Calcium isotope fractionation during microbially induced carbonate mineral precipitation

We report the calcium isotope fractionation during the microbially-induced precipitation of calcium carbonate minerals in pure cultures of the marine sulfate-reducing bacterium Desulfovibrio bizertensis. These data are used to explore how the calcium isotope fractionation factor during microbially-induced carbonate mineral precipitation differs from the better-constrained calcium isotope fractionation factors during biogenic or abiotic carbonate mineral precipitation. Bacterial growth was then modulated with antibiotics, and the evolution of δ44Ca in solution was monitored under different microbial growth rates. The faster the microbial growth rate, the larger the calcium isotope fractionation during carbonate mineral precipitation, ranging from Δ44Ca(s-f) between -1.07‰ and -0.48‰. The reported calcium isotope fractionation can help us understand the link between calcium isotope fractionation and microbial metabolism in carbonate minerals precipitated during sedimentary diagenesis.The work was supported by ERC 307582 StG (CARBONSINK) to AVT and NERC 700 NE/R013519/1 to HJ

Water chemistry reveals a significant decline in coral calcification rates in the southern Red Sea

Experimental and field evidence support the assumption that global warming and ocean acidification is decreasing rates of calcification in the oceans. Local measurements of coral growth rates in reefs from various locations have suggested a decline of ~6-10% per decade since the late 1990’s. Here we show by measuring open water strontium-to-alkalinity ratios along the Red Sea that the net contribution of hermatypic corals to the CaCO3 budget of the southern and central Red Sea declined by ~100% between 1998 and 2015 and remained low between 2015 and 2018. Measured differences in total-alkalinity of the Red Sea surface water indicate a 26±16% decline in total CaCO3 deposition rates along the basin. These findings suggest that coral reefs of the southern Red Sea are under severe stress and demonstrate the strength of geochemical measurements as cost-effective indicators for calcification trends on regional scales.Blavatnik fellowship to Z

The calcium isotopic composition of carbonate hardground cements: A new record of changes in ocean chemistry?

Reconstructing changes in the calcium isotopic composition (δ44Ca) of the ocean over Earth history has been challenging. This difficulty is due to the large range of calcium isotope fractionation factors during mineral precipitation and the potential for overwriting the initial δ44Ca of minerals during shallow marine diagenesis. We present a new δ44Ca record measured in carbonate hardground cements, an inorganic carbonate-mineral precipitate that rapidly forms at or near the sediment-water interface. The range in the δ44Ca for any particular carbonate hardground cements is between 0.05 and 0.56‰. In some cases, the progressive increase in the δ44Ca during precipitation can be observed, consistent with precipitation in a ‘closed-system’. Our data show an average calcium isotope fractionation during carbonate hardground cement precipitation that is −0.57 ± 0.27‰, similar to the calcium isotope fractionation factor for inorganic calcite precipitates in previous laboratory and modelling studies, and closer to what is considered a kinetic end member calcium isotope fractionation than growth at equilibrium. This is consistent with the rapid carbonate mineral precipitation expected for carbonate hardground cements. Our δ44Ca record over the Phanerozoic is similar to other calcium-bearing mineral records over the same time interval, with average δ44Ca becoming lower going back in time by about 0.5 to 0.7‰. Our results add further support for the evolution of seawater δ44Ca over time, and we discuss the possible causes of these changes with suggestions for future studies

Modelling the Effects of Non-Steady State Transport Dynamics on the Sulfur and Oxygen Isotope Composition of Sulfate in Sedimentary Pore Fluids

We present the results of an isotope-enabled reactive transport model of a sediment column undergoing active microbial sulfate reduction to explore the response of the sulfur and oxygen isotopic composition of sulfate under perturbations to steady state. In particular, we test how perturbations to steady state influence the cross plot of δ34S and δ18O for sulfate. The slope of the apparent linear phase (SALP) in the cross plot of δ34S and δ18O for sulfate has been used to infer the mechanism, or metabolic rate, of microbial metabolism, making it important that we understand how transient changes might influence this slope. Tested perturbations include changes in boundary conditions and changes in the rate of microbial sulfate reduction in the sediment. Our results suggest that perturbations to steady state influence the pore fluid concentration of sulfate and the δ34S and δ18O of sulfate but have a minimal effect on SALP. Furthermore, we demonstrate that a constant advective flux in the sediment column has no measurable effect on SALP. We conclude that changes in the SALP after a perturbation are not analytically resolvable after the first 5% of the total equilibration time. This suggests that in sedimentary environments the SALP can be interpreted in terms of microbial metabolism and not in terms of environmental parameters.</jats:p

Proglacial methane emissions driven by meltwater and groundwater flushing in a high-Arctic glacial catchment

Glacial groundwater is a conduit for geologic methane release in areas of glacier retreat on Svalbard, representing a large, climate-sensitive source of the greenhouse gas. Methane emissions from glacial melt rivers are known to occur in other regions of the Arctic, but such emissions have not yet been considered on Svalbard. Over the summer of 2021, we monitored methane concentrations in the proglacial groundwater springs and river network of an ∼ 20 km2 valley glacier in central Svalbard to estimate melt season emissions from a single catchment. We measured methane concentrations in the glacial river of up to 3170 nM (nearly 800 times higher than the atmospheric equilibrium concentration) and found the methane to be of thermogenic origin through isotopic analysis. We estimated a total of 1.0 t of methane emissions during the 2021 melt season from the catchment, of which nearly two-thirds are being flushed from the glacier bed by the melt river. These findings provide further evidence that terrestrial glacier forefields on Svalbard are hotspots for methane emissions, with a climate feedback loop driven by glacier melt. As the first investigation into methane emissions from glacial melt rivers on Svalbard, our study suggests that summer meltwater flushing of methane from beneath the ∼ 1400 land-terminating glaciers across Svalbard may represent an important seasonal source of emissions. Glacial melt rivers, including those from small valley glaciers, may be a growing emission point for subglacial methane across other rapidly warming regions of the Arctic

Testing for ocean acidification during the Early Toarcian using δ44/40Ca and δ88/86Sr

During the Early Toarcian, volcanic gases released by the Karoo-Ferrar large igneous province are widely believed to have caused severe environmental disturbances, including ocean acidification. Here we show records of δ Ca and δ Sr through the Early Toarcian, as recorded in three groups of biogenic calcite: Megateuthididae belemnites, Passaloteuthididae belemnites, and brachiopods of the species Soaresirhynchia bouchardi. We evaluate the data to eliminate the influence on isotopic composition of varying temperature, calcification rate, and salinity, through the section that may mask the environmental signals. Neither δ Ca nor δ Sr show negative isotope excursions across the suggested acidification interval as would be expected had acidification occurred. A profile of δ B, re-interpreted from a published study, shows no variation through the interval. Taken together, these data provide little support for ocean acidification at this time. In our belemnites, values of δ Sr are independent of temperature or Sr/Ca. For brachiopods, too few data are available to determine whether such dependences exist. Values of δ Ca show a weak temperature control of magnitude +0.020 ± 0.004 ‰/°C (2 s.d.). In belemnites, δ Ca also correlates positively with Mg/Ca and Sr/Ca. 44/40 88/86 44/40 88/86 11 88/86 44/40 44/4

Semiquantitative Estimates of Rainfall Variability During the 8.2 kyr Event in California Using Speleothem Calcium Isotope Ratios

A multiproxy record from a fast-growing stalagmite reveals variable hydroclimate on the California coast across the 8.2 kyr event and a precursor event likely caused by initial drainage of proglacial Lake Agassiz. Using speleothem δ Ca, we develop the first semiquantitative estimates of paleorainfall variability for California through calibration with measurements of the modern climate and cave environment. We find that the magnitude of rainfall variability during the 8.2 kyr event approached the multiyear variability observable in the recent past (1950–2019) and the magnitude of variability during the precursor event likely exceeded this range. Additionally, we observe other instances of multidecadal variability comparable in magnitude to the precursor event during the record. Our work suggests that speleothem calcium isotope ratios are a powerful semiquantitative means to reconstruct paleorainfall, although numerous factors must be assessed in each cave system before applying this approach. 4

Physical weathering of carbonate host-rock by precipitation of soluble salts in caves: A case study in El Orón-Arco Cave (Region of Murcia, SE Spain)

The dissolution of carbonate host-rock by freshwater in phreatic or vadose conditions is the most common mechanism for the formation of caves; however, circulation of saline solutions through carbonate materials and precipitation of soluble salts may also play an important role. We studied the stable isotope composition (δ18O and δ34S of sulfate, δ18O and δD of structurally-bound gypsum hydration water and 87Sr/86Sr) and salinity of fluid inclusions in gypsum speleothems found in El Orón-Arco Cave (Cartagena, SE Spain). We suggest that physical weathering of carbonate host-rock was driven by precipitation of soluble sea-salts (mostly gypsum and halite), and this process controlled the recent geomorphological evolution of the cave. The Triassic carbonate host-rock shows clear evidence for salt weathering, including gypsum/halite infillings in cracks of the bedrock, mechanical spalling of the carbonate, and detachment of rock fragments that lead to the formation cave voids and in-situ accumulations of piles of unsorted rubble. Sulfur and oxygen isotopes of gypsum sulfate (3.0‰ < δ18O < 11.6‰ and 16.7‰ < δ34S < 20.7‰) are generally lower than modern seawater sulfate and suggest contributions from a 34S-depleted source (i.e. oxidation of pyrite). The δ18O and δD of gypsum hydration water are relatively low compared to expected values for the evaporation of pure seawater to gypsum saturation, suggesting that gypsum precipitation involved a secondary calcium-sulfate source or recycling of gypsum from previous stages, along with mixing of seawater and meteoric water seepage to the cave. The 87Sr/86Sr in gypsum shows intermediate values between modern seawater and Triassic carbonate values because of interaction between the solution and the bedrock. The salinities of the speleothem-forming solutions are relatively high (13.2 ± 3.2 wt% eq. NaCl) compared to gypsum formed from evaporated brackish solutions (i.e. ~4–8 wt% eq. NaCl) and indicate dissolution of earlier evaporites before secondary gypsum precipitation. This cave-forming mechanism, which is related to saline water circulation and precipitation of evaporitic minerals, may be common in other coastal caves

Local and Regional Indian Summer Monsoon Precipitation Dynamics During Termination II and the Last Interglacial

To date Indian summer monsoon (ISM) dynamics have been assessed by changes in stalagmite δ18O. However, stalagmite δ18O is influenced by multiple environmental factors (e.g., atmospheric moisture transport, rainfall amount at the study site, and ISM seasonality), precluding simple and clear reconstructions of rainfall amount or variability. This study aims to disentangle these environmental factors by combining δ18O, δ44Ca, and elemental data from a stalagmite covering Termination II and the last interglacial from Mawmluh Cave, NE India, to produce a semiquantitative reconstruction of past ISM rainfall. We interpret δ18O as a mixed signal of rainfall source dynamics and rainfall amount and coupled δ44Ca and X/Ca ratios as indicators of local infiltration rate and prior calcite precipitation in the karst zone. The wettest conditions in our studied interval (135 and 100 kyrs BP; BP = before present, with the present being 1950 CE) occurred during Marine Isotope Stage 5e. Our multiproxy data set suggests a likely change in seasonal distribution of Marine Isotope Stage 5e rainfall compared to the Holocene; the wet season was longer with higher‐than‐modern dry season rainfall. Using the last interglacial as an analogue for future anthropogenic warming, our data suggest a more erratic ISM behavior in a warmer world