Anne M. Johansen

Chemical composition of aerosols collected over the tropical North Atlantic Ocean

Ambient aerosol samples were collected over the tropical northern Atlantic Ocean during the month of April 1996 onboard the R/V Seward Johnson. Dichotomous high-volume collector samples were analyzed for ferrous iron immediately after collection, while trace metals, anions, and cations were determined upon return to the laboratory. Data are analyzed with the aid of enrichment factor, principal component, and weighted multiple linear regression analyses. Average mineral aerosol concentrations amounted to 19.3±16.4 μg m^(−3) whereby the chemical characteristics and air mass back trajectories indicated the dust to be of a typical shale composition and Saharan origin. Calcite accounted for 3.0 and 7.9% of the mineral aerosol during the first and second halves of the cruise, respectively. Total iron concentrations (averaging 0.84±0.61 μg m^(−3)) are crustally derived, of which 0.51±0.56% is readily released as Fe(II). Eighty-six percent of this Fe(II) is present in the fine (<3 μm diameter) aerosol fraction and correlates with NSS-SO_4^(2−) and oxalate. Approximately 23% of the measured NSS-SO_4^(2−) in both size fractions appears to be biogenically derived, and the rest is of anthropogenic nature. Biogenic SO_4^(2−) /methanesulfonic acid (MSA) ratios could not be easily extracted by employing a multiple linear regression analysis analogous to that of Johansen et al. [1999], possibly due to the varying characteristics of the aerosol chemistry and air temperature during the cruise. Because of the presence of anthropogenic SO_4^(2−), the non-sea-salt (NSS)- SO_4^(2−)/MSA ratio, 37.4±6.4, is elevated over what would be expected if the NSS - SO_4^(2−) were purely biogenic. Cl^− depletion is seen in all samples and averages 18.3±9.1%. The release of Cl from the aerosol phase appears to occur through acid displacement reactions with primarily HNO_3 in the coarse and H_2SO_4 in the fine fraction.

Chemical characterization of ambient aerosol collected during the southwest monsoon and intermonsoon seasons over the Arabian Sea: Labile-Fe(II) and other trace metals

Atmospheric deposition of iron (Fe) to certain regions of the oceans is an important nutrient source of Fe to the biota, and the ability of the biota to uptake Fe is dependent on the speciation of the Fe. Therefore understanding the speciation of Fe in the atmosphere is critical to understanding the role of Fe as a nutrient source in surface ocean waters. Labile ferrous iron (Fe(II)) concentrations as well as total concentrations for Fe and other important trace metals, cations, and anions were determined over the Arabian Sea for two nonconsecutive months during 1995. Ambient aerosol samples were collected during the Indian Ocean intermonsoon and southwest monsoon seasons over the Arabian Sea. Sampling took place aboard the German research vessel Meteor in the months of May (leg M32/3; intermonsoon) and July/August (leg M32/5; southwest monsoon). Both cruise tracks followed the 65th east meridian, traveling for 30 days each (from north to south during leg M32/3 and from south to north during leg M32/5). A high-volume dichotomous virtual impactor with an aerodynamic cutoff size of 3 μm was used to collect the fine and coarse aerosol fractions for metal analysis. A low volume collector was used to collect aerosol samples for anion and cation analysis. The analysis for labile-Fe(II) was done immediately after sample collection to minimize any possible Fe redox reactions which might occur during sample storage. The analytical procedure involved filter extraction in a formate/formic acid buffered solution at pH 4.2 followed by colorimetric quantification of soluble Fe(II). Metals, anions, and cations were analyzed after the cruise. Total atmospheric aqueous-labile-Fe(II) concentrations during the intermonsoon were between 4.75 and 80%) was present in the fine fraction (<3.0 μm). During the southwest monsoon, atmospheric aqueous-labile-Fe(II) concentrations were consistently below the detection limit (<0.34 to <0.089 ng m^(−3), depending on the volume of air sampled). Air mass back trajectories (5 day, three dimensional) showed that air masses sampled during the southwest monsoon had advected over the open Indian Ocean, while air masses sampled during the intermonsoon had advected over northeast Africa, the Saudi Arabian peninsula, and southern Asia. These calculations were consistent with the results of the statistical analysis performed on the data set which showed that the variance due to crustal species during the intermonsoon samples was greater than the variance due to crustal species during the southwest monsoon. The factor scores for the crustal components were also greater when the back trajectories had advected over the nearby continental masses. Principal component analysis was also performed with the intermonsoon samples where aqueous labile Fe(II) was above the detection limit. Aqueous labile Fe(II) did not correlate well with other species indicating possible atmospheric processing of the iron during advection.

A revised nitrogen budget for the Arabian Sea

Despite its importance for the global oceanic nitrogen (N) cycle, considerable uncertainties exist about the N fluxes of the Arabian Sea. On the basis of our recent measurements during the German Arabian Sea Process Study as part of the Joint Global Ocean Flux Study (JGOFS) in 1995 and 1997, we present estimates of various N sources and sinks such as atmospheric dry and wet depositions of N aerosols, pelagic denitrification, nitrous oxide (N2O) emissions, and advective N input from the south. Additionally, we estimated the N burial in the deep sea and the sedimentary shelf denitrification. On the basis of our measurements and literature data, the N budget for the Arabian Sea was reassessed. It is dominated by the N loss due to denitrification, which is balanced by the advective input of N from the south. The role of N fixation in the Arabian Sea is still difficult to assess owing to the small database available; however, there are hints that it might be more important than previously thought. Atmospheric N depositions are important on a regional scale during the intermonsoon in the central Arabian Sea; however, they play only a minor role for the overall N cycling. Emissions of N2O and ammonia, deep-sea N burial, and N inputs by rivers and marginal seas (i.e., Persian Gulf and Red Sea) are of minor importance. We found that the magnitude of the sedimentary denitrification at the shelf might be ∼17% of the total denitrification in the Arabian Sea, indicating that the shelf sediments might be of considerably greater importance for the N cycling in the Arabian Sea than previously thought. Sedimentary and pelagic denitrification together demand ∼6% of the estimated particulate organic nitrogen export flux from the photic zone. The main northward transport of N into the Arabian Sea occurs in the intermediate layers, indicating that the N cycle of the Arabian Sea might be sensitive to variations of the intermediate water circulation of the Indian Ocean.

Measurements of Trace Metal (Fe, Cu, Mn, Cr) Oxidation States in Fog and Stratus Clouds

The oxidation state of four transition metals (Fe, Mn, Cu, and Cr) in cloudwater has been investigated during several cloud events at Whiteface Mountain (NY), one cloud event at San Pedro Hill (CA), and one fog event at Bakers-field (CA). Samples were collected and immediately analyzed for the oxidation states of four transition metals: Fe(II) [44 measurements], Cu(I) [30 measurements], Mn(IV) [27 measurements], and Cr(III) [3 measurements]. Extreme care was taken to minimize contamination and interferences when measuring these oxidation states. Par-ticulate and dissolved concentrations of these metals were also determined. Other measurements performed-relevant to the redox chemistry of these metals-included pH, total elemental concentrations (Fe, Cu, Mn, Cr, Al, K, Ca, Na, and Mg), organic anions (formate, acetate, glyco-late, oxalate), inorganic anions (chloride, sulfate, nitrate, sulfite), cations (sodium, calcium, magnesium, potassium), peroxides, and formaldehyde. These measurements were then used in thermodynamic-speciation models to understand the speciation of ambient fog and cloudwater. From this analysis, two different cases were found for Fe(III)soluble speciation. Fe(III) was found to exist either as Fe(OH)2+ or Fe(Oxalate)2. However, an unidentified strong chelating ligand with Fe(III) was also suggested by the data. Cu(I) and Cu(II) were calculated to be predominantly Cu+ and Cu2+ (with less than 10% as Cu(II)-oxalate complexes). A chemical kinetic model was also used to investigate the transition-metal chemistry. The model results indicate that Fe(II) should be the predominant chemical form of Fe during daylight conditions. This prediction is in agreement with the field measurements in which the highest ratios of Fe(II)/Fe total were found in samples collected during the day. The model results also indicated that Fe(III) should be the predominant form of Fe during nighttime conditions, which is also in agreement with the field measurements. In the model, Cu(II) and Mn(II) were the predominant oxidation states during daylight and nighttime conditions with Cu(I) and Mn(III) increasing during daylight conditions. Mn(III) concentrations were never high enough to influence the redox chemistry of Cr. Overall, Cr(VI) in cloudwater is predicted to be reduced to Cr(III) if free S(IV) is present.

Chemical characterization of ambient aerosol collected during the southwest monsoon and intermonsoon seasons over the Arabian Sea: Anions and cations

Ambient aerosol samples were collected over the northern Indian Ocean during two 1 month-long research cruises (German R/V Meteor) that took place during the intermonsoon (May) and SW monsoon (July/August) of 1995. A high volume and two small volume collectors were used to collect samples, which were subsequently analyzed for ferrous iron, 32 elements, and anions and cations. The present paper focuses on the bulk aerosol material, the ions, while utilizing some of the trace metal data that were presented in more detail in our previous paper [Siefert et al., 1999]. Data are analyzed and interpreted with the aid of principal component and multiple linear regression analyses. Intermonsoon samples were strongly influenced by continental material, both of crustal and anthropogenic origin. The crustal component (24.5±13% of the total suspended particulate mass (TSP), 6.0±4.4 μg m^(−3)) contained 3.2% gypsum (CaSO_4). While more than half of the TSP (21.2±9.6 μg m^(−3)) during the SW monsoon was sea-salt-derived due to the strong winds prevailing during this season, only 1.7±1.1% (0.7±0.4 μg m^(−3)) was found to be of crustal origin. Sulfate (SO_4^(2−)) sources were determined and quantified with linear regression analyses utilizing specific tracers for the independent variables. Lead (Pb) was found to be a more reliable surrogate for anthropogenic SO_4^(2−) compared to nitrate (NO_3^−) during the relatively polluted intermonsoon. Soluble calcium (Ca^(2+)) served as the tracer for gypsum, and methane sulfonate (MSA) served as the tracer for biogenically derived SO_4^(2−) during both seasons. On the basis of this analysis, 75% of the non-sea-salt sulfate (NSS-SO_4^(2−)) (0.8±0.2 μg m^(−3), representing ∼2.4% of TSP) was found to be of biogenic origin during the SW monsoon with the remaining 25% of anthropogenic origin. During the intermonsoon, NSS-SO_4^(2−) accounted for 2.1±1.2 μg m^(−3) (∼9.2% of TSP) and had a composition that was 65% anthropogenic, 21% biogenic, and 14% gypsum-derived. Linear regression analyses revealed that the bio-SO_4^(2−)/MSA weight ratios appear to be consistent with the temperature dependence proposed by Hynes et al. [1986]. In this case the yield of SO_4^(2−) increased relative to MSA with an increase in temperature. Three samples during the SW monsoon, near the coast of Oman, showed lower temperatures, due to coastal upwelling, than the rest of the samples; at 24°C the bio-SO_4^(2−)/MSA weight ratio was 6.8±0.5. The remainder of the SW monsoon samples were collected at an average temperature of 27.2°C, for which the bio-SO_4^(2−)/MSA weight ratio was 13.5±4.4. At an average temperature of 28.9°C during the intermonsoon, sampling gave a ratio of 17.7±4.8. These observations indicate a temperature dependence factor between 24° and 29°C of 2.2 (i.e., a 2.2 increase in the ratio of bio-SO_4^(2−)/MSA with every degree temperature increase). Cl− deficits determined during both seasons appear to indicate that different mechanisms may govern the observed depletion of Cl− in each season.

Iron sources and dissolved‐particulate interactions in the seawater of the Western Equatorial Pacific, iron isotope perspectives

This work presents iron isotope data in the western equatorial Pacific. Marine aerosols and top core margin sediments display a slightly heavy Fe isotopic composition (δ 56 Fe) of 0.33 ± 0.11‰ (2SD) and 0.14 ± 0.07‰, respectively. Samples reflecting the influence of Papua New Guinea runoff (Sepik River and Rabaul volcano water) are characterized by crustal values. In seawater, Fe is mainly supplied in the particulate form and is found with a δ 56 Fe between A0.49 and 0.34 ± 0.07‰. The particulate Fe seems to be brought mainly by runoff and transported across continental shelves and slopes. Aerosols are suspected to enrich the surface Vitiaz Strait waters, while hydrothermal activity likely enriched New Ireland waters. Dissolved Fe isotopic ratios are found between A0.03 and 0.53 ± 0.07‰. They are almost systematically heavier than the corresponding particulate Fe, and the difference between the signature of both phases is similar for most samples with Δ 56 Fe DFe – PFe = +0.27 ± 0.25‰ (2SD). This is interpreted as an equilibrium isotopic fractionation revealing exchange fluxes between both phases. The dissolved phase being heavier than the particles suggests that the exchanges result in a net nonreductive release of dissolved Fe. This process seems to be locally significantly more intense than Fe reductive dissolution documented along reducing margins. It may therefore constitute a very significant iron source to the ocean, thereby influencing the actual estimation of the iron residence time and sinks. The underlying processes could also apply to other elements.

Chemical characterization of ambient aerosol collected during the northeast monsoon season over the Arabian Sea: Labile-Fe(II) and other trace metals

[1] Ambient aerosol samples were collected over the Arabian Sea during the month of March of 1997, aboard the German R/V Sonne, as part of the German Joint Global Ocean Flux Study (JGOFS) project. This is the third study in a series of analogous measurements taken over the Arabian Sea during different seasons of the monsoon. Dichotomous high-volume collector samples were analyzed for ferrous iron immediately after collection, while trace metals, anions, and cations were determined upon return to the laboratory. The main crustal component was geochemically well represented by the average crustal composition and amounted to 5.94 ± 3.08 m gm 3 . An additional crustal constituent of clay-like character, rich in water-soluble Ca and Mg, was seen in the fine fraction in air masses of Arabian origin. Total ferrous iron concentrations varied from 3.9 to 17.2 ng m 3 and averaged 9.8 ± 3.4 ng m 3 , with 87.2% of Fe(II) present in the fine aerosol fraction. Fe(II) concentrations accounted for on average 1.3 ± 0.5% of the total Fe. While ferrous iron in the coarse fraction appeared to be correlated with the main crustal component, the fine Fe(II) fraction exhibited a more complex behavior. The anthropogenic contribution to the aerosol, as traced by Pb, Zn, and some anions and cations, was found to be considerably larger, especially during the first 10 days of this cruise, than in previously collected samples from the inter-monsoon and southwest monsoon of 1995. INDEX TERMS: 0305 Atmospheric Composition and Structure: Aerosols and particles (0345, 4801); 0365 Atmospheric Composition and Structure: Troposphere— composition and chemistry; 4801 Oceanography: Biological and Chemical: Aerosols (0305); 4805 Oceanography: Biological and Chemical: Biogeochemical cycles (1615); 4875 Oceanography: Biological and Chemical: Trace elements; KEYWORDS: ferrous iron, trace metals, aerosol particles, Indian Ocean Citation: Johansen, A. M., and M. R. Hoffmann, Chemical characterization of ambient aerosol collected during the northeast monsoon season over the Arabian Sea: Labile-Fe(II) and other trace metals, J. Geophys. Res., 108(D14), 4408, doi:10.1029/2002JD003280, 2003.

Chemical characterization of ambient aerosol collected during the northeast monsoon season over the Arabian Sea: Anions and cations

Ambient aerosol samples were collected over the Arabian Sea during the month of March 1997, aboard the German R/V Sonne, as part of the German JGOFS project (Joint Global Ocean Flux Study). This is the third study in a series of analogous measurements taken over the Arabian Sea during different seasons of the monsoon. Dichotomous high volume collector samples were analyzed for anions and cations upon return to the laboratory. Anthropogenic pollutant concentrations were larger during the first part of the cruise, when air masses originated over the Indian subcontinent. Total NSS-SO_4^(2−) concentrations amounted to 2.94 ± 1.06 μg m^(−3) of which 92.1 ± 4.5% was present in the fine fraction. NSS-SO_4^(2−) source apportionment analysis with multivariate linear regression models revealed that in the coarse fraction half is biogenically and half anthropogenically derived, while in the fine fraction only 6% seemed of biogenic origin and 84% anthropogenic and 10% crustal in nature. Chloride deficits up to 99.1% in the fine fraction were observed. The average Cl^− deficit in the fine fraction was 89.0 ± 9.4%, potentially related to NSS-SO_4^(2−) acid displacement and Cl reactive species formation, while in the coarse fraction it was 25.6 ± 21.3%, with NO_3^− being the preferred species for acid displacement.

Ultrafine Particulate Ferrous Iron and Anthracene Associations with Mitochondrial Dysfunction

The ultrafine size fraction of ambient particles (ultrafine particles [UFP], diameter < 100 nm) has been identified as being particularly potent in their adverse health effects, yet, the detailed mechanisms for why UFP display such distinctive toxicity are not well understood. In the present study, mitochondria were exposed to ambient UFP while monitoring mitochondrial electron transport chain (ETC) activity as a model system for biochemical toxicity. UFP samples were collected in rural and urban environments, and chemically characterized for trace metals, ferrous (Fe(II)) and easily reducible ferric (Fe(III)) iron, polycyclic aromatic hydrocarbons (PAHs), and surface constituents with X-ray photoelectron spectroscopy (XPS). Fixed doses of UFP (8 μg mL−1) inhibited mitochondrial ETC function compared to controls in 94% of the samples after the 20 min of exposure. Significant moderate to weak correlations exist between initial %ETC inhibition (0 – 10 min) and Fe(II) (R = 0.55, P = 0.03, N = 15), anthracene (R = 0.74, P < 0.01, N = 13), and %C–O surface bonds (R = 0.56, P = 0.03, N = 15), whereby anthracene and %C–O correlate with each other (R = 0.58, P = 0.03, N = 14). Multivariate linear regression showed that when combined, Fe(II) and anthracene best describe the initial %ETC inhibition (R = 0.91, P = 0.00, N = 14). No significant associations were identified with total Fe and other trace metals. Results from this study indicate that Fe(II) and anthracene-related, C–O containing, surface structures may contribute to the initial detrimental behavior of UFP, also supporting the idea that the Fe(II)/Fe(III) and certain efficient hydroquinone/quinone redox pairs play important roles due to their potential to produce reactive oxygen species (ROS).

Global estimates of mineral dust aerosol iron and aluminum solubility that account for particle size using diffusion-controlled and surface-area-controlled approximations

Mineral aerosol deposition is recognized as the dominant source of iron to the open ocean and the solubility of iron in the dust aerosol is highly variable, with measurements ranging from 0.01–80%. Global models have difficulty capturing the observed variations in solubility, and have ignored the solubility dependence on aerosol size. We introduce two idealized physical models to estimate the size dependence of mineral aerosol solubility: a diffusion-controlled model and a surface-area-controlled model. These models produce differing time- and space-varying solubility maps for aerosol Fe and Al given the dust age at deposition, size-resolved dust entrainment fields, and the aerosol acidity. The resulting soluble iron deposition fluxes are substantially different, and more realistic, than a globally uniform solubility approximation. The surface-area-controlled solubility varies more than the diffusion-controlled solubility and better captures the spatial pattern of observed solubility in the Atlantic. However, neither of these two models explains the large solubility variation observed in the Pacific. We then examine the impacts of spatially variable, size-dependent solubility on marine biogeochemistry with the Biogeochemical Elemental Cycling (BEC) ocean model by comparing the modeled surface ocean dissolved Fe and Al with observations. The diffusion-based variable solubility does not significantly improve the simulation of dissolved Fe relative to a 5% globally uniform solubility, while the surface-area-based variable solubility improves the simulation in the North Atlantic but worsens it in the Pacific and Indian Oceans.