Characteristics of sub-micron aerosols in the Yellow Sea and its environmental implications.

The Yellow Sea, characterized by an influx of both natural marine and anthropogenic pollutants, coupled with favorable photochemical conditions, serve as key sites for potential interactions between atmospheric gases and aerosols. A recent air monitoring campaign in the Yellow Sea revealed aerosol contributions from four sources, with the highest mass concentrations and dominance of NO3- (38.1 ± 0.37 %) during winds from China. Indications of potential secondary aerosol formation were observed through the presence of hydrolysis and oxidation products of nitrate and volatile organic compounds. Correlations between time series distributions of biomass burning organic aerosols and particle number counts (Dp 100-500 nm, R2 = 0.94) further suggest potential size growth through adsorption and scavenging processes. The results from this study provide observational evidence of a shift in atmospheric compositions from sulfate to nitrate, leading to an increased atmospheric nitrogen deposition in the Yellow Sea.

Use of molecular composition and compound-specific isotope analysis for source appointment of PAHs in sediments of a highly industrialized area.

This study utilized both conventional molecular analysis and compound-specific isotopic techniques to identify the sources of polycyclic aromatic hydrocarbons (PAHs) in sediments of Ulsan Bay, South Korea. The concentrations of 15 traditional and 11 emerging PAHs were determined in sediments from 21 source sites and 26 bay sites. The concentrations and compositions of traditional and emerging PAHs varied significantly, even at sites close to the source areas. The results obtained from diagnostic ratios and the positive matrix factorization model for source identification were inconsistent in adjacent source areas. The δ13C profiles of PAHs, such as phenanthrene (Phe), fluoranthene (Fl), pyrene (Py), and benz[a]anthracene (BaA) in the sediments showed distinct features depending on the surrounding sources. In urban sediments, lighter δ13CPhe values were observed (mean: -25.1‰), whereas relatively heavier values of δ13CPy were found in petroleum industry areas (mean: -23.4‰). The Bayesian isotope mixing model indicates that the predominant source of PAHs in Ulsan Bay sediments was the petroleum industry (45%), followed by the non-ferrous metals industry (30%), automobile industry (18%), and urban areas (6.3%). These results demonstrated the utility of stable isotopes in assessing the sources and contributions of PAHs in small-scale regions. However, there are still limitations in compound-specific isotope analysis of PAHs, including insufficient end-members for each source, difficulty in analysis, and the influence of non-point sources; thus, further study is needed to expand its application.

Emissions from ships' activities in the anchorage zone: A potential source of sub-micron aerosols in port areas.

Busan Port is among the world's top ten most air-polluted ports, but the role of the anchorage zone as a significant contributor to pollution has not been studied. To assess the emission characteristics of sub-micron aerosols, a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed in Busan, South Korea from September 10 to October 6, 2020. The concentration of all AMS-identified species and black carbon were highest when the winds came from the anchorage zone (11.9 µg·m-3) and lowest with winds from the open ocean (6.64 µg·m-3). The positive matrix factorization model identified one hydrocarbon-like organic aerosol (HOA) and two oxygenated organic aerosol (OOA) sources. HOAs were highest with winds from Busan Port, while oxidized OOAs were predominant with winds from the anchorage zone (less oxidized) and the open ocean (more oxidized). We calculated the emissions from the anchorage zone using ship activity data and compared them to the total emissions from Busan Port. Our results suggest that emissions from ship activities in the anchorage zone should be considered a significant source of pollution in the Busan Port area, especially given the substantial contributions of gaseous emissions (NOx: 8.78%; volatile organic compounds: 7.52%) and their oxidized moieties as secondary aerosols.

Mobile measurement of vehicle emission factors in a roadway tunnel: A concentration gradient approach.

Tunnels are the preferred experimental environments for estimating vehicle emission factors (EFs) under real-world driving conditions. In this study, online measurements of traffic-related air pollutants (including CO2, NOX, SO2, O3, particulate matter [PM], and volatile organic compounds [VOCs]) were conducted using a mobile laboratory in the Sujungsan Tunnel in Busan, Korea. Mobile measurements generated concentration profiles of the target exhaust emissions inside the tunnel. These data were used to produce a zonation of the tunnel, i.e., mixing and accumulation zones. There were differences between the CO2, SO2, and NOX profiles, and a starting point that was free from ambient air mixing effects could be set at 600 m from the tunnel entrance. The EFs of vehicle exhaust emissions were calculated using pollutant concentration gradients. The average EFs for CO2, NO, NO2, SO2, PM10, PM2.5, and ∑VOCs were 149,000, 380, 55, 29.2, 9.64, 4.33, and 16.7 mg km-1·veh-1, respectively. Among the VOC groups, alkanes contributed more than 70% of the VOC EF. Mobile measurement-derived EFs were validated using the conventional EFs from stationary measurements. The EF results from the mobile measurements matched those from the stationary measurements, while the absolute concentration differences between them implied complex aerodynamic movements of the target pollutants inside the tunnel. This study demonstrated the usefulness and advantages of applying mobile measurements in a tunnel environment and indicated the potential of the approach for observation-based policymaking.

Capillary flow velocity profile analysis on paper-based microfluidic chips for screening oil types using machine learning.

We conceived a novel approach to screen oil types on a wax-printed paper-based microfluidic platform. Various oil samples spontaneously flowed through a micrometer-scale channel via capillary action while their components were filtered and partitioned. The resulting capillary flow velocity profile fluctuated during the flow, which was used to screen oil types. Raspberry Pi camera captured the video clips, and a custom Python code analyzed them to obtain the capillary flow velocity profiles. 106 velocity profiles (each with 125 frames for 5 s) were recorded from various oil samples to build a training database. Principal component analysis (PCA), support vector machine (SVM), and linear discriminant analysis (LDA) were used to classify the oil types into heavy-to-medium crude, light crude, marine fuel, lubricant, and diesel oils. The second-order polynomial SVM model with PCA as a pre-processing step showed the highest accuracy: 90% in classifying crude oils and 81% in classifying non-crude oils. The assay took less than 30 s from the sample to answer, with 5 s of the capillary action-driven flow. This simple and effective assay will allow rapid preliminary screening of oil types, enable early tracking, and reduce the number of suspect samples to be analyzed by laboratory fingerprinting analysis.

Chemical characterization of sub-micron aerosols over the East Sea (Sea of Japan).

Studies of the land-sea-air interactions of aerosol are scarce considering their significant role in global environmental changes. Here, we investigated potential sources of sub-micron aerosols over the East Sea (Sea of Japan), which is strongly influenced by continental and marine aerosols. A high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was used to measure the size-resolved chemical compositions of sub-micron aerosols during the period March 10-15, 2020. Concentrations of all AMS species, black carbon (BC), PM10 (particulate matter <10 µm) and PM2.5 (particulate matter <2.5 µm) were higher when cruising in industrialized coastal areas compared to the offshore region. A positive matrix factorization (PMF) model identified five distinct sources, i.e., hydrocarbon-like organic aerosol, semi-volatile and low-volatile oxygenated aerosols, methanesulfonic acid (MSA), and dimethyl sulfide (DMS; C2H6S) oxidation, which accounted for 5.98 %, 21.6 %, 28.3 %, 34.5 %, and 9.64 % of the total organic mass, respectively. The spatiotemporal variation of MSA, as well as the MSA to sulfate ratio (MSA:SO42-) over the East Sea, was determined for the first time. The mass concentrations of MSA displayed a similar time series distribution pattern to those of DMS. The time series distributions of the MSA:SO42- ratio displayed distinct differences, with higher ratios downwind of the ocean (0.216 ± 0.083 µg·m-3) than land (0.089 ± 0.030 µg·m-3). The growth of ultrafine particles (10-35 nm) was observed during two of the elevated MSA:SO42- ratio events, suggesting a potential role of MSA in new particle formation.

Best available technique for the recovery of marine benthic communities in a gravel shore after the oil spill: A mesocosm-based sediment triad assessment.

Ecotoxicological effects of spilled oils are well documented, but study of recovery of marine benthic communities is limited. Long-term recovery of hard bottom communities during physical and biological remediations after a spill was monitored. A 60-day experiment was conducted using a mesocosm with monitoring of eight endpoints by use of the sediment quality triad (SQT). First, physical treatment of hot water + high pressure flushing maximally removed residual oils (max=93%), showing the greatest recovery among SQT variables (mean=72%). Physical cleanup generally involved adverse effects such as depression of the microphytobenthic community during the initial period. Next, biological treatments, such as fertilizer, emulsifier, enzyme and augmentation of the microbes, all facilitated removal of oil (max=66%) enhancing ecological recovery. Analysis of the microbiome confirmed that oil-degrading bacteria, such as Dietzia sp. and Rosevarius sp. were present. A mixed bioremediation, including fertilizer + multi-enzyme + microbes (FMeM) maximized efficacy of remediation as indicated by SQT parameters (mean=47%). Natural attenuation with "no treatment" showed comparable recovery to other remediations. Considering economic availability, environmental performance, and technical applicability, of currently available techniques, combined treatments of physical removal via hand wiping followed by FMeM could be most effective for recovery of the rocky shore benthic community.

Determination of anthropogenic organics in dichlomethane extracts of aerosol particulate matter collected from four different locations in China and Republic of Korea by GC-MS and FTICR-MS.

In this study, the hypothesis that particulate matter in east of Korea peninsula would be significantly influenced by particulate matter originated from east of China was evaluated. To test the hypothesis, water-insoluble compounds in particulate matter samples collected from three different locations in Korea and one in China were characterized by atmospheric pressure photoionization (APPI) coupled with Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and gas chromatography mass spectrometry (GC-MS). Each sample was collected twice, in winter and in spring. The GC-MS data revealed the presence of high levels of polycyclic aromatic hydrocarbons (PAHs), such as benzo[a]anthracene in the samples from Tianjin, China. The sample collected in the winter from Baengnyeong Island, which is the location in Korea that is geographically closest to the east coast of China was also rich in aromatic compounds. Meanwhile, the APPI FTICR-MS data showed that polycondensed PAHs and two- to four-ring PAHs with long alkyl chains were abundant in the winter samples from Tianjin and Baengnyeong Island which stems most likely from coal combustion in the eastern China. In contrast, nonaromatic compounds with a biogenic origin were mostly observed in samples collected from islands located in eastern (Ulleung Island) and southern (Jeju Island) Korea. A principal component analysis by FTICR-MS and GC-MS also showed that the samples from Tianjin and those collected from Baengnyeong Island in the winter are strongly associated with coal combustion, whereas the other samples are mainly influenced by vehicle emissions. Therefore, it is concluded that the atmosphere from east of China has significant influence over atmosphere in west of Korea peninsula.

Sediment quality assessment combining chemical and biological (non)target analysis.

Aquatic sediments act as a storage for diverse mixtures of organic and inorganic contaminants. Nevertheless, most evaluations of contaminated sediments have been limited to the assessment of concentrations of target compounds and lethal effects on some test species. To identify the organic contaminants causing sub-lethal effects of contaminated sediment, this study combined chemical and biological (non)target analysis involving comprehensive two-dimensional gas chromatography coupled with a time-of-flight Mass Spectrometer (GCxGC/ToF-MS) analysis, embryonic malformation and high-throughput sequencing (RNA-seq) analysis on developing flounder. Polycyclic aromatic hydrocarbons were more abundant in the sediment extract of Yeongil Bay (SEY), while Jinhae Bay (SEJ) was contaminated with a large amount of unidentified chemicals. The unidentified chemicals of SEJ included branched alkanes, oxygenated cycloalkanes, heterogeneous hydrocarbons, and other unknown compounds. Percentage of pericardial edema was the highest in embryonic flounder exposed to SEY. Consistent with the morphogenesis results, the expression level of genes related to heart formation including the nkx2.5 and robo1 was greater in embryonic flounder exposed to SEY. In the analyses of differential gene expression profiles (cutoff P < 0.05), by RNA-seq, embryos exposed to SEJ showed changes related to cell differentiation, cell part morphogenesis, neurogenesis, and neuron development. Genes related to neurogenesis and positive regulation of molecular functions variated significantly in embryos exposed to SEY. These results demonstrated the advantages of combining target and non-target analysis to accurately evaluate the major chemical groups causing sediment toxicity. Therefore, this work provided a useful approach to tracking and revealing the causes of toxic effects and identifying potential toxic mechanisms.

Development of a portable oil type classifier using laser-induced fluorescence spectrometer coupled with chemometrics.

Due to the recurrent small spills, oil pollution along coastal regions is still a major environmental issue. Standardized oil fingerprinting techniques are useful for oil spill identifications, but time- and resource-consuming. There have been ongoing needs for simple yet rapid approach for field screening of oil spill. Laser induced fluorescence (LIF) technology can be incorporated into a spectrometer, and with the integration of chemometrics can be consolidated as a potentially useful portable oil type classification device. Using a LIF spectrometer, 775 oil spectra were calibrated into supervised classification models and validated with 162 oil spectra. Reliability of the device to accurately remove background emission from fluorescence spectra was verified. Prediction performance and model robustness were further validated by comparison between commonly used classification models such as partial least square discriminant analysis (PLS-DA) and support vector machine-discriminant analysis (SVM-DA). Robustness in both models were comparable with PLS-DA having a lower number of misclassification (PLS-DA: 5.50%, SVM-DA: 13.8%) while SVM-DA having a lower number of unassigned samples (PLS-DA: 10.9%; SVM-DA: 16 1.39%). This study explicitly demonstrated the development of a new convenient and handy device which can be used as part of the screening process for oil spill fingerprinting.

High-throughput screening of oil fingerprint using FT-IR coupled with chemometrics.

An important element of the oil spill emergency response is the ability to rapidly identify the properties of oil spilled. Chemometrics provides large numbers of multivariate analysis tools that allow for more extensive use of data. Fourier transformed infrared spectroscopy coupled with classification and prediction models such as partial least square (PLS) and PLS-DA (discriminant analysis) allows the rapid identification of oil type and characteristics. By searching for the maximum covariance with the variables of interest, PLS allows the visualization of relations between samples and variables. The framework of this study is based on two main steps: The first is classification of oil and the second is prediction of physicochemical properties. Separated into four main categories: crude, light fuel, heavy fuel, and lubricant, spectrums of 92 oils were calibrated to predict the oil type and physicochemical properties of 26 oils. The predictability and robustness of the model was further validated using weathered oil. The classification and prediction models have accuracy of >95%. Most of the PLS models have root mean square error of calibration and prediction ranging from 0.10-3.07 and 0.3-2.8, respectively. External cross validations using weathered oils showed high prediction accuracy (relative standard deviations <5%). By increasing the number of oil type and samples, this approach is a promising method and can be included as part of the oil spill fingerprinting protocols.

Alkylated phenanthrene distributions in black rockfish (Sebastes schlegelii) and biotransformation into hydroxylated metabolites after intragastric administration.

Marine organisms such as fish are at risk of exposure to petrogenic polycyclic aromatic hydrocarbons (PAHs) released in oil spills. PAH toxicities are affected by the rates of PAH biotransformation and elimination in fish tissues, but little information on these rates is available. In this study, the biotransformation and tissue distribution of methylated phenanthrenes-typical petrogenic PAHs found after oil spills-in black rockfish (Sebastes schlegelii) were investigated. Two groups of fish were used. Each fish in one group was given a single intragastric dose of 3-methylphenanthrene, and each fish in the other group was given a single intragastric dose of 3,6-dimethylphenanthrene. The fish were allowed to recover in purified sea water for 196 h. Methylated phenanthrenes were detected in only blood and liver for 24 h after dosing, but the concentrations decreased over time and > 98% had been eliminated by the end of the study. Four mono-hydroxylated metabolites of 3,6-dimethylphenanthrene and six mono-hydroxylated metabolites of 3-methylphenanthrene were tentatively identified for the first time from tandem mass spectrometry analyses of fish bile. The concentrations of these metabolites in bile remained constant for 192 h, suggesting that the metabolites could be used as biomarkers of rockfish exposure to petrogenic PAHs.

Handheld UV fluorescence spectrophotometer device for the classification and analysis of petroleum oil samples.

Oil spills can be environmentally devastating and result in unintended economic and social consequences. An important element of the concerted effort to respond to spills includes the ability to rapidly classify and characterize oil spill samples, preferably on-site. An easy-to-use, handheld sensor is developed and demonstrated in this work, capable of classifying oil spills rapidly on-site. Our device uses the computational power and affordability of a Raspberry Pi microcontroller and a Pi camera, coupled with three ultraviolet light emitting diodes (UV-LEDs), a diffraction grating, and collimation slit, in order to collect a large data set of UV fluorescence fingerprints from various oil samples. Based on a 160-sample (in 5x replicates each with slightly varied dilutions) database this platform is able to classify oil samples into four broad categories: crude oil, heavy fuel oil, light fuel oil, and lubricating oil. The device uses principal component analysis (PCA) to reduce spectral dimensionality (1203 features) and support vector machine (SVM) for classification with 95% accuracy. The device is also able to predict some physiochemical properties, specifically saturate, aromatic, resin, and asphaltene percentages (SARA) based off linear relationships between different principal components (PCs) and the percentages of these residues. Sample preparation for our device is also straightforward and appropriate for field deployment, requiring little more than a Pasteur pipette and not being affected by dilution factors. These properties make our device a valuable field-deployable tool for oil sample analysis.

Long-Term Ecological Impacts from Oil Spills: Comparison of Exxon Valdez, Hebei Spirit, and Deepwater Horizon.

The long-term ecological impacts of the Exxon Valdez oil spill (EVOS) are compared to two extensively studied and more recent large spills: Deepwater Horizon (DWH) and the Hebei Spirit oil spill (HSOS). Each of the three spills differed in magnitude and duration of oil released, environmental conditions, ecological communities, response and clean up measures, and ecological recovery. The EVOS began on March 24, 1989, and released 40.8 million liters of Alaska North Slope crude oil into the cold, nearly pristine environment of Prince William Sound, Alaska. EVOS oiled wildlife and rocky intertidal shorelines and exposed early life stages of fish to embryotoxic levels of polycyclic aromatic hydrocarbons (PAH). Long-term impacts following EVOS were observed on seabirds, sea otters, killer whales, and subtidal communities. The DWH spill began on April 20, 2010, and released 507 million liters of light Louisiana crude oil from 1600 m on the ocean floor into the Gulf of Mexico over an 87-day period. The DWH spill exposed a diversity of complex aquatic communities in the deep ocean, offshore pelagic areas, and coastal environments to petroleum hydrocarbons. Large-scale persistent ecological effects included impacts to deep ocean corals, failed recruitment of oysters over multiple years, damage to coastal wetlands, and reduced dolphin, sea turtle, and seabird populations. The HSOS began on December 7, 2007, and released approximately 13 million liters of Middle East crude oils into ecologically sensitive areas of the Taean area of western Korea. Environmental conditions and the extensive initial cleanup of HSOS oil stranded on shorelines limited the long-term impacts to changes in composition and abundance of intertidal benthic communities. Comparisons of EVOS, DWH, and HSOS show the importance and complexity of the interactions among the environment, oil spill dynamics, affected ecological systems, and response actions.

Formation and distribution of phenanthrene and its metabolites (monohydroxy-phenanthrenes) in Korean rockfish (Sebastes schlegelii).

This study investigated the tissue distribution of phenanthrene (PHE) and the formation of monohydroxy-phenanthrene (OH-PHE) metabolites in Korean rockfish (Sebastes schlegelii). PHE was intragastrically administered to two groups of rockfish. The first group was exposed to PHE at a low dose (10 mg/kg body weight) and the second group was exposed at a high dose (30 mg/kg body weight). The rockfish were analyzed and the levels of PHE were higher in the liver, followed by muscle, and then bile. PHE concentrations in the liver, muscle, and bile were 1.4-26, 0.10-2.01, and not detected (ND)-0.13 µg/g wet weight, respectively. All five monohydroxylated PHE metabolites (1-OH-PHE, 2-OH-PHE, 3-OH-PHE, 4-OH-PHE, and 9-OH-PHE) were detected only in bile. Among these OH-PHE metabolites, 3-OH-PHE was found at the highest concentration from all fish bile samples in both PHE exposure groups, indicating that regioselective OH-PHE formation occurs in rockfish and 3-OH PHE could be a good biomarker of exposure of Korean rockfish to PHE. Suspect screening analysis of the rockfish bile was performed by LC-QTOF/MS, and the formation of two OH-PHE-DNA adducts (thymine-OH-PHE and cytosine-OH-PHE) were identified in the bile sample collected 6 h after rockfish were exposed to the high PHE dose, indicating that OH-PHE metabolites may be toxic to fish. This is the first report on the formation characteristics of OH-PHE metabolites in rockfish and their use as biomarkers of exposure of rockfish to parent PHE.

Rapid recovery of coastal environment and ecosystem to the Hebei Spirit oil spill's impact.

The 2007 Hebei Spirit oil spill (HSOS), the largest in the national history, has negatively impacted the entire environment and ecosystem along the west coast of South Korea. Although many studies have reported the damages and impacts from the HSOS, quantitative assessment evaluating the recovery time and status have not been documented. Here, we first address the recovery timeline of the HSOS, by comprehensive analyses of 10-years accumulated data in quantitative manner. Concentrations of residual oils in seawater, sediments, and oysters rapidly dropped to backgrounds in 16, 75, and 33 months, respectively. Also, damaged benthic communities of intertidal and subtidal areas were fully recovered only after ~6 years. The present results collectively indicated unexpectedly fast recovery of the damaged environment and ecosystem from such a huge oil spill. The high tidal mixing (~9 m tidal height) and intensive human cleanup (~1.2 million volunteers) at the initial cleanup period might have contributed to rapid recovery; cf. 4-5 times faster than the Exxon Valdez oil spill. However, potential risk to human health remains unclear. Thus, it is warranted to conduct more in depth epidemiological studies to address chronic health effects associated with the cleanup volunteers as well as the local residents who have been living nearby the oil spill impacted sites.

Environmental significance of lubricant oil: A systematic study of photooxidation and its consequences.

Lubricant (lube) oil discharge from ships has been widely considered as normal "operational consumption", but is now deemed to be oil pollution. Despite the chronic contamination of the marine environment by lube oil, the number of studies related to its environmental impact, characteristics, and toxicity is limited. This study is the first attempt to investigate the environmental fate of lube oil subjected to photooxidation using in situ mesocosms. A tiered approach using thin-layer chromatography-flame ionization detection (TLC-FID), Fourier-transform infrared spectroscopy (FTIR) and gas chromatography-mass spectrometry (GC-MS) demonstrated compositional changes in lube oil and the water-soluble fraction (WSF). Total polycyclic aromatic hydrocarbons (ΣPAHs) in lube oil after 96 h of photooxidation were measured at 79.8 and 41 µg/g in the control (Con) and exposure (Exp) groups, respectively. Meanwhile, the ΣPAHs concentration in WSF after 96 h was very low, at 0.25 and 0.45 µg/L in Con and Exp, respectively. FTIR and GC-MS helped identify bond changes and photoproducts in WSF. A wide range of photoproducts, including carboxylic acids, esters, anhydrides, aldehydes and ketones, were identified in WSF. Toxic effects of WSF in both the Con and Exp groups obtained after 96 h of photooxidation were evaluated on olive flounder (Paralichthys olivaceus) embryos. Morphological defects, especially tail fin fold defects, were found to be significantly elevated in both the Con and Exp groups, with marginally higher frequency in Exp. The results of this study demonstrate the need for further research on lube oil weathering, including monitoring over prolonged periods of time.

Stability of mechanically and chemically dispersed oil: Effect of particle types on oil dispersion.

Oil spill dispersant (OSD) application is one of the preferred cleanup options to cope with oil spills at sea. OSD, in principle, can enhance biodegradation of oil because of its effectiveness in producing relatively small droplets and dispersing them into the water column. Under turbulent conditions, suspended particulate matter (SPM) which are present naturally in the environment can interact with oil to form aggregates known as oil-SPM aggregates (OSA) which also enhances biodegradation of oil. Despite its high dispersion effectiveness, chemically dispersed oil (CDO) has a tendency to resurface with increasing time which decreases the biodegradation potential. Meanwhile, the presence of SPM prevents recoalescence of dispersed oil which can enhance stability of oil droplets. This study focused on the effects of SPM on the dispersion effectiveness and stability of mechanically dispersed oil (MDO) and CDO. Dispersion tests of MDO and CDO extended to 72 h with and without SPM to see the initial effectiveness and the prolonged stability of dispersed oil. In the presence of SPM, the oil dispersed by MDO increased by 14.8-40.7%, while the resurfacing oil by CDO decreased by 8.7-19.4%. Regardless of SPM type, oil dispersion effectiveness and stability of MDO and CDO were significantly increased. Long-term stability test for 3 months showed that stability of OSA increased as the particle size decreased and particle counts increased.

Activation of the nucleotide excision repair pathway by crude oil exposure: A translational study from model organisms to the Hebei Spirit Oil Spill Cohort.

In order to gain insight into the human health implications of the Hebei Spirit Oil Spill (HSOS), the mechanism of toxicity of the Iranian heavy crude (IHC), the main oil component in the HSOS was investigated in Caenorhabditis elegans and zebrafish. The identified mechanism was translated to humans using blood samples from Taean residents, who experienced HSOS with different levels of exposure to the spill. C. elegans TF RNAi screening with IHC oil revealed the nucleotide excision repair (NER) pathway as being significantly involved by oil exposure. To identify the main toxicity contributors within the chemical mixture of the crude oil, further studies were conducted on C. elegans by exposure to C3-naphthalene, an alkylated polycyclic aromatic hydrocarbon (PAH), which constitutes one of the major components of IHC oil. Increased expression of NER pathway genes was observed following exposure to the IHC oil, C3-naphthalene enriched fraction and C3-naphthalene. As the NER pathway is conserved in fish and humans, the same experiment was conducted in zebrafish, and the data were similar to what was seen in C. elegans. Increased expression of NER pathway genes was observed in human samples from the high exposure group, which suggests the involvement of the NER pathway in IHC oil exposure. Overall, the study suggests that IHC oil may cause bulk damage to DNA and activation of the NER system and Alkylated PAHs are the major contributor to DNA damage. Our study provides an innovative approach for studying translational toxicity testing from model organisms to human health.

Molecular level determination of water accommodated fraction with embryonic developmental toxicity generated by photooxidation of spilled oil.

In this study, developmental toxicity was increased as the oil was further degraded under natural sunlight. Detailed chemical composition of the degraded oils was examined by use of gas chromatography (GC) and (-) electrospray ionization ultrahigh resolution mass spectrometry (UHR-MS). Baseline toxicities were estimated based on chemical activities of polycyclic aromatic hydrocarbons, and it was obvious that the predicted chemical activities can not explain increased toxicity alone. However, the ultrahigh resolution mass spectral abundance of polar compounds including O3 and O4 class compounds was significantly increased as the photodegradation proceeded. Further examination of double bond equivalence values of the compounds showed that polar compounds with both non-aromatic and aromatic polar structures were increased. Statistical analysis indicates that the increased toxicity can be well explained by the increased polar compounds. Therefore, the oxygenated compounds identified in this study can play an important role in toxicity of degraded oils.