Effects of suspended particles and dispersants on marine oil snow formation of crude oil/diesel oil.

Marine oil snow (MOS) potentially forms after an oil spill. To fully understand the mechanism of its formation, we investigated the effects of suspended particles (SP) and dispersants on MOS formation of crude oil and diesel oil by laboratory experiments. In the crude oil experiment, the SP concentration of 0.2 g L-1 was more suitable for crude oil MOS formation. The addition of dispersants significantly stimulated N and TV during MS/MOS formation of SP at 0.4 g L-1 and 0.8 g L-1 concentration (p < 0.05). Without SP, the dispersants also stimulated crude oil MOS formation. Furthermore, the concentration of SP had a significantly positive effect on the reduction of the total amount of N-alkanes (p < 0.05). In the diesel oil experiment, after adding dispersants to diesel oil, the maximum N, Dm, and TV values at a SP concentration of 0.2 g L-1 were significantly higher than those at 0.4 g L-1 and 0.8 g L-1 (p < 0.05). Besides, we found that dispersants stimulated MOS formation in diesel oil at a SP concentration of 0.2 g L-1. However, the dispersants had an inhibitory effect on diesel oil MOS formation without SP. Notably, the MOS formed by diesel oil appeared white, unlike the black MOS associated with crude oil. These findings are important for the environmental impact of oil spills and elevated SP concentrations.

Tar ball pollution under the influence of ocean circulation in the Bohai Sea, China.

The deposition of tar balls of unknown sources on the coast poses a great threat to the fishery, tourism and coastal biodiversity in the Bohai Sea. This work aimed to identify the sources of tar balls by using oil fingerprint technique. Tar ball samples were collected from the seashore of two islands of the western Bohai Sea and divided into two groups (Group I and Group II). Principal component analysis showed that although Caofeidian oilfield was one of the closest oilfields to the sampling area it was not a source. Fingerprints of characteristic hopanes and steranes showed that samples of Group I were similar to the crude oils from the nearby Jidong oilfield, and samples of Group II were similar to the Penglai-19-3 crude oils. Combined with cross-plots of the samples and the reference oils, it indicated that Group I may come from Jidong and Group II may come from Penglai-19-3. The weathering characteristics of alkanes and polycyclic aromatic hydrocarbons showed that the samples were affected by natural weathering processes (e.g., evaporation, photooxidation and biodegradation). It revealed that oil pollution from the nearby oilfields can also affect other areas under the influence of ocean circulation. It is the first study on source identification of tar balls from the Bohai Sea and the effects of ocean circulation on the tar ball transport. This study can considerably help to further understand the evolution of tar balls and consequently determine their sources.

Chemometric techniques in oil spill identification: A case study in Dalian 7.16 oil spill accident of China.

Chemometric methods have unique advantages regarding comprehensive consideration of multiple parameters and the classification of samples or variables. Classification of oil spill sources was carried out by using chemometric techniques, such as Repeatability Limit, hierarchical cluster analysis (HCA), Student's t-test and Principal component analysis (PCA) Biplot. In addition, this paper takes the fingerprint identification of a Dalian "7.16″ oil spill accident as an example to illustrate the effectiveness of chemometric techniques in oil identification. PCA scores plot (explaining 82.77% of variance accounted for three PCs) showed that samples belong to four clusters and result of HCA method further confirmed that. The residual oil in Jinshatan Beach and Haibei Square may be caused by the explosion of Dalian "7-16" oil pipeline accident. The use of chemometric techniques is significant in providing independent validation for classifying the types of spilled oil in the investigation of oil spill pollution. The results will be of great significance to improve the accuracy and efficiency of oil spill identification based on oil fingerprint.

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.

Biodegradation of marine oil spill residues using aboriginal bacterial consortium based on Penglai 19-3 oil spill accident, China.

Bioremediation, mainly by indigenous bacteria, has been regarded as an effective way to deal with the petroleum pollution after an oil spill accident. The biodegradation of crude oil by microorganisms co-incubated from sediments collected from the Penglai 19-3 oil platform, Bohai Sea, China, was examined. The relative susceptibility of the isomers of alkylnaphthalenes, alkylphenanthrenes and alkyldibenzothiophene to biodegradation was also discussed. The results showed that the relative degradation values of total petroleum hydrocarbon (TPH) are 43.56% and 51.29% for sediments with untreated microcosms (S-BR1) and surfactant-treated microcosms (S-BR2), respectively. TPH biodegradation results showed an obvious decrease in saturates (biodegradation rate: 67.85-77.29%) and a slight decrease in aromatics (biodegradation rate: 47.13-57.21%), while no significant difference of resins and asphaltenes was detected. The biodegradation efficiency of alkylnaphthalenes, alkylphenanthrenes and alkyldibenzothiophene for S-BR1 and S-BR2 samples reaches 1.28-84.43% and 42.56-86.67%, respectively. The efficiency of crude oil degradation in sediment with surfactant-treated microcosms cultures added Tween 20, was higher than that in sediment with untreated microcosms. The biodegradation and selective depletion is not only controlled by thermodynamics but also related to the stereochemical structure of individual isomer compounds. Information on the biodegradation of oil spill residues by the bacterial community revealed in this study will be useful in developing strategies for bioremediation of crude oil dispersed in the marine ecosystem.

In situ microbial remediation of crude oil-soaked marine sediments using zeolite carrier with a polymer coating.

Marine oil spill pollution is an important environmental problem in the world, especially crude oil-soaked marine sediments, because they are difficult to be remediated. In this study, in situ bioremediation of oil-soaked sediment was performed in the middle of the Bohai Sea. Oil-degrading bacteria were adsorbed on powdery zeolite (PZ)/granular zeolites (GZ) surfaces and then wrapped with poly-γ glutamic acid (γ-PGA). Settling column and wave flume experiments were conducted to model marine conditions and to select appropriate biological reagents. The optimal conditions were as follows: the average diameter of GZ 3 mm, mass ratio of GZ/PZ 2:1, and concentration of γ-PGA 7%. After bioremediation, over 50% of most oil-spilled pollutants n-alkanes (C12 to C27) and polycyclic aromatic hydrocarbons were degraded in 70 days. This work resulted in a successful trial of in situ bioremediation of oil-soaked marine sediments.

Petroleum hydrocarbons in a water-sediment system from Yellow River estuary and adjacent coastal area, China: Distribution pattern, risk assessment and sources.

Aliphatic hydrocarbons (AHs), biomarker and polycyclic aromatic hydrocarbons (PAHs) concentrations of surface water and sediment samples collected from Yellow River Estuary and adjacent coastal area in China were measured to determine their spatial distributions, analyze their sources and evaluate the ecological risk of PAHs in the water-sediment system. The spatial distributions of n-alkane in sediments are mainly controlled by the mixing inputs of terrigenous and marine components. In comparison with AHs, the total concentrations of Σ16PAHs in surface sediments from a transect of the offshore area were noticeably higher than that of the riverine and estuary areas. Additionally, the AHs and total PAHs concentrations all indicated an overall pattern of a seaward decrease. The PAHs concentrations during the dry season (mainly in the form of dissolved phase) were higher than that of PAHs (mainly dissolved phase and particulate phase form) in the flooding season. In comparison with global concentration levels of PAHs, the level of PAHs in suspended particulate matter and sediments from the Yellow River Estuary was lower than those from other countries, while the concentration of PAHs in the dissolved phase were in the middle range. Petroleum contamination, mainly from oil exploration and discharge of pollutants from rivers, was the main source of n-alkanes. The PAHs in the river were mostly of petrogenic origin, while those in the estuarial and marine areas originated mainly from pyrogenic sources. The results of the toxicology assessment suggested that the PAHs in sediments from Yellow River Estuary and adjacent coastal area exhibited a low potential eco-toxicological contamination level.

New diagnostic ratios based on phenanthrenes and anthracenes for effective distinguishing heavy fuel oils from crude oils.

The heavy fuel oils (HFOs) and crude oils are the main oil types in the marine oil spill accidents in China. It is usually a challenge to distinguish the HFOs from crude oils due to the highly similar physicochemical characteristics. In this paper, the distributions of phenanthrene (Phe), anthracene (Ant), methyl-phenanthrene (MP) and methyl-anthracene (MA) in hundreds of HFOs and crude oils samples which were collected from all over the world were characterized. Nine new diagnostic indexes, such as Ant/(Ant+Phe) and other eight diagnostic ratios based on the MP isomers and MA, were developed for effective distinguishing HFOs from crude oils. The histogram with normal fit plots, the double ratio plots and Bayes discriminant analysis (BDA) method were employed to illustrate the effectiveness of the new diagnostic indexes. BDA model based on nine new diagnostic indexes demonstrated high precision with discriminant ratio which lay between 93.92% and 99.32%.

Distributions and sources of petroleum, aliphatic hydrocarbons and polycyclic aromatic hydrocarbons (PAHs) in surface sediments from Bohai Bay and its adjacent river, China.

Surface sediment samples from Bohai Bay and its adjacent river, China, were analyzed for aliphatic hydrocarbon, PAHs and biomarkers in order to determine the distribution, composition and source of organic matter in a coastal environment. Results suggested that the input of organic matter from anthropogenic activities has a more significant influence on its distribution than that from natural processes. Petroleum contamination, mainly from offshore oil exploration and discharge of pollutants from rivers, was the main source of n-alkanes. PAHs were mostly of pyrogenic origin; while some sites in Yellow River Estuary were derived mainly from the petrogenic sources. The toxic assessment suggested that the PAHs in surface sediments will not cause immediately adverse biological effects in sediments from Bohai Bay and its adjacent river, China.

Study of weathering effects on the distribution of aromatic steroid hydrocarbons in crude oils and oil residues.

The composition and distribution of triaromatic steroid hydrocarbons in oil residues after biodegradation and photo-oxidation processes were detected, and the diagnostic ratios for oil spill identification were developed and evaluated based on the relative standard deviation (RSD) and the repeatability limit. The preferential loss of C27 methyl triaromatic steranes (MTAS) relative to C28 MTAS and C29 MTAS was shown during the photo-oxidation process. In contrast to the photochemical degradation, the MTAS with the original 20R biological configuration was preferentially degraded during the biodegradation process. The RSD of most of the diagnostic ratios of MTAS ranged from 9 to 84% during the photo-oxidation process. However, the RSDs of such ratios derived from MTAS were all <5% even in high biodegradation, and such parameters may also provide new methods on oil spill identification. The parameters of monoaromatic sterane and monoaromatic sterane are not used well for oil spill identification after photo-oxidation. The triaromatic steroid hydrocarbons retained their molecular compositions after biodegradation and photo-oxidation and most of the diagnostic ratios derived from them could be efficiently used in oil spill identification.

Fingerprint and weathering characteristics of crude oils after Dalian oil spill, China.

In an attempt to analyze the chemical characterization of oil residues and examine the suitability of chemical fingerprinting methods in oil spill investigations, multiple parameters sensitive to both sources and degree of weathering were used to characterize oil residues from "7-16" Dalian oil spill, China. Oil residues collected 90 days to 120 days after the spill showed a weathering pattern where significant amounts of light to middle molecular weight normal alkanes were depleted with pristane and phytane as dominant peaks. Diagnostic ratios developed from n-alkane and selected isoprenoids (e.g. Pr/Ph, n-C17/Pr, n-C18/Ph, carbon preference index, LMW/HMW-alkanes ratio), all display obvious changes over weathering time, indicating that these ratios are not valid for oil source identification. Furthermore, the biomarker ratios of hopanes and steranes with relative standard deviations (RSDs) of 0.88-4.08% were useful for source identification even for severely weathered oil residues. In addition, RSD of δ(13)C values of individual n-alkanes in oil residue varied from 0.07% to 0.20%, which suggest that stable carbon isotope profile of n-alkanes can also be a useful tool for tracing the source of an oil spill.

Chemical characterization of naturally weathered oil residues in the sediment from Yellow River Delta, China.

With its close proximity to Shengli Oilfield, China's second largest oilfield, the Yellow River Delta is at high risk for crude oil contamination. The massive oil discharge in oilfield may offer a chance for a natural experiment to investigate compositional changes of oil residues and study the stability of source- and weathering-dependent molecular parameters in oil residues after spills. The results demonstrate that the conventional diagnostic ratios, such as C2920S/(20S+20R), C29/C30H, C30ßα/αß, C3122S/(22S+22R), C2-DBTs/C2-PHENs, C3-DBTs/C3-PHENs, DBT/MCHRY, CHRY/PHENs, are also valid for oil source identification even after extensive weathering of spilled oils in terrestrial environment, although some exceptions were encountered for extensively weathered sample. Moreover, the ratios of selected specific biomarkers (the oleanane index, the gammacerane index) have been developed and assessed as source indicators. Finally, we find that some maturity parameters based on alkyl naphthalenes and methyl phenanthrenes in petroleum geochemistry, such as the methylnaphthalene ratios (TMNr, TeMNr, PMNr), the methylphenanthrene ratios (MPI-1, MPDF), can be applied for the source identification and correlation at their lightly to moderately weathered stage.