Photooxidation of dimethylsulfide (DMS) in the Canadian Arctic

Photolysis of dimethylsulfide (DMS), a secondary photochemical process mediated by chromophoric dissolved organic matter (CDOM), has previously been demonstrated to be an important loss term of DMS in the surface layer of warm seas and the Southern Ocean. The role of photolysis in regulating the DMS dynamics in northern polar seas remains, however, less clear. This study for the first time determined the apparent quantum yield (AQY) spectra of DMS photooxidation in Canadian Arctic seas covering Baffin Bay, the Mackenzie estuary and shelf, and the Canada Basin. The DMS AQY was fairly invariant at salinities < 25 but rose rapidly with further increasing salinity in an exponential manner. Salinity can therefore be used as a quantitative indicator of the DMS AQY. The DMS AQY in the ultraviolet (UV) wavelengths was linearly and positively correlated with the spectral slope coefficient (275–295 nm) of the CDOM absorption spectrum, suggesting that marine CDOM photosensitizes the degradation of DMS more efficiently than does terrestrial CDOM or that coastal waters contain higher concentrations of substrates (most likely dissolved organic matter and redox metals) that compete for DMS-oxidizing radical intermediates. High concentrations of nitrate (~ 12 μmol L&minus;1) in deep water samples boosted DMS photooxidation by 70–80%, due likely to radical chemistry of nitrate photolysis. Coupled optical-photochemical modeling, based on the obtained DMS AQY spectra, shows that UV-A (320–400 nm) accounted for 60–75% of the DMS photolysis in the sunlit surface layer and that photochemistry degraded DMS on an e-folding time from 9 to 100 d (mean: 29 d). The photooxidation term on average accounted for 21% of the DMS gross loss rate and was comparable to the atmospheric DMS ventilation rate estimated for the same geographic regions. The methodology adopted here to study the relationship between CDOM quality/origin and DMS AQYs, if applicable to other ocean areas, may bring results of global significance for DMS cycling and might have implications for probing other CDOM-driven photochemical processes

Photoproduction of ammonium in the southeastern Beaufort Sea and its biogeochemical implications

International audiencePhotochemistry of dissolved organic matter (DOM) plays an important role in marine biogeochemical cycles, including the regeneration of inorganic nutrients. DOM photochemistry affects nitrogen cycling by converting bio-refractory dissolved organic nitrogen to labile inorganic nitrogen, mainly ammonium (NH4+). During the August 2009 Mackenzie Light and Carbon (MALINA) Program, the absorbed photon-based efficiency spectra of NH4+ photoproduction (i.e. photoammonification) were determined using water samples from the SE Beaufort Sea, including the Mackenzie River estuary, shelf, and Canada Basin. The photoammonification efficiency decreased with increasing wavelength across the ultraviolet and visible regimes and was higher in offshore waters than in shelf and estuarine waters. The efficiency was positively correlated with the molar nitrogen:carbon ratio of DOM and negatively correlated with the absorption coefficient of chromophoric DOM (CDOM). Combined with collateral measurements of CO2 and CO photoproduction, this study revealed a stoichiometry of DOM photochemistry with a CO2 : CO : NH4+ molar ratio of 165 : 11 : 1 in the estuary, 60 : 3 : 1 on the shelf, and 18 : 2 : 1 in the Canada Basin. The NH4+ efficiency spectra, along with solar photon fluxes, CDOM absorption coefficients and sea ice concentrations, were used to model the monthly surface and depth-integrated photoammonification rates in 2009. The summertime (June-August) rates at the surface reached 6.6 nmol l-1 d-1 on the Mackenzie Shelf and 3.7 nmol l-1 d-1 further offshore; the depth-integrated rates were correspondingly 8.8 μmol m-2 d-1 and 11.3 μmol m-2 d-1. The offshore depth-integrated rate in August (8.0 μmol m-2 d-1) was comparable to the missing dissolved inorganic nitrogen (DIN) source required to support the observed primary production in the upper 10-m layer of that area. The yearly NH4+ photoproduction in the entire study area was estimated to be 1.4 × 108 moles, with 85% of it being generated in summer when riverine DIN input is low. Photoammonification could mineralize 4% of the annual dissolved organic nitrogen (DON) exported from the Mackenzie River and provide a DIN source corresponding to 7% of the riverine DIN discharge and 1400 times the riverine NH4+ flux. Under a climate warming-induced ice-free scenario, these quantities could increase correspondingly to 6%, 11%, and 2100 times. Photoammonification is thus a significant nitrogen cycling term and may fuel previously unrecognized autotrophic and heterotrophic production pathways in the surface SE Beaufort Sea

Photoproduction of ammonium in the southeastern Beaufort Sea and its biogeochemical implications

Photochemistry of dissolved organic matter (DOM) plays an important role in marine biogeochemical cycles, including the regeneration of inorganic nutrients. DOM photochemistry affects nitrogen cycling by converting bio-refractory dissolved organic nitrogen to labile inorganic nitrogen, mainly ammonium (NH&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;+&lt;/sup&gt;). During the August 2009 Mackenzie Light and Carbon (MALINA) Program, the absorbed photon-based efficiency spectra of NH&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;+&lt;/sup&gt; photoproduction (i.e. photoammonification) were determined using water samples from the SE Beaufort Sea, including the Mackenzie River estuary, shelf, and Canada Basin. The photoammonification efficiency decreased with increasing wavelength across the ultraviolet and visible regimes and was higher in offshore waters than in shelf and estuarine waters. The efficiency was positively correlated with the molar nitrogen:carbon ratio of DOM and negatively correlated with the absorption coefficient of chromophoric DOM (CDOM). Combined with collateral measurements of CO&lt;sub&gt;2&lt;/sub&gt; and CO photoproduction, this study revealed a stoichiometry of DOM photochemistry with a CO&lt;sub&gt;2&lt;/sub&gt; : CO : NH&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;+&lt;/sup&gt; molar ratio of 165 : 11 : 1 in the estuary, 60 : 3 : 1 on the shelf, and 18 : 2 : 1 in the Canada Basin. The NH&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;+&lt;/sup&gt; efficiency spectra, along with solar photon fluxes, CDOM absorption coefficients and sea ice concentrations, were used to model the monthly surface and depth-integrated photoammonification rates in 2009. The summertime (June&amp;ndash;August) rates at the surface reached 6.6 nmol l&lt;sup&gt;−1&lt;/sup&gt; d&lt;sup&gt;−1&lt;/sup&gt; on the Mackenzie Shelf and 3.7 nmol l&lt;sup&gt;−1&lt;/sup&gt; d&lt;sup&gt;−1&lt;/sup&gt; further offshore; the depth-integrated rates were correspondingly 8.8 μmol m&lt;sup&gt;−2&lt;/sup&gt; d&lt;sup&gt;−1&lt;/sup&gt; and 11.3 μmol m&lt;sup&gt;−2&lt;/sup&gt; d&lt;sup&gt;−1&lt;/sup&gt;. The offshore depth-integrated rate in August (8.0 μmol m&lt;sup&gt;−2&lt;/sup&gt; d&lt;sup&gt;−1&lt;/sup&gt;) was comparable to the missing dissolved inorganic nitrogen (DIN) source required to support the observed primary production in the upper 10-m layer of that area. The yearly NH&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;+&lt;/sup&gt; photoproduction in the entire study area was estimated to be 1.4 × 10&lt;sup&gt;8&lt;/sup&gt; moles, with 85% of it being generated in summer when riverine DIN input is low. Photoammonification could mineralize 4% of the annual dissolved organic nitrogen (DON) exported from the Mackenzie River and provide a DIN source corresponding to 7% of the riverine DIN discharge and 1400 times the riverine NH&lt;sub&gt;4&lt;/sub&gt;&lt;sup&gt;+&lt;/sup&gt; flux. Under a climate warming-induced ice-free scenario, these quantities could increase correspondingly to 6%, 11%, and 2100 times. Photoammonification is thus a significant nitrogen cycling term and may fuel previously unrecognized autotrophic and heterotrophic production pathways in the surface SE Beaufort Sea

Corrigendum to "Photoproduction of ammonium in the southeastern Beaufort Sea and its biogeochemical implications" published in Biogeosciences, 9, 3047–3061, 2012

International audienc

Temporal Trends in the Use of Computed Tomographic Pulmonary Angiography for Suspected Pulmonary Embolism in the Emergency Department : A Retrospective Analysis.

Recently, validated clinical decision rules have been developed that avoid unnecessary use of computed tomographic pulmonary angiography (CTPA) in patients with suspected pulmonary embolism (PE) in the emergency department (ED). To measure any resulting change in CTPA use for suspected PE. Retrospective analysis. 26 European EDs in 6 countries. Patients with CTPA performed for suspected PE in the ED during the first 7 days of each odd month between January 2015 and December 2019. The primary end points were the CTPAs done for suspected PE in the ED and the number of PEs diagnosed in the ED each year adjusted to an annual census of 100 000 ED visits. Temporal trends were estimated using generalized linear mixed regression models. 8970 CTPAs were included (median age, 63 years; 56% female). Statistically significant temporal trends for more frequent use of CTPA (836 per 100 000 ED visits in 2015 vs. 1112 in 2019; P &lt; 0.001), more diagnosed PEs (138 per 100 000 in 2015 vs. 164 in 2019; P = 0.028), a higher proportion of low-risk PEs (annual percent change [APC], 13.8% [95% CI, 2.6% to 30.1%]) with more ambulatory management (APC, 19.3% [CI, 4.1% to 45.1%]), and a lower proportion of intensive care unit admissions (APC, -8.9% [CI, -17.1% to -0.3%]) were observed. Data were limited to 7 days every 2 months. Despite the recent validation of clinical decision rules to limit the use of CTPA, an increase in the CTPA rate along with more diagnosed PEs and especially low-risk PEs were instead observed. None specific for this study