Micropollutants in urban stormwater: occurrence,concentrations, and atmospheric contributions for a wide range of contaminants in three French catchments

This study aimed at: (a) providing information on the occurrence and concentration ranges in urban stormwater for a wide array of pollutants (n?=?77); (b) assessing whether despite the differences between various catchments (land use, climatic conditions, etc.), the trends in terms of contamination level are similar; and (c) analyzing the contribution of total atmospheric fallout (TAF) with respect to sources endogenous to this contamination. The studied contaminants include conventional stormwater contaminants (polycyclic aromatic hydrocarbons (PAHs), Zn, Cu, Pb, etc.), in addition to poorly or undocumented pollutants such as nonylphenol and octylphenol ethoxylates (NPnEO and OPnEO), bisphenol A (BPA), polybrominated diphenyl ethers (PBDEs), a wide variety of pesticides, and various metals of relevance (As, Ti, Sr, V). Sampling and analysis were performed using homogeneous methods on three urban catchments with different land use patterns located in three distinct French towns. For many of these pollutants, the results do not allow highlighting a significant difference in stormwater quality at the scale of the three urban catchments considered. Significant differences were, however, observed for several metals (As, Cr, Cu, Ni, Sr and Zn), PAHs, and PBDEs, though this assessment would need to be confirmed by further experiments. The pollutant distributions between dissolved and particulate phases were found to be similar across the three experimental sites, thus suggesting no site dependence. Lastly, the contributions of TAF to stormwater contamination for micropollutants were quite low. This finding held true not only for PAHs, as previously demonstrated in the literature, but also for a broader range of molecules such as BPA, NPnEO, OPnEO, and PBDEs, whose high local production is correlated with the leaching of urban surfaces, buildings, and vehicles.     

Monitoring of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere of southern Luxembourg using XAD-2 resin-based passive samplers

XAD-2 resin-based passive samplers (PAS) with dimensions adapted to 100 mL accelerated solvent extraction cells were used to study the temporal and spatial variations of 17 PAHs on five sites in the atmosphere of southern Luxembourg. This new design allowed extracting the PAS without emptying the resin from the shelter. PAH analyses were done with gas chromatography–tandem mass spectrometry. PAS were deployed for 1 year with varying sampling periodicities, and 16 PAHs were detected with concentrations ranging from 1 ng/PAS for chrysene to 9,727 ng/PAS for naphthalene. The PAS were found adapted to the monitoring of temporal and spatial variations for lightweight PAHs (up to four aromatic rings) though not for heavy PAHs with five aromatic rings or more, as these compounds are preferably in the particle phase of the atmosphere and the amount of these PAHs trapped on the PAS will be too low.     

The influence of the level of definition of functional specifications on the environmental performances of a complex system. EcoCSP approach

The tendency towards a homogenous mode of development modelled on that of Western countries means that sustainable development has become increasingly urgent. It is necessary to thoroughly redefine products and their expected performances in such a way that the consequences are compatible with sustainable development. In the domain of product design, this means that it is no longer sufficient to use assessment tools “after the fact” to check the impact of products whose functional unit (FU) was defined prior to production; it is now necessary to rethink the definition of the FU itself. This article aims to present an approach based on a combination of life cycle analysis methods and problem-solving by constraint satisfaction. This original approach makes it possible to vary the design of the different dimensions of the FUs of a complex system and thus to make it easier to identify the best architecture along with the best functional definition of the system. In this study, the EcoCSP approach is applied to define the functional performances of an ecological passenger ferry. The complexity of couplings between subsystems and the sheer number of those subsystems mean that the designer has to use “intelligent” tools. These simulate a great number of scenarios and help him/her to fine-tune the system and make the right technological choices with regard to the right functional specifications.     

Influence of Relative Humidity and Ozone on the Sampling of Volatile Organic Compounds on Carbotrap/Carbosieve Adsorbents

By using a dynamic dilution system, the atmospheric measurement of 11 selected toxics VOCs (ethylene, acetylene, propene, 1-butene, 1,3-butadiene, 1-pentene, 1-hexene, benzene, toluene, ethylbenzene, m+p-xylene) from the list WHO of 1996 and TO-14 method of US EPA by preconcentration by thermal desorption (TD), analysis by gas chromatography (GC), identification and quantification with a flame ionisation detector (FID) was developed and validated in term of metrology, especially the techniques of sampling of these VOCs with adsorbents cartridges "Air Toxics" when used with an "UMEG sampler" equipped in the inlet with a nafion membrane. In particular the influence of climatic conditions (temperature and relative humidity) and the influence of chemical factors like ozone, on the representativity of sampling were studied. Experiments made with various humidities showed that the addition of a nafion membrane in the inlet of the sampling system was required. Without this membrane, losses of compounds were observed for RH >50%. With this membrane, storage for 2 weeks in a refrigerator, as for canisters, did not induce a loss of compounds. No significative decrease of concentrations of the studied VOCs after 14 days storage, which are known to react with ozone, were observed with an ozone concentrations of 55 ppb. One explanation is that nafion membrane, placed in the inlet of the sampler, will neutralize ozone before entering the sampling tubes. This observation is in accordance with literature which states that the sampling of VOCs on Carbotrap cartridges without ozone scrubber induce a loss of compounds.     

Air quality assessment by tree bark biomonitoring in urban, industrial and rural environments of the Rhine Valley: PCDD/Fs, PCBs and trace metal evidence

Tree barks were used as biomonitors to evaluate past atmospheric pollution within and around the industrial zones of Strasbourg (France) and Kehl (Germany) in the Rhine Valley. The here estimated residence time for trace metals, PCBs and PCDD/Fs in tree bark is >10 years. Thus, all pollution observed by tree bark biomonitoring can be older than 10 years. The PCB baseline concentration (sum of seven PCB indicators (Σ₇PCB_ind)) determined on tree barks from a remote area in the Vosges mountains is 4 ng g⁻¹ and corresponds to 0.36 × 10⁻³ ng toxic equivalent (TEQ) g⁻¹ for the dioxin-like PCBs (DL-PCBs). The northern Rhine harbor suffered especially from steel plant, waste incinerator and thermal power plant emissions. The polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/Fs) concentrations analyzed in tree barks from this industrial area range between 392 and 1420 ng kg⁻¹ dry-weight (dw) corresponding to 3.9 ng TEQ_PCDD/Fs kg⁻¹ to 17.8 ng TEQ_PCDD/Fs kg⁻¹, respectively. Highest PCDD/F values of 7.2 ng TEQ kg⁻¹ to 17.8 ng TEQ kg⁻¹ have been observed close to and at a distance of <2 km southwest of the chemical waste incinerator. However, very close to this incinerator lowest TEQ dioxin-like PCB (TEQ_DL-PCB) values of 0.006 ng TEQ g⁻¹ have been found. On the other hand close to and southwest and northeast of the steel plant the values are comparatively higher and range between 0.011 ng TEQ g⁻¹ and 0.026 ng TEQ g⁻¹. However, even stronger Σ₇PCB_ind enrichments have been observed at a few places in the city center of Kehl, where ΣDL-PCB values of up to 0.11 ng TEQ g⁻¹ have been detected. These enrichments, however, are the result of ancient pollutions since recent long-term measurements at the same sites indicate that the atmospheric PCB concentrations are close to baseline. Emissions from an old landfill of waste and/or great fires might have been the reasons of these PCB enrichments. Other urban environments of the cities of Kehl and Strasbourg show significantly lower Σ₇PCB_ind concentrations. They suffer especially from road and river traffic and have typically Σ₇PCB_ind concentrations ranging from 11 ng g⁻¹ to 29 ng g⁻¹. The PCB concentration of 29 ng g⁻¹ has been found in tree bark close to the railway station of Strasbourg. Nevertheless, the corresponding TEQ_DL-PCB are low and range between 0.2 × 10⁻³ ng TEQ g⁻¹ and 7 × 10⁻³ ng TEQ g⁻¹. Samples collected near road traffic are enriched in Fe, Sb, Sn and Pb. Cd enrichments were found close to almost all types of industries. Rural environments not far from industrial sites suffered from organic and inorganic pollution. In this case, TEQ_DL-PCB values may reach up to 58 × 10⁻³ ng TEQ g⁻¹ and the corresponding V, Cr, Co, Ni, and Cd concentrations are comparatively high.     

Characterization of particulate polycyclic aromatic hydrocarbons in the east of France urban areas

Background

Air samples collected on three different urban sites in East of France (Strasbourg, Besan?on, and Spicheren), from April 2006 to January 2007, were characterized to measure the concentrations of polycyclic aromatic hydrocarbons (PAHs) in the particulate phase (PM₁₀) and to examine their seasonal variation, diurnal variations, and emission sources.

Results

The average concentrations of ??PAHs were 12.6, 9.5, and 8.9?ng?m^?3 for the Strasbourg, Besan?on, and Spicheren sites, respectively. Strong seasonal variations of individual PAH concentrations were found at the three sampling sites, with higher levels in the winter that gradually decreased to the lowest levels in the summer. The diurnal variations of PAH concentrations in summer presented highest concentrations during the morning (04:00?C10:00) and the evening (16:00?C22:00) times, indicating the important contribution from vehicle emissions, in the three sampling sites. Furthermore, the ratio of BaP/BeP suggests that the photochemical degradation of PAHs can suppress their concentrations in the midday/afternoon (10:00?C16:00), time interval of highest global irradiance. In winter, concentrations of PAH were highest during the evening (16:00?C22:00) time, suggesting that domestic heating can potentially be an important source for particulate PAH, for the three sampling sites.

Conclusion

Diagnostic ratios were used to identify potential sources of PAHs. Results showed that vehicle emissions may be the major source of PAHs, especially in summer, with a prevalent contribution of diesel engines rather than gasoline engines at the three sites studied, independently of the seasons.     

Adsorption/thermal desorption-GC/MS for the analysis of pesticides in the atmosphere

An analytical methodology using Automatic Thermal Desorption (ATD) and GC/MS was developed for the determination of the pesticides alachlor, atrazine, captan, formothion, lindane and phosalone in atmospheric samples. This methodology was developed to evaluate the atmospheric contamination by pesticides during treatments and by post-application. Atmospheric samples were collected by using (4 i.d. x 89 mm) stainless steel sampling tubes containing 125 mg of adsorbents at a flow rate of 80 ml min-1. Different types of adsorbents were tested for their ability to efficiently trap pesticides under study: Tenax TA, Carbopack Y, Carbopack B, Carbotrap, Carboxen, Chromosorb 106 and XAD-4. Results of experiment show that Tenax gives the better results for all the pesticides used but the use of the thermal-desorption method, especially for pesticides with low volatility and/or poor thermal stability presents some difficulties. This method was validated by the analysis of the contamination of atmosphere, through volatilization by post-application processes, of atrazine in a parcel of 1 ha.     

Influence of ozone on the sampling and storage of volatile organic compounds in canisters

A dynamic dilution system was used for the study of the influence of ozone on the sampling and storage of volatile organic compounds (VOCs) at 0, 4, 7 and 14 days in “TO-Can” canisters at two ozone concentrations, 60 and 150 ppbv. Among the 31 ozone precursors VOCs, a representative mixture containing five alkenes, five aromatics, acetylene and 1,3 butadiene was selected using the Clausius–Clapeyron equation. Here, we demonstrate that the presence of ozone have no influence on the concentrations of VOCs after 14 days storage period and consequently no problem of representativity of the sampling appears after 14 days of storage. The main explanation is the degradation of ozone in contact with deactivated walls of canisters.     

A multiresidue method for the analysis of phenols and nitrophenols in the atmosphere

A method using GC-MS and derivatization with N-(t-butyldimethylsilyl)-N-methyltrifluoroacetamide (MTBSTFA) was developed for the analysis of 20 phenolic compounds in atmospheric samples (gas and particles). Air sampling was carried out using a Hi-Vol sampler with glass fibre filter and XAD-2 resin at a flow rate of 60 m(3) h(-1). The particle and gas phases were collected separately over a period of 4 h. Samples were Soxhlet extracted, evaporated to dryness under nitrogen and refilled with acetonitrile. 100 microl of these extracts were derivatized with 100 microl of MTBSTFA at 80 degrees C for 1 h under strong stirring. Phenolic compounds were injected into a GC-MS in splitless mode and quantified as their TBDMS derivatives in the SIM mode. Mass spectral analysis of the derivatives of the 20 compounds studied indicates that the spectra are highly specific showing an ion at [M - 57]+ which is useful for structure confirmation or analysis at low levels using selected ion monitoring. Quantification limits varied between 5 microg l(-1) and 10 microg l(-1) which correspond to 20 pg m(-3) and 40 pg m(-3) for 250 m(3) of air sampled. This method was successfully applied to atmospheric samples.     

Sampling and Analysis of Quaternary Ammonium Compounds (QACs) Traces in Indoor Atmosphere

Quaternary Ammonium Compounds (QACs) are widely found in disinfectants used in hospitals. Benzalkonium chloride (BAC) and didecyldimethylammonium chloride (DDAC) predominate in the disinfecting formulations. These compounds are strong irritants and can play a role in the induction of Occupational Asthma among the professionals of health and cleaning. In order to evaluate the potential health effect of these quaternary ammonium compounds to hospital employers, the development of an analytical method for their quantification in indoor air was developed. DDAC aerosols are trapped by adsorption on XAD-2 resin SKC tube. The air in hospital buildings was sampled using a constant debit Gillian pump at a flow of 1.0 l/min (+/-5%). Ion Chromatography (IC) was chosen for the analysis of DDAC especially for its high sensitivity and specificity. The Limit of Detection (LOD) by IC for DDAC is 0.56 mug/ml. Therefore the LOD of atmospheric DDAC is 28 microg/m(3) with an air volume of 100 l and a desorption volume of 5 ml. All DDAC air samples were lower than the LOD of the analytical method by IC. Under the standard conditions of use of the disinfecting solutions (Surfanios, Ampholysine Plus and Amphospray 41), the insignificant volatility of DDAC would not seem to be able to contaminate the indoor hospital atmosphere during the disinfection process. However, the DDAC can contaminate working atmospheres if it is put in suspension by aerosolisation.