The effect of desiccation on the emission of volatile bromocarbons from two common temperate macroalgae

Exposure of intertidal macroalgae during low tide has been linked to the emission of a variety of atmospherically-important trace gases into the coastal atmosphere. In recent years, several studies have investigated the role of inorganic iodine and organoiodides as antioxidants and their emission during exposure to combat oxidative stress, yet the role of organic bromine species during desiccation is less well understood. In this study the emission of dibromomethane (CH2Br2) and bromoform (CHBr3) during exposure and desiccation of two common temperate macroalgae, Fucus vesiculosus and Ulva intestinalis, is reported. Determination of the impact exposure may have on algal physiological processes is difficult as intertidal species are adapted to desiccation and may undergo varying degrees of desiccation before their physiology is affected. For this reason we include comparisons between photosynthetic capacity (Fv/Fm) and halocarbon emissions during a desiccation time series. In addition, the role of rewetting with freshwater to simulate exposure to rain was also investigated. Our results show that an immediate flux of bromocarbons occurs upon exposure, followed by a decline in bromocarbon emissions. We suggest that this immediate bromocarbon pulse may be linked to volatilisation or emissions of existing bromocarbon stores from the algal surface rather than the production of bromocarbons as an antioxidant response

Tracer Measurements in Growing Sea Ice Support Convective Gravity Drainage Parameterizations

Gravity drainage is the dominant process redistributing solutes in growing sea ice. Modeling gravity drainage is therefore necessary to predict physical and biogeochemical variables in sea ice. We evaluate seven gravity drainage parameterizations, spanning the range of approaches in the literature, using tracer measurements in a sea ice growth experiment. Artificial sea ice is grown to around 17 cm thickness in a new experimental facility, the Roland von Glasow air‐sea‐ice chamber. We use NaCl (present in the water initially) and rhodamine (injected into the water after 10 cm of sea ice growth) as independent tracers of brine dynamics. We measure vertical profiles of bulk salinity in situ, as well as bulk salinity and rhodamine in discrete samples taken at the end of the experiment. Convective parameterizations that diagnose gravity drainage using Rayleigh numbers outperform a simpler convective parameterization and diffusive parameterizations when compared to observations. This study is the first to numerically model solutes decoupled from salinity using convective gravity drainage parameterizations. Our results show that (1) convective, Rayleigh number‐based parameterizations are our most accurate and precise tool for predicting sea ice bulk salinity; and (2) these parameterizations can be generalized to brine dynamics parameterizations, and hence can predict the dynamics of any solute in growing sea ic

Southern hemispheric halon trends and global halon emissions, 1978–2011

The atmospheric records of four halons, H-1211 (CBrClF2), H-1301 (CBrF3), H-2402 (CBrF2CBrF2) and H-1202 (CBr2F2), measured from air collected at Cape Grim, Tasmania, between 1978 and 2011, are reported. Mixing ratios of H-1211, H-2402 and H-1202 began to decline in the early to mid-2000s, but those of H-1301 continue to increase up to mid-2011. These trends are compared to those reported by NOAA (National Oceanic and Atmospheric Administration) and AGAGE (Advanced Global Atmospheric Experiment). The observations suggest that the contribution of the halons to total tropospheric bromine at Cape Grim has begun to decline from a peak in 2008 of about 8.1 ppt. An extrapolation of halon mixing ratios to 2060, based on reported banks and predicted release factors, shows this decline becoming more rapid in the coming decades, with a contribution to total tropospheric bromine of about 3 ppt in 2060. Top-down global annual emissions of the halons were derived using a two-dimensional atmospheric model. The emissions of all four have decreased since peaking in the late 1980s–mid-1990s, but this decline has slowed recently, particularly for H-1301 and H-2402 which have shown no decrease in emissions over the past five years. The UEA (University of East Anglia) top-down model-derived emissions are compared to those reported using a top-down approach by NOAA and AGAGE and the bottom-up estimates of HTOC (Halons Technical Options Committee). The implications of an alternative set of steady-state atmospheric lifetimes are discussed. Using a lifetime of 14 yr or less for H-1211 to calculate top-down emissions estimates would lead to small, or even negative, estimated banks given reported production data. Finally emissions of H-1202, a product of over-bromination during the production process of H-1211, have continued despite reported production of H-1211 ceasing in 2010. This raises questions as to the source of these H-1202 emissions

References

www.biogeosciences-discuss.net/11/10673/2014/ doi:10.5194/bgd-11-10673-2014 © Author(s) 2014. CC Attribution 3.0 License. This discussion paper is/has been under review for the journal Biogeosciences (BG). Please refer to the corresponding final paper in BG if available. The effect of desiccation on the emission of volatile bromocarbons from two common temperate macroalga

Reporting corporate sustainability and the challenges of political rhetoric

Where organisations set out their sustainable values and make publically available their sustainable strategy, the rhetoric establishes an agenda against which, should deviation occur, the company can be publically held to account. As a result of recent scandals, it is not surprising that some people remain cautious or even cynical with regard to corporate sustainability, especially where it is found that the actual practices of an organisation are different to that reported. The research provides a review of company reports to identify how multinational organisations advocate their sustainable position. Both construction and non-construction companies are considered with regard to the use of the term 'sustainable'. The review finds that the multinational organisations, both construction and non-construction have in recent years provided a position on sustainability. While heavy construction companies are setting a commitment toward sustainability, the positions stated against which the companies may be measured are often vague. There were, however, company reports where commitments to sustainability were detailed and the statements could be considered measureable. Nevertheless, most company reports use sustainability terms that remain generic and lend themselves to a more flexible approach to sustainability or, cynically, are providing the rhetoric for public relations

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

Accelerating growth of HFC-227ea (1,1,1,2,3,3,3-heptafluoropropane) in the atmosphere

We report the first measurements of 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), a substitute for ozone depleting compounds, in air samples originating from remote regions of the atmosphere and present evidence for its accelerating growth. Observed mixing ratios ranged from below 0.01 ppt in deep firn air to 0.59 ppt in the current northern mid-latitudinal upper troposphere. Firn air samples collected in Greenland were used to reconstruct a history of atmospheric abundance. Year-on-year increases were deduced, with acceleration in the growth rate from 0.029 ppt per year in 2000 to 0.056 ppt per year in 2007. Upper tropospheric air samples provide evidence for a continuing growth until late 2009. Furthermore we calculated a stratospheric lifetime of 370 years from measurements of air samples collected on board high altitude aircraft and balloons. Emission estimates were determined from the reconstructed atmospheric trend and suggest that current "bottom-up" estimates of global emissions for 2005 are too high by a factor of three

Extreme renormalisations of dimer eigenmodes by strong light–matter coupling

This is the final version. Available from IOP Publishing via the DOI in this record. We explore by theoretical means an extreme renormalisation of the eigenmodes of a dimer of dipolar meta-atoms due to strong light-matter interactions. Firstly, by tuning the height of an enclosing photonic cavity, we can lower the energy level of the symmetric ‘bright’ mode underneath that of the anti-symmetric ‘dark’ mode. This is possible due to the polaritonic nature of the symmetric mode, that shares simultaneously its excitation with the cavity and the dimer. For a heterogeneous dimer, we show that the polariton modes can be smoothly tuned from symmetric to anti-symmetric, resulting in a variable mode localisation from extended throughout the cavity to concentrated around the vicinity of the dimer. In addition, we reveal a critical point where one of the meta-atoms becomes ‘shrouded’, with no response to a driving electric field, and thus the field re-radiated by the dimer is only that of the other meta-atom. We provide an exact analytical description of the system from first principles, as well as full-wave electromagnetic simulations that show a strong quantitative agreement with the analytical model. Our description is relevant for any such physical dimer where dipolar interactions are the dominant mechanism.Juan de la Cierva program (MINECO, Spain

A 60 yr record of atmospheric carbon monoxide reconstructed from Greenland firn air

We present the first reconstruction of the Northern Hemisphere (NH) high latitude atmospheric carbon monoxide (CO) mole fraction from Greenland firn air. Firn air samples were collected at three deep ice core sites in Greenland (NGRIP in 2001, Summit in 2006 and NEEM in 2008). CO records from the three sites agree well with each other as well as with recent atmospheric measurements, indicating that CO is well preserved in the firn at these sites. CO atmospheric history was reconstructed back to the year 1950 from the measurements using a combination of two forward models of gas transport in firn and an inverse model. The reconstructed history suggests that Arctic CO in 1950 was 140–150 nmol mol-1, which is higher than today's values. CO mole fractions rose by 10–15 nmol mol-1 from 1950 to the 1970s and peaked in the 1970s or early 1980s, followed by a ˜ 30 nmol mol-1 decline to today's levels. We compare the CO history with the atmospheric histories of methane, light hydrocarbons, molecular hydrogen, CO stable isotopes and hydroxyl radicals (OH), as well as with published CO emission inventories and results of a historical run from a chemistry-transport model. We find that the reconstructed Greenland CO history cannot be reconciled with available emission inventories unless unrealistically large changes in OH are assumed. We argue that the available CO emission inventories strongly underestimate historical NH emissions, and fail to capture the emission decline starting in the late 1970s, which was most likely due to reduced emissions from road transportation in North America and Europe