Adaptation of a load-inject valve for a flow injection chemiluminescence system enabling dual-reagent injection enhances understanding of environmental Fenton chemistry.

Environmental Fenton chemistry has been poorly constrained within the marine environment at a multi-component level. A simple, unique, reconfiguration of a flow-injection analytical system combined with luminol chemiluminescence allows quasi-simultaneously the measurement, using a single load-inject valve and a single photon multiplier tube, of reduced iron, Fe(II), and hydrogen peroxide. The system enables rapid, every 22s, measurements with good accuracy at environmentally relevant concentrations, less than 5% relative standard deviations on both a 5 nM Fe(II) standard and a 60 nM hydrogen peroxide standard. Limits of detection were as low as 40 pM Fe(II) and 100 pM hydrogen peroxide. The system showed excellent capability by measuring from within an organic rich seawater the photochemically induced production of Fe(II) and hydrogen peroxide and their subsequent cycling and Fenton like interactions.

Ocean acidification and marine trace gas emissions.

The oceanic uptake of man-made CO(2) emissions is resulting in a measureable decrease in the pH of the surface oceans, a process which is predicted to have severe consequences for marine biological and biogeochemical processes [Caldeira K, Wickett ME (2003) Nature 425:365; The Royal Society (2005) Policy Document 12/05 (Royal Society, London)]. Here, we describe results showing how a doubling of current atmospheric CO(2) affects the production of a suite of atmospherically important marine trace gases. Two CO(2) treatments were used during a mesocosm CO(2) perturbation experiment in a Norwegian fjord (present day: approximately 380 ppmv and year 2100: approximately 750 ppmv), and phytoplankton blooms were stimulated by the addition of nutrients. Seawater trace gas concentrations were monitored over the growth and decline of the blooms, revealing that concentrations of methyl iodide and dimethylsulfide were significantly reduced under high CO(2.) Additionally, large reductions in concentrations of other iodocarbons were observed. The response of bromocarbons to high CO(2) was less clear cut. Further research is now required to understand how ocean acidification might impact on global marine trace gas fluxes and how these impacts might feed through to changes in the earth's future climate and atmospheric chemistry.

Volcanic carbon dioxide vents show ecosystem effects of ocean acidification.

The atmospheric partial pressure of carbon dioxide (p(CO(2))) will almost certainly be double that of pre-industrial levels by 2100 and will be considerably higher than at any time during the past few million years. The oceans are a principal sink for anthropogenic CO(2) where it is estimated to have caused a 30% increase in the concentration of H(+) in ocean surface waters since the early 1900s and may lead to a drop in seawater pH of up to 0.5 units by 2100 (refs 2, 3). Our understanding of how increased ocean acidity may affect marine ecosystems is at present very limited as almost all studies have been in vitro, short-term, rapid perturbation experiments on isolated elements of the ecosystem. Here we show the effects of acidification on benthic ecosystems at shallow coastal sites where volcanic CO(2) vents lower the pH of the water column. Along gradients of normal pH (8.1-8.2) to lowered pH (mean 7.8-7.9, minimum 7.4-7.5), typical rocky shore communities with abundant calcareous organisms shifted to communities lacking scleractinian corals with significant reductions in sea urchin and coralline algal abundance. To our knowledge, this is the first ecosystem-scale validation of predictions that these important groups of organisms are susceptible to elevated amounts of p(CO(2)). Sea-grass production was highest in an area at mean pH 7.6 (1,827 (mu)atm p(CO(2))) where coralline algal biomass was significantly reduced and gastropod shells were dissolving due to periods of carbonate sub-saturation. The species populating the vent sites comprise a suite of organisms that are resilient to naturally high concentrations of p(CO(2)) and indicate that ocean acidification may benefit highly invasive non-native algal species. Our results provide the first in situ insights into how shallow water marine communities might change when susceptible organisms are removed owing to ocean acidification.

Direct evidence for a marine source of C1 and C2 alkyl nitrates.

Alkyl nitrates are a significant component of the "odd nitrogen" reservoir and play an important role in regulating tropospheric ozone levels in remote marine regions. Measurements of methyl and ethyl nitrate in seawater and air samples along two Atlantic Ocean transects provide the first direct evidence for an oceanic source of these compounds. Equatorial surface waters were highly supersaturated (up to 800%) in both species, with the waters in the temperate regions generally being closer to equilibrium. A simple box model calculation suggests that the equatorial source could be a major component of the local atmospheric alkyl nitrate budget.