Warren J. De Bruyn

Processes controlling the distribution of aerosol particles in the lower marine boundary layer during the First Aerosol Characterization Experiment (ACE 1)

The goals of the International Global Atmospheric Chemistry (IGAC) Programs First Aerosol Characterization Experiment (ACE 1) are to determine and understand the properties and controlling factors of the aerosol in the remote marine atmosphere that are relevant to radiative forcing and climate. A key question in terms of this goal and the overall biogeochemical sulfur cycle is what factors control the formation, growth, and evolution of particles in the marine boundary layer (MBL). To address this question, simultaneous measurements of dimethylsulfide (DMS), sulfur dioxide (SO2), the aerosol chemical mass size distribution, and the aerosol number size distribution from 5 to 10,000 nm diameter were made on the National Oceanic and Atmospheric Administration (NOAA) ship Discoverer. From these data we conclude that the background MBL aerosol during ACE 1 often was composed of four distinct modes: an ultrafine (UF) mode (Dp = 5–20 nm), an Aitken mode (Dp = 20–80 nm), an accumulation mode (Dp = 80–300 nm), and a coarse mode (Dp > 300 nm). The presence of UF mode particles in the MBL could be explained by convective mixing between the free troposphere (FT) and the MBL associated with cloud pumping and subsidence following cold frontal passages. There was no evidence of major new particle production in the MBL. Oceanic emissions of DMS appeared to contribute to the growth of Aitken and accumulation mode particles. Coarse mode particles were comprised primarily of sea salt. Although these particles result from turbulence at the air-sea interface, the instantaneous wind speed accounted for only one third of the variance in the coarse mode number concentration in this region.

Atmospheric sulfur cycle simulated in the global model GOCART: Comparison with field observations and regional budgets

We present a detailed evaluation of the atmospheric sulfur cycle simulated in the Georgia Tech/Goddard Global Ozone Chemistry Aerosol Radiation and Transport (GOCART) model. The model simulations of SO2, sulfate, dimethylsulfide (DMS), and methanesulfonic acid (MSA) are compared with observations from different regions on various timescales. The model agrees within 30% with the regionally averaged sulfate concentrations measured over North America and Europe but overestimates the SO2 concentrations by more than a factor of 2 there. This suggests that either the emission rates are too high, or an additional loss of SO2 which does not lead to a significant sulfate production is needed. The average wintertime sulfate concentrations over Europe in the model are nearly a factor of 2 lower than measured values, a discrepancy which may be attributed largely to the sea-salt sulfate collected in the data. The model reproduces the sulfur distributions observed over the oceans in both long-term surface measurements and short-term aircraft campaigns. Regional budget analyses show that sulfate production from SO2 oxidation is 2 to 3 times more efficient and the lifetimes of SO2 and sulfate are nearly a factor of 2 longer over the ocean than over the land. This is due to a larger free tropospheric fraction of SO2 column over the ocean than over the land, hence less loss to the surface. The North Atlantic and northwestern Pacific regions are heavily influenced by anthropogenic activities, with more than 60% of the total SO2 originating from anthropogenic sources. The average production efficiency of SO2 from DMS oxidation is estimated at 0.87 to 0.91 in most oceanic regions.

Shipboard measurements of dimethyl sulfide and SO2southwest of Tasmania during the First Aerosol Characterization Experiment (ACE 1)

Measurements of seawater dimethylsulfide (DMS), atmospheric dimethylsulfide, and sulfur dioxide (SO 2 ) were made on board the R/VDiscoverer in the Southern Ocean, southeast of Australia, as part of the First Aerosol Characterization Experiment (ACE 1). The measurements covered a latitude range of 40°S–55°S during November-December 1995. Seawater DMS concentrations ranged from 0.4 to 6.8 nM, with a mean of 1.7±1.1 nM (1σ). The highest DMS concentrations were found in subtropical convergence zone waters north of 44°S, and the lowest were found in polar waters south of 49°S. In general, seawater DMS concentrations increased during the course of the study, presumably due to the onset of austral spring warming. Atmospheric DMS concentrations ranged from 24 to 350 parts per trillion by volume (pptv), with a mean of 112±61 pptv (1σ). Atmospheric SO2 was predominantly of marine origin with occasional anthropogenic input, as evidenced by correlation with elevated 222 Rn and air mass trajectories. Concentrations ranged from 3 to 1000 pptv with a mean of 48.8± 49 pptv (1σ) and a median 15.8 pptv. The mean SO2 concentration observed in undisturbed marine air was 11.9±7.6 pptv (1σ), and the mean DMS to SO2 ratio in these conditions was 13±9 (1σ). Diurnal variations in

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.

Air-Sea Gas Exchange Of Co2 and Dms In the North Atlantic By Eddy Covariance

We report the first simultaneous eddy covariance flux measurements of CO2 and dimethylsulfide (DMS) over the open ocean for two North Atlantic cruises. After normalization for Schmidt number, the two gases give essentially identical gas transfer coefficients and wind speed dependences for the wind speed range 2–10 ms−1. The data indicate a linear relationship between the gas transfer coefficient and mean wind speed, with measured gas transfer coefficients slightly above the Wanninkhof (1992) parameterization, particularly at low wind speeds.

Photochemical degradation of phenanthrene as a function of natural water variables modeling freshwater to marine environments.

Photolysis rates of phenanthrene as a function of ionic strength (salinity), oxygen levels and humic acid concentrations were measured in aqueous solution over the range of conditions found in fresh to marine waters. Photolysis followed first order kinetics, with an estimated photodegradation half-life in sunlight in pure water of 10.3±0.7h, in the mid-range of published results. Photolysis rate constants decreased by a factor of 5 in solutions with humic acid concentrations from 0 to 10 mg C L(-1). This decrease could be modeled entirely based on competitive light absorption effects due to the added humics. No significant ionic strength or oxygen effects were observed, consistent with a direct photolysis mechanism. In the absence of significant solution medium effects, the photodegradation lifetime of phenanthrene will depend only on solar fluxes (i.e. temporal and seasonal changes in sunlight) and not vary with a freshwater to marine environment.

Photochemical production of hydrogen peroxide in size-fractionated Southern California coastal waters

Hydrogen peroxide (H(2)O(2)) photochemical production was measured in bulk and size-fractionated surf zone and source waters (Orange County, California, USA). Post-irradiation (60 min; 300 W ozone-free xenon lamp), maximum H(2)O(2) concentrations were approximately 10000 nM (source) and approximately 1500 nM (surf zone). Average initial hydrogen peroxide production rates (HPPR) were higher in bulk source waters (11+/-7.0 nM s(-1)) than the surf zone (2.5+/-1 nM s(-1)). A linear relationship was observed between non-purgeable dissolved organic carbon and absorbance coefficient (m(-1) (300 nm)). HPPR increased with increasing absorbance coefficient for bulk and size-fractionated source waters, consistent with photochemical production from CDOM. However, HPPR varied significantly (5x) for surf zone samples with the same absorbance coefficients, even though optical properties suggested CDOM from salt marsh source waters dominates the surf zone. To compare samples with varying CDOM levels, apparent quantum yields (Phi) for H(2)O(2) photochemical production were calculated. Source waters showed no significant difference in Phi between bulk, large (>1000 Da (>1 kDa)) and small (<1 kDa) size fractions, suggesting H(2)O(2) production efficiency is homogeneously distributed across CDOM size. However, surf zone waters had significantly higher Phi than source (bulk 0.086+/-0.04 vs. 0.034+/-0.013; <1 kDa 0.183+/-0.012 vs. 0.027+/-0.018; >1 kDa 0.151+/-0.090 vs. 0.016+/-0.009), suggesting additional production from non-CDOM sources. H(2)O(2) photochemical production was significant for intertidal beach sand and senescent kelp (sunlight; approximately 42 nM h(-1) vs. approximately 5 nM h(-1)), on the order of CDOM production rates previously measured in coastal and oceanic waters. This is the first study of H(2)O(2) photochemical production in size-fractionated coastal waters showing significant production from non-CDOM sources in the surf zone.

Hydrogen peroxide measurements in recreational marine bathing waters in Southern California, USA

Hydrogen peroxide (H(2)O(2)) was measured in the surf zone at 13 bathing beaches in Southern California, USA. Summer dry season concentrations averaged 122 +/- 38 nM with beaches with tide pools having lower levels (50-90 nM). No significant differences were observed for ebb waters at a salt marsh outlet vs. a beach (179 +/- 20 vs. 163 +/- 26 nM), and between ebb and flood tides at one site (171 +/- 24 vs. 146 +/- 42 nM). H(2)O(2) levels showed little annual variation. Diel cycling was followed over short (30 min; 24 h study) and long (d) time scales, with maximum afternoon concentration = 370 nM and estimated photochemical production rate of 44 nM h(-1). There was no correlation between the absorbance coefficient at 300 nm (used as a measure of chromophoric dissolved organic matter (CDOM) levels) and H(2)O(2). H(2)O(2) concentrations measured in this study are likely sufficient to inhibit fecal indicator bacteria in marine recreational waters through indirect photoinactivation.

Photoproduction of hydrogen peroxide in aqueous solution from model compounds for chromophoric dissolved organic matter (CDOM)

To explore whether quinone moieties are important in chromophoric dissolved organic matter (CDOM) photochemistry in natural waters, hydrogen peroxide (H2O2) production and associated optical property changes were measured in aqueous solutions irradiated with a Xenon lamp for CDOM model compounds (dihydroquinone, benzoquinone, anthraquinone, napthoquinone, ubiquinone, humic acid HA, fulvic acid FA). All compounds produced H2O2 with concentrations ranging from 15 to 500 μM. Production rates were higher for HA vs. FA (1.32 vs. 0.176 mM h(-1)); values ranged from 6.99 to 0.137 mM h(-1) for quinones. Apparent quantum yields (Θ app; measure of photochemical production efficiency) were higher for HA vs. FA (0.113 vs. 0.016) and ranged from 0.0018 to 0.083 for quinones. Dihydroquinone, the reduced form of benzoquinone, had a higher production rate and efficiency than its oxidized form. Post-irradiation, quinone compounds had absorption spectra similar to HA and FA and 3D-excitation-emission matrix fluorescence spectra (EEMs) with fluorescent peaks in regions associated with CDOM.

Diel cycles of hydrogen peroxide in marine bathing waters in Southern California, USA: In situ surf zone measurements

Hydrogen peroxide is photochemically produced in natural waters. It has been implicated in the oxidative-induced mortality of fecal indicator bacteria (FIB), a microbial water quality measure. To assess levels and cycling of peroxide in beach waters monitored for FIB, diel studies were carried out in surf zone waters in July 2009 at Crystal Cove State Beach, Southern California, USA. Maximum concentrations of 160-200 nM were obtained within 1h of solar noon. Levels dropped at night to 20-40 nM, consistent with photochemical production from sunlight. Day-time production and night-time dark loss rates averaged 16 ± 3 nM h(-1) and 12 ± 4 nM h(-1) respectively. Apparent quantum yields averaged 0.07 ± 0.02. Production was largely dominated by sunlight, with some dependence on chromophoric dissolved organic matter (CDOM) levels in waters with high absorption coefficients. Peroxide levels measured here are sufficient to cause oxidative-stress-induced mortality of bacteria, affect FIB diel cycling and impact microbial water quality in marine bathing waters.