Elisabeth Deschaseaux

Dimethylated sulfur compounds in coral-reef ecosystems

Environmental context Dimethylated sulfur compounds can exert multiple biological and environmental effects including climate regulation. Climate change and other anthropogenic factors are predicted to affect coral-reef ecosystems where these sulfur compounds are particularly abundant. We review the processes that regulate the production of dimethylated sulfur compounds in coral reefs and the potential consequences of environmental changes on their biogenic cycle in such fragile ecosystems under future climate change scenarios. Abstract Dimethylsulfoniopropionate (DMSP) and its main breakdown products dimethylsulfide (DMS) and dimethylsulfoxide (DMSO) are biogenic species in the marine environment. In coral reefs, these dimethylated sulfur compounds (DSCs) have been reported at greater concentrations than in other marine ecosystems, which is most likely attributable to the extraordinary large biodiversity of coral reef communities (e.g. corals, macroalgae, coralline algae, invertebrates) and to the unique ability of zooxanthellate corals to synthesise DMSP from both the animal host and algal symbionts. Besides the various biological functions that have been attributed to DSCs, including thermoregulation, osmoregulation, chemoattraction and antioxidant response, DMS is suspected to take part in a climate feedback loop that could help counteract global warming. Nowadays, anthropogenic effects such as pollution, overfishing, increased sedimentation and global climate change are imminently threatening the health of coral reef communities around the world, with possible consequences on the natural cycle of DSCs within these ecosystems. This review provides insight into the biogeochemistry of DSCs in coral reefs and discusses the implications of projected changes in DSC production in these increasingly stressed ecosystems under future climate change scenarios. It shows that DSC dynamics will incontestably be affected in the near future, with possible feedback consequences on local climate.

Quantification of dimethylsulfoniopropionate (DMSP) in Acropora spp. of reef-building coral using mass spectrometry with deuterated internal standard

AbstractDimethylsulfoniopropionate (DMSP) in scleractinian coral is usually analysed indirectly as dimethylsulfide (DMS) using gas chromatography (GC) with a sulfur-specific detector. We developed a headspace GC method for mass spectral analysis of DMSP in branching coral where hexa-deuterated DMSP (d6-DMSP) was added to samples and standards to optimise the analytical precision and quantitative accuracy. Using this indirect HS-GC-MS method, we show that common coral sample handling techniques did not alter DMSP concentrations in Acropora aspera and that endogenous DMS was insignificant compared to the store of DMSP in A. aspera. Field application of the indirect HS-GC-MS method in all seasons over a 5-year period at Heron Island in the southern Great Barrier Reef indicated that healthy colonies of A. aspera ordinarily seasonally conserve their branch tip store of DMSP; however, this store increased to a higher concentration under extended thermal stress conditions driven by a strong El Niño Southern Oscillation event. A liquid chromatography mass spectral method (LC-MS) was subsequently developed for direct analysis of DMSP in branching coral, also utilising the d6-DMSP internal standard. The quantitative comparison of DMSP in four species of Acropora coral by indirect HS-GC-MS and direct LC-MS analyses gave equivalent concentrations in A. aspera only; in the other three species, HS-GC-MS gave consistently higher concentrations, indicating that indirect analysis of DMSP may lead to artificially high values for some coral species. Graphical AbstractDimethylsulfoniopropionate (DMSP) was quantified in Acropora spp. of branching coral using deuterated stable isotope dilution mass spectrometry

The relative abundance of dimethylsulfoniopropionate (DMSP) among other zwitterions in branching coral at Heron Island, southern Great Barrier Reef

AbstractDimethylsulfoniopropionate (DMSP) and eleven other target zwitterions were quantified in the branch tips of six Acropora species and Stylophora pistillata hard coral growing on the reef flat surrounding Heron Island in the southern Great Barrier Reef (GBR), Australia. Hydrophilic interaction liquid chromatography mass spectrometry (HILIC-MS) was used for sample analysis with isotope dilution MS applied to quantify DMSP. The concentration of DMSP was ten times greater in A. aspera than A. valida, with this difference being maintained throughout the spring, summer and winter seasons. In contrast, glycine betaine was present in significantly higher concentrations in these species during the summer than the winter. Exposure of branch tips of A. aspera to air and hypo-saline seawater for up to 1 h did not alter the concentrations of DMSP present in the coral when compared with control samples. DMSP was the most abundant target zwitterion in the six Acropora species examined, ranging from 44-78% of all target zwitterions in A. millepora and A. aspera, respectively. In contrast, DMSP only accounted for 7% in S. pistillata, with glycine betaine and stachydrine collectively accounting for 88% of all target zwitterions in this species. The abundance of DMSP in the six Acropora species examined points to Acropora coral being an important source for the biogeochemical cycling of sulfur throughout the GBR, since this reef-building branching coral dominates the coral cover of the GBR. Graphical AbstractHILIC-MS extracted ion chromatogram showing zwitterionic metabolites from the branching coral Acropora isopora

Sea spray aerosol in the Great Barrier Reef and the presence of nonvolatile organics

Sea spray aerosol (SSA) particles produced from the ocean surface in regions of biological activity can vary greatly in size, number and composition and in their influence on cloud formation. Algal species such as phytoplankton can alter the SSA composition. Numerous studies have investigated nascent SSA properties, but all of these have focused on aerosol particles produced by seawater from non-coral related phytoplankton and in coastal regions. Bubble chamber experiments were performed with seawater samples taken from the reef flat around Heron Island in the Great Barrier Reef during winter 2011. Here we show that the SSA from these samples was comprised of an internal mixture of varying fractions of sea salt, semi-volatile organics as well as non-volatile (below 550°C) organics. A relatively constant volume fraction of semi-volatile organics of 10%-13% was observed while non-volatile organic volume fractions varied from 29%-49% for 60 nm SSA. SSA organic fractions were estimated to reduce the activation ratios of SSA to cloud condensation nuclei by up to 14% when compared with artificial sea salt. Additionally, a sea salt calibration was applied so that a compact Time-of-Flight Aerosol Mass Spectrometer could be used to quantify the contribution of sea salt to sub-micron SSA, which yielded organic volume fractions of 3%-6%. Overall, these results indicate a high fraction of organics associated with wintertime Aitken mode SSA generated from Great Barrier Reef seawater. Further work is required to fully distinguish any differences coral reefs have on SSA composition when compared to open oceans.

High zinc exposure leads to reduced dimethylsulfoniopropionate (DMSP) levels in both the host and endosymbionts of the reef-building coral Acropora aspera

Dimethylsulfoniopropionate (DMSP) is a biogenic compound that could be involved in metal detoxification in both the host and endosymbionts of symbiotic corals. Acropora aspera, a common reef-building coral of the Great Barrier Reef, was exposed to zinc doses from 10 to 1000μg/L over 96h, with zinc being a low-toxic trace metal commonly used in the shipping industry. Over time, significantly lower DMSP concentrations relative to the control were found in both the host and symbionts in the highest zinc treatment where zinc uptake by both partners of the symbiosis was the highest. This clearly indicates that DMSP was consumed or stopped being produced under high and extended zinc exposure. This drop in DMSP was first observed in the host tissue, suggesting that the coral host was the first to respond to metal contamination. Such decrease in DMSP concentrations could influence the long-term health of corals under zinc exposure.