Diversity begets diversity: chemical and microbial diversity co-vary in freshwater to influence ecosystem functioning

Invisible to the naked eye lies a tremendous diversity of organic molecules and organisms that make major contributions to important biogeochemical cycles. However, how the diversity and composition of these two communities are inter-linked remains poorly characterised in freshwaters, despite the potential for chemical and microbial diversity to promote one another. Here we exploited gradients in chemodiversity within a common microbial pool to test how chemical and biological diversity covary and characterized the implications for ecosystem functioning. We found that both chemodiversity and genes associated with organic matter decomposition increased as more plant litterfall accumulated in experimental lake sediments, consistent with scenarios of future environmental change. Chemical and microbial diversity were also positively correlated, with dissolved organic matter having stronger effects on microbes than vice versa. Under our experimental scenarios that increased sediment organic matter from 5 to 25% or darkened overlying waters by 2.5-times, the resulting increases in chemodiversity could increase greenhouse gas concentrations in lake sediments by an average of 1.5- to 2.7-times, when all the other effects of litterfall and water color were considered. Our results open a major new avenue for research in aquatic ecosystems by exposing connections between chemical and microbial diversity and their implications for the global carbon cycle in greater detail than ever before.Funding came from a Natural Environment Research Council grant NE/L006561/1 to AJT and a Gates Cambridge Scholarship to AF

Drivers of organic molecular signatures in the Amazon River

Author Posting. © American Geophysical Union, 2021. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 35(6), (2021): e2021GB006938, https://doi.org/10.1029/2021GB006938.As climate-driven El Niño Southern Oscillation (ENSO) events are projected to increase in frequency and severity, much attention has focused on impacts regarding ecosystem productivity and carbon balance in Amazonian rainforests, with comparatively little attention given to carbon dynamics in fluvial ecosystems. In this study, we compared the wet 2012 La Niña period to the following normal hydrologic period in the Amazon River. Elevated water flux during the La Niña period was accompanied by dilution of inorganic ion concentrations. Furthermore, the La Niña period exported 2.77 Tg C yr−1 more dissolved organic carbon (DOC) than the normal period, an increase greater than the annual amount of DOC exported by the Mississippi River. Using ultra-high-resolution mass spectrometry, we detected both intra- and interannual differences in dissolved organic matter (DOM) composition, revealing that DOM exported during the dry season and the normal period was more aliphatic, whereas compounds in the wet season and following the La Niña event were more aromatic, with ramifications for its environmental role. Furthermore, as this study has the highest temporal resolution DOM compositional data for the Amazon River to-date we showed that compounds were highly correlated to a 6-month lag in Pacific temperature and pressure anomalies, suggesting that ENSO events could impact DOM composition exported to the Atlantic Ocean. Therefore, as ENSO events increase in frequency and severity into the future it seems likely that there will be downstream consequences for the fate of Amazon Basin-derived DOM concurrent with lag periods as described here.This work was partially supported by National Science Foundation grant OCE-1464396 to Robert G. M. Spencer and funding from the Harbourton Foundation to Robert G. M. Spencer, R. Max Holmes, and Bernhard Peucker-Ehrenbrink.2021-12-1

An international laboratory comparison of dissolved organic matter composition by high resolution mass spectrometry: Are we getting the same answer?

High-resolution mass spectrometry (HRMS) has become a vital tool for dissolved organic matter (DOM) characterization. The upward trend in HRMS analysis of DOM presents challenges in data comparison and interpretation among laboratories operating instruments with differing performance and user operating conditions. It is therefore essential that the community establishes metric ranges and compositional trends for data comparison with reference samples so that data can be robustly compared among research groups. To this end, four identically prepared DOM samples were each measured by 16 laboratories, using 17 commercially purchased instruments, using positive-ion and negative-ion mode electrospray ionization (ESI) HRMS analyses. The instruments identified ~1000 common ions in both negative- and positive-ion modes over a wide range of m/z values and chemical space, as determined by van Krevelen diagrams. Calculated metrics of abundance-weighted average indices (H/C, O/C, aromaticity, and m/z) of the commonly detected ions showed that hydrogen saturation and aromaticity were consistent for each reference sample across the instruments, while average mass and oxygenation were more affected by differences in instrument type and settings. In this paper we present 32 metric values for future benchmarking. The metric values were obtained for the four different parameters from four samples in two ionization modes and can be used in future work to evaluate the performance of HRMS instruments

Analytical and computational advances, opportunities, and challenges in marine organic biogeochemistry in an era of "Omics"

© The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Steen, A. D., Kusch, S., Abdulla, H. A., Cakic, N., Coffinet, S., Dittmar, T., Fulton, J. M., Galy, V., Hinrichs, K., Ingalls, A. E., Koch, B. P., Kujawinski, E., Liu, Z., Osterholz, H., Rush, D., Seidel, M., Sepulveda, J., & Wakeham, S. G. Analytical and computational advances, opportunities, and challenges in marine organic biogeochemistry in an era of "Omics". Frontiers in Marine Science, 7, (2020): 718, doi:10.3389/fmars.2020.00718.Advances in sampling tools, analytical methods, and data handling capabilities have been fundamental to the growth of marine organic biogeochemistry over the past four decades. There has always been a strong feedback between analytical advances and scientific advances. However, whereas advances in analytical technology were often the driving force that made possible progress in elucidating the sources and fate of organic matter in the ocean in the first decades of marine organic biogeochemistry, today process-based scientific questions should drive analytical developments. Several paradigm shifts and challenges for the future are related to the intersection between analytical progress and scientific evolution. Untargeted “molecular headhunting” for its own sake is now being subsumed into process-driven targeted investigations that ask new questions and thus require new analytical capabilities. However, there are still major gaps in characterizing the chemical composition and biochemical behavior of macromolecules, as well as in generating reference standards for relevant types of organic matter. Field-based measurements are now routinely complemented by controlled laboratory experiments and in situ rate measurements of key biogeochemical processes. And finally, the multidisciplinary investigations that are becoming more common generate large and diverse datasets, requiring innovative computational tools to integrate often disparate data sets, including better global coverage and mapping. Here, we compile examples of developments in analytical methods that have enabled transformative scientific advances since 2004, and we project some challenges and opportunities in the near future. We believe that addressing these challenges and capitalizing on these opportunities will ensure continued progress in understanding the cycling of organic carbon in the ocean.The Hanse-Wissenschaftskolleg Delmenhorst, Germany, sponsored the “Marine Organic Biogeochemistry” workshop in April 2019, of which this working group report was a part. The workshop was funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) – project number: 422798570. The Geochemical Society provided additional funding for the conference. AS was supported by DOE grant DE-SC0020369

Particulate Organic Matter Mobilization and Transformation Along a Himalayan River Revealed by ESI‐FT‐ICR‐MS

Tracing pathways and transformations of particulate organic carbon from landscape sources to oceanic sinks is commonly done using the isotopic composition or biomarker content of particulate organic matter (POM). However, similarity of source characteristics and complex mixing in rivers often preclude a robust deconvolution of individual contributions. Moreover, these approaches are limited in detecting organic matter transformations. This impedes understanding of carbon cycling. Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT‐ICR‐MS) can simultaneously identify many molecular formulas from mixtures of organic matter, and provide direct information on its compositional variability. Here, we investigate how FT‐ICR‐MS can give insight into POM dynamics on a landscape scale, focusing on the trans‐Himalayan Kali Gandaki River, Nepal. Using molecular information, we identify source tracers in the solvent extractable lipid fraction of riverine POM, finding up to 102 indicative molecular formulas for individual sources. Further, we assess molecular transformations of the lipid fraction of POM during its transfer from litter into topsoil, and onwards into the river. A large number of shared mass formulas and a well‐preserved isoprenoidal patterns suggest efficient incorporation of litter into topsoil. In contrast, we observe a selective loss of mass formulas and a preferential export of formulas with low double bond equivalents and a low nominal oxidation state of carbon after organic matter entrainment in the river. Our results demonstrate the potential of FT‐ICR‐MS for source‐to‐sink studies, allowing detailed organic matter source characterization and discrimination, and tracking of molecular transformations along organic matter pathways spanning different spatial and temporal scales.Plain Language Summary: The transfer of organic matter (OM) by rivers from landscape sources into the ocean followed by its burial in marine sediments is an important carbon sink. Therefore, OM is often traced along this journey using its isotopic or biomarker composition. But contributions of OM sources to river sediments can be difficult to estimate because of similar source characteristics, mixing of many sources and changes of the molecular composition along the way. Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT‐ICR‐MS) is a novel method able to identify many molecular formulas from OM mixtures at once providing direct information about their molecular composition. Here, we investigate how FT‐ICR‐MS contributes to understanding the transport and transformation of particulate OM focusing on a Himalayan river in Nepal. We use the molecular information to identify tracers for individual OM sources in the landscape. We then assess molecular transformations during the transfer of litter into topsoil, and onwards into the river. Our data suggest efficient incorporation of litter into topsoil, but we observe a selective loss of molecular formulas upon entrainment of sources into the river. Our results reveal that FT‐ICR‐MS is useful for detailed source characterization and tracking of molecular transformations along OM pathways.Key Points: Organic matter sourcing and transformations in a Himalayan river studied by FT‐ICR‐MS measurements of solvent extractable lipids. Identification of up to 102 indicator mass formulas for different organic matter sources in the landscape using indicator species analysis. Mass formulas preserved during incorporation of litter into topsoil but selectively lost during entrainment of sources into the river.Helmholtz Impuls und VernetzungsfondGFZ expedition fundinghttp://doi.org/10.5880/GFZ.4.6.2022.00

Transformation of dissolved organic matter by two Indo‐Pacific sponges

Dissolved organic matter (DOM) is the largest organic carbon reservoir in the ocean and an integral component of biogeochemical cycles. The role of free‐living microbes in DOM transformation has been studied thoroughly, whereas little attention has been directed towards the influence of benthic organisms. Sponges are efficient filter feeders and common inhabitants of many benthic communities circumglobally. Here, we investigated how two tropical coral reef sponges shape marine DOM. We compared bacterial abundance, inorganic and organic nutrients in off reef, sponge inhalant, and sponge exhalant water of Melophlus sarasinorum and Rhabdastrella globostellata. DOM and bacterial cells were taken up, and dissolved inorganic nitrogen was released by the two Indo‐Pacific sponges. Both sponge species utilized a common set of 142 of a total of 3040 compounds detected in DOM on a molecular formula level via ultrahigh‐resolution mass spectrometry. In addition, species‐specific uptake was observed, likely due to differences in their associated microbial communities. Overall, the sponges removed presumably semi‐labile and semi‐refractory compounds from the water column, thereby competing with pelagic bacteria. Within minutes, sponge holobionts altered the molecular composition of surface water DOM (inhalant) into a composition similar to deep‐sea DOM (exhalent). The apparent radiocarbon age of DOM increased consistently from off reef and inhalant to exhalant by about 900 14C years for M. sarasinorum. In the pelagic, similar transformations require decades to centuries. Our results stress the dependence of DOM lability definition on the respective environment and illustrate that sponges are hotspots of DOM transformation in the ocean.Helmholtz Institute for Functional Marine Biodiversity at the University of OldenburgMinistry for Science and Culture of Lower Saxony http://dx.doi.org/10.13039/501100010570Carl‐von‐Ossietzky University OldenburgAlfred‐Wegener‐Institute, Helmholtz‐Center for Polar and Marine ResearchVolkswagen Foundation http://dx.doi.org/10.13039/501100001663https://doi.org/10.5061/dryad.m0cfxpp6

Terrigenous dissolved organic matter persists in the energy-limited deep groundwaters of the Fennoscandian Shield

The deep terrestrial biosphere encompasses the life belowthe photosynthesisfueled surface that perseveres in typically nutrient and energy depleted anoxic groundwaters. The composition and cycling of this vast dissolved organic matter (DOM) reservoir relevant to the global carbon cycle remains to be deciphered. Here we show that recent Baltic Sea-influenced to ancient preHolocene saline Fennoscandian Shield deep bedrock fracture waters carried DOM with a strong terrigenous signature and varying contributions from abiotic and biotic processes. Removal of easily degraded carbon at the surfaceto-groundwater transition and corresponding microbial community assembly processes likely resulted in the highly similar DOM signatures across the notably different water types that selected for a core microbiome. In combination with the aliphatic character, depleted d13C signatures in DOM indicated recent microbial production in the oldest, saline groundwater. Our study revealed the persistence of terrestrially-sourced carbon in severely energy limited deep continental groundwaters supporting deep microbial life

Molecular dissolved organic matter composition and environmental parameters from a laboratory incubation study

Dissolved organic matter (DOM) in the oceans constitutes a major carbon pool involved in global biogeochemical cycles. More than 96% of the marine DOM resists microbial degradation for thousands of years. The composition of this refractory DOM (RDOM) exhibits a molecular signature which is ubiquitously detected in the deep oceans. Surprisingly efficient microbial transformation of labile into RDOM was shown experimentally, implying that microorganisms produce far more RDOM than needed to sustain the global pool. By assessing the microbial formation and transformation of DOM in unprecedented molecular detail for 3 years, we show that most of the newly formed RDOM is molecularly different from deep sea RDOM. Only <0.4% of the net community production was channeled into RDOM molecularly undistinguishable from deep sea DOM. Our study provides novel experimentally derived molecular evidence and data for global models on the production, turnover and accumulation of marine DOM