Ft. McHenry tunnel study: Source profiles and mercury emissions from diesel and gasoline powered vehicles

During the fall of 1998, the US Environmental Protection Agency and the Florida Department of Environmental Protection sponsored a 7-day study at the Ft. McHenry tunnel in Baltimore, MD with the objective of obtaining PM_2.5 vehicle source profiles for use in atmospheric mercury source apportionment studies. PM_2.5 emission profiles from gasoline and diesel powered vehicles were developed from analysis of trace elements, polycyclic aromatic hydrocarbons (PAH), and condensed aliphatic hydrocarbons. PM_2.5 samples were collected using commercially available sampling systems and were extracted and analyzed using conventional well-established methods. Both inorganic and organic profiles were sufficiently unique to mathematically discriminate the contributions from each source type using a chemical mass balance source apportionment approach. However, only the organic source profiles provided unique PAH tracers (e.g., fluoranthene, pyrene, and chrysene) for diesel combustion that could be used to identify source contributions generated using multivariate statistical receptor modeling approaches. In addition, the study found significant emission of gaseous elemental mercury (Hg⁰), divalent reactive gaseous mercury (RGM), and particulate mercury (Hg(p)) from gasoline but not from diesel powered motor vehicles. Fuel analysis supported the tunnel measurement results showing that total mercury content in all grades of gasoline (284±108 ng L⁻¹) was substantially higher than total mercury content in diesel fuel (62±37 ng L⁻¹) collected contemporaneously at local Baltimore retailers.     

Measurements of GEM fluxes and atmospheric mercury concentrations (GEM,RGM and Hgp) from an agricultural field amended with biosolids in Southern Ont., Canada (October 2004–November 2004)

Five weeks of gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particle bound mercury (Hg^p) concentrations as well as fluxes of GEM were measured at Maryhill, Ontario, Canada above a biosolids amended field. The study occurred during the autumn of 2004 (October–November) to capture the effects of cool weather conditions on the behaviour of mercury in the atmosphere. The initial concentration of total mercury (Hg) in the amended soil was relatively low (0.4 μg g⁻¹±10%).A micrometeorological approach was used to infer the flux of GEM using a continuous two-level sampling system with inlets at 0.40 and 1.25 m above the soil surface to measure the GEM concentration gradient. The required turbulent transfer coefficients were derived from meteorological parameters measured on site. The average GEM flux over the study was 0.1±0.2 ng m⁻² h⁻¹(±one standard deviation). The highest averaged hourly GEM fluxes occurred when the averaged net radiation was highest, although the slight diurnal patterns observed were not statistically significant for the complete flux data series. GEM emission fluxes responded to various local events including the passage of a cold front when the flux increased to 2 ng m⁻² h⁻¹ and during a biosolids application event at an adjacent field when depositional fluxes peaked at −3 ng m⁻² h⁻¹. Three substantial rain events during the study kept the surface soil moisture near field capacity and only slightly increased the GEM flux. Average concentrations of RGM (2.3±3.0 pg m⁻³), Hg^p (3.0±6.2 pg m⁻³) and GEM (1.8±0.2 ng m⁻³) remained relatively constant throughout the study except when specific local events resulted in elevated concentrations. The application of biosolids to an adjacent field produced large increases in Hg^p (25.8 pg m⁻³) and RGM (21.7 pg m⁻³) concentrations only when the wind aligned to impact the experimental equipment. Harvest events (corn) in adjacent fields also corresponded to higher concentrations of GEM and Hg^p but with no elevated peaks in RGM concentrations. Diurnal patterns were not statistically significant for RGM and Hg^p at Maryhill.     

Atmospheric mercury species in the European Arctic: Measurements and modelling

Concentrations of different species of mercury in arctic air and precipitation have been measured at Ny-Ålesund (Svalbard) and Pallas (Finland) during 1996–1997. Typical concentrations for vapour phase mercury measured at the two stations were in the range of 0.7–2 ng m⁻³ whereas particulate mercury concentrations were below 5 pg m⁻³. Total mercury in precipitation was in the range 3–30 ng l⁻¹. In order to evaluate the transport and deposition of mercury to the arctic from European anthropogenic sources, the Eulerian transport model HMET has been modified and extended to also include mercury species. A scheme for chemical conversion of elemental mercury to other species of mercury and deposition characteristics of different mercury species have been included in the model. European emission inventories for three different forms of Hg (Hg⁰, HgCl₂ and Hg_p) have been implemented in the numerical grid system for the HMET model.     

Characteristics of mercury exchange flux between soil and air in the heavily air-polluted area,eastern Guizhou,China

To investigate the characteristics of mercury exchange between soil and air in the heavily air-polluted area, total gaseous mercury (TGM) concentration in air and Hg exchange flux were measured in Wanshan Hg mining area (WMMA) in November, 2002 and July–August, 2004. The results showed that the average TGM concentrations in the ambient air (17.8–1101.8 ng m⁻³), average Hg emission flux (162–27827 ng m⁻² h⁻¹) and average Hg dry deposition flux (0–9434 ng m⁻² h⁻¹) in WMMA were 1–4 orders of magnitude higher than those in the background area. It is said that mercury-enriched soil is a significant Hg source of the atmosphere in WMMA. It was also found that widely distributed roasted cinnabar banks are net Hg sources of the atmosphere in WMMA. Relationships between mercury exchange flux and environmental parameters were investigated. The results indicated that the rate of mercury emission from soil could be accelerated by high total soil mercury concentration and solar irradiation. Whereas, highly elevated TGM concentrations in the ambient air can restrain Hg emission from soil and even lead to strongly atmospheric Hg deposition to soil surface. A great amount of gaseous mercury in the heavily polluted atmosphere may cycle between soil and air quickly and locally. Vegetation can inhibit mercury emission from soil and are important sinks of atmospheric mercury in heavily air-polluted area.     

Fine,ultrafine and nanoparticle trace element compositions near a major freeway with a high heavy-duty diesel fraction

Trace elements and metals in the ultrafine (<0.18 μm) and accumulation (0.18–2.5 μm) particulate matter (PM) modes were measured during the winter season, next to a busy Southern California freeway with significant (∼20%) diesel traffic. Both ambient and concentrated size-segregated impactor samples were taken in order to collect enough mass for chemical analysis. Data at this location were compared to a site located 1 mile downwind of the freeway, which was reflective of urban background. The most abundant trace elements in the accumulation mode detected by inductively coupled plasma mass spectroscopy (ICPMS) were S (138 ng m⁻³), Na (129 ng m⁻³), and Fe (89 ng m⁻³) while S (35 ng m⁻³) and Fe (35 ng m⁻³) were the most abundant in the ultrafine mode. The concentrations of several trace elements, including Mg, Al, and Zn, and in particular Ca, Cu, and Pb, did not uniformly increase with size within fine PM, an indication that various roadway sources exist for these elements. Calculation of crustal enrichment factors for the two sites indicates that the freeway traffic contributed to enriched levels of ultrafine Cu, Ba, P and Fe and possibly Ca. The results of this study show that trace elements constitute a small fraction of PM mass in the nanoparticle size range, but these can and should be characterized due to their likely importance to human health.     

Mercury deposition through litterfall in an Atlantic Forest at Ilha Grande,Southeast Brazil

Atmospheric Hg transfer to the forest soil through litterfall was investigated in a primary rainforest at Ilha Grande (Southeast Brazil) from January to December 1997. Litter mass deposition reached 10.0 t ha⁻¹ y⁻¹, with leaves composing 50–84% of the total litter mass. Concentrations of Hg in the total fallen litter varied from 20 to 244 ng g⁻¹, with higher concentrations during the dry season, between June and August (225 ± 17 ng g⁻¹), and lower concentrations during the rainy season (99 ± 54 ng g⁻¹). This seasonal variability was reflected in the Hg flux through litterfall, which corresponded to a Hg input to the forest floor of 122 μg m⁻² y⁻¹, with average Hg deposition of 16.5 ± 1.5 μg m⁻² month⁻¹ during and just after the dry season (June–September) and 7.0 ± 3.6 μg m⁻² month⁻¹ in the rest of the year. The variability in meteorological conditions (determining atmospheric Hg availability to foliar scavenging) may explain the pulsed pattern of Hg deposition, since litterfall temporal variability was generally unrelated with such deposition, except by a peak in litterfall production in September. Comparisons with regional data on Hg atmospheric deposition show that litterfall promotes Hg deposition at Ilha Grande two to three orders of magnitude higher than open rainfall deposition in non-industrialized areas and approximately two times higher than open rainfall deposition in industrialized areas in Rio de Janeiro State. The observed input suggests that atmospheric Hg transfer through litterfall may explain a larger fraction of the total Hg input to forest soils in Southeast Brazil than those recorded at higher latitudes.     

Identification,abundance and seasonal variation of anthropogenic organic aerosols from a mega-city in China

PM_2.5 aerosols were collected in Nanjing, a typical mega-city in China, during summer and winter 2004 and were characterized for aromatic and cyclic compounds using a GC/MS technique to understand the air pollution problem. They include polycyclic aromatic hydrocarbons (PAHs), hopanes, phthalates and hydroxy-PAHs (OH-PAHs). PAHs, hopanes and OH-PAHs presented higher concentrations in winter (26–178, 3.0–18, and 0.013–0.421 ng m⁻³, respectively) than in summer (12–96, 1.6–11, and 0.029–0.171 ng m⁻³, respectively) due to an enhanced coal burning for house heating and atmospheric inversion layers developed in the cold season. In contrast, phthalates are more abundant in summer (109–368 ng m⁻³, average 230 ng m⁻³) than in winter (33–390 ng m⁻³, average 170 ng m⁻³) due to an enhanced evaporation from plastics during the hot season and the subsequent deposition on the pre-existing particles. Generally, all the identified compounds showed higher concentrations in nighttime than in daytime due to inversion layers and increased emissions from heavy-duty trucks at night. PAHs, hopanes and phthalates in Nanjing aerosols are 5–100 times more abundant than those in Los Angeles, USA, indicating a serious air pollution problem in the city. Concentrations of OH-PAHs are 1–3 orders of magnitude less than their parent PAHs and comparable to those reported from other international cities. Source identification using diagnostic ratios of the organic tracers suggests that PAHs in Nanjing urban area are mainly derived from coal burning, whereas hopanes are more attributable to traffic emissions.     

Snow-to-air exchanges of mercury in an Arctic seasonal snow pack in Ny-Ålesund,Svalbard

The study of mercury (Hg) cycle in Arctic regions is a major subject of concern due to the dramatic increases of Hg concentrations in ecosystem in the last few decades. The causes of such increases are still in debate, and an important way to improve our knowledge on the subject is to study the exchanges of Hg between atmosphere and snow during springtime. We organized an international study from 10 April to 10 May 2003 in Ny-Ålesund, Svalbard, in order to assess these fluxes through measurements and derived calculations.Snow-to-air emission fluxes of Hg were measured using the flux chamber technique between ∼0 and 50 ng m⁻² h⁻¹. A peak in Gaseous Elemental Mercury (GEM) emission flux from the snow to the atmosphere has been measured just few hours after an Atmospheric Mercury Depletion Event (AMDE) recorded on 22 April 2004. Surprisingly, this peak in GEM emitted after this AMDE did not correspond to any increase in Hg concentration in snow surface. A peak in GEM flux after an AMDE was observed only for this single event but not for the four other AMDEs recorded during this spring period.In the snow pack which is seasonal and about 40 cm depth above permafrost, Hg is involved in both production and incorporation processes. The incorporation was evaluated to ∼5–40 pg m² h. Outside of AMDE periods, Hg flux from the snow surface to the atmosphere was the consequence of GEM production in the air of snow and was about ∼15–50 ng m⁻² h⁻¹, with a contribution of deeper snow layers evaluated to ∼0.3–6.5 ng m⁻² h⁻¹. The major part of GEM production is then mainly a surface phenomenon. The internal production of GEM was largely increasing when snow temperatures were close to melting, indicating a chemical process occurring in the quasi-liquid layer at the surface of snow grains.     

Atmospheric distribution of polycyclic aromatic hydrocarbons and deposition to Galveston Bay,Texas, USA

Estimates of the atmospheric deposition to Galveston Bay of polycyclic aromatic hydrocarbons (PAHs) are made using precipitation and meteorological data that were collected continuously from 2 February 1995 to 6 August 1996 at Seabrook, TX, USA. Particulate and vapor phase PAHs in ambient air and particulate and dissolved phases in rain samples were collected and analyzed. More than 95% of atmospheric PAHs were in the vapor phase and about 73% of PAHs in the rain were in the dissolved phase. Phenanthrene and napthalene were the dominant compounds in air vapor and rain dissolved phases, respectively, while 5 and 6 ring PAH were predominant in the particulate phase of both air and rain samples. Total PAH concentrations ranged from 4 to 161 ng m⁻³ in air samples and from 50 to 312 ng l⁻¹ in rain samples. Temporal variability in total PAH air concentrations were observed, with lower concentrations in the spring and fall (4–34 ng m ⁻³) compared to the summer and winter (37–161 ng m⁻³). PAHs in the air near Galveston Bay are derived from both combustion and petroleum vaporization. Gas exchange from the atmosphere to the surface water is estimated to be the major deposition process for PAHs (1211 μg m^{− 2} yr^{− 1}), relative to wet deposition (130 μg m⁻² yr^{− 1}) and dry deposition (99 μg m⁻² yr^{− 1}). Annual deposition of PAHs directly to Galveston Bay from the atmosphere is estimated as 2  t yr⁻¹.     

Pre- and post-catalyst-, fuel-, velocity- and acceleration-dependent benzene emission data of gasoline-driven EURO-2 passenger cars and light duty vehicles

The benzene emission characteristics of six gasoline-driven EURO-2 vehicles, three passenger cars and three light duty vehicles, have been determined by time-resolved chemical ionization mass spectrometry. Aliquots of the exhaust gas were monitored pre- and post-catalyst with two independently operating mass spectrometers. Each vehicle was driven with two different fuels having benzene contents of 1 and 2 vol%. Seven driving cycles—including the European (EDC) and the US (FTP-75) driving cycle—with a total driving time of about 8800 s were studied. Herein, we discuss the average emission characteristics of the entire fleet at transient driving in the velocity range of 0–150 km h⁻¹. The conversion efficiencies of the involved catalytic systems were deduced from the pre- and post-catalyst data. On average, the vehicles showed optimal benzene conversion efficiencies (>95%) in the velocity range of 30–90 km h⁻¹. When driving below 20 or above 100 km h⁻¹ reduced benzene conversion was found (80–82%). No benzene conversion was observed when driving above 130 km h⁻¹. In contrast, the post-catalyst benzene emissions exceeded those of the untreated exhaust gas by 19–49%. Thus on an average, benzene was formed across the catalysts under these conditions. In addition, the influence of the benzene content of the gasoline on the tail-pipe emissions was also studied. The use of the gasoline with 1 vol% benzene instead of 2 vol% induced a 20–30% reduction of the post-catalyst emissions when driving below 50 km h⁻¹. The fuel effect became smaller above 100 km h⁻¹ and was even negative at high engine load (>130 km h⁻¹). Thus under these conditions, when benzene is formed across the catalyst, the amount of the emitted benzene was independent of the benzene level of the fuel.     

The composition and sources of PM2.5 organic aerosol in two urban areas of Chile

Fine particle (PM_2.5) samples were collected, using a charcoal diffusion denuder, in two urban areas of Chile, Santiago and Temuco, during the winter and spring season of 1998. Molecular markers of the organic aerosol were determined using GC/MS. Diagnostic ratios and molecular tracers were used to investigate the origin of carbonaceous aerosols. As main sources, road and non-road engine emissions in Santiago, and wood burning in Temuco were identified. Cluster analysis was used to compare the chemical characteristics of carbonaceous aerosols between the two urban environments. Distinct differences between Santiago and Temuco samples were observed. High concentrations of isoprenoid (30–69 ng m⁻³) and unresolved complex mixture (UCM) of hydrocarbons (839–1369 ng m⁻³) were found in Santiago. High concentrations of polynuclear aromatic hydrocarbons (751±304 ng m⁻³) and their oxygenated derivatives (4±2 ng m⁻³), and of n-alk-1-enes (16±13 ng m⁻³) were observed in Temuco.     

Source apportionment of secondary organic aerosol during a severe photochemical smog episode

The UCD/CIT air quality model was modified to predict source contributions to secondary organic aerosol (SOA) by expanding the Caltech Atmospheric Chemistry Mechanism to separately track source apportionment information through the chemical reaction system as precursor species react to form condensable products. The model was used to predict source contributions to SOA in Los Angeles from catalyst-equipped gasoline vehicles, non-catalyst equipped gasoline vehicles, diesel vehicles, combustion of high sulfur fuel, other anthropogenic sources, biogenic sources, and initial/boundary conditions during the severe photochemical smog episode that occurred on 9 September 1993. Gasoline engines (catalyst+non-catalyst equipped) were found to be the single-largest anthropogenic source of SOA averaged over the entire model domain. The region-wide 24-h average concentration of SOA produced by gasoline engines was predicted to be 0.34 μg m⁻³ with a maximum 24-h average concentration of 1.81 μg m⁻³ downwind of central Los Angeles. The region-wide 24-h average concentration of SOA produced by diesel engines was predicted to be 0.02 μg m⁻³, with a maximum 24-h average concentration of 0.12 μg m⁻³ downwind of central Los Angeles. Biogenic sources are predicted to produce a region-wide 24-h average SOA value of 0.16 μg m⁻³, with a maximum 24-h average concentration of 1.37 μg m⁻³ in the less-heavily populated regions at the northern and southern edges of the air basin (close to the biogenic emissions sources). SOA concentrations associated with anthropogenic sources were weakly diurnal, with slightly lower concentrations during the day as mixing depth increased. SOA concentrations associated with biogenic sources were strongly diurnal, with higher concentrations of aqueous biogenic SOA at night when relative humidity (RH) peaked and little biogenic SOA formation during the day when RH decreased.     

Polycyclic aromatic hydrocarbons in the urban atmospheric particulate matter in the city of Naples (Italy)

An investigation on PAH in the atmospheric particulate matter of the city of Naples has been carried out. Urban atmospheric particulate matter was sampled in three sampling sites (West, East and central areas of the city), whose characteristics were representative of the prevailing conditions. In each site, 24 h samplings for 7 consecutive days were performed during three sampling campaigns, in 1996–1997. The results were comparable with those reported in literature for similar investigations. Total PAH were in the range 2–130 ng m⁻³, with a seasonal variation (autumn/winter vs. summer) in the range 1.5–4.5. The relative contribution of diesel engines vs. gasoline fuelled engines was evidenced.     

Origin of low-molecular-weight dicarboxylic acids and their concentration and size distribution variation in suburban aerosol

The concentrations and size distributions of low molecular weight dicarboxylic acids in suburban particulate matter collected in early and mid-autumn 2002 and early and mid-summer 2003 in Tainan, Taiwan, were analyzed. PM_2.5 contained, on average, 449.3 ng m⁻³ oxalic acid, 53.0 ng m⁻³ malic acid, 45.5 ng m⁻³ maleic acid, 29.6 ng m⁻³ succinic acid, 20.8 ng m⁻³ malonic acid, and 11.6 ng m⁻³ tartaric acid. Bar tartaric acid, concentrations were higher during the day, indicating that these acids are photochemical products. Furthermore, the malonic acid–succinic acid ratio of 0.79 during daytime and 0.60 during nighttime demonstrates that more succinic acid is converted to malonic acid during daytime, and that aerosol dicarboxylic acids predominantly originate from photochemical oxidation during daytime. The concentration peak of oxalic acid occurred in the condensation and droplet modes (0.32–1.0 μm), as did that of sulfate. In early summer, succinic acid, malonic acid, and oxalic acid major concentration peaks occurred at 0.32–0.54 μm, indicative of the relationship created by photochemical decomposition of succinc acid into malonic acid into oxalic acid. This photochemical decomposition accelerated in mid-summer such that most concentration peaks for succinic and malonic acids also occurred at 0.32–1.0 μm. Mid-summer is also the wettest period of the four in Tainan, with 85% RH. As a result of hygroscopic reactions in mid-summer, malonic acid and oxalic acid major concentration peaks shifted from 0.32–0.54 μm or 0.54–1.0 μm to 1.0–1.8 μm, thus extending the range in which these species were found to larger particle sizes, and this shift was highly correlated with a shift in succinic acid size distribution. This latter observation offers additional evidence that succinic acid is photochemically decomposed into malonic acid and oxalic acid and that the presence of malonic and oxalic acids in the wet mid-summer atmosphere is made more obvious via hygroscopic growth. Close correlation between succinic acid and Na⁺ and succinic acid and NO₃⁻ in the coarse mode is related to sea spray.     

Mercury emissions as landfill gas from a large-scale abandoned landfill site in Seoul

The composition of landfill gas (LFG) was analyzed for vapor-phase mercury (Hg) (primarily in its elemental form, Hg⁰) and relevant environmental parameters from 42 out of 106 ventpipes placed across two different sectors of the Nan-Ji-Do (NJD) landfill site in Seoul, Korea during September/October 2000. Results of our studies showed that large quantities of Hg emanated through these ventpipes which were infiltrated deep into the waste layer. The mean concentration of Hg, computed using the data sets collected from 42 ventpipes, was 420 ng m⁻³ with a range of 3.45–2952 ng m⁻³. Because large differences were apparent in its concentration levels not only between the two sectors of 1 and 2 but also between the plain and slope areas, evaluation of the data was made by dividing them into four different categories, namely plain areas of sectors 1 and 2 and slope areas of sectors 1 and 2. By categorizing the data in such a manner, the emission fluxes of ventilated Hg were estimated for each data group at the NJD site. The flux values of Hg for each data group were distinguished so that the enhanced fluxes were observed in plain compared to slope areas. The computed LFG fluxes of Hg from the whole NJD site were on the order of 23 g on an annual basis. The overall results of our study suggest that the vent emission of Hg from the study site is comparable in magnitude to those reported previously (e.g., the Florida landfill sites in US), while the LFG emissions of Hg may not necessarily be the most dominant source in the NJD site.     

Pesticides analysed in rainwater in Alsace region (Eastern France): Comparison between urban and rural sites

Current-used pesticides commonly applied in Alsace region (Eastern France) on diverse crops (maize, vineyard, vegetables, etc.) were analysed, together with Lindane, in rainwater between January 2002 and June 2003 simultaneously on two sites situated in a typical rural (Erstein, France) and urban area (Strasbourg, France).Rainwater samples were collected on a weekly basis by using two automatic wet only collectors associated with an open collector for the measurement of rainwater height.Pesticides were analysed by GC-MSMS and extracted from rainwater by SPME. Two runs were performed. The first one was performed by using a PDMS (100 μm) fibre for pesticides where direct injection into GC is possible (alachlor, atrazine, azinphos-ethyl, azinphos-methyl, captan, chlorfenvinphos, dichlorvos, diflufenican, α- and β-endosulfan, iprodione, lindane, metolachlor, mevinphos, parathion-methyl, phosalone, phosmet, tebuconazole, triadimefon and trifluralin). The second run was performed by using PDMS/DVB fibre and this run concerns pesticides where a preliminary derivatisation step with pentafluorobenzylbromide (PFBBr) is required for very low volatiles (bromoxynil,2,4-MCPA, MCPP and 2,4-D) or thermo labiles (chlorotoluron, diuron and isoproturon) pesticides.Results showed that the more concentrated pesticides detected were those used as herbicides in large quantities in Alsace region for maize crops (alachlor, metolachlor and atrazine). Maximum concentrations for these herbicides have been measured during intensive applications periods on maize crops following by rapid decrease immediately after use.For Alachlor, most important peaks have been observed between 21 and 28 April 2003 (3327 ng L⁻¹ at Erstein and 5590 ng L⁻¹ at Strasbourg). This is also the case for Metolachlor where most important peak was observed during the same week.Concentrations of pesticides measured out of application periods were very low for many pesticides and some others where never detected during this period. This is the case for diflufenican which was detected only during application. Two important peaks of concentrations were observed; a first one (101 ng L⁻¹) in Erstein in November 2002 (4–11 November) and a second one (762 ng L⁻¹) also in Erstein (28 April–15 May).The same behaviour can be seen for chlorfenvinphos and phosalone which have been detected, respectively, 2 and 4 times in Erstein and Strasbourg at high concentrations (28 April 2003–15 May 2003, 187 ng L⁻¹ of phosalone and 157 ng L⁻¹ of chlorfenvinphos in Erstein).MCPP, 2,4 MCPA and 2,4-D have been detected at high concentrations in rainwater but for the other pesticides very episodically and mainly during their use in agriculture. Maximal concentrations of MCPP and 2,4 MCPA have been measured in Erstein between 28 April and 15 May (904 and 746 ng L⁻¹, respectively).Comparison between rural and urban sites showed that concentrations in rural areas are generally higher except for pesticides commonly applied in urban areas like Diuron.No seasonal phenomenon was observed for Diuron. This herbicide has been detected in practically all of the rainwater samples in Strasbourg (40/41) with a maximum of 1025 ng L⁻¹ (16–23 September 2002) in 38 samples on 41 in Erstein with a maximum of 317 ng L⁻¹ (15–23 October 2002). The total concentration of Diuron measured between 4 March 2002 and 20 July 2003 is of 4721 ng L⁻¹ in Strasbourg and 5025 ng L⁻¹ in Erstein. This result shows that wet deposition of Diuron in urban and rural sites was equivalent and can be explained by the “urban use” of this molecule together with its potential persistence.     

Estimates of air-sea exchange of mercury in the Baltic Sea

The concentrations of total gaseous mercury (TGM) in air over the southern Baltic Sea and dissolved gaseous mercury (DGM) in the surface seawater were measured during summer and winter. The summer expedition was performed on 02–15 July 1997, and the winter expedition on 02–15 March 1998. Average TGM and DGM values obtained were 1.70 and 17.6 ng m⁻³ in the summer and 1.39 and 17.4 ng m⁻³ in the winter, respectively. Based on the TGM and DGM data, surface water saturation and air-water fluxes were calculated. The results indicate that the seawater was supersaturated with gaseous mercury during both seasons, with the highest values occurring in the summer. Flux estimates were made using the thin film gas-exchange model. The average Hg fluxes obtained for the summer and winter measurements were 38 and 20 ng m⁻² d⁻¹, respectively. The annual mercury flux from this area was estimated by a combination of the TGM and DGM data with monthly average water temperatures and wind velocities, resulting in an annual flux of 9.5 μg m⁻² yr⁻¹. This flux is of the same order of magnitude as the average wet deposition input of mercury in this area. This indicates that reemissions from the water surface need to be considered when making mass-balance estimates of mercury in the Baltic Sea as well as modelling calculations of long-range transboundary transport of mercury in northern Europe.     

Detection,occurrence and fate of 22 psychiatric pharmaceuticals in psychiatric hospital and municipal wastewater treatment plants in Beijing,China

The liquid chromatography–electrospray ionization-tandem mass spectrometer (LC–MS/MS) method coupled with an automated solid-phase extraction procedure has been developed to identify 22 psychiatric pharmaceuticals, including seven anxiolytic-sedative-hypnotics, six antidepressants, and nine anti-schizophrenia drugs, in wastewater samples from two psychiatric hospital wastewater treatment plants (P-WWTPs) and three municipal wastewater treatment plants (M-WWTPs) in Beijing, China. Analyte recoveries from spiking experiments in the WWTP influent and effluent at three concentrations ranged from 70% to 110%, excluding sulpiride, ziprasidone, and olanzapine. Method detection limits for five, eight, and nine analytes in the WWTP influent and effluent were 20–80, 1–16, and <1 ng L^?1, respectively. High psychiatric pharmaceutical concentrations (e.g., ～942 ng L^?1oxazepam, 5552–12,782 ng L^?1 clozapine, 2762–9832 ng L^?1sulpiride, and 2030–4967 ng L^?1quetiapine) were frequently observed in P-WWTP influent compared to M-WWTPs. Although P-WWTPs typically had higher removal rates, significantly higher concentrations of the target compounds were observed in the P-WWTP secondary effluent than in the M-WWTP influent (e.g., ～752 ng L^?1oxazepam, ～8183 ng L^?1 clozapine, ～10,833 ng L^?1sulpiride, and ～1168 ng L^?1quetiapine). Thus, the discharge control of psychiatric pharmaceuticals from psychiatric hospitals requires improvement.     

The temporal distribution characteristics of total gaseous mercury at an urban monitoring site in Seoul during 1999–2000

In order to assess the temporal variabilities of atmospheric mercury (Hg) from an area moderately impacted by man-made source processes, the concentrations of total gaseous mercury were measured routinely from an urban monitoring station during January 1999–August 2000. The mean hourly concentration of Hg from overall measurements was computed to be 5.26±3.27 ng m⁻³ (N=11, 572). Using these measurement data, we inspected various aspects on the temporal distribution of Hg. When analyzed over 24 h scale, the pattern was characterized by high concentration during nighttime relative to daytime (e.g., values approaching 9 ng m⁻³). This pattern was prominent during winter and seen persistently across fall, spring, and summer. When divided seasonally, the highest mean of 6.01 ng m⁻³ was observed during winter. It appears that such wintertime dominance is most likely to come from the anthropogenic sources such as household heating systems from late fall to early spring. A close inspection of the Hg data however indicated that the seasonal variation proceeded quite dynamically. Inspection of seasonally divided data groups generally showed substantial variabilities among different months. In order to analyze the factors affecting Hg distributions over different time scale, we conducted the correlation analysis. Whereas Hg generally exhibited strong correlations with such parameters as PM, SO₂, and NO₂, its relationship varied diurnally and seasonally. The overall results of the present study suggest that changes in its source signatures can vary over varying time scale under the influence of strong man-made source processes.     

Dry deposition of ammonia,nitric acid,ammonium, and nitrate to alpine tundra at Niwot Ridge,Colorado

Micrometeorological measurements and ambient air samples, analyzed for concentrations of NH₃, HNO₃, NH₄⁺, and NO₃⁻, were collected at an alpine tundra site on Niwot Ridge, Colorado. The measured concentrations were extremely low and ranged between 5 and 70 ng N m⁻³. Dry deposition fluxes of these atmospheric species were calculated using the micrometeorological gradient method. The calculated mean flux for NH₃ indicates a net deposition to the surface and indicates that NH₃ contributed significantly to the total N deposition to the tundra during the August–September measurement period. Our pre-measurement estimate of the compensation point for NH₃ in air above the tundra was 100–200 ng N m⁻³; thus, a net emission of NH₃ was expected given the low ambient concentrations of NH₃ observed. Based on our results, however, the NH₃ compensation point at this alpine tundra site appears to have been at or below about 20 ng N m⁻³. Large deposition velocities (>2 cm s⁻¹) were determined for nitrate and ammonium and may result from reactions with surface-derived aerosols.