Balance and imbalance in biogeochemical cycles reflect the operation of closed, exchange, and open sets.

Biogeochemical reactions modulate the chemical composition of the oceans and atmosphere, providing feedbacks that sustain planetary habitability over geological time. Here, we mathematically evaluate a suite of biogeochemical processes to identify combinations of reactions that stabilize atmospheric carbon dioxide by balancing fluxes of chemical species among the ocean, atmosphere, and geosphere. Unlike prior modeling efforts, this approach does not prescribe functional relationships between the rates of biogeochemical processes and environmental conditions. Our agnostic framework generates three types of stable reaction combinations: closed sets, where sources and sinks mutually cancel for all chemical reservoirs; exchange sets, where constant ocean-atmosphere conditions are maintained through the growth or destruction of crustal reservoirs; and open sets, where balance in alkalinity and carbon fluxes is accommodated by changes in other chemical components of seawater or the atmosphere. These three modes of operation have different characteristic timescales and may leave distinct evidence in the rock record. To provide a practical example of this theoretical framework, we applied the model to recast existing hypotheses for Cenozoic climate change based on feedbacks or shared forcing mechanisms. Overall, this work provides a systematic and simplified conceptual framework for understanding the function and evolution of global biogeochemical cycles.

High rates of rock organic carbon oxidation sustained as Andean sediment transits the Amazon foreland-floodplain.

The oxidation of organic carbon contained within sedimentary rocks ("petrogenic" carbon, or hereafter OCpetro) emits nearly as much CO2 as is released by volcanism, thereby playing a key role in the long-term global C budget. High erosion rates in mountains have been shown to increase OCpetro oxidation. However, these settings also export unweathered material that may continue to react in downstream floodplains. The relative importance of OCpetro oxidation in mountains versus floodplains remains difficult to assess as disparate methods have been used in the different environments. Here, we investigate the sources and fluxes of rhenium (Re) in the Rio Madre de Dios to quantify OCpetro oxidation from the Andes to the Amazon floodplain using a common approach. Dissolved rhenium concentrations (n = 131) range from 0.01 to 63 pmol L-1 and vary depending on lithology and geomorphic setting. We find that >75% of the dissolved Re derives from OCpetro oxidation and that this proportion increases downstream. We estimate that in the Andes, OCpetro oxidation releases 11.2+4.5/-2.8 tC km-2 y-1 of CO2, which corresponds to ~41% of the total OCpetro denudation (sum of oxidized and solid OCpetro). A Re mass balance across the Rio Madre de Dios shows that 46% of OCpetro oxidation takes place in the Andes, 14% in the foreland-lowlands, and 40% in the Andean-fed floodplains. This doubling of OCpetro oxidation flux downstream of the Andes demonstrates that, when present, floodplains can greatly increase OCpetro oxidation and CO2 release.

Race and ethnic minority, local pollution, and COVID-19 deaths in Texas.

The costs of COVID-19 are extensive, and, like the fallout of most health and environmental crises in the US, there is growing evidence that these costs weigh disproportionately on communities of color. We investigated whether county-level racial composition and fine particulate pollution (PM2.5) are indicators for COVID-19 incidence and death rates in the state of Texas. Using county-level data, we ran linear regressions of percent minority as well as historic 2000-2016 PM2.5 levels against COVID-19 cases and deaths per capita. We found that a county's percent minority racial composition, defined as the percentage of population that identifies as Black or Hispanic, highly correlates with COVID-19 case and death rates. Using Value-of-Statistical-Life calculations, we found that economic costs from COVID-19 deaths fall more heavily on Black and Hispanic residents in Harris County, the most populous county in Texas. We found no consistent evidence or significant correlations between historic county-average PM2.5 concentration and COVID-19 incidence or death. Our findings suggest that public health and economic aid policy should consider the racially-segregated burden of disease to better mitigate costs and support equity for the duration and aftermath of health crises.

The kinetics of siderophore-mediated olivine dissolution.

Silicate minerals represent an important reservoir of nutrients at Earth's surface and a source of alkalinity that modulates long-term geochemical cycles. Due to the slow kinetics of primary silicate mineral dissolution and the potential for nutrient immobilization by secondary mineral precipitation, the bioavailability of many silicate-bound nutrients may be limited by the ability of micro-organisms to actively scavenge these nutrients via redox alteration and/or organic ligand production. In this study, we use targeted laboratory experiments with olivine and the siderophore deferoxamine B to explore how microbial ligands affect nutrient (Fe) release and the overall rate of mineral dissolution. Our results show that olivine dissolution rates are accelerated in the presence of micromolar concentrations of deferoxamine B. Based on the non-linear decrease in rates with time and formation of a Fe3+ -ligand complex, we attribute this acceleration in dissolution rates to the removal of an oxidized surface coating that forms during the dissolution of olivine at circum-neutral pH in the presence of O2 and the absence of organic ligands. While increases in dissolution rates are observed with micromolar concentrations of siderophores, it remains unclear whether such conditions could be realized in natural environments due to the strong physiological control on microbial siderophore production. So, to contextualize our experimental results, we also developed a feedback model, which considers how microbial physiology and ligand-promoted mineral dissolution kinetics interact to control the extent of biotic enhancement of dissolution rates expected for different environments. The model predicts that physiological feedbacks severely limit the extent to which dissolution rates may be enhanced by microbial activity, though the rate of physical transport modulates this limitation.

Glacial weathering, sulfide oxidation, and global carbon cycle feedbacks.

Connections between glaciation, chemical weathering, and the global carbon cycle could steer the evolution of global climate over geologic time, but even the directionality of feedbacks in this system remain to be resolved. Here, we assemble a compilation of hydrochemical data from glacierized catchments, use this data to evaluate the dominant chemical reactions associated with glacial weathering, and explore the implications for long-term geochemical cycles. Weathering yields from catchments in our compilation are higher than the global average, which results, in part, from higher runoff in glaciated catchments. Our analysis supports the theory that glacial weathering is characterized predominantly by weathering of trace sulfide and carbonate minerals. To evaluate the effects of glacial weathering on atmospheric pCO2, we use a solute mixing model to predict the ratio of alkalinity to dissolved inorganic carbon (DIC) generated by weathering reactions. Compared with nonglacial weathering, glacial weathering is more likely to yield alkalinity/DIC ratios less than 1, suggesting that enhanced sulfide oxidation as a result of glaciation may act as a source of CO2 to the atmosphere. Back-of-the-envelope calculations indicate that oxidative fluxes could change ocean-atmosphere CO2 equilibrium by 25 ppm or more over 10 ky. Over longer timescales, CO2 release could act as a negative feedback, limiting progress of glaciation, dependent on lithology and the concentration of atmospheric O2 Future work on glaciation-weathering-carbon cycle feedbacks should consider weathering of trace sulfide minerals in addition to silicate minerals.

Sulphide oxidation and carbonate dissolution as a source of CO2 over geological timescales.

The observed stability of Earth's climate over millions of years is thought to depend on the rate of carbon dioxide (CO2) release from the solid Earth being balanced by the rate of CO2 consumption by silicate weathering. During the Cenozoic era, spanning approximately the past 66 million years, the concurrent increases in the marine isotopic ratios of strontium, osmium and lithium suggest that extensive uplift of mountain ranges may have stimulated CO2 consumption by silicate weathering, but reconstructions of sea-floor spreading do not indicate a corresponding increase in CO2 inputs from volcanic degassing. The resulting imbalance would have depleted the atmosphere of all CO2 within a few million years. As a result, reconciling Cenozoic isotopic records with the need for mass balance in the long-term carbon cycle has been a major and unresolved challenge in geochemistry and Earth history. Here we show that enhanced sulphide oxidation coupled to carbonate dissolution can provide a transient source of CO2 to Earth's atmosphere that is relevant over geological timescales. Like drawdown by means of silicate weathering, this source is probably enhanced by tectonic uplift, and so may have contributed to the relative stability of the partial pressure of atmospheric CO2 during the Cenozoic. A variety of other hypotheses have been put forward to explain the 'Cenozoic isotope-weathering paradox', and the evolution of the carbon cycle probably depended on multiple processes. However, an important role for sulphide oxidation coupled to carbonate dissolution is consistent with records of radiogenic isotopes, atmospheric CO2 partial pressure and the evolution of the Cenozoic sulphur cycle, and could be accounted for by geologically reasonable changes in the global dioxygen cycle, suggesting that this CO2 source should be considered a potentially important but as yet generally unrecognized component of the long-term carbon cycle.