Reviews and Syntheses: Ocean acidification and its potential impacts on marine ecosystems

Ocean acidification, a complex phenomenon that lowers seawater pH, is the net outcome of several contributions. They include the dissolution of increasing atmospheric CO₂ that adds up with dissolved inorganic carbon (dissolved CO₂, H₂CO₃, HCO₃⁻, and CO₃²⁻) generated upon mineralization of primary producers (PP) and dissolved organic matter (DOM). The aquatic processes leading to inorganic carbon are substantially affected by increased DOM and nutrients via terrestrial runoff, acidic rainfall, increased PP and algal blooms, nitrification, denitrification, sulfate reduction, global warming (GW), and by atmospheric CO₂ itself through enhanced photosynthesis. They are consecutively associated with enhanced ocean acidification, hypoxia in acidified deeper seawater, pathogens, algal toxins, oxidative stress by reactive oxygen species, and thermal stress caused by longer stratification periods as an effect of GW. We discuss the mechanistic insights into the aforementioned processes and pH changes, with particular focus on processes taking place with different timescales (including the diurnal one) in surface and subsurface seawater. This review also discusses these collective influences to assess their potential detrimental effects to marine organisms, and of ecosystem processes and services. Our review of the effects operating in synergy with ocean acidification will provide a broad insight into the potential impact of acidification itself on biological processes. The foreseen danger to marine organisms by acidification is in fact expected to be amplified by several concurrent and interacting phenomena

Spatial and temporal variations and factors controlling the concentrations of hydrogen peroxide and organic peroxides in rivers

Hydrogen peroxide (H2O2) and organic peroxides (ROOH) were examined in water samples collected from the upstream and downstream sites of two Japanese rivers (the Kurose and the Ohta). H2O2 concentrations during monthly measurements varied between 6 and 213nM in the Kurose River and 33 and 188nM in the Ohta River. ROOH varied between 0 and 73nM in the Kurose River and 1 and 80nM in the Ohta. Concentrations of peroxides were higher during the summer months than in winter. H2O2 concentrations correlated well with the measured content of dissolved organic carbon and/or the fluorescence intensity of the fluorescent dissolved organic matter (FDOM) in the water from these rivers, which suggested that the dissolved organic matter and FDOM are the major sources of H2O2. Further characterisation of FDOM components by excitation emission matrix spectroscopy and parallel factor (PARAFAC) analysis indicated that fulvic acid is a dominant source of H2O2 in river waters, which accounted for 23-70% of H2O2 production in the Ohta River, 25-61% in the upstream and 28-63% in the downstream waters of the Kurose River, respectively. A fluorescent whitening agent and its photoproduct (4-biphenyl carboxaldehyde) together contributed 3-7% of H2O2 production in the downstream waters of the Kurose River. Tryptophan-like substances were a minor source of H2O2 (< 1%) in both rivers. An increase in the H2O2 concentration was observed in the diurnal samples collected at noon compared with the samples collected during the period before sunrise and after sunset, thus indicating that H2O2 was produced photochemically. This study demonstrates that H2O2 and ROOH are produced mainly from the photodegradation of FDOMs, such as fulvic acid

Photo-flocculation of microbial mat extracellular polymeric substances and their transformation into transparent exopolymer particles: Chemical and spectroscopic evidences

Upon exposure to sunlight extracellular polymeric substances (EPS) were partially transformed into transparent exopolymer particles (TEP) and unstable flocs of different sizes without the addition of any precursors. Parallel factor (PARAFAC) modelling of the sample fluorescence spectra identified humic-like and protein-like or tyrosine-like components in both untreated and irradiated EPS samples. After 58 hours of solar irradiation, humic-like substances were entirely decomposed, while the regenerated protein-like substance from EPS was the key component in the irradiated samples. Degradation and reformation of EPS occurred which was confirmed by the results of size exclusion chromatography, dissolved organic carbon, total protein and total polysaccharide analyses. Irradiated EPS was composed of -COOH or C = O (amide I band) and -NH and -CN (amide II band), while Fourier transform infrared spectroscopy (FTIR) of TEP revealed more acidic -COOH and -C-O groups, indicating typical acidic protein-like TEP. The regenerated protein-like substances could form complexes with free metals originating from degraded EPS in irradiated samples, which could be responsible for the formation of TEP/floc in the aqueous media. These results suggest that TEP/floc formation from EPS could occur by a complexation mechanism between dissolved organic matter and metals, thereby causing ionic charge neutralisation upon sunlight exposure