ALBERT

Description: Present day oceans are well ventilated, with the exception of mid-depth oxygen minimum zones (OMZs) under high surface water productivity, regions of sluggish circulation, and restricted marginal basins. In the Mesozoic, however, entire oceanic basins transiently became dysoxic or anoxic. The Cretaceous ocean anoxic events (OAEs) were characterised by laminated organic-carbon rich shales and low-oxygen indicating trace fossils preserved in the sedimentary record. Yet assessments of the intensity and extent of Cretaceous near-bottom water oxygenation have been hampered by deep or long-term diagenesis and the evolution of marine biota serving as oxygen indicators in today's ocean. Sedimentary features similar to those found in Cretaceous strata were observed in deposits underlying Recent OMZs, where bottom-water oxygen levels, the flux of organic matter, and benthic life have been studied thoroughly. Their implications for constraining past bottom-water oxygenation are addressed in this review. We compared OMZ sediments from the Peruvian upwelling with deposits of the late Cenomanian OAE 2 from the north-west African shelf. Holocene laminated sediments are encountered at bottom-water oxygen levels of 〈 7 μmol kg−1 under the Peruvian upwelling and 〈 5 μmol kg−1 in California Borderland basins and the Pakistan Margin. Seasonal to decadal changes of sediment input are necessary to create laminae of different composition. However, bottom currents may shape similar textures that are difficult to discern from primary seasonal laminae. The millimetre-sized trace fossil Chondrites was commonly found in Cretaceous strata and Recent oxygen-depleted environments where its diameter increased with oxygen levels from 5 to 45 μmol kg−1. Chondrites has not been reported in Peruvian sediments but centimetre-sized crab burrows appeared around 10 μmol kg−1, which may indicate a minimum oxygen value for bioturbated Cretaceous strata. Organic carbon accumulation rates ranged from 0.7 and 2.8 g C cm−2 kyr−1 in laminated OAE 2 sections in Tarfaya Basin, Morocco, matching late Holocene accumulation rates of laminated Peruvian sediments under Recent oxygen levels below 5 μmol kg−1. Sediments deposited at 〉 10 μmol kg−1 showed an inverse exponential relationship of bottom-water oxygen levels and organic carbon accumulation depicting enhanced bioirrigation and decomposition of organic matter with increased oxygen supply. In the absence of seasonal laminations and under conditions of low burial diagenesis, this relationship may facilitate quantitative estimates of palaeo-oxygenation. Similarities and differences between Cretaceous OAEs and late Quaternary OMZs have to be further explored to improve our understanding of sedimentary systems under hypoxic conditions.

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 discovery that foraminifera are able to use nitrate instead of oxygen as energy source for their metabolism has challenged our understanding of nitrogen cycling in the ocean. It was evident before that only prokaryotes and fungi are able to denitrify. Rate 5 estimates of foraminiferal denitrification were very sparse on a regional scale. Here, we present estimates of benthic foraminiferal denitrification rates from six stations at intermediate water depths in and below the Peruvian oxygen minimum zone (OMZ). Foraminiferal denitrification rates were calculated from abundance and assemblage composition of the total living fauna in both, surface and subsurface sediments, 10 as well as from individual species specific denitrification rates. A comparison with total benthic denitrification rates as inferred by biogeochemical models revealed that benthic foraminifera account for the total denitrification on the shelf between 80 and 250m water depth. They are still important denitrifiers in the centre of the OMZ around 320m (29–56% of the benthic denitrification) but play only a minor role at the lower OMZ 15 boundary and below the OMZ between 465 and 700m (3–7% of total benthic denitrification). Furthermore, foraminiferal denitrification was compared to the total benthic nitrate loss measured during benthic chamber experiments. Foraminiferal denitrification contributes 1 to 50% to the total nitrate loss across a depth transect from 80 to 700 m, respectively. Flux rate estimates ranged from 0.01 to 1.3 mmolm−2 d−1. Fur20 thermore we show that the amount of nitrate stored in living benthic foraminifera (3 to 705 μmolL−1) can be higher by three orders of magnitude as compared to the ambient pore waters in near surface sediments sustaining an important nitrate reservoir in Peruvian OMZ sediments. The substantial contribution of foraminiferal nitrate respiration to total benthic nitrate loss at the Peruvian margin, which is one of the main nitrate sink 25 regions in the world oceans, underpins the importance of previously underestimated role of benthic foraminifera in global biochemical cycles.

Description: In this study we explore the correlation of I/Ca ratios in three calcitic and one aragonitic foraminiferal species. I/Ca ratios are evaluated as possible proxies for changes in ambient redox conditions across the Peruvian oxygen minimum zone to the ambient oxygen concentrations in the habitat of the foraminiferal species studied. We test cleaning and measurement methods to determine I/Ca ratios in benthic foraminifera from the Peruvian oxygen minimum zone. All species show a positive trend in their I/Ca ratios as a function of higher oxygen concentrations and these trends are all statistically significant except for the aragonitic species Hoeglundina elegans. The most promising species appears to be Uvigerina striata which shows a highly statistically significant correlation between I/Ca ratios and bottom water (BW) oxygenation (I/Ca = 0.032(± 0.004)[O2]BW + 0.29(± 0.03), R2 = 0.61, F = 75, P 〈 0.0001). Although I/Ca ratios in benthic foraminifera might prove to be a valuable proxy for changing redox-conditions the iodine volatility in acidic solutions, the species dependency ofI/Ca–[O2]BW correlations, and the individual variability of single tests severely interfere with the observed I/Ca–[O2]BW relationship.

Description: Oceanic oxygen decline due to anthropogenic climate change is a matter of growing concern. A quantitative oxygen proxy is highly desirable in order to identify and monitor recent dynamics as well as to reconstruct pre-Anthropocene changes in amplitude and extension of oxygen depletion. Geochemical proxies like foraminiferal I/Ca ratios seem to be promising redox proxies. Nevertheless, recent studies on microanalyses of benthic foraminiferal I/Ca ratios at the Peruvian oxygen minimum zone (OMZ) measured with secondary-ion mass spectrometry (SIMS) revealed a possible association of iodine with organic accumulations within the test. Here, we present a new study on the micro-distribution of nitrogen, sulfur, and iodine within the test walls of Uvigerina striata from the Peruvian OMZ measured with Nano-SIMS. A quantification of the foraminiferal I/Ca ratios from our NanoSIMS study is in good agreement with quantitative results from a previous SIMS study. Additionally, we compared uncleaned specimens with specimens that have been treated with an oxidative cleaning procedure. Both nitrogen and sulfur, which are used as tracer for organic matter, show a patchy distribution within the test walls of the uncleaned specimens and a statistically significant correlation with the iodine distribution. This patchy organic-rich phase has a different geochemical signature than the pristine calcitic parts of the test and another phase that shows a banding-like structure and that is characterized by a strong sulfur enrichment. All three elements, sulfur, nitrogen, and iodine, are strongly depleted in the cleaned specimens, even within the massive parts of the test walls that lack the connection with the test pores. These results indicate that the organic parts of the test walls are located inside a microporous framework within the foraminiferal calcite. This has to be considered in the interpretation of geochemical proxies on foraminiferal calcite, especially for microanalytical methods, since the chemical signature of these organic parts likely alters some element-to-calcium ratios within the foraminiferal test.

Description: Deciphering the dynamics of dissolved oxygen in the mid-depth ocean during the last deglaciation is essential to understand the influence of climate change on modern oxygen minimum zones (OMZs). Many paleo-proxy records from the Eastern Pacific Ocean indicate an extension of oxygen depleted conditions during the deglaciation but the degree of deoxygenation has not been quantified to date. The Peruvian OMZ, one of the largest OMZs in the world, is a key area to monitor such changes in near-bottom water oxygenation in relation to changing climatic conditions. Here, we analysed the potential to use the composition of foraminiferal assemblages from the Peruvian OMZ as a quantitative redox-proxy. A multiple regression analysis was applied to a joint dataset of living (rose Bengal stained, fossilizable calcareous species) benthic foraminiferal distributions from the Peruvian continental margin. Bottom-water oxygen concentrations ([O2]BW) during sampling were used as dependant variable. The correlation was significant (R2 = 0.82; p 〈 0.05) indicating that the foraminiferal assemblages are rather governed by oxygen availability than by the deposition of particulate organic matter (R2 = 0.53; p = 0.31). We applied the regression formula to four sediment cores from the northern part of the Peruvian OMZ between 3° S and 8° S and 600 m to 1250 m water depths; thereby recording oxygenation changes at the lower boundary of the Peruvian OMZ. Each core displayed a similar trend of decreasing oxygen levels since the Last Glacial Maximum (LGM). The overall [O2]BW change from the Last Glacial Maximum and the Holocene was constrained to 30 μmol/kg at the lower boundary of the OMZ, whereas at shallower depths [O2]BW was relatively stable along the deglaciation. The deoxygenation trend was time-transgressive. It commenced at the southern core, and gradually spread to deeper waters and to the northernmost core location. This pattern indicates a gradual expansion of the OMZ during the last deglaciation, as a result of increasing surface productivity in the Eastern Equatorial Pacific and decreasing advective oxygen supply to intermediate waters off Peru.

Description: From 2008 through 2019, a comprehensive research project, SFB 754, Climate - Biogeochemistry Interactions in the Tropical Ocean, was funded by the German Research Foundation to investigate the climate-biogeochemistry interactions in the tropical ocean with a particular emphasis on the processes determining the oxygen distribution. During three 4-year long funding phases, a consortium of more than 150 scientists conducted or participated in 34 major research cruises and collected a wealth of physical, biological, chemical, and meteorological data. A common data policy agreed upon at the initiation of the project provided the basis for the open publication of all data. Here we provide an inventory of this unique data set and briefly summarize the various data acquisition and processing methods used.

Description: Many benthic organisms show aggregated distribution patterns due to the spatial heterogeneity of niches or food availability. In particular, high-abundance patches of benthic foraminifera have been reported that extend from centimetres to metres in diameter in salt marshes or shallow waters. The dimensions of spatial variations of shelf or deep-sea foraminiferal abundances have not yet been identified. Therefore, we studied the distribution of Globobulimina turgida dwelling in the 0–3 cm surface sediment at 118 m water depth in the Alsbäck Deep, Gullmar Fjord, Sweden. Standing stock data from 58 randomly replicated samples depicted a log-normal distribution of G. turgida with weak evidence for an aggregated distribution on a decimetre scale. A model simulation with different patch sizes, outlines, and impedances yielded no significant correlation with the observed variability of G. turgida standing stocks. Instead, a perfect match with a random log-normal distribution of population densities was obtained. The data–model comparison revealed that foraminiferal populations in the Gullmar Fjord were not moulded by any underlying spatial structure beyond 10 cm diameter. Log-normal population densities also characterise data from contiguous, gridded, or random sample replicates reported in the literature. Here, a centimetre-scale heterogeneity was found and interpreted to be a result of asexual reproduction events and restricted mobility of juveniles. Standing stocks of G. turgida from the Alsbäck Deep temporal data series from 1994 to 2021 showed two distinct cohorts of samples of either high or low densities. These cohorts are considered to represent two distinct ecological settings: hypoxic and well-ventilated conditions in the Gullmar Fjord. Environmental forcing is therefore considered to impact the population structure of benthic foraminifera rather than their reproduction dynamics.