Technical Note: Determination of formaldehyde mixing ratios in polluted air with PTR-MS: laboratory experiments and field measurements

International audienceFormaldehyde (HCHO), the most abundant carbonyl compound in the atmosphere, is generated as an intermediate product in the oxidation of nonmethane hydrocarbons. Proton transfer reaction mass spectrometry (PTR-MS) has the capability to detect HCHO from ion signals at m/z 31 with high time-resolution. However, the detection sensitivity is low compared to other detectable species, and is considerably affected by humidity, due to back reactions between protonated HCHO and water vapor prior to analysis. We performed a laboratory calibration of HCHO by PTR-MS and examined the detection sensitivity and humidity dependence at various field strengths. Subsequently, we deployed the PTR-MS instrument in a field campaign at Mount Tai in China in June 2006 to measure HCHO in various meteorological and photochemical conditions; we also conducted intercomparison measurements by Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS). Correction of interference in the m/z 31 signals by fragments from proton transfer reactions with methyl hydroperoxide, methanol, and ethanol greatly improves agreement between the two methods, giving the correlation [HCHO]MAX-DOAS = (0.99±0.16) [HCHO]PTR-MS + (0.02±0.38), where error limits represent 95% confidence levels

Microbial community in a sediment-hosted CO2 lake of the southern Okinawa Trough hydrothermal system

Increasing levels of CO2 in the atmosphere are expected to cause climatic change with negative effects on the earth's ecosystems and human society. Consequently, a variety of CO2 disposal options are discussed, including injection into the deep ocean. Because the dissolution of CO2 in seawater will decrease ambient pH considerably, negative consequences for deep-water ecosystems have been predicted. Hence, ecosystems associated with natural CO2 reservoirs in the deep sea, and the dynamics of gaseous, liquid, and solid CO2 in such environments, are of great interest to science and society. We report here a biogeochemical and microbiological characterization of a microbial community inhabiting deep-sea sediments overlying a natural CO2 lake at the Yonaguni Knoll IV hydrothermal field, southern Okinawa Trough. We found high abundances (>109 cm−3) of microbial cells in sediment pavements above the CO2 lake, decreasing to strikingly low cell numbers (107 cm−3) at the liquid CO2/CO2-hydrate interface. The key groups in these sediments were as follows: (i) the anaerobic methanotrophic archaea ANME-2c and the Eel-2 group of Deltaproteobacteria and (ii) sulfur-metabolizing chemolithotrophs within the Gamma- and Epsilonproteobacteria. The detection of functional genes related to one-carbon assimilation and the presence of highly 13C-depleted archaeal and bacterial lipid biomarkers suggest that microorganisms assimilating CO2 and/or CH4 dominate the liquid CO2 and CO2-hydrate-bearing sediments. Clearly, the Yonaguni Knoll is an exceptional natural laboratory for the study of consequences of CO2 disposal as well as of natural CO2 reservoirs as potential microbial habitats on early Earth and other celestial bodies

Disturbance of deep-sea environments induced by the M9.0 Tohoku Earthquake

The impacts of the M9.0 Tohoku Earthquake on deep-sea environment were investigated 36 and 98 days after the event. The light transmission anomaly in the deep-sea water after 36 days became atypically greater (∼35%) and more extensive (thickness ∼1500 m) near the trench axis owing to the turbulent diffusion of fresh seafloor sediment, coordinated with potential seafloor displacement. In addition to the chemical influx associated with sediment diffusion, an influx of 13C-enriched methane from the deep sub-seafloor reservoirs was estimated. This isotopically unusual methane influx was possibly triggered by the earthquake and its aftershocks that subsequently induced changes in the sub-seafloor hydrogeologic structures. The whole prokaryotic biomass and the development of specific phylotypes in the deep-sea microbial communities could rise and fall at 36 and 98 days, respectively, after the event. We may capture the snap shots of post-earthquake disturbance in deep-sea chemistry and microbial community responses

Comparisons of trace constituents from ground stations and the DC‐8 aircraft during PEM‐West B

Chemical data from ground stations in Asia and the North Pacific are compared with data from the DC‐8 aircraft collected during the Pacific Exploratory Measurements in the Western Pacific Ocean (PEM‐West B) mission. Ground station sampling took place on Hong Kong, Taiwan, Okinawa, and Cheju; and at three Pacific islands, Shemya, Midway, and Oahu. Aircraft samples were collected during 19 flights, most over the western North Pacific. Aluminum was used as an indicator of mineral aerosol, and even though the aircraft did sample Asian dust, strong dust storms were not encountered. The frequency distribution for non‐sea‐salt sulfate (nss SO4=) in the aircraft samples was bimodal: the higher concentration mode (∼1 μg m−3) evidently originated from pollution or, less likely, from volcanic sources, while the lower mode, with a peak at 0.040 μg m−3, probably was a product of biogenic emissions. In addition, the concentrations of aerosol sulfate varied strongly in the vertical: arithmetic mean SO4= concentrations above 5000 m ( = 0.21±0.69 μg m−3) were substantially lower than those below ( = 1.07±0.87 μg m−3), suggesting the predominance of the surface sources. Several samples collected in the stratosphere exhibited elevated SO4=, however, probably as a result of emissions from Mount Pinatubo. During some boundary layer legs on the DC‐8, the concentrations of CO and O3 were comparable to those of clean marine air, but during other legs, several chemically distinct air masses were sampled, including polluted air in which O3 was photochemically produced. In general, the continental outflow sampled from the aircraft was substantially diluted with respect to what was observed at the ground stations. Higher concentrations of aerosol species, O3, and CO at the Hong Kong ground station relative to the aircraft suggest that much of the continental outflow from southeastern Asia occurs in the lower troposphere, and extensive long‐range transport out of this part of Asia is not expected. In comparison, materials emitted farther to the north apparently are more susceptible to long‐range transport

Significant discharge of CO2 from hydrothermalism associated with the submarine volcano of El Hierro Island

The residual hydrothermalism associated with submarine volcanoes, following an eruption event, plays an important role in the supply of CO2 to the ocean. The emitted CO2 increases the acidity of seawater. The submarine volcano of El Hierro, in its degasification stage, provided an excellent opportunity to study the effect of volcanic CO2 on the seawater carbonate system, the global carbon flux, and local ocean acidification. A detailed survey of the volcanic edifice was carried out using seven CTD-pH-ORP tow-yo studies, localizing the redox and acidic changes, which were used to obtain surface maps of anomalies. In order to investigate the temporal variability of the system, two CTD-pH-ORP yo-yo studies were conducted that included discrete sampling for carbonate system parameters. Meridional tow-yos were used to calculate the amount of volcanic CO2 added to the water column for each surveyed section. The inputs of CO2 along multiple sections combined with measurements of oceanic currents produced an estimated volcanic CO2 flux = 6.0 105 ± 1.1 105 kg d−1 which is ~0.1% of global volcanic CO2 flux. Finally, the CO2 emitted by El Hierro increases the acidity above the volcano by ~20%.En prens

Mechanisms for a nutrient-conserving carbon pump in a seasonally stratified, temperate continental shelf sea

Continental shelf seas may have a significant role in oceanic uptake and storage of carbon dioxide (CO2) from the atmosphere, through a ‘continental shelf pump’ mechanism. The northwest European continental shelf, in particular the Celtic Sea (50°N 8°W), was the target of extensive biogeochemical sampling from March 2014 to September 2015, as part of the UK Shelf Sea Biogeochemistry research programme (UK-SSB). Here, we use the UK-SSB carbonate chemistry and macronutrient measurements to investigate the biogeochemical seasonality in this temperate, seasonally stratified system. Following the onset of stratification, near-surface biological primary production during spring and summer removed dissolved inorganic carbon and nutrients, and a fraction of the sinking particulate organic matter was subsequently remineralised beneath the thermocline. Water column inventories of these variables throughout 1.5 seasonal cycles, corrected for air-sea CO2 exchange and sedimentary denitrification and anammox, isolated the combined effect of net community production (NCP) and remineralisation on the inorganic macronutrient inventories. Overall inorganic inventory changes suggested that a significant fraction (>50%) of the annual NCP of around 3 mol-C m–2 yr–1 appeared to be stored within a long-lived organic matter (OM) pool with a lifetime of several months or more. Moreover, transfers into and out of this pool appeared not to be in steady state over the one full seasonal cycle sampled. Accumulation of such a long-lived and potentially C-rich OM pool is suggested to be at least partially responsible for the estimated net air-to-sea CO2 flux of ∼1.3 mol-C m–2 yr–1 at our study site, while providing a mechanism through which a nutrient-conserving continental shelf pump for CO2 could potentially operate in this and other similar regions

Sea ice dynamics across the Mid-Pleistocene transition in the Bering Sea.

Sea ice and associated feedback mechanisms play an important role for both long- and short-term climate change. Our ability to predict future sea ice extent, however, hinges on a greater understanding of past sea ice dynamics. Here we investigate sea ice changes in the eastern Bering Sea prior to, across, and after the Mid-Pleistocene transition (MPT). The sea ice record, based on the Arctic sea ice biomarker IP25 and related open water proxies from the International Ocean Discovery Program Site U1343, shows a substantial increase in sea ice extent across the MPT. The occurrence of late-glacial/deglacial sea ice maxima are consistent with sea ice/land ice hysteresis and land-glacier retreat via the temperature-precipitation feedback. We also identify interactions of sea ice with phytoplankton growth and ocean circulation patterns, which have important implications for glacial North Pacific Intermediate Water formation and potentially North Pacific abyssal carbon storage