (Fo89–71) melt inclusion glasses in rapidly quenched mafic tephras from volcanic front volcanoes of the Central American Volcanic Arc (CAVA) in Guatemala, Nicaragua, and Costa Rica, were analyzed by secondary ion mass spectrometry (SIMS) in order to derive the minimum eruptive output of CO2, along with H2O, Cl, and S. Details of the analytical method are provided that establish melt inclusion CO2 analyses with the Cameca ims6f at the Helmholtz Centre Potsdam. The highest CO2 concentrations (up to 1800 mg/g) are observed in Nicaraguan samples, while melt inclusions from Guatemala and Costa Rica have CO2 contents between 50 and 500 mg/g. CO2 does not positively covary with sediment/slab fluid tracers such as Ba/La, Ba/Th, or U/La. Instead, the highest CO2 concentrations occur in the inclusions with the most depleted incompatible element compositions and low H2O, approaching the composition of mid‐ocean ridge basalts (MORBs), whereas the most H2O‐rich inclusions are relatively CO2‐poor (〈800 mg/g). This suggests that CO2 degassing was more extensive in the melts with the highest slab contribution. CO2/Nb ratios in the least degassed CAVA melt inclusions are similar to those of primitive MORBs. These are interpreted here as recording a minimum CO2 output rate from the mantle wedge, which amounts to 2.8 × 104 g/s for the ∼1100 km long CAVA. Previously published estimates from quiescent degassing and numerical modeling, which also encompassed the slab contribution, are 3 times higher. This comparison allows us to estimate the proportion of the total CO2 output derived from the mantle wedge.

Description: Regionally traceable paleosols in the lower Moodies Group of the Barberton greenstone belt (ca. 3.22 Ga, northeastern South Africa and Swaziland) contain locally abundant silicified nodules, originally composed of pedogenic carbonates and sulfates, interbedded with heavy-mineral laminae dominated by pyrite. Pyrite grains show rounded detrital cores and secondary idiomorphic rims with trace element concentrations and 34 S ratios clearly different from those of the cores. While cores have low Co and Ni concentrations and high Co/Ni ratios, rims show as much as 5.5 wt% of these elements and low Co/Ni ratios, reflecting the weathering of nearby ultramafic rocks. In-situ sulfur isotope analyses of pyrite cores show 34 S VCDT (Vienna Canyon Diablo troilite) values between +5 and –5, while the rims show 34 S VCDT values between –20 and –24.5, suggesting biogenic fractionation of sulfur. The close spatial association and microtextural evidence for nearly contemporaneous formation of the pedogenic sulfate nodules and the secondary pyrite rims suggests microbial processing of sulfur in the paleosols, which provided reduced and 34 S-depleted sulfur for the growth of authigenic pyrite. This indicates that vadose-zone soil-forming processes in the Archean involved not only physical and chemical modification of moist, unconsolidated sediment in a terrestrial environment but also already included its microbiological modification.