Bromocarbons in the tropical coastal and open ocean atmosphere during the 2009 Prime Expedition Scientific Cruise (PESC-09)

Abstract. Atmospheric concentrations of very short-lived species (VSLS) bromocarbons, including CHBr3, CH2Br2, CHCl2Br, CHClBr2, and CH2BrCl, were measured in the Strait of Malacca and the South China and Sulu–Sulawesi seas during a two-month research cruise in June–July 2009. The highest bromocarbon concentrations were found in the Strait of Malacca, with smaller enhancements in coastal regions of northern Borneo. CHBr3 was the most abundant bromocarbon, ranging from 5.2 pmol mol−1 in the Strait of Malacca to 0.94 pmol mol−1 over the open ocean. Other bromocarbons showed lower concentrations, in the range of 0.8–1.3 pmol mol−1 for CH2Br2, 0.1–0.5 pmol mol−1 for CHCl2Br, and 0.1–0.4 pmol mol−1 for CHClBr2. There was no significant correlation between bromocarbons and in situ chlorophyll a, but positive correlations with both MODIS and SeaWiFS satellite chlorophyll a. Together, the short-lived bromocarbons contribute an average of 8.9 pmol mol−1 (range 5.2–21.4 pmol mol−1) to tropospheric bromine loading, which is similar to that found in previous studies from global sampling networks (Montzka et al., 2011). Statistical tests showed strong Spearman correlations between brominated compounds, suggesting a common source. Log–log plots of CHBr3/CH2Br2 versus CHBr2Cl/CH2Br2 show that both chemical reactions and dilution into the background atmosphere contribute to the composition of these halocarbons at each sampling point. We have used the correlation to make a crude estimate of the regional emissions of CHBr3 and to derive a value of 32 Gg yr−1 for the Southeast (SE) Asian region (10° N–20° S, 90–150° E). Finally, we note that satellite-derived chlorophyll a (chl a) products do not always agree well with in situ measurements, particularly in coastal regions of high turbidity, meaning that satellite chl a may not always be a good proxy for marine productivity. We would like to thank MOSTI (Malaysian Ministry of Science, Technology and Innovation). for giving opportunities and financial support for the University of Malaya (UM) and Universiti Kebangsaan Malaysia to participate in this scientific cruise, and other Malaysian public universities and agencies who helped during sampling. The Malaysian Royal Navy is thanked for their help and assistance in all aspects of the cruise. We also thank the SHIVA European FP7 project (grant 226224), NERC, NERC-NCAS and the British Council, through a PMI2 grant, for their support. Neil Harris would like to thank NERC for his Research Fellowship; Emma Leedham and Matt Ashfold thank NERC for studentships, and Doreena Dominick, Lin Chin Yik, Fatimah Ahamad and Nur Ily Hamizah for their assistance and the Ministry of Higher Education Malaysia (KPT’s) ERGS grant ER025-2013A. Finally, we also would like to thank Universiti Kebangsaan Malaysia (UKM) for the ICONIC-2013-004 grant, MOSTI e-science grant 04-01-02-SF-0752 for Universiti Kebangsaan Malaysia (UKM), UKM GGPM-2013-080 and UKM DPP-2014-162 and GUP-2013-057 for financial support.This paper was originally published in Atmospheric Chemistry and Physics, 14, 8137-8148, doi:10.5194/acp-14-8137-2014, 201

Evidence for strong, widespread chlorine radical chemistry associated with pollution outflow from continental Asia

The chlorine radical is a potent atmospheric oxidant, capable of perturbing tropospheric oxidative cycles normally controlled by the hydroxyl radical. Significantly faster reaction rates allow chlorine radicals to expedite oxidation of hydrocarbons, including methane, and in polluted environments, to enhance ozone production. Here we present evidence, from the CARIBIC airborne dataset, for extensive chlorine radical chemistry associated with Asian pollution outflow, from airborne observations made over the Malaysian Peninsula in winter. This region is known for persistent convection that regularly delivers surface air to higher altitudes and serves as a major transport pathway into the stratosphere. Oxidant ratios inferred from hydrocarbon relationships show that chlorine radicals were regionally more important than hydroxyl radicals for alkane oxidation and were also important for methane and alkene oxidation (>10%). Our observations reveal pollution-related chlorine chemistry that is both widespread and recurrent, and has implications for tropospheric oxidizing capacity, stratospheric composition and ozone chemistry

Dopamine acting at D1-like, D2-like and α1-adrenergic receptors differentially modulates theta and gamma oscillatory activity in primary motor cortex

The loss of dopamine (DA) in Parkinson’s is accompanied by the emergence of exaggerated theta and beta frequency neuronal oscillatory activity in the primary motor cortex (M1) and basal ganglia. DA replacement therapy or deep brain stimulation reduces the power of these oscillations and this is coincident with an improvement in motor performance implying a causal relationship. Here we provide in vitro evidence for the differential modulation of theta and gamma activity in M1 by DA acting at receptors exhibiting conventional and non-conventional DA pharmacology. Recording local field potentials in deep layer V of rat M1, co-application of carbachol (CCh, 5 μM) and kainic acid (KA, 150 nM) elicited simultaneous oscillations at a frequency of 6.49 ± 0.18 Hz (theta, n = 84) and 34.97 ± 0.39 Hz (gamma, n = 84). Bath application of DA resulted in a decrease in gamma power with no change in theta power. However, application of either the D1-like receptor agonist SKF38393 or the D2-like agonist quinpirole increased the power of both theta and gamma suggesting that the DA-mediated inhibition of oscillatory power is by action at other sites other than classical DA receptors. Application of amphetamine, which promotes endogenous amine neurotransmitter release, or the adrenergic α1-selective agonist phenylephrine mimicked the action of DA and reduced gamma power, a result unaffected by prior co-application of D1 and D2 receptor antagonists SCH23390 and sulpiride. Finally, application of the α1-adrenergic receptor antagonist prazosin blocked the action of DA on gamma power suggestive of interaction between α1 and DA receptors. These results show that DA mediates complex actions acting at dopamine D1-like and D2-like receptors, α1 adrenergic receptors and possibly DA/α1 heteromultimeric receptors to differentially modulate theta and gamma activity in M1

Renewed and emerging concerns over the production and emission of ozone-depleting substances

Stratospheric ozone depletion, first observed in the 1980s, has been caused by the increased production and use of substances such as chlorofluorocarbons (CFCs), halons and other chlorine-containing and bromine-containing compounds, collectively termed ozone-depleting substances (ODSs). Following controls on the production of major, long-lived ODSs by the Montreal Protocol, the ozone layer is now showing initial signs of recovery and is anticipated to return to pre-depletion levels in the mid-to-late twenty-first century, likely 2050–2060. These return dates assume widespread compliance with the Montreal Protocol and, thereby, continued reductions in ODS emissions. However, recent observations reveal increasing emissions of some controlled (for example, CFC-11, as in eastern China) and uncontrolled substances (for example, very short-lived substances (VSLSs)). Indeed, the emissions of a number of uncontrolled VSLSs are adding significant amounts of ozone-depleting chlorine to the atmosphere. In this Review, we discuss recent emissions of both long-lived ODSs and halogenated VSLSs, and how these might lead to a delay in ozone recovery. Continued improvements in observational tools and modelling approaches are needed to assess these emerging challenges to a timely recovery of the ozone layer

Efficiency of short-lived halogens at influencing climate through depletion of stratospheric ozone

Halogens released from long-lived anthropogenic substances, such as chlorofluorocarbons, are the principal cause of recent depletion of stratospheric ozone, a greenhouse gas. Recent observations show that very short-lived substances, with lifetimes generally under six months, are also an important source of stratospheric halogens. Short-lived bromine substances are produced naturally by seaweed and phytoplankton, whereas short-lived chlorine substances are primarily anthropogenic. Here we used a chemical transport model to quantify the depletion of ozone in the lower stratosphere from short-lived halogen substances, and a radiative transfer model to quantify the radiative effects of that ozone depletion. According to our simulations, ozone loss from short-lived substances had a radiative effect nearly half that from long-lived halocarbons in 2011 and, since pre-industrial times, has contributed a total of about −0.02 W m−2 to global radiative forcing. We find natural short-lived bromine substances exert a 3.6 times larger ozone radiative effect than long-lived halocarbons, normalized by halogen content, and show atmospheric levels of dichloromethane, a short-lived chlorine substance not controlled by the Montreal Protocol, are rapidly increasing. We conclude that potential further significant increases in the atmospheric abundance of short-lived halogen substances, through changing natural processes or continued anthropogenic emissions, could be important for future climate