The Enzymology of Ocean Global Change.

A small subset of marine microbial enzymes and surface transporters have a disproportionately important influence on the cycling of carbon and nutrients in the global ocean. As a result, they largely determine marine biological productivity and have been the focus of considerable research attention from microbial oceanographers. Like all biological catalysts, the activity of these keystone biomolecules is subject to control by temperature and pH, leaving the crucial ecosystem functions they support potentially vulnerable to anthropogenic environmental change. We summarize and discuss both consensus and conflicting evidence on the effects of sea surface warming and ocean acidification for five of these critical enzymes [carbonic anhydrase, ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCO), nitrogenase, nitrate reductase, and ammonia monooxygenase] and one important transporter (proteorhodopsin). Finally, we forecast how the responses of these few but essential biocatalysts to ongoing global change processes may ultimately help to shape the microbial communities and biogeochemical cycles of the future greenhouse ocean.

Microbial rhodopsins are increasingly favoured over chlorophyll in High Nutrient Low Chlorophyll waters.

Microbial rhodopsins are simple light-harvesting complexes that, unlike chlorophyll photosystems, have no iron requirements for their synthesis and phototrophic functions. Here, we report the environmental concentrations of rhodopsin along the Subtropical Frontal Zone off New Zealand, where Subtropical waters encounter the iron-limited Subantarctic High Nutrient Low Chlorophyll (HNLC) region. Rhodopsin concentrations were highest in HNLC waters where chlorophyll-a concentrations were lowest. Furthermore, while the ratio of rhodopsin to chlorophyll-a photosystems was on average 20 along the transect, this ratio increased to over 60 in HNLC waters. We further show that microbial rhodopsins are abundant in both picoplankton (0.2-3 µm) and in the larger (>3 µm) size fractions of the microbial community containing eukaryotic plankton and/or particle-attached prokaryotes. These findings suggest that rhodopsin phototrophy could be critical for microbial plankton to adapt to resource-limiting environments where photosynthesis and possibly cellular respiration are impaired.

Growth rate-dependent synthesis of halomethanes in marine heterotrophic bacteria and its implications for the ozone layer recovery.

Halomethanes (e.g., CH3 Cl, CH3 Br, CH3 I and CHBr3 ) are ozone-depleting compounds that, in contrast to the human-made chlorofluorocarbons, marine organisms synthesize naturally. Therefore, their production cannot be totally controlled by human action. However, identifying all their natural sources and understanding their synthesis regulation can help to predict their production rates and their impact on the future recovery of the Earth's ozone layer. Here we show that the synthesis of mono-halogenated halocarbons CH3 Cl, CH3 Br, and CH3 I is a generalized process in representatives of the major marine heterotrophic bacteria groups. Furthermore, halomethane production was growth rate dependent in all the strains we studied, implying uniform synthesis regulation patterns among bacterioplankton. Using these experimental observations and in situ halomethane concentrations, we further evaluated the potential production rates associated with higher bacterial growth rates in response to global warming in a coastal environment within the Southern California Bight. Our estimates show that a 3°C temperature rise would translate into a 35%-84% increase in halomethane production rate by 2100. Overall, these data suggest that marine heterotrophic bacteria are significant producers of these climate-relevant gases and that their contribution to the atmospheric halogen budget could increase in the future, impacting the ozone layer recovery.

Microbial rhodopsins are major contributors to the solar energy captured in the sea.

All known phototrophic metabolisms on Earth rely on one of three categories of energy-converting pigments: chlorophyll-a (rarely -d), bacteriochlorophyll-a (rarely -b), and retinal, which is the chromophore in rhodopsins. While the significance of chlorophylls in solar energy capture has been studied for decades, the contribution of retinal-based phototrophy to this process remains largely unexplored. We report the first vertical distributions of the three energy-converting pigments measured along a contrasting nutrient gradient through the Mediterranean Sea and the Atlantic Ocean. The highest rhodopsin concentrations were observed above the deep chlorophyll-a maxima, and their geographical distribution tended to be inversely related to that of chlorophyll-a. We further show that proton-pumping proteorhodopsins potentially absorb as much light energy as chlorophyll-a-based phototrophy and that this energy is sufficient to sustain bacterial basal metabolism. This suggests that proteorhodopsins are a major energy-transducing mechanism to harvest solar energy in the surface ocean.

Distribution of Extracellular Flavins in a Coastal Marine Basin and Their Relationship to Redox Gradients and Microbial Community Members.

The flavins (including flavin mononucleotide (FMN) and riboflavin (RF)) are a class of organic compounds synthesized by organisms to assist in critical redox reactions. While known to be secreted extracellularly by some species in laboratory-based cultures, flavin concentrations are largely unreported in the natural environment. Here, we present pore water and water column profiles of extracellular flavins (FMN and RF) and two degradation products (lumiflavin and lumichrome) from a coastal marine basin in the Southern California Bight alongside ancillary geochemical and 16S rRNA microbial community data. Flavins were detectable at picomolar concentrations in the water column (93-300 pM FMN, 14-40 pM RF) and low nanomolar concentrations in pore waters (250-2070 pM FMN, 11-210 pM RF). Elevated pore water flavin concentrations displayed an increasing trend with sediment depth and were significantly correlated with the total dissolved Fe (negative) and Mn (positive) concentrations. Network analysis revealed a positive relationship between flavins and the relative abundance of Dehalococcoidia and the MSBL9 clade of Planctomycetes, indicating possible secretion by members of these lineages. These results suggest that flavins are a common component of the so-called shared extracellular metabolite pool, especially in anoxic marine sediments where they exist at physiologically relevant concentrations for metal oxide reduction.

Mosaic patterns of B-vitamin synthesis and utilization in a natural marine microbial community.

Aquatic environments contain large communities of microorganisms whose synergistic interactions mediate the cycling of major and trace nutrients, including vitamins. B-vitamins are essential coenzymes that many organisms cannot synthesize. Thus, their exchange among de novo synthesizers and auxotrophs is expected to play an important role in the microbial consortia and explain some of the temporal and spatial changes observed in diversity. In this study, we analyzed metatranscriptomes of a natural marine microbial community, diel sampled quarterly over one year to try to identify the potential major B-vitamin synthesizers and consumers. Transcriptomic data showed that the best-represented taxa dominated the expression of synthesis genes for some B-vitamins but lacked transcripts for others. For instance, Rhodobacterales dominated the expression of vitamin-B12 synthesis, but not of vitamin-B7 , whose synthesis transcripts were mainly represented by Flavobacteria. In contrast, bacterial groups that constituted less than 4% of the community (e.g., Verrucomicrobia) accounted for most of the vitamin-B1 synthesis transcripts. Furthermore, ambient vitamin-B1 concentrations were higher in samples collected during the day, and were positively correlated with chlorophyll-a concentrations. Our analysis supports the hypothesis that the mosaic of metabolic interdependencies through B-vitamin synthesis and exchange are key processes that contribute to shaping microbial communities in nature.

Functional Genomics and Phylogenetic Evidence Suggest Genus-Wide Cobalamin Production by the Globally Distributed Marine Nitrogen Fixer Trichodesmium.

Only select prokaryotes can biosynthesize vitamin B12 (i.e., cobalamins), but these organic co-enzymes are required by all microbial life and can be vanishingly scarce across extensive ocean biomes. Although global ocean genome data suggest cyanobacteria to be a major euphotic source of cobalamins, recent studies have highlighted that >95% of cyanobacteria can only produce a cobalamin analog, pseudo-B12, due to the absence of the BluB protein that synthesizes the α ligand 5,6-dimethylbenzimidizole (DMB) required to biosynthesize cobalamins. Pseudo-B12 is substantially less bioavailable to eukaryotic algae, as only certain taxa can intracellularly remodel it to one of the cobalamins. Here we present phylogenetic, metagenomic, transcriptomic, proteomic, and chemical analyses providing multiple lines of evidence that the nitrogen-fixing cyanobacterium Trichodesmium transcribes and translates the biosynthetic, cobalamin-requiring BluB enzyme. Phylogenetic evidence suggests that the Trichodesmium DMB biosynthesis gene, bluB, is of ancient origin, which could have aided in its ecological differentiation from other nitrogen-fixing cyanobacteria. Additionally, orthologue analyses reveal two genes encoding iron-dependent B12 biosynthetic enzymes (cbiX and isiB), suggesting that iron availability may be linked not only to new nitrogen supplies from nitrogen fixation, but also to B12 inputs by Trichodesmium. These analyses suggest that Trichodesmium contains the genus-wide genomic potential for a previously unrecognized role as a source of cobalamins, which may prove to considerably impact marine biogeochemical cycles.

Proteorhodopsin light-enhanced growth linked to vitamin-B1 acquisition in marine Flavobacteria.

Proteorhodopsins (PR) are light-driven proton pumps widely distributed in bacterioplankton. Although they have been thoroughly studied for more than a decade, it is still unclear how the proton motive force (pmf) generated by PR is used in most organisms. Notably, very few PR-containing bacteria show growth enhancement in the light. It has been suggested that the presence of specific functions within a genome may define the different PR-driven light responses. Thus, comparing closely related organisms that respond differently to light is an ideal setup to identify the mechanisms involved in PR light-enhanced growth. Here, we analyzed the transcriptomes of three PR-harboring Flavobacteria strains of the genus Dokdonia: Dokdonia donghaensis DSW-1(T), Dokdonia MED134 and Dokdonia PRO95, grown in identical seawater medium in light and darkness. Although only DSW-1(T) and MED134 showed light-enhanced growth, all strains expressed their PR genes at least 10 times more in the light compared with dark. According to their genomes, DSW-1(T) and MED134 are vitamin-B1 auxotrophs, and their vitamin-B1 TonB-dependent transporters (TBDT), accounted for 10-18% of all pmf-dependent transcripts. In contrast, the expression of vitamin-B1 TBDT was 10 times lower in the prototroph PRO95, whereas its vitamin-B1 synthesis genes were among the highest expressed. Our data suggest that light-enhanced growth in DSW-1(T) and MED134 derives from the use of PR-generated pmf to power the uptake of vitamin-B1, essential for central carbon metabolism, including the TCA cycle. Other pmf-generating mechanisms available in darkness are probably insufficient to power transport of enough vitamin-B1 to support maximum growth of these organisms.

Vitamin B1 in marine sediments: pore water concentration gradient drives benthic flux with potential biological implications.

Vitamin B1, or thiamin, can limit primary productivity in marine environments, however the major marine environmental sources of this essential coenzyme remain largely unknown. Vitamin B1 can only be produced by organisms that possess its complete synthesis pathway, while other organisms meet their cellular B1 quota by scavenging the coenzyme from exogenous sources. Due to high bacterial cell density and diversity, marine sediments could represent some of the highest concentrations of putative B1 producers, yet these environments have received little attention as a possible source of B1 to the overlying water column. Here we report the first dissolved pore water profiles of B1 measured in cores collected in two consecutive years from Santa Monica Basin, CA. Vitamin B1 concentrations were fairly consistent between the two years ranging from 30 pM up to 770 pM. A consistent maximum at ~5 cm sediment depth covaried with dissolved concentrations of iron. Pore water concentrations were higher than water column levels and represented some of the highest known environmental concentrations of B1 measured to date, (over two times higher than maximum water column concentrations) suggesting increased rates of cellular production and release within the sediments. A one dimensional diffusion-transport model applied to the B1 profile was used to estimate a diffusive benthic flux of ~0.7 nmol m(-2) d(-1). This is an estimated flux across the sediment-water interface in a deep sea basin; if similar magnitude B-vitamin fluxes occur in shallow coastal waters, benthic input could prove to be a significant B1-source to the water column and may play an important role in supplying this organic growth factor to auxotrophic primary producers.

Diel changes in trace metal concentration and distribution in coastal waters: Catalina Island as a study case.

Understanding biogeochemical cycling of trace metals in the ocean requires information about variability in metal concentrations and distribution over short, e.g., diel, time scales. Such variability and the factors that influence it are poorly characterized. To address this shortcoming, we measured trace metal concentrations in the total dissolved, colloidal, and soluble fractions every 3-4 h for several consecutive days and nights in surface waters from a coastal station. Our results show that both the concentration and the size partitioning of some biologically essential (Fe, Cu, Co, and Cd) and anthropogenic (Pb) metals are subjected to diel variations that may be related to both inorganic and biological processes (e.g., photolysis of high-molecular-weight dissolved organic matter, photoinduced reduction/oxidation of metal(hydrous)oxides, uptake by growing phytoplankton, degradation of organic matter, lysis, and grazing). The largest fluctuations were observed in the soluble and colloidal pools. Soluble Fe varied during the day-night cycle by a factor of 40, and the contribution of colloidal Pb to the total dissolved fraction increased from 6±3% during the day to as much as 70-80% during the night. Our results suggest that changes occurring over time scales of hours need to be considered when collecting and interpreting trace metal data from the surface ocean.

Discovery of a SAR11 growth requirement for thiamin's pyrimidine precursor and its distribution in the Sargasso Sea.

Vitamin traffic, the production of organic growth factors by some microbial community members and their use by other taxa, is being scrutinized as a potential explanation for the variation and highly connected behavior observed in ocean plankton by community network analysis. Thiamin (vitamin B1), a cofactor in many essential biochemical reactions that modify carbon-carbon bonds of organic compounds, is distributed in complex patterns at subpicomolar concentrations in the marine surface layer (0-300 m). Sequenced genomes from organisms belonging to the abundant and ubiquitous SAR11 clade of marine chemoheterotrophic bacteria contain genes coding for a complete thiamin biosynthetic pathway, except for thiC, encoding the 4-amino-5-hydroxymethyl-2-methylpyrimidine (HMP) synthase, which is required for de novo synthesis of thiamin's pyrimidine moiety. Here we demonstrate that the SAR11 isolate 'Candidatus Pelagibacter ubique', strain HTCC1062, is auxotrophic for the thiamin precursor HMP, and cannot use exogenous thiamin for growth. In culture, strain HTCC1062 required 0.7 zeptomoles per cell (ca. 400 HMP molecules per cell). Measurements of dissolved HMP in the Sargasso Sea surface layer showed that HMP ranged from undetectable (detection limit: 2.4 pM) to 35.7 pM, with maximum concentrations coincident with the deep chlorophyll maximum. In culture, some marine cyanobacteria, microalgae and bacteria exuded HMP, and in the Western Sargasso Sea, HMP profiles changed between the morning and evening, suggesting a dynamic biological flux from producers to consumers.

The role of B vitamins in marine biogeochemistry.

The soluble B vitamins (B1, B7, and B12) have long been recognized as playing a central metabolic role in marine phytoplankton and bacteria; however, the importance of these organic external metabolites in marine ecology has been largely disregarded, as most research has focused on inorganic nutrients and trace metals. Using recently available genomic data combined with culture-based surveys of vitamin auxotrophy (i.e., vitamin requirements), we show that this auxotrophy is widespread in the marine environment and occurs in both autotrophs and heterotrophs residing in oligotrophic and eutrophic environments. Our analysis shows that vitamins originate from the activities of some bacteria and algae and that taxonomic changes observed in marine phytoplankton communities could be the result of their specific vitamin requirements and/or vitamin availability. Dissolved vitamin concentration measurements show that large areas of the world ocean are devoid of B vitamins, suggesting that vitamin limitation could be important for the efficiency of carbon and nitrogen fixation in those regions.

The distribution of thiamin and pyridoxine in the western tropical North Atlantic Amazon River plume.

B-vitamins are recognized as essential organic growth factors for many organisms, although little is known about their abundance and distribution in marine ecosystems. Despite their metabolic functions regulating important enzymatic reactions, the methodology to directly measure different B-vitamins in aquatic environments has only recently been developed. Here, we present the first direct measurements of two B-vitamins, thiamin (B1), and pyridoxine (B6), in the Amazon River plume-influenced western tropical North Atlantic (WTNA) Ocean, an area known to have high productivity, carbon (C) and dinitrogen (N2) fixation, and C sequestration. The vitamins B1 and B6 ranged in concentrations from undetectable to 230 and 40 pM, respectively. Significantly higher concentrations were measured in the surface plume water at some stations and variation with salinity was observed, suggesting a possible riverine influence on those B-vitamins. The influences of vitamins B1 and B6 on biogeochemical processes such as C and N2 fixation were investigated using a linear regression model that indicated the availability of those organic factors could affect these rates in the WTNA. In fact, significant increases in C fixation and N2 fixation were observed with increasing vitamin B1 concentrations at some low and mesohaline stations (stations 9.1 and 1; p value <0.017 and <0.03, respectively). N2 fixation was also found to have a significant positive correlation with B1 concentrations at station 1 (p value 0.029), as well as vitamin B6 at station 9.1 (p value <0.017). This work suggests that there can be a dynamic interplay between essential biogeochemical rates (C and N2 fixation) and B-vitamins, drawing attention to potential roles of B-vitamins in ecosystem dynamics, community structure, and global biogeochemistry.

The central role of selenium in the biochemistry and ecology of the harmful pelagophyte, Aureococcus anophagefferens.

The trace element selenium (Se) is required for the biosynthesis of selenocysteine (Sec), the 21st amino acid in the genetic code, but its role in the ecology of harmful algal blooms (HABs) is unknown. Here, we examined the role of Se in the biology and ecology of the harmful pelagophyte, Aureococcus anophagefferens, through cell culture, genomic analyses, and ecosystem studies. This organism has the largest and the most diverse selenoproteome identified to date that consists of at least 59 selenoproteins, including known eukaryotic selenoproteins, selenoproteins previously only detected in bacteria, and novel selenoproteins. The A. anophagefferens selenoproteome was dominated by the thioredoxin fold proteins and oxidoreductase functions were assigned to the majority of detected selenoproteins. Insertion of Sec in these proteins was supported by a unique Sec insertion sequence. Se was required for the growth of A. anophagefferens as cultures grew maximally at nanomolar Se concentrations. In a coastal ecosystem, dissolved Se concentrations were elevated before and after A. anophagefferens blooms, but were reduced by >95% during the peak of blooms to 0.05 nM. Consistent with this pattern, enrichment of seawater with selenite before and after a bloom did not affect the growth of A. anophagefferens, but enrichment during the peak of the bloom significantly increased population growth rates. These findings demonstrate that Se inventories, which can be anthropogenically enriched, can support proliferation of HABs, such as A. anophagefferens through its synthesis of a large arsenal of Se-dependent oxidoreductases that fine-tune cellular redox homeostasis.

Vitamin b(1) and b(12) uptake and cycling by plankton communities in coastal ecosystems.

While vitamin B(12) has recently been shown to co-limit the growth of coastal phytoplankton assemblages, the cycling of B-vitamins in coastal ecosystems is poorly understood as planktonic uptake rates of vitamins B(1) and B(12) have never been quantified in tandem in any aquatic ecosystem. The goal of this study was to establish the relationships between plankton community composition, carbon fixation, and B-vitamin assimilation in two contrasting estuarine systems. We show that, although B-vitamin concentrations were low (pM), vitamin concentrations and uptake rates were higher within a more eutrophic estuary and that vitamin B(12) uptake rates were significantly correlated with rates of primary production. Eutrophic sites hosted larger bacterial and picoplankton abundances with larger carbon normalized vitamin uptake rates. Although the >2 µm phytoplankton biomass was often dominated by groups with a high incidence of vitamin auxotrophy (dinoflagellates and diatoms), picoplankton (<2 µm) were always responsible for the majority of B(12)-vitamin uptake. Multiple lines of evidence suggest that heterotrophic bacteria were the primary users of vitamins among the picoplankton during this study. Nutrient/vitamin amendment experiments demonstrated that, in the Summer and Fall, vitamin B(12) occasionally limited or co-limited the accumulation of phytoplankton biomass together with nitrogen. Combined with prior studies, these findings suggest that picoplankton are the primary producers and users of B-vitamins in some coastal ecosystems and that rapid uptake of B-vitamins by heterotrophic bacteria may sometimes deprive larger phytoplankton of these micronutrients and thus influence phytoplankton species succession.

Multiple B-vitamin depletion in large areas of the coastal ocean.

B vitamins are some of the most commonly required biochemical cofactors in living systems. Therefore, cellular metabolism of marine vitamin-requiring (auxotrophic) phytoplankton and bacteria would likely be significantly compromised if B vitamins (thiamin B(1), riboflavin B(2), pyridoxine B(6), biotin B(7), and cobalamin B(12)) were unavailable. However, the factors controlling the synthesis, ambient concentrations, and uptake of these key organic compounds in the marine environment are still not well understood. Here, we report vertical distributions of five B vitamins (and the amino acid methionine) measured simultaneously along a latitudinal gradient through the contrasting oceanographic regimes of the southern California-Baja California coast in the Northeast Pacific margin. Although vitamin concentrations ranged from below the detection limits of our technique to 30 pM for B(2) and B(12) and to ∼500 pM for B(1), B(6), and B(7), each vitamin showed a different geographical and depth distribution. Vitamin concentrations were independent of each other and of inorganic nutrient levels, enriched primarily in the upper mesopelagic zone (depth of 100-300 m), and associated with water mass origin. Moreover, vitamin levels were below our detection limits (ranging from ≤0.18 pM for B(12) to ≤0.81 pM for B(1)) in extensive areas (100s of kilometers) of the coastal ocean, and thus may exert important constraints on the taxonomic composition of phytoplankton communities, and potentially also on rates of primary production and carbon sequestration.

Status of metal contamination in surface waters of the coastal ocean off Los Angeles, California since the implementation of the Clean Water Act.

In order to establish the status of metal contamination in surface waters in the coastal ocean off Los Angeles, California, we determined their dissolved and particulate pools and compared them with levels reported in the 1970s prior the implementation of the Clean Water Act. These measurements revealed a significant reduction in particulate toxic metal concentrations in the last 33 years with decreases of ∼100-fold for Pb and ∼400-fold for Cu and Cd. Despite these reductions, the source of particulate metals appears to be primarily anthropogenic as enrichment factors were orders of magnitude above what is considered background crustal levels. Overall, dissolved trace metal concentrations in the Los Angeles coastal waters were remarkably low with values in the same range as those measured in a pristine coastal environment off Mexico's Baja California peninsula. In order to estimate the impact of metal contamination on regional phytoplankton, the internalization rate of trace metals in a locally isolated phytoplankton model organism (Synechococcus sp. CC9311) was also determined showing a rapid internalization (in the order of a few hours) for many trace metals (e.g., Ag, Cd, Cu, Pb) suggesting that those metals could potentially be incorporated into the local food webs.

CO2 and vitamin B12 interactions determine bioactive trace metal requirements of a subarctic Pacific diatom.

Phytoplankton growth can be limited by numerous inorganic nutrients and organic growth factors. Using the subarctic diatom Attheya sp. in culture studies, we examined how the availability of vitamin B(12) and carbon dioxide partial pressure (pCO(2)) influences growth rate, primary productivity, cellular iron (Fe), cobalt (Co), zinc (Zn) and cadmium (Cd) quotas, and the net use efficiencies (NUEs) of these bioactive trace metals (mol C fixed per mol cellular trace metal per day). Under B(12)-replete conditions, cells grown at high pCO(2) had lower Fe, Zn and Cd quotas, and used those trace metals more efficiently in comparison with cells grown at low pCO(2). At high pCO(2), B(12)-limited cells had ~50% lower specific growth and carbon fixation rates, and used Fe ~15-fold less efficiently, and Zn and Cd ~3-fold less efficiently, in comparison with B(12)-replete cells. The observed higher Fe, Zn and Cd NUE under high pCO(2)/B(12)-replete conditions are consistent with predicted downregulation of carbon-concentrating mechanisms. Co quotas of B(12)-replete cells were ∼5- to 14-fold higher in comparison with B(12)-limited cells, suggesting that >80% of cellular Co of B(12)-limited cells was likely from B(12). Our results demonstrate that CO(2) and vitamin B(12) interactively influence growth, carbon fixation, trace metal requirements and trace metal NUE of this diatom. This suggests the need to consider complex feedback interactions between multiple environmental factors for this biogeochemically critical group of phytoplankton in the last glacial maximum as well as the current and future changing ocean.

Increased mercury in forest soils under elevated carbon dioxide.

Fossil fuel combustion is the primary anthropogenic source of both CO2 and Hg to the atmosphere. On a global scale, most Hg that enters ecosystems is derived from atmospheric Hg that deposits onto the land surface. Increasing concentrations of atmospheric CO2 may affect Hg deposition to terrestrial systems and storage in soils through CO(2)-mediated changes in plant and soil properties. We show, using free-air CO2 enrichment (FACE) experiments, that soil Hg concentrations are almost 30% greater under elevated atmospheric CO2 in two temperate forests. There were no direct CO2 effects, however, on litterfall, throughfall or stemflow Hg inputs. Soil Hg was positively correlated with percent soil organic matter (SOM), suggesting that CO(2)-mediated changes in SOM have influenced soil Hg concentrations. Through its impacts on SOM, elevated atmospheric CO2 may increase the Hg storage capacity of soils and modulate the movement of Hg through the biosphere. Such effects of rising CO2, ones that transcend the typically studied effects on C and nutrient cycling, are an important next phase for research on global environmental change.