Quantifying CO2 Removal at Enhanced Weathering Sites: a Multiproxy Approach.

Enhanced weathering is a carbon dioxide (CO2) mitigation strategy that promises large scale atmospheric CO2 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 CO2 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, δ13C, 87Sr/86Sr, 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 CaCO3 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.

Using Organic Contaminants to Constrain the Terrestrial Journey of the Martian Meteorite Lafayette.

A key part of the search for extraterrestrial life is the detection of organic molecules since these molecules form the basis of all living things on Earth. Instrument suites such as SHERLOC (Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals) onboard the NASA Perseverance rover and the Mars Organic Molecule Analyzer onboard the future ExoMars Rosalind Franklin rover are designed to detect organic molecules at the martian surface. However, size, mass, and power limitations mean that these instrument suites cannot yet match the instrumental capabilities available in Earth-based laboratories. Until Mars Sample Return, the only martian samples available for study on Earth are martian meteorites. This is a collection of largely basaltic igneous rocks that have been exposed to varying degrees of terrestrial contamination. The low organic molecule abundance within igneous rocks and the expectation of terrestrial contamination make the identification of martian organics within these meteorites highly challenging. The Lafayette martian meteorite exhibits little evidence of terrestrial weathering, potentially making it a good candidate for the detection of martian organics despite uncertainties surrounding its fall history. In this study, we used ultrapure solvents to extract organic matter from triplicate samples of Lafayette and analyzed these extracts via hydrophilic interaction liquid chromatography-mass spectrometry (HILIC-MS). Two hundred twenty-four metabolites (organic molecules) were detected in Lafayette at concentrations more than twice those present in the procedural blanks. In addition, a large number of plant-derived metabolites were putatively identified, the presence of which supports the unconfirmed report that Lafayette fell in a semirural location in Indiana. Remarkably, the putative identification of the mycotoxin deoxynivalenol (or vomitoxin), alongside the report that the collector was possibly a student at Purdue University, can be used to identify the most likely fall year as 1919.

Relationships between riverine and terrestrial dissolved organic carbon: Concentration, radiocarbon signature, specific UV absorbance.

The transfer of dissolved organic carbon (DOC) from land to watercourses plays a major role in the carbon cycle, and in the transport and fate of associated organic and inorganic contaminants. We investigated, at global scale, how the concentrations and properties of riverine DOC depend upon combinations of terrestrial source solutions. For topsoil, subsoil, groundwater and river solutions in different Köppen-Geiger climatic zones, we compiled published and new values of DOC concentration ([DOC]), radiocarbon signature (DO14C), and specific UV absorbance (SUVA). The average value of each DOC variable decreased significantly in magnitude from topsoil to subsoil to groundwater, permitting the terrestrial sources to be distinguished. We used the terrestrial data to simulate the riverine distributions of each variable, and also relationships between pairs of variables. To achieve good matches between observed and simulated data, it was necessary to optimise the distributions of water fractions contributed by each of the three terrestrial sources, and also to reduce the mean input terrestrial [DOC] values, to about 60% of the measured ones. One possible explanation for the required lowering of the modelled terrestrial [DOC] values might be unrepresentative sampling of terrestrial DOC, including dilution effects; another is the loss of DOC during riverine transport. High variations in simulated riverine DOC variables, which match observed data, are due predominantly to variations in source solution values, with a lesser contribution from the different combinations of source waters. On average, most DOC in rivers draining catchments with forest and/or grass-shrub land cover comes in similar amounts from topsoil and subsoil, with about 10% from groundwater. In rivers draining croplands, subsoil and groundwater solutions are the likely dominant DOC sources, while in wetland rivers most DOC is from topsoil.

A rapid throughput technique to isolate pyrogenic carbon by hydrogen pyrolysis for stable isotope and radiocarbon analysis.

RATIONALE: Rapid, reliable isolation of pyrogenic carbon (PyC; also known as char, soot, black carbon, or biochar) for the determination of stable carbon isotope (δ13 C) composition and radiocarbon (14 C) dating is needed across multiple fields of research in geoscience, environmental science and archaeology. Many current techniques do not provide reliable isolation from contaminating organics and/or are relatively time-consuming. Hydrogen pyrolysis (HyPy) does provide reliable isolation of PyC, but the current methodology is time consuming. METHODS: We explored the potential for subjecting multiple samples to HyPy analysis by placing up to nine individual samples in custom-designed borosilicate sample vessels in a single reactor run. We tested for cross-contamination between samples in the same run using materials with highly divergent radiocarbon activities (~0.04-116.3 pMC), δ13 C values (-11.9 to -26.5‰) and labile carbon content. We determined 14 C/13 C using accelerator mass spectrometry and δ13 C values using an elemental analyser coupled to a continuous flow isotope ratio mass spectrometer. RESULTS: Very small but measurable transfer between samples of highly divergent isotope composition was detectable. For samples having a similar composition, this cross-contamination is considered negligible with respect to measurement uncertainty. For samples having divergent composition, we found that placing a sample vessel loaded with silica mesh adsorbent between samples eliminated measurable cross-contamination in all cases for both 14 C/13 C and δ13 C values. CONCLUSIONS: It is possible to subject up to seven samples to HyPy in the same reactor run for the determination of radiocarbon content and δ13 C value without diminishing the precision or accuracy of the results. This approach enables an increase in sample throughput of 300-600%. HyPy process background values are consistently lower than the nominal laboratory process background for quartz tube combustion in the NERC Radiocarbon Laboratory, indicating that HyPy may also be advantageous as a relatively 'clean' radiocarbon pre-treatment method.

8.2 ka event North Sea hydrography determined by bivalve shell stable isotope geochemistry.

The abrupt 8.2 ka cold event has been widely described from Greenland and North Atlantic records. However, its expression in shelf seas is poorly documented, and the temporal resolution of most marine records is inadequate to precisely determine the chronology of major events. A robust hydrographical reconstruction can provide an insight on climatic reaction times to perturbations to the Atlantic Meridional Overturning Circulation. Here we present an annually-resolved temperature and water column stratification reconstruction based on stable isotope geochemistry of Arctica islandica shells from the Fladen Ground (northern North Sea) temporally coherent with Greenland ice core records. Our age model is based on a growth increment chronology obtained from four radiometrically-dated shells covering the 8290-8100 cal BP interval. Our results indicate that a sudden sea level rise (SSLR) event-driven column stratification occurred between ages 8320-8220 cal BP. Thirty years later, cold conditions inhibited water column stratification but an eventual incursion of sub-Arctic waters into the North Sea re-established density-driven stratification. The water temperatures reached their minimum of ~3.7 °C 55 years after the SSLR. Intermittently-mixed conditions were later established when the sub-Arctic waters receded.

Carbon sequestration potential and physicochemical properties differ between wildfire charcoals and slow-pyrolysis biochars.

Pyrogenic carbon (PyC), produced naturally (wildfire charcoal) and anthropogenically (biochar), is extensively studied due to its importance in several disciplines, including global climate dynamics, agronomy and paleosciences. Charcoal and biochar are commonly used as analogues for each other to infer respective carbon sequestration potentials, production conditions, and environmental roles and fates. The direct comparability of corresponding natural and anthropogenic PyC, however, has never been tested. Here we compared key physicochemical properties (elemental composition, δ13C and PAHs signatures, chemical recalcitrance, density and porosity) and carbon sequestration potentials of PyC materials formed from two identical feedstocks (pine forest floor and wood) under wildfire charring- and slow-pyrolysis conditions. Wildfire charcoals were formed under higher maximum temperatures and oxygen availabilities, but much shorter heating durations than slow-pyrolysis biochars, resulting in differing physicochemical properties. These differences are particularly relevant regarding their respective roles as carbon sinks, as even the wildfire charcoals formed at the highest temperatures had lower carbon sequestration potentials than most slow-pyrolysis biochars. Our results challenge the common notion that natural charcoal and biochar are well suited as proxies for each other, and suggest that biochar's environmental residence time may be underestimated when based on natural charcoal as a proxy, and vice versa.

Deciphering diet and monitoring movement: Multiple stable isotope analysis of the viking age settlement at Hofstaðir, Lake Mývatn, Iceland.

OBJECTIVES: A previous multi-isotope study of archaeological faunal samples from Skútustaðir, an early Viking age settlement on the southern shores of Lake Mývatn in north-east Iceland, demonstrated that there are clear differences in δ(34)S stable isotope values between animals deriving their dietary protein from terrestrial, freshwater, and marine reservoirs. The aim of this study was to use this information to more accurately determine the diet of humans excavated from a nearby late Viking age churchyard. MATERIALS AND METHODS: δ(13)C, δ(15)N, and δ(34)S analyses were undertaken on terrestrial animal (n = 39) and human (n = 46) bone collagen from Hofstaðir, a high-status Viking-period farmstead ∼10 km north-west of Skútustaðir. RESULTS: δ(34)S values for Hofstaðir herbivores were ∼6‰ higher relative to those from Skútustaðir (δ(34)S: 11.4 ± 2.3‰ versus 5.6 ± 2.8‰), while human δ(13)C, δ(15)N, and δ(34)S values were broad ranging (-20.2‰ to -17.3‰, 7.4‰ to 12.3‰, and 5.5‰ to 14.9‰, respectively). DISCUSSION: Results suggest that the baseline δ(34)S value for the Mývatn region is higher than previously predicted due to a possible sea-spray effect, but the massive deposition of Tanytarsus gracilentus (midges) (δ(34)S: -3.9‰) in the soil in the immediate vicinity of the lake is potentially lowering this value. Several terrestrial herbivores displayed higher bone collagen δ(34)S values than their contemporaries, suggesting trade and/or movement of animals to the region from coastal areas. Broad ranging δ(13)C, δ(15)N, and δ(34)S values for humans suggest the population were consuming varied diets, while outliers within the dataset could conceivably have been migrants to the area.

Rapid Removal of Atmospheric CO2 by Urban Soils.

The measured calcium carbonate content of soils to a depth of 100 mm at a large urban development site has increased over 18 months at a rate that corresponds to the sequestration of 85 t of CO2/ha (8.5 kg of CO2 m(-2)) annually. This is a consequence of rapid weathering of calcium silicate and hydroxide minerals derived from the demolition of concrete structures, which releases Ca that combines with CO2 ultimately derived from the atmosphere, precipitating as calcite. Stable isotope data confirm an atmospheric origin for carbonate carbon, and 14C dating indicates the predominance of modern carbon in the pedogenic calcite. Trial pits show that carbonation extends to depths of ≥1 m. Work at other sites shows that the occurrence of pedogenic carbonates is widespread in artificially created urban soils containing Ca and Mg silicate minerals. Appropriate management of fewer than 12000 ha of urban land to maximize calcite precipitation has the potential to remove 1 million t of CO2 from the atmosphere annually. The maximal global potential is estimated to be approximately 700-1200 Mt of CO2 per year (representing 2.0-3.7% of total emissions from fossil fuel combustion) based on current rates of production of industry-derived Ca- and Mg-bearing materials.

Investigation of growth responses in saprophytic fungi to charred biomass.

We present the results of a study testing the response of two saprophytic white-rot fungi species, Pleurotus pulmonarius and Coriolus versicolor, to charred biomass (charcoal) as a growth substrate. We used a combination of optical microscopy, scanning electron microscopy, elemental abundance measurements, and isotope ratio mass spectrometry ((13)C and (15)N) to investigate fungal colonisation of control and incubated samples of Scots Pine (Pinus sylvestris) wood, and charcoal from the same species produced at 300 degrees C and 400 degrees C. Both species of fungi colonise the surface and interior of wood and charcoals over time periods of less than 70 days; however, distinctly different growth forms are evident between the exterior and interior of the charcoal substrate, with hyphal penetration concentrated along lines of structural weakness. Although the fungi were able to degrade and metabolise the pine wood, charcoal does not form a readily available source of fungal nutrients at least for these species under the conditions used in this study.