Changes to the chemical state of the Northern Hemisphere atmosphere during the second half of the twentieth century

The NOx (NO and NO2) and HOx (OH and HO2) budgets of the atmosphere exert a major influence on atmospheric composition, controlling removal of primary pollutants and formation of a wide range of secondary products, including ozone, that can influence human health and climate. However, there remain large uncertainties in the changes to these budgets over recent decades. Due to their short atmospheric lifetimes, NOx and HOx are highly variable in space and time, and so the measurements of these species are of limited value for examining long-term, large-scale changes to their budgets. Here, we take an alternative approach by examining long-term atmospheric trends of alkyl nitrates, the production efficiency of which is dependent on the atmospheric [NO] ∕ [HO2] ratio. We derive long-term trends in the alkyl nitrates from measurements in firn air from the NEEM site, Greenland. Their mixing ratios increased by a factor of 3–5 between the 1970s and 1990s. This was followed by a steep decline to the sampling date of 2008. Moreover, we examine how the trends in the alkyl nitrates compare to similarly derived trends in their parent alkanes (i.e. the alkanes which, when oxidised in the presence of NOx, lead to the formation of the alkyl nitrates). The ratios of the alkyl nitrates to their parent alkanes increased from around 1970 to the late 1990s. This is consistent with large changes to the [NO] ∕ [HO2] ratio in the Northern Hemisphere atmosphere during this period. Alternatively, they could represent changes to concentrations of the hydroxyl radical, OH, or to the transport time of the air masses from source regions to the Arctic

Origins and composition of fine atmospheric carbonaceous aerosol in the Sierra Nevada Mountains, California

In this paper we report chemically resolved measurements of organic aerosol (OA) and related tracers during the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) at the Blodgett Forest Research Station, California from 15 August–10 October 2007. OA contributed the majority of the mass to the fine atmospheric particles and was predominately oxygenated (OOA). The highest concentrations of OA were during sporadic wildfire influence when aged plumes were impacting the site. In situ measurements of particle phase molecular markers were dominated by secondary compounds and along with gas phase compounds could be categorized into six factors or sources: (1) aged biomass burning emissions and oxidized urban emissions, (2) oxidized urban emissions (3) oxidation products of monoterpene emissions, (4) monoterpene emissions, (5) anthropogenic emissions and (6) local methyl chavicol emissions and oxidation products. There were multiple biogenic components that contributed to OA at this site whose contributions varied diurnally, seasonally and in response to changing meteorological conditions, e.g. temperature and precipitation events. Concentrations of isoprene oxidation products were larger when temperatures were higher during the first half of the campaign (15 August–12 September) due to more substantial emissions of isoprene and enhanced photochemistry. The oxidation of methyl chavicol, an oxygenated terpene emitted by ponderosa pine trees, contributed similarly to OA throughout the campaign. In contrast, the abundances of monoterpene oxidation products in the particle phase were greater during the cooler conditions in the latter half of the campaign (13 September–10 October), even though emissions of the precursors were lower, although the mechanism is not known. OA was correlated with the anthropogenic tracers 2-propyl nitrate and carbon monoxide (CO), consistent with previous observations, while being comprised of mostly non-fossil carbon (>75%). The correlation between OA and an anthropogenic tracer does not necessarily identify the source of the carbon as being anthropogenic but instead suggests a coupling between the anthropogenic and biogenic components in the air mass that might be related to the source of the oxidant and/or the aerosol sulfate. Observations of organosulfates of isoprene and α-pinene provided evidence for the likely importance of aerosol sulfate in spite of neutralized aerosol although acidic plumes might have played a role upwind of the site. This is in contrast to laboratory studies where strongly acidic seed aerosols were needed in order to form these compounds. These compounds together represented only a minor fraction (<1%) of the total OA mass, which may be the result of the neutralized aerosol at the site or because only a small number of organosulfates were quantified. The low contribution of organosulfates to total OA suggests that other mechanisms, e.g. NO_x enhancement of oxidant levels, are likely responsible for the majority of the anthropogenic enhancement of biogenic secondary organic aerosol observed at this site

Alkyl nitrates in outflow from North America over the North Atlantic during Intercontinental Transport of Ozone and Precursors 2004

This paper is based on alkyl nitrate measurements made over the North Atlantic as part of the International Consortium for Research on Atmospheric Transport and Transformation (ICARTT). The focus is on the analysis of air samples collected on the UK BAe-146 aircraft during the Intercontinental Transport of Ozone and Precursors (ITOP) project, but air samples collected on board the NASA DC-8 and NOAA WP-3D aircraft as part of a Lagrangian experiment are also used. The ratios between the alkyl nitrates and their parent hydrocarbons are compared with those expected from chemical theory. Further, a box model is run to investigate the temporal evolution of the alkyl nitrates in three Lagrangian case studies and compared to observations. The air samples collected during ITOP do not appear to be strongly influenced by oceanic sources, but rather are influenced by emissions from the N.E. United States and from Alaskan fires. There also appears to be a widespread common source of ethyl nitrate and 1-propyl nitrate other than from their parent hydrocarbons. The general agreement between the alkyl nitrate data and photochemical theory suggests that during the first few days of transport from the source region, photochemical production of alkyl nitrates, and thus ozone, had taken place. The observations in the more photochemically processed air masses are consistent with the alkyl nitrate production reactions no longer dominating the peroxy radical self/cross reactions. Further, the results also suggest that the rates of photochemical processing in the Alaskan smoke plumes were small

The importance of cylinder passivation for preparation and long-term stability of multicomponent monoterpene primary reference materials

Monoterpenes play an important role in atmospheric chemistry due to their large anthropogenic and biogenic emission sources and high chemical reactivity. As a consequence, measurements are required to assess how changes in emissions of monoterpenes impact air quality. Accurate and comparable measurements of monoterpenes in indoor and outdoor environments require gaseous primary reference materials (PRMs) that are traceable to the international system of units (SI). PRMs of monoterpenes are challenging to produce due to the high chemical reactivity and low vapour pressures of monoterpenes and also their propensity to convert into other compounds, including other terpenes. In this paper, the long-term stability of gravimetrically prepared static monoterpene PRMs produced in differently passivated cylinders, including sampling canisters, was assessed. We demonstrate that static PRMs of multiple monoterpenes can be prepared and used as a suitable long-term standard. For the first time the effect of cylinder pressure and decanting from one cylinder to another on the chemical composition and amount fraction of monoterpenes was also studied. Gravimetrically prepared PRMs of limonene in high pressure cylinders were compared to a novel portable dynamic reference gas generator based on dilution of pure limonene vapour emitted from a permeation tube.</p

Characterisation of gas reference materials for underpinning atmospheric measurements of stable isotopes of nitrous oxide

The precise measurement of the amount fraction of atmospheric nitrous oxide (N2O) is required to understand global emission trends. Analysis of the site-specific stable isotopic composition of N2O provides a means to differentiate emission sources. The availability of accurate reference materials of known N2O amount fractions and isotopic composition is critical for achieving these goals. We present the development of nitrous oxide gas reference materials for underpinning measurements of atmospheric composition and isotope ratio. Uncertainties target the World Metrological Organisation Global Atmosphere Watch (WMO-GAW) compatibility goal of 0.1 nmol mol−1 and extended compatibility goal of 0.3 nmol mol−1, for atmospheric N2O measurements in an amount fraction range of 325–335 nmol mol−1. We also demonstrate the stability of amount fraction and isotope ratio of these reference materials and present a characterisation study of the cavity ring-down spectrometer used for analysis of the reference materials.</p

The multi-seasonal NO_y budget in coastal Antarctica and its link with surface snow and ice core nitrate: results from the CHABLIS campaign

International audienceMeasurements of individual NOy components were carried out at Halley station in coastal Antarctica. The measurements were made as part of the CHABLIS campaign (Chemistry of the Antarctic Boundary Layer and the Interface with Snow) and cover over half a year, from austral winter 2004 through to austral summer 2005. They are the longest duration and most extensive NOy budget study carried out to date in polar regions. Results show clear dominance of organic NOy compounds (PAN and MeONO2) during the winter months, with low concentrations of inorganic NOy, but a reversal of this situation towards summer when the balance shifts in favour of inorganic NOy. Multi-seasonal measurements of surface snow nitrate correlate strongly with inorganic NOy species. One case study in August suggested that particulate nitrate was the dominant source of nitrate to the snowpack, but this was not the consistent picture throughout the measurement period. An analysis of NOx production rates showed that emissions of NOx from the snowpack dominate over gas-phase sources of "new NOx", suggesting that, for certain periods in the past, the flux of NOx into the boundary layer can be calculated from ice core nitrate data

Random Convex Hulls and Extreme Value Statistics

In this paper we study the statistical properties of convex hulls of $N$ random points in a plane chosen according to a given distribution. The points may be chosen independently or they may be correlated. After a non-exhaustive survey of the somewhat sporadic literature and diverse methods used in the random convex hull problem, we present a unifying approach, based on the notion of support function of a closed curve and the associated Cauchy's formulae, that allows us to compute exactly the mean perimeter and the mean area enclosed by the convex polygon both in case of independent as well as correlated points. Our method demonstrates a beautiful link between the random convex hull problem and the subject of extreme value statistics. As an example of correlated points, we study here in detail the case when the points represent the vertices of $n$ independent random walks. In the continuum time limit this reduces to $n$ independent planar Brownian trajectories for which we compute exactly, for all $n$, the mean perimeter and the mean area of their global convex hull. Our results have relevant applications in ecology in estimating the home range of a herd of animals. Some of these results were announced recently in a short communication [Phys. Rev. Lett. {\bf 103}, 140602 (2009)].Comment: 61 pages (pedagogical review); invited contribution to the special issue of J. Stat. Phys. celebrating the 50 years of Yeshiba/Rutgers meeting

The Making of a Productivity Hotspot in the Coastal Ocean

Highly productive hotspots in the ocean often occur where complex physical forcing mechanisms lead to aggregation of primary and secondary producers. Understanding how hotspots persist, however, requires combining knowledge of the spatio-temporal linkages between geomorphology, physical forcing, and biological responses with the physiological requirements and movement of top predators.) off the Baja California peninsula, Mexico.We have identified the set of conditions that lead to a persistent top predator hotspot, which increases our understanding of how highly migratory species exploit productive regions of the ocean. These results will aid in the development of spatially and environmentally explicit management strategies for marine species of conservation concern

CHronic hypERtension and L-citRulline studY (CHERRY): an Early-Phase Randomised Controlled Trial in Pregnancy.

Oral supplementation with L-citrulline, which is sequentially converted to L-arginine then nitric oxide, improves vascular biomarkers and reduces blood pressure in non-pregnant, hypertensive human cohorts and pregnant mice with a pre-eclampsia-like syndrome. This early-phase randomised feasibility trial assessed the acceptability of L-citrulline supplementation to pregnant women with chronic hypertension and its effects on maternal BP and other vascular outcomes. Pregnant women with chronic hypertension were randomised at 12-16 weeks to receive 3-g L-citrulline twice daily (n = 24) or placebo (n = 12) for 8 weeks. Pregnant women reported high acceptability of oral L-citrulline. Treatment increased maternal plasma levels of citrulline, arginine and the arginine:asymmetric dimethylarginine ratio, particularly in women reporting good compliance. L-citrulline had no effect on diastolic BP (L-citrulline: - 1.82 95% CI (- 5.86, 2.22) vs placebo: - 5.00 95% CI (- 12.76, 2.76)), uterine artery Doppler or angiogenic biomarkers. Although there was no effect on BP, retrospectively, this study was underpowered to detect BP changes < 9 mmHg, limiting the conclusions about biological effects. The increase in arginine:asymmetric dimethylarginine ratio was less than in non-pregnant populations, which likely reflects altered pharmacokinetics of pregnancy, and further pharmacokinetic assessment of L-citrulline in pregnancy is advised.Trial Registration EudraCT 2015-005792-25 (2017-12-22) and ISRCTN12695929 (2018-09-20) In pregnant women with chronic hypertension, L-citrulline is an acceptable intervention which increased plasma L-citrulline bioavailability but did not affect BP, potentially due to altered pharmacokinetics of pregnancy