Four selected high molecular weight heterocyclic aromatic hydrocarbons: Ecotoxicological hazard assessment, environmental relevance and regulatory needs under REACH.

Little is known about the ecotoxicity of heterocyclic aromatic hydrocarbons (NSO-HETs) to aquatic organisms. In the environment, NSO-HETs have been shown to occur in a strong association with their unsubstituted carbocyclic analogues, the polycyclic aromatic hydrocarbons (PAH), for which much more information is available. The present study addressed this issue by investigating the toxicity of four selected NSO-HETs in green algae (Desmodesmus subspicatus), daphnids (Daphnia magna) and fish embryos (Danio rerio). The four high molecular weight NSO-HETs dibenz[a,j]acridine (DBA), 7H-dibenzo[c,g]carbazole (DBC), benzo[b]naphtho[2,1-d]thiophene (BNT) and benzo[b]naphtho[1,2-d]furan (BNF) were selected, based on the results of a previous research project, indicating a lack of toxicity data and a high potential for persistence and bioaccumulation. The solubilities of the NSO-HETs in the test media were determined and turned out to be comparatively low (2.7-317 µg/L) increasing in the following order: DBA < BNT « DBC « BNF. Exposure concentrations during the toxicity tests were quantified with GC-MS and decreased strongly possibly due to sorption or metabolising during the test periods (48-96 h). Therefore, the estimated effect concentrations were related to the mean measured concentrations, as endpoints related to nominal concentrations would have underestimated the toxicity many times over. Within the range of the substance solubilities, BNF affected all test organisms with fish embryos being the most sensitive (fish: EC50 6.7 µg/L, algae: EC10 17.8 µg/L, daphnids: EC50 55.8 µg/L). DBC affected daphnids (EC50 2.5 µg/L,) and algae (EC10 3.1 µg/L), but not fish embryos. The lowest toxicity endpoint was observed for BNT affecting only algae (NOEC 0.556 µg/L) and neither daphnids nor fish embryos. DBA did not show any effects on the tested organisms in the range of the water solubility. However, we would expect effects in long-term toxicity studies to fish and aquatic invertebrates for all substances at lower concentrations, which needs further investigation. All four NSO-HETs were identified in mussels (Mytilus edulis) from the German coasts, in green kale (Brassica oleracea var. acephala) and in freshwater harbor sediment in concentrations between 0.07 and 2 µg/kg, highlighting their relevance as environmental contaminants. There is a need to regulate the four NSO-HETs within the REACH regulation due to their intrinsic properties and their environmental relevance. However, acquisition of additional experimental data appears to be pivotal for a regulation under REACH.

Heavy metals in aromatic spices by inductively coupled plasma-mass spectrometry.

Objective of this study was to determine the content of Cd, Hg, As and Pb in common spices traded in the Italian market, using inductively coupled plasma-mass spectrometry (ICP-MS). The results were compared with the maximum limits established by the national Legislative Decree (LD) no. 107 implementing the Council Directive 88/388/EEC and by international organisations, such as Food and Agriculture Organization (FAO) and World Health Organization (WHO). Food safety for spices was assessed considering the tolerable weekly intake (TWI) and the provisional tolerable weekly intake (PTWI), respectively, for Cd and Hg and the 95% lower confidence limit of the benchmark dose of 1% extra risk (BMDL01) for As and Pb. Investigated elements in all samples were within the maximum limits as set by the national and international normative institutions. Nevertheless, the heavy metal content of some spices exceeded the PTWI, TWI and BMDL01, which needs attention when considering consumer's health.

Evaluating the Effects of Aromatics Content in Gasoline on Gaseous and Particulate Matter Emissions from SI-PFI and SIDI Vehicles.

We assessed the emissions response of a fleet of seven light-duty gasoline vehicles for gasoline fuel aromatic content while operating over the LA92 driving cycle. The test fleet consisted of model year 2012 vehicles equipped with spark-ignition (SI) and either port fuel injection (PFI) or direct injection (DI) technology. Three gasoline fuels were blended to meet a range of total aromatics targets (15%, 25%, and 35% by volume) while holding other fuel properties relatively constant within specified ranges, and a fourth fuel was formulated to meet a 35% by volume total aromatics target but with a higher octane number. Our results showed statistically significant increases in carbon monoxide, nonmethane hydrocarbon, particulate matter (PM) mass, particle number, and black carbon emissions with increasing aromatics content for all seven vehicles tested. Only one vehicle showed a statistically significant increase in total hydrocarbon emissions. The monoaromatic hydrocarbon species that were evaluated showed increases with increasing aromatic content in the fuel. Changes in fuel composition had no statistically significant effect on the emissions of nitrogen oxides (NOx), formaldehyde, or acetaldehyde. A good correlation was also found between the PM index and PM mass and number emissions for all vehicle/fuel combinations with the total aromatics group being a significant contributor to the total PM index followed by naphthalenes and indenes.

Assessment of soil pollution based on total petroleum hydrocarbons and individual oil substances.

Different oil products like gasoline, diesel or heavy oils can cause soil contamination. The assessment of soils exposed to oil products can be conducted through the comparison between a measured concentration and an intervention value (IV). Several national policies include the IV based on the so called total petroleum hydrocarbons (TPH) measure. However, the TPH assessment does not indicate the individual substances that may produce contamination. The soil quality assessment can be improved by including common hazardous compounds as polycyclic aromatic hydrocarbons (PAHs) and aromatic volatile hydrocarbons like benzene, toluene, ethylbenzene and xylenes (BTEX). This study, focused on 62 samples collected from different sites throughout The Netherlands, evaluates TPH, PAH and BTEX concentrations in soils. Several indices of pollution are defined for the assessment of individual variables (TPH, PAH, B, T, E, and X) and multivariables (MV, BTEX), allowing us to group the pollutants and simplify the methodology. TPH and PAH concentrations above the IV are mainly found in medium and heavy oil products such as diesel and heavy oil. On the other hand, unacceptable BTEX concentrations are reached in soils contaminated with gasoline and kerosene. The TPH assessment suggests the need for further action to include lighter products. The application of multivariable indices allows us to include these products in the soil quality assessment without changing the IV for TPH. This work provides useful information about the soil quality assessment methodology of oil products in soils, focussing the analysis into the substances that mainly cause the risk.

[Study on quantification assessment and odor fingerprint of volatile aromatic hydrocarbons from sewage treatment plant].

The malodorous volatile organic compounds (MVOCs) from a typical municipal sewage treatment plant in Guangzhou were detected and analyzed using thermal-desorption/GC-MS and electronic nose, respectively. The results showed that: (1) Aromatic hydrocarbons were the main malodorous volatile organic compounds of the sewage treatment plant, with concentrations ranging from 96.61 microg x m(-3) to 818.03 microg x m(-3), accounting for more than 50% of the total MVOCs, much higher than other MVOCs species. (2) Volatile aromatic hydrocarbons (VAH) in municipal sewage treatment plant were mainly from domestic wastewater, and the sludge treatment process played an important part in release of these pollutants. The total concentration of aromatic hydrocarbons emitted from each processing unit in a descending order was: the sludge dehydration room > sludge thickener > aeration tank > grille > biochemical pool> grit chamber. (3) rincipal component analysis (PCA) was able to distinguish the characteristic of odor emission from each processing unit, with the recognition index reaching 71% , and the PCA recognition index of simulated gases which simulated the VAH levels of different processes reached 94% , indicating that there was big difference among the srmll of the VAH emitted from different processes. (4) The comparison of the original odor fingerprint and simulated odor fingerprint measured by the sensor T70/2 showed that the original odor fingerprint was greater than the simulated odor fingerprint, and the correlation analysis indicated that the VAH had a great contribution to the odor fingerprint of each unit, and the contribution of VAH odor of the aeration tank tq the original odor fingerprint reached 0. 98.

Assessment of halogenated POPs and PAHs in three cities in the Yangtze River Delta using high-volume samplers.

The objective of this study was to quantify organic chlorinated pesticides, polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and polycyclic aromatic hydrocarbons (PAHs) in air samples collected from July 2009 to April 2010 in Suzhou, Wuxi and Nantong in the Yangtze River Delta (YRD) and to identify potential sources of these pollutants during the period. Gas- and particle-phase concentrations of these species were determined using gas chromatography-mass spectrometry on samples collected using high volume samplers. Phenanthrene, fluoranthene, hexachlorobenzene (HCB), p,p'-DDE, tri-CB (#18), tri-CB (#28) and deca-BDE (#209) were the most abundant compounds in the YRD. Average concentrations of these pollutants in Suzhou, Wuxi and Nantong, respectively, were 88.4, 105 and 69.5 ng/m(3) for PAHs, 162, 237 and 136 pg/m(3) for HCB, 35.7, 41.7 and 34.7 pg/m(3) for hexachlorocyclohexane, 131, 83.1 and 229 pg/m(3) for DDTs, 63.4, 52.4 and 31.7 pg/m(3) for chlordanes, 80.5, 51.8 and 65.1 pg/m(3) for PCBs, 30.4, 32.0 and 54.6 pg/m(3) for PBDEs (tri- to hepta-BDE) and 882, 807 and 1200 pg/m(3) for deca-BDE (#209). Concentrations of the emerging persistent organic pollutant, deca-BDE (#209), in the three cities were greater than those of other countries. Massive production and/or the use of commercialized deca-BDE (#209) may occur in metropolitan areas and development zones in the YRD.

[Pollution characteristics of volatile organic compounds from wastewater treatment system of vitamin C production].

Using a portable gas chromatography and mass spectrometry (GC-MS), the volatile organic compounds (VOCs) pollution in each unit of the wastewater treatment system for vitamin C production was studied, and the species characteristics of volatile organic compounds (VOCs) were analyzed and summarized. The results showed that 32 kinds of volatile organic compounds were identified, and the total mass concentration range of volatilizing VOCs was 0.9629-32.0970 mg x m(-3). The most species and the largest concentration (25 and 32.0970 mg x m(-3)) of volatilizing VOCs were found in grit chamber, which was located in the most front-end of the wastewater treatment system and was in semi-closed state. The proportion of molecular sulfide in the grit chamber was as high as 30.02%; Higher proportions of aromatic hydrocarbons were monitored in the subsequent processing units, with percentages of 21.06%-31.48%. The main types of VOCs monitored were chlorinated hydrocarbons and ketones, accounting for 6.39%-55.80% and 10.40%-58.08% of the total amount, respectively; 14 kinds of VOCs were detected in every unit of the wastewater treatment system: acetone, 2-butanone, n-hexane, chloroform, chlorobenzene etc, among which, vinyl chloride, styrene and 1,3-butadiene belong to the highly toxic substances. The vinyl chloride concentration exceeded the standard of "atmospheric pollutants emission standards" (GB 16297-1996), while 1,3-butadiene and other pollutants have no national standard limits. The results of this study provide a scientific basis for the revision of China's pharmaceutical wastewater VOCs emission standards.

Air pollution and general practitioner access and utilization: a population based study in Sarnia, 'Chemical Valley,' Ontario.

BACKGROUND: Health impacts of poor environmental quality have been identified in studies around the world and in Canada. While many of the studies have identified associations between air pollution and mortality or morbidity, few have focused on the role of health care as a potential moderator of impacts. This study assessed the determinants of health care access and utilization in the context of ambient air pollution in Sarnia, Ontario, Canada. METHODS: Residents of Sarnia participated in a Community Health Study administered by phone, while several ambient air pollutants including nitrogen dioxide (NO2), sulphur dioxide (SO2) and the volatile organic compounds benzene, toluene, ethylbenzene, mp- and o-xylene (BTEX) were monitored across the city. Land Use Regression models were used to estimate individual exposures to the measured pollutants and logistic regression models were utilized to assess the relative influence of environmental, socioeconomic and health related covariates on general practitioner access and utilization outcomes. RESULTS: The results show that general practitioner use increased with levels of exposure to nitrogen dioxide (NO2- Odds Ratio [OR]: 1.16, p < 0.05) and sulphur dioxide (SO2- OR: 1.61, p < 0.05). Low household income was a stronger predictor of having no family doctor in areas exposed to high concentrations of NO2 and SO2. Respondents without regular care living in high pollution areas were also more likely to report travelling or waiting for care in excess of 20 minutes (OR: 3.28, p < 0.05) than their low exposure counterparts (OR: 1.11, p > 0.05). CONCLUSIONS: This study provides evidence for inequitable health care access and utilization in Sarnia, with particular relevance to its situation as a sentinel high exposure environment. Levels of exposure to pollution appears to influence utilization of health care services, but poor access to primary health care services additionally burden certain groups in Sarnia, Ontario, Canada.

Facile on-site detection of substituted aromatic pollutants in water using thin layer chromatography combined with surface-enhanced Raman spectroscopy.

A novel facile method for on-site detection of substituted aromatic pollutants in water using thin layer chromatography (TLC) combined with surface-enhanced Raman spectroscopy (SERS) was explored. Various substituted aromatics in polluted water were separated by a convenient TLC protocol and then detected using a portable Raman spectrometer with the prepared silver colloids serving as SERS-active substrates. The effects of operating conditions on detection efficacy were evaluated, and the application of TLC-SERS to on-site detection of artificial and real-life samples of aromatics/polluted water was systematically investigated. It was shown that commercially available Si 60-F(254) TLC plates were suitable for separation and displayed low SERS background and good separation efficiency, 2 mM silver colloids, 20 mM NaCl (working as aggregating agent), 40 mW laser power, and 50 s intergration time were appropriate for the detection regime. Furthermore, qualitative and quantitative detection of most of substituted aromatic pollutants was found to be readily accomplished using the developed TLC-SERS technique, which compared well with GC-MS in terms of identification ability and detection accuracy, and a limit of detection (LOD) less than 0.2 ppm (even at ppb level for some analytes) could be achieved under optimal conditions. The results reveal that the presented convenient method could be used for the effective separation and detection of the substituted aromatic pollutants of water on site, thus reducing possible influences of sample transportation and contamination while shortening the overall analysis time for emergency and routine monitoring of the substituted aromatics/polluted water.

Assessment of the impact of the vehicular traffic on BTEX concentration in ring roads in urban areas of Bari (Italy).

A BTEX monitoring campaign, consisting of two weekly periods, was carried out in Bari, south-eastern Italy, in order to evaluate the impact of the vehicular traffic on the air quality at the main access roads of the city. Twenty-one sampling sites were selected: the pollution produced by the traffic in the vicinity of all exits from the ring road and some access roads to the city, those with higher traffic density, were monitored. Contemporarily the main meteorological parameters (ambient temperature, wind, atmospheric pressure and natural radioactivity) were investigated. It was found that in the same traffic conditions, barriers, buildings and local meteorological conditions can have important effects on the atmospheric dispersion of pollutants. This situation is more critical in downtown where narrow roads and high buildings avoid an efficient dispersion producing higher levels of BTEX. High spatial resolution monitoring allowed both detecting the most critical areas of the city with high precision and obtaining information on the mean level of pollution, meaning air quality standard of the city. The same concentration pattern and the correlation among BTEX levels in all sites confirmed the presence of a single source, the vehicular traffic, having a strong impact on air quality.

A novel total petroleum hydrocarbon fractionation strategy for human health risk assessment for petroleum hydrocarbon-contaminated site management.

Human health risk assessments for petroleum, oil, and lubricant (POL)-contaminated sites are more complicated than for sites contaminated by single compounds due to the complex composition and various analytical methods associated with total petroleum hydrocarbons (TPH). Although several TPH fractionation methods are commonly used, including that of the TPH Criteria Working Group (TPHCWG), an efficient and economical human health risk assessment method is not yet available. To address this concern, a new modified fractionation strategy is recommended in this study, which resolves the problems of the current TPH fractionation methods while retaining reliability in the results. For the purpose of this study, the distribution characteristics of the 13 TPHCWG fractions were examined, and human health risk assessments for the POL-contaminated sites were performed. The results show that aliphatic EC8-16 and aromatic EC10-21 among the 13 TPH fractions are major contributors to human health risks along all exposure routes, making up approximately 96% of the hazard index (HI) of the TPH fractions, on average. Therefore, it is reasonable to concentrate on aliphatic EC8-16 and aromatic EC10-21 fractions, rather than to study all of the TPH fractions, in evaluating human health risk for TPH-contaminated sites.

Identification of intermediates and assessment of ecotoxicity in the oxidation products generated during the ozonation of clofibric acid.

The degradation of an aqueous solution of clofibric acid was investigated during catalytic and non-catalytic ozonation. The catalyst, TiO(2), enhanced the production of hydroxyl radicals from ozone and raised the fraction or clofibric acid degraded by hydroxyl radicals. The rate constant for the reaction of clofibric acid and hydroxyl radicals was not affected by the presence of the catalyst. The toxicity of the oxidation products obtained during the reaction was assessed by means of Vibrio fischeri and Daphnia magna tests in order to evaluate the potential formation of toxic by-products. The results showed that the ozonation was enhanced by the presence of TiO(2,) the clofibric acid being removed completely after 15 min at pH 5. The evolution of dissolved organic carbon, specific ultraviolet absorption at 254 nm and the concentration of carboxylic acids monitored the degradation process. The formation of 4-chlorophenol, hydroquinone, 4-chlorocatechol, 2-hydroxyisobutyric acid and three non-aromatic compounds identified as a product of the ring-opening reaction was assessed by exact mass measurements performed by liquid chromatography coupled to time-of-flight mass spectrometry (LC-TOF-MS). The bioassays showed a significant increase in toxicity during the initial stages of ozonation following a toxicity pattern closely related to the formation of ring-opening by-products.

Concentrations and risk assessment of selected monoaromatic hydrocarbons in buses and bus stations of Hangzhou, China.

Air pollution surveys of ten selected monoaromatic hydrocarbons (MAHCs) were conducted in buses and bus stations in Hangzhou, China. The mean concentrations of MAHCs in the air of buses and bus stations were 95.9 and 36.5 microg/m(3), respectively, of which toluene was the highest in all the sampling sites. Mean concentrations of all MAHCs in buses were statistically higher than those nearby bus stations (p<0.05). MAHCs concentrations in buses largely depend on vehicle conditions (including vehicle type, fuel type, interior decoration, etc.) and traffic conditions (mainly traffic density). Among the investigated buses, microbuses had the highest MAHCs level, while electric buses had the lowest. Buses driven in downtown had the highest MAHCs level, followed by those in suburban areas and tourist areas. The mean concentration ratio of toluene to benzene was 2.1+/-0.9, indicating that vehicle emission was the dominant source of MAHCs. Interior decorations, such as painting and surface coating, could also contribute to the MAHCs in the buses. The mean lifetime carcinogenic risks for passengers and bus drivers were 1.11x10(-5) and 4.00x10(-5), respectively, which were way above the limit set by USEPA. The health risk caused by MAHCs in bus microenvironment should be cautioned.

Health risk assessment for polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins and dibenzofurans, and polychlorinated naphthalenes in seafood from Guangzhou and Zhoushan, China.

This study determined the concentrations of organochlorine contaminants in common seafood in two Chinese coastal cities (Guangzhou and Zhoushan), and assessed the health risk due to the daily consumption of contaminated seafood. Twenty-six pooled samples, belonging to five food categories (fish, bivalves, shrimp, crab, and cephalopods), were purchased from local markets in Guangzhou and Zhoushan in 2003 and 2004. These samples were analyzed for total polychlorinated biphenyls (PCBs), non- and mono-ortho-PCBs (coplanar PCBs), polychlorinated naphthalenes (PCNs), and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs). The concentrations of total PCBs and coplanar PCBs in fish samples were higher in Guangzhou than in Zhoushan, while the levels of PCNs and PCDDs/DFs were comparable between the two cities. The total daily intake values of dioxin-like compounds were 1.05 and 0.86pg WHO-TEQ/kg body weight in Guangzhou and Zhoushan, respectively. Hazard ratios of non-cancer risk in the two cities were all less than unity.

Comparative assessment of coal tars obtained from 10 former manufactured gas plant sites in the eastern United States.

A comparative analysis was performed on eleven coal tars obtained from former manufactured gas plant sites in the eastern United States. Bulk properties analyzed included percent ash, Karl Fisher water content, viscosity and average molecular weight. Chemical properties included monocyclic- and polycyclic-aromatic hydrocarbon (PAH) concentrations, alkylated aromatic concentrations, and concentrations of aliphatic and aromatic fractions. It was found that there was at least an order-of-magnitude variation in all properties measured between the eleven coal tars. Additionally, two coal tars obtained from the same manufactured gas plant site had very different properties, highlighting that there can be wide variations in coal tar properties from different samples obtained from the same site. Similarities were also observed between the coal tars. The relative chemical distributions were similar for all coal tars, and the coal tars predominantly consisted of PAHs, with naphthalene being the single-most prevalent compound. The C(9-22) aromatic fraction, an indicator of all PAHs up to a molecular weight of approximately 276 gmole(-1), showed a strong power-law relationship with the coal tar average molecular weight (MW (ct)). And the concentrations of individual PAHs decreased linearly as MW (ct) increased up to ca. 1000 gmole(-1), above which they remained low and variable. Implications of these properties and their variation with MW (ct) on groundwater quality are discussed. Ultimately, while these similarities do allow generalities to be made about coal tars, the wide range of coal tar bulk and chemical properties reported here highlights the complex nature of coal tars.

Assessment of occupational exposure to VOCs at the Gantry gasoline Terminal.

The gasoline components dispersed in the workplace environment have direct impact on human health because of their carcinogenic and mutagenic potential. The volatile portion of these compounds generally consists of a mixture of monoaromatics such as benzene, toluene, ethylbenzene, xylenes and substituted benzene compounds. Investigation of levels of these chemicals at the petroleum liquid storage, and distribution facilities is of growing importance for assessing the occupational exposure of workers at these locations. A continuous monitoring was conducted at the Gantry Terminal of a refinery with portable samplers for determining 8-hr TWA at various locations involving petroleum liquid loading and distribution in road tank trucks, rail cars, and drums. After thermal desorption, the concentrations were determined in the laboratory with advanced Varian Model 2200GC/MS system. TVOCs level ranged between 0.10 to 1.97 mg/m3.The 8-hr TWA for benzene, toluene, and xylenes were low and within the limits for occupational exposure of gasoline components.

Verification of statistical-overlap theory in micellar electrokinetic chromatography.

The limited peak capacity of neutral compounds in micellar electrokinetic chromatography (MEKC) causes peak overlap in a simple 38-compound sample that is predicted by statistical-overlap theory (SOT). The low-concentration sample was prepared in-house from several compound classes to span the entire migration-time range and was resolved partially in a pH=7 phosphate buffer containing 50 mM sodium dodecyl sulfate. Peaks, singlets, doublets, and other multiplets were identified on the basis of known migration times and were counted at 13 voltages spanning 4 - 26 kV. These numbers agreed well with predictions of a simple SOT based on the assumption of an inhomogeneous Poisson distribution of migration times. Because the dispersion theory of MEKC is simple, the standard deviations of single-component peaks were modeled theoretically. As part of a new way to implement SOT, probability distributions of the numbers of peaks, singlets, and so on, were computed by Monte Carlo simulation. These distributions contain all theoretical information on peak multiplicity predictable by SOT and were used to evaluate the agreement between experiment and theory. The peak capacity of MEKC was calculated numerically and substituted into the simplest equations in SOT, affirming that peak overlap arises from limited peak capacity.

Oil spill in the Rio de la Plata estuary, Argentina: 1. Biogeochemical assessment of waters, sediments, soils and biota.

Aliphatic (ALI) and aromatic (ARO) hydrocarbon concentrations, composition and sources were evaluated in waters, sediments, soils and biota to assess the impact of approximately 1000 tons of oil spilled in Rio de la Plata coastal waters. Total ALI levels ranged from 0.4-262 microg/l in waters, 0.01-87 microg/g in sediments, 5-39 microg/g in bivalves, 12-323 microg/g in macrophytes to 948-5187 microg/g in soils. ARO varied from non-detected 10 microg/l, 0.01-1.3 mug/g, 1.0-16 microg/g, 0.5-6.9 microg/g to 22-67 microg/g, respectively. Offshore (1, 5, 15 km) waters and sediments were little affected and contained low background hydrocarbon levels reflecting an effective wind-driven transport of the slick to the coast. Six months after the spill, coastal waters, sediments, soils and biota still presented very high levels exceeding baseline concentrations by 1-3 orders of magnitude. UCM/resolved aliphatic ratio showed a clear trend of increasing decay: coastal waters (3.3) < macrophytes (6.7) < soils (9.4) < offshore sediments (13) < coastal sediments (17) < clams (52). All environmental compartments consistently indicated that the most impacted area was the central sector close to Magdalena city, specially low-energy stream embouchures and bays which acted as efficient oil traps. The evaluation of hydrocarbon composition by principal component analysis indicated the predominance of biogenic (algae, vascular plant cuticular waxes), background anthropic, pyrogenic and diagenetic hydrocarbons, offshore and in non-impacted coastal sites. In contrast, polluted stations presented petrogenic signatures characterized by the abundance of isoprenoids, low molecular weight n-alkanes and methylated aromatics in different stages of alteration. The petrogenic/biogenic ratio ( n-C23) and petrogenic/pyrogenic relationship (methylated/unsubstitued PAH) discriminated the samples according to the different degree of impact. The following paper present the results of the study of the progress of hydrocarbon disappearance in sediments and soils 13 and 42 months after the spill.

An initial assessment of the use of gradient elution in microemulsion and micellar liquid chromatography.

Novel microemulsion and micellar HPLC separations have been achieved using gradient elution and columns packed with reverse phase material. Initial attempts at gradient microemulsion liquid chromatography proved impossible on use of a microemulsion successfully used in capillary electrophoresis. Optimisation of the microemulsion composition allowed the generation of stable microemulsions to achieve separations in HPLC. The novel use of organic-solvent micellar chromatography in gradient elution mode was shown to give efficient separations. A range of efficient separations of pharmaceuticals and related impurities were obtained. Acidic, basic, and neutral solutes were resolved covering a wide range of water solubilities and polarities. Elution times were in the order of 4-15 minutes. Separations were briefly compared to those accomplished with a micellar HPLC system. It is proposed that gradient elution in both microemulsion and micellar HPLC can be regarded as a highly successful means of achieving resolution of complex mixtures and should be considered for routine analysis and further investigation.