Sr-isotopic ratios trace mixing and dispersion in CO2 push-pull injection experiments at the CO2CRC Otway Research Facility, Australia

Analysis of 87Sr/86Sr ratios and modelling of formation water, injection water and produced water compositions from the CO2CRC Otway Research Facility in Victoria, Australia are used to test tracer behaviour and response in push-pull experiments. Such experiments are an essential pre-requisite to understanding the controls imposed by reservoir heterogeneities on CO2 dissolution rates which may be an important stabilising mechanism for geological carbon storage. The experiments (Otway stage 2B extension in 2014) comprised two sequential tests in which ~100 t of CO2-saturated water was injected with combinations of Sr and Br or Li and Fluorescein tracers, each injection being followed by two staged extractions of ~10 t and a final extraction of ~50 t all spaced at ~10 day intervals. Analysis of the 87Sr/86Sr ratios of the produced fluids from the first injection, spiked with SrCl2 and NaBr, is consistent with Sr behaving conservatively. This contrasts with previous interpretations in which Br was argued to have behaved conservatively while Sr, which dilutes ~three times as fast as Br, was thought to be lost to a mineral phase. Such Sr-loss cannot explain the evolution of 87Sr/86Sr ratios. The analysis of 87Sr/86Sr ratios in the waters produced after the second injection episode, spiked with LiCl and Fluorescein tracers, allows calculation of the fractions of the formation waters and the injection waters from both tests 1 and 2. The Sr, Li and SO4 tracers (the later formed by oxidation of formation sulphide) all indicate similar rates of dilution that is consistent with conservative behaviour. The results of the two injection episodes with spaced extractions are compared with two subsequent push-pull injections in which the produced waters, spiked with methanol, were extracted continuously. These continuous extraction experiments exhibited significantly less dilution over the same range of produced to injected water volumes (up to only ~0.6) than the earlier experiments with spaced extractions. This implies that some process related to the pauses in extraction enhances mixing of injected and formation waters. Achieving the objective of using push-pull experiments to assess reservoir heterogeneities and CO2 dissolution rates will require better assessment of the various tracers to establish which behave conservatively followed a proper understanding of the causes of the variations in mixing as fluids are extracted from the formations

Quantifying CO2 Removal at Enhanced Weathering Sites: a Multiproxy Approach

Enhanced weathering is a carbon dioxide (CO 2) mitigation strategy that promises large scale atmospheric CO 2 removal. The main challenge associated with enhanced weathering is monitoring, reporting, and verifying (MRV) the amount of carbon removed as a result of enhanced weathering reactions. Here, we study a CO 2 mineralization site in Consett, Co. Durham, UK, where steel slags have been weathered in a landscaped deposit for over 40 years. We provide new radiocarbon, δ 13 C, 87 Sr/ 86 Sr, and major element data in waters, calcite precipitates, and soils to quantify the rate of carbon removal. We demonstrate that measuring the radiocarbon activity of CaCO 3 deposited in waters draining the slag deposit provides a robust constraint on the carbon source being sequestered (80% from the atmosphere, 2σ = 8%) and use downstream alkalinity measurements to determine the proportion of carbon exported to the ocean. The main phases dissolving in the slag are hydroxide minerals (e.g., portlandite) with minor contributions (<3%) from silicate minerals. We propose a novel method for quantifying carbon removal rates at enhanced weathering sites, which is a function of the radiocarbon-apportioned sources of carbon being sequestered, and the proportion of carbon being exported from the catchment to the oceans

Continental carbonate facies of a Neoproterozoic panglaciation, north-east Svalbard

The Marinoan panglaciation (ca 650 to 635 Ma) is represented in north-east Svalbard by the 130 to 175 m thick Wilsonbreen Formation which contains syn-glacial carbonates in its upper 100 m. These sediments are now known to have been deposited under a CO2-rich atmosphere, late in the glaciation, and global climate models facilitate testing of proposed analogues. Precipitated carbonates occur in four of the seven facies associations identified: Fluvial Channel (including stromatolitic and intraclastic limestones in ephemeral stream deposits); Dolomitic Floodplain (dolomite-cemented sand and siltstones, and microbial dolomites); Calcareous Lake Margin (intraclastic dolomite and wave-rippled or aeolian siliciclastic facies); and Calcareous Lake (slump-folded and locally re-sedimented rhythmic/stromatolitic limestones and dolomites associated with ice-rafted sediment). There is no strong cyclicity, and modern analogues suggest that sudden changes in lake level may exert a strong control on facies geometry. Both calcite and dolomite in stromatolites and rhythmites display either primary or early diagenetic replacive growth. Oxygen isotope values (−12 to +15‰VPDB) broadly covary with δ13C. High δ13C values of +3·5 to +4·5‰ correspond to equilibration with an atmosphere dominated by volcanically degassed CO2 with δ13C of −6 to −7‰. Limestones have consistently negative δ18O values, while rhythmic and playa dolomites preserve intermediate compositions, and dolocretes possess slightly negative to strongly positive δ18O signatures, reflecting significant evaporation under hyperarid conditions. Inferred meltwater compositions (−8 to −15·5‰) could reflect smaller Rayleigh fractionation related to more limited cooling than in modern polar regions. A common pseudomorph morphology is interpreted as a replacement of ikaite (CaCO3·H2O), which may also have been the precursor for widespread replacive calcite mosaics. Local dolomitization of lacustrine facies is interpreted to reflect microenvironments with fluctuating redox conditions. Although differing in (palaeo)latitude and carbonate abundance, the Wilsonbreen carbonates provide strong parallels with the McMurdo Dry Valleys of Antarctica

Integrating Suspended Sediment Flux in Large Alluvial River Channels: Application of a Synoptic Rouse‐Based Model to the Irrawaddy and Salween Rivers

A large portion of freshwater and sediment is exported to the ocean by a small number of major rivers. Many of these megarivers are subject to substantial anthropogenic pressures, which are having a major impact on water and sediment delivery to deltaic ecosystems. Due to hydrodynamic sorting, sediment grain size and composition vary strongly with depth and across the channel in large rivers, complicating flux quantification. To account for this, we modified a semi‐empirical Rouse model, synoptically predicting sediment concentration, grain‐size distribution, and organic carbon (%OC) concentration with depth and across the river channel. Using suspended sediment depth samples and flow velocity data, we applied this model to calculate sediment fluxes of the Irrawaddy (Ayeyarwady) and the Salween (Thanlwin), the last two free‐flowing megarivers in Southeast Asia. Deriving sediment‐discharge rating curves, we calculated an annual sediment flux of urn:x-wiley:jgrf:media:jgrf21236:jgrf21236-math-0001 Mt/year for the Irrawaddy and urn:x-wiley:jgrf:media:jgrf21236:jgrf21236-math-0002 Mt/year for the Salween, together exporting 46% as much sediment as the Ganges‐Brahmaputra system. The mean flux‐weighted sediment exported by the Irrawaddy is significantly coarser (D84 = 193 ± 13 μm) and OC‐poorer (0.29 ± 0.08 wt%) compared to the Salween (112 ± 27 μm and 0.59 ± 0.16 wt%, respectively). Both rivers export similar amounts of particulate organic carbon, with a total of urn:x-wiley:jgrf:media:jgrf21236:jgrf21236-math-0003 Mt C/year, 53% as much as the Ganges‐Brahmaputra. These results underline the global significance of the Irrawaddy and Salween rivers and warrant continued monitoring of their sediment flux, given the increasing anthropogenic pressures on these river basins

Global silicate weathering flux overestimated because of sediment–water cation exchange

Rivers carry the dissolved and solid products of silicate mineral weathering, a process that removes CO2 from the atmosphere and provides a key negative climate feedback over geological timescales. Here we show that in some river systems, a reactive exchange pool on river suspended particulate matter, bonded weakly to mineral surfaces, increases the mobile cation flux by 50%. The chemistry of both river waters and the exchange pool demonstrate exchange equilibrium, confirmed by Sr isotopes. Global silicate weathering fluxes are calculated based on riverine dissolved sodium (Na+) from silicate minerals. The large exchange pool supplies Na+ of non- silicate origin to the dissolved load, especially in catchments with widespread marine sediments, or where rocks have equilibrated with saline basement fluids. We quantify this by comparing the riverine sediment exchange pool and river water chemistry. In some basins, cation exchange could account for the majority of sodium in the river water, significantly reducing estimates of silicate weathering. At a global scale, we demonstrate that silicate weathering fluxes are over-estimated by 12-28%. This over-estimation is greatest in regions of high erosion and high sediment loads where the negative climate feedback has a maximum sensitivity to chemical weathering reactions. In the context of other recent findings that reduce the net CO2 consumption through chemical weathering, the magnitude of the continental silicate weathering fluxes and its implications for solid Earth CO2 degassing fluxes needs to be further investigated

Orbitally forced ice sheet fluctuations during the Marinoan Snowball Earth glaciation

Two global glaciations occurred during the Neoproterozoic. Snowball Earth theory posits that these were terminated after millions of years of frigidity when initial warming from rising atmospheric CO2 concentrations was amplified by the reduction of ice cover and hence a reduction in planetary albedo. This scenario implies that most of the geological record of ice cover was deposited in a brief period of melt-back. However, deposits in low palaeo-latitudes show evidence of glacial–interglacial cycles. Here we analyse the sedimentology and oxygen and sulphur isotopic signatures of Marinoan Snowball glaciation deposits from Svalbard, in the Norwegian High Arctic. The deposits preserve a record of oscillations in glacier extent and hydrologic conditions under uniformly high atmospheric CO2 concentrations. We use simulations from a coupled three-dimensional ice sheet and atmospheric general circulation model to show that such oscillations can be explained by orbital forcing in the late stages of a Snowball glaciation. The simulations suggest that while atmospheric CO2 concentrations were rising, but not yet at the threshold required for complete melt-back, the ice sheets would have been sensitive to orbital forcing. We conclude that a similar dynamic can potentially explain the complex successions observed at other localities

JWST-TST DREAMS: Quartz Clouds in the Atmosphere of WASP-17b

Clouds are prevalent in many of the exoplanet atmospheres that have been observed to date. For transiting exoplanets, we know if clouds are present because they mute spectral features and cause wavelength-dependent scattering. While the exact composition of these clouds is largely unknown, this information is vital to understanding the chemistry and energy budget of planetary atmospheres. In this work, we observe one transit of the hot Jupiter WASP-17b with JWST's MIRI LRS and generate a transmission spectrum from 5-12 $\rm{\mu}$m. These wavelengths allow us to probe absorption due to the vibrational modes of various predicted cloud species. Our transmission spectrum shows additional opacity centered at 8.6 $\rm{\mu}$m, and detailed atmospheric modeling and retrievals identify this feature as SiO$_2$(s) (quartz) clouds. The SiO$_2$(s) clouds model is preferred at 3.5-4.2$\sigma$ versus a cloud-free model and at 2.6$\sigma$ versus a generic aerosol prescription. We find the SiO$_2$(s) clouds are comprised of small ${\sim}0.01$ $\rm{\mu}$m particles, which extend to high altitudes in the atmosphere. The atmosphere also shows a depletion of H$_2$O, a finding consistent with the formation of high-temperature aerosols from oxygen-rich species. This work is part of a series of studies by our JWST Telescope Scientist Team (JWST-TST), in which we will use Guaranteed Time Observations to perform Deep Reconnaissance of Exoplanet Atmospheres through Multi-instrument Spectroscopy (DREAMS).Comment: 19 pages, 7 figures, accepted for publication in ApJ

Nightside clouds and disequilibrium chemistry on the hot Jupiter WASP-43b

Hot Jupiters are among the best-studied exoplanets, but it is still poorly understood how their chemical composition and cloud properties vary with longitude. Theoretical models predict that clouds may condense on the nightside and that molecular abundances can be driven out of equilibrium by zonal winds. Here we report a phase-resolved emission spectrum of the hot Jupiter WASP-43b measured from 5 μm to 12 μm with the JWST’s Mid-Infrared Instrument. The spectra reveal a large day–night temperature contrast (with average brightness temperatures of 1,524 ± 35 K and 863 ± 23 K, respectively) and evidence for water absorption at all orbital phases. Comparisons with three-dimensional atmospheric models show that both the phase-curve shape and emission spectra strongly suggest the presence of nightside clouds that become optically thick to thermal emission at pressures greater than ~100 mbar. The dayside is consistent with a cloudless atmosphere above the mid-infrared photosphere. Contrary to expectations from equilibrium chemistry but consistent with disequilibrium kinetics models, methane is not detected on the nightside (2σ upper limit of 1–6 ppm, depending on model assumptions). Our results provide strong evidence that the atmosphere of WASP-43b is shaped by disequilibrium processes and provide new insights into the properties of the planet’s nightside clouds. However, the remaining discrepancies between our observations and our predictive atmospheric models emphasize the importance of further exploring the effects of clouds and disequilibrium chemistry in numerical models.Peer reviewe

Nightside clouds and disequilibrium chemistry on the hot Jupiter WASP-43b

Hot Jupiters are among the best-studied exoplanets, but it is still poorly understood how their chemical composition and cloud properties vary with longitude. Theoretical models predict that clouds may condense on the nightside and that molecular abundances can be driven out of equilibrium by zonal winds. Here we report a phase-resolved emission spectrum of the hot Jupiter WASP-43b measured from 5-12 μm with JWST's Mid-Infrared Instrument (MIRI). The spectra reveal a large day-night temperature contrast (with average brightness temperatures of 1524±35 and 863±23 Kelvin, respectively) and evidence for water absorption at all orbital phases. Comparisons with three-dimensional atmospheric models show that both the phase curve shape and emission spectra strongly suggest the presence of nightside clouds which become optically thick to thermal emission at pressures greater than ~100 mbar. The dayside is consistent with a cloudless atmosphere above the mid-infrared photosphere. Contrary to expectations from equilibrium chemistry but consistent with disequilibrium kinetics models, methane is not detected on the nightside (2σ upper limit of 1-6 parts per million, depending on model assumptions)