Transport of volatile chlorinated hydrocarbons in unsaturated aggregated media

Transport of volatile hydrocarbons in soils is largely controlled by interactions of vapours with the liquid and solid phase. Sorption on solids of gaseous or dissolved comPounds may be important. Since the contact time between a chemical and a specific sorption site can be rather short, kinetic or mass-transfer resistance effects may be relevant. An existing mathematical model describing advection and diffusion in the gas phase and diffusional transport from the gaseous phase into an intra-aggregate water phase is modified to include linear kinetic sorption on ps-solid and water-solid interfaces. The model accounts for kinetic mass transfer between all three phases in a soil. The solution of the Laplace-transformed equations is inverted numerically. We performed transient column experiments with 1,1,2-Trichloroethane, Trichloroethylene, and Tetrachloroethylene using air-dry solid and water-saturated porous glass beads. The breakthrough curves were calculated based on independently estimated parameters. The model calculations agree well with experimental data. The different transport behaviour of the three compounds in our system primarily depends on Henry's constants.

The quest for planarizing distortions in hydrocarbons: two stereoisomeric 4.5.5.5 fenestranes

According to semiempirical calculations the planarizing distortions in the central C(C)4 substructure of fenestranes, represented as 1, can be enhanced by a variety of structural modifications. Based on these results we selected the 7-hydroxy-c,c,c,c- and c,t,c,c[4.5.5.5]fenestranones 13 and 16 as precursors for the introduction of a bridgehead double bond. The efficient synthesis of these precursors and their chemical transformations are reported. Attempts to activate the hydroxyl group in 16 for introduction of a bridgehead double bond led to the rearrangement of the [4.5.5.5]fenestrane to a triquinacane skeleton. (C) 2011 Elsevier Ltd. All rights reserved.

Occurrence, finger printing and ecological risk assessment of polycyclic aromatic hydrocarbons (PAHs) in the Chenab River, Pakistan

Seventeen polycyclic aromatic hydrocarbons (PAHs) were studied in surface waters (including particulate phase) from the Chenab River, Pakistan and ranged from 289-994 and 437-1290 ng l-1 in summer and winter (2007-09), respectively. Concentrations for different ring-number PAHs followed the trend: 3-rings > 2-rings > 4-rings > 5-rings > 6-rings. The possible sources of PAHs are identified by calculating the indicative ratios; appropriating petrogenic sources of PAHs in urban and sub-urban regions with pyrogenic sources in agricultural region. Factor analysis based on principal component analysis identified the origins of PAHs from industrial activities, coal and trash burning in agricultural areas and municipal waste disposal from surrounding urban and sub-urban areas via open drains into the riverine ecosystem. Water quality guidelines and toxic equivalent factors highlighted the potential risk of low molecular weight PAHs to the aquatic life of the Chenab River. The flux estimated for PAHs contaminants from the Chenab River to the Indus River was >50 tons/year.

Aspiration toxicology of hydrocarbons and lamp oils studied by in vitro technology

Medical literature regularly reports on accidental poisoning in children after aspiration of combustibles such as lamp oils which usually contain hydrocarbons or rape methyl esters (RMEs). We aimed to analyze the toxic potential of alkanes and different combustible classes in vitro with regard to biologic responses and mechanisms mediating toxicity. Two different in vitro models were used, i.e. (i) a captive bubble surfactometer (CBS) to assess direct influence of combustibles on biophysical properties of surfactant film and (ii) cell cultures (BEAS-2B and R3/1 cells, primary macrophages, re-differentiated epithelia) closely mimicking the inner lung surface. Biological endpoints included cell viability, cytotoxicity and inflammatory mediator release. CBS measurements demonstrate that combustibles affect film dynamics, i.e. the surface tension/area characteristics during compression and expansion, in a dose and molecular chain length dependent manner. Cell culture results confirm the dose dependent toxicity. Generally, cytotoxicity and cytokine release are higher in short-chained alkanes and hydrocarbon-based combustibles than in long-chained substances, e.g. highest inducible cytotoxicity in BEAS-2B was for hexane 84.6%, decane 74% and hexadecane 30.8%. Effects of RME-based combustibles differed between the cell models. Our results confirm data from animal experiments and give new insights into the mechanisms underlying the adverse health effects observed.

Occupational exposure to polycyclic aromatic hydrocarbons and DNA damage by industry: a nationwide study in Germany

Exposure to polycyclic aromatic hydrocarbons (PAH) and DNA damage were analyzed in coke oven (n = 37), refractory (n = 96), graphite electrode (n = 26), and converter workers (n = 12), whereas construction workers (n = 48) served as referents. PAH exposure was assessed by personal air sampling during shift and biological monitoring in urine post shift (1-hydroxypyrene, 1-OHP and 1-, 2 + 9-, 3-, 4-hydroxyphenanthrenes, SigmaOHPHE). DNA damage was measured by 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodGuo) and DNA strand breaks in blood post shift. Median 1-OHP and SigmaOHPHE were highest in converter workers (13.5 and 37.2 microg/g crea). The industrial setting contributed to the metabolite concentrations rather than the air-borne concentration alone. Other routes of uptake, probably dermal, influenced associations between air-borne concentrations and levels of PAH metabolites in urine making biomonitoring results preferred parameters to assess exposure to PAH. DNA damage in terms of 8-oxo-dGuo and DNA strand breaks was higher in exposed workers compared to referents ranking highest for graphite-electrode production. The type of industry contributed to genotoxic DNA damage and DNA damage was not unequivocally associated to PAH on the individual level most likely due to potential contributions of co-exposures.

Polycyclic aromatic hydrocarbons (PAHs) and their polar derivatives (oxygenated PAHs, azaarenes) in soils along a climosequence in Argentina

We evaluated the effects of soil properties and climate on concentrations of parent and oxygenated polycyclic aromatic compounds (PAHs and OPAHs) and azaarenes (AZAs) in topsoil and subsoil at 20 sites along a 2100-km north (N)–south (S) transect in Argentina. The concentrations of Σ29PAHs, Σ15OPAHs and Σ4AZAs ranged 2.4–38 ng g− 1, 0.05–124 ng g− 1 and not detected to 0.97 ng g− 1, respectively. With decreasing anthropogenic influence from N to S, low molecular weight PAHs increasingly dominated. The octanol–water partitioning coefficients correlated significantly with the subsoil to topsoil concentration ratios of most compounds suggesting leaching as the main transport process. Organic C concentrations correlated significantly with those of many compounds typical for atmosphere–soil partitioning. Lighter OPAHs were mainly detected in the S suggesting biological sources and heavier OPAHs in the N suggesting a closer association with parent-PAHs. Decreasing alkyl-naphthalene/naphthalene and 9,10-anthraquinone (9,10-ANQ)/anthracene ratios from N to S indicated that 9,10-ANQ might have originated from low-temperature combustion.

A 2600-year record of past polycyclic aromatic hydrocarbons (PAHs) deposition at Holzmaar (Eifel, Germany)

Polycyclic aromatic hydrocarbons (PAHs) are a proxy for climate- and human-related historical fire activity which has rarely been used beyond 1800 AD. We explored the concentration and composition patterns of PAHs together with other proxies (charcoal, C, N, S, δ13C, δ15N, and δ34S) in a sediment core of Holzmaar as indicators of variations in climate and anthropogenic activity over the past 2600 years. The concentrations of pyrogenic PAHs remained low (< 500 ng g− 1) from the pre-Roman Iron Age (600 BC) until the first significant increases to ca. 1000–1800 ng g− 1 between 1700 and 1750 AD related to regional iron production. The highest increases in pyrogenic PAH concentrations occurred with industrialization peaking in the 1960s. PAH concentrations in most recent sediments decreased to pre-industrial levels because of emission control measures and the switch from coal to oil and gas as major fuel sources. Fluxes of PAHs (mg km− 2 yr− 1) increased in the order Migration Period and Early Middle Ages < pre-Roman Iron Ages < Roman era < High Middle Ages and Renaissance < pre-industrial modern period < industrial modern period. The changes of PAHs fluxes in pre-industrial times parallel known changes in local, regional and continental anthropogenic activity and climatic variations or their interactions across these historical periods. Perylene, a mainly biologically produced compound, was the dominant PAH in pre-industrial times. The Migration Period and the Early Middle Ages witnessed the most profound and simultaneous changes to the sedimentary organic matter properties in the past 2600 years including the lowest PAH fluxes because of reduced human activity and more negative δ13C and δ15N values probably in response to colder and wetter conditions.

First intercomparison study on the analysis of oxygenated polycyclic aromatic hydrocarbons (oxy-PAHs) and nitrogen heterocyclic polycyclic aromatic compounds (N-PACs) in contaminated soil

Oxygenated polycyclic aromatic hydrocarbons (oxy-PAHs) and nitrogen heterocyclic polycyclic aromatic compounds (N-PACs) are toxic, highly leachable and often abundant at sites that are also contaminated with PAHs. However, due to lack of regulations and standardized methods for their analysis, they are seldom included in monitoring and risk-assessment programs. This intercomparison study constitutes an important step in the harmonization of the analytical methods currently used, and may also be considered a first step towards the certification of reference materials for these compounds. The results showed that the participants were able to determine oxy-PAHs with accuracy similar to PAHs, with average determined mass fractions agreeing well with the known levels in a spiked soil and acceptable inter- and intra-laboratory precisions for all soils analyzed. For the N-PACs, the results were less satisfactory, and have to be improved by using analytical methods more specifically optimized for these compounds.

Microbial formation and degradation of oxygen-containing polycyclic aromatic hydrocarbons (OPAHs) in soil during short-term incubation

We tested whether OPAHs were formed during 19-wk incubation of a fertile soil at optimum moisture in the dark. The soil had initial mean (±s.e., n = 3) concentrations of 22 ± 1.7 (Σ28PAHs) and 4.2 ± 0.34 μg g−1 (Σ14OPAHs). After 19 wk, individual PAH and OPAH concentrations had decreased by up to 14 and 37%, respectively. Decreases in % of initial concentrations were positively correlated with their KOW values for PAHs (r = 0.48, p = 0.022) and 9 OPAHs (r = 0.78, p = 0.013) but negatively, albeit not significantly, for 5 OPAHs (r = −0.75, p = 0.145) suggesting net formation of some OPAHs. The latter was supported by significantly increasing 1-indanone/fluorene ratios while the other OPAH to parent-PAH ratios remained constant or tended to increase. We conclude that OPAHs are formed in soils during microbial turnover of PAHs in a short time.

Oxygenated polycyclic aromatic hydrocarbons and azaarenes in urban soils: A comparison of a tropical city (Bangkok) with two temperate cities (Bratislava and Gothenburg)

Environmental conditions in the tropics favor the formation of polar polycyclic aromatic compound (polar PACs, such as oxygenated PAHs [OPAHs] and azaarenes [AZAs]), but little is known about these hazardous compounds in tropical soils. The objectives of this work were to determine (i) the level of contamination of soils (0–5 and 5–10 cm layers) from the tropical metropolis of Bangkok (Thailand) with OPAHs and AZAs and (ii) the influence of urban emission sources and soil properties on the distribution of PACs. We hypothesized that the higher solar insolation and microbial activity in the tropics than in the temperate zone will lead to enhanced secondary formation of OPAHs. Hence, OPAH to related parent-PAH ratios will be higher in the tropical soils of Bangkok than in temperate soils of Bratislava and Gothenburg. The concentrations of ∑15OPAHs (range: 12–269 ng g−1) and ∑4AZAs (0.1–31 ng g−1) measured in soils of Bangkok were lower than those in several cities of the industrialized temperate zone. The ∑15OPAHs (r = 0.86, p < 0.01) and ∑4AZAs (r = 0.67, p < 0.01) correlated significantly with those of ∑20PAHs highlighting similar sources and related fate. The octanol–water partition coefficient did not explain the transport to the subsoil, indicating soil mixing as the reason for the polar PAC load of the lower soil layer. Data on PAC concentrations in soils of Bratislava and Gothenburg were taken from published literature. The individual OPAH to parent-PAH ratios in soils of Bangkok were mostly higher than those of Bratislava and Gothenburg (e.g. 9-fluorenone/fluorene concentration ratio was 12.2 ± 6.7, 5.6 ± 2.4, and 0.7 ± 02 in Bangkok, Bratislava and Gothenburg soils, respectively) supporting the view that tropical environmental conditions and higher microbial activity likely lead to higher OPAH to parent-PAH ratios in tropical than in temperate soils.