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Abstract Glycerol dialkyl glycerol tetraethers (GDGTs) are a group of membrane spanning lipids produced by both Archaea and Bacteria. Branched GDGTs (brGDGTs) are a class of these tetraether lipids known to be produced by certain bacteria and are commonly found in terrestrial environments. Due to their environmental ubiquity, high preservation potential, and role in membrane adaptation, brGDGTs form the basis of many widely employed paleoenvironmental proxies. The tetramethylated brGDGT Ia is the most commonly reported branched tetraether in culturedAcidobacteriaand is a key component of brGDGT‐based temperature indices. Herein, we report the first total synthesis of brGDGT Ia, thereby elucidating the relative configuration of the methyl branches as syn. We further demonstrate that VCD spectroscopy is a suitable tool to determine the absolute configuration of these cryptochiral compounds, a method waiting to be applied to the natural lipid, but currently hampered by its limited availability. 

Sphingolipids have long been of interest to the scientific community for their roles in eukaryotic cell structuring and disease pathology. Less is known about the occurrence and function of these diverse compounds in the bacterial domain of life, with most studies on bacterial sphingolipids focused on eukaryotic disease research and host-pathogen or host-symbiont interactions. Thus, bacterial contributions to environmental sphingolipid pools are poorly understood and the function of these lipids outside of pathogenicity remains largely unexplored. This report marks the first instance of sphingolipid production in a member of the phylum Acidobacteria, a globally ubiquitous phylum of soil bacteria. The occurrence of core- and intact-ceramides is reported for the AcidobacteriumSolibacter usitatusunder various environmentally relevant conditions. Shifts in the production of ceramides across temperature, pH, and oxygen gradients in this organism suggest that these compounds play a role in the physiological adaptation to environmental fluctuations. Additionally, the genetic basis of bacterial ceramide biosynthesis in this species is assessed and used to explore the potential for ceramide biosynthesis across the bacterial domain of life. The extent of the biosynthetic potential for Acidobacteria to produce ceramides coupled to the abundance of their genes in soil metagenomes suggests that soil sphingolipids should not be solely attributed to eukaryotic production. 

Abstract. As global warming progresses, changes in high-latitude precipitation are expected to impart long-lasting impacts on Earth systems, including glacier mass balance and ecosystem structures. Reconstructing past changes in high-latitude precipitation and hydroclimate from networks of continuous lake records offers one way to improve forecasts of precipitation and precipitation–evaporation balances, but these reconstructions are currently hindered by the incomplete understanding of controls on lake and soil water isotopes. Here, we study the distribution of modern water isotopes in Icelandic lakes, streams, and surface soils collected in 2002, 2003, 2004, 2014, 2019, and 2020 to understand the geographic, geomorphic, and environmental controls on their regional and interannual variability. We find that lake water isotopes in open-basin (through-flowing) lakes reflect local precipitation, with biases toward the cold season, particularly in lakes with sub-annual residence times. Closed-basin lakes have water isotope and deuterium excess values consistent with evaporative enrichment. Interannual and seasonal variabilities of lake water isotopes at repeatedly sampled sites are consistent with instrumental records of winter snowfall; summer relative humidity; and atmospheric circulation patterns, such as the North Atlantic Oscillation. Summer surface soil water isotopes span the entire range of seasonal precipitation values in Iceland and appear to be consistently overprinted by evaporative enrichment, which can occur throughout the year, although the sampling depths were shallower than rooting depths for many plant types. This dataset provides new insight into the functionality of water isotopes in Icelandic environments and offers renewed possibilities for optimized site selection and proxy interpretation in future paleohydrological studies on this North Atlantic outpost. 

Abstract. Soil water isotope datasets are useful for understanding connections between the hydrosphere, atmosphere, biosphere, and geosphere. However, they have been underproduced because of the technical challenges associated with collecting those datasets. Here, we present the results of testing and automation of the Soil Water Isotope Storage System (SWISS). The unique innovation of the SWISS is that we are able to automatically collect water vapor from the critical zone at a regular time interval and then store that water vapor until it can be measured back in a laboratory setting. Through a series of quality assurance and quality control tests, we tested whether the SWISS is resistant to both atmospheric intrusion and leaking in both laboratory and field settings. We assessed the accuracy and precision of the SWISS through a series of experiments in which water vapor of known composition was introduced into the flasks, stored for 14 d, and then measured. From these experiments, after applying an offset correction to report our values relative to Vienna Standard Mean Ocean Water (VSMOW), we assess the precision of the SWISS to be ±0.9 ‰ and ±3.7 ‰ for δ18O and δ2H, respectively. We deployed three SWISS units at three different field sites to demonstrate that the SWISS stores water vapor reliably enough that we are able to differentiate dynamics both between the sites as well within a single soil column. Overall, we demonstrate that the SWISS retains the stable isotope composition of soil water vapor for long enough to allow researchers to address a wide range of ecohydrologic questions. 

Stable isotope data have made pivotal contributions to nearly every discipline of the physical and natural sciences. As the generation and application of stable isotope data continues to grow exponentially, so does the need for a unifying data repository to improve accessibility and promote collaborative engagement. This paper provides an overview of the design, development, and implementation of IsoBank (www.isobank.org), a community-driven initiative to create an open-access repository for stable isotope data implemented online in 2021. A central goal of IsoBank is to provide a web-accessible database supporting interdisciplinary stable isotope research and educational opportunities. To achieve this goal, we convened a multi-disciplinary group of over 40 analytical experts, stable isotope researchers, database managers, and web developers to collaboratively design the database. This paper outlines the main features of IsoBank and provides a focused description of the core metadata structure. We present plans for future database and tool development and engagement across the scientific community. These efforts will help facilitate interdisciplinary collaboration among the many users of stable isotopic data while also offering useful data resources and standardization of metadata reporting across eco-geoinformatics landscapes. 

Distributions of branched glycerol dialkyl glycerol tetraethers (brGDGTs) are frequently employed for reconstructing terrestrial paleotemperatures from lake sediment archives. Although brGDGTs are globally ubiquitous, the microbial producers of these membrane lipids remain unknown, precluding a full understanding of the ways in which environmental parameters control their production and distribution. Here, we advance this understanding in three ways. First, we present 43 new high-latitude lake sites characterized by low mean annual air temperatures (MATs) and high seasonality, filling an important gap in the global dataset. Second, we introduce a new approach for analyzing brGDGT data in which compound fractional abundances (FAs) are calculated within structural groups based on methylation number, methylation position, and cyclization number. Finally, we perform linear and nonlinear regressions of the resulting FAs against a suite of environmental parameters in a compiled global lake sediment dataset (n = 182). We find that our approach deconvolves temperature, conductivity, and pH trends in brGDGTs without increasing calibration errors from the standard approach. We also find that it reveals novel patterns in brGDGT distributions and provides a methodology for investigating the biological underpinnings of their structural diversity. Warm-season temperature indices outperformed MAT in our regressions, with Months Above Freezing yielding the highest-performing model (adjusted R2 = 0.91, RMSE = 1.97 °C, n = 182). The natural logarithm of conductivity had the second-strongest relationship to brGDGT distributions (adjusted R2 = 0.83, RMSE = 0.66, n = 143), notably outperforming pH in our dataset (adjusted R2 = 0.73, RMSE = 0.57, n = 154) and providing a potential new proxy for paleohydrology applications. We recommend these calibrations for use in lake sediments globally, including at high latitudes, and detail the advantages and disadvantages of each. 

Abstract Background Lagoons are common along coastlines worldwide and are important for biogeochemical element cycling, coastal biodiversity, coastal erosion protection and blue carbon sequestration. These ecosystems are frequently disturbed by weather, tides, and human activities. Here, we investigated a shallow lagoon in New England. The brackish ecosystem releases hydrogen sulfide particularly upon physical disturbance, causing blooms of anoxygenic sulfur-oxidizing phototrophs. To study the habitat, microbial community structure, assembly and function we carried out in situ experiments investigating the bloom dynamics over time. Results Phototrophic microbial mats and permanently or seasonally stratified water columns commonly contain multiple phototrophic lineages that coexist based on their light, oxygen and nutrient preferences. We describe similar coexistence patterns and ecological niches in estuarine planktonic blooms of phototrophs. The water column showed steep gradients of oxygen, pH, sulfate, sulfide, and salinity. The upper part of the bloom was dominated by aerobic phototrophic Cyanobacteria , the middle and lower parts by anoxygenic purple sulfur bacteria ( Chromatiales ) and green sulfur bacteria ( Chlorobiales ), respectively. We show stable coexistence of phototrophic lineages from five bacterial phyla and present metagenome-assembled genomes (MAGs) of two uncultured Chlorobaculum and Prosthecochloris species. In addition to genes involved in sulfur oxidation and photopigment biosynthesis the MAGs contained complete operons encoding for terminal oxidases. The metagenomes also contained numerous contigs affiliating with Microviridae viruses, potentially affecting Chlorobi . Our data suggest a short sulfur cycle within the bloom in which elemental sulfur produced by sulfide-oxidizing phototrophs is most likely reduced back to sulfide by Desulfuromonas sp . Conclusions The release of sulfide creates a habitat selecting for anoxygenic sulfur-oxidizing phototrophs, which in turn create a niche for sulfur reducers. Strong syntrophism between these guilds apparently drives a short sulfur cycle that may explain the rapid development of the bloom. The fast growth and high biomass yield of Chlorobi -affiliated organisms implies that the studied lineages of green sulfur bacteria can thrive in hypoxic habitats. This oxygen tolerance is corroborated by oxidases found in MAGs of uncultured Chlorobi . The findings improve our understanding of the ecology and ecophysiology of anoxygenic phototrophs and their impact on the coupled biogeochemical cycles of sulfur and carbon.