The extraction of aged polycyclic aromatic hydrocarbon (PAH) residues from a clay soil using sonication and a Soxhlet procedure: a comparative study

A sonication method was compared with Soxhlet extraction for recovering polycyclic aromatic hydrocarbons (PAH) from a clay soil that had been contaminated with tar materials for several decades. Using sonication over an 8 h extraction period, maximum extraction of the 16 US EPA priority PAH was obtained with dichloromethane (DCM)-acetone (1 + 1). The same procedure using hexane-acetone (1 + 1) recovered 86% of that obtained using DCM-acetone (1 + 1). PAH recovery was dependent on time of extraction up to a period of 8 h. The sonication procedure showed that individual PAH are extracted at differing rates depending on the number of fused rings in the molecule. Soxhlet extraction [with DCM-acetone (1 + 1)] over an 8 h period recovered 95% of the PAH removed by the sonication procedure using DCM-acetone (1 + 1), indicating that rigorous sonication can achieve PAH recoveries similar to those obtained by Soxhlet extraction. The lower recovery with the Soxhlet extraction was explained by the observed losses of the volatile PAH components after 1-4 h of extraction. The type of solvent used, the length of time of extraction and extraction method influenced the quantification of PAH in the soil. Therefore, the study has implications for PAH analyses in soils and sediments, and particularly for contaminated site assessments where the data from commercial laboratories are being used. The study emphasizes the importance of establishing (and being consistent in the application of) a vigorous extraction, particularly for commercial laboratories that handle samples of soil in batches (at different times) from a single site investigation or remediation process. The strong binding of PAH to soil, forming aged residues, has significant implications for extraction efficiency. This paper illustrates the problem of the underestimation of PAH using the US EPA method 3550, specifically where a surrogate spike is routinely employed and the efficiency of the extraction procedure for aged residues is unknown. The implications of this study for environmental monitoring, particularly where numerous batches of samples from a single site assessment or remediation program are submitted to commercial laboratories, is that it would be advisable for these laboratories to check their existing method's extraction efficiencies by conducting a time course sonication extraction on their particular soil to determine the optimum extraction time.     

Evaluation of two adsorbents for diffusive sampling and thermal desorption-gas chromatographic analysis of monoterpenes in air

Tube type samplers with two different adsorbents, Chromosorb 106 and Tenax TA, were evaluated by laboratory experiments and field tests for simultaneous diffusive sampling of alpha-pinene, beta-pinene and delta 3-carene and subsequent thermal desorption-gas chromatographic analysis. No statistically significant effects of exposure time, concentrations of monoterpenes or relative humidity were found for samplers with Chromosorb 106 when running a factorial design, with the exception of the adsorption of delta 3-carene, for which some weak effects were noted. Samplers with Tenax TA were affected by the sampling time as well as the concentration for all terpenes, with a strong interaction effect between these two factors. The terpenes showed good storage stability on both adsorbents. No effect of back-diffusion was noted when using Chromosorb 106, while Tenax TA showed some back-diffusion effects. The uptake rates, in ml min-1, for the terpenes on Chromosorb 106 were 0.36 for alpha-pinene, 0.36 for beta-pinene and 0.40 for delta 3-carene. The corresponding average values on Tenax TA were 0.30 for alpha-pinene, 0.32 for beta-pinene and 0.38 for delta 3-carene. The field validation proved that diffusive sampling on Chromosorb 106 agreed well with pumped sampling on charcoal for stationary samples, while the personal samples indicated a discrepancy of 25% between Chromosorb 106 and charcoal samples. Tenax TA generally gave lower results than Chromosorb 106 in all field samples. Samplers packed with Chromosorb 106 could be used to monitor terpene levels in workplaces such as sawmills. The major advantages with this method are the sampling procedure, which is simple to perform compared to other techniques, the easily automated analysis procedure and the possibility to reuse the samplers.     

Determination of Ni(CO)4, Fe(CO)5, Mo(CO)6, and W(CO)6 in sewage gas by using cryotrapping gas chromatography inductively coupled plasma mass spectrometry

Evidence for the occurrence of Ni(CO)4 in addition to Mo(CO)6 and W(CO)6 in fermentation gases from a municipal sewage treatment plant is presented for the first time. The gases were sampled at the top of the sewage sludge digester using Tedlar bags, and were analysed using cryotrapping followed by gas chromatography coupled with inductively coupled mass spectrometry (GC-ICP-MS). The use of an ICP-MS as an element-specific detector gives sufficiently low detection limits for metals and was coupled to a packed column gas chromatograph. This method provides information about the speciation of volatile transition metals in contrast to previously used methods for the determination of Ni(CO)4 in gas samples. The element-specific detection of three different isotopes (m/z 58, 60, 62) and the correspondence of the samples' retention times with those of the standard provided convincing evidence that Ni(CO)4 is present in the fermentation gas. The concentrations found were in the sub-ppb level, which is at least one order of magnitude lower than the threshold level of 1 ppb (v/v). In addition, Mo(CO)6 and W(CO)6 were also measured in the sub-ppb range in contrast to the absence of Fe(CO)5. The stabilities of Ni(CO)4, Fe(CO)5, and Mo(CO)6 were tested in a carbon monoxide atmosphere. In the presence of distilled water, the following order of stability was found after 11 weeks: Fe(CO)5 < Ni(CO)4 < Mo(CO)6. In the presence of an aqueous solution containing nickel, molybdenum, tungsten and iron, however, only Fe(CO)5 was significantly decomposed (< 0.3% recovery); Ni(CO)4 and Mo(CO)6 were stable after 11 weeks. No W(CO)6 was formed. The low stability of Fe(CO)5 in the presence of water could be the reason why no volatile iron compound was found in sewage gas. This study showed that GC-ICP-MS can be employed to identify species-specific traces of metal carbonyls in process gases such as sewage gas.     

Study of Meteorological Aspects and Urban Concentration of SO2 in Atmospheric Environment of La Plata, Argentina

This article presents and discusses SO₂ (ppbv) concentration measurements combined with meteorological data (mainly wind speed and direction) for a five-year campaign (1996 to 2000), in a site near an oil refinery plant close to the city of La Plata and surroundings (aprox. 740.000 inh.), considered one of the six most affected cities by air pollution in the country. Since there is no monitoring network in the area, the obtained results should be considered as medium term accumulated data that enables to determine trends by analyzing together gas concentrations and meteorological parameters. Preliminary characterization of the behaviour of the predominant winds of the region in relation with potential atmospheric gas pollutants from seasonal wind roses is possible to carry out from the data. These results are complemented with monthly averaged SO₂ measurements. In particular, for year 2000, pollutant roses were determined which enable predictions about contamination emission sources. As a general result we can state that there is a clear increase in annual SO₂ concentration and that the selected site should be considered as a key site for future survey monitoring network deployment. Annual SO₂ average concentration and prevailing seasonal winds determined in this work, together with the potential health impact of SO₂ reveals the need for a comprehensive and systematic study involving particulate matter an other basic pollutant gases.     

Documentation of cumulative impacts in environmental impact statements

The National Environmental Policy Act (NEPA) of 1969 and the Council on Environmental Quality (CEQ) regulations in the United States require federal agencies to apply an environmental impact assessment (EIA) in decision-making related to their actions. One aspect requires an examination of direct, indirect and cumulative impacts (CIs). Historically, cumulative impact assessment (CIA) has been given limited attention in EIA and resultant environmental impact statements (EISs), not because of its lack of importance, but owing to limitations in methodologies and procedures, including documentation consistency. The objectives of this study were to identify deficiencies in the documentation of CIs and CIA in EISs and to formulate appropriate recommendations (potential solutions) related to such deficiencies. The study involved the systematic review of 33 EISs (11 each from the U.S. Department of Agriculture: Forest Service, the U.S. Army Corps of Engineers, and the U.S. Department of Transportation: Federal Highway Administration). The results indicate that improvements have been made in documentation practices since 1990; however, inconsistencies and inadequacies still exist. Therefore, the following recommendations were developed: (1) CIs should be reported in a separate part of the “Environmental Consequences” section, and they should be addressed for each pertinent environmental resource; (2) a summary of CIs should be included; (3) any CIs considered not significant should be mentioned plus the reason(s) for their non-significance; (4) spatial and temporal boundaries addressed within the CIA process should be defined for pertinent environmental resources; and (5) utilized guidelines and methodologies should be described.     

Trends in motor-vehicle related air pollutants in central London

Results of intermittent monitoring of six aromatic hydrocarbons (benzene, toluene, ethyl-benzene, m-xylene, p-xylene and o-xylene), carbon monoxide and oxides of nitrogen over a thirteen year period at a site in central London (Exhibition Road) are presented. Four monitoring regimes were undertaken; namely, 1979, 1982/83, 1986/87 and 1991/92. The summertime daytime mean ambient concentrations of the measured parameters at this site are presented. The reported concentrations show a reduction from 1979 to 1992 by approximately a factor of two, despite national increases in motor fuel consumption and the volume of traffic. Relevant European Community legislation covering emissions from motor-vehicles are outlined and comparisons are made with emissions from motor vehicles predicted from the UK national inventory. The importance of the frequency of measurements was also noted.     

Overstory mortality as an indicator of forest health in California

The interagency Forest Health Monitoring Program involves a network of about 4200 forest plots on a triangular grid across the United States. We present data on recent mortality of trees 27.9 cm diameter from the first three years of measurements in California (1992–1994). Three plot designs were used to collect data representative of a 1-ha stand at each site; the designs differed primarily in total area sampled (0.067, 0.4 and 1.0 ha). Approximately 50 sites were visited each year yielding a total of about 150. Field tallies showed few cases of recent mortality in the smallest plot size. Cumulative distribution functions of recent dead tree densities in the 0.067-ha plots differed significantly from those generated by tallies from entire 1-ha stands. We conclude that an area of 0.067 ha is unsuitable to assess and monitor overstory mortality in Pacific Coast forests.The U.S. government right to retain a non-exclusive, royalty free licence in and to any copyright is acknowledged.     

A ten channel fibre-optic device for distributed sensing of underground hydrocarbon leakage

With millions of fuel storage tanks and oil pipelines installed around the world, there is inevitably frequent leakage of potentially hazardous hydrocarbons. As many of these installations are below ground, it can often be many years before the extent of the leak is discovered. We have previously reported the development of a sensor for the detection of such subterranean leaks, using infrared reflectometry to interrogate a hydrocarbon sensitive membrane. However, a single sensor cannot provide any information about the flow rate or direction of the leak. This paper describes the extension of the technology to a multi-channel distributed sensing system, using optical fibres capable of distributing the sensors over large subterranean areas. Results are reported from the evaluation of the device, which consisted of monitoring the movement of different hydrocarbons (gasoline, diesel and insulating oil) through a vertical sand-filled vessel.     

Study of the relationships between bone lead levels and its variation with time and the cumulative blood lead index, in a repeated bone lead survey

The study aims were to: (i) investigate long term human lead metabolism by measuring the change of lead concentration in the tibia and calcaneus; and (ii) assess whether improved industrial hygiene was resulting in a slow accumulation of lead in an exposed workforce. 109Cd excited K X-ray fluorescence was used to measure tibia lead and calcaneus lead concentrations in 101 workers in a secondary lead smelter. 51 subjects had had similar bone lead measurements 5 years previously. Most of the other subjects had been hired since the first survey. Measurements of whole blood lead were available for the large majority of subjects. Tibia lead concentrations fell significantly (p<0.001) in the 51 subjects with repeated bone lead measurements, from a mean of 39 microg Pb (g bone mineral)(-1) to 33 microg Pb (g bone mineral)(-1). The change correlated negatively with the initial tibia lead concentration, producing an estimate for an overall half-life of 15 years, with a 95% confidence interval of 9 to 55 years. Adding continuing lead exposure and recirculation of bone lead stores to the regression models produced half-life estimates of 12 and 9 years, respectively, for release of lead from the tibia. The repeat subjects showed no net change in calcaneus lead (64 microg Pb (g bone mineral)(-1) initially, 65 microg Pb (g bone mineral)(-1) 5 years later). Subjects not measured previously had average lead concentrations of 15 microg Pb (g bone mincral)(-1) in the tibia and 13 microg Pb (g bone mineral)(-1) in the calcaneus. The rate of clearance of lead from the tibia (9 to 15 years) is towards the more rapid end of previous estimates. The lack of a significant fall in the calcaneus lead was surprising. Attempts should be made to repeat this observation. If confirmed, it would have implications for models of lead metabolism. The relatively low lead concentrations in the non-repeat subjects are reassuring. However, observation after a longer period of employment would be desirable.     

Determination of n-alkanes and polycyclic aromatic hydrocarbons in atmospheric particulate and vapour phases in Oviedo, Spain, by GC-MS

A GC-MS procedure for the determination of hydrocarbons in air samples from Oviedo, Spain, was developed. Air hydrocarbons were sampled with a high volume sampler equipped with a holder containing a glass fiber filter, to trap the particulate phase, and two polyurethane foams to capture hydrocarbons of the vapour phase. Compounds were extracted with CH2Cl2 by Soxhlet extraction and then fractionated using column chromatography with alumina silica. Analyses of the fractions were performed by GC-MS in the electron ionization mode. PAHs and n-alkanes were the compounds examined in this work. Samples collected in the vicinity of the Faculty of Chemistry (a semi-urban area) were analysed. The total concentration of PAHs in the air samples analysed ranged from 28 to 76 ng m(-3). The total concentration of n-alkanes and PAHs in the vapour phase exceeded the concentration in the particulate phase in the samples analysed.