PAHs and hopanes in the surface sediments of Qatar coast and their ecological risks: Comparison with regional and global coastal regions.

The distribution, characteristics, sources and ecological risks of polycyclic aromatic hydrocarbons (PAHs) and hopanes in the surface sediments collected along the Qatar coast were investigated. Concentration of ∑14PAHs and hopanes ranged between 0.076 and 7.04 ng g-1 (mean: 2.60 ng g-1), 100 and 700 ng g-1 (mean: 205 ng g-1), respectively. Sediment samples were dominated by high molecular weight PAHs composition (4-6 rings). Diagnostic ratios of PAH concentrations showed both petrogenic and pyrogenic origins of PAHs, with a higher percentage of pyrogenic sources. The ecological risk levels of PAHs were estimated using sediment quality guidelines (SQG), mean probable effect level quotient values (PEL-Q), carcinogenic toxic equivalent quantity (TEQ), and risk quotient (RQ) evaluation methods. The calculated TEQ values (0.00012-0.85 ng g-1) were lesser than those in other locations around the globe, and were also within the safe level (600 ng g-1) suggested by the Canadian soil quality guidelines.

Occurrence, distribution and sources of petroleum contamination in reef-associated sediments of the Gulf of Mannar, India.

The distribution of saturated hydrocarbons and polycyclic aromatic hydrocarbons (PAHs) was assessed in superficial sediment samples collected from Mandapam island groups, Gulf of Mannar, India. The hydrocarbon distribution pattern and the n-alkane indices (e.g., carbon preference index (CPI) and natural n-alkanes ratio (NAR)) were deployed to differentiate between the biogenic and anthropogenic sources. Petroleum pollution was indicated by the pristane/phytane ratio close to 1. Presence of a prominent unresolved complex mixture (UCM) as well as hopane concentrations further supported this assertion. The evaluation of petrogenic sources of contamination were also comprehended by various diagnostic ratios of PAHs. The sites associated with shipping activities, tourism, and located near the mainland and accessible portions of the islands exhibited high petroleum contamination. Correlation analysis underlines the significance of combining petroleum-specific marker compounds and diagnostic ratios to improve the assessment of human influence on marine ecosystems.

Simple multi-residue analysis of persistent organic pollutants and molecular tracers in atmospheric samples.

We present a simple, selective and sensitive analytical method to quantitatively determine a wide range of halogenated persistent organic pollutants and molecular tracers in atmospheric samples. Identification and quantification was carried out by high-resolution gas chromatography, hyphenated with low-resolution mass spectrometry operating in electron impact (EI) and electron capture negative ionization (ECNI) mode. Optimization on a number of instrumental parameters was conducted to obtain ultra-trace detection limits, in the range of few fg/m3 for organohalogen compounds. Repeatability and reproducibility of the method was thoroughly evaluated. The analysis was validated with standard reference materials and successfully applied to actual atmospheric samples. The proposed multi-residue method provides a precise, affordable and practical procedure of sample analysis for environmental research laboratories with conventional instrumentation on a routine basis.•A simple combination of alumina, florisil and silica gel adsorbents was applied to sufficiently isolate polychlorinated biphenyls, organochlorine pesticides, polycyclic aromatic hydrocarbons, long chain n-alkanes, hopanes and steranes.•Full elution was achieved in two successive fractions, using small volumes of n-hexane and n-hexane/dichloromethane to recover all target substances.•To maximize analytical response, optimization was applied for three operating parameters in ECNI mode: i) ion source temperature; ii) emission current; and iii) electron energy.

A small-scale neutral alumina column chromatography method for carbon isotope determination of hopanes in crude oils or rock extracts.

This paper presents a small-scale column chromatography method for separating hopanes in crude oil or rock extracts using neutral alumina as a solid phase adsorbent and a Pasteur pipette as a separation device. Three oil samples were selected to study the effect of solid phase adsorbent type and column length on the separation of hopanes. The oil samples were eluted with mixed reagents (V hexane: V petroleum ether = 8:2) and collected at intervals of 0.5 ml. Ten Fractions were collected and tested for the compounds using GC-MS. A quantitative approach was used to reveal distribution characteristics of compounds in each eluted Fraction. Experimental results showed that 100-200 um neutral alumina exhibited significant differences in the adsorptive capacity of biomarkers from oil samples and rock extracts. The elution order of the biomarkers in the chromatographic column (the length is 180 mm) was n-alkanes, steranes and hopanes. The separation of hopanes could be realized by collecting the eluted Fractions 4 and 5. Compared with the urea complexation, the purity of hopanes separated by column chromatography was higher. The concentration of n-alkanes (nC16-nC34) could be reduced from 1.99 to 4.83 mg/ml to 0.79-0.94 mg/ml, and the content of steranes can be reduced from the original 12% to 0.45%. Residual n-alkanes and steranes were not visible in the GC-MS detection. The Total Ion Chromatography (TIC) of hopanes was consistent with the distribution characteristics of the m/z191 mass chromatogram. The isolated hopanes could meet the detection requirements of isotope ratio mass spectrometry. The C29Ts/C29αß ratio of hopanes decreased gradually from 1.63 to 0.73 as the column length increased. It is speculated that the variation of the C29Ts/C29αß ratio is not only affected by maturity but also by the oil and gas migration. This method is a new attempt in the field of compound purification and can be widely used in the study of stable carbon isotopes of hopanes monomeric hydrocarbons.

The fingerprint stability of the biomarker hopanes and steranes in soot emissions from in-situ burning of oil.

The behavior of emissions is an important concern of in-situ burning (ISB) of spilled oils. In particular, the heavy soot originated from ISB can negatively impact the atmospheric environment. To track the behavior of ISB soot, the conservative biomarkers, such as hopanes and steranes, can be potentially used. In this study, the stability of chemical fingerprints of hopanes and steranes in the ISB soot were investigated based on the burning of two different types of oils, including one ultra-light condensate (i.e., surrogate Sanchi condensate) and one heavy oil. The results indicate that the chromatographic patterns and diagnostic ratios of hopanes and steranes in the ISB soot emissions almost remain identical to their corresponding source oils, proving the various oil source identification of ISB soot can be realized. This work attempts to provide novel insights into the application of biomarkers in the management of ISB emissions.

An Investigation into Which Methods Best Explain Children's Exposure to Traffic-Related Air Pollution.

There have been several methods employed to quantify individual-level exposure to ambient traffic-related air pollutants (TRAP). These include an individual's residential proximity to roads, measurement of individual pollutants as surrogates or markers, as well as dispersion and land use regression (LUR) models. Hopanes are organic compounds still commonly found on ambient particulate matter and are specific markers of combustion engine primary emissions, but they have not been previously used in personal exposure studies. In this paper, children's personal exposures to TRAP were evaluated using hopanes determined from weekly integrated filters collected as part of a personal exposure study in Windsor, Canada. These hopane measurements were used to evaluate how well other commonly used proxies of exposure to TRAP performed. Several of the LUR exposure estimates for a range of air pollutants were associated with the children's summer personal hopane exposures (r = 0.41-0.74). However, all personal hopane exposures in summer were more strongly associated with the length of major roadways within 500 m of their homes. In contrast, metrics of major roadways and LUR estimates were poorly correlated with any winter personal hopanes. Our findings suggest that available TRAP exposure indicators have the potential for exposure misclassification in winter vs. summer and more so for LUR than for metrics of major road density. As such, limitations are evident when using traditional proxy methods for assigning traffic exposures and these may be especially important when attempting to assign exposures for children's key growth and developmental windows. If long-term chronic exposures are being estimated, our data suggest that measures of major road lengths in proximity to homes are a more-specific approach for assigning personal TRAP exposures.

Occurrences and Potential Sources of Halogenated Polycyclic Aromatic Hydrocarbons Associated with PM2.5 in Mumbai, India.

Occurrences of chlorinated and brominated polycyclic aromatic hydrocarbons (ClPAHs and BrPAHs, respectively) in fine aerosol particulate matter <2.5 µm in diameter were investigated in urban and suburban sites in Mumbai, India; and the possible sources from association with indicators, such as hopanes, steranes, and trace elements are discussed. The mean concentrations of total ClPAHs and BrPAHs were 0.54 and 0.25 ng/m3 in the urban site and 0.16 and 0.02 ng/m3 in the suburban site during the campaign, respectively. The variations in total Cl-/BrPAH concentrations showed a similar trend between the urban and suburban sites, whereas the composition profiles varied in each air sample. The relationships between the concentrations among individual compounds in the urban site suggest that dominant sources of Cl-/BrPAHs could be common to PAHs but not in the suburban site. Principal component analysis using the data set of certain compounds showed that Cl-/BrPAH concentrations in urban and suburban sites are occasionally driven by specific sources of either coal combustion or traffic emissions. In contrast, most air samples during the campaign could be attributed to a mix of those sources. Environ Toxicol Chem 2022;41:312-320. © 2021 SETAC.

Investigation of aliphatic hydrocarbons in core sediments of Brunei Bay, East Malaysia.

The distribution of aliphatic hydrocarbons in three sediment cores from Brunei Bay was investigated in order to understand their sources and the biogeochemical processes of these hydrocarbons. The total concentrations of C15 to C37n-alkanes ranged from 0.70 to 16.5 µg g-1. Traces of hopanes with C29-C31 carbon homologs were detected in the study area. The carbon preference index (CPI15-37) ranged from 1.23 to 3.42 coupled with the natural n-alkane ratio (NAR19-32) ratios (1.52 to 5.34), and the presence of unresolved complex mixtures and hopanes, suggested slight contamination by anthropogenic hydrocarbons, presumably derived from activities along the coasts. The presence of C27 trisnorhopene and diploptene, as well as their association with long-chain and short-chain n-alkanes, revealed a depositional environment of organic matter in the sediment cores.

Environmental fate of petroleum biomarkers in Deepwater Horizon oil spill residues over the past 10 years.

The long-term fate of three groups of petroleum biomarker compounds (terpanes, steranes, and triaromatic steranes) was investigated in the Deepwater Horizon (DWH) oil spill residues collected from Alabama (USA) beaches over the past 10 years. This is the first study to investigate the long-term fate of these three groups of petroleum biomarkers in DWH oil spill samples over 10 years. We employed the highly recalcitrant C30 αß-hopane as an internal biomarker to quantify the degradation levels of different biomarker compounds, and also to estimate the overall weathering levels of DWH oil spill residues. The data show that four lower molecular weight tricyclic terpanes (TR21, TR22, TR23, and TR24), three lower molecular weight steranes (S21, S22, and C27), and all triaromatic steranes degraded over the 10-year study period. All other terpanes (including hopanes) and steranes remained recalcitrant. There have been contradicting literature data on the degradation levels of homohopanes, and this field study demonstrates that all the homohopanes remained recalcitrant after 10 years of natural weathering. Our data also show that despite some degradation, the relative diagnostic ratios of the biomarkers remained stable for all three groups of biomarkers over the 10-year period.

Influence of boiler output and type on gaseous and particulate emissions from the combustion of coal for residential heating.

The study describes gaseous and particulate emissions from the combustion of two types of coal (hard and brown) in three types of boilers (one modern-type and two old-type boilers) used for residential heating. The importance of the heat outputs (nominal and two reduced outputs) for the emission of pollutants was also studied. Three outputs (95-108%, 58-73% and 26-50%) covered the expected operation of these boilers in real households under different outdoor air temperatures in the winter. Gaseous components (NOx, SO2, CO, CO2, OGC) and particulate organic compounds (n-alkanes, polycyclic aromatic hydrocarbons, hopanes) were determined in the emissions. In general, the emission factors (EFs) of the products of incomplete combustion were higher from the combustion of coal in old-type boilers than from that in the modern-type boilers. The EFs of particulate matter varied between 11.6 and 17.0 g kg-1 (hard coal, the oldest-type boiler), and 0.290 and 0.544 g kg-1 (brown coal, the modern-type boiler). The trends between the EFs of particulate organic compounds and the outputs of boilers were observed only with the automatic boiler (modern-type boiler). Similar trends for old-type boilers were not observed, probably due to the high instability of the combustion process as a result of the old construction of these boilers. Diagnostic ratios of the PAHs and the homohopane index, used for source apportionment of particulate matter in ambient air, were calculated. While the calculated homohopane indexes were similar to those reported in the literature, the calculated diagnostic ratios for PAHs related to coal combustion were different.

Hopane-type triterpenes from Cnidoscolus spinosus and their bioactivities.

Chemical investigation of the aerial parts of Cnidoscolus spinosus resulted in the isolation of relatively infrequent hopane-type triterpenes, 3ß-acetoxy-hop-22(29)-ene (1), first reported here as natural product, together with 3-oxo-hop-22(29)-ene (2), and 3ß-hydroxy-hop-22(29)-ene (3). ß-Amyrin palmitate and three phytosterols were also characterized. The structures of the compounds were established using spectroscopic methods, and those of 1 and 2 were confirmed by crystallographic analysis. Selected biological activities for the isolated hopane-type triterpenes were tested through a series of assays for determining the cytotoxic, anti-inflammatory, α-glucosidase inhibition and antiparasitic activities. Compounds 1-3 did not show cytotoxic activity, compound 1 displayed an important inhibitory effect in the mouse ear induced inflammation assay, and significantly inhibited the yeast α-glucosidase activity in vitro and in silico. Additionally, compounds 2 and 3 showed marginal activities against Trypanosoma cruzi and Leishmania mexicana. Therefore, the bioactivities of hopane-type triterpenes deserve further investigation, particularly their anti-inflammatory properties.

Discerning natural and anthropogenic organic matter inputs to salt marsh sediments of Ria Formosa lagoon (South Portugal).

Sedimentary organic matter (OM) origin and molecular composition provide useful information to understand carbon cycling in coastal wetlands. Core sediments from threors' Contributionse transects along Ria Formosa lagoon intertidal zone were analysed using analytical pyrolysis (Py-GC/MS) to determine composition, distribution and origin of sedimentary OM. The distribution of alkyl compounds (alkanes, alkanoic acids and alkan-2-ones), polycyclic aromatic hydrocarbons (PAHs), lignin-derived methoxyphenols, linear alkylbenzenes (LABs), steranes and hopanes indicated OM inputs to the intertidal environment from natural-autochthonous and allochthonous-as well as anthropogenic. Several n-alkane geochemical indices used to assess the distribution of main OM sources (terrestrial and marine) in the sediments indicate that algal and aquatic macrophyte derived OM inputs dominated over terrigenous plant sources. The lignin-derived methoxyphenol assemblage, dominated by vinylguaiacol and vinylsyringol derivatives in all sediments, points to large OM contribution from higher plants. The spatial distributions of PAHs (polyaromatic hydrocarbons) showed that most pollution sources were mixed sources including both pyrogenic and petrogenic. Low carbon preference indexes (CPI > 1) for n-alkanes, the presence of UCM (unresolved complex mixture) and the distribution of hopanes (C29-C36) and steranes (C27-C29) suggested localized petroleum-derived hydrocarbon inputs to the core sediments. Series of LABs were found in most sediment samples also pointing to domestic sewage anthropogenic contributions to the sediment OM.

Composition of organic compounds from low-temperature burning of lignite and their application as tracers in ambient air.

Levoglucosan, a product from thermal decomposition of cellulose, is widely known as an organic tracer of biomass burning, but has also been reported from coal smoke particulate matter (PM) including lignites. This study provides direct evidence that levoglucosan is generated not only during low-temperature burning/smoldering of xylite, but also from other lignite types including detritic and detroxylitic brown coals from Poland. Moreover, only trace amounts of mannosan and galactosan have been detected in PM of lignite smoke. The hopanes in lignite smoke PM comprise the thermodynamically unstable ßß-hopanes and hopenes, with values of the homohopane index 22S/(22S + 22R) ranging from 0.02 to 0.12. This is characteristic for immature organic matter, and combined with the presence of anhydrosaccharides can be used as tracers for lignite combustion in ambient air. Furthermore, almost all Miocene lignite smoke PM samples contain α-, ß-, γ-, and δ-tocopherols, and prist-1-ene. This is the first report of the occurrence of all four tocopherol isomers in the geological record (in lignite extracts) and in lignite smoke PM samples. Lower α-tocopherol is observed for the lignite burn-test samples than in the corresponding lignite extracts, probably due to partial chain degradation to prist-1-ene during combustion.

Petroleum biomarkers as tracers of low-level chronic oil contamination of coastal environments: A systematic approach in a subtropical mangrove.

Petroleum biomarkers (hopanes, terpanes and steranes) are frequently assessed in estuarine sediments as tracers of oil input. In order to compare distinct patterns of hydrocarbon accumulation in mudflats, salt marsh and mangrove, sediments from two transects (control and impacted areas) were sampled in Paranaguá Bay, SW Atlantic. Concentrations of n-alkanes, polycyclic aromatic hydrocarbons (PAHs) and petroleum biomarkers (hopanes, terpanes and steranes) were determined, as well as bulk parameters (TOC, grain size and δ13C). N-alkanes concentrations were similar between control and impacted sites (respectively, 3.03 ±â€¯1.20 µg g-1 and 4.11 ±â€¯3.02 µg g-1) and reflected a high biogenic input. Conversely, PAHs and petroleum biomarker concentrations were three to six times higher in impacted site than the control site (respectively, 60.4 ±â€¯23.3 ng g-1 and 22.0 ±â€¯25.0 ng g-1 for PAHs and 197.7 ±â€¯51.8 ng g-1 and 40.2 ±â€¯32. ng g-1 for hopanes). Despite these differences, concentrations were lower than those reported for highly impacted areas worldwide. Diagnostic ratios and hydrocarbon parameters (e.g. total PAHs and total petroleum biomarkers) helped to distinguish human impact in the ecological zones, suggesting different sources and/or levels of weathering, confirmed by ANOVA tests. TOC played a fundamental role to the concentration of hydrocarbons, showing similar distributions along the transects. Petroleum biomarkers could clearly indicate the preferential sites of deposition and assign different levels of anthropic contamination by hydrocarbons, thus providing clear information about the chronic petroleum pollution in coastal sediments.

Comparison of emissions of gaseous and particulate pollutants from the combustion of biomass and coal in modern and old-type boilers used for residential heating in the Czech Republic, Central Europe.

The chemical composition of emissions from old-type (an overfire boiler, a boiler with down-draft combustion) and modern-type (an automatic and a gasification boiler) boilers was compared. The boilers were operated with different fuels (brown and hard coal, wet and dry wood, wood pellets and brown coal briquettes) with reduced output (40-60%). The emissions were characterized by the contents of gaseous components (NOx, SO2, CO, CO2, OGC); and particulate organic compounds (alkanes, polycyclic aromatic hydrocarbons, saccharides), including organic markers (monosaccharide anhydrides, diterpenoids, methoxyphenols, hopanes), which are used for source apportionment of particulate matter in ambient air. In general, emissions of the products of incomplete combustion (CO, particles, polycyclic aromatic hydrocarbons) were higher from the combustion of solid fuels in old-type boilers than from that in modern-type boilers. The modern-type (especially automatic) boilers were the most environmentally friendly. The highest concentrations of particulate matter (81.6-89.4 g kg-1) and particulate organic compounds (sum of PAHs: 225-275 mg kg-1) including organic markers were found in emissions from old-type (overfire) boilers, especially with the combustion of brown and hard coal. Characteristic ratios of selected organic compounds/markers applied for source identification were calculated. Computed characteristic ratios for monosaccharide anhydrides (biomass combustion) agreed with values in the literature. Homohopane indexes, frequently used for identification of coal combustion, and other characteristic ratios for PAHs, were different from the literature data. In our opinion, characteristic ratios for PAHs are not suitable for use in source apportionment.

Oil pollution in soils and sediments from the Northern Peruvian Amazon.

Oil has been extracted from the Northern Peruvian Amazon for over four decades. However, few scientific studies have assessed the impacts of such activities in the environment and health of indigenous communities in the region. We have investigated the occurrence of petrogenic hydrocarbon pollution in soils and sediments from areas favoured as hunting or fishing grounds by local indigenous inhabitants. The study was conducted in one of the most productive oil blocks in Peru, located in the headwaters of the Amazon river. Soils and river sediments, in the vicinity of oil extraction and processing infrastructure, contained an oil pollution signature as attested by the occurrence of hopanes and steranes. Given the lack of any other significant source of oil pollution in the region, the sources of hydrocarbons are likely to be the activities of the oil industry in the oil block, from voluntary discharges or accidental spills. Spillage of produced water was commonplace until 2009. Moreover, petrogenic compounds were absent in control samples in sites far removed from any oil infrastructure in the oil block. Our findings suggest that wildlife and indigenous populations in this region of the Amazon are exposed to the ingestion of oil polluted soils and sediments. The data obtained supports previous claims that the local spillage of oil and produced waters in the water courses in the Corrientes and Pastaza basins could have eventually reached the main water course of the Amazon.

Identification of sources of tar balls deposited along the Southwest Caspian Coast, Iran using fingerprinting techniques.

In 2012, a significant number of tar balls occurred along the Southwest coasts of the Caspian Sea (Iran). Several oil fields of Turkmenistan, Azerbaijan and Iran might be sources of oil spills and lead to the formation of these tar balls. For source identification, 6 tar ball samples were collected from the Southwest beaches of the Caspian Sea and subjected to fingerprint analysis based on the distribution of the source-specific biomarkers of pentacyclic tri-terpanes and steranes. Comparing the diagenic ratios revealed that the tar balls were chemically similar and originated from the same source. Results of double ratio plots (e.g., C29/C30 versus ∑C31-C35/C30 and C28 αßß/(C27 αßß+C29 αßß) versus C29 αßß/(C27 αßß+C28 αßß)) in the tar balls and oils from Iran, Turkmenistan and Azerbaijan indicated that the tar balls might be the result of spills from Turkmenistan oil. Moreover, principle component analysis (PCA) using biomarker ratios on the tar balls and 20 crude oil samples from different wells of Azerbaijan, Iran and Turkmenistan oils showed that the tar balls collected at the Southwest beaches are highly similar to the Turkmenistan oil but one of the Azerbaijan oils (from Bahar field oils) was found to be also slightly close to the tar balls. The weathering characterizations based on the presence of UCM (unresolved complex mixture) and low/high molecular weight ratios (L/H) of alkanes and PAHs indicated the tar ball samples have been significantly influenced by natural weathering processes such as evaporation, photo-degradation and biodegradation. This is the first study of its kind in Iran to use fingerprinting for source identification of tar balls.

Non-polar organic compounds in marine aerosols over the northern South China Sea: Influence of continental outflow.

Filter samples of total suspended particle (TSP) collected during a cruise campaign over the northern South China Sea (SCS) from September to October 2013 were analyzed for non-polar organic compounds (NPOCs) as well as organic carbon (OC), elemental carbon (EC) and water-soluble ions. A total of 115 NPOCs species in groups of n-alkanes, polycyclic aromatic hydrocarbons (PAHs), iso-/antiso-alkanes, hopanes, steranes, methylalkanes, branched alkanes, cycloalkanes, alkenes and phthalates were detected. The characteristics of NPOCs in marine TSP samples were investigated to understand the sources from the Asian continent and other regions. The concentrations of total NPOCs ranged from 19.8 to 288.2 ng/m(3) with an average of 87.9 ng/m(3), which accounted for 0.8-1.7% (average 1.0%) of organic matter (OM). n-Alkanes was the predominant group, accounting for 43.1-79.5%, followed by PAHs (5.5-44.4%) and hopanes (1.6-11.4%). We found that primary combustion (biomass burning/fossil fuel combustion) was the dominant source for the majority of NPOCs (89.1%). Biomass burning in southern/southeastern China via long-range transport was proposed to be a major contributor of NPOCs in marine aerosols over the northern SCS, suggested by the significant correlations between nss-K(+) and NPOCs groups as well as the analysis of air mass back-trajectory and fire spots. For the samples with strong continental influence, the strong enhancement in concentrations of n-alkanes, PAHs, hopanes and steranes were attributed to fossil fuel (coal/petroleum) combustion. In addition, terrestrial plants waxes were another contributor to NPOCs.

Characteristics of hopanoid hydrocarbons in ambient PM10 and motor vehicle emissions and coal ash in Taiyuan, China.

Hopanoid hydrocarbon content in ambient particulate matter (PM) of less than or equal to 10 µm aerodynamic diameter (PM10) was sampled at seven sites representative of different functional districts, and measured by gas chromatography-mass spectrometry. 17α(H),21ß(H)-hopane (C30αß) and 17α(H),21ß(H)-30-norhopane (C29αß) were dominant in all samples. Hopanes in motor vehicle emissions from various fuel-type engines (gasoline, diesel and natural gas) and coal ash were qualitatively measured, and the amount of C30αß was about two to three times greater than that of C29αß. Distinct seasonal variations (winter/summer differences) were observed at higher concentrations (45.54-108.29 ng/m(3)) of total hopanes in winter and lower (2.59-28.26 ng/m(3)) in summer. There were also clear spatial variations of hopanes in Taiyuan, with samples with greater hopane concentrations in downtown areas, but less in summer. The spatial distribution reversed in winter. Distributions and relative abundances of selected hopanes from PM10 and source emissions indicated that in summer, vehicle exhaust was the dominant fossil fuel combustion source (C30αß was >C29αß), and that the contribution of coal combustion was slightly greater at suburban sites. However, the contribution of coal combustion sources increased significantly at all sites in winter, especially in suburban areas, where C29αß exceeded C30αß. Hopanoid indexes revealed a classification of vehicle exhaust and coal combustion emissions in PM10. The results imply that during rapid urbanization, it is crucial to strengthen the construction of infrastructure such as central heating in new city districts and to increase the use of natural gas instead of residential coal burning.

Focused ultrasound solid-liquid extraction for the determination of organic biomarkers in beachrocks.

Beachrocks are consolidated coastal sedimentary formations resulting mainly from the relative rapid cementation of beach sediments by different calcium carbonate polymorphs. Although previous works have already studied the elemental composition and the mineral phases composing these cements, few of them have focused their attention on the organic matter present therein. This work describes an extraction methodology based on focused ultrasound solid-liquid extraction (FUSLE), followed by analysis using large volume injection (LVI) in a programmable temperature vaporizer (PTV) combined with gas chromatography-mass spectrometry (GC-MS) in order to determine organics such as polycyclic aromatic hydrocarbons (PAHs) and biomarkers (hopanes), which can increase and confirm the information obtained so far. This goal has been achieved after the optimization of the main parameters affecting the extraction procedure, such as, extraction solvent, FUSLE variables (amplitude, extraction time and pulse time) and also variables affecting the LVI-PTV (vent time, injection speed and cryo-focusing temperature). The developed method rendered results comparable to traditional extraction methods in terms of accuracy (77-109%) and repeatability (RSD<23%). Finally, the analyses performed over real beachrock samples from the Bay of Biscay (Northern Spain) revealed the presence of the 16 EPA priority PAHs, as well as some organic biomarkers which could increase the knowledge about such beachrock formation.