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.     

Variability of atmospheric pesticide concentrations between urban and rural areas during intensive pesticide application

Intensive pesticide use leads to the contamination of water, soil and atmosphere. Atmospheric transport is responsible for pesticide dispersal over long distances. In this study, we evaluate the local dispersal of pesticides from agricultural to urban areas. For this purpose, three high-volume samplers, each equipped with a glass fiber filter and XAD-2 resin for the sampling of particulate and gas phase have been placed in a south-west transect (predominant wind direction) characteristic of rural and urban areas. The urban site (Strasbourg centre) is situated in the middle of two rural sites. Samples were taken simultaneously at three sites during pesticide treatments in autumn and spring 2002–2003. Sampling took place for 24 h at a flow rate of 10–15 m³ h⁻¹. The pesticides studied were those commonly used in the Alsace region for all crops (maize, cereal, vines …). Many of the pesticides analysed in atmospheric samples were not detected or observed very episodically at very low concentrations. For metolachlor, alachlor, trifluralin, atrazine and diflufenican, higher concentrations were observed, essentially during the application of these compounds. Moreover, some “spraying peaks” were observed for alachlor in the south rural site (near crops) at a level of 31 ng m⁻³ on 16–17 May 2003. These results show site and time dependence of atmospheric contamination by pesticides. A limited dispersal was also observed especially in the urban area during the application periods of pesticides.     

Atmospheric deposition of organochlorine contaminants to Galveston Bay,Texas

Atmospheric monitoring of PCBs and chlorinated pesticides (e.g., HCHs, chlordanes, and DDTs) in Galveston Bay was conducted at Seabrook, Texas. Air and wet deposition samples were collected from 2 February 1995 and continued through 6 August 1996. Vapor total PCB (tPCB) concentrations in air ranged from 0.21 to 4.78 ng m⁻³ with a dominance of tri-chlorinated PCBs. Dissolved tPCBs in rain ranged from 0.08 to 3.34 ng l⁻¹, with tetra-chlorinated PCBs predominating. The predominant isomers found in air and rain were α- and γ-HCH, α- and γ-chlordanes, 4,4′-DDT, and dieldrin. The concentrations of PCBs and pesticides in the air and rain revealed no clear seasonal trend. Elevated levels of PCBs in the air occurred when temperatures were high and wind came from urban and industrialized areas (S, SW, NW, and W of the site). Concentrations of HCHs were elevated in April, May, and October, perhaps due to local and/or regional applications of γ-HCH (lindane). Other pesticides showed no notable temporal variation. When winds originated from the Gulf of Mexico (southeasterly), lower concentrations of organochlorines were detected in the air. The direct deposition rate (wet+dry) of PCBs to Galveston Bay (6.40 μg m⁻² yr⁻¹) was significantly higher than that of pesticides by a factor of 5–10. The net flux from gas exchange estimated for PCBs was from Galveston Bay water to the atmosphere (78 μg m⁻² yr⁻¹). Gas exchange of PCBs from bay water to the atmosphere was the dominant flux.     

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.     

A mobile pollutant measurement laboratory—measuring gas phase and aerosol ambient concentrations with high spatial and temporal resolution

A mobile pollutant measurement laboratory was designed and built at the Paul Scherrer Institute (Switzerland) for the measurement of on-road ambient concentrations of a large set of trace gases and aerosol parameters with high time resolution (<15 s for most instruments), along with geographical and meteorological information. This approach allowed for pollutant level measurements both near traffic (e.g. in urban areas or on freeways/main roads) and at rural locations far away from traffic, within short periods of time and at different times of day and year. Such measurements were performed on a regular base during the project year of gas phase and aerosol measurements (YOGAM). This paper presents data measured in the Zürich (Switzerland) area on a late autumn day (6 November) in 2001. The local urban particle background easily reached 50 000 cm⁻³, with additional peak particle number concentrations of up to 400 000 cm⁻³. The regional background of the total particle number concentration was not found to significantly correlate with the distance to traffic and anthropogenic emissions of carbon monoxide and nitrogen oxides. On the other hand, this correlation was significant for the number concentration of particles in the size range 50–150 nm, indicating that the particle number concentration in this size range is a better traffic indicator than the total number concentration. Particle number size distribution measurements showed that daytime urban ambient air is dominated by high number concentrations of ultrafine particles (nanoparticles) with diameters <50 nm, which are immediately formed by traffic exhaust and thus belong to the primary emissions. However, significant variation of the nanoparticle mode was also observed in number size distributions measured in rural areas both at daytime and nighttime, suggesting that nanoparticles are not exclusively formed by primary traffic emissions. While urban daytime total number concentrations were increased by a factor of 10 compared to the nighttime background, corresponding factors for total surface area and total volume concentrations were 2 and 1.5, respectively.     

Influence of usage and chemical–physical properties on the atmospheric transport and deposition of pesticides to agricultural regions of Manitoba,Canada

This study quantified the masses of 14 pesticides deposited as wet (precipitation) versus dry (gaseous and particle) atmospheric deposition at a research farm in southwestern Manitoba, Canada. The concentration in air of these pesticides was also measured. Total bulk deposition amounts (wet + dry) ranged from 0.009 to 2.3 μg m^?2 for the 12 pesticides detected, and for the six pesticides with both wet and dry deposition detections, dry deposition contributed 12–51% of the total deposition over the crop growing season. Although not applied at the site, eight herbicides registered for use in Canada, as well as lindane (γ-HCH), were all frequently detected (92–100%) in the 12 air samples analyzed during the crop growing season, with by-product isomer α-HCH (75%), clopyralid (50%) and atrazine (8%) detected to a lesser extent. The chemical’s physicochemical properties and the relative mean mass of each agricultural pesticide applied in the province of Manitoba and in a 13 km radius were significant parameters in explaining the trends in the concentrations of pesticides detected in our samples. The important contribution of dry deposition to total pesticide deposition warrants greater attention in arid and semi-arid areas such as the Prairie Region of Canada, also because under a changing climate this region is estimated to experience more severe droughts while the more favorable conditions predicted for pest infestations could lead to increased pesticide applications in agricultural and urban areas.     

Air concentrations and wet deposition of major inorganic ions at five non-urban sites in China, 2001–2003

Air and precipitation measurements at five sites were undertaken from 2001 to 2003 in four different provinces in China, as part of the acid rain monitoring program IMPACTS. The sites were located in Tie Shan Ping (TSP) in Chongqing, Cai Jia Tang (CJT) in Hunan, Lei Gong Shan (LGS) and Liu Chong Guan (LCG) in Guizhou and Li Xi He (LXH) in Guangdong. The site characteristics are quite varied with TSP and LCG located relatively near big cites while the three others are situated in more regionally representative areas. The distances to urban centres are reflected in the air pollution concentrations, with annual average concentrations of SO₂ ranging from 0.5 to above 40 μg S m⁻³. The main components in the airborne particles are (NH₄)₂SO₄ and CaSO₄. Reduced nitrogen has a considerably higher concentration level than oxidised nitrogen, reflecting the high ammonia emissions from agriculture. The gas/particle ratio for the nitrogen compounds is about 1:1 at all the three intensive measurement sites, while for sulphur it varies from 2.5 to 0.5 depending on the distance to the emission sources. As in air, the predominant ions in precipitation are sulphate, calcium and ammonium. The volume weighted annual concentration of sulphate ranges from about 70 μeq l⁻¹ at the most rural site (LGS) to about 200 μeq l⁻¹ at TSP and LCG. The calcium concentration ranges from 25 to 250 μeq l⁻¹, while the total nitrogen concentration is between 30 and 150 μeq l⁻¹; ammonium is generally twice as high as nitrate. China's acid rain research has traditionally been focused on urban sites, but these measurements show a significant influence of long range transported air pollutants to rural areas in China. The concentration levels are significantly higher than seen in most other parts of the world.     

Urban and rural ultrafine (PM0.1) particles in the Helsinki area

In June 1996–June 1997 Berner low-pressure impactors were used at an urban and at a rural site in the Helsinki area for sampling ultrafine particles (UFP, PM_0.1). Ten sample pairs, each pair measured simultaneously, were collected in the size range of 0.03–15 μm of particle aerodynamic diameter. More than 40 chemical components were measured. Surprisingly, the average UFP mass concentration was higher at the rural site (520 ng/m³) than at the urban site (490 ng/m³). The average chemical composition of UFP was similar at the two sites. The most abundant of the measured components were sulphate (32 and 40 ng/m³ for the urban and rural sites, respectively), ammonium (22 and 25 ng/m³), nitrate (4 and 11 ng/m³) and the Ca²⁺ ion (5 and 7 ng/m³). The most important metals at both sites were Ca, Na, Fe, K and Zn with concentrations between 0.7 and 5 ng/m³. Of the heavy metals, Ni, V, Cu, and Pb were important with average ultrafine concentrations between about 0.1 and 0.2 ng/m³. Also the organic anions oxalate (urban 2.1 ng/m³ and rural 1.9 ng/m³) and methanesulphonate (1.3 and 1.7 ng/m³) contributed similarly at both sites. The measured species accounted for only about 15–20% of the total ultrafine mass. The fraction that was not measured includes mainly carbonaceous material and water. It was estimated that the amount of water was about 10% (50 ng/m³) and that of carbonaceous material about 70% (350 ng/m³) at both sites. Aitken modes were observed for most components with the average mass mean mode diameters being between about 0.06 and 0.12 μm. The average concentrations in the Aitken mode differed clearly from those in the UFP for several components.The average contribution of ultrafine mass to the fine particle mass (PM_2.5) was about 7% at the urban site and 8.5% at the rural site. At both sites the contribution of ultrafine to fine was especially high for Se, Ag, B, and Ni (10–20%) and at the rural site also for Co (20%), Ca²⁺ (16%) and Mo (11%). Enrichment in the ultrafine particles suggests that local sources may exist for these elements.Aitken modes turned out to be useful indicators of local sources for several components. The Aitken modes of Ba, Ca, Mg and Sr were similar in several samples, suggesting a common local combustion source for these elements, possibly traffic exhaust. Co, Fe, Mo and Ni formed another group of elements often having similar Aitken modes, the likely source being combustion of heavy fuel oil.     

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.     

Bioaccumulation of polybrominated diphenyl ethers in harbor seals from the northwest Atlantic

Polybrominated diphenyl ethers (PBDEs) were analyzed in blubber of harbor seals (Phoca vitulina concolor) collected between 1991 and 2005 along the northwest Atlantic. ∑PBDE concentrations (mono- to hexa-BDEs) detected in blubber samples (n = 42) ranged from 80 to 25 720 ng g⁻¹ lw, (overall mean 2403 ± 5406 ng g⁻¹ lw). By age, mean ∑PBDE concentrations were: 3645 ± 7388, 2945 ± 5995, 1385 ± 1265, and 326 ± 193 ng g⁻¹ lw in pups, yearlings, adult males, and adult females, respectively. Unlike the trend for PCBs, no decreasing gradient from urban to rural/remote areas was observed for PBDEs in these samples, likely reflecting inputs from local sources. No significant temporal trend was observed for PBDEs in harbor seals between 1991 and 2005, although congener profiles shifted over time. Tetra-BDE-47 was the dominant congener, followed by BDEs-99, -100, -153, -154, and -155 in varying order, suggesting exposure to the penta-BDE product. In adult males, the hexa-BDEs contributed more to the total (22%) than BDEs-99 and -100 (14%), and concentrations of BDE-155 were elevated compared with -154. Higher BDEs were detected in a subset of seals (n = 12) including hepta-BDE-183, the marker for the octa-BDE mixture, and octa-BDE-197, along with several unidentified hepta- and octa- congeners. BDE-209 was detected in seal blubber at concentrations ranging from 1.1 to 8 ng g⁻¹ lw, indicating that deca-BDE is bioavailable in this marine food web. This is the first study to document the accumulation of BDE-209 at measurable levels in wild harbor seals. While the PBDE patterns in blubber indicate exposure to all three BDE commercial mixtures, the data also suggest that BDE-209 debromination by seal prey fish may contribute to the loading of lower brominated congeners (hexa- to octa-BDEs) in these seals.     

Measurement and analysis of atmospheric concentrations of isoprene and its reaction products in central Texas

A field experiment was conducted in August 1998 to investigate the concentrations of isoprene and isoprene reaction products in the surface and mixed layers of the atmosphere in Central Texas. Measured near ground-level concentrations of isoprene ranged from 0.3 (lower limit of detection – LLD) to 10.2 ppbv in rural regions and from 0.3 to 6.0 ppbv in the Austin urban area. Rural ambient formaldehyde levels ranged from 0.4 ppbv (LLD) to 20.0 ppbv for 160 rural samples collected, while the observed range was smaller at Austin (0.4–3.4 ppbv) for a smaller set of samples (37 urban samples collected). Methacrolein levels did not vary as widely, with rural measurements from 0.1 ppbv (LLD) to 3.7 ppbv and urban concentrations varying between 0.2 and 5.7 ppbv. Isoprene flux measurements, calculated using a simple box model and measured mixed-layer isoprene concentrations, were in reasonable agreement with emission estimates based on local ground cover data. Ozone formation attributable to biogenic hydrocarbon oxidation was also calculated. The calculations indicated that if the ozone formation occurred at low VOC/NO_x ratios, up to 20 ppbv of ozone formed could be attributable to biogenic photooxidation. In contrast, if the biogenic hydrocarbon reaction products were formed under low NO_x conditions, ozone production attributable to biogenics oxidation would be as low as 1 ppbv. This variability in ozone formation potentials implies that biogenic emissions in rural areas will not lead to peak ozone levels in the absence of transport of NO_x from urban centers or large rural NO_x sources.     

Air quality measurements in urban green areas – a case study

The influence of traffic-induced pollutants (e.g. CO, NO, NO₂ and O₃) on the air quality of urban areas was investigated in the city of Essen, North Rhine-Westphalia (NRW), Germany. Twelve air hygiene profile measuring trips were made to analyse the trace gas distribution in the urban area with high spatial resolution and to compare the air hygiene situation of urban green areas with the overall situation of urban pollution. Seventeen measurements were made to determine the diurnal concentration courses within urban parks (summer conditions: 13 measurements, 530 30 min mean values, winter conditions: 4 measurements, 128 30 min mean values). The measurements were carried out during mainly calm wind and cloudless conditions between February 1995 and March 1996. It was possible to establish highly differentiated spatial concentration patterns within the urban area. These patterns were correlated with five general types of land use (motorway, main road, secondary road, residential area, green area) which were influenced to varying degrees by traffic emissions. Urban parks downwind from the main emission sources show the following typical temporal concentration courses: In summer rush-hour-dependent CO, NO and NO₂ maxima only occurred in the morning. A high NO₂/NO ratio was established during weather conditions with high global radiation intensities (K>800 W m⁻²), which may result in a high O₃ formation potential. Some of the values measured found in one of the parks investigated (Gruga Park, Essen, area: 0.7 km²), which were as high as 275 μg m⁻³ O₃ (30-min mean value) were significantly higher than the German air quality standard of 120 μg m⁻³ (30-min mean value, VDI Guideline 2310, 1996) which currently applies in Germany and about 20% above the maximum values measured on the same day by the network of the North Rhine–Westphalian State Environment Agency. In winter high CO and NO concentrations occur in the morning and during the afternoon rush-hour. The highest concentrations (CO=4.3 mg m⁻³, NO=368 μg m⁻³, 30-min mean values) coincide with the increase in the evening inversion. The maximum measured values for CO, NO and NO₂ do not, however, exceed the German air quality standards in winter and summer.     

Characterization of PM2.5-bound polycyclic aromatic hydrocarbons in Atlanta

Twenty-four hour PM_2.5 samples from a rural site, an urban site, and a suburban site (next to a major highway) in the metropolitan Atlanta area in December 2003 and June 2004 were analyzed for 19 polycyclic aromatic hydrocarbons (PAH). Extraction of the air samples was conducted using an accelerated solvent extraction method followed by isotope dilution gas chromatography/mass spectrometry determination. Distinct seasonal variations were observed in total PAH concentration (i.e. significantly higher concentrations in December than in June). Mean concentrations for total particulate PAHs in December were 3.16, 4.13, and 3.40 ng m^?3 for the urban, suburban and rural sites, respectively, compared with 0.60, 0.74, and 0.24 ng m^?3 in June. Overall, the suburban site, which is impacted by a nearby major highway, had higher PAH concentration than did the urban site. Total PAH concentrations were found to be well correlated with PM_2.5, organic carbon (OC), and elemental carbon (EC) in both months (r² = 0.36–0.78, p < 0.05), although the slopes from the two months were different. PAHs represented on average 0.006% of total PM_2.5 mass and 0.017% of OC in June, compared with 0.033% of total PM_2.5 and 0.14% of OC in December. Total PAH concentrations were also correlated with potassium ion (r² = 0.39, p = 0.014) in December, but not in June, suggesting that in winter biomass burning can potentially be an important source for particulate PAH. Retene was found at a higher median air concentration at the rural site than at the urban and suburban sites—unlike the rest of the PAHs, which were found at lower levels at the rural site. Retene also had a larger seasonal difference and had the weakest correlation with the rest of the PAHs measured, suggesting that retene, in particular, might be associated with biomass burning.     

Urban influence on cloud cover estimated from satellite data

Quantitative assessment of the influence of a big city on the cloud cover was made using time series of satellite measurements. Data from the advanced very high resolution radiometer (AVHRR) on board NOAA satellites received during 1993–1996 over the Central European part of Russia have been processed to derive statistics on spatial distribution of cloudiness for a territory of approximately 7000 km² covering Moscow (55.7 N, 37.6 E) and adjacent areas. Two basic cloud cover characteristics were studied: the total fractional cloud cover and the frequency of occurrence of cloudless scenes (or the clear-sky frequency). Results of the study show that the urban effect is most pronounced during spring and summer periods when a considerable increase in the cloud amount over most of the built-up city area is observed. The winter period presents only a slight evidence of the urban-induced modification of the cloud amount spatial distribution pattern. The average clear-sky frequency in the centre of the city was found to be 5.4% lower than in the nearest suburbs. No well-defined seasonal variations of the urban–rural difference in the clear-sky frequency were detected.     

Exposure to cadmium in male urban and rural workers and effects on FSH,LH and testosterone

ObjectiveThis cross-sectional study was conducted to assess the relationship between exposure to cadmium and circulating reproductive hormone levels in urban and rural male workers.Materials and MethodsUrinary cadmium, blood cadmium, luteinizing hormone (LH), follicle stimulating hormone (FSH) and testosterone were obtained from 86 non-smoking traffic policemen and 86 subjects working as roadmen in a rural area. All subjects were monitored to evaluate airborne exposure to cadmium.ResultsThe mean value of exposure to cadmium was 1.3 ng m^?3 in traffic policemen, while the mean value was less than 0.5 ng m^?3 in roadmen. The mean concentrations of urinary cadmium (1.4 vs. 0.9 μg g^?1 creatinine; p = 0.001), blood cadmium (1.1 vs. 0.7 μg l^?1; p = 0.000), FSH (2.6 vs. 3.2 μlU ml^?1; p = 0.02) and LH (2.6 vs. 3.1 μlU ml^?1; p = 0.03) were significantly different between traffic policemen and roadmen. No differences were found in the mean values of testosterone between the two groups. Multiple linear regression models showed associations between (a) urinary cadmium, airborne cadmium, working life, job category and consumption of water from water supply (b) blood cadmium, airborne cadmium and job category (c) the values of FSH and age, working life, job category, urinary cadmium and blood cadmium (d) the values of LH and both the age and working life.ConclusionThe above results must be confirmed by further studies, but they indicate the influence of exposure to the cadmium present in urban air on the circulating FSH, even at low doses.     

Preliminary study of the determination of ambient carbonyls in Xalapa City,Veracruz, Mexico

A preliminary study of ambient carbonyls was performed in Xalapa City to measure carbonyls in the atmosphere of this City, because it has an explosive increase in population and traffic density, but few industries. The city is located at the eastern flanks of the Sierra Madre Oriental, between 1350 and 1550 m above sea level. Acetone was the most abundant carbonyl in June, followed by formaldehyde and acetaldehyde, whereas acetaldehyde was the most abundant one in November. Higher concentrations were observed in autumn than in spring, probably due to stagnation conditions in autumn and heavy rains from late spring to early autumn. The very high concentrations of acetaldehyde found in November could have been caused by an accidental leak or spill from a truck, since no stationary sources were identified and acetaldehyde concentrations steeply rose and constantly decreased after few days. Moreover, a highly transited highway traverses Xalapa. The most important ozone and carbon monoxide concentrations were below the Mexican Air Quality Standards; 216 μg m⁻³ (0.11 ppm) for 1 h average and 12.6 mg m⁻³ (11 ppm) for 8 h moving average, respectively. The low concentrations of the main carbonyls, compared with the values reported for other urban areas, and of carbon monoxide, seem to indicate that air quality is still satisfactory in Xalapa City.     

PM10 and PM2.5 concentrations in Central and Eastern Europe:: results from the Cesar study

Between November 1995 and October 1996, particulate matter concentrations (PM₁₀ and PM_2.5) were measured in 25 study areas in six Central and Eastern European countries: Bulgaria, Czech Republic, Hungary, Poland, Romania and Slovak Republic. To assess annual mean concentration levels, 24-h averaged concentrations were measured every sixth day on a fixed urban background site using Harvard impactors with a 2.5 and 10 μm cut-point. The concentration of the coarse fraction of PM₁₀ (PM_10−2.5) was calculated as the difference between the PM₁₀ and the PM_2.5 concentration. Spatial variation within study areas was assessed by additional sampling on one or two urban background sites within each study area for two periods of 1 month. QA/QC procedures were implemented to ensure comparability of results between study areas. A two to threefold concentration range was found between study areas, ranging from an annual mean of 41 to 98 μg m⁻³ for PM₁₀, from 29 to 68 μg m⁻³ for PM_2.5 and from 12 to 40 μg m⁻³ for PM_10−2.5. The lowest concentrations were found in the Slovak Republic, the highest concentrations in Bulgaria and Poland. The variation in PM₁₀ and PM_2.5 concentrations between study areas was about 4 times greater than the spatial variation within study areas suggesting that measurements at a single sampling site sufficiently characterise the exposure of the population in the study areas. PM₁₀ concentrations increased considerably during the heating season, ranging from an average increase of 18 μg m⁻³ in the Slovak Republic to 45 μg m⁻³ in Poland. The increase of PM₁₀ was mainly driven by increases in PM_2.5; PM_10−2.5 concentrations changed only marginally or even decreased. Overall, the results indicate high levels of particulate air pollution in Central and Eastern Europe with large changes between seasons, likely caused by local heating.     

Risks from sediments contaminated with organochlorine pesticides in Hangzhou,China

In September 2009, we investigated the residues, enantiomer fractions (EFs) and biological risks of organochlorine pesticides (OCPs), including dichlorodiphenyltrichloroethanes (DDTs) and hexachlorocyclohexanes (HCHs), in three different depth ranges (0–5 cm, 5–10 cm and 10–15 cm) of sediments from 15 sites in Hangzhou, China. The concentration (ng g^?1 dry weight) ranges of HCHs and DDTs in surface sediments were 0.74–5.8 and 0.76–17, respectively. The vertical distribution of mean OCP concentrations was in the order of 10–15 cm > 5–10 cm > 0–5 cm and implied that the residues of HCHs and DDTs gradually decreased after they were banned. The residues of OCPs in the study area mainly originated from the historical OCP use. The isomer ratios of <alpha>-HCH (α-HCH)/<gamma>-HCH (γ-HCH) (0.10–7.6) implied that HCH residues were derived not only from historical technical HCH use but also from additional use of lindane in this area. The isomer ratios of o,p′-DDT/p,p′-DDT (51% of samples were in the range of 0.3–1.3) suggested that both dicofol-type DDT and technical DDT applications may be present in most study areas. The (+)-enantiomers of α-HCH and o,p′-DDT were more prevalent than (?)-enantiomer in most samples with the fractions contain different enantiomers greater than 0.5. DDTs, especially p,p′-DDE, are the main OCP species of more ecotoxicological concern in Hangzhou.     

Impact of mineral components and selected trace metals on ambient PM10 concentrations

PM10 levels of the mineral components Si, Al, Fe, Ca, Mg and some trace metals were measured at three different sites in the urban area of Vienna (Austria). Observed trace metal concentrations varied between less than 0.1 ng m^?3 (Cd) and approximately 200 ng m^?3 (Zn), mineral components showed enhanced concentrations ranging from 0.01 μg m^?3 (Ca) to 16.3 μg m^?3 (Si). The contribution of the respective mineral oxides to PM10 mass concentrations accounted on average for 26.4 ± 16% (n = 1090) of the PM10 mass, with enhanced rates in spring and autumn (monthly averages of up to 40%) and decreased contributions in the cold season (monthly averages below 10%). The atmospheric occurrence of Al, Ti and Sr could be assigned to crustal sources, whereas for the elements Ba, Ca, Fe, Mg, Mn and V an increased contribution of non-crustal origin was observed. PM10 levels of As, Cd, Co, Cr, Cu, Ni, Pb, Sb, Sn and Zn were predominantly derived from man-made emissions. Intersite comparison indicated that urban PM10 mass concentrations and PM10 levels of As, Pb and Zn were predominantly influenced from the transport of aerosols from outside into the city, whereas for the elements Ba, Mg, Ca, Cu and Fe a distinctly increased impact of local emissions was observed. The contribution of these urban emissions to total PM10 concentrations was estimated by calculating the so-called “urban impact”, which was found to be 32.7 ± 18% (n = 392) in the case of PM10 mass concentrations. The investigated elements accounted on average for 31.3 ± 19% (n = 392) of the observed PM10 mass increase. The mean values for the “urban impacts” of individual elements varied between 25.5% (As) and 77.0% (Ba).     

Levels of persistent organic pollutants in air in China and over the Yellow Sea

The occurrence of persistent toxic substances (PTS) in China and possibly their regional transport in the Yellow and East China Seas region was studied. Organochlorines in atmospheric gas-phase and particulate matter were collected by high-volume sampling (filters and polyurethane foams) during 2 weeks in June 2003 (dry season) simultaneously at a Yellow Sea coastal site in an urban area, Qingdao, China, and a rural island site, Gosan, Jeju Island, Korea. Using GC methods, the samples were analysed for 9 persistent organic pollutants (POPs) regulated under the global POP convention, namely aldrin, chlordane (cis- and trans-isomers CC and TC), DDT and metabolites (o,p′-DDT, p,p′-DDD, and p,p′-DDE), dieldrin, endrin, heptachlor, hexachlorobenzene (HCB), mirex and PCB (congeners number 28, 52, 101, 153 and 180), and for hexachlorocyclohexane (α-, β- and γ-isomers), a PTS and now considered for regulation under the convention, too. At the coastal site additionally o,p′-DDE and -DDD, β-endosulfan, isodrin, heptachlorepoxide and δ-HCH, and at the island site additionally p,p′-DDT and 12 additional PCB congeners were analysed. 9 samples were collected at the coastal and 15 (for PCBs 5) at the island site. Long-range advection pathways were determined based on analysed back-trajectory calculations.The mean concentrations of DDT and its metabolites, HCB, HCH, and PCB at the coast were in the 100–1000 pg m⁻³ range. Higher concentrations prevailed during nighttime. The levels were in general lower at the island site, but not for DDT. Local sources are likely. PCBs were even 2 orders of magnitude lower, suggesting that PCBs are not subject to regional transport but elevated concentrations in air are limited to the source areas. Organochlorine pesticide levels on the other hand were seemingly determined by regional transport over Mainland China rather than by emissions in the coastal area. The currently used pesticides mirex and chlordane were found at elevated levels, i.e. 79 (6.6–255) and 36 (<6–71) pg m⁻³, respectively, at the coast but not over the island. The POPs pesticides aldrin, dieldrin and endrin, never registered in China, were mostly found at <10 pg m⁻³ except for endrin at the coastal site (up to 400 pg m⁻³) and aldrin at the island site (up to 50 pg m⁻³).