Aliphatic Fractions Research Articles

Thermolysis of Asphaltenes of Timan–Pechora Heavy Oils

The hydrocarbon composition of the thermolysis products of asphaltenes from biodegraded oils of the Labagan and Usa oilfields and non-biodegraded oil of the Salyukinskoe oilfield of the Timan–Pechora sedimentary basin has been studied. The IR spectra of the asphaltenes are identical, indicating their similar structural group composition. The thermolysis of the asphaltenes has been carried out in an argon flow successively at 300 and 350°C. It has been shown that desorption of saturated and aromatic components from the pores of the asphaltenes predominantly occurs at 300°C. For the initial biodegraded oils and the oil that did not undergo biochemical oxidation, a number of geochemical parameters calculated in terms of acyclic hydrocarbons (HCs) and polycyclic biomarkers turns out to be similar to those obtained for the thermolysis products of the asphaltenes heated at 350°C. The values of the methylphenanthrene index are similar for the thermolysis products of asphaltenes and the parent oils. This similarity, in turn, allows the genetic identification of oils and evaluation of their catagenetic maturity by asphaltene thermolysis products in the case when biomarkers of the aliphatic fraction are lost during biodegradation. An analysis of the supermolecular structure of the asphaltenes of the oils under study has shown a general trend of its change by heating at 350°C, which consists in a sharp decrease in the particle size and loosening of the particle packing due to the appearance of pronounced porosity.

Organic geochemistry and kinetics for natural gas generation from mudstone and coal in the Xihu Sag, East China Sea Shelf Basin, China

Abstract A comparative study on organic geochemistry and kinetics was performed on two representative coal measure mudstone and coal samples of the Eocene Pinghu Formation in the Xihu Sag, East China Sea Shelf Basin, China. Gas chromatography–mass spectrometry analysis of the aliphatic fractions of the source rock extracts was performed to characterize the maturity, depositional conditions, and source materials in the samples. The kerogens isolated from the mudstone and coal were pyrolyzed in a closed-system at two heating rates to determine the kinetics for natural gas generation, and the results were extrapolated to geological conditions. Biomarker assemblages show that the mudstone (type III kerogen) and coal (type II/III kerogen) contain predominantly terrigenous source materials with the effect of microbial reworking, and were deposited under oxic conditions within an unstratified water column. The mudstone has slightly more algal material input and less oxic conditions during deposition than the coal. The rocks are at the early-mature stage but the coal is slightly more mature than the mudstone. The activation energies for natural gas generation from the mudstone and coal distribute mainly in the range of 47–62 kcal/mol and 50–69 kcal/mol with a frequency factor of 2.0 × 1011 s−1 and 1.0 × 1013 s−1, respectively. The lower activation energies for the mudstone than the coal suggests an earlier onset of natural generation. Assuming a constant burial heating rate of 3 °C/Ma for the calculated activation energy distributions, the calculated temperature for a given transformation ratio can differ by > 60 °C, indicating varying kinetic stability due to different kerogen composition and structure. This significant and unexpected difference suggests that more attentions should be paid to the kinetic heterogeneity of coal bearing source rocks, and we must be particularly cautious about selecting appropriate kinetic models in petroleum system modeling.

Molecular structure characterization of low-medium rank coals via XRD, solid state 13C NMR and FTIR spectroscopy

In-depth understanding of coal molecular structures is crucial to the clean and efficient coal conversion, as they are the dominant factors determining the reactivity and reaction behaviors of coals in thermal conversions such as combustion, pyrolysis, gasification and liquefaction. However, the molecular structures of coals are still far from clear due to the intrinsic complexity and heterogeneity of coals. This work probes the molecular structures of eight coals of various metamorphic grades with combined spectral techniques of X-ray diffraction (XRD), solid state 13C NMR and FTIR spectra. The structural parameters were correlated with the coalification indicator Ro to investigate the structural evolutions during coal metamorphism. Consistent results concerning the structural evolution during coalification were obtained with different techniques. From the parameters of proximate and ultimate analysis, the increasing aromaticity and decreasing aliphatic fractions with rising coalification degree are observed. XRD patterns show the ubiquitous presence of amorphous carbon, the gradually condensing aromatic layers, and the size-growing but graphitizing crystallites during coalification. 13C NMR spectra reveal different types of carbons presented, the increasing aromatic and decreasing aliphatic components, the growing size and weight but reducing number of side-chains of the aromatic clusters. FTIR spectra indicate shortening and reducing of aliphatic chains, as well as enhancing aromaticity with the deepening metamorphism. These findings shed light on the structure features of coals and are potentially useful to the clean and efficient coal utilization.

Kinetika Kimia Antibakteri Fraksi Alkana Alifatik Hasil Pirolisis Cangkang Biji Jambu Mete (CNS)

Chemical kinetics research antibacterial of aliphatic alkane fraction from the results of pyrolysis Cashew Nut Shell (CNS) (Annacardium occidentale L.) on Eschericia coli have been carried out. Cashew nuts are prepared by separating the shell and seeds for pyrolysis and purifying using a fractional distillation device. The results of E. coli anti-bacterial activity test from aliphatic alkane fractional distillation results of cashew nut shell pyrolysis products showed that the inhibitory power was different from each concentration variation of 100%, 75%, 50%, 25%, and 12.5%, with inhibitor zone: 8.02; 7.16; 5.56; 4.52 dan 4.26 mm which indicates that the inhibition is weak category for 12.5% and 25%, medium category for 50%, 75% and 100%. The clear zone that has been formed are calculated in terms of its chemical kinetics including the reaction order and the activity rate constant. The reaction order (n) antibacterial of aliphatic alkane fraction from the results of pyrolysis CNS on E. coli was 0.3145 with a constant activity rate of (k) = 1,7791.

Environmental aspects of petroleum storage in above ground tank

Oil pollution is a severing global environmental problem causing a number of adverse negative impacts on human health air ecosystem and eventually the natural income that is why soil, water, air pollution with petroleum hydrocarbons have become the focus of increasing public and research concern petroleum hydrocarbon contaminants in the air environment are caused by human activities when harmful or excessive quantities of substances are introduced into Earth’s atmosphere. Sources of air pollution include gases such as carbon monoxide, sulfur dioxide, hydrogen sulfide, methane, the aliphatic and polycyclic aromatic hydrocarbons (PAH’s) fractions of petroleum are readily evolved to air during refinery and choosing the wrong storage tanks also leak to the soil change the chemical composition of spilled toxicity and biological impacts of the oil and add great difficulties to the identification of the residual spilled oil in the impacted environment and economic cost of air pollution in illness, health care costs, lost productivity so coordination between humans to conserves natural resources for future generation.

Efficient biodegradation of petroleum n-alkanes and polycyclic aromatic hydrocarbons by polyextremophilic Pseudomonas aeruginosa san ai with multidegradative capacity.

Pseudomonas aeruginosa san ai, an alkaliphilic, metallotolerant bacterium, degraded individual selected petroleum compounds, i.e., n-alkanes (n-hexadecane, n-nonadecane) and polycyclic aromatic hydrocarbons (fluorene, phenanthrene, pyrene) with efficiency of 80%, 98%, 96%, 50% and 41%, respectively, at initial concentrations of 20 mg L−1 and in seven days. P. aeruginosa san ai showed a high biodegradative capacity on complex hydrocarbon mixtures, the aliphatic and aromatic fractions from crude oil. The efficiency of P. aeruginosa san ai degradation of crude oil fractions in seven days reached stage 3–4 of the oil biodegradation scale, which ranges from 0 (no biodegradation) to 10 (maximum biodegradation). Identified metabolites concomitant with genomic and enzymatic data indicated the terminal oxidation pathway for the n-alkane degradation, and the salicylate and phthalate pathways for fluorene biodegradation. Polyextremophilic P. aeruginosa san ai, as a biosurfactant producer with multidegradative capacity for hydrocarbons, can be used in an improved strategy for environmental bioremediation of hydrocarbon-contaminated sites, including extreme habitats characterized by low or elevated temperatures, acidic or alkaline pH or high concentrations of heavy metals.

Cultivation substrata differentiate the properties of river biofilm EPS and their binding of heavy metals: A spectroscopic insight

River biofilms inevitably serve as recipients of heavy metals including copper (Cu) and cadmium (Cd) following their introduction in fluvial systems. Nevertheless, the effects of cultivation substrata on the characteristics of river biofilm extracellular polymeric substances (EPS) and the binding behaviors of heavy metals on biofilms remain unclear. Integrating spectroscopic methods with chemometric analyses, we explored the binding behaviors of Cu(II) and Cd(II) onto biofilm EPS cultivated from two representative substrata at the molecular level. Chemical analysis revealed that biofilm cultivated on polyethylene (PE) pieces contained more non-fluorescent protein fractions, whereas EPS from periphyton grown on mineral, i.e., cobblestones was richer in aromatic fractions and polysaccharides. Excitation-emmision matrix combined with parallel factor analysis suggested a stronger interaction between fluorophores in periphytic EPS with Cu(II) compared to fluorophores in plastic biofilm EPS. Integrated use of infrared spectroscopy and two-dimensional correlation analyses revealed that, during the heavy metal binding processes, the amines and phenolics in plastic biofilm EPS gave the fastest responses to metal binding. While the amides and the aliphatic fractions in periphytic EPS showed a preferential binding to heavy metals. This study differentiates the effects of cultivation substrata on structuring the biofilm EPS characteristics and offers new insights into the environmental behaviors of heavy metal discharge into fluvial systems in river biofilm matrix.

Comparative analysis of the chemical composition and water permeability of the cuticular wax barrier in Welsh onion (Allium fistulosum L.).

Cuticular wax is a hydrophobic barrier between the plant surface and the environment that effectively reduces the loss of water. The surface of Welsh onion leaves is covered with wax. To explain the relationship between wax composition and water loss, we conducted this experiment. The water permeability and wax composition of leaves were determined by chemical and GC-MS methods. We performed a comparative analysis of the differences between the two cultivars and analyzed the relationship between water permeability and waxy components. Overall, the permeability to water was higher in 'Zhangqiu' than in 'Tenko'. The wax amount of 'Tenko' was 1.28-fold higher than that of 'Zhangqiu' and was primarily explained by the much larger amounts of ketones and alcohols in the former. Among the waxy components, C29 ketones were most abundant. There were substantial discrepancies in wax composition, total wax content, and water permeability between the two cultivars. The main reason for the discrepancy in water permeability may be the significantly lower aliphatic fraction in 'Zhangqiu' than in 'Tenko'. This study makes a vital contribution to drought resistance research on allium plants.

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.

Pattern recognition analysis of gas chromatographic and infrared spectroscopic fingerprints of crude oil for source identification

In this study, a chemometric strategy was developed for analysis of gas chromatographic (GC) and infrared spectroscopic (FT-IR) fingerprints of nine crude oil samples from the main oil wells of Iran to classify them and to find their origins. In this regard, a fractionation method based on saturated, aromatic, resin, and asphaltene (SARA) test was used. Then, these fractions were analyzed by GC-FID and GC–MS. Also, nine crude oil samples were analyzed by FT-IR.The obtained GC fingerprints were aligned using correlation optimized warping (COW) and auto-scaled, and then analyzed using principal component analysis (PCA) and hierarchical cluster analysis (HCA). Evaluation of PCA scores plot (explaining 89.35% of variance for two PCs) and HCA dendrogram showed that aromatic fractions belong to three classes. The clustering results of aliphatic and resin fractions also showed the presence of three clusters but with different samples due to the difference in their composition. The results of unsupervised classification were then used as a starting point for partial least squares-discriminant analysis (PLS-DA) and counter propagation-artificial neural network (CP-ANN).On the other side, FTIR fingerprints of crude oil samples were also clustered using PCA and HCA. Evaluation of PCA scores plot (explaining 95.15% of variance for two PCs) and HCA dendrogram showed that samples belong to three clusters. These initial results were used as a starting point for PLS-DA and CP-ANN. Accuracy of PLS-DA was 0.890 for calibration and 0.818 for test sets. Also, CP-ANN accuracy values were 1.000 and 0.818 for train and test sets, respectively.

Deep resistivity \u201cturnover\u201d effect at oil generation \u201cpeak\u201d in the Woodford Shale, Anadarko Basin, USA

The Devonian Woodford Shale in the Anadarko Basin is a highly organic, hydrocarbon source rock. Accurate values of vitrinite reflectance (Ro) present in the Woodford Shale penetrated by 52 control wells were measured directly. These vitrinite reflectance values, when plotted against borehole resistivity for the middle member of the Woodford Shale in the wells, display a rarely reported finding that deep resistivity readings decrease as Ro increases when Ro is greater than 0.90%. This phenomenon may be attributed to that aromatic and resin compounds containing conjugated pi bonds generated within source rocks are more electrically conductive than aliphatic compounds. And aromatic and resin fractions were generated more than aliphatic fraction when source rock maturity further increases beyond oil peak. The finding of the relationship between deep resistivity and Ro may re-investigate the previously found linear relationship between source rock formation and aid to unconventional play exploration.

Biodegradation of aliphatic and polycyclic aromatic hydrocarbons in seawater by autochthonous microorganisms

The bioremediation of petroleum spills in marine environments is still a challenge nowadays, and the technology available towards this goal must be improved. The search for efficient and applicable systems requires the prospection, isolation and characterization of autochthonous microorganisms with potential for bioremediation. Here, microorganisms were isolated from “Lagoa do Peixe” National Park, a site with a history of frequent petroleum spills in Brazil. The isolation methodology was based on the enrichment of microorganisms able to biodegrade petroleum hydrocarbons. After preliminary tests of 2,3,5-triphenyl tetrazolium chloride (TTC) redox indicator, two bacteria were able to produce biosurfactants and metabolize complex carbon sources in a solid medium: Bacillus methylotrophicus SSNPLPB5 and Pseudomonas sihuiensis SNPLPB7. Biodegradation assays using aliphatic and polycyclic aromatic hydrocarbons (PAHs) sources showed that both bacteria are able to biodegrade: (i) up to 92.1% and 42.4% of the medium (C8 to C19) and long (C20 to C33) chain aliphatic contaminant fraction, respectively; (ii) 31.1% of isoprenoid (pristane) and (iii) 46% of anthracene, 33.9% of phenanthrene and 35.3% of pyrene, after 46 days of incubation in seawater. The isolates were shown to produce biosurfactants such as surfactins, iturins, mono- and di-rhamnolipids, which reduced the surface tension, pH and showed emulsifying activity of the cell-free supernatant at the end of the incubation time, with potential application in petroleum spills bioremediation.

First Investigation of Seasonal Concentration Behaviors and Sources Assessment of Aliphatic Hydrocarbon in Waters and Sediments from Wadi El Bey, Tunisia.

The contents, composition profiles, and sources of aliphatic hydrocarbons were examined in surface sediment and water samples collected from Wadi El Bey, in Tunisia, during different year seasons in 14 stations receiving domestic effluent, industrial discharge, and agricultural drainage wastes. The target substances were analyzed by gas chromatography coupled with mass spectrometric detection (GC/MS). Total concentrations of n-alkanes (n-C14-n-C38) ranged from 0.08 ± 0.01 to 18.14 ± 0.1µg/L in waters and 0.22 ± 0.04 to 31.9 ± 24.6µg/g in sediments, while total aliphatic fraction ranged from 0.08 ± 0.01 to 196 ± 140µg/L in waters and 0.22 ± 0.04 to 1977 ± 1219µg/g in sediments, which means that almost all sites were affected by hydrocarbon contents in sediments exceeding the recommended limit (100µg/g). Various diagnostic indices (ADIs) were used to identify the hydrocarbon sources, namely the concentration ratios of individual compounds (n-C17/pristane, n-C18/phytane, pristane/phytane, n-C29/n-C17, n-C31/n-C19) as well as cumulative quantities (Carbon Preference Index, natural n-alkanes ratio, terrigenous/aquatic compounds ratio, unresolved complex mixture percentage, low molecular weight vs. high molecular weight homologues, Alkane Proxy and Terrestrial Marine Discriminants). In general, these indexes indicated that the origin of aliphatic hydrocarbons affecting sediments and waters of Wadi El Bey were linked to both biogenic and petrogenic inputs, attesting the impact of plankton and terrestrial plants and of oil contamination, respectively. The average carbon chain length computation (ACL), used to further index the chemical environment, ranged from 25.5 to 31.1 in sediments and 47.9-116 in waters. This finding could depend on the severe disturbances suffered by the ecosystem as a consequence of heavy anthropogenic inputs. Petroleum contamination associated with high eutrophication rates in Wadi El Bey must be strictly controlled, due to possible harmful effects induced on ecosystem and humans.

Functional and Genomic Characterization of a Pseudomonas aeruginosa Strain Isolated From the Southwestern Gulf of Mexico Reveals an Enhanced Adaptation for Long-Chain Alkane Degradation

Indigenous bacterial populations play an important role in the restoration of crude oil-polluted marine environments. The identification and characterization of these bacteria are key in defining bioremediation strategies for the mitigation of possible future oil spills. In this work, we characterized Pseudomonas aeruginosa strain GOM1, which was isolated from the water column in the southwestern Gulf of Mexico. Phylogenetic analysis revealed that GOM1 strain was most closely related to P. aeruginosa WC55, a strain isolated from the northern Gulf of Mexico after the Deepwater Horizon oil spill. The hydrocarbon-degrading capacity of P. aeruginosa GOM1 was investigated using various approaches. This strain degraded 96% of the aliphatic fraction (C12-C38) of crude oil during a 30-day incubation period, exhibiting a high activity on long-chain alkanes, and expressing alkane hydroxylases AlkB1, AlkB2 and AlmA. Addition of nitrogen and phosphate to seawater culture medium enhanced hexadecane degradation by GOM1. Additionally, the strain exhibited high surfactant/rhamnolipid production and emulsifying activity when grown in a complex medium in the presence of hexadecane. Comparisons of growth kinetics, hydrocarbon degradation and gene expression between GOM1 and the closely related P. aeruginosa laboratory strain PAO1 revealed that the marine isolate is better adapted to degrade alkanes. Taken together, our results place P. aeruginosa GOM1 as a potentially effective candidate to be included in a consortium for use in the bioremediation of oil-polluted sites.

Fungal proliferation and hydrocarbon removal during biostimulation of oily sludge with high total petroleum hydrocarbon.

A laboratory-scale study was conducted to investigate the effect of bioaugmentation (BA) and biostimulation (BS) on the remediation of oily sludge with high total petroleum hydrocarbon (TPH) content (269,000mg/kg d.w. sludge). TPH concentration significantly decreased by 30.4% (P < 0.05) in the BS treatment after 13-week incubation, and 17.0 and 9.1% of TPH was removed in the BA and control treatments (amended with sterile water only), respectively. Aliphatic and other fractions (i.e., saturated n-alkanes and cyclic saturated alkanes) were reduced in the BS treatment, whereas no decrease in aromatic hydrocarbons occurred in any treatment. Gas chromatography-mass spectrometry analysis of aliphatic fractions showed that low-chain-length alkanes (C8-C20) were the most biodegradable fractions. The BS treatment supported fungal proliferation, with Sordariomycetes and Eurotiomycetes as the dominant classes. BS increased fungal diversity and decreased fungal abundance, and changed bacterial community structure. The findings show the potential of using BS to treat oily sludge with high TPH content. Graphical abstract.

The Analysis of n-Alkane Hydrocarbons in the Sediment around the Coast of Makassar Using Mopi Indicator

This study aims to determine the content of n-alkanes in the sediment around the coast of Makassar using the MOPI (Marine Oil Pollution Index) indicator. The method includes the sediment sampling from nine different stations with the Phleger Corer Sampler in gravimetric analysis to identify the concentration of organic material extract and aliphatic fraction. To identify the characteristic of n-alkane hydrocarbons, gas chromatography of mass spectra method was applied. The results of the aliphatic fraction (F1) analysis of the coastal sediments which were contaminated with low biogenic - petrogenic have a MOPI scores of 3, which is supported by a high UCM (Unresolved Complex Mixture) and n-alkane identified between C1-C44. While the sediments that come from natural processes, pure - biogenic and biogenic, have MOPI scores ​​between 1 and 2. This is supported by the chromatogram profile with an area of ​​UCM generally smaller by n-alkanes identified between C15-C58

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.

Structural characteristics of humic-like acid from microbial utilization of lignin involving different mineral types.

This paper determines the impact of two clay minerals (kaolinite and montmorillonite) and three oxides (goethite, δ-MnO2, and bayerite) on the elemental composition and FTIR spectra of humic-like acid (HLA) extracted from microbial-mineral residue formed from the microbial utilization of lignin in liquid shake flask cultivation. Goethite, bayerite, and δ-MnO2 showed higher enrichment capabilities of C and O + S in the HLA than kaolinite and montmorillonite. Goethite showed the highest retention of organic C, followed by bayerite, but kaolinite exhibited the least exchangeability. Kaolinite and montmorillonite enhanced microbial consumption of N, resulting in the absence of N in HLA. A few aliphatic fractions were preferentially gathered on the surfaces of kaolinite and montmorillonite, making the H/C ratios of HLA from the clay mineral treatments higher than those of HLA from the oxide treatments. δ-MnO2 was considered the most effective catalyst for abiotic humification, and goethite and bayerite ranked second and third in this regard. This trend was proportional to their specific surface areas (SSAs). However, comparing the effects of different treatments on the promotion of HLA condensation by relying solely on the SSA of minerals was not sufficient, and other influencing mechanisms had to be considered as well. Additionally, Si-O-Al and Si-O of kaolinite participated in HLA formation, and Si-OH, Si-O, and Si-O-Al of montmorillonite also contributed to this biological process. Fe-O and phenolic -OH of goethite, Mn-O of δ-MnO2, and Al-O of bayerite were all involved in HLA formation through ligand exchange and cation bridges. Lignin was better protected from microbial decomposition by the kaolinite, bayerite, and δ-MnO2 treatments, which caused lignin-like humus (HS) formation. Under the treatments of δ-MnO2, goethite, and bayerite, HLA showed a greater degree of condensation compared to HLA precipitated by kaolinite and montmorillonite. Contributions from Si-O, and Si-O-Al of clay minerals, and Fe-O, Mn-O, and Al-O of oxides were the mechanisms by which minerals catalyzed the formation of HS from lignin.

Influence of organic carbon fractions of freshwater biofilms on the sorption for phenanthrene and ofloxacin: The important role of aliphatic carbons

Sorption to biofilms is thought to be a crucial process controlling the fate of trace organic contaminants in aquatic systems. The organic composition of biofilms is regarded as the determining factor in the sorption mechanism of biofilm organic carbon fractions; however, its role is not well known. Here, the sorption of phenanthrene and ofloxacin was modeled with classic and emerging organic contaminants, respectively, by comparatively investigating nine type of freshwater biofilms cultured in a river, lake, and reservoir in spring, summer, and autumn. The chemical features of the nine biofilms were analyzed using elemental analysis, infrared spectroscopy, X-ray photoelectron spectroscopy, and carbon-13 nuclear magnetic resonance. Results showed that the freshwater biofilms were aliphatic-rich natural amorphous solid substances with O-containing functional groups, and their surface polarity was significantly lower than their bulk polarity. All the isotherms of phenanthrene and ofloxacin sorption by the biofilms were linear. The organic carbon-normalized partition coefficient values for phenanthrene and ofloxacin on the nine biofilms ranged from 91.9 to 364.2 L g−1 and 3.2 to 43.2 L g−1, respectively. The van der Waals interaction between a majority of aliphatic carbon (73.4%–83.9%) in biofilms and the two sorbates was much stronger than π-π interactions between a minority of aromatic carbon (12.7%–21.7%) and sorbates. The surface polarity of the biofilms regulated polar interactions including the hydrogen bonding and electron donor–acceptor interactions. Both the aliphatic carbon and surface polarity in the biofilms enhanced the sorption of phenanthrene and ofloxacin. The sorption characteristics and mechanisms of polycyclic aromatic hydrocarbons and antibiotics on biofilms shown in our present and previous studies are different from those of other ubiquitous natural solid materials such as soils and sediments. This study provides insight into the importance of aliphatic carbon fractions of freshwater biofilms for the sorption of classic and emerging organic contaminants.

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.