The Aqueous Phase Yield Of Alkyl Nitrates From Roo+No: Implications For Photochemical Production In Seawater

Alkyl nitrates have been observed in remote oceanic regions of the troposphere and in the surface ocean. The mechanism for their production in the oceans is not known. A likely source is the reaction of ROO + NO (where R is an alkyl group). Steady-state laboratory experiments show that alkyl nitrates are produced in the aqueous phase via this reaction, with branching ratios of 0.23 +/- 0.04, 0.67 +/- 0.03, and 0.71 +/- 0.04 for methyl, ethyl, and propyl nitrate respectively. The branching ratios in aqueous solution are significantly higher than in the gas phase. Irradiation of surface seawaters yield rates of alkyl nitrate production on the order of 10(-18) mol cm(-3) s(-1), suggesting that the reaction of ROO and NO is an important source of alkyl nitrates in seawater

Nutrient availability determines dimethyl sulfide and isoprene distribution in the eastern Atlantic Ocean

Continuous high-resolution underway measurements of dimethyl sulfide (DMS) and isoprene in the ocean surface were conducted from Germany to South Africa in November 2008. DMS, total dimethylsulfoniopropionate (DMSPt), isoprene and 19'-hexanoyloxyfucoxanthin (19'-hex) correlated in nitrogen-depleted regions when they were clustered by nitrogen to phosphorous ratio (N:P). The 19'-hex-containing algae groups might be a common source of DMS, DMSPt, and isoprene in the low N: P regions. Additionally, DMS and isoprene correlated in nitrate-depleted regions when they were clustered against nitrate concentrations. Correlations between DMS and isoprene were also found within nitrate-depleted eddies encountered along the cruise track. Eddies with N: P of similar to 2.8 showed the highest positive correlations between DMS and isoprene. We conclude that the DMS/isoprene relationships in the eastern Atlantic Ocean were influenced by nutrient availability, with implications for using nutrients to predict the DMS and isoprene concentrations over a range of oceanographic areas depleted in nitroge

Correction to Oceanic Uptake and the Global Atmospheric Acetone Budget

In the paper ‘‘Oceanic uptake and the global atmospheric acetone budget’’ by C. A. Marandino et al. (Geophys. Res. Lett., 32, L15806, doi:10.1029/2005GL023285) it was recently determined that a calculation error was made during flux data processing

Dimethylsulfide Gas Transfer Coefficients from Algal Blooms in the Southern Ocean

Air-sea dimethylsulfide (DMS) fluxes and bulk air-sea gradients were measured over the Southern Ocean in February-March 2012 during the Surface Ocean Aerosol Production (SOAP) study. The cruise encountered three distinct phytoplankton bloom regions, consisting of two blooms with moderate DMS levels, and a high biomass, dinoflagellate-dominated bloom with high seawater DMS levels (\u3e 15 nM). Gas transfer coefficients were considerably scattered at wind speeds above 5 m s(-1). Bin averaging the data resulted in a linear relationship between wind speed and mean gas transfer velocity consistent with that previously observed. However, the wind-speed-binned gas transfer data distribution at all wind speeds is positively skewed. The flux and seawater DMS distributions were also positively skewed, which suggests that eddy covariance-derived gas transfer velocities are consistently influenced by additional, log-normal noise. A flux footprint analysis was conducted during a transect into the prevailing wind and through elevated DMS levels in the dinoflagellate bloom. Accounting for the temporal/spatial separation between flux and seawater concentration significantly reduces the scatter in computed transfer velocity. The SOAP gas transfer velocity data show no obvious modification of the gas transfer-wind speed relationship by biological activity or waves. This study highlights the challenges associated with eddy covariance gas transfer measurements in biologically active and heterogeneous bloom environments

Atmospheric Variability Of Methyl Chloride During the Last 300 Years From an Antarctic Ice Core and Firn Air

Measurements of methyl chloride (CH3Cl) in Antarctic polar ice and firn air are used to describe the variability of atmospheric CH3Cl during the past 300 years. Firn air results from South Pole and Siple Dome suggest that the atmospheric abundance of CH3Cl increased by about 10% in the 50 years prior to 1990. Ice core measurements from Siple Dome provide evidence for a cyclic natural variability on the order of 10%, with a period of about 110 years in phase with the 20th century rise inferred from firn air. Thus, the CH3Cl increase measured in firn air may largely be a result of natural processes, which may continue to affect the atmospheric CH3Cl burden during the 21st century

The Dominion Range Ice Core, Queen Maud Mountains, Antarctica - General Site and Core Characteristics with Implications

The Transantarctic Mountains of East Antarctica provide a new milieu for retrieval of ice-core records. We report here on the initial findings from the first of these records, the Dominion Range ice-core record. Sites such as the Dominion Range are valuable for the recovery of records detailing climate change, volcanic activity, and changes in the chemistry of the atmosphere. The unique geographic location of this site and a relatively low accumulation rate combine to provide a relatively long record of change for this potentially sensitive climatic region. As such, information concerning the site and general core characteristics are presented, including ice surface, ice thickness, bore-hole temperature, mean annual net accumulation, crystal size, crystal fabric, oxygen-isotope composition, and examples of ice chemistry and isotopic composition of trapped gases

Methyl Bromide In Preindustrial Air: Measurements From an Antarctic Ice Core

This paper presents the first ice core measurements of methyl bromide (CH3Br). Samples from a shallow Antarctic ice core (Siple Dome, West Antarctica), ranging in mean gas dates from 1671 to 1942, had a mean CH3Br mixing ratio of 5.8 ppt. These results extend the existing historical record derived from air and Antarctic firn air to about 350 years before present. Model simulations illustrate that the ice core results are consistent with estimates of the impact of anthropogenic activity ( fumigation, combustion, and biomass burning) on the atmospheric CH3Br burden, given the large current uncertainties in the modern atmospheric CH3Br budget. A preindustrial scenario assuming no fumigation, no combustion, and a 75% reduction in biomass-burning sources yields aSouthern Hemisphere mean mixing ratio of 5.8 ppt, in good agreement with the ice core results. There is a significant imbalance between the known CH3Br sources and sinks in the modern atmospheric CH3Br budget. The ice core data do not sufficiently constrain the model to determine how much of the unknown source\u27\u27 was present in the preindustrial budget. The results do indicate that most of the southern hemispheric component of this unknown source\u27\u27 is not anthropogenic

Aromatic acids in a Eurasian Arctic ice core: a 2,600-year proxy record of biomass burning

Wildfires and their emissions have significant impacts on ecosystems, climate, atmospheric chemistry, and carbon cycling. Well-dated proxy records are needed to study the long-term climatic controls on biomass burning and the associated climate feedbacks. There is a particular lack of information about long-term biomass burning variations in Siberia, the largest forested area in the Northern Hemisphere. In this study we report analyses of aromatic acids (vanillic and para-hydroxybenzoic acids) over the past 2600 years in the Eurasian Arctic Akademii Nauk ice core. These compounds are aerosol-borne, semi-volatile organic compounds derived from lignin combustion. The analyses were made using ion chromatography with electrospray mass spectrometric detection. The levels of these aromatic acids ranged from below the detection limit (0.01 to 0.05 ppb; 1 ppb  =  1000 ng L−1) to about 1 ppb, with roughly 30 % of the samples above the detection limit. In the preindustrial late Holocene, highly elevated aromatic acid levels are observed during three distinct periods (650–300 BCE, 340–660 CE, and 1460–1660 CE). The timing of the two most recent periods coincides with the episodic pulsing of ice-rafted debris in the North Atlantic known as Bond events and a weakened Asian monsoon, suggesting a link between fires and large-scale climate variability on millennial timescales. Aromatic acid levels also are elevated during the onset of the industrial period from 1780 to 1860 CE, but with a different ratio of vanillic and para-hydroxybenzoic acid than is observed during the preindustrial period. This study provides the first millennial-scale record of aromatic acids. This study clearly demonstrates that coherent aromatic acid signals are recorded in polar ice cores that can be used as proxies for past trends in biomass burning

Methanethiol, Dimethyl Sulfide and Acetone Over Biologically Productive Waters in the Southwest Pacific Ocean

Atmospheric methanethiol (MeSHa), dimethyl sulfide (DMSa) and acetone (acetonea) were measured over biologically productive frontal waters in the remote southwest Pacific Ocean in summertime 2012 during the Surface Ocean Aerosol Production (SOAP) voyage. MeSHa mixing ratios varied from below the detection limit (\u3c 10 ppt) up to 65 ppt and were 3 %–36 % of parallel DMSa mixing ratios. MeSHa and DMSa were correlated over the voyage (R2=0.3, slope = 0.07) with a stronger correlation over a coccolithophore-dominated phytoplankton bloom (R2=0.5, slope 0.13). The diurnal cycle for MeSHa shows similar behaviour to DMSa with mixing ratios varying by a factor of ∼ 2 according to time of day with the minimum levels of both MeSHa and DMSa occurring at around 16:00 LT (local time, all times in this paper are in local time). A positive flux of MeSH out of the ocean was calculated for three different nights and ranged from 3.5 to 5.8 µmol m−2 d−1, corresponding to 14 %–24 % of the DMS flux (MeSH ∕ (MeSH + DMS)). Spearman rank correlations with ocean biogeochemical parameters showed a moderate-to-strong positive, highly significant relationship between both MeSHa and DMSa with seawater DMS (DMSsw) and a moderate correlation with total dimethylsulfoniopropionate (total DMSP). A positive correlation of acetonea with water temperature and negative correlation with nutrient concentrations are consistent with reports of acetone production in warmer subtropical waters. Positive correlations of acetonea with cryptophyte and eukaryotic phytoplankton numbers, and high-molecular-weight sugars and chromophoric dissolved organic matter (CDOM), suggest an organic source. This work points to a significant ocean source of MeSH, highlighting the need for further studies into the distribution and fate of MeSH, and it suggests links between atmospheric acetone levels and biogeochemistry over the mid-latitude ocean. In addition, an intercalibration of DMSa at ambient levels using three independently calibrated instruments showed ∼ 15 %–25 % higher mixing ratios from an atmospheric pressure ionisation chemical ionisation mass spectrometer (mesoCIMS) compared to a gas chromatograph with a sulfur chemiluminescence detector (GC-SCD) and proton transfer reaction mass spectrometer (PTR-MS). Some differences were attributed to the DMSa gradient above the sea surface and differing approaches of integrated versus discrete measurements. Remaining discrepancies were likely due to different calibration scales, suggesting that further investigation of the stability and/or absolute calibration of DMS standards used at sea is warranted

Aromatic acids in an Arctic ice core from Svalbard: a proxy record of biomass burning

This study presents vanillic acid and parahydroxybenzoic acid levels in an Arctic ice core from Lomonosovfonna, Svalbard covering the past 800 years. These aromatic acids are likely derived from lignin combustion in wildfires and long-range aerosol transport. Vanillic and para-hydroxybenzoic acid are present throughout the ice core, confirming that these compounds are preserved on millennial timescales. Vanillic and para-hydroxybenzoic acid concentrations in the Lomonosovfonna ice core ranged from below the limits of detection to 0.2 and 0.07 ppb, respectively (1 ppb =1000 ng L-1). Vanillic acid levels are high (maximum of 0.1 ppb) from 1200 to 1400 CE, then gradually decline into the twentieth century. The largest peak in the vanillic acid in the record occurs from 2000 to 2008 CE. In the para-hydrobenzoic acid record, there are three centennialscale peaks around 1300, 1550, and 1650 CE superimposed on a long-term decline in the baseline levels throughout the record. Ten-day air mass back trajectories for a decade of fire seasons (March-November, 2006-2015) indicate that Siberia and Europe are the principle modern source regions for wildfire emissions reaching the Lomonosovfonna site. The Lomonosovfonna data are similar to those from the Eurasian Arctic Akademii Nauk ice core during the early part of the record (1220-1400 CE), but the two ice cores diverge markedly after 1400 CE. This coincides with a shift in North Atlantic climate marked by a change of the North Atlantic Oscillation from a positive to a more negative state