Atmospheric deposition of nitrogen, sulfur and chloride in Thessaloniki, Greece

In the present study, the wet and dry depositions of particulate NO₃⁻, SO₄²⁻, Cl⁻ and NH₄⁺ were measured using a wet/dry sampler as a surrogate surface. Gas phase compounds of nitrogen, sulfur and chloride (HNO₃, NH₃, SO₂ and HCl) were measured by an annular denuder system (ADS) equipped with a back up filter for the collection of particles with diameter ≤ 5 μm. Ambient concentrations of NO, NO₂ and SO₂ were also taken into consideration. Sampling was conducted at an urban site in the center of the city of Thessaloniki, northern Greece. The presence of the aerosol species was examined by cold/warm period and the possible compounds in dry deposits were also considered. Dry deposition fluxes were found to be well correlated with ambient particle concentrations in order to be used for the calculation of particle deposition velocity. Average particulate deposition velocities calculated were 0.36, 0.20, 0.20 and 0.10 cm s^− 1 for Cl⁻, NO₃⁻, SO₄²⁻ and NH₄⁺, respectively. Total dry deposition fluxes (gas and particles) were estimated at 3.24 kg ha^− 1 year^− 1 for chloride (HCl + p-Cl), 9.97 kg ha^− 1 year^− 1 for nitrogen oxidized (NO + NO₂ + HNO₃ + p-NO₃), 5.32 kg ha^− 1 year^− 1 for nitrogen reduced (NH₃ + p-NH₄) and 15.77 kg ha^− 1 year^− 1 for sulfur (SO₂ + p-SO₄). 70–90% total dry deposition was due to gaseous species deposition. The contribution of dry deposition to the total (wet + dry) was at the level of 60–70% for sulfur and nitrogen (oxidized and reduced), whereas dry chloride deposition contributed 35% to the total. The dry-to-wet deposition ratio of all the studied species was found to be significantly associated with the precipitation amount, with nitrogen species being better and higher correlated. Wet, dry and total depositions measured in Thessaloniki, were compared with other countries of Europe, US and Asia.     

Traffic aerosols (18 nm particle size 18 μm) source apportionment during the winter period

In November 2004–January 2005, a micro orifice uniform deposit impactor (MOUDI) and a Nanometer (nanometer)-MOUDI were used in the center of Taiwan to measure particle size (18 nm particle size 18 μm) distributions of atmospheric aerosols at a traffic site during the winter period. The average Mass in Media Aerodynamic Diameter (MMAD) of suspended particles is 0.99 μm this study. As for the ultra fine and nanometer (nanometer) particle mode, the composition order for these major ions species was SO₄²⁻ NH₄⁺ NO₃⁻ Mg²⁺ Ca²⁺ Na⁺ K⁺ Cl⁻. An ion Chromatography (DIONEX-100) was used to analyze major anion species, Cl⁻, NO₃⁻, SO₄²⁻ and cation species, NH₄⁺Na⁺, K⁺, Ca²⁺Mg²⁺. Their concentrations were also extracted from various particles size modes (nanometer (nanometer), ultra fine, fine and coarse). The results obtained in this study also indicated that the average portions for the major ionic species (SO₄²⁻, NH₄⁺ and Mg²⁺) in the nanometer (nanometer), ultra fine, fine and coarse particulate modes are about 34%, 37%, 63% and 30%, respectively at this traffic sampling site during the winter period.     

In-cloud scavenging of gases and aerosols at a mountain site in Central Switzerland

An in-cloud scavenging case study of the major ions (NH₄ ⁺, SO₄ ^2- and NO₃ ^-) determining the cloudwater composition at a mountain site (1620 m.a.s.l.) is presented. A comparison between in-cloud measurements of the cloudwater composition, liquid water content, gas concentrations and aerosol concentrations and pre-cloud gas and aerosol concentrations yields the following results. Cloudwater concentrations resulted from scavenging of about half of the available NH₃, aerosol NH₄ ⁺, aerosol NO₃ ^-, and aerosol SO₄ ^2-. Approximately a third of the SO₂ was scavenged by the cloudwater and oxidized to SO₄ ^2-. Cloud acidity during the first two hours of cloud interception (pH 3.24) was determined mostly by the scavenged gases (NH₃, SO₂, and HNO₃); aerosol contributions to the acidity were found to be small. Observations of gas and aerosol concentrations at three elevations prior to several winter precipitation events indicated that NH₃ concentrations are typically half (12–80 %) of the total (gas and aerosol) N (-III) concentrations. HNO₃ typically is present at much lower concentrations (1–55 %) than aerosol NO₃ ^-. Concentrations of SO₂ are a substantial component of total sulfur, with concentrations averaging 60 % (14–76 %) of the total S (IV and VI).     

Particle-size distribution of inorganic water soluble ions in the venezuelan savannah atmosphere during burning and nonburning periods

The results presented are the first complete analysis of inorganic soluble ions in a tropical savannah region. Atmospheric particles were collected in six rural Venezuelan savannah sites. Concentrations and size distribution of NO₃ ^–, SO₄ ^2-, CI^–, PO₄ ^3-, NH₄ ⁺, Na⁺, K⁺, Ca²⁺ and Mg²⁺ were determined in samples collected with Hi Vol samplers equipped with five-stage cascade impactors. Concentrations were higher in the dry season, with a maximum during the burning periods. Using Na⁺ as a reference, the results show a deficit of Cl^– and, with the exception of Mg²⁺, an enrichment of all other ions with respect to marine aerosols. Significant variations were observed in particle-size distribution between different periods. Various pairs of ions present similar size distributions: SO₄ ^2- and NH₄ ⁺; Cl^– and Na⁺; PO₄ ^3- and K⁺; Ca²⁺, Mg²⁺ and NO₃ ^–; indicating that the ions were produced by the same source and/or were involved in similar atmospheric processes. Possible primary sources, the gas-to-particle atmospheric process, environmental implication of long-range transport of nutrients during dry seasons, etc., are discussed.     

Wet deposition of atmospheric inorganic reactive nitrogen (Nr) across an urban-industrial-rural transect of Nr emission hotspot (India)

The present study comprehensively reports the simultaneous measurement of wet deposition of total inorganic nitrogen (TIN; which is the sum of the NH₄⁺-N and NO₃^?-N) at three different sites in Nr emission hotspot of Indo-Gangetic plain (IGP) over a year-long temporal scale from October 2017 to September 2018. At rural Meetli (MTL) site, urban Baraut (BRT) site and industrial Loni (LNI) site, the annual wet deposition of NH₄⁺-N was estimated as 21.87, 19.48 and 7.43 kg N ha^?1 yr^?1, respectively; the annual wet deposition NO₃^?-N was estimated as 12.96, 12.17 and 4.44 kg N ha^?1 yr^?1, respectively; and the annual wet deposition of TIN was estimated as 34.83, 31.64 and 11.87 kg N ha^?1 yr^?1, respectively. NH₄⁺-N was dominantly contributing species in annual, monsoon and non-monsoon-time wet deposition of TIN at all sites. The spatial gradient (variability) in percent contribution of NH₄⁺ to total annual volume-weighted mean (VWM) concentration of all analyte ions was observed as MTL (43.23%)?>?BRT (37.90%)?>?LNI (30%). On the other hand, the spatial gradient in percent contribution of NO₃^? to total annual VWM concentration of all analyte ions was observed as MTL (7.45%)?>?BRT (6.89%)?>?LNI (5.32%). The extremely narrow range of NH₄⁺-N/NO₃^?-N ratios (ranging from 1.60 at BRT site to 1.69 at LNI site) showed the approximately equal relative abundance of oxidized and reduced nitrogen (N) deposition across all sites. Inferences from enrichment factor analysis, principal component analysis and Pearson’s correlation coefficient analysis suggested that across all sites, virtually all NH₄⁺-N and NO₃^?-N depositions were originated anthropogenically. The annual wet deposition of TIN measured in this study showed?≥?6865%,?≥?6228% and?≥?2274% increment than the natural N deposition rate at MTL, BRT and LNI site, respectively. These empirically measured annual wet depositions of TIN also emanated theoretical transgression of critical N load threshold across all sites therefore signifying probable undermining of long-term elastic stability and resilience of ecosystems against stressor in the study domain.

     

Atmospheric inorganic nitrogen in marine aerosol and precipitation and its deposition to the North and South Pacific Oceans

Aerosol and rain samples were collected between 48°N and 55°S during the KH-08-2 and MR08-06 cruises conducted over the North and South Pacific Ocean in 2008 and 2009, to estimate dry and wet deposition fluxes of atmospheric inorganic nitrogen (N). Inorganic N in aerosols was composed of ~68% NH₄⁺ and ~32% NO₃^– (median values for all data), with ~81% and ~45% of each species being present on fine mode aerosol, respectively. Concentrations of NH₄⁺ and NO₃⁻ in rainwater ranged from 1.7–55 μmol L⁻¹ and 0.16–18 μmol L⁻¹, respectively, accounting for ~87% by NH₄⁺ and ~13% by NO₃⁻ of total inorganic N (median values for all data). A significant correlation (r = 0.74, p < 0.05, n = 10) between NH₄⁺ and methanesulfonic acid (MSA) was found in rainwater samples collected over the South Pacific, whereas no significant correlations were found between NH₄⁺ and MSA in rainwater collected over the subarctic (r = 0.42, p > 0.1, n = 6) and subtropical (r = 0.33, p > 0.5, n = 6) western North Pacific, suggesting that emissions of ammonia (NH₃) by marine biological activity from the ocean could become a significant source of NH₄⁺ over the South Pacific. While NO₃⁻ was the dominant inorganic N species in dry deposition, inorganic N supplied to surface waters by wet deposition was predominantly by NH₄⁺ (42–99% of the wet deposition fluxes for total inorganic N). We estimated mean total (dry + wet) deposition fluxes of atmospheric total inorganic N in the Pacific Ocean to be 32–64 μmol m⁻² d⁻¹, with 66–99% of this by wet deposition, indicating that wet deposition plays a more important role in the supply of atmospheric inorganic N than dry deposition.     

A summer and winter apportionment of particulate matter at urban and rural areas in northern France

The apportionment of atmospheric aerosols undertaken in Northern France during two sampling campaigns allowed to determine the influence of the atmospheric contribution of a heavy industrialized urban center on the particulate matter composition at a nearby rural site. The concentrations of major components and trace elements sampled by bulk filtration have been determined on June–July 2000 and January–February 2001, and the comparison of these two campaigns shows very well the importance of wind directions. The sources of 10 trace elements (Al, Ba, Cu, Fe, K, Mn, Pb, Sr, Ti and Zn) and 7 major components (Cl⁻, NO₃⁻, SO₄²⁻, NH₄⁺, Na, Mg and Ca) are better identified by studying their elemental contribution at each sampling site according to wind sectors. This kind of study shows that the concentrations recorded at the urban sampling site are always higher than those observed at the rural site as well during the summer campaign (about + 35%) as during the winter campaign (+ 90%), because of the predominance of the W–NW wind sector, corresponding to the influence of the urban and industrialized areas.     

Factors Influencing Nitrogen Speciation in Coastal Rainwater

Rainwater was collected from 129 rain events between February 2002 and August 2003 and analyzed for ammonium (NH₄⁺), nitrate (NO₃⁻), organic nitrogen (ON) and free amino acids (AA). Inorganic nitrogen (NO₃⁻ + NH₄⁺) was the dominant form of N representing 85% of total nitrogen based on volume-weighted averages. The remainder of the N occurred as organic nitrogen species of which free amino acids contribute approximately 17%. A significant, and in some cases the majority (> 75%), of the remaining ON could be accounted for by macromolecular uncharacterized humic like substances. This has important ramifications with respect to the long range transport of atmospheric ON because humic materials are recalcitrant and therefore may travel long distances from their source. There was a distinct seasonality to the N speciation data with maximum concentrations of NH₄⁺, ON and AA occurring in the spring. Air-mass back trajectory analysis indicates there is a strong anthropogenic component to the NO₃⁻, NH₄⁺ and AA signal but not ON. There was a strong positive correlation between amino acid concentrations and ammonium which suggests they have similar sources and sinks in rainwater. Finally, large episodic additions of NH₄⁺ and AA during tropical events could significantly impact short term bioavailable N budgets in estuaries impacted by these storms. Approximately three times as much NH₄⁺ and AA were deposited during Hurricane Isabel (317 μ moles ⋅ m⁻² and 84 μ moles ⋅ m⁻² respectively) compared to the mean impact of average summertime rain events at this location.     

Asian Dust effects on Total Suspended Particulate (TSP) compositions at Gosan in Jeju Island, Korea

The compositions of TSP between AD and NAD storm periods were compared to study their long-term variations and chemical characteristics. TSP samples were collected at Gosan site in Jeju Island of Korea from February to May of 1992–2004. The major ionic and elemental species of TSP aerosols were analyzed. During AD periods, the concentrations of crust components (nss-Ca²⁺, Al, Fe, Ca, Mg, Ba, Sr, Ti) increased remarkably, and the concentrations of anthropogenic components (nss-SO₄²⁻, NO₃⁻, S, Zn, Pb, Cr, Ni, Cd), with the exception of NH₄⁺, increased weakly. The concentration ratios of all major components between AD and NAD periods showed ranges from 1.2 to 8.5, except for NH₄⁺. The slope of the linear regression indicated that the contribution of CO₃²⁻ may have comprised up to 17% of the total anions. Our results suggested that the AD storm greatly influenced TSP compositions. Linear regression analyses indicated that NH₄⁺ was not correlated with NO₃⁻, but highly correlated with nss-SO₄²⁻ during both periods. The nss-SO₄²⁻ was also correlated with NH₄⁺, K⁺, nss-Mg²⁺, and nss-Ca²⁺ during both periods. Interestingly, NO₃⁻ was associated with nss-Ca²⁺ and nss-Mg²⁺ during AD periods. Of the metal elements, Fe, Ca, Mg, Ti, Mn, Ba, Sr, V, and Co were highly correlated with Al during both periods, signifying that these metals were mostly originated from soils.     

An Investigation into the Ionic Chemical Composition and Mixing State of Biomass Burning Particles Recorded During TRACE-P P3B Flight#10

In this study bulk airborne aerosol composition measured by the PILS-IC (integration time of 3 min 24 s) during TRACE-P P3B Flight 10 are used to investigate the ionic chemical composition and mixing state of biomass burning particles. A biomass burning plume, roughly 3–4 days old, moderately influenced by urban pollution aerosols recorded in the Philippine Sea is investigated. Focusing on the fine particle NO₃⁻, SO₄²⁻, K⁺, NH₄⁺, and water-soluble organics, the observed correlations and nearly 1-to-1 molar ratios between K⁺ and NO₃⁻ and between NH₄⁺ and (SO₄²⁻+ inferred Organics) suggest the presence of fine-mode KNO₃, (NH₄)₂SO₄, and NH₄(Organics) aerosols. Under the assumption that these ion pairs existed, and because KNO₃ is thermodynamically less favored than K₂SO₄ in a mixture of NO₃⁻, SO₄²⁻, K⁺, NH₄⁺, and Organic anions, the measurements suggest that aerosols could be composed of biomass burning particles (KNO₃) mixed to a large degree externally with the (NH₄)₂SO₄ aerosols. A “closed-mode” thermodynamic aerosol simulation predicts that a degree of external mixing (by SO₄²⁻ mass) of 60 to 100% is necessary to achieve the observed ionic associations in terms of the existence of KNO₃. However, the degree of external mixing is most likely larger than 90%, based on both the presence of KNO₃ and the amounts of NH₄NO₃. Calculations are also shown that the aerosol mixing state significantly impacts particle growth by water condensation/evaporation. In the case of P3B Flight #10, the internal mixture is generally more hygroscopic than the external mixture. This method for estimating particle mixing state from bulk aerosol data is less definitive than single particle analysis, but because the data are quantitative, it may provide a complementary method to single particle chemical analysis.     

模拟氮沉降对温带阔叶红松林地氮素净矿化量的影响

采用埋置PVC管的树脂芯方法原位测定了不同氮形态及其剂量作用下长白山阔叶红松林地0～7 cm和0～15 cm土壤氮素净氨化、净硝化和净矿化量的季节和年际变化规律.近3年的观测结果表明,对照处理不同土层氮素年净矿化量中以净氨化占主导地位,约占净矿化量的53％～72％,高剂量NO3-N的输入使该比例减少至37％～66％,而NH4-N的输入却使该比例增至86％～92％.随着模拟氮沉降量增加,土壤氮素年净矿化量也随之增加,尤其外源NH+4-N输入对净矿化量的促进作用更为明显,但随着施肥年限的延长,这种促进作用逐渐减弱.与林地0～15 cm土壤相比,氮沉降量增加对0～7 cm土壤氮素净氨化和净矿化量的促进作用更为明显,尤其是NH4Cl处理的促进作用更大.通过将实验结果与前人报道的野外原位观测整合,逐步回归分析后发现土壤氮素年净矿化量随着氮素年沉降量的增加而增大,氮沉降量对不同区域森林土壤氮素年净矿化量的贡献率约为38％;大气氮沉降量、森林有机层pH及其碳/氮比值可解释不同区域森林表层土壤氮素年净矿化量一半的变化.研究结果将利于有效预测区域林地氮素净矿化量特征及其对环境变化的响应.     

A Long Term Study on Chemical Composition of Rainwater at Dayalbagh, a Suburban Site of Semiarid Region

Rainwater samples were collected for the monsoon period of 1988 and 1991–1996 at Dayalbagh (Agra), a suburban site situated in semiaridregion. The mean pH was 7.01 ±1.03 well above 5.6, which is the reference pH. Concentration of Ca²⁺ was observed to be highest followed by Mg²⁺, NH₄ ⁺,SO₄ ^2–, Cl^–,NO₃ ^–, Na⁺, F^– and K⁺. The ratios of SO₄ ^2– + NO₃ ^– andCa²⁺ + Mg²⁺ (TA/TC) have been considered as indicatorfor acidity. In the Agra region ratio of TA/TC is quite below 1.0 indicating alkaline nature of rainwater. The lowest value of 0.24 was observed in 1991 likely due to the lowest rain depth of the decade. The highest value of 0.54 was observed in 1996, a year with a large rain depth and increase in line (vehicular traffic) and area sources (population growth). Good correlation between Ca²⁺ and NO₃ ^–,Ca²⁺ and SO₄ ^2– andSO₄ ^2– and NO₃ ^–,indicates that wind carried dust and soil play a significant role in neutralization of precipitation acidity.     

Seasonal variation of gaseous HNO3 and NH3 at a Tropical Savannah site

Gaseous nitric acid and ammonia were sampled with annular denuders at a forest savannah site from April to December 1987. The analysis of the extract was made spectrophotometrically and by a selective electrode for NO₃ ^– and NH₄ ⁺, respectively. Higher concentrations were observed during the vegetation burning period at the end of the dry season. In the studied savannah area, large soil emissions of NO occur during the rainy season, although very low concentrations of HNO₃ (0.035 ppb) and also of particulate NO₃ ^– (0.43 g m^-3) were observed; it is likely that NO_x are lost by fast vertical transport to the upper troposphere. During the nonburning period, the average concentration of NH₃ was 2.7 ppb, which is much lower than values given in the literature for the tropical America atmosphere. The concentrations of HNO₃ and NH₃ were always below the values needed to produce ammonium nitrate aerosols.     

Atmospheric Dry Deposition to Marble and Red Stone

This paper presents dry deposition flux and deposition velocity of atmospheric particles on white marble and red stone at Dayalbagh, a suburban site of semi arid region, which is 10 km away from the industrial sector of the Agra city where due to agricultural practices vegetation predominates. The wind speed at Agra is mostly in the range of 1–2 m s^–1. The atmospheric calm conditions at Agra in summer, monsoon, and winter seasons are 47%, 35%, and 76%, respectively. Industrial areas of the city are away from Dayalbagh and are located in the NE, E, SE, and SW sectors. The main industrial activities, which are in operation in Agra city and its outskirts, are foundry and forging industry. The other industrial activities in Agra are rubber processing, lime oxidation and pulverization, chemicals, engineering and brick refractory kilns. Dry deposition samples were collected on dry days on white marble and red stone (0.224 m × 0.224 m × 0.02 m) using surface washing method. Both slabs were fixed to an iron stand (1.5 m height) at an angle of about 80 from the horizontal and exposed for 24 h on the roof of the faculty building. The order of deposition flux on white marble is NH₄⁺ > Mg²⁺ > Ca²⁺ > Na⁺ > Cl^– > K⁺ > NO₃^– > SO₄^2– > F^– and that on red stone is NH₄⁺ > Mg²⁺ > Ca²⁺ > SO₄^2– > Na⁺ > NO₃^– > K⁺ > F^– > Cl^–. Average dry deposition flux of major ions varies from 3.4 to 128.5 M m^–2 d^–1. The sum of major cations on white marble and red stone are 516.4 and 450.4 eq m^–2 d^–1, respectively while sum of major anions are 425.3 and 400.4 eq m^–2 d^–1 on white marble and red stone, respectively. Higher deposition of all ions was observed when wind blows from NE as most of the Agra Iron foundries and Ferozabad glass industries lie in this direction. The mean values of dry deposition velocity of ions vary between 0.22 cm s^–1 to 1.49 cm s^–1. Deposition velocity for all ions is higher on white marble than red stone inspite of rougher surface of red stone as compared to white marble. This could be due to the chemical nature of white marble, which is made of dolomite and hence adds significant amount of ions by dissolution during washing. Seasonally the deposition velocity was highest in winter.     

Chemical and isotopic interpretation of major ion compositions from precipitation: a one-year temporal monitoring study in Wrocław,SW Poland

The chemical compositions (Na⁺, NH₄ ⁺, K⁺, Mg²⁺, Ca²⁺, Cl^?, NO₂ ^?, NO₃ ^?, SO₄ ^2?, HCO₃ ^?) of wet precipitation and nitrogen isotope compositions δ¹⁵N(NH₄ ⁺) were studied from January to December 2010 in Wroc?aw (SW Poland). Results of a principle component analysis show that 82 % of the data variability can be explained by three main factors: 1) F1 (40 %) observed during vegetative season (electrical conductivity, HCO₃ ^?, NO₃ ^?, NO₂ ^?, NH₄ ⁺ and SO₄ ^2?), mainly controlling rainwater mineralization; 2) F2 (26 %) observed during vegetative and heating seasons (K⁺, Ca²⁺ and Mg²⁺), probably representing a combination of two processes: anthropogenic dusts and fertilizers application in agricultural fields, and 3) F3 (16 %) reported mainly during heating season (Na⁺ and Cl^?) probably indicating the influence of marine aerosols. Variations of δ¹⁵N(NH₄ ⁺) from ?11.5 to 18.5?‰ identify three main pathways for the formation of NH₄ ⁺: 1) equilibrium fractionation between NH₃ and NH₄ ⁺; 2) kinetic exchange between NH₃ and NH₄ ⁺; 3) NH₄ ⁺ exchange between atmospheric salts particles and precipitation. The coupled chemical/statistical analysis and δ¹⁵N(NH₄ ⁺) approach shows that while fossil fuels burning is the main source of NH₄ ⁺ in precipitation during the heating season, during the vegetative season NH₄ ⁺ originates from local sewage irrigation fields in Osobowice or agricultural fertilizers.     

The chemical composition of rainwater over Büyükçekmece Lake, Istanbul

In the present study, the precipitation near Büyükçekmece Lake, which is one of the important drinking water sources of Istanbul city, was studied during October 2001–July 2002. Seventy-nine bulk precipitation samples were collected at two sampling stations near the Lake (41°2′35″N, 28°35′25″E and 41°5′30″N, 28°37′7″E). The study comprised the determination of H⁺, Cl⁻, NO₃⁻, SO₄²⁻, NH₄⁺, Na, K, Mg, Ca, Al, Ba, Fe, Cu and Mn concentrations in bulk deposition rain event samples. The average volume-weighted pH value was found to be 4.81, which points out that the rain is slightly acidic. High sulfate concentrations were observed together with high H⁺ ion values. Sulfur emissions were the major cause for the observed high hydrogen ion levels. On the basis of factor analysis and correlation matrix analysis, it has been found that in this region, acid neutralization is brought about by calcium rather than the ammonium ion. The varimax rotated factor analysis grouped the variables into four factors, which are crustal, marine and two anthropogenic sources.     

Vertical distribution of dimethylsulfide,sulfur dioxide,aerosol ions,and radon over the Northeast Pacific Ocean

Dimethylsulfide (DMS), sulfur dioxide (SO₂), methanesulfonate (MSA), nonsea-salt sulfate (nss-SO₄ ^2–), sodium (Na⁺), ammonium (NH₄ ⁺), and nitrate (NO₃ ^–) were determined in samples collected by aircraft over the open ocean in postfrontal maritime air masses off the northwest coast of the United States (3–12 May 1985). Measurements of radon daughter concentrations and isentropic trajectory calculations suggested that these air masses had been over the Pacific for 4–8 days since leaving the Asian continent. The DMS and MSA profiles showed very similar structures, with typical concentrations of 0.3–1.2 and 0.25–0.31 nmol m^–3 (STP) respectively in the mixed layer, decreasing to 0.01–0.12 and 0.03–0.13 nmol m^–3 (STP) at 3.6 km. These low atmospheric DMS concentrations are consistent with low levels of DMS measured in the surface waters of the northeastern Pacific during the study period.The atmospheric SO₂ concentrations always increased with altitude from <0.16–0.25 to 0.44–1.31 nmol m^–3 (STP). The nonsea-salt sulfate (ns-SO₄ ^2–) concentrations decreased with altitude in the boundary layer and increased again in the free troposphere. These data suggest that, at least under the conditions prevailing during our flights, the production of SO₂ and nss-SO₄ ^2– from DMS oxidation was significant only within the boundary layer and that transport from Asia dominated the sulfur cycle in the free troposphere. The existence of a sea-salt inversion layer was reflected in the profiles of those aerosol components, e.g., Na⁺ and NO₃ ^–, which were predominantly present as coarse particles. Our results show that long-range transport at mid-tropospheric levels plays an important role in determining the chemical composition of the atmosphere even in apparently remote northern hemispheric regions.     

Major ionic composition of precipitation in the Nam Co region, Central Tibetan Plateau

A total of 48 precipitation samples have been collected from individual precipitation events at the Nam Co Monitoring and Research Station for Multisphere Interactions (Nam Co Station, 30°47′N, 90°58′E; 4730 m a.s.l) located in the central Tibetan Plateau from August 2005 to August 2006. All samples were analyzed for major cations (NH₄⁺, Na⁺, K⁺, Ca²⁺ and Mg²⁺) and anions (Cl⁻, NO₃⁻ and SO₄²⁻), conductivity and pH. Precipitation pH values ranged from 6.03 to 7.38 with an average value of 6.59. The high pH is due to large inputs of crustal aerosols in the atmosphere, which contain a large fraction of carbonate. Ca²⁺ is the dominant cation in precipitation with an average value of 65.58 μeq L^− 1 (4.91–301.41 μeq L^− 1), accounting for 54% of the total cations in precipitation. HCO₃⁻ is the predominant anion, accounting for 62% of the total anions. When compared with data from a snow pit in the Zhadang Glacier 50 km away (5800 m a.s.l), major ion concentration in precipitation at the Nam Co Station is much higher due to local aerosol inputs. Correlation and empirical orthogonal function (EOF) analysis indicate that regional crustal aerosols and species from combustion emissions of residents are the major sources for these ions, lake salt aerosols from the Nam Co nearby and regional mineral aerosols from dry lake sediments are secondary sources, and sea salt contribution is the least due to the long distance transport.     

Rainwater chemistry and bulk atmospheric deposition in a tropical semiarid ecosystem: the Brazilian Caatinga

We assessed the rainwater chemistry, the potential sources of its main inorganic components and bulk atmospheric deposition in a rural tropical semiarid region in the Brazilian Caatinga. Rainfall samples were collected during two wet seasons, one during an extremely dry year (2012) and one during a year with normal rainfall (2013). According to measurements of the main inorganic ions in the rainwater (H⁺, Na⁺, NH₄ ⁺, K⁺, Ca²⁺, Mg²⁺, Cl^?, NO₃ ^?, and SO₄ ^2?), no differences were observed in the total ionic charge between the two investigated wet seasons. However, Ca²⁺, K⁺, NH₄ ⁺ and NO₃ ^? were significant higher in the wetter year (p < 0.05) which was attributed to anthropogenic activities, such as organic fertilizer applications. The total ionic contents of the rainwater suggested a dominant marine contribution, accounting for 76 % and 58 % of the rainwater in 2012 and 2013, respectively. The sum of the non-sea-salt fractions of Cl^?, SO₄ ^2?, Mg²⁺, Ca²⁺ and K⁺ were 19 % and 33 % in 2012 and 2013, and the nitrogenous compounds accounted for 2.8 % and 6.0 % of the total ionic contents in 2012 and 2013, respectively. The ionic ratios suggested that Mg²⁺ was probably the main neutralizing constituent of rainwater acidity, followed by Ca²⁺. We observed a low bulk atmospheric deposition of all major rainwater ions during both wet seasons. Regarding nitrogen deposition, we estimated slightly lower annual inputs than previous global estimates. Our findings contribute to the understanding of rainfall chemistry in northeastern Brazil by providing baseline information for a previously unstudied tropical semiarid ecosystem.     

Field measurements of NO and NO2 emissions from fertilized and unfertilized soils

Field measurements of NO and NO₂ emissions from soils have been performed in Finthen near Mainz (F.R.G.) and in Utrera near Seville (Spain). The applied method employed a flow box coupled with a chemiluminescent NO _x detector allowing the determination of minimum flux rates of 2 g N m^-2 h^-1 for NO and 3 g m^-2 h^-1 for NO₂.The NO and NO₂ flux rates were found to be strongly dependent on soil surface temperatures and showed strong daily variations with maximum values during the early afternoon and minimum values during the early morning. Between the daily variation patterns of NO and NO₂, there was a time lag of about 2 h which seem to be due to the different physico-chemical properties of NO and NO₂. The apparent activation energy of NO emission calculated from the Arrhenius equation ranged between 44 and 103 kJ per mole. The NO and NO₂ emission rates were positively correlated with soil moisture in the upper soil layer.The measurements carried out in August in Finthen clearly indicate the establishment of NO and NO₂ equilibrium mixing ratios which appeared to be on the order of 20 ppbv for NO and 10 ppbv for NO₂. The soil acted as a net sink for ambient air NO and NO₂ mixing ratios higher than the equilibrium values and a net source for NO and NO₂ mixing ratios lower than the equilibrium values. This behaviour as well as the observation of equilibrium mixing ratios clearly indicate that NO and NO₂ are formed and destroyed concurrently in the soil.Average flux rates measured on bare unfertilized soils were about 10 g N m^-2 h^-1 for NO₂ and 8 g N m^-2 h^-1 for NO. The NO and NO₂ flux rates were significantly reduced on plant covered soil plots. In some cases, the flux rates of both gases became negative indicating that the vegetation may act as a sink for atmospheric NO and NO₂.Application of mineral fertilizers increased the NO and NO₂ emission rates. Highest emission rates were observed for urea followed by NH₄Cl, NH₄NO₃ and NaNO₃. The fertilizer loss rates ranged from 0.1% for NaNO₃ to 5.4% for urea. Vegetation cover substantially reduced the fertilizer loss rate.The total NO _x emission from soil is estimated to be 11 Tg N yr^-1. This figure is an upper limit and includes the emission of 7 Tg N yr^-1 from natural unfertilized soils, 2 Tg N yr^-1 from fertilized soils as well as 2 Tg N yr^-1 from animal excreta. Despite its speculative character, this estimation indicates that NO _x emission by soil is important for tropospheric chemistry especially in remote areas where the NO _x production by other sources is comparatively small.