Occurrence and fate of the human pharmaceutical metabolite ritalinic acid in the aquatic system

To investigate the occurrence and fate of ritalinic acid - the main human metabolite of the psychostimulant drug methylphenidate - in the aquatic environment, a HPLC-electrospray-MS/MS method for the quantification of ritalinic acid in wastewater, surface water and bank filtrate was developed. Carbamazepine known as very stable in the aquatic environment was analyzed as anthropogenic marker in parallel. Furthermore, the removal of ritalinic acid was studied in a sewage treatment plant using an activated sludge system during a field study and in lab-scale plants. In good agreement between lab-scale and field studies a low removal rate of 13% and 23%, respectively, was determined. As a consequence, the concentration of ritalinic acid in the wastewater effluents were in the range of <50-170 ngL(-1) which corresponds to a mean specific load per capita of 17.7 μgd(-1). Ritalinic acid has further been detected in German rivers at concentrations of 4-23 ngL(-1) and in bank filtrate samples in 100-850 m distance from the river up to 5 ngL(-1) demonstrating the widespread occurrence of this stable metabolite in the aquatic environment. A comparison to available sales data shows that a significant amount of methylphenidate applied can be found in waters as ritalinic acid.     

Mercury emissions from automobiles using gasoline,diesel, and LPG

Mercury (Hg) emissions from gasoline, diesel, and liquefied petroleum gas (LPG) vehicles were measured and speciated (particulate, oxidized, and elemental mercury). First, three different fuel types were analyzed for their original Hg contents; 571.1±4.5 ng L⁻¹ for gasoline, 185.7±2.6 ng L⁻¹ for diesel, and 1230.3±23.5 ng L⁻¹ for LPG. All three vehicles were then tested at idling and driving modes. Hg in the exhaust gas was mostly in elemental form (Hg⁰), and no detectable levels of particulate (Hg^p) or oxidized (Hg²⁺) mercury were measured. At idling modes, Hg concentrations in the exhaust gas of gasoline, diesel, and LPG vehicles were 1.5–9.1, 1.6–3.5, and 10.2–18.6 ng m⁻³, respectively. At driving modes, Hg concentrations were 3.8–16.8 ng m⁻³ (gasoline), 2.8–8.5 ng m⁻³ (diesel), and 20.0–26.9 ng m⁻³ (LPG). For all three vehicles, Hg concentrations at driving modes were higher than at idling modes. Furthermore, Hg emissions from LPG vehicle was highest of all three vehicle types tested, both at idling and driving modes, as expected from the fact that it had the highest original fuel Hg content.     

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.     

Occurrence of antibiotics in water,sediments, aquatic plants,and animals from Baiyangdian Lake in North China

This study investigated the presence and distribution of 22 antibiotics, including eight quinolones, nine sulfonamides and five macrolides, in the water, sediments, and biota samples from Baiyangdian Lake, China. A total of 132 samples were collected in 2008 and 2010, and laboratory analyses revealed that antibiotics were widely distributed in the lake. Sulfonamides were the dominant antibiotics in the water (0.86–1563 ng L⁻¹), while quinolones were prominent in sediments (65.5–1166 μg kg⁻¹) and aquatic plants (8.37–6532 μg kg⁻¹). Quinolones (17.8–167 μg kg⁻¹) and macrolides [from below detection limit (BDL) to 182 μg kg⁻¹] were often found in aquatic animals and birds. Salvinia natans exhibited the highest bioaccumulation capability for quinolones among three species of aquatic plants. Geographical differences of antibiotic concentrations were greatly due to anthropogenic activities. Sewage discharged from Baoding City was likely the main source of antibiotics in the lake. Risk assessment of antibiotics on aquatic organisms suggested that algae and aquatic plants might be at risk in surface water, while animals were likely not at risk.     

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.     

Analysis of perfluoroalkyl carboxylates in vacuum cleaner dust samples in Japan

Perfluorooctanoic acid (PFOA) has long been an environmental contaminant of concern owing to its potential health risk. However, exposure to perfluorinated carboxylic acids (PFCAs) other than PFOA is not well understood. In this study, we investigated the concentrations of PFCAs in vacuum cleaner dust in Japan to measure the PFCAs contamination in an indoor environment. Most of the 77 samples contained PFCAs with 6–13 carbon atoms. The median concentration of perfluorononanoic acid (PFNA, 23.2 ng g⁻¹) was highest among PFCAs, followed by PFOA (20.8 ng g⁻¹) and perfluoroundecanoic acid (PFUnDA, 12.9 ng g⁻¹). The 90th percentile concentrations of PFNA, PFUnDA and perfluorotridecanoic acid (PFTrDA) were 948, 283 and 110 ng g⁻¹, respectively, and these were detected at greater concentrations than neighboring, even-numbered PFCAs. The proportion of long-chain PFCAs in vacuum cleaner dust from Japan was relatively higher than those reported for other countries. Factor analysis showed three independent factors. Odd-numbered long chain PFCAs (PFNA, PFUnDA and PFTrDA), which can correspond to factor 1, were major components of PFCAs in vacuum cleaner dust. Short chain PFCAs (factor 2) and even numbered long chain PFCAs (factor 3) were also statistically separated. These findings suggest that there are several sources of PFCAs with different origins in indoor environment. Further investigations into the origins of PFCAs are needed to evaluate indoor contamination with PFCAs.     

Responses of antioxidant status and Na+–K+-ATPase activity in gill of rainbow trout,Oncorhynchus mykiss,chronically treated with carbamazepine

In recent years, chemical pollution by the residual pharmaceuticals has been increasingly important issue due to its widely present in the aquatic environment. However, the toxicological effects of residual pharmaceuticals on fish have not been adequately researched. The aim of this work is to investigate the toxic effect of CBZ, an anticonvulsant drug commonly present in aquatic environment, on antioxidant status and Na⁺–K⁺-ATPase in gill of rainbow trout exposed to sublethal CBZ (1.0 μg L⁻¹, 0.2 mg L⁻¹ and 2.0 mg L⁻¹) for 7, 21 and 42 d. After prolonged exposure of CBZ at higher test concentration (0.2 or 2.0 mg L⁻¹), oxidative stress was apparent as reflected by the significant higher LPO and CP levels in fish gill, as well as the significant inhibition of antioxidant enzymes activities including SOD, CAT, GR and GPx. Besides, reduced glutathione level and Na⁺–K⁺-ATPase activity were significantly lower than those of the control after 42 d of exposure to CBZ at higher test concentration (0.2 or 2.0 mg L⁻¹). The results of this study indicate that chronic exposure of CBZ has altered multiple physiological indices in fish gill; however, before those parameters are used as special biomarkers for monitoring residual pharmaceuticals in aquatic environment, more detailed experiments in laboratory need to be performed in the future.     

Removal and reductive dechlorination of triclosan by Chlorella pyrenoidosa

Triclosan that is widely used as antimicrobial agent has been detected as contaminant in various aquatic environments. In this work, removal and biodegradation of triclosan in water by using a ubiquitous green alga, Chlorella pyrenoidosa was investigated. When C. pyrenoidosa was exposed to a series concentration of triclosan from 100 to 800 ng mL⁻¹, more than 50% of triclosan was eliminated by algal uptake from the culture medium during the first 1 h exposure and reached equilibrium after the 6 h treatment. In the biodegradation experiments, a removal percentage of 77.2% was obtained after C. pyrenoidosa was cultivated with 800 ng mL⁻¹ triclosan for 96 h. A major metabolite from the reductive dechlorination of triclosan was identified by using liquid chromatography coupled with electrospray ionization-mass spectrometry. The ultrastructural morphology of algal cells grown in the presence of triclosan was observed by using transmission electron microscopy and the growth of algal cells was detected. It was found that the trilcosan treatment resulted in the disruption of the chloroplast and the release of organic material into aquatic environment, which indicated that triclosan may affect membrane metabolism.     

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.     

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.     

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.     

Reproductive performance in East Greenland polar bears (Ursus maritimus) may be affected by organohalogen contaminants as shown by physiologically-based pharmacokinetic (PBPK) modelling

Polar bears (Ursus maritimus) feed mainly on ringed seal (Phoca hispida) and consume large quantities of blubber and consequently have one of the highest tissue concentrations of organohalogen contaminants (OHCs) worldwide. In East Greenland, studies of OHC time trends and organ system health effects, including reproductive, were conducted during 1990–2006. However, it has been difficult to determine the nature of the effects induced by OHC exposures on wild caught polar bears using body burden data and associated changes in reproductive organs and systems. We therefore conducted a risk quotient (RQ) evaluation to more quantitatively evaluate the effect risk on reproduction (embryotoxicity and teratogenicity) based on the critical body residue (CBR) concept and using a physiologically-based pharmacokinetic (PBPK) model. We applied modelling approaches to PCBs, p,p′-DDE, dieldrin, oxychlordane, HCHs, HCB, PBDEs and PFOS in East Greenland polar bears based on known OHC pharmacokinetics and dynamics in laboratory rats (Rattus rattus). The results showed that subcutaneous adipose tissue concentrations of dieldrin (range: 79–1271 ng g⁻¹ lw) and PCBs (range: 4128–53 923 ng g⁻¹ lw) reported in bears in the year 1990 were in the range to elicit possible adverse health effects on reproduction in polar bears in East Greenland (all RQs ⩾ 1). Similar results were found for PCBs (range: 1928–17 376 ng g⁻¹ lw) and PFOS (range: 104–2840 ng g⁻¹ ww) in the year 2000 and for dieldrin (range: 43–640 ng g⁻¹ lw), PCBs (range: 3491–13 243 ng g⁻¹ lw) and PFOS (range: 1332–6160 ng g⁻¹ ww) in the year 2006. The concentrations of oxychlordane, DDTs, HCB and HCHs in polar bears resulted in RQs < 1 and thus appear less likely to be linked to reproductive effects. Furthermore, sumRQs above 1 suggested risk for OHC additive effects. Thus, previous suggestions of possible adverse health effects in polar bears correlated to OHC exposure are supported by the present study. This study also indicates that PBPK models may be a supportive tool in the evaluation of possible OHC-mediated health effects for Arctic wildlife.     

Organic Matter of the Troposphere—II.: Natural Background of biogenic lipid matter in aerosols over the rural western United States

Higher plant waxes are the predominant natural components in the lipid fractions (> C₁₅) of aerosols sampled over rural and oceanic regions. Hydrocarbon, fatty acid, ketone and fatty alcohol fractions of the lipids were characterized in terms of their contents of homologous compound series and specific biogenic molecular markers. Particulate samples from the rural western United States have been analyzed and compared with samples from urban Los Angeles and remote areas over the Atlantic Ocean. The samples from rural sites contained predominantly vascular plant wax and lesser amounts of higher plant sterols and resin residues. Urban samples and, to varying degrees, some rural samples contained primarily higher weight residues of petroleum products. The loadings of hydrocarbons derived from higher plant waxes ranged approximately from 10 to 160 ng m⁻³ of air (for fatty acids, 10–100 ng m⁻³ and for fatty alcohols, 10–200 ng m⁻³). Higher molecular weight lipids (i.e. plant epicuticular wax, terpenes, etc.) from flora comprise a significant component of the organic carbon in rural aerosols. Primary biogenic residues are major components of aerosols in all areas and they are important components in the global cycling of organic carbon.     

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.     

Determination of priority pesticides in water samples combining SPE and SPME coupled to GC–MS. A case study: Suquía River basin (Argentina)

This study reports a combined method using solid phase extraction (SPE), followed by solid phase microextraction (SPME) to concentrate different pesticides, including chlorinated, organophosphorus, triazines, pyretroids and chloroacetamides, present at trace levels in water samples. Identification and quantification was carried out by gas chromatography coupled to Mass Spectrometry (GC–MS). The optimized methodology showed LOQs at ng L^?1 levels (ranging 0.2–3.5 ng L^?1) in addition to acceptable precision and robustness (recoveries ranged 63–104%, RSD from 4% to 23%), presenting a novel method to reach trace levels, similar to that obtainable using EC detector, with structural confirmation by MS during the analysis of a wide range of environmental pollutants.This method was applied to the study of temporal and spatial distribution of pesticides in the Suquía River basin (Córdoba-Argentina). As expected, highest levels of agrochemicals were observed in areas with intensive agricultural practices, being atrazine (max. = 433.9 ng L^?1), alpha-cypermetrine (max. = 121.7 ng L^?1) and endosulfan sulfate (max. = 106.7 ng L^?1) predominant. In urban areas, the prevalent pesticide was alpha-cypermethrine. These results draw attention to the need of pesticide monitoring programs in rivers, considering both urban and rural sections.     

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.     

The dry-deposition of speciated mercury to the Florida Everglades: Measurements and modeling

The Florida Everglades Dry-Deposition Study (FEDDS) was designed to test the viability of using new and existing measurement techniques in the estimation of the dry-depositional loading of speciated mercury (elemental gaseous, reactive gaseous and particulate) to a mixed sawgrass (Cladium jamaicense) and cattail (Typha domingensis) stand within the Florida Everglades. Measurement intensives were performed during 24 February–04 March 1999 and 05–21 June 2000, which corresponded to the climatological dry and wet seasons in South Florida, respectively. During these intensives, direct measurements of mercury dry-deposition were made using a newly developed surrogate water surface technique. These direct measurements were compared with modeled estimates of mercury dry-deposition to the site that were obtained through the use of an inferential or “bigleaf” model that was modified for use with speciated mercury. On-site measurements of ambient speciated mercury concentrations and numerous micrometeorological variables were used as input to the model.The average mercury dry-deposition measured during the 1999 FEDDS measurement intensive was 13.3±4.0 ng m⁻² day⁻¹, while the modeled deposition for this period was 3.4±2.3 ng m⁻² day⁻¹. The average mercury dry-deposition measured during the 2000 FEDDS measurement intensive was lower, 5.9±2.8 ng m⁻² day⁻¹, while the average modeled deposition for this period was 1.8±0.6 ng m⁻² day⁻¹. A least-squares linear regression suggests that the model was able to explain 74% and 73% of the variability in the datasets for the 1999 and 2000 FEDDS intensives, respectively. While reported reductions in total mercury emissions across South Florida between study periods could explain the reductions in both the measured and predicted mercury dry-deposition estimates, the increased presence of cumulus convection during the summer-intensive could have also resulted in a removal of reactive and particulate mercury species within the atmosphere of South Florida.     

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.     

Recreational atmospheric pollution episodes: Inhalable metalliferous particles from firework displays

The use of fireworks creates an unusual and distinctive anthropogenic atmospheric pollution event. We report on aerosol samples collected during Las Fallas in Valencia, a 6-day celebration famous for its firework displays, and add comparative data on firework- and bonfire-contaminated atmospheric aerosol samples collected from elsewhere in Spain (Barcelona, L’Alcora, and Borriana) and during the Guy Fawkes celebrations in London. Specific high-profile official firework events during Las Fallas included the afternoon Mascletà and the nightly aerial displays (especially in the climactic final 2 days of the fiesta) and were accompanied by pollution spikes in suspended particles, NO, SO₂, and the creation and dispersal of an aerosol cloud enriched in a range of metallic elements. Notable metal aerosol concentration increases recorded during Las Fallas were potassium (from 500 to 5900 ng m⁻³), aluminium (as Al₂O₃ from around 600 to 2200 ng m⁻³), titanium (from 200 to 700 ng m⁻³), magnesium (from 100 to 500 ng m⁻³), lead (from 17 to 379 ng m⁻³), barium (from 39 to 322 ng m⁻³), strontium (from 3 to 112 ng m⁻³), copper (from 12 to 71 ng m⁻³), and antimony (from 1 to 52 ng m⁻³). Firework-contaminated aerosols of similarly metalliferous composition were also identified at the other monitoring sites, although different sites show variations attributable to other sources such as bonfires and local industry. Unusual levels of the trace elements Ba, Sr and (to a lesser extent) Cu, always in proportions with Ba dominant, along with strongly enhanced K, Pb, and Sb, are identified as being particularly characteristic of firework aerosols. Although firework-related recreational pollution episodes are transient in nature, they are highly concentrated, contribute significantly to total annual metal emissions, and are on average fine enough to be easily inhaled and a health risk to susceptible individuals.