Hydrocarbon emission fingerprints from contemporary vehicle/engine technologies with conventional and new fuels

The present paper presents results from the analysis of 29 individual C₂–C₉ hydrocarbons (HCs) specified in the European Commission Ozone Directive. The 29 HCs are measured in exhaust from common, contemporary vehicle/engine/fuel technologies for which very little or no data is available in the literature. The obtained HC emission fingerprints are compared with fingerprints deriving from technologies that are being phased out in Europe. Based on the total of 138 emission tests, thirteen type-specific fingerprints are extracted (Mean ± SD percentage contributions from individual HCs to the total mass of the 29 HCs), essential for receptor modelling source apportionment. The different types represent exhaust from Euro3 and Euro4 light-duty (LD) diesel and petrol-vehicles, Euro3 heavy-duty (HD) diesel exhaust, and exhaust from 2-stroke preEuro, Euro1 and Euro2 mopeds. The fuels comprise liquefied petroleum gas, petrol/ethanol blends (0–85% ethanol), and mineral diesel in various blends (0–100%) with fatty acid methyl esters, rapeseed methyl esters palm oil methyl esters, soybean oil methyl or sunflower oil methyl esters. Type-specific tracer compounds (markers) are identified for the various vehicle/engine/fuel technologies.An important finding is an insignificant effect on the HC fingerprints of varying the test driving cycle, indicating that combining HC fingerprints from different emission studies for receptor modelling purposes would be a robust approach.The obtained results are discussed in the context of atmospheric ozone formation and health implications from emissions (mg km^?1 for LD and mopeds and mg kW h^?1 for HD, all normalised to fuel consumption: mg dm^?3 fuel) of the harmful HCs, benzene and 1,3-butadiene.Another important finding is a strong linear correlation of the regulated “total” hydrocarbon emissions (tot-HC) with the ozone formation potential of the 29 HCs (ΣPO₃ = (1.66 ± 0.04) × tot-RH; r² = 0.93). Tot-HC is routinely monitored in emission control laboratories, whereas C₂–C₉ are not. The revealed strong correlations broadens the usability of data from vehicle emission control laboratories and facilitates the comparison of the ozone formation potential of HCs in exhaust from of old and new vehicle/engine/fuel technologies.     

Tracing sources of atmospheric sulphur using epiphytic lichens

The overall objective of this work was to measure the spatial variation of sulphur isotopic composition of lichens across the island of Newfoundland in order to assess the degree to which the atmosphere is being affected by long-range transport of anthropogenic sulphur from eastern North America, and/or local pollution sources. A contour map (based on over 80 composite samples of the lichen Alectoria sarmentosa) illustrates the spatial distribution of sulphur isotopic composition of the Newfoundland atmosphere. It shows a gradient of delta(34)S of sulphur in lichen, decreasing from the coast to the interior of the island. It also shows local anomalies corresponding to the city of St. John's, the Come-By-Chance Oil Refinery, mining areas and fossil-fuel powered pulp and paper mills in central and western Newfoundland. The study strongly suggests that the isotopic composition of sulphur in the Newfoundland atmosphere is influenced more by the ocean (sea salt sulphate) and local anthropogenic activities in the province, than by long-range transport of continental North American sulphate.     

Quantifying road dust resuspension in urban environment by Multilinear Engine: A comparison with PMF2

Atmospheric PM pollution from traffic comprises not only direct emissions but also non-exhaust emissions because resuspension of road dust that can produce high human exposure to heavy metals, metalloids, and mineral matter. A key task for establishing mitigation or preventive measures is estimating the contribution of road dust resuspension to the atmospheric PM mixture. Several source apportionment studies, applying receptor modeling at urban background sites, have shown the difficulty in identifying a road dust source separately from other mineral sources or vehicular exhausts. The Multilinear Engine (ME-2) is a computer program that can solve the Positive Matrix Factorization (PMF) problem. ME-2 uses a programming language permitting the solution to be guided toward some possible targets that can be derived from a priori knowledge of sources (chemical profile, ratios, etc.). This feature makes it especially suitable for source apportionment studies where partial knowledge of the sources is available.In the present study ME-2 was applied to data from an urban background site of Barcelona (Spain) to quantify the contribution of road dust resuspension to PM₁₀ and PM_2.5 concentrations. Given that recently the emission profile of local resuspended road dust was obtained (Amato, F., Pandolfi, M., Viana, M., Querol, X., Alastuey, A., Moreno, T., 2009. Spatial and chemical patterns of PM₁₀ in road dust deposited in urban environment. Atmospheric Environment 43 (9), 1650–1659), such a priori information was introduced in the model as auxiliary terms of the object function to be minimized by the implementation of the so-called “pulling equations”.ME-2 permitted to enhance the basic PMF solution (obtained by PMF2) identifying, beside the seven sources of PMF2, the road dust source which accounted for 6.9 μg m^?3 (17%) in PM₁₀, 2.2 μg m^?3 (8%) of PM_2.5 and 0.3 μg m^?3 (2%) of PM₁. This reveals that resuspension was responsible of the 37%, 15% and 3% of total traffic emissions respectively in PM₁₀, PM_2.5 and PM₁. Therefore the overall traffic contribution resulted in 18 μg m^?3 (46%) in PM₁₀, 14 μg m^?3 (51%) in PM_2.5 and 8 μg m^?3 (48%) in PM₁. In PMF2 this mass explained by road dust resuspension was redistributed among the rest of sources, increasing mostly the mineral, secondary nitrate and aged sea salt contributions.     

Electrochemical oxidation of bisphenol A. Application to the removal of bisphenol A using a carbon fiber electrode

Leachate samples with a high strength of ammonium-nitrogen (NH4+-N) were collected from a local landfill site in Hong Kong. Two experiments were carried out to study (1) the inhibition of microbial activity of activated sludge by NH4+-N and (2) the chemical precipitation of NH4+-N from leachate as a preliminary treatment prior to the activated sludge process. The experimental results demonstrated that the efficiency of COD removal decreased from 97.7% to 78.1%, and the dehydrogenase activity of activated sludge decreased from 9.29 to 4.93 microg TF/mg MLSS, respectively, when the NH4+-N concentration increased from 53 to 800 mg/l. The experiment also demonstrated that the NH4+-N in the leachate can be quickly precipitated as MgNH4PO4 x 6H2O after addition of MgCl2 x 6H2O + Na2HPO4 x 12H2O. The NH4+-N concentration was reduced from 5618 to 112 mg/l within 15 min when a molar ratio of Mg2+:NH+:PO4(3-) = 1:1:1 was used. The optimum pH to reach the minimum solubility of MgNH4PO4 x 6H2O was found to be in the range of 8.5-9.0. Attention should be given to the high salinity formed in the treated leachate by using MgCl2 x 6H2O + Na2HPO4 x 12H2O, which may affect microbial activity in the following biological treatment processes. Using two other combinations of chemicals [MgO + 85%H3PO4 and Ca(H2PO4)2 x H2O + MgSO4 x 7H2O] could minimise salinity generation after precipitation, while they were less efficient for NH4+-N removal.     

Formaldehyde Dose-Response in Healthy Nonsmokers

Industrial, commercial, and domestic levels of formaldehyde exposure range from <0.1 to >5.0 ppm. Irritation of the eyes and upper respiratory tract predominate, and bronchoconstriction is described in case reports. However, pulmonary function and irritant symptoms together have not been assessed over a range of HCHO concentrations in a controlled environment. We investigated dose response in both symptoms and pulmonary function associated with 3-h exposures to 0.0-3.0 ppm HCHO in a controlled environmental chamber. Ten subjects were randomly exposed to 0.0, 0.5, 1.0, and 2.0 ppm HCHO at rest plus 2.0 ppm HCHO with exercise and nine additional subjects were randomly exposed to 0.0,1.0,2.0, and 3.0 ppm HCHO at rest plus 2.0 ppm HCHO with exercise. Significant dose-response relationships in odor and eye irritation were observed (p < 0.05). Nasal flow resistance was increased at 3.0 ppm (p < 0.01), but not at 2.0 ppm HCHO. There were no significant decrements in pulmonary function (FVC, FEV₁, FEF_25-75%, SGaw) or increases in bronchial reactivity to methacholine (log PD_35SGaw) with exposure to 0.5-3.0 ppm HCHO at rest or to 2.0 ppm HCHO with exercise.     

Comparison of inclined plate sedimentation and dissolved air flotation for the minimisation of subsequent nitrogenous disinfection by-product formation

The formation of disinfection by-products (DBPs), including both nitrogenous disinfection by-products (N-DBPs) and carbonaceous disinfection by-products (C-DBPs), was investigated upon chlorination of water samples following two treatment processes: (i) coagulation-inclined plate sedimentation (IPS)-filtration and (ii) coagulation-dissolved air flotation (DAF)-filtration. The removal of algae, dissolved organic nitrogen (DON), dissolved organic carbon (DOC) and UV₂₅₄ by coagulation-DAF-filtration was superior to coagulation-IPS-filtration. On average, 53%, 53% and 31% of DOC, DON and UV₂₅₄ were removed by coagulation-DAF-filtration process, which were higher than 47%, 31% and 27% of that by coagulation-IPS-filtration process. Additionally, coagulation-IPS-filtration performed less well at removing the low molecular weight organics than coagulation-DAF-filtration process. The concentrations of chloroform, dichloroacetamide (DCAcAm) and dichloroacetonitrile (DCAN) formed during chlorination after coagulation-DAF-filtration reached their maximum values of 13, 1.5 and 4.7 μg L⁻¹, respectively, and were lower than those after coagulation-IPS-filtration with the maximum detected levels of 17, 2.9 and 6.3 μg L⁻¹. However, the trichloronitromethane (TCNM) concentration after the two processes was similar, suggesting that DON may have less of a contribution to TCNM formation than DCAcAm and DCAN.     

Heavy metal distribution in sediments and ecological risk assessment: The role of diagenetic processes in reducing metal toxicity in bottom sediments

This paper describes the heavy metal distributions in river and lagoonal sediments of Jacarepaguá Basin, Rio de Janeiro, Brazil. The occurrence of metal phase translocation from the reducible to the oxidizable was observed for Fe, Mn and Ni, from the fluvial environment to the lagoonal. Cu was mainly associated with the oxidizable phase while Zn and Pb were mainly associated with the reducible phase in both environments. It has been demonstrated that metal sulfide formation and complexation by organic complexes are very important aspects in terms of toxicity reduction. By means of a risk assessment methodology, based on available sediment data, it was demonstrated that the lagoonal system is exposed to a low potential ecological risk and that Zn was the metal of greater concern with respect to the system pollution.     

The relationships between mercury and selenium in plankton and fish from a tropical food web

Background, aim, and scope  Selenium (Se) has been shown to reduce mercury (Hg) bioavailability and trophic transfer in aquatic ecosystems. The study of methylmercury (MeHg) and Se bioaccumulation by plankton is therefore of great significance in order to obtain a better understanding of the estuarine processes concerning Hg and Se accumulation and biomagnification throughout the food web. In the western South Atlantic, few studies have documented trace element and MeHg in fish tissues. No previous study about trace elements and MeHg in plankton has been conducted concerning tropical marine food webs. Se, Hg, and MeHg were determined in two size classes of plankton, microplankton (70–290 μm) and mesoplankton (≥290 μm), and also in muscle tissues and livers of four fish species of different trophic levels (Mugil liza, a planktivorous fish; Bagre spp., an omnivorous fish; Micropogonias furnieri, a benthic carnivorous fish; and Centropomus undecimalis, a pelagic carnivorous fish) from a polluted estuary in the Brazilian Southeast coast, Guanabara Bay. Biological and ecological factors such as body length, feeding habits, and trophic transfer were considered in order to outline the relationships between these two elements. The differences in trace element levels among the different trophic levels were investigated. Materials and methods  Fish were collected from July 2004 to August 2005 at Guanabara Bay. Plankton was collected from six locations within the bay in August 2005. Total mercury (THg) was determined by cold vapor atomic absorption spectrometry (CV-AAS) with sodium borohydride as a reducing agent. MeHg analysis was conducted by digesting samples with an alcoholic potassium hydroxide solution followed by dithizone-toluene extraction. MeHg was then identified and quantified in the toluene layer by gas chromatography with an electron capture detector (GC-ECD). Se was determined by AAS using graphite tube with Pin platform and Zeeman background correction. Results and discussion  Total mercury, MeHg, and Se increased with plankton size class. THg and Se values were below 2.0 and 4.8 μg g⁻¹ dry wt in microplankton and mesoplankton, respectively. A large excess of molar concentrations of Se in relation to THg was observed in both plankton size class and both fish tissues. Plankton presented the lowest concentrations of this element. In fish, the liver showed the highest THg and Se concentrations. THg and Se in muscle were higher in Centropomus undecimalis (3.4 and 25.5 nmol g⁻¹) than in Micropogonias furnieri (2.9 and 15.3 nmol g⁻¹), Bagre spp (1.3 and 3.4 nmol g⁻¹) and Mugil liza (0.3 and 5.1 nmol g⁻¹), respectively. The trophic transfer of THg and Se was observed between trophic levels from prey (considering microplankton and mesoplankton) to top predator (fish). The top predators in this ecosystem, Centropomus undecimalis and Micropogonias furnieri, presented similar MeHg concentrations in muscles and liver. Microplankton presented lower ratios of methylmercury to total mercury concentration (MeHg/THg) (34%) than those found in mesoplankton (69%) and in the muscle of planktivorous fish, Mugil liza (56%). The other fish species presented similar MeHg/THg in muscle tissue (of around 100%). M. liza showed lower MeHg/THg in the liver than C. undecimalis (35%), M. furnieri (31%) and Bagre spp. (22%). Significant positive linear relationships were observed between the molar concentrations of THg and Se in the muscle tissue of M. furnieri and M. liza. These fish species also showed significant inverse linear relationships between hepatic MeHg and Se, suggesting a strong antagonistic effect of Se on MeHg assimilation and accumulation. Conclusions  Differences found among the concentrations THg, MeHg, and Se in microplankton, mesozooplankton, and fishes were probably related to the preferred prey and bioavailability of these elements in the marine environment. The increasing concentration of MeHg and Se at successively higher trophic levels of the food web of Guanabara Bay corresponds to a transfer between trophic levels from the lower trophic level to the top-level predator, suggesting that MeHg and Se were biomagnified throughout the food web. Hg and Se were positively correlated with the fish standard length, suggesting that larger and older fish bioaccumulated more of these trace elements. THg, MeHg, and Se were a function of the plankton size. Recommendations and perspectives  There is a need to assess the role of selenium in mercury accumulation in tropical ecosystems. Without further studies of the speciation of selenium in livers of fishes from this region, the precise role of this element, if any, cannot be verified in positively affecting mercury accumulation. Further studies of this element in the study of marine species should include liver samples containing relatively high concentrations of mercury. A basin-wide survey of selenium in fishes is also recommended.     

Accumulation of lead, zinc, copper and cadmium by 12 wetland plant species thriving in metal-contaminated sites in China

The concentrations of lead, zinc, copper and cadmium accumulated by 12 emergent-rooted wetland plant species including different populations of Leersia hexandra, Juncus effusus and Equisetum ramosisti were investigated in field conditions of China. The results showed that metal accumulation by wetland plants differed among species, populations and tissues. Populations grown in substrata with elevated metals contained significantly higher metals in plants. Metals accumulated by wetland plants were mostly distributed in root tissues, suggesting that an exclusion strategy for metal tolerance widely exists in them. That some species/populations could accumulate relatively high metal concentrations (far above the toxic concentration to plants) in their shoots indicates that internal detoxification metal tolerance mechanism(s) are also included. The factors affecting metal accumulation by wetland plants include metal concentrations, pH, and nutrient status in substrata. Mostly concentrations of Pb and Cu in both aboveground and underground tissues of the plants were significantly positively related to their total and/or DTPA-extractable fractions in substrata while negatively to soil N and P, respectively. The potential use of these wetland plants in phytoremediation is also discussed.     

Comparative study of extraction methods for the determination of PAHs from contaminated soils and sediments

The following four methods were compared on the extraction efficiency of 16 EPA (US Environmental Protection Agency) polycyclic aromatic hydrocarbons (PAHs): German method of the Verband Deutscher Landwirtschaftlicher Untersuchungs und Forschungsanstalten (VDLUFA), two methods of the International Organization for Standardization using shaking (ISO A) and Soxhlet extraction (ISO B) and an ultrasonic method. Recovery rates of 16 PAHs were determined in two soils. Extraction efficiency was evaluated in five soils and three sediments. Effect of drying soils and sediments on extraction efficiency was tested using the VDLUFA and the ultrasonic methods. Our study shows that the number of aromatic rings, rather than extraction procedures, significantly influenced recovery rates of individual PAHs. No significant differences in extraction efficiency of the four methods were observed for less polluted samples. For highly polluted soils, extraction efficiency decreased in the following order: VDLUFA method > ISO A > ultrasonic method > ISO B. Influence of soil moisture on extraction efficiency depended to some extent on both solvent used and content of PAHs in samples. A mixture of dichloromethane/acetone (5:1) is recommended for PAH extraction from moist samples when the ultrasonic method is used.