Abstract Protein metal-binding sites support essential biological functions shaped by protein fold, subunit interactions, and cofactor chemistry. Because these sites encode both biochemical function and environmental constraint, they offer a route to connect protein evolution with changes in Earth’s surface environment through time. Of particular interest is iron (Fe), the most widely used metal in biology and a cofactor central to both anaerobic and aerobic metabolism. Here, we systematically compare the immediate chemical environments of functionally essential Fe-binding sites in three-dimensional protein structures to test whether Fe coordination spheres differ across oxygen contexts. Using a curated dataset of experimentally determined structures, we identify a clear shift in the local chemistry of Fe-binding environments from anaerobic to aerobic proteins. Aerobic Fe sites are significantly more hydrophilic than anaerobic ones, and amino-acid composition analyses show reduced cysteine use in aerobic Fe-binding neighborhoods. These patterns suggest that as Earth’s surface environments became more oxygenated, proteins retained Fe as a core redox metal while reconfiguring local coordination chemistry in ways less vulnerable to oxidative damage. More broadly, this study introduces and applies the Coordination Sphere Analysis and Comparison (CSAC) workflow, an open and archived Python workflow for extracting local metal-binding environments from structure datasets, providing a framework for linking metalloprotein structure to evolutionary and geobiological transitions across Earth history.

Planet Earth has evolved from an entirely anoxic planet with possibly a different tectonic regime to the oxygenated world with horizontal plate tectonics that we know today. For most of this time, Earth has been inhabited by a purely microbial biosphere albeit with seemingly increasing complexity over time. A rich record of this geobiological evolution over most of Earth's history provides insights into the remote detectability of microbial life under a variety of planetary conditions. We leverage Earth's geobiological record with the aim of a) illustrating the current state of knowledge and key knowledge gaps about the early Earth as a reference point in exoplanet science research; b) compiling biotic and abiotic mechanisms that controlled the evolution of the atmosphere over time; and c) reviewing current constraints on the detectability of Earth's early biosphere with state-of-the-art telescope technology. We highlight that life may have originated on a planet with a different tectonic regime and strong hydrothermal activity, and under these conditions, biogenic CH_4 gas was perhaps the most detectable atmospheric biosignature. Oxygenic photosynthesis, which is responsible for essentially all O_2 gas in the modern atmosphere, appears to have emerged concurrently with the establishment of modern plate tectonics and the continental crust, but O_2 accumulation to modern levels only occurred late in Earth's history, perhaps tied to the rise of land plants. Nutrient limitation in anoxic oceans, promoted by hydrothermal Fe = fluxes, may have limited biological productivity and O_2 production. N_2O is an alternative biosignature that was perhaps significant on the redox-stratified Proterozoic Earth. We conclude that the detectability of atmospheric biosignatures on Earth was not only dependent on biological evolution but also strongly controlled by the evolving tectonic context.

Metaproteomics is an increasingly popular methodology that provides information regarding the metabolic functions of specific microbial taxa and has potential for contributing to ocean ecology and biogeochemical studies. A blinded multi-laboratory intercomparison was conducted to assess comparability and reproducibility of taxonomic and functional results and their sensitivity to methodological variables. Euphotic zone samples from the Bermuda Atlantic Time-series Study (BATS) in the North Atlantic Ocean collected by in situ pumps and the autonomous underwater vehicle (AUV) Clio were distributed with a paired metagenome, and one-dimensional (1D) liquid chromatographic data-dependent acquisition mass spectrometry analysis was stipulated. Analysis of mass spectra from seven laboratories through a common bioinformatic pipeline identified a shared set of 1056 proteins from 1395 shared peptide constituents. Quantitative analyses showed good reproducibility: pairwise regressions of spectral counts between laboratories yielded R2 values averaged 0.62 +/- 0.11, and a S & oslash;rensen similarity analysis of the top 1000 proteins revealed 70 %-80 % similarity between laboratory groups. Taxonomic and functional assignments showed good coherence between technical replicates and different laboratories. A bioinformatic intercomparison study, involving 10 laboratories using eight software packages, successfully identified thousands of peptides within the complex metaproteomic datasets, demonstrating the utility of these software tools for ocean metaproteomic research. Lessons learned and potential improvements in methods were described. Future efforts could examine reproducibility in deeper metaproteomes, examine accuracy in targeted absolute quantitation analyses, and develop standards for data output formats to improve data interoperability. Together, these results demonstrate the reproducibility of metaproteomic analyses and their suitability for microbial oceanography research, including integration into global-scale ocean surveys and ocean biogeochemical models.

Sulfur (S) is a central element in global biogeochemical cycling and Earth's redox evolution. Minerals that contain S are an important record of local environmental conditions at the time of their formation based on chemical speciation and redox. However, the oxidation state of S for hundreds of different S-containing minerals and thousands of S-containing mineral localities is unknown, largely sulfides and sulfosalts, and the redox state alone does not fully capture mineral chemistry diversity, thus limiting understanding of S redox evolution. Here, we use mineral chemistry network analysis and the weighted Mineral Element Electronegativity Coefficient of Variation (wMEE(CV)) metric to investigate the element interactions and localities of S-containing minerals from the Mineral Evolution Database (MED) to infer the redox state of S in minerals where the redox state is unknown (S-U). Louvain community detection of the S mineral chemistry redox network reveals that there are three main network communities that are separated by redox state. The S6+ community includes minerals that contain the S6+ redox state and a small number of S4+ and S2+ minerals, the S2- community includes S2--containing minerals, and the S-U community includes minerals in which the redox state of S is unknown. The wMEE(CV) values of the S-U community closely overlap with the wMEE(CV) values of the S2- community, and do not overlap with the wMEE(CV) values of the S6+ community, indicating the S-U community minerals contain predominately reduced S. Assuming that S-U community minerals contain reduced S, as supported by their network chemical associations and wMEE(CV) values, then reduced S-containing minerals make up approximately 81 % of S-containing mineral localities in the S mineral chemistry network, even though the majority of all mineral localities (S-containing and non-S-containing) are oxygen (O)-containing minerals. Additionally, reduced S-containing minerals make up the majority (similar to 75 %) of all non-O containing mineral localities in the MED, representing the importance of reduced S as an electron source and substrate in the evolution of microbial metabolic networks. The range wMEE(CV) values of S6+ community minerals expands through time due primarily to formation of chemically diverse sulfate minerals, coinciding with crustal oxidation from the late Proterozoic to Phanerozoic and the expansion of the marine sulfate reservoir. The intersection of shared constituent elements among reduced and oxidized S in the mineral chemistry network represents redox convergence of weathered S in the geosphere that was crucial in the formation of natural resource deposits and the evolution of biogeochemical cycles.

Abstract Uranium (U) is an important global energy resource and a redox sensitive trace element that reflects changing environmental conditions and geochemical cycling. The redox evolution of U mineral chemistry can be interrogated to understand the formation and distribution of U deposits and the redox processes involved in U geochemistry throughout Earth history. In this study, geochemical modeling using thermodynamic data, and mineral chemistry network analysis are used to investigate U geochemistry and deposition through time. The number of U6+ mineral localities surpasses the number of U4+ mineral localities in the Paleoproterozoic. Moreover, the number of sedimentary U6+ mineral localities increases earlier in the Phanerozoic than the number of U4+ sedimentary mineral localities, likely due to the necessity of sufficient sedimentary organic matter to reduce U6+–U4+. Indeed, modeling calculations indicate that increased oxidative weathering due to surface oxygenation limited U4+ uraninite (UO2) formation from weathered granite and basalt. Louvain network community detection shows that U6+ forms minerals with many more shared elements and redox states than U4+. The range of weighted Mineral Element Electronegativity Coefficient of Variation (wMEECV) values of U6+ minerals increases through time, particularly during the Phanerozoic. Conversely, the range of wMEECV values of U4+ minerals is consistent through time due to the relative abundance of uraninite, coffinite, and brannerite. The late oxidation and formation of U6+ minerals compared to S6+ minerals illustrates the importance of the development of land plants, organic matter deposition, and redox‐controlled U deposition from ground water in continental sediments during this time‐period.

The mineral record contains chemical signatures that reflect the evolving redox conditions of Earth's crust, and reveal trends in the bioavailability of life's critical elements. In particular, shifting redox states of transition metal elements that are used as co-factors by enzymes across all domains of life can be tracked in preserved mineral chemistry. The transition metal iron (Fe) is one of the most abundant elements in Earth's core, mantle, and crust, and is commonly a major constituent of rock-forming minerals. Additionally, Fe is the most widely used metal in biology, and Earth's redox history has profoundly impacted the chemical speciation and availability of Fe in aqueous systems. The diverse mineral chemistry of Fe can therefore reveal new insights into the redox evolution of Earth's crust and subsequent biological impacts. Here, we apply a new mineral chemistry network analysis platform, dragon, to investigate the mineral chemistry of iron (Fe) over geologic-time. We present bipartite network graphs of iron minerals linked to their constituent elements or ions for several geological time intervals. These graphs illustrate the increasing importance of oxygen (O) abundance in the atmosphere from the Paleoarchean to the Mesoproterozoic in regard to the the emergence of new Fe minerals, as well as the influence of free O on trends in element electronegativity in mineral formation and electron transfer processes. The proportion of oxygen containing Fe minerals had the sharpest increase during the time periods of the Kenorland and Columbia supercontinent assembly events. Indeed, the rise of O is associated with O becoming more centralized in the network as well as with an increase through time in the number of Fe minerals containing combinations of high and low electronegativity elements. The importance of oxygen in the expansion of Fe mineral chemical diversity, and its influence on the bioavailability of Fe in the environment, is illustrated clearly in the Fe mineral chemistry network.

Earth surface redox conditions are intimately linked to the co-evolution of the geosphere and biosphere. Minerals provide a record of Earth's evolving surface and interior chemistry in geologic time due to many different processes (e.g. tectonic, volcanic, sedimentary, oxidative, etc.). Here, we show how the bipartite network of minerals and their shared constituent elements expanded and evolved over geologic time. To further investigate network expansion over time, we derive and apply a novel metric (weighted mineral element electronegativity coefficient of variation; wMEECV) to quantify intra-mineral electronegativity variation with respect to redox. We find that element electronegativity and hard soft acid base (HSAB) properties are central factors in mineral redox chemistry under a wide range of conditions. Global shifts in mineral element electronegativity and HSAB associations represented by wMEECV changes at 1.8 and 0.6 billion years ago align with decreased continental elevation followed by the transition from the intermediate ocean and glaciation eras to post-glaciation, increased atmospheric oxygen in the Phanerozoic, and enhanced continental weathering. Consequently, network analysis of mineral element electronegativity and HSAB properties reveal that orogenic activity, evolving redox state of the mantle, planetary oxygenation, and climatic transitions directly impacted the evolving chemical complexity of Earth's crust.

Agricultural data are crucial to many aspects of production, commerce, and research involved in feeding the global community. However, in most agricultural research disciplines standard best practices for data management and publication do not exist. Here we propose a set of best practices in the areas of peer review, minimal dataset development, data repositories, citizen science initiatives, and support for best data management. We illustrate some of these best practices with a case study in dairy agroecosystems research. While many common, and increasingly disparate data management and publication practices are entrenched in agricultural disciplines, opportunities are readily available for promoting and adopting best practices that better enable and enhance data-intensive agricultural research and production.

The geosphere of primitive Earth was the source of life's essential building blocks, and the geochemical interactions among chemical elements can inform the origins of biological roles of each element. Minerals provide a record of the fundamental properties that each chemical element contributes to crustal composition, evolution, and subsequent biological utilization. In this study, we investigate correlations between the mineral species and bulk crustal composition of each chemical element. There are statistically significant correlations between the number of elements that each element forms minerals with (#-mineral-elements) and the log of the number of mineral species that each element occurs in, and between #-mineral-elements and the log of the number of mineral localities of that element. There is a lesser correlation between the log of the crustal percentage of each element and #-mineral-elements. In the crustal percentage vs. #-mineral-elements plot, positive outliers have either important biological roles (S, Cu) or toxic biological impacts (Pb, As), while negative outliers have no biological importance (Sc, Ga, Br, Yb). In particular, S is an important bridge element between organic (e.g., amino acids) and inorganic (metal cofactors) biological components. While C and N rarely form minerals together, the two elements commonly form minerals with H, which coincides with the role of H as an electron donor/carrier in biological nitrogen and carbon fixation. Both abundant crustal percentage vs. #-mineral-elements insiders (elements that follow the correlation) and less abundant outsiders (positive outliers from the correlation) have important biological functions as essential structural elements and catalytic cofactors.

The flow of energy and elements between the geosphere and biosphere can be traced through the changing redox chemistry of Earth’s surface. Deep-time trends in the mineral record, including mineral age and elemental composition, reveal a dynamic history of changing redox states and chemical speciation. We present a user-friendly exploratory network analysis platform called dragon (Deep-time Redox Analysis of the Geobiology Ontology Network) to facilitate investigation of the expanding redox chemical network preserved in the mineral record throughout Earth’s history and beyond. The utility of dragon is demonstrated by showing that as oxygen became more central in the Fe mineral chemistry network, the number of combinations of high and low electronegativity elements increased in Fe minerals through time, thus illustrating the importance of oxygen in expanding the chemical diversity of Fe minerals and influencing the bioavailability of Fe in the environment. Dragon opens up many possibilities for the investigation chemical linkages between minerals and biology.

Transition metal cofactors are crucial for many biological processes. Despite being primarily considered to be toxic, the transition metal cadmium (Cd) was discovered to be a substitute cofactor for zinc (Zn) in photosynthetic carbon fixation pathways of marine diatoms. However, it is not known how conditions in the geosphere impacted Cd availability and its incorporation as an alternative metal cofactor for phytoplankton. We employed mineral chemistry network analysis to investigate which geochemical factors may have influenced the availability of Cd and Zn during the putative time period that the alternative Cd‐based pathway evolved. Our results show that Zn minerals are more chemically diverse than are Cd minerals, but Zn‐ and Cd‐containing minerals have similar network centrality values when specifically considering sulfur (S)‐containing species. Cadmium and Zn sulfides are the most common Cd‐ and Zn‐containing mineral species over the past 500 million years. In particular, the Cd and Zn sulfides, respectively greenockite and sphalerite, were highly abundant during this time period. Furthermore, S‐containing Cd and Zn minerals are commonly co‐located in geologic time, allowing them to be weathered and transported to the ocean in tandem, rather than from separate sources. We suggest that the simultaneous weathering of Cd and Zn sulfides allowed for Cd to be a bioavailable direct substitute for Zn in protein complexes during periods of Zn depletion. The biogeochemical cycles of Zn and Cd exemplify the importance of the coevolution of the geosphere and biosphere in shaping primary production in the modern ocean.

Intact polar membrane lipids (IPLs) are the building blocks of all cell membranes. There is a wide range of phosphorus-free IPL structures, including amino acid containing IPLs, that can be taxonomically specific. Trimethylornithine membrane lipids (TMOs) were discovered in northern wetland Planctomycete species that were isolated and described in the last decade. The trimethylated terminal nitrogen moiety of the ornithine amino acid in the TMO structure gives the lipid a charged polar head group, similar to certain phospholipids. Since their discovery, TMOs have been identified in various other recently described northern latitude Planctomycete species, and in diverse environments including tundra soil, a boreal eutrophic lake, meso-oligotrophic lakes, and hot springs. The majority of environments or enrichment cultures in which TMOs have been observed include predominately heterotrophic microbial communities involved in the degradation of recalcitrant material and/or low oxygen methanogenic conditions at primarily northern latitudes. Other ecosystems occupied with microbial communities that possess similar metabolic pathways, such as tropical peatlands or coastal salt marshes, may include TMO producing Planctomycetes as well, further allowing these lipids to potentially be used to understand microbial community responses to environmental change in a wide range of systems. The occurrence of TMOs in hot springs indicates that these unique lipids could have broad environmental distribution with different specialized functions. Opportunities also exist to investigate the application of TMOs in microbiome studies, including forensic necrobiomes. Further environmental and microbiome lipidomics research involving TMOs will help reveal the evolution, functions, and applications of these unique membrane lipids.

The incorporation of metal cofactors into protein active sites and/or active regions expanded the network of microbial metabolism during the Archean eon. The bioavailability of crucial metal cofactors is largely influenced by earth surface redox state, which impacted the timing of metabolic evolution. Vanadium (V) is a unique element in geo-bio-coevolution due to its complex redox chemistry and specific biological functions. Thus, the extent of microbial V utilization potentially represents an important link between the geo- and biospheres in deep time. In this study, we used geochemical modeling and network analysis to investigate the availability and chemical speciation of V in the environment, and the emergence and changing chemistry of V-containing minerals throughout earth history. The redox state of V shifted from a more reduced V(III) state in Archean aqueous geochemistry and mineralogy to more oxidized V(IV) and V(V) states in the Proterozoic and Phanerozoic. The weathering of vanadium sulfides, vanadium alkali metal minerals, and vanadium alkaline earth metal minerals were potential sources of V to the environment and microbial utilization. Community detection analysis of the expanding V mineral network indicates tectonic and redox influence on the distribution of V mineral-forming elements. In reducing environments, energetic drivers existed for V to potentially be involved in early nitrogen fixation, while in oxidizing environments vanadate ( VO43-]]> ) could have acted as a metabolic electron acceptor and phosphate mimicking enzyme inhibitor. The coevolving chemical speciation and biological functions of V due to earth's changing surface redox conditions demonstrate the crucial links between the geosphere and biosphere in the evolution of metabolic electron transfer pathways and biogeochemical cycles from the Archean to Phanerozoic.

The flow of energy and elements between the geosphere and biosphere can be traced through changing redox chemistry of Earth's surface. Deep-time trends in the mineral record, including mineral age and elemental composition, reveal a dynamic history of changing redox states and chemical speciation. We present a user-friendly exploratory network analysis platform called dragon (Deep-time Redox Analysis of the Geobiology Ontology Network) to facilitate investigation of the expanding redox chemical network preserved in the mineral record throughout Earth's history and beyond. Given a user-indicated focal element or set of focal elements, dragon constructs interactive bipartite networks of minerals and their constituent elements over a specified range in geologic-time using information from the Mineral Evolution Database (https://rruff.info/evolution/). Written in the open-source language R as a Shiny application, dragon launches a browser-based dashboard to explore mineral evolution in deep-time. We demonstrate dragon's utility through examining the mineral chemistry of lithium over deep-time. dragon is freely available from CRAN under a GPL-3 License, with source code and documentation hosted at https://github.com/sjspielman/dragon.

This chapter highlights the use of data-driven discovery to address remaining gaps in our understanding of deep carbon.

Ocean metaproteomics is an emerging field enabling discoveries about marine microbial communities and their impact on global biogeochemical processes. Recent ocean metaproteomic studies have provided insight into microbial nutrient transport, colimitation of carbon fixation, the metabolism of microbial biofilms, and dynamics of carbon flux in marine ecosystems. Future methodological developments could provide new capabilities such as characterizing long-term ecosystem changes, biogeochemical reaction rates, and in situ stoichiometries. Yet challenges remain for ocean metaproteomics due to the great biological diversity that produces highly complex mass spectra, as well as the difficulty in obtaining and working with environmental samples. This review summarizes the progress and challenges facing ocean metaproteomic scientists and proposes best practices for data sharing of ocean metaproteomic data sets, including the data types and metadata needed to enable intercomparisons of protein distributions and annotations that could foster global ocean metaproteomic capabilities.