Storage and hydrolysis of seawater samples for inorganic carbon isotope analysis

Preservation of seawater samples was tested for total inorganic carbon (ΣCO2), stable carbon isotope (δ13C), and radiocarbon (14C) applications using foil bags and storage by refrigeration and freezing. The aim was to preserve representative samples with minimal storage effects but without using toxic methods such as mercuric chloride poisoning. Hydrolysis of samples to CO2 was based on existing methods. Results of IAEA-C2 standard used with deionized water stored in the foil bags showed complete reaction yields, 14C results within 2σ of the consensus value, and δ13C that were internally consistent, indicating that there were no procedural effects associated with the foil bags. 14C results were statistically indistinguishable across the storage times, for frozen and refrigerated seawater samples from a coastal site, Elie Ness, Fife, UK. The scatter of ΣCO2 concentrations and δ13C was within scatter observed in other studies for lake- and seawater samples preserved by acidification or using mercuric chloride. However, both ΣCO2 and δ13C were less variable for frozen samples compared with refrigerated samples. The foil bags are lighter, safer to transport, and similar in cost to glass bottles and allow sample collection in the field and transfer to the hydrolysis vessel without exposure of the sample to atmosphere. Storage of seawater samples in the foil bags was considered a reliable, alternative method to poisoning for ΣCO2, δ13C, and 14C, and freezing the samples is recommended for storage time beyond a week

Deglacial Si remobilisation from the deep-ocean reveals biogeochemical and physical controls on glacial atmospheric CO2 levels

During the last glacial period, the sluggish deep Ocean circulation sequestered carbon into the abyss leading to the lowering of atmospheric CO2. The impact of this redistribution on biologically essential nutrients remains poorly constrained. Using sedimentary δ30 Si of diatoms and biogenic accumulation rates in the Eastern Equatorial Pacific (EEP), we present evidences for the remobilisation of dissolved Silica (DSi) along with carbon from the deep ocean during the Last Deglaciation. Because DSi is essential for diatoms growing in the surface ocean, its concentration in the abyss during the glacial periods amounts to a negative feedback on the oceanic CO2 uptake. However, this effect can be muted by the increased Fe inputs during glacial periods which reduces diatom Si requirements in Fe limited regions such as the EEP. Our results from the EEP suggest that the efficiency of the biological CO2 pump and the size of the local CO2 source is tightly controlled by changes in DSi utilisation driven by Fe availability across the last glacial-interglacial transition.We use a modified PANDORA box model to illustrate that the inventory of DSi in the global ocean surface is controlled by Fe availability in HNLC areas rather than by straightforward Si supply though upwelling. The Holocene is characterised by a fast mode of Si cycling driven by high biological requirement for Si under conditions of iron limitation and efficient overturning, promoting CO2 outgassing and an inefficient biological C pump via the rapid exhaustion of DSi in the surface. The last glacial period saw slower marine Si cycling as a result of decreased DSi biological requirement under Fe-replete conditions in the sea surface and increased Si and CO2 sequestration in the abyssal ocean. The switch between the two modes of Si cycling happened at 15 ka BP, i.e. mid-deglaciation, and resulted in contrasting biological carbon drawdown responses in the EEP and globally between both phases of the deglacial CO2 rise. This illustrates that in addition to deep-sea CO2 storage and overturning, the efficiency of the biological pump also plays a crucial role in determining ocean-atmosphere CO2 exchange and shows the dual controls of ocean circulation and Fe-Si availability in this process.</p

Coherent response of the Indian Monsoon Rainfall to Atlantic Multi-decadal Variability over the last 2000 years

Indian Summer Monsoon (ISM) rainfall has a direct effect on the livelihoods of two billion people in the Indian-subcontinent. Yet, our understanding of the drivers of multi-decadal variability of the ISM is far from being complete. In this context, large-scale forcing of ISM rainfall variability with multi-decadal resolution over the last two millennia is investigated using new records of sea surface salinity (δ18Ow) and sea surface temperatures (SSTs) from the Bay of Bengal (BoB). Higher δ18Ow values during the Dark Age Cold Period (1550 to 1250 years BP) and the Little Ice Age (700 to 200 years BP) are suggestive of reduced ISM rainfall, whereas lower δ18Ow values during the Medieval Warm Period (1200 to 800 years BP) and the major portion of the Roman Warm Period (1950 to 1550 years BP) indicate a wetter ISM. This variability in ISM rainfall appears to be modulated by the Atlantic Multi-decadal Oscillation (AMO) via changes in large-scale thermal contrast between the Asian land mass and the Indian Ocean, a relationship that is also identifiable in the observational data of the last century. Therefore, we suggest that inter-hemispheric scale interactions between such extra tropical forcing mechanisms and global warming are likely to be influential in determining future trends in ISM rainfall

Coherent response of the Indian Monsoon Rainfall to Atlantic Multi-decadal Variability over the last 2000 years

Indian Summer Monsoon (ISM) rainfall has a direct effect on the livelihoods of two billion people in the Indian-subcontinent. Yet, our understanding of the drivers of multi-decadal variability of the ISM is far from being complete. In this context, large-scale forcing of ISM rainfall variability with multi-decadal resolution over the last two millennia is investigated using new records of sea surface salinity (δ18Ow) and sea surface temperatures (SSTs) from the Bay of Bengal (BoB). Higher δ18Ow values during the Dark Age Cold Period (1550 to 1250 years BP) and the Little Ice Age (700 to 200 years BP) are suggestive of reduced ISM rainfall, whereas lower δ18Ow values during the Medieval Warm Period (1200 to 800 years BP) and the major portion of the Roman Warm Period (1950 to 1550 years BP) indicate a wetter ISM. This variability in ISM rainfall appears to be modulated by the Atlantic Multi-decadal Oscillation (AMO) via changes in large-scale thermal contrast between the Asian land mass and the Indian Ocean, a relationship that is also identifiable in the observational data of the last century. Therefore, we suggest that inter-hemispheric scale interactions between such extra tropical forcing mechanisms and global warming are likely to be influential in determining future trends in ISM rainfall

Isotopic fractionation of carbon during uptake by phytoplankton across the South Atlantic subtropical convergence

The stable isotopic composition of particulate organic carbon (δ13CPOC) in the surface waters of the global ocean can vary with the aqueous CO2 concentration ([CO2(aq)]) and affects the trophic transfer of carbon isotopes in the marine food web. Other factors such as cell size, growth rate and carbon concentrating mechanisms decouple this observed correlation. Here, the variability in δ13CPOC is investigated in surface waters across the south subtropical convergence (SSTC) in the Atlantic Ocean, to determine carbon isotope fractionation (ϵp) by phytoplankton and the contrasting mechanisms of carbon uptake in the subantarctic and subtropical water masses. Our results indicate that cell size is the primary determinant of δ13CPOC across the Atlantic SSTC in summer. Combining cell size estimates with CO2 concentrations, we can accurately estimate "p within the varying surface water masses in this region. We further utilize these results to investigate future changes in "p with increased anthropogenic carbon availability. Our results suggest that smaller cells, which are prevalent in the subtropical ocean, will respond less to increased [CO2(aq)] than the larger cells found south of the SSTC and in the wider Southern Ocean. In the subantarctic water masses, isotopic fractionation during carbon uptake will likely increase, both with increasing CO2 availability to the cell, but also if increased stratification leads to decreases in average community cell size. Coupled with decreasing δ13C of [CO2(aq)] due to anthropogenic CO2 emissions, this change in isotopic fractionation and lowering of δ13CPOC may propagate through the marine food web, with implications for the use of δ13CPOC as a tracer of dietary sources in the marine environment

Tracing the role of Arctic shelf processes in Si and N cycling and export through the Fram Strait: insights from combined silicon and nitrate isotopes

Nutrient cycles in the Arctic Ocean are being altered by changing hydrography, increasing riverine inputs, glacial melt and sea-ice loss due to climate change. In this study, combined isotopic measurements of dissolved nitrate (δ15N-NO3 and δ18O-NO3) and silicic acid (δ30Si(OH)4) are used to understand the pathways that major nutrients follow through the Arctic Ocean. Atlantic waters were found to be isotopically lighter (δ30Si(OH)4=+ 1.74 ‰) than their polar counterpart (δ30Si(OH)4=+ 1.85 ‰) owing to partial biological utilisation of dissolved Si (DSi) within the Arctic Ocean. Coupled partial benthic denitrification and nitrification on Eurasian Arctic shelves lead to the enrichment of δ15N-NO3 and lighter δ18O-NO3 in the polar surface waters (δ15N-NO3= 5.44 ‰, δ18O-NO3= 1.22 ‰) relative to Atlantic waters (δ15N-NO3= 5.18 ‰, δ18O-NO3= 2.33 ‰). Using a pan-Arctic DSi isotope dataset, we find that the input of isotopically light δ30Si(OH)4 by Arctic rivers and the subsequent partial biological uptake and biogenic Si burial on Eurasian shelves are the key processes that generate the enriched isotopic signatures of DSi exported through Fram Strait. A similar analysis of δ15N-NO3 highlights the role of N-limitation due to denitrification losses on Arctic shelves in generating the excess dissolved silicon exported through Fram Strait. We estimate that around 40 % of DSi exported in polar surface waters through Fram Strait is of riverine origin. As the Arctic Ocean is broadly N-limited and riverine sources of DSi are increasing faster than nitrogen inputs, a larger silicic acid export through the Fram Strait is expected in the future. Arctic riverine inputs therefore have the potential to modify the North Atlantic DSi budget and are expected to become more important than variable Pacific and glacial DSi sources over the coming decades.</p

Permafrost degradation and nitrogen cycling in Arctic rivers: Insights from stable nitrogen isotope studies

Abstract. Across the Arctic, vast areas of permafrost are being degraded by climate change, which has the potential to release substantial quantities of nutrients, including nitrogen into large Arctic rivers. These rivers heavily influence the biogeochemistry of the Arctic Ocean, so it is important to understand the potential changes to rivers from permafrost degradation. This study utilized dissolved nitrogen species (nitrate and dissolved organic nitrogen (DON)) along with nitrogen isotope values (δ15N-NO3- and δ15N-DON) of samples collected from permafrost sites in the Kolyma River and the six largest Arctic rivers. Large inputs of DON and nitrate with a unique isotopically heavy δ15N signature were documented in the Kolyma, suggesting the occurrence of denitrification and highly invigorated nitrogen cycling in the Yedoma permafrost thaw zones along the Kolyma. We show evidence for permafrost-derived DON being recycled to nitrate as it passes through the river, transferring the high 15N signature to nitrate. However, the potential to observe these thaw signals at the mouths of rivers depends on the spatial scale of thaw sites, permafrost degradation, and recycling mechanisms. In contrast with the Kolyma, with near 100 % continuous permafrost extent, the Ob River, draining large areas of discontinuous and sporadic permafrost, shows large seasonal changes in both nitrate and DON isotopic signatures. During winter months, water percolating through peat soils records isotopically heavy denitrification signals in contrast with the lighter summer values when surface flow dominates. This early year denitrification signal was present to a degree in the Kolyma, but the ability to relate seasonal nitrogen signals across Arctic Rivers to permafrost degradation could not be shown with this study. Other large rivers in the Arctic show different seasonal nitrogen trends. Based on nitrogen isotope values, the vast majority of nitrogen fluxes in the Arctic rivers is from fresh DON sourced from surface runoff through organic-rich topsoil and not from permafrost degradation. However, with future permafrost thaw, other Arctic rivers may begin to show nitrogen trends similar to the Ob. Our study demonstrates that nitrogen inputs from permafrost thaw can be identified through nitrogen isotopes, but only on small spatial scales. Overall, nitrogen isotopes show potential for revealing integrated catchment wide nitrogen cycling processes. </jats:p