Chemical ionization tandem mass spectrometer for the in situ measurement of methyl hydrogen peroxide

A new approach for measuring gas-phase methyl hydrogen peroxide [(MHP) CH_3OOH] utilizing chemical ionization mass spectrometry is presented. Tandem mass spectrometry is used to avoid mass interferences that hindered previous attempts to measure atmospheric CH_3OOH with CF_3O− clustering chemistry. CH_3OOH has been successfully measured in situ using this technique during both airborne and ground-based campaigns. The accuracy and precision for the MHP measurement are a function of water vapor mixing ratio. Typical precision at 500 pptv MHP and 100 ppmv H_2O is ±80 pptv (2 sigma) for a 1 s integration period. The accuracy at 100 ppmv H_2O is estimated to be better than ±40%. Chemical ionization tandem mass spectrometry shows considerable promise for the determination of in situ atmospheric trace gas mixing ratios where isobaric compounds or mass interferences impede accurate measurements

Physiological constrains on Sverdrup's Critical-Depth-Hypothesis: the influences of dark respiration and sinking

Discussions on the controls initiating the onset of the phytoplankton spring bloom in particular in the North Atlantic have since Sverdrup been dominated by the role of physical and biological drivers. Undoubtedly, these drivers play an important role in phytoplankton dynamics and thus the onset of the spring bloom. However, they neglect the cells ability to modify vital rates in response to changes in the external environment. In this study, we use a non-hydrostatic convection model coupled to an Individual-Based-Model to simulate changes phytoplankton cells during the transition from winter conditions as driven by convective mixing, and the onset of thermal stratification resulting in the spring bloom. The comparison between a simulation using a standard fixed rate approach in line with the original Sverdrup hypothesis and a simulation parameterized to include variable respiration and sinking rates showed that the latter approach was able to capture the observed phytoplankton concentration during deep convective mixing, the timing and magnitude of the spring bloom as well as simulating realistic physiological rates. In contrast, the model employing fixed rate parameterizations could only replicate field observations when employing unrealistic parameter values. These results highlight the necessity to consider not only the physical and biological external controls determining phytoplankton dynamics but also the cells ability to modify critical physiological rates in response to external constraints. Understanding these adaptive qualities will be of increasing importance in the future as species assemblages and physical controls change with changing climate

Unstable Identities: The European Court of Human Rights and the Margin of Appreciation

All legal systems work under a master narrative – the self-conception of most actors of the system itself. A master narrative is a short and simple story and it is the underlying premise upon which any legal system is based. It is a simple story because it paints the system in quick broad brushstrokes and at (most) times is oblivious to the paradoxes within it. Furthermore, a master narrative is important for legitimization purposes because the actors’ legitimacy will depend on their (perceived) conformity with the system’s master narrative. Therefore, legitimacy is self-referential; the yardsticks for a legitimate action are contained within the system’s master narrative, not outside of it. When talking about different international courts it is important to remember that they are embedded within a master narrative that is contextual and contingent and, at different points, more or less contested. This paper explores the question of what happens when the master-narrative is in a period of transition (from a state cantered to a post-national world order) and when the actors’ legitimacy, their interpretative endeavours the very fundamentals are in a state of flux. I use the margin of appreciation discussion as a focal point of describing the conflicting narratives under which the European Court of Human Rights works, narratives in which the different actors (judges, attorneys, NGO activists, government agents) and their consequences in terms of the interpretation of the European Convention on Human Rights

Extended followup of a cohort of chromium production workers

Background The current study evaluates the mortality of 2,354 workers first employed at a Baltimore chromate production plant between 1950 and 1974. Methods The National Death Index (NDI Plus) was used to determine vital status and cause of death. Cumulative chromium (VI) exposure and nasal and skin irritation were evaluated as risk factors for lung cancer mortality. Results There are 91,186 person-years of observation and 217 lung cancer deaths. Cumulative chromium (VI) exposure, nasal irritation, nasal perforation, nasal ulceration, and other forms of irritation (e.g., skin irritation) were associated with lung cancer mortality. Conclusion Cumulative chromium (VI) exposure was a risk factor for lung cancer death. Cancer deaths, other than lung cancer, were not significantly elevated. Irritation may be a possible mechanism for chromium (VI)-induced lung cancer. Am. J. Ind. Med. © 2015 The Authors. American Journal of Industrial Medicine Published by Wiley Periodicals, Inc

Airborne measurements of western U.S. wildfire emissions: Comparison with prescribed burning and air quality implications

Wildfires emit significant amounts of pollutants that degrade air quality. Plumes from three wildfires in the western U.S. were measured from aircraft during the Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC^4RS) and the Biomass Burning Observation Project (BBOP), both in summer 2013. This study reports an extensive set of emission factors (EFs) for over 80 gases and 5 components of submicron particulate matter (PM_1) from these temperate wildfires. These include rarely, or never before, measured oxygenated volatile organic compounds and multifunctional organic nitrates. The observed EFs are compared with previous measurements of temperate wildfires, boreal forest fires, and temperate prescribed fires. The wildfires emitted high amounts of PM_1 (with organic aerosol (OA) dominating the mass) with an average EF that is more than 2 times the EFs for prescribed fires. The measured EFs were used to estimate the annual wildfire emissions of carbon monoxide, nitrogen oxides, total nonmethane organic compounds, and PM_1 from 11 western U.S. states. The estimated gas emissions are generally comparable with the 2011 National Emissions Inventory (NEI). However, our PM_1 emission estimate (1530 ± 570 Gg yr^(−1)) is over 3 times that of the NEI PM_(2.5) estimate and is also higher than the PM_(2.5) emitted from all other sources in these states in the NEI. This study indicates that the source of OA from biomass burning in the western states is significantly underestimated. In addition, our results indicate that prescribed burning may be an effective method to reduce fine particle emissions

Acclimation, Adaptation, Traits and Trade-Offs in Plankton Functional Type Models: Reconciling Terminology for Biology and Modelling

We propose definitions in terminology to enhance ongoing collaborations between biologists and modellers on plankton ecology. Organism functional type should refer to commonality in ecology not biogeochemistry; the latter is largely an emergent property of the former, while alignment with ecology is also consistent with usage in terrestrial science. Adaptation should be confined, as in genetics, to consideration of species inter-generational change; most so-called adaptive plankton models are thus acclimative, modifying vital rates in response to stimuli. Trait trade-off approaches should ideally only be considered for describing intra-generational interactions; in applications between generations, and certainly between unrelated species, such concepts should be avoided. We suggest that systems biology approaches, through to complex adaptive/acclimative systems modelling, with explicit modelling of feedback processes (which we suggest should define mechanistic models), would provide realistic and flexible bases upon which to develop descriptions of functional type models

Organic nitrate chemistry and its implications for nitrogen budgets in an isoprene- and monoterpene-rich atmosphere: constraints from aircraft (SEAC^4RS) and ground-based (SOAS) observations in the Southeast US

Formation of organic nitrates (RONO_2) during oxidation of biogenic volatile organic compounds (BVOCs: isoprene, monoterpenes) is a significant loss pathway for atmospheric nitrogen oxide radicals (NO_x), but the chemistry of RONO_2 formation and degradation remains uncertain. Here we implement a new BVOC oxidation mechanism (including updated isoprene chemistry, new monoterpene chemistry, and particle uptake of RONO_2) in the GEOS-Chem global chemical transport model with  ∼  25  ×  25 km^2 resolution over North America. We evaluate the model using aircraft (SEAC^4RS) and ground-based (SOAS) observations of NO_x, BVOCs, and RONO_2 from the Southeast US in summer 2013. The updated simulation successfully reproduces the concentrations of individual gas- and particle-phase RONO_2 species measured during the campaigns. Gas-phase isoprene nitrates account for 25–50 % of observed RONO_2 in surface air, and we find that another 10 % is contributed by gas-phase monoterpene nitrates. Observations in the free troposphere show an important contribution from long-lived nitrates derived from anthropogenic VOCs. During both campaigns, at least 10 % of observed boundary layer RONO_2 were in the particle phase. We find that aerosol uptake followed by hydrolysis to HNO_3 accounts for 60 % of simulated gas-phase RONO_2 loss in the boundary layer. Other losses are 20 % by photolysis to recycle NO_x and 15 % by dry deposition. RONO_2 production accounts for 20 % of the net regional NO_x sink in the Southeast US in summer, limited by the spatial segregation between BVOC and NO_x emissions. This segregation implies that RONO_2 production will remain a minor sink for NO_x in the Southeast US in the future even as NO_x emissions continue to decline

Gas Phase Production and Loss of Isoprene Epoxydiols

Isoprene epoxydiols (IEPOX) form in high yields from the OH-initiated oxidation of isoprene under low-NO conditions. These compounds contribute significantly to secondary organic aerosol formation. Their gas-phase chemistry has, however, remained largely unexplored. In this study, we characterize the formation of IEPOX isomers from the oxidation of isoprene by OH. We find that cis-β- and trans-β-IEPOX are the dominant isomers produced, and that they are created in an approximate ratio of 1:2 from the low-NO oxidation of isoprene. Three isomers of IEPOX, including cis-β- and trans-β, were synthesized and oxidized by OH in environmental chambers under high- and low-NO conditions. We find that IEPOX reacts with OH at 299 K with rate coefficients of (0.84 ± 0.07) × 10^(–11), (1.52 ± 0.07) × 10^(–11), and (0.98 ± 0.05) × 10^(–11) cm^3 molecule^(–1) s^(–1) for the δ1, cis-β, and trans-β isomers. Finally, yields of the first-generation products of IEPOX + OH oxidation were measured, and a new mechanism of IEPOX oxidation is proposed here to account for the observed products. The substantial yield of glyoxal and methylglyoxal from IEPOX oxidation may help explain elevated levels of those compounds observed in low-NO environments with high isoprene emissions

Formation of Low Volatility Organic Compounds and Secondary Organic Aerosol from Isoprene Hydroxyhydroperoxide Low-NO Oxidation

Gas-phase low volatility organic compounds (LVOC), produced from oxidation of isoprene 4-hydroxy-3-hydroperoxide (4,3-ISOPOOH) under low-NO conditions, were observed during the FIXCIT chamber study. Decreases in LVOC directly correspond to appearance and growth in secondary organic aerosol (SOA) of consistent elemental composition, indicating that LVOC condense (at OA below 1 μg m^(–3)). This represents the first simultaneous measurement of condensing low volatility species from isoprene oxidation in both the gas and particle phases. The SOA formation in this study is separate from previously described isoprene epoxydiol (IEPOX) uptake. Assigning all condensing LVOC signals to 4,3-ISOPOOH oxidation in the chamber study implies a wall-loss corrected non-IEPOX SOA mass yield of ∼4%. By contrast to monoterpene oxidation, in which extremely low volatility VOC (ELVOC) constitute the organic aerosol, in the isoprene system LVOC with saturation concentrations from 10^(–2) to 10 μg m^(–3) are the main constituents. These LVOC may be important for the growth of nanoparticles in environments with low OA concentrations. LVOC observed in the chamber were also observed in the atmosphere during SOAS-2013 in the Southeastern United States, with the expected diurnal cycle. This previously uncharacterized aerosol formation pathway could account for ∼5.0 Tg yr^(–1) of SOA production, or 3.3% of global SOA