A preconcentration procedure for the determination of cadmium in biological material after on-line cloud point extraction

In this paper, a method involving on-line preconcentration with cloud point extraction for the determination of cadmium in biological samples is presented. The procedure is based on the sorption of micelles containing Cd(II) ions and the reagent 4-(5'-bromo-2'-thiazolylazo)orcinol (Br-TAO) in a minicolumn packed with polyester. The surfactant Triton X-114 was used in the formation of micelles. After sorption, the Cd(II) ions were desorbed from the minicolumn with acid eluent and determined by flame atomic absorption spectrometry. Parameters influencing the cloud point extraction were studied. The method showed a detection limit of 0.5 μg l(-1) and an enhancement factor of 27. The accuracy was tested by determination of cadmium in certified reference materials (spinach leaves 1570a and tomato leaves 1573a) from the National Institute of Standards and Technology.     

Evaluating urban PM10 pollution benefit induced by street cleaning activities

Despite their burden in urban particulate air pollution, road traffic non-exhaust emissions are often uncontrolled and information about the effectiveness of mitigation measures on paved roads is still scarce. The present study is aimed to evaluate the effectiveness of mechanical sweeping/water flushing treatments in mitigating urban road dust resuspension and to quantify the real benefit in terms of ambient PM₁₀ concentrations. To this aim a specific campaign was carried out in a heavily trafficked central road of Barcelona (Spain), a Mediterranean city suffering from a traffic-related pollution, both for a high car density and a frequent lack of precipitation. Several street washings were performed by means of mechanical sweepers and pressure water during night in all traffic lanes and sidewalks. PM₁₀ levels were simultaneously compared with four reference urban background air quality stations to interpret any meteorological variability. At the downwind measurement site, PM₁₀ concentrations registered a mean daily decrease of 8.8 μg m^?3 during the 24 h after street washing treatments. However 3.7–4.9 μg m^?3 of such decrease were due to the meteorological variability detected at the upwind site, as well as at two of the reference sites. This reveals that an effective decrease of 4–5 μg m^?3 (7–10%) can be related to street washing efficiency. Mitigation of road dust resuspension was confirmed by investigating the chemical composition of airborne-PM₁₀ filters. Concentrations of Cu, Sb, Fe and mineral matter decrease significantly with respect to concentrations of elemental carbon, used as tracer for exhaust diesel emissions. High efficiency of street washing in reducing road dust loads was found by performing periodic samplings both on the treated and the untreated areas.     

Effect of ceramic industrial particulate emission control on key components of ambient PM10

The relationship between specific particulate emission control and ambient levels of some PM₁₀ components (Zn, As, Pb, Cs, Tl) was evaluated. To this end, the industrial area of Castellón (Eastern Spain) was selected, where around 40% of the EU glazed ceramic tiles and a high proportion of EU ceramic frits are produced. The PM₁₀ emissions from the ceramic processes were calculated over the period 2000–2006, taking into account the degree of implementation of corrective measures throughout the study period. Abatement systems were implemented in the majority of the fusion kilns for frit manufacture in the area as a result of the application of the Directive 1996/61/EC, leading to a marked decrease in PM₁₀ emissions. By contrast, emissions from tile manufacture remained relatively constant because of the few changes in the implementation of corrective measures. On the other hand, ambient PM₁₀ levels and composition measurements were carried out from 2002 to 2006. A high correlation between PM₁₀ emissions from frit manufacture and ambient levels of Zn, As, Pb and Cs (R² from 0.61 to 0.98) was observed. On the basis of these results, the potential impact of the implementation of corrective measures to reduce emissions from tile manufacture was quantified, resulting in a possible decrease of 3–5 μg/m³ and 2 μg/m³ in ambient mineral PM₁₀ (on an annual basis) in urban and suburban areas, respectively. This relatively simple methodology allows us to estimate the direct effect of a reduction in primary particulate emissions on ambient levels of key particulate components, and to make a preliminary quantification of the possibilities of air quality improvement by means of further emission reduction. Therefore, it is a useful tool for developing future air quality plans in the study area and in other industrialised areas.     

Decision-making in controlling development of driving/piloting situations

This paper introduces the presentation of several works carried out, in France, in the field of transport ergonomics and psychology. It aims at pointing out the original features of the French ergonomics approach of dynamic situations; these features are related to the method used (the analysis of an activity in actual working conditions is emphasized) and the specific definitions of several concepts such as the concepts of ‘work activity’, ‘task’ and ‘situation’. This introductory paper proposes to define these notions and to show their relevance to an analysis of driving activities.     

A methodology to determine gaseous emissions in a composting plant

Environmental impacts associated to different waste treatments are of interest in the decision-making process at local, regional and international level. However, all the environmental burdens of an organic waste biological treatment are not always considered. Real data on gaseous emissions released from full-scale composting plants are difficult to obtain. These emissions are related to the composting technology and waste characteristics and therefore, an exhaustive sampling campaign is necessary to obtain representative and reliable data of a single plant. This work proposes a methodology to systematically determine gaseous emissions of a composting plant and presents the results obtained in the application of this methodology to a plant treating source-separated organic fraction of municipal solid waste (OFMSW) for the determination of ammonia and total volatile organic compounds (VOC). Emission factors from the biological treatment process obtained for ammonia and VOC were 3.9 kg Mg OFMSW⁻¹ and 0.206 kg Mg OFMSW⁻¹ respectively. Emissions associated to energy use and production were also quantified (60.5 kg CO₂ Mg OFMSW⁻¹ and 0.66 kg VOC Mg OFMSW⁻¹). Other relevant parameters such as energy and water consumption and amount of rejected waste were also determined. A new functional unit is presented to relate emission factors to the biodegradation efficiency of the composting process and consists in the reduction of the Respiration Index of the treated material. Using this new functional unit, the atmospheric emissions released from a composting plant are directly related to the plant specific efficiency.     

Source apportionment of urban fine and ultra-fine particle number concentration in a Western Mediterranean city

Extensive measurements on particle number concentration and size distribution (13–800 nm), together with detailed chemical composition of PM_2.5 have constituted the main inputs of the database used for a source apportionment analysis. Data were collected at an urban background site in Barcelona, Western Mediterranean.The source identification analysis helped us to distinguish five emission sources (vehicle exhausts, mineral dust, sea spray, industrial source and fuel-oil combustion) and two atmospheric processes (photochemical induced nucleation and regional/urban background particles derived from coagulation and condensation processes). After that, a multilinear regression analysis was applied in order to quantify the contribution of each factor.This study reveals that vehicle exhausts contribute dominantly to the number concentration in all the particle sizes (52–86%), but especially in the range 30–200 nm. This work also points out the importance of the regional and/or urban formed aerosols (secondary inorganic particles) on the total number concentration (around 25% of the total number), with a higher impact on the accumulation mode. The photo-chemically induced nucleation of aerosols only represents a small proportion of the total number as an annual mean (3%), but is very relevant when considering only the nucleation mode (13–20 nm) fraction (23%). The other sources recognized registered sporadic contributions to the total number, coinciding with specific meteorological scenarios.This study discloses the main sources and features affecting and controlling the fine and ultra-fine aerosols in a typical city in the Western Mediterranean coast. Whereas the road traffic appears to be the most important source of sub-micrometric aerosols, other sources may not be negligible under specific meteorological conditions.     

Physicochemical variations in atmospheric aerosols recorded at sea onboard the Atlantic–Mediterranean 2008 Scholar Ship cruise (Part I): Particle mass concentrations,size ratios,and main chemical components

We report on ambient atmospheric aerosols present at sea during the Atlantic–Mediterranean voyage of Oceanic II (The Scholar Ship) in spring 2008. A record was obtained of hourly PM₁₀, PM_2.5, and PM₁ particle size fraction concentrations and 24-h filter samples for chemical analysis which allowed for comparison between levels of crustal particles, sea spray, total carbon, and secondary inorganic aerosols. On-board monitoring was continuous from the equatorial Atlantic to the Straits of Gibraltar, across the Mediterranean to Istanbul, and back via Lisbon to the English Channel. Initially clean air in the open Atlantic registered PM₁₀ levels <10 μg m^?3 but became progressively polluted by increasingly coarse PM as the ship approached land. Away from major port cities, the main sources of atmospheric contamination identified were dust intrusions from North Africa (NAF), smoke plumes from biomass burning in sub-Saharan Africa and Russia, industrial sulphate clouds and other regional pollution sources transported from Europe, sea spray during rough seas, and plumes emanating from islands. Under dry NAF intrusions PM₁₀ daily mean levels averaged 40–60 μg m^?3 (30–40 μg m^?3 PM_2.5; c. 20 μg m^?3 PM₁), peaking briefly to >120 μg m^?3 (hourly mean) when the ship passed through curtains of higher dust concentrations amassed at the frontal edge of the dust cloud. PM₁/PM₁₀ ratios ranged from very low during desert dust intrusions (0.3–0.4) to very high during anthropogenic pollution plume events (0.8–1).     

Occurrence of cyclophosphamide and epirubicin in wastewaters by direct injection analysis–liquid chromatography–high-resolution mass spectrometry

Background, aim, and scope

According to the high incidence of cancer worldwide, the amount of cytostatic drugs administered to patients has increased. These compounds are excreted to wastewaters, and therefore become potential water contaminants. At this stage, very little is known on the presence and elimination of cytostatic compounds in wastewater treatment plants (WWTP). The aim of this study was to develop a liquid chromatography?Chigh-resolution mass spectrometry (LC?COrbitrap?CMS) method for the determination of cyclophosphamide and epirubicin in wastewaters. These compounds represent two outmost used cytostatic agents.

Materials and methods

Extraction and analytical conditions were optimized for cyclophosphamide and epirubicin in wastewater. Both solid-phase extraction using Oasis 200?mg hydrophilic?Clipophilic balanced (HLB) cartridges and direct injection analysis were evaluated. Mass spectral characterization and fragmentation conditions were optimized at 50,000 resolving power (full width at half maximum, m/z 200) to obtain maximum sensitivity and identification performance. Quality parameters (recoveries, limits of detection, and repetitivity) of the methods developed were determined, and best performance was obtained with direct water analysis of the centrifuged wastewater. Finally, this method was applied to determine the presence of cyclophosphamide and epirubicin in wastewaters from a hospital effluent, an urban effluent, and influents and effluents from three WWTP.

Results and discussion

Cyclophosphamide and epirubicin were recovered after 50?mL preconcentration on solid-phase extraction 200?mg Oasis HLB cartridges (87% and 37%, respectively), and no breakthrough was observed by extracting 500?mL of water. Limits of detection were of 0.35 and 2.77?ng/L for cyclophosphamide and epirubicin, respectively. On the other hand, direct injection of water spiked at 1???g/L provided recoveries of 107% for cyclophosphamide and 44% for epirubicin and limits of detection from 3.1 to 85?ng?L^?1, respectively. The analysis of wastewaters using direct injection analysis revealed the presence of cyclophosphamide and epirubicin in WWTP influents and hospital and urban effluents at levels ranging from 5.73 to 24.8???g?L^?1.

Conclusions

The results obtained in this study demonstrate the capability of LC?COrbitrap?CMS for accurate trace analysis of these very polar contaminants. This method permitted to identify cyclophosphamide and epirubicin in wastewaters and influents of WWTP, but no traces were detected in WWTP effluents. The methodology herein developed is sensitive and robust and applicable for screening of a large number of samples since no preconcentration is needed.     

Sources and Concentrations of Indoor Nitrogen Dioxide in Barcelona,Spain

Abstract

Sources and concentrations of indoor nitrogen dioxide (NO₂) were examined in Barcelona, Spain, during 1996– 1999. A total of 340 dwellings of infants participating in a hospital-based cohort study were selected from different areas of the city. Passive filter badges were used for indoor NO₂ measurement over 7–30 days. Dwelling inhabitants completed a questionnaire on housing characteristics and smoking habits. Data on outdoor NO₂ concentrations were available for the entire period of the study in the areas of the city where indoor concentrations were determined. Bivariate analysis was performed to investigate relationships between indoor NO₂ concentrations on one hand and outdoor NO₂ concentrations, housing, and occupant characteristics on the other. Stepwise multiple linear regression was performed with variables that were 1996 and 27.02 ppb in 1999, with the highest yearly value of 27.82 ppb in 1997. In the same time period, mean outdoor NO₂ concentration ranged between 25.26 and 25.78 ppb with a peak of 30.5 ppb in 1998. Multiple regression analysis showed that principal sources of indoor NO₂ concentrations were the use of a gas cooker, the absence of an extractor fan when cooking, and cigarette smoking. The absence of central heating was also associated with higher NO₂ concentrations. Finally, each ppb increase in outdoor NO₂ was associated with a 1% increase in indoor concentrations.     

Removal of PAHs from water using an immature coal (leonardite)

It has been studied an immature coal (leonardite) as an adsorbent for removing PAHs [fluorene, pyrene, benzo(k)fluoranthene, benzo(a)pyrene and benzo(g,h,i)perylene] from water. To determine the efficiency of leonardite as an adsorbent of PAHs, factors such as pH, contact time and equilibrium sorption were evaluated in a series of batch experiments. There were no significant differences in the removal percentages for the various pH values studied, except for fluorene. The adsorption of fluorene was higher at lower pH values. The equilibrium time was reached at 24h. At this time, more than 82% of the pyrene, benzo(k)fluoranthene, benzo(a)pyrene and benzo(g,h,i)perylene had been removed. During the first 2h, the adsorption rate increased rapidly. After that time, however, there was a minor decrease. Equilibrium data were fitted to Freundlich models to determine the water-leonardite partitioning coefficient. Physical adsorption caused by the aromatic nature of the compounds was the main mechanism that governed the removal process. The polarity of the humic substances in leonardite may also have influenced the adsorption capacity.