Aliphatic Hydrocarbon Fractions Research Articles

Functional and structural responses of a halophilic consortium to oily sludge during biodegradation.

Biotreatment of oily sludge and the involved microbial communities, particularly in saline environments, have been rarely investigated. We enriched a halophilic bacterial consortium (OS-100) from petroleum refining oily sludge, which degraded almost 86% of the aliphatic hydrocarbon (C10-C30) fraction of the oily sludge within 7 days in the presence of 100g/L NaCl. Two halophilic hydrocarbon-degrading bacteria related to the genera Chromohalobacter and Halomonas were isolated from the OS-100 consortium. Hydrocarbon degradation by the OS-100 consortium was relatively higher compared to the isolated bacteria, indicating potential synergistic interactions among the OS-100 community members. Exclusion of FeCl2, MgCl2, CaCl2, trace elements, and vitamins from the culture medium did not significantly affect the hydrocarbon degradation efficiency of the OS-100 consortium. To the contrary, hydrocarbon biodegradation dropped from 94.1 to 54.4% and 5% when the OS-100 consortium was deprived from phosphate and nitrogen sources in the culture medium, respectively. Quantitative PCR revealed that alkB gene expression increased up to the 3rd day of incubation with 11.277-fold, consistent with the observed increments in hydrocarbon degradation. Illumina-MiSeq sequencing of 16S rRNA gene fragments revealed that the OS-100 consortium was mainly composed of the genera Halomonas, Idiomarina, Alcanivorax and Chromohalobacter. This community structure changed depending on the culturing conditions. However, remarkable changes in the community structure were not always associated with remarkable shifts in the hydrocarbonoclastic activity and vice versa. The results show that probably synergistic interactions between community members and different subpopulations of the OS-100 consortium contributed to salinity tolerance and hydrocarbon degradation.

Aliphatic Biomarker Signatures of Crude Oil from Tarakan Subbasin, Tarakan Basin, North Kalimantan, Indonesia

Organic geochemical studies of crude oil from Pamusian Field, Tarakan Subbasin, Tarakan Basin, North Kalimantan, have been done. Biomarker aliphatic hydrocarbon fractions were identified using a combined gas chromatography-mass spectrometer (GC - MS). Identified biomarkers consist of n-alkane groups, isoprenoids, bicyclic sesquiterpenoids, and pentacyclic triterpenoids. The most abundant aliphatic hydrocarbon biomarker is pristane followed by n-C19. The existence of n-alkanes shows a homologous (n-C16- n-C30) with a unimodal distribution type. The abundance of n-C19 is higher than other n-alkanes, supported by LHCPI value of 2.03, as an indicator of organic matter derived from microbial organisms. The amount of long chain n-alkanes (n-C25- n-C30) is almost the same as medium chain n-alkanes (n-C19 - n-C24) indicating the source of organic compounds is not only from microbial organisms, but also from terrestrial higher plants. The presence of 8β (H)-drimane compounds together with homodrimane shows the presence of bacterial input on the formation of oil from organic compounds. Ratio of Pr/Ph is 3.76, ratio of drimane/homodrimane is 1.058, ratio of Pr/n-C17 is 34.41, and ratio of Ph/n-C18 is 16.02 indicating the source of organic compounds came from terrestrial higher plants deposited in the oxic environment, and disposed to increase biodegradation. The CPI value is 0.95, and the highest amount of 17α (H), 21β (H)-hopane compounds suggest that Tarakan Subbasin oil was mature, and the source of organic compounds was derived from bacteria Keywords: Tarakan Basin, organic geochemistry, aliphatic hydrocarbon fraction, CPI

Holistic approach to waste mobil oil bioremediation: Valorizing waste through biosurfactant production for soil restoration

The combustion of mobil oil leads to the emission of toxic compounds in the environment. In this study, the aromatic and aliphatic hydrocarbon fractions present in a waste mobil oil collected from automobile market were comprehensively identified and their toxicity was evaluated using wheat grain. Lysinibacillus sphaericus strain IITR51 isolated and characterized previously could degrade 30–80% of both aliphatic and aromatic hydrocarbons in liquid culture. Interestingly, the strain IITR51 produced 627 mg/L of rhamnolipid biosurfactant by utilizing 3% (v/v) of waste mobil oil in the presence of 1.5% glycerol as additional carbon source. In a soil microcosm study by employing strain IITR51, 50–86% of 3–6 ring aromatic hydrocarbons and 63–98% of aliphatic hydrocarbons (C8 to C22) were degraded. Addition of 60 μg/mL rhamnolipid biosurfactant enhanced the degradation of both aliphatic and aromatic hydrocarbons from 76.88% to 61.21%–94.11% and 78.27% respectively. The degradation of mobil oil components improved the soil physico-chemical properties and increased soil fertility to 64% as evident by the phytotoxicity assessments. The findings indicate that strain IITR51 with degradation capability coupled with biosurfactant production could be a candidate for restoring hydrocarbon contaminated soils.

Low-Calorie Coal Liquefaction Products as an Alternative Fuel Oil

Liquefaction of low-rank coal has been done to optimize the utilization of low-rank coal, which is less economical for obtaining alternative fuel oil. Coal samples were taken from the Bukit Pinang coal mine, Samarinda Ulu, East Kalimantan. Coal was liquefied using the NEDOL procedure at PUSPITEK, Serpong, South Tangerang, Indonesia. This Bukit Pinang coal liquefaction produces five fractions consisting of Naphta, Light Oil (LO), Middle Oil (MO), Heavy Oil (HO), and Coal Liquid Bottom (CLB) fractions. The liquefaction yield was dominated by the HO and CLB fractions (> 50% by weight). The naphtha, MO and LO fractions were fractionated using SiO2 GF254 Thin Layer Chromatography (TLC) plate. It produced aliphatic and aromatic hydrocarbon fractions. Aliphatic hydrocarbon fractions were analyzed using a Gas Chromatography-Mass Spectrometer (GC-MS), while the aromatic hydrocarbon fractions were not analyzed. Mass spectrum studies showed that the components consisted of n-alkanes, isoalkanes (branched alkanes), cycloalkanes and alkyl cycloalkanes. The aliphatic hydrocarbon components resulting from the liquefaction of low-rank coal showed its equivalence with the components that make up fuel oil. Therefore, this coal liquefaction can be suggested as an optimization for low-rank coal, which is less economical.

Occurrence, sources and spatial distribution of n-alkanes in surface soils from the Amu Darya Delta, Uzbekistan, arid Central Asia

Central Asia (CA) has attracted global attention because of either water scarcity or ecosystem degradation. The Amu Darya Delta (ADD), one of the most important oases in CA, is endowed with valuable wetlands and biological resources that provide good ecosystem services to inhabitants. However, the region has experienced climate warming and large-scale anthropogenic changes since the last century. To assess the influences of anthropogenic interventions on the soil environment in this area, surface soil samples collected from the ADD were analysed for aliphatic hydrocarbon fractions and five heavy metals (HMs; including Cd, Zn, Cu, Ni and V). The results indicated that the n-alkanes extracted from surface soils were composed of homologous series from C14 to C35. Relatively high abundances of short-chain n-alkanes (<n-C21) were observed in cluster 1 samples (mainly from the lakeshore of the Aral Sea), while significantly high abundances of mid-chain (n-C21 to n-C25) and long-chain (n-C26 to n-C32) n-alkanes were found in cluster 3 samples, which were distributed in urban and agricultural drainage areas. In addition, very-long-chain n-alkanes (>n-C33) occurred in most surface soils, which might be a sign of a hot and arid climatic environment. Notably, almost all samples presented a clear even carbon dominance of short-chain n-alkanes, especially for cluster 1, which possibly represented the influence of hydrocarbon contamination and highly saline carbonate environments in addition to bacterial degradation. The biomarker indices and HM enrichment index indicated greater effects of crude oil pollution on cluster 1 (specifically samples 2, 4, 5, 6, 13, 16 and 34) and anthropogenic activities such as traffic emissions and agricultural drainage on cluster 3 samples. The results of this study provide evidence that the n-alkane composition and abundance in surface soils respond sensitively to anthropogenic interventions, arid climate and petroleum hydrocarbon pollution.

Sustainable strategies for combating hydrocarbon pollution: Special emphasis on mobil oil bioremediation

The global rise in industrialization and vehicularization has led to the increasing trend in the use of different crude oil types. Among these mobil oil has major application in automobiles and different machines. The combustion of mobil oil renders a non-usable form that ultimately enters the environment thereby causing problems to environmental health. The aliphatic and aromatic hydrocarbon fraction of mobil oil has serious human and environmental health hazards. These components upon interaction with soil affect its fertility and microbial diversity. The recent advancement in the omics approach viz. metagenomics, metatranscriptomics and metaproteomics has led to increased efficiency for the use of microbial based remediation strategy. Additionally, the use of biosurfactants further aids in increasing the bioavailability and thus biodegradation of crude oil constituents. The combination of more than one approach could serve as an effective tool for efficient reduction of oil contamination from diverse ecosystems. To the best of our knowledge only a few publications on mobil oil have been published in the last decade. This systematic review could be extremely useful in designing a micro-bioremediation strategy for aquatic and terrestrial ecosystems contaminated with mobil oil or petroleum hydrocarbons that is both efficient and feasible. The state-of-art information and future research directions have been discussed to address the issue efficiently.

Development of updated RfD and RfC values for medium carbon range aromatic and aliphatic total petroleum hydrocarbon fractions

ABSTRACT Using total petroleum hydrocarbon (TPH) measurements as a tool for assessing potential human health risks associated with exposures to petroleum products in the environment poses unique challenges, as TPH represents highly variable and complex mixtures containing hundreds of individual chemicals with wide-ranging chemical and physical properties. Current risk assessment practice generally involves analysis of environmental samples for various TPH fractions and summation of risk across those fractions. The United States Environmental Protection Agency (USEPA) derived provisional toxicity criteria for low, medium, and high carbon range aromatic and aliphatic hydrocarbon fractions over a decade ago. These criteria have been used, in whole or in part, to derive risk-based cleanup levels for TPH contamination in soil and groundwater. Herein, we evaluate and update oral and inhalation toxicity criteria for two of these fractions – medium carbon range aromatics and aliphatics – using, where applicable, newer data, updated modeling techniques, and new/alternative analyses of certain endpoints, human relevance, and uncertainty. The results of the analyses support an ~10-fold increase in the USEPA provisional reference concentration (p-RfC) values from 0.1 mg/m3 to 1 mg/m3 for both medium carbon range aromatics (different uncertainty factor) and aliphatics (new study and different judgment of toxicity data from existing study). Compared to the USEPA provisional oral reference dose (p-RfD) values for the medium carbon range aromatics and aliphatics of 0.03 mg/kg-day and 0.01 mg/kg-day, respectively, the present analyses suggest the RfD for medium carbon range aromatics could be increased >6.6-fold to 0.2 mg/kg-day (updated modeling and different uncertainty factors), and the RfD for medium carbon range aliphatics could be increased ~20-fold to 0.2 mg/kg-day (new study). These updated toxicity criteria could be used by regulatory agencies to reevaluate risk-based screening levels or by risk managers to support cleanup levels for medium carbon range aromatics and aliphatics, while still ensuring adequate health protection. Implications: Petroleum products represent complex mixtures of hydrocarbons broadly comprised of aliphatic compounds (straight-chain, branched-chain, and cyclic alkanes and alkenes) and aromatic compounds such as benzene, alkylbenzenes, and polycyclic aromatic hydrocarbons. The complex nature of petroleum products presents challenges for assessing potential health risks associated with exposure to petroleum hydrocarbon contamination in the environment. It has been over ten years since the U.S. Environmental Protection Agency derived provisional toxicity criteria for low, medium, and high carbon range aromatic and aliphatic hydrocarbon fractions. In that time, risk assessment guidance and tools have evolved, and new studies have been published. Our analyses indicate that current provisional toxicity criteria for medium carbon range aromatics and aliphatics fractions are overly conservative by approximately an order of magnitude.

Effect of novel Ni2P-loaded catalysts on algal pyrolysis bio-oil

This study focused on conversion of algal biomass to bio-oil through in-situ catalytic fast pyrolysis. In particular, novel Ni2P-loaded and unmodified (zeolite, activated carbon and chicken manure biochar) catalysts were evaluated to determine their effect on in-situ upgrading of algal pyrolysis products. Among the catalysts evaluated, Ni2P-loaded zeolite achieved the highest bio-oil hydrocarbon (34.97 %) and calorific value (32.66 MJ/kg), and the lowest O/C (0.075) and N/C (0.074) ratios. There was a 137 % increase of the aliphatic hydrocarbon fraction and a 72 % increase of the biochar specific surface area (SSA) with the loading of Ni2P to zeolite. Additionally, unfavourable major oxygen- and nitrogen-containing compound, phytol and tetradecanamide, decreased seven- and six-fold, respectively, compared to the non-catalytic baseline case. Ni2P-loaded biochar achieved a reduction in the bio-oil acidity from a pH of 4.52–6.78 and a 41 % decrease of the carboxylic acids content. Biochar produced from the zeolite formulations exhibited especially favourable sorbent quality with SSA greater than 500 m2/g. According to the proposed catalytic mechanism, the generation of n-heptadecane and hexadecanamide may be due to the decomposition of phytol and tetradecanamide, and the catalytic activity was correlated to the pore size of the catalyst (22.22 Å). Direct addition reactions were the dominant pathway in the formation of liquid hydrocarbons. These results suggest that it is feasible to develop an in-situ multi-catalyst system to achieve high-quality bio-oil production. Thus, the development of novel Ni2P-loaded catalysts addressed a promising approach for biomass conversion into hydrocarbon-rich products with low risk to the environment.

A sediment record of terrestrial organic matter inputs to Dongting Lake and its environmental significance from 1855 to 2019

The extensive anthropogenic activities and their potential impacts on lakes during the Anthropocene could be recorded in the sediments. In this study, the composition of biomarkers (i.e., n-alkanes and n-fatty acids), total organic carbon (TOC), and particle size in 210Pb-dated sediment cores from West Dongting Lake were investigated to trace the historical trend of anthropogenic inputs and their environmental significance. The TOC content was in the range of 3.15–27.32 mg g−1. The n-alkanes and n-fatty acids were distributed from C11–C33 and C12:0–C34:0, respectively. The short- and long-chain biomarkers accounted for a significant proportion of the total. Aquatic plants and algae living in West Dongting Lake were the main source (short-chain) followed by leaf waxes derived from terrestrial C3 plants (long-chain), as demonstrated by their concentrations. The variations of the key indicators i.e., the carbon preference index (CPI), aquatic plant n-alkane proxy (Paq), vascular plant n-alkane proxy (Pwax), and the ratio of unit short- to long-chain n-alkanes (L/H) also indicated that the aliphatic hydrocarbon fractions were mainly composed of short- and long-chain biomarkers. The sedimentary biomarkers had a significant temporal heterogeneity, which was controlled by different factors and sedimentary processes. Fine particles (<16 µm) were the dominant particle size (66.91%–78.52%) in the sediment. Both values of the dry/wet climate proxy (Kd) and average particle size were consistent over time. The dominance of terrestrial C3 plant-derived long-chain molecules gradually changed, with algae-derived short-chain molecules then becoming dominant. The hot and drought climate conditions and enhanced agricultural inputs from 1855 to 2019 in the watershed resulted in a decrease of terrestrial C3 plants and rapid growth of algae in the lake water.

Specific enrichment of hydrocarbonclastic bacteria from diesel-amended soil on biochar particles

Biochar has been proposed as a suitable biostimulant for the remediation of hydrocarbon contamination, and also has the potential to act as a carrier for hydrocarbonoclastic microorganisms which could bioaugment endogenous microbial communities. However, the evidence regarding the biostimulatory effects of biochars on hydrocarbon bioremediation is somewhat equivocal, possibly due to variability of the physicochemical properties of biochar and soil across studies. Here, we use standard biochars with defined properties produced from softwood pellets (SWP) and rice husk (RH) at pyrolysis temperatures of 550 °C or 700 °C to test the effects of biochar amendment on microbial community composition and hydrocarbon degradation in soil microcosms contaminated with diesel oil. Combining this approach for the first time with specific analysis of microbial community composition using amplicon sequence variants (ASVs), we find that oil contamination causes extreme short-term loss of soil microbial diversity, and highly-specific selection of a limited set of genera defined by 13 ASVs. Biochar ameliorates the short-term loss of diversity, and in the longer term (9 weeks), changes community composition in a type-specific manner. The majority of the 13 selected ASVs are further enriched on biochar particles, although SWP biochars perform better than RH biochar in enrichment of putative hydrocarbonoclastic Aquabacterium spp. However, complete degradation of normal (n) alkanes from the aliphatic hydrocarbon fraction is prevented in the presence of biochar amendment, possibly due to their adsorption onto the char surface. Furthermore, we show that putative hydrocarbon degraders released from diesel-amended soil can subsequently be enriched to high levels on SWP biochar particles in growth medium supplemented with diesel oil as the sole carbon source; these include selected ASVs representing the genera Rhodococcus, Aquabacterium, and Cavicella. This work suggests that use of biochar pre-enriched with endogenous, conditionally-rare hydrocarbon degrading bacteria is a promising strategy for bioaugmentation of diesel-contaminated soils.

Organic Geochemistry Characteristics of Aliphatic Hydrocarbon Fraction of Crude Oil from Tarakan Basin, North Borneo, Indonesia

The study of organic geochemistry of crude oil from Pamusian field, Tarakan Basin, North Borneo has been done. The oil is fractionated by column chromatography and identified using gas chromatography-mass spectrometer (GC-MS). The presence of long chain n-alkanes, cadinane, 4β(H)-eudesmane, and 18α (H)-oleanane indicates organic matter derived from resin dammar Angiospermae family Dipterocarpaeae. It is also reported that there are drimane together with homodrimane and hopane as an indicator of bacterial input. The LHCPI value of 2.03 also indicates a high input of photosynthetic bacteria. Pr/Ph ratio of 3.76 and a drimane/homodrimane ratio of 1.058 indicating the oxic depositional environment of the sample. Isomer analysis of 18α(H)-oleanane and 17α(H),21β(H)-hopane provides information that the crude oil from Tarakan Basin is mature.

Aliphatic hydrocarbon biomarkers of Sekar Kurung Gresik crude oil

Characterization of petroleum biomarker from Sekar Kurung Gresik, was carried out to investigate its organic composition, depositional environment and oil maturity. The oil sample was extracted and fractionated using column chromatography to derive aliphatic hydrocarbon fraction. The aliphatic hydrocarbon compounds were analyzed using gas chromatography-mass spectrometer (GC-MS). The GC-MS analysis shows that n-alkanes compound (C14-C28), isoprenoid alkanes (iC15 iC16 and iC18-iC20), a bicyclic sesquiterpene, eudesmane, cadinane, hopane, bicadinane, gammacerane and diasterane were observed. The identified compounds show that the crude oil compounds were derived from terrestrial higher plants, the contribution of bacterial activity and the oxic deposition environment (Pr/Ph = 5.3 (&lt;1)). The oil analyzed is a mature oil.

Anthropogenically driven differences in n-alkane distributions of surface sediments from 19 lakes along the middle Yangtze River, Eastern China.

During the past few decades, the Yangtze River basin has undergone massive anthropogenic change. In order to evaluate the impacts of human interventions on sediment n-alkanes of lakes across this region, the aliphatic hydrocarbon fractions of 19 surface sediment samples collected from lakes along the middle reaches of the Yangtze River (MYR) were analyzed using gas chromatography-mass spectrometry. The n-alkanes extracted from the sediments contained a homologous series from C15 to C34, with a notable predominance of odd carbon compounds except for sediments from the more intensively industrialized Lake Daye, in which > C21 n-alkanes showed no odd/even predominance, and carbon preference index (CPI) approached unity. Abundance values of middle-chain (C21, C23, and C25) and long-chain (C27, C29, C31, and C33) n-alkanes in Lake Daye were approximately 4 to 3 times greater than the average for other lakes, reaching 272.4 and 486.3μg/g TOC, respectively, in the study. Short-chain n-alkanes (C15, C17, and C19) in the sediments varied in abundance from 10.0 to 76.2μg/g TOC across the study and showed a moderate correlation with total phosphorus (TP) concentrations in the overlying water. The results indicated anthropogenic eutrophication enhanced the accumulation of short-chain n-alkanes in sediments because the primary producers in which they are synthesized are highly susceptible to nutrient forcing. Middle-chain n-alkane abundances were less affected by eutrophication and generally enriched in macrophyte lakes, while long-chain n-alkanes tend to be low in sediments from more eutrophic water. In the case of Lake Daye, direct discharges of petroleum products from heavy industry have introduced quantities of petroleum n-alkanes (> C21), far exceeding the amounts of biogenic input, and the sediment > C21 n-alkanes detected in this study showed typical characteristics of petroleum source. In other lakes, inputs of petroleum products from surface runoff of vehicle/traffic emissions associated with urbanization and economic growth contributed comparatively few n-alkanes to sediments, resulting in declines in CPI for > C21 n-alkanes, most obviously in Lakes Huanggai, Donghu, and Futou. Calculated CPI values suggest that a major proportion of the n-alkanes present in these lakes are derived from biogenic input. The results of this study provided evidences that n-alkane profiles of lake sediments respond sensitively to human-induced eutrophication and different sources of petroleum pollution.

Biostimulation potentials of corn steep liquor in enhanced hydrocarbon degradation in chronically polluted soil.

The effects of corn steep liquor (CSL) on hydrocarbon degradation and microbial community structure and function was evaluated in field-moist soil microcosms. Chronically polluted soil treated with CSL (AB4) and an untreated control (3S) was compared over a period of 6weeks. Gas chromatographic fingerprints of residual hydrocarbons revealed removal of 95.95% and 94.60% aliphatic and aromatic hydrocarbon fractions in AB4 system with complete disappearance of nC1-nC8, nC10, nC15, nC20-nC23 aliphatics and aromatics such as naphthalene, acenaphthylene, fluorene, phenanthrene, pyrene, benzo(a)anthracene, and indeno(123-cd)pyrene in 42days. In 3S system, there is removal of 61.27% and 66.58% aliphatic and aromatic fractions with complete disappearance of nC2 and nC21 aliphatics and naphthalene, acenaphthylene, fluorene, phenanthrene, pyrene, and benzo(a)anthracene aromatics in 42 days. Illumina shotgun sequencing of the DNA extracted from the two systems showed the preponderance of Actinobacteria (31.46%) and Proteobacteria (38.95%) phyla in 3S and AB4 with the dominance of Verticillium (22.88%) and Microbacterium (8.16%) in 3S, and Laceyella (24.23%), Methylosinus (8.93%) and Pedobacter (7.73%) in AB4. Functional characterization of the metagenomic reads revealed diverse metabolic potentials and adaptive traits of the microbial communities in the two systems to various environmental stressors. It also revealed the exclusive detection of catabolic enzymes in AB4 system belonging to the aldehyde dehydrogenase superfamily. The results obtained in this study showed that CSL is a potential resource for bioremediation of hydrocarbon-polluted soils.

Formation of bitumen in the Elgin–Franklin complex, Central Graben, North Sea: implications for hydrocarbon charging

Abstract The Elgin–Franklin complex contains gas condensates in Upper Jurassic reservoirs in the North Sea Central Graben. Upper parts of the reservoirs contain bitumens, which previous studies have suggested were formed by the thermal cracking of oil as the reservoirs experienced temperatures of &gt;150°C during rapid Plio-Pleistocene subsidence. Bitumen-stained cores contaminated by oil-based drilling muds have been analysed by hydropyrolysis. Asphaltene-bound aliphatic hydrocarbon fractions were dominated by n -hexadecane and n -octadecane originating from fatty acid additives in the muds. Uncontaminated asphaltene-bound aromatic hydrocarbon fractions, however, contained a PAH distribution very similar to normal North Sea oils, suggesting that the bitumens may not have been derived from oil cracking. 1D basin models of well 29/5b-6 and a pseudo-well east of the Elgin–Franklin complex utilize a thermal history derived from the basin's rifting and subsidence histories, combined with the conservation of energy currently not contained in the thermal histories. Vitrinite reflectance values predicted by the conventional kinetic models do not match the measured data. Using the pressure-dependent PresRo ® model, however, a good match was achieved between observed and measured data. The predicted petroleum generation is combined with published diagenetic cement data from the Elgin and Franklin fields to produce a composite model for petroleum generation, diagenetic cement and bitumen formation.

Remediation of a soil chronically contaminated with hydrocarbons through persulfate oxidation and bioremediation

The impact of remediation combining chemical oxidation followed by biological treatment on soil matrix and microbial community was studied, of a chronically hydrocarbon contaminated soil sourced from a landfarming treatment. Oxidation by ammonium persulfate produced a significant elimination of polycyclic aromatic hydrocarbons (PAHs) and an increase in PAH bioavailability. Organic-matter oxidation mobilized nutrients from the soil matrix. The bacterial populations were affected negatively, with a marked diminution in the diversity indices. In this combined treatment with oxidation and bioremediation working in tandem, the aliphatic-hydrocarbon fractions were largely eliminated along with additional PAHs. The chemical and spectroscopic analyses indicated a change in soil nutrients. In spite of the high residual-sulfate concentration, a rapid recovery of the cultivable bacterial population and the establishment of a diverse and equitable microbial community were obtained. Pyrosequencing analysis demonstrated a marked succession throughout this twofold intervention in accordance with the chemical and biologic shifts observed. These remediation steps produced different effects on the soil physiology. Spectroscopic analysis became a useful tool for following and comparing those treatments, which involved acute changes in a matrix of such chronically hydrocarbon-contaminated soil. The combined treatment increased the elimination efficiency of both the aliphatic hydrocarbons and the PAHs at the expense of the mobilized organic matter, thus sustaining the recovery of the resilient populations throughout the treatment. The high-throughput–DNA-sequencing techniques enabled the identification of the predominant populations that were associated with the changes observed during the treatments.

Identification of 15-nor-cleroda-3,12-diene in a Dominican amber

An unknown compound dominant in the aliphatic hydrocarbon fraction of the solvent extract of a Dominican amber sample was isolated and purified using column chromatography and preparative gas chromatography. 1D and 2D NMR analyses allowed its structure to be assigned as 15-nor-cleroda-3,12-diene. The bridgehead methyl group (CH3 at C-19) has a 13C chemical shift of 19.6ppm, typical for a trans-decalin framework (Nogueira, 2001), indicating the diterpenoid has a trans A/B ring structure. ROESY correlations indicate that the methyl groups at C-19, C-20 were axial and the C-17 methyl group was equatorial, while the H-10 and H-8 were axial and on the other side of Ring B. Taken together, a 5R,8R,9S,10R-configuration for the new nor-clerodadiene can be established. The absolute configuration of 5R,8R,9S,10R was further confirmed by comparing the experimental and calculated electronic circular dichroism (ECD) spectra of this diterpenoid. The identified diene appears to originate from a Hymenaea species (Fabaceae). Non-oxidative decarboxylation of cleroda-3,13-diene-15-oic acid (kovalenic acid) present in Hymenaea species or oxidative decarboxylation of 3-cleroden-15-oic acid in Dominican amber are considered to be the two viable pathways leading to the formation of the identified 15-nor-cleroda-3,12-diene, although the former pathway is more likely.

A possible shale gas prospect? First results of the organic composition and thermal maturity of the Carboniferous Namoi Formation, northern NSW, Australia

ABSTRACTThe Namoi Formation in the Werrie Syncline, north and west of Tamworth, is part of the well-preserved Devonian–Carboniferous fore arc in the New England Fold Belt. The formation is between 640–914 m thick and consists of dominant olive-green mudstones with lenses of sandstone and oolitic limestone. To assess shale gas prospectivity, we analysed five outcrop samples from the Namoi Formation in the Keepit area. Well-preserved aliphatic and aromatic hydrocarbon fractions do not show evidence of weathering or biodegradation. n-Alkanes in all samples have a unimodal distribution maximising at C26 to C28. Little odd-to-even n-alkane carbon number predominance and relatively low Pr/n-C17 and Ph/n-C18 ratios are consistent with a high thermal maturity. Based on the distribution of alkylnaphthalenes and alkylphenanthrenes, the Namoi Formation is in the gas window. Calibration of the methylphenanthrene index and ratio with vitrinite reflectance suggests a calculated reflectance around 2.1%, which given a normal geothermal gradient is equivalent to a maximum temperature of 205°C for the deepest burial of the formation. There is a dominance of parent polycyclic aromatic hydrocarbons (PAH) over alkylated PAHs, supporting a high thermal maturity. Some samples contain biomarkers suggestive of a marine depositional environment, including the C30 sterane index and the C31/C30 hopane ratio. The Namoi Formation is a prospective shale-gas source, as it has been buried sufficiently to be well within the gas window. Where it is exposed at the surface gas will have been lost, but elsewhere it will be buried beneath other sediments and may still retain gas. Key exploration uncertainties include information on organic richness, lateral variation in thermal maturity, mineralogy, and porosity–permeability relationships.

Insights into the biodegradation of weathered hydrocarbons in contaminated soils by bioaugmentation and nutrient stimulation

The potential for biotransformation of weathered hydrocarbon residues in soils collected from two commercial oil refinery sites (Soil A and B) was studied in microcosm experiments. Soil A has previously been subjected to on-site bioremediation and it was believed that no further degradation was possible while soil B has not been subjected to any treatment. A number of amendment strategies including bioaugmentation with hydrocarbon degrader, biostimulation with nutrients and soil grinding, were applied to the microcosms as putative biodegradation improvement strategies. The hydrocarbon concentrations in each amendment group were monitored throughout 112 days incubation. Microcosms treated with biostimulation (BS) and biostimulation/bioaugmentation (BS + BA) showed the most significant reductions in the aliphatic and aromatic hydrocarbon fractions. However, soil grinding was shown to reduce the effectiveness of a nutrient treatment on the extent of biotransformation by up to 25% and 20% for the aliphatic and aromatic hydrocarbon fractions, respectively. This is likely due to the disruption to the indigenous microbial community in the soil caused by grinding. Further, ecotoxicological responses (mustard seed germination and Microtox assays) showed that a reduction of total petroleum hydrocarbon (TPH) concentration in soil was not directly correlable to reduction in toxicity; thus monitoring TPH alone is not sufficient for assessing the environmental risk of a contaminated site after remediation.

Influence of particle size and organic carbon content on distribution and fate of aliphatic and aromatic hydrocarbon fractions in chalks

Abstract Although great efforts had been devoted to investigate the fate and transport of various hydrocarbon sources in major aquifers, there is still a need to better understand and predict their behaviour for robust risk assessment. In this study, the fate and distribution of the aliphatic and polycyclic aromatic hydrocarbons (PAHs) of diesel fuel in chalk aquifer was investigated using a series of leaching column tests and then modelled using the Contaminant Transport module of the Goldsim software. Specifically the influence of chalk particle size on the behaviour and fate of the hydrocarbons was investigated. Distribution coefficient ( K d ) between the water and chalk solid phase according to chalk particle sizes was determined for each hydrocarbon group. The larger sizes of chalk particles have higher K d values. After 60 d of leaching using a water flow of 45 mm d −1 , most of the aliphatic and aromatic hydrocarbon compounds of the diesel were retained within the top 5 cm chalk layer and none of the targeted hydrocarbons were detected in the leachate from the four particles sizes chalk. Further to this, the results showed that the chalk is capable of holding more hydrocarbons than sand and chalk can limit their migration of hydrocarbons. The numerical results and the Monte Carlo analysis showed that the migration of the alkanes and PAHs is greatly retarded by the organic carbon in chalk. It is also observed that the initial mass of the alkanes and PAHs and their respective partition coefficients are important for the decaying of the source at the surface immediately after the spill and the rate-limited dissolution is responsible for entrapping the hydrocarbons in the top layer of the chalk. Overall these results can help to better inform risk assessment and help decision for the remediation strategy.