Analysis of polycyclic aromatic hydrocarbons (PAHs) in airborne particles by direct sample introduction thermal desorption GC/MS

The technique of thermal desorption (TD)–GC/MS was evaluated for measuring airborne, 4–6 ring polycyclic aromatic hydrocarbons (PAHs) collected onto quartz filters. TD provides a more readily automated and sensitive alternative to traditional solvent extraction, decreasing the time/cost of analysis and reducing the risk of analyte loss or sample contamination. The developed method was successfully applied to the analysis of PAH standard solutions loaded on sorbent tubes packed with quartz wool and the graphitized carbon black sorbent Carbograph2. The optimized method showed high desorption efficiency over the whole range of target PAHs with good precision, linearity and sensitivity. The proposed method was verified on an urban dust Standard Reference Material (SRM 1649a); the experimentally determined concentrations agreed with the certified ranges (95% confidence limit) for all target compounds except benzo[a]anthracene, which fell just outside the narrow certified range. The desorption efficiency and the reproducibility of the method was evaluated by analysing pieces of real sample filters sampled from urban air for a period of 24 h. The results confirmed the homogeneity of the filter and showed high recovery efficiencies for all target PAHs.     

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.     

Dehalogenation of polychlorinated biphenyls and polybrominated diphenyl ethers using a hybrid bioinorganic catalyst

The environmentally prevalent polybrominated diphenyl ether (PBDE) #47 and polychlorinated biphenyls (PCBs) #28 and #118 were challenged for 24 hours with a novel biomass-supported Pd catalyst (Bio-Pd(0)). Analysis of the products via GC-MS revealed the Bio-Pd(0) to cause the challenged compounds to undergo stepwise dehalogenation with preferential loss of the least sterically hindered halogen atom. A mass balance for PCB #28 showed that it is degraded to three dichlorobiphenyls (33.9%), two monochlorobiphenyls (12%), and biphenyl (30.7%). The remaining mass was starting material. In contrast, while PCB #118 underwent degradation to yield five tetra- and five trichlorinated biphenyls, no less chlorinated products or biphenyl were detected, and the total mass of degraded products was 0.3%. Although the Bio-Pd(0) material was developed for treatment of PCBs, a mass balance for PBDE #47 showed that the biocatalyst could prove a potentially useful method for treatment of PBDEs. Specifically, 10% of PBDE #47 was converted to identifiable lower brominated congeners, predominantly the tribrominated PBDE #17 and the dibrominated PBDE #4, 75% remained intact, while 15% of the starting mass was unaccounted for.     

Quality Control for Environmental Policy Appraisal Tools: An Empirical Investigation of Relations Between Quality,Quality Control and Effectiveness

The spectre of regulatory reform carried out in a range of Western countries has generated concern amongst parts of the environmental policy community. Quality and effectiveness are said to be at stake, but empirically there is a dearth of data on the relationship between provisions for quality control and the effects on quality and effectiveness. This research addresses this lacuna by analysing the effects of different quality control provisions in the Netherlands and Denmark for a globally institutionalized environmental appraisal tool—Environmental Assessment (EA). Extensive technical provisions for quality control in the Netherlands have led to it being described as the ‘Rolls Royce’ of EA systems, while in Denmark the polity is expected to take charge of quality control. The effects of quality control are investigated through surveys and in-depth interviews with actors centrally engaged with EA implementation. The results show that quality control provisions are poorly related to the perceived quality and effectiveness of EA. Only the appropriateness of the scope of EA reports is perceived to be strongly related to quality control provisions. The findings are relevant for environmental policy communities concerned with quality control systems and effectiveness of policy appraisal tools and policy-makers contemplating regulatory reforms.     

Rapid measurement of emissions from military aircraft turbine engines by downstream extractive sampling of aircraft on the ground: Results for C-130 and F-15 aircraft

Aircraft emissions affect air quality on scales from local to global. More than 20% of the jet fuel used in the U.S. is consumed by military aircraft, and emissions from this source are facing increasingly stringent environmental regulations, so improved methods for quickly and accurately determining emissions from existing and new engines are needed. This paper reports results of a study to advance the methods used for detailed characterization of military aircraft emissions, and provides emission factors for two aircraft: the F-15 fighter and the C-130 cargo plane. The measurements involved outdoor ground-level sampling downstream behind operational military aircraft. This permits rapid change-out of the aircraft so that engines can be tested quickly on operational aircraft. Measurements were made at throttle settings from idle to afterburner using a simple extractive probe in the dilute exhaust. Emission factors determined using this approach agree very well with those from the traditional method of extractive sampling at the exhaust exit. Emission factors are reported for CO₂, CO, NO, NO_x, and more than 60 hazardous and/or reactive organic gases. Particle size, mass and composition also were measured and are being reported separately. Comparison of the emissions of nine hazardous air pollutants from these two engines with emissions from nine other aircraft engines is discussed.     

Remediation of chlorinated ethenes,ethanes, and methanes in groundwater using carbon‐ and iron‐based electron donor

Field‐scale pilot tests were performed to evaluate enhanced reductive dechlorination (ERD) of dissolved chlorinated solvents at a former manufacturing facility located in western North Carolina (the site). Results of the site assessment indicated the presence of two separate chlorinated solvent–contaminated groundwater plumes, located in the northern and southern portions of the site. The key chlorinated solvents found at the site include 1,1,2,2‐tetrachloroethane, trichloroethene, and chloroform. A special form of EHC^® manufactured by Adventus Americas was used as an electron donor at this site. In this case, EHC is a pH‐buffering electron donor containing controlled release carbon and ZV Iron MicroSphere 200, a micronscale zero‐valent iron (ZVI) manufactured by BASF. Approximately 3,000 pounds of EHC were injected in two Geoprobe^® boreholes in the saprolite zone (southern plume), and 3,500 pounds of EHC were injected at two locations in the partially weathered rock (PWR) zone (northern plume) using hydraulic fracturing techniques. Strong reducing conditions were established immediately after the EHC injection in nearby monitoring wells likely due to the reducing effects of ZV Microsphere 200. After approximately 26 months, the key chlorinated VOCs were reduced over 98 percent in one PWR well. Similarly, the key chlorinated solvent concentrations in the saprolite monitoring wells decreased 86 to 99 percent after initial increases in concentrations of the parent chlorinated solvents. The total organic carbon and metabolic acid concentrations indicated that the electron donor lasted over 26 months after injection in the saprolite aquifer. © 2009 Wiley Periodicals, Inc.     

Benzene Exposure Assessment at Indoor, Outdoor and Personal Levels. The French Contribution to the Life MACBETH Programme

Many VOC represent hazards to human health through chronic exposure. Recent European and world-wide legislation proposes limit values for ambient concentrations of these compounds. However, very little experimental data exists for true population exposure. In 1996, the European MACBETH initiative set out to measure population exposure to benzene in six European cities. This study details the French contribution to this program. Six campaigns were carried out, each comprising measurements at 100 outdoor sites and the participation of 50 non-smoking volunteers who wore personal samplers and had passive monitors installed in their homes. Iso-concentration maps were drawn for each campaign and the results showed that outdoor concentrations were significantly lower than indoors. Almost 75% of the volunteers were exposed to mean concentrations higher than the limit value of 5µgm³. It is demonstrated that personal exposure levels cannot be deduced simply by combining indoor and outdoor background concentrations. It is also shown that there is need for better knowledge of the contributions to overall exposure of outdoor microenvironments and the authors hope that future European directives will take this into account.     

Use of preserved museum fish to evaluate historical and current mercury contamination in fish from two rivers in Oklahoma, USA

We examined the effects of a commonly used preservation technique on mercury concentration in fish tissue. After fixing fish muscle tissue in formalin followed by preservation in isopropanol, we found that mercury concentration in fish muscle tissue increased by 18%, reaching an asymptote after 40 days. We used formalin–isopropanol-preserved longear sunfish (Lepomis megalotis) from the Sam Noble Oklahoma Museum of Natural History to examine historical changes and predict current mercury concentrations in fish from two rivers in southeastern Oklahoma. Glover River was free-flowing, while Mountain Fork River was impounded in 1970 and a coldwater trout fishery was established upstream from the collection site in 1989. Mercury concentrations in longear sunfish from Glover River showed no historical changes from 1963 to 2001. Mercury concentrations in longear sunfish from Mountain Fork River showed no change from 1925 to 1993 but declined significantly from 1993 to 2003. We also compared mercury concentrations of the most recently collected longear sunfish in the museum to mercury concentrations of unpreserved fish collected from the rivers in 2006. Concentrations of mercury in museum fish were not significantly different from mercury concentrations in unpreserved fish we collected from the rivers. Our study indicates that preserved museum fish specimens can be used to evaluate historical changes and predict current levels of mercury contamination in fish.