An official website of the United States government
Abstract The oceanic biogeochemical cycling of iron is globally important yet difficult to fully understand due to the many chemical processes involved. There is potential to use scandium, which has a similar ionic size and charge density to trivalent iron but lacks redox cycling, as a simpler analog for specific parts of the iron cycle, if we can sufficiently develop our understanding of scandium's reactivity. Here we move closer to this understanding. We look at particle reactivity and solubility through a 24‐hr incubation experiment: 5 nmol/kg of dissolved scandium and/or iron were added to filtered and unfiltered California Current System water. Particulate scandium formed only in the unfiltered treatments, at a quantity unlikely to have been taken up biologically. This is the first direct observation of scavenging of scandium, an attribute shared with iron. Our results also serve as the first test of scandium solubility in seawater: 1.9 nmol/kg of dissolved scandium was stable in the filtered treatment, 50 times more than the highest natural concentrations so far observed. This indicates that, in contrast to iron, scandium's oceanic cycling is unlikely to be influenced by solubility limits. We also compare particulate depth profiles: labile particulate iron was disproportionally higher than that of scandium in shelf‐influenced samples, likely due to iron reductively dissolving in the sediments, which scandium cannot do, and then precipitating in oxic seawater. Due to this combination of behaviors, our results suggest that paired observations of scandium and iron may help distinguish between iron sourced from sediment resuspension and reductive dissolution.
more »
« less
Influence of vitamin B12 availability on oceanic dimethylsulfide and dimethylsulfoniopropionate
Environmental contextCobalamin, or vitamin B12, is receiving increased attention as a critical trace nutrient in the growth and metabolic processes of oceanic phytoplankton and bacterial communities. We present evidence that indicates B12 has a more significant role in the biogeochemical cycling of the climatically important compounds dimethylsulfide and dimethylsulfoniopropionate than previously understood. Several possible mechanisms are examined that link cellular-level processes involving B12 to global-scale biogeochemical processes involving the oceanic cycling of dimethylsulfoniopropionate and dimethylsulfide.AbstractEvidence is presented showing that dissolved dimethylsulfoniopropionate (DMSPd) and dimethylsulfide (DMS) concentrations are influenced by the availability of vitamin B12 in two oceanographically distinct regions with different DMS production capacities, the central equatorial Pacific Ocean and the Ross Sea, Antarctica. In both locations, addition of B12 to incubation experiments resulted in decreases in DMS and, in some cases, DMSPd concentrations relative to unamended controls. In no case did increasing iron availability significantly (α=0.1) alter DMS concentrations relative to controls. The relative decreases in DMS between B12 addition and control experiments were significant (α=0.1) in five of seven experiments conducted at ambient iron levels. Overall, DMS concentrations were on average 33.4% (±15.1%; 1 standard deviation) lower, relative to unamended controls, by the end of incubation experiments when B12 was added. Declines in DMSPd were observed in three of five experiments. Similar trends were observed when B12 was added to iron-supplemented bottle incubation experiments (30.4±10.4% lower final DMS concentrations in +B12Fe treatments relative to +Fe treatments). Several possible molecular-level explanations exist for this link between B12 and DMS production, including potential B12 dependence of methyltransferase enzymes involved in both DMS and DMSP degradation. Although the enzymology of these reactions remains unclear, the relationships described here provide evidence for plausible mechanisms behind the microbial modulation of oceanic DMS.
more »
« less
- Award ID(s):
- 0739446
- PAR ID:
- 10081178
- Date Published:
- Journal Name:
- Environmental Chemistry
- Volume:
- 13
- Issue:
- 2
- ISSN:
- 1448-2517
- Page Range / eLocation ID:
- 293
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Volatile organic compounds (VOCs) are constituents of marine ecosystems including coral reefs, where they are sources of atmospheric reactivity, indicators of ecosystem state, components of defense strategies, and infochemicals. Most VOCs result from sunlight-related processes; however, their light-driven dynamics are still poorly understood. We studied the spatial variability of a suite of VOCs, including dimethylsulfide (DMS), and the other dimethylsulfoniopropionate-derived compounds (DMSPCs), namely, DMSP, acrylate, and dimethylsulfoxide (DMSO), in waters around colonies of two scleractinian corals ( Acropora pulchra and Pocillopora sp.) and the brown seaweed Turbinaria ornata in Mo’orean reefs, French Polynesia. Concentration gradients indicated that the corals were sources of DMSPCs, but less or null sources of VOCs other than DMS, while the seaweed was a source of DMSPCs, carbonyl sulfide (COS), and poly-halomethanes. A focused study was conducted around an A. pulchra colony where VOC and DMSPC concentrations and free-living microorganism abundances were monitored every 6 h over 30 h. DMSPC concentrations near the polyps paralleled sunlight intensity, with large diurnal increases and nocturnal decrease. rDNA metabarcoding and metagenomics allowed the determination of microbial diversity and the relative abundance of target functional genes. Seawater near coral polyps was enriched in DMS as the only VOC, plus DMSP, acrylate, and DMSO, with a large increase during the day, coinciding with high abundances of symbiodiniacean sequences. Only 10 cm below, near the coral skeleton colonized by a turf alga, DMSPC concentrations were much lower and the microbial community was significantly different. Two meters down current from the coral, DMSPCs decreased further and the microbial community was more similar to that near the polyps than that near the turf alga. Several DMSP cycling genes were enriched in near-polyp with respect to down-current waters, namely, the eukaryotic DMS production and DMS oxidation encoding genes, attributed to the coral and the algal symbiont, and the prokaryotic DMS production gene dddD , harbored by coral-associated Gammaproteobacteria . Our results suggest that solar radiation-induced oxidative stress caused the release of DMSPCs by the coral holobiont, either directly or through symbiont expulsion. Strong chemical and biological gradients occurred in the water between the coral branches, which we attribute to layered hydrodynamics.more » « less
-
This dataset includes the concentrations of dissolved inorganic macronutrients (phosphate, nitrate plus nitrite (N+N), silicic acid, and nitrite), chlorophyll a and phaeophytin, and particulate organic nitrogen and carbon measured shipboard in samples collected from phytoplankton shipboard incubation experiments conducted on the FeOA cruise SKQ202209S on R/V Sikuliaq in the Northeast Pacific from June to July 2022. This project investigates the effects of ocean acidification on the associations between iron and organic ligands in seawater and on iron bioavailability to marine phytoplankton communities. The project used a combination of shipboard incubation experiments and depth profiles to characterize iron speciation and cycling across coastal upwelling, oligotrophic open ocean, and iron-limited subarctic oceanographic regimes in the NE Pacific. Surface seawater was incubated at pH of 8.1, 7.6, and 7.1 with natural iron and with dissolved iron amendments in order to investigate interactions between pH and iron bioavailability across the different regimes. Understanding how pH influences iron and its relationship with ligands provides important information for assessing the impacts of ocean acidification on primary production and biogeochemical processes.more » « less
-
Phytoplankton blooms in the Arctic marginal ice zone (MIZ) can be prolific dimethylsulfide (DMS) producers, thereby influencing regional aerosol formation and cloud radiative forcing. Here we describe the distribution of DMS and its precursor dimethylsulfoniopropionate (DMSP) across the Baffin Bay receding ice edge in early summer 2016. Overall, DMS and total DMSP (DMSPt) increased towards warmer waters of Atlantic origin concurrently with more advanced ice-melt and bloom stages. Relatively high DMS and DMSPt (medians of 6.3 and 70 nM, respectively) were observed in the surface layer (0–9 m depth), and very high values (reaching 74 and 524 nM, respectively) at the subsurface biomass maximum (15–30 m depth). Microscopic and pigment analyses indicated that subsurface DMS and DMSPt peaks were associated with Phaeocystis pouchetii, which bloomed in Atlantic-influenced waters and reached unprecedented biomass levels in Baffin Bay. In surface waters, DMS concentrations and DMS:DMSPt ratios were higher in the MIZ (medians of 12 nM and 0.15, respectively) than in fully ice-covered or ice-free conditions, potentially associated with enhanced phytoplanktonic DMSP release and bacterial DMSP cleavage (high dddP:dmdA gene ratios). Mean sea–air DMS fluxes (micromol m–2 d–1) increased from 0.3 in ice-covered waters to 10 in open waters (maximum of 26) owing to concurrent trends in near-surface DMS concentrations and physical drivers of gas exchange. Using remotely sensed sea-ice coverage and a compilation of sea–air DMS flux data, we estimated that the pan-Arctic DMS emission from the MIZ was 5–13 Gg S yr–1. North of 80 oN, DMS emissions might have increased by around 10% yr–1 between 2003 and 2014, likely exceeding open-water emissions in June and July. We conclude that DMS emissions from the MIZ must be taken into account to evaluate plankton-climate feedbacks in the Arctic.more » « less
-
Biogenic volatile organic compounds (VOCs) play key roles in coral reef ecosystems, where, together with dimethylated sulfur compounds, they are indicators of ecosystem health and are used as defense strategies and infochemicals. Assessment and prediction of the exchange rates of VOCs between the oceans and atmosphere, with implications for atmospheric reactivity and climate, are hampered by poor knowledge of the regulating processes and their temporal variability, including diel cycles. Here, we measured the variation over 36h of the concentrations of DMSPCs (dimethylsulfoniopropionate (DMSP)-related compounds, namely DMSP, dimethylsulfoxide, acrylate, dimethylsulfide, and methanethiol as dimethyl disulfide) and VOCs (COS, CS2, isoprene, the iodomethanes CH3I and CH2ClI, and the bromomethanes CHBr3and CH2Br2), in surface waters inside the shallow, northern coral-reef lagoon of Mo’orea (French Polynesia) and 4 km offshore, in the tropical open ocean. Comparisons with concurrent measurements of sea surface temperature, solar radiation, biogeochemical variables (nutrients, organic matter), and the abundances and taxonomic affiliations of microbial plankton were conducted with the aim to explain interconnections between DMSPCs, VOCs, and their environment across diel cycles. In open ocean waters, deeper surface mixing and low nutrient levels resulted in low phytoplankton biomass and bacterial activity. Consequently, the diel patterns of VOCs were more dependent on photochemical reactions, with daytime increases for several compounds including dissolved dimethylsulfoxide, COS, CS2, CH3I, and CH2ClI. A eukaryotic phytoplankton assemblage dominated by dinoflagellates and haptophytes provided higher cell-associated DMSP concentrations, yet the occurrence of DMSP degradation products (dimethylsulfide, dimethyl disulfide) was limited by photochemical loss. Conversely, in the shallow back reef lagoon the proximity of seafloor sediments, corals and abundant seaweeds resulted in higher nutrient levels, more freshly-produced organic matter, higher bacterial activity, and larger algal populations ofMamiellales, diatoms andCryptomonadales. Consequently, DMSP and dimethylsulfoxide concentrations were lower but those of most VOCs were higher. A combination of photobiological and photochemical processes yielded sunny-daytime increases and nighttime decreases of dimethylsulfide, dimethyl disulfide, COS, isoprene, iodomethanes and bromomethanes. Our results illustrate the important role of solar radiation in DMSPC and VOC cycling, and are relevant for the design of sampling strategies that seek representative and comparable measurements of these compounds.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1071/EN15043
