Application of various molecular markers for investigating petrogenic inputs in coastal systems strongly impacted by anthropogenic stressors.

In this study, multiple molecular markers [polycyclic aromatic hydrocarbons (PAHs), linear and branched alkanes, unresolved complex mixture (UCM), hopanes, and steranes] were applied to explore petroleum-related inputs in complex coastal systems influenced by various human-induced pressures. To investigate anthropogenic impacts related to petrogenic emissions, we analysed surface sediments from coastal areas of southern Baltic, including harbour/shipyard channels, offshore dumping sites, shipping routes, and major sinks for particulate matter discharged by large rivers. This study indicates a large spatial variability in the contamination degree of examined sites by petroleum-derived chemicals. Hopanes and steranes along with UCM appeared to have the highest potential to identify petroleum sources in studied locations, whereas investigations based on alkanes and PAHs seemed to be considerably affected by inputs of modern biogenic and combustion-derived materials, respectively. However, the combined use of all these markers provides deeper insight into the complexity of sedimentary organic matter in human-impacted environments.

Levels, spatial distributions, and provision of petroleum hydrocarbons and phthalates in sediments from Obhur lagoon, Red Sea coast of Saudi Arabia.

The levels, spatial distribution, and sources of petroleum hydrocarbons and phthalates were assessed in surface sediment samples from the urban lagoon of Obhur near Jeddah, the largest city on the Red Sea coast of Saudi Arabia. The lagoon was divided into the inner zone, middle zone, and outer zone based on its geomorphological features and developmental activities. n-Alkanes, hopane and sterane biomarkers, and unresolved complex mixture were the major petroleum hydrocarbon compounds of the total extractable organic matter. Phthalates were also measured in the sediment samples. In the three zones, n-alkanes ranged from 89.3 ± 88.5 to 103.2 ± 114.9 ng/g, whereas the hopane and sterane biomarkers varied from 69.4 ± 75.3 to 77.7 ± 69.9 ng/g and 72.5 ± 77.9-89.5 ± 82.2 ng/g, respectively. The UCM concentrations ranged from 821 ± 1119 to 1297 ± 1684 ng/g and phthalates from 37.4 ± 34.5 65 ± 68 ng/g. The primary origins of these anthropogenic hydrocarbons in the lagoon sediments were petroleum products (boat engine discharges, boat washing, lubricants, and wastewater flows) and plasticizers (plastic waste and litter). The proportions of anthropogenic hydrocarbons derived from petroleum products in the sediment's TEOM ranged from 43 ± 33 to 62 ± 15%, while the percentages for plasticizers varied from 2.9 ± 1.2 to 4.0 ± 1.6%. The presence and inputs of these contaminants from petroleum and plastic wastes in the lagoon's sediments will eventually have an impact on its habitats, including the benthic nursery and spawning areas.

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.

Insights about levels and source appointment of petroleum hydrocarbons in Brazilian semi-arid coastal: baseline status assessment for ocean decade targets.

The Ocean decade (2021-2030) for sustainable development proclaimed in 2017 by the UN, seeks to promote and conserve the sustainable use of oceans, seas, and marine resources. For this, the distribution of n-alkanes, polycyclic aromatic hydrocarbons (PAHs), and biomarkers, in sediments from the Fortaleza coastal zone (Mucuripe harbor (MH) and Inner Continental shelf (ICS)) were used to assess the impacts of anthropogenic activities in the area. The concentrations of total n-alkanes (Σ16 n-alkanes) in MH and ICS sediments varied from 35.9 to 94.9 and 17.9 to 197.3 µg g-1, respectively, while the isoprenoids phytane and pristane in MH and ICS sediments ranged from 0.1 to 1.69 ug g-1 and from 0.14 and 1.20 µg g-1, respectively. Most of the sediment samples presented carbon preference index (CPI) values close to unity, indicating that the area is submitted to petroleum-related sources. The concentrations of Σ16 PAHs in MH and ICS sediments varied from 87.0 to 562.0 and 98 to 288.0 ng g-1. This work presents the first investigation of the petroleum biomarkers hopanes and steranes in the Fortaleza coastal zone, in which ΣBiomarkers varied from 0.10 to 1.79 and 0.02 to 0.24 ug g-1 in MH and ICS sediments, respectively. The presence at stations of biomarkers also indicates petrogenic input. The diagnosis of the distribution of pollutants in the investigated zones of the Fortaleza coast suggests contamination from urban areas and oil spills and vessel traffic.

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.

Degradation of alkane hydrocarbons by Priestia megaterium ZS16 and sediments consortia with special reference to toxicity and oxidative stress induced by the sediments in the vicinity of an oil refinery.

Petroleum hydrocarbon is a critical ecological issue with impact on ecosystems through bioaccumulation. It poses significant risks to human health. Due to the extent of alkane hydrocarbon pollution in some environments, biosurfactants are considered as a new multifunctional technology for the efficient removal of petroleum-based contaminants. To this end, Yamuna river sediments were collected at different sites in the vicinity of Mathura oil refinery, UP (India). They were analysed by atomic absorption spectrophotometry and gas chromatography-mass spectrometry (GC-MS) for heavy metals and organic pollutants. Heptadecane, nonadecane, oleic acid ester and phthalic acid were detected. In total 107 bacteria were isolated from the sediments and screened for biosurfactant production. The most efficient biosurfactant producing strain was tested for its capability to degrade hexadecane efficiently at different time intervals (0 h, 7 d, 14 d and 21 d). FT-IR analysis defined the biosurfactant as lipopeptide. 16S rRNA gene sequencing identified the bacterium as Priestia megaterium. The strain lacks resistance to common antibiotics thus making it an important candidate for remediation. The microbial consortia present in the sediments were also investigated for their capability to degrade C16, C17 and C18 alkane hydrocarbons. By using gas chromatography-mass spectrophotometry the metabolites were identified as 1-docosanol, dodecanoic acid, 7-hexadecenal, (Z)-, hexadecanoic acid, docosanoic acid, 1-hexacosanal, 9-octadecenoic acid, 3-octanone, Z,Z-6,28-heptatriactontadien-2-one, heptacosyl pentafluoropropionate, 1,30-triacontanediol and decyl octadecyl ester. Oxidative stress in Vigna radiata L. roots was observed by using Confocal Laser Scanning Microscopy. A strong reduction in seed germination and radicle and plumule length was observed when Vigna radiata L. was treated with different concentrations of sediment extracts, possibly due to the toxic effects of the pollutants in the river sediments. Thus, this study is significant since it considers the toxicological effects of hydrocarbons and to degrade them in an environmentally friendly manner.

Assessment of contaminants in sand production from petroleum wells offshore Sabah.

Sand production remains a huge obstacle in many oil and gas fields around the world, but the hazards of contaminants riding on the produced sand are often not emphasised. Improper disposal of the sand could see the toxic leaching into the environment including the food chain, endangering all living organisms. The impending sand production from an oilfield offshore Sabah also suffers from the lack of hazards identification; hence, this study was conducted to assess the contaminant on the produced sand. Sand samples were collected from multiple wells in the area, with the contaminants extracted using n-hexane and subjected to chemical and thermal analyses. FTIR and GC-MS detected traces of harmful pollutants like naphthalene, amine substances, cyclohexanol, and short-chain alkanes. It was discovered that the volatile fraction of the contaminants was able to evaporate at 33 °C, while high energy was needed to remove 100% of the contaminants from the sand. Overall, the produced sand from the oilfield was unsafe and required treatment before it could be dumped or used.

An experimental oil spill at a tidal freshwater wetland along the St. Lawrence River re-visited after 21 years.

In 1999, a tidal wetland located along the St. Lawrence River close to Ste. Croix de Lotbinière (Quebec, Eastern Canada) was the site of an experimental oil spill. Test plots were established and subjected to an experimental crude oil spill to evaluate natural attenuation, nutrient amendment and vegetation cropping as countermeasures. In 2020, this study re-visited the test plots to investigate residual oil and habitat recovery. Only concentrations of mid-chain length n-alkanes (C10-C36), but not of polycyclic aromatic hydrocarbons (PAHs), were significantly above detection limit, and were detected in both test plot and control sediments. Hydrocarbon, total organic carbon, nitrogen and phosphate contents did not differ significantly between test plot and control sediments. Microbial analyses did not detect significant differences in microbial load, microbial diversity or microbial community composition between test plot and control sediments. Key genes for the aerobic and anaerobic degradation of n-alkanes as well as for the aerobic degradation of PAHs were detected in all sediment samples. Associated gene abundances did not differ significantly between test plot and control sediments. This study shows that oil-exposed test plot sediments of the Ste. Croix wetland can be considered completely recovered after 21 years irrespective of the performed countermeasure.

Chemical Variability of Hexane Extracts from Five Subspecies of Calendula suffruticosa from Spain.

The chemical profile of the hexane extracts of the subspecies carbonellii, greuteri, marginata, trialata, and vejerensis of Calendula suffruticosa growing in Spain, herein described for the first time, were studied to access their value as a chemo taxonomical tool and search for potentially useful compounds. The subsp. greuteri and carbonellii showed higher extract yields. Terpenoids were the most abundant chemical class in subsp. carbonellii, greuteri, trialata, and vejerensis, while alkanes were the most abundant in subsp. marginata. Differences in chemical constituents were identified among the subspecies of C. suffruticosa analysed, which the PCA can prove. The subsp. trialata and greuteri showed more significant phytochemical similarity, which might indicate genetic proximity between these two subspecies. C. suffruticosa subsp. marginata presented the fewest number of compounds and in the smallest quantities, and C. suffruticosa subsp. vejerensis presented the largest number, however, both showed no alcohols. Furthermore, some of the compounds found in significant amounts are known for their pharmacological and nutraceutical properties, denoting potential use.

Source identification and weathering processes of tar ball deposited Qinhuangdao coast along the Bohai Sea, China.

Deposition of tar balls on the Qinhuangdao beaches along the coasts of the Bohai Sea (China) could affect people's leisure activities and tourism, and even affect the marine ecosystem. In 2020, representative tar balls collected from Qinhuangdao beaches, fingerprint analysis based on diagnostic ratios suggested that these tar balls were all very similar and may belong to the same source. Source identification by cross plot and principal component analysis (PCA), showed that the tar balls were likely from Penglai 19-3 crude oil. The weathering characterizations based on polycyclic aromatic hydrocarbons (PAHs), alkanes parameters and unresolved complex mixture (UCM), indicated that the tar balls had been significantly influenced by natural weathering processes such as evaporation, biodegradation and photooxidation. The study of this leakage provides a powerful support for determining the leakage source, evaluating the potential weathering mechanism and determining the accident liability. This is the first time to use fingerprint technology to identify the source of tar balls in Qinhuangdao coastal zone in the Bohai Sea.

Ozone pollution in the plate and logistics capital of China: Insight into the formation, source apportionment, and regional transport.

As the logistics and plate capital of China, the sources and regional transport of O3 in Linyi are different from those in other cities because of the significant differences in industrial structure and geographical location. Twenty-five ozone pollution episodes (OPEs, 52 days) were identified in 2021, with a daily maximum 8-h moving average O3 concentration (O3-MDA8) of 184.5 ± 22.5 µg/m3. Oxygenated volatile organic compounds (OVOCs) and aromatics were the dominant contributors to ozone formation potential (OFP), with contributions of approximately 23.5-52.7% and 20.0-40.8%, respectively, followed by alkenes, alkanes, and alkynes. Formaldehyde, an OVOC with high concentrations emitted from the plate industry and vehicles, contributed the most to OFP (22.7 ± 5.5%), although formaldehyde concentrations only accounted for 9.4 ± 2.7% of the total non-methane hydrocarbon (NMHC) concentrations. The source apportionment results indicated that the plate industry was the dominant O3 contributor (27.0%), followed by other sources (21.6%), vehicle-related sources (18.0%), solvent use (16.9%), liquefied petroleum gas (LPG)/natural gas (NG) (8.8%), and combustion sources (7.7%). Therefore, there is an urgent need to control the plating industry in Linyi to mitigate O3 pollution. The backward trajectory, potential source contribution function (PSCF), and concentration weighted trajectory (CWT) models were used to identify the air mass pathways and potential source areas of air pollutants during the OPEs. O3 pollution was predominantly affected by air masses that originated from eastern and local regions, while trajectories from the south contained the highest O3 concentrations (207.0 µg/m3). The potential source area was from east and south Linyi during the OPEs. Therefore, it is critical to implement regional joint prevention and control measures to lower O3 concentrations.

n-Alkanes and Polycyclic Aromatic Hydrocarbons in Deposition Dust and PM10 of Interiors in Touggourt Region, Algeria.

The occurrence of pollutants in environment displays its maximum impact on human health and on the global "quality" of life in the places where humans spend most of their time, i.e., indoors. A field study was undertaken in the region of Touggourt, Algeria. The goal was that of obtaining information on the main sources of indoor pollutant emissions (n-alkanes and polycyclic aromatic compounds) associated with deposition dusts (DDs) and suspended particulates (PM10). A multi-service clinic, two schools, a coffee bar, three houses, and an asphalt distribution center were investigated. Forty-five samples in total were collected, including 31 deposition dusts and 14 airborne particulates. That would improve the current understanding of pollution features in central Algeria reached through previous investigations in the Touggourt region. Capillary gas chromatography coupled with mass spectrometric detection was adopted to determine the concentrations of n-alkanes and PAHs. In deposition dust, total n-alkanes (TNAs) ranged between 37 and 794 ng/(m2 day) in the summer and 33-1,724 ng/(m2 day) in the fall. Meanwhile, TNAs loads in the PM10 samples ranged between 778 and 2,024 ng/m3. According to Carbon Preference Index (CPI), Cmax, and wax n-alkanes (WaxCn) approaches, both DD and PM10 were released overall by anthropogenic sources, though the contribution of natural emissions could not be neglected. Total polycyclic aromatic hydrocarbons (TPAHs) associated with DD ranged from 4.4 ng/(m2 day) to 127 ng/(m2 day) during the summer period, and 2.0-224 ng/(m2 day) in the fall; TPAHs' concentrations in PM10 ranged between 40 ng/m3 and 984 ng/m3. Preliminary information about the sources of PAHs was drawn by calculating the concentration ratios between diagnostic pairs (DRs) of PAHs. According to PAH DR values, the pollution sources influenced at distinct extents all of the sites and locations investigated. Anyway, the PAH occurrence was associated with petrogenic sources, with the prevalence of gasoline fuel cars, at most sites. A wide variability was also observed by comparing the concentrations of pollutants observed in the summer and in the fall. This was in agreement with the results of n-alkanes emissions.

Molecular signatures of organic particulates as tracers of emission sources.

Chemical signature of airborne particulates and deposition dusts is subject of study since decades. Usually, three complementary composition markers are investigated, namely, (i) specific organic compounds; (ii) concentration ratios between congeners, and (iii) percent distributions of homologs. Due to its intrinsic limits (e.g., variability depending on decomposition and gas/particle equilibrium), the identification of pollution sources based on molecular signatures results overall restricted to qualitative purposes. Nevertheless, chemical fingerprints allow drawing preliminary information, suitable for successfully approaching multivariate analysis and valuing the relative importance of sources. Here, the state-of-the-art is presented about the molecular fingerprints of non-polar aliphatic, polyaromatic (PAHs, nitro-PAHs), and polar (fatty acids, organic halides, polysaccharides) compounds in emissions. Special concern was addressed to alkenes and alkanes with carbon numbers ranging from 12 to 23 and ≥ 24, which displayed distinct relative abundances in petrol-derived spills and exhausts, emissions from microorganisms, high vegetation, and sediments. Long-chain alkanes associated with tobacco smoke were characterized by a peculiar iso/anteiso/normal homolog fingerprint and by n-hentriacontane percentages higher than elsewhere. Several concentration ratios of PAHs were identified as diagnostic of the type of emission, and the sources of uncertainty were elucidated. Despite extensive investigations conducted so far, the origin of uncommon molecular fingerprints, e.g., alkane/alkene relationships in deposition dusts and airborne particles, remains quite unclear. Polar organics resulted scarcely investigated for pollution apportioning purposes, though they looked as indicative of the nature of sources. Finally, the role of humans and living organisms as actual emitters of chemicals seems to need concern in the future.

Fingerprint analysis reveals sources of petroleum hydrocarbons in soils of different geographical oilfields of China and its ecological assessment.

The distribution and characteristics of petroleum in three different geographic oilfields in China: Shengli Oilfield (SL), Nanyang Oilfield (NY), and Yanchang Oilfield (YC) were investigated. The average concentration of the total petroleum hydrocarbons (TPHs) conformed to be in the following law: SL Oilfield > NY Oilfield > YC Oilfield. Fingerprint analysis on the petroleum contamination level and source was conducted by the geochemical indices of n-alkanes and PAHs, such as low to high molecular weight (LMW/HMW) hydrocarbons, n-alkanes/pristine or phytane (C17/ Pr, C18/Ph), and ratio of anthracene/ (anthracene + phenanthrene) [Ant/(Ant + Phe)]. Soils adjacent to working well oils indicated new petroleum input with higher ratio of low to high molecular weight (LMW/HMW) hydrocarbons. The oil contamination occurred in the grassland soils might result of rainfall runoff. Petroleum source, petroleum combustion source, and biomass combustion were dominant PAHs origination of soils collected from oil exploitation area, petrochemical-related sites, farmland and grassland, respectively. The suggestive petroleum control strategies were proposed in each oilfield soils. Ecological potential risk of PAHs was assessed according to the toxic equivalent quantity (TEQ) of seven carcinogenic PAHs. The results showed that high, medium, and low ecological risk presented in petro-related area, grassland soils, and farmland soils, respectively. High ecological risk was persistent in abandoned oil well areas over abandoned time of 15 years, and basically stable after 5 years. This study can provide a critical insight to ecological risk management and source control of the petroleum contamination.

Detailing the organic matter in suspended sediments as a tool to assess the impact of land occupation in water bodies: a case of Barigui Watershed (Southern Brazil).

Suspended sediments were collected to examine the organic carbon content and n-alkanes in order to assess the impact on water bodies caused by soil and land occupation. For this, samples from distinct areas based on the level of land occupation of the Barigui Watershed and different areas under the influence of human activities were examined. The number of industries increasing along the river was also considered. Twenty-two sediment samples were collected using a time-integrated sediment sampler. Samples were extracted with dichloromethane:methanol (DCM:methanol) (2:1) in an ultrasound bath, treated and injected using gas chromatography coupled with mass spectrometry (GC-MS) for separation and quantification. Twenty-one n-alkanes were identified and were used to track both biogenic and anthropogenic inputs. The concentration of total n-alkanes varied from 38.72 to 222.76 µg g-1, due to the impact of urbanization. Diagnostic indexes indicated high numbers of plants, bacteria and petroleum as n-alkanes sources. The following results were obtained using: carbon preference index (CPI), 1.96-2.22 (rainy season) and 2.12-5.80 (summer season); average chain length (ACL), 30.37-31.17 (rainy season) and 30.05-30.50 (summer season) and terrigenous aquatic ratio (TAR), 0.39-5.47 (rainy season) and 2.98-5.06 (summer season); n-alkanes had two main sources: terrestrial plant and petroleum. It is clear that the source of n-alkanes is different in each season (rainy and dry) demonstrated by n-alkanes occurrence. During the rainy season, there was an increase in organic matter of oil origin which was mainly associated with the increased runoff and rain drainage. Finally, the input of organic matter associated with land occupation and erosion can be distinguished by higher concentration in the most urbanized site (PB).

Source identification of n-alkanes and isoprenoids using diagnostic ratios and carbon isotopic composition on crude oils and surface waters from the Gulf of Mexico.

Diagnostic ratios and compound-specific isotopic analysis (CSIA) are two tools that can help identify and differentiate the petrogenic and biogenic sources of hydrocarbons found in environmental samples. The present study aims to evaluate the concentration and type of n-alkanes and isoprenoids found in the oligotrophic waters of the Gulf of Mexico (n = 14), and through the typical diagnostic ratios reported for n-alkanes and its carbon isotopic composition (δ13C) to establish and differentiate the possible source of the hydrocarbons. Additionally, crude oil samples (n = 10) extracted in the Gulf of Mexico were evaluated by CSIA as a possible source of hydrocarbons to the study area. We found that the CSIA of δ13C for n-alkanes (n-C11 to n-C30) and isoprenoids (pristane and phytane) found in the surface water samples varied from - 25.55 to - 37.59‰ and from - 23.78 to - 33.97‰ in the crude oil samples, values which are more related to petrogenic sources. An analysis of the δ13C for pristane vs. phytane suggests that only three surface water samples show an origin in common that those observed in crude oils of the Gulf of Mexico. A low incidence of odd- and even-numbered n-alkanes higher than n-C25 in the water samples indicate low to negligible presence of terrigenous sources into the area, which was supported by the carbon isotopic composition of the individual n-alkanes.

Normal alkanes in sediments from the Persian Gulf: spatial pattern and implications for autochthonous, allochthonous, and petroleum-originated contaminants.

Surface sediments (n = 124) were gathered to evaluate spatial pattern and source apportionment of ∑24n-alkanes in the Persian Gulf. Moran's I indices revealed that ∑24n-alkanes were randomly distributed in sampling space in general. One noticeable exception was a significant spatial high-high cluster (Z-score = 8.6). Profile of n-alkanes observed for this cluster maximized at n-C20, n-C18, n-C16, and n-C22. Detection of very low carbon preference indices and strong even carbon-numbered predominance suggested that bacterial inputs were the process making this cluster. Based on diagnostic ratios and GIS techniques, in situ production of organic materials was widespread in the studied space. Allochthonous and petroleum-based inputs were not traceable for 73.8% and 24.7% of the area, respectively. Petrogenic source apportionment map proposed that petroleum-originated contaminants were probably limited to 6.32 km2 of the sampling matrix. The biogenic inputs (autochthonous and allochthonous inputs) and not the petroleum contaminants were the main source of n-alkanes deposited.

Separation performance of the copolymer and homopolymer of aliphatic polycarbonate diols as the stationary phases for capillary gas chromatography.

This work presents the investigation of two aliphatic polycarbonate diols (CAPC and HAPC) as the stationary phases for capillary gas chromatography (GC). The CAPC and HAPC capillary columns showed moderate polarity and high column efficiency of 3704 - 4545 plates/m measured by n-octanol and naphthalene at 120 °C. It was found that despite their similar chemical compositions, CAPC and HAPC differ largely in their selectivity towards the isomers of alkanes, methylpyridines and xylenes. As demonstrated, the CAPC column exhibits advantageous comprehensive performance over the HAPC column and the commercial PEG column. Particularly, the CAPC column exhibits higher resolving performance towards the isomers indicated above and the Grob mixture than the HAPC column. Also, it shows distinct advantages over the PEG column in separating the Grob mixture, the isomers of diethylbenzenes and cymenes, and practical analysis of chemical products and the essential oil from the leaves of Rhododendron dauricum L. Additionally, the CAPC column has excellent repeatability and reproducibility on analyte retention times with the relative standard deviation (RSD) values in the range of 0.05% - 0.08% for run-to-run, 0.12% - 0.19% for day-to-day and 2.6% - 4.9% for column-to-column, respectively. Its applications to purity test of chemical products and GC-MS analysis of the essential oil demonstrate its promising future for practical GC analyses.

Distribution and Sources of n-Alkanes and Polycyclic Aromatic Hydrocarbons in Sediments Around Oil Production Facilities in the Escravos River Basin, Niger Delta, Nigeria.

This study provides data on the characteristic levels, spatial patterns, sources, and risk of n-alkanes (AHs) [octane, n-C8, to tetracontane, n-C40] and polycyclic aromatic hydrocarbons (PAHs) in surficial sediments from the Escravos River Basin (ERB), Nigeria. The n-alkane and PAH concentrations in sediments were quantified by chromatographic methods. The concentrations of AHs and PAHs in the ERB sediments varied from 95 to 3430 µg g-1 and from 0.75 to 213 µg g-1, respectively. Both the concentrations of AHs and PAHs in ERB sediments exceeded their respective guideline values. The carbon preference index and other AH markers provide evidence that the AHs in the ERB sediments originated from petroleum sources. Ecological risk assessment indicated that the ecological risk relating to an organism's contact with PAHs in the ERB sediments was high. The possible carcinogenic risk arising from human exposure with PAHs in surface sediments through accidental oral ingestion and skin contact exceeded the safe level of 10-6, indicating a considerable probable cancer risk for fishermen and other inhabitants of the ERB. PAH isomer ratios and multivariate statistics suggested that the PAHs in sediments from the ERB originated from gas flaring inputs, discharges from oil drilling platforms, diesel engines, ships, and speed boats, and combustion of wood and other biomass.

Microbial production and consumption of hydrocarbons in the global ocean.

Seeps, spills and other oil pollution introduce hydrocarbons into the ocean. Marine cyanobacteria also produce hydrocarbons from fatty acids, but little is known about the size and turnover of this cyanobacterial hydrocarbon cycle. We report that cyanobacteria in an oligotrophic gyre mainly produce n-pentadecane and that microbial hydrocarbon production exhibits stratification and diel cycling in the sunlit surface ocean. Using chemical and isotopic tracing we find that pentadecane production mainly occurs in the lower euphotic zone. Using a multifaceted approach, we estimate that the global flux of cyanobacteria-produced pentadecane exceeds total oil input in the ocean by 100- to 500-fold. We show that rapid pentadecane consumption sustains a population of pentadecane-degrading bacteria, and possibly archaea. Our findings characterize a microbial hydrocarbon cycle in the open ocean that dwarfs oil input. We hypothesize that cyanobacterial hydrocarbon production selectively primes the ocean's microbiome with long-chain alkanes whereas degradation of other petroleum hydrocarbons is controlled by factors including proximity to petroleum seepage.