Fate, behaviour and microbial response of diluted bitumen and conventional crude spills in a simulated warm freshwater environment.

Diluted bitumen (DB), one of the most transported unconventional crude oils in Canada's pipelines, raises public concerns due to its potential spillage into freshwater environments. This study aimed to compare the fate and behaviour of DB versus conventional crude (CC) in a simulated warm freshwater environment. An equivalent of 10 L of either DB or CC was spilled into 1200 L of North Saskatchewan River (NSR) water containing natural NSR sediment (2.4 kg) in a mesoscale spill tank and its fate and behaviour at air/water temperatures of 18 °C/24 °C were monitored for 56 days. Oil mass distribution analysis showed that 42.3 wt % of CC and 63.6 wt% of DB resided in the oil slicks at the end of 56-day tests, consisting mainly high molecular weight (HMW) compounds (i.e., resins and asphaltenes). The lost oil contained mainly low molecular weight (LMW) compounds (i.e., light saturates and some aromatics) into the atmosphere, water column, and sediment through collective weathering processes. Notably, weathered CC emulsified with water and remained floating until the end, while the weathered DB mat started to lose its buoyancy after 24 days under quiescent conditions and resurfaced once waves were applied. Analysis of the microbial communities of water pre- and post-spills revealed the replacement of indigenous microbial communities with hydrocarbon-degrading species. Exposure to CC reduced the microbial diversity by 12%, while exposure to DB increased the diversity by 10%. During the early stages of the spill (up to Day 21), most dominant species were positively correlated with the benzene, toluene, ethylbenzene, and xylenes (BTEX) content or polycyclic aromatic hydrocarbon (PAH) content of the water column, while the dominant species at the later stages (Days 21-56) of the spill were negatively correlated with BTEX or PAH content and positively correlated with the total organic carbon (TOC) content in waters.

Multiple liquid-liquid extraction of dissolved compounds in immortelle hydrosol with four different solvents.

Immortelle, a revered Mediterranean medicinal plant, is celebrated for its potent essential oil renowned in the cosmetic industry for its skin-enhancing properties. Yet, immortelle hydrosol, an often-overlooked byproduct, holds promise in cosmetics due to its compatibility with polar active ingredients. This study investigates the chemical composition of immortelle hydrosol by employing liquid-liquid extraction (LLE) to transfer volatile organic components into nonpolar solvents. Four solvents - chloroform, dichloromethane, hexane, and benzene - were assessed through ten consecutive extractions from industrially produced immortelle hydrosol. Quantification was achieved using GC analysis with tetradecane as an internal standard. Chloroform emerged as the most efficient solvent, yielding 2447.0 mg/L of volatile compounds, surpassing dichloromethane, hexane, and benzene. Key compounds in immortelle hydrosol included 3-pentanone, 2-methyl-1-butanol, and γ-terpineol. Importantly, the study revealed that a portion of essential oil compounds persists in the hydrosol even after ten LLE cycles, with optimal results achievable in five extractions (~92 % in most cases).

Benzoates and in situ formed benzene in food supplements and risk assessment.

Upward trend in the use of food supplements urged the assessment of their safety. Eighty-eight liquid herbal supplements collected in Novi Sad (Serbia) in 2018 (36 samples) and 2021 (52 samples) were analysed for the presence of benzoates and sorbates (HPLC-UV) and benzene (HS-GC/MS). Benzoic acid varied from 599 to 9253 mg/kg and sorbic acid between 185 and 1658 mg/kg. The acceptable daily intake of sorbic acid was not reached, but in case of benzoic acid, it was exceeded by 5.3% of the samples. The presence of benzene was confirmed in 41.2% of benzoate preserved supplements (0.9-51.7 µg/kg). Benzene exposure revealed no health concern: maximum hazard quotients ranged from 0.39% (toddlers) to 0.84% (adolescents); minimum margins of exposure were between 35,680 (adolescents) and 77,419 (toddlers); estimates of lifetime cancer risk did not reach one extra cancer case per 100 000 persons. However, measures to mitigate benzene presence in food should be considered.

Rapid on-site detection of underground petroleum pipeline leaks and risk assessment using portable gas chromatography-mass spectrometry and solid phase microextraction.

Locating underground pipeline leaks can be challenging due to their hidden nature and variable terrain conditions. To sample soil gas, solid-phase microextraction (SPME) was employed, and a portable gas chromatography/mass spectrometry (GC/MS) was used to detect the presence and concentrations of petroleum hydrocarbon volatile organic compounds (pH-VOCs), including benzene, toluene, ethylbenzene, and xylene (BTEX). We optimized the extraction method through benchtop studies using SPME. The appropriate fibre materials and exposure time were selected for each BTEX compound. Before applying SPME, we preconditioned the soil vapour samples by keeping the temperature at around 4 °C and using ethanol as a desorbing agent and moisture filters to minimize the impact of moisture. To conduct this optimisation, airbags were applied to condition the soil vapour samples and SPME sampling. By conditioning the samples using this method, we were able to improve analytical efficiency and accuracy while minimizing environmental impacts, resulting in more reliable research data in the field. The study employed portable GC/MS data to assess the concentration distribution of BTEX in soil vapour samples obtained from 1.5 m below the ground surface at 10 subsurface vapour monitoring locations at the leak site. After optimization, the detection limits of BTEX were almost 100 µg/m3, and the measurement repeatabilities were approximately 5% and 15% for BTEX standards in the laboratory and soil vapour samples in the field, respectively. The soil vapour samples showed a hotspot region with high BTEX concentrations, reaching 30 mg/m3, indicating a diesel return pipeline leak caused by a gasket failure in a flange. The prompt detection of the leak source was critical in minimizing environmental impact and worker safety hazards.

Benzene exposure assessment of printing workers treating petroleum-based cleaner in South Korea.

This study was conducted to check whether benzene is contained inside the petroleum-based cleaning agent used in the printing industry and measure whether it is actually exposed to the air. Benzene was analyzed inside the cleaning agent and air exposure evaluation was done by area sampling. Risk assessment was performed using the Chemical Hazard Risk Management (CHARM) technique. Most products contained benzene based on the results obtained from this study. As a result of collecting air samples and checking whether the workers were exposed to benzene actually, benzene was detected in three samples. As a result of the risk assessment, most of printing businesses scored more than four points. Benzene was detected in all petroleum-based cleaning products. In addition, benzene was detected in some of air samples. Considering the fact that even small exposure level of benzene is dangerous to worker health and most of the printing businesses in South Korea operate on a small scale with fewer than five employees so the health management system is poor, it is necessary to prepare appropriate measures to prevent work diseases provoked by benzene exposure.

Benzene Exposure From Selected Work Tasks on Offshore Petroleum Installations on the Norwegian Continental Shelf, 2002-2018.

OBJECTIVES: Work on offshore petroleum installations may cause exposure to benzene. Benzene is a carcinogenic agent, and exposure among workers should be as low as reasonably practicable. We aimed to assess short-term (less than 60 min) benzene exposure from the most frequent work tasks on offshore installations on the Norwegian continental shelf and identify determinants of exposure. In addition, we aimed to assess the time trend in task-based benzene measurements from 2002 to 2018. METHODS: The study included 763 task-based measurements with a sampling duration of less than 60 min, collected on 28 offshore installations from 2002 to 2018. The measurements were categorized into 10 different tasks. Multilevel mixed-effect Tobit regression models were developed for two tasks: sampling and disassembling/assembling equipment. Benzene source, season, indoors or outdoors, design of process area, year of production start, sampling method, and work operation were considered as potential determinants for benzene exposure in the models. RESULTS: The overall geometric mean (GM) benzene exposure was 0.02 ppm (95% confidence intervals 95%(CI: 0.01-0.04). The pipeline inspection gauge (PIG) operation task was associated with the highest exposure, with a GM of 0.33 ppm, followed by work on flotation cells, disassembling/assembling, and sampling, with GMs of 0.16, 0.04, and 0.01 ppm, respectively. Significant determinants for the disassembling/assembling task were work operation (changing or recertifying valves, changing or cleaning filters, and breaking pipes) and benzene source. For sampling, the benzene source was a significant determinant. Overall, the task-based benzene exposure declined annually by 10.2% (CI 95%: -17.4 to -2.4%) from 2002 to 2018. CONCLUSIONS: The PIG operation task was associated with the highest exposure out of the ten tasks, followed by work on flotation cells and when performing disassembling/assembling of equipment. The exposure was associated with the type of benzene source that was worked on. Despite the decline in task-based exposure in 2002-2018, technical measures should still be considered in order to reduce the exposure.

Source and composition analysis of petroleum hydrocarbons in the refinery circulating water.

Oil leakage from water coolers in refinery circulating water occurs from time to time, which affects the long-term and stable operation of refinery units. So far, workers in the refineries still adopt manual check methods, opening water coolers one by one and checking the water's smell and color to find out the spilled water coolers. In this study, a more rapid method of source appointment of oil spill in the circulating water by combining chemical fingerprinting with model recognition was developed. Firstly, chemical fingerprints including benzene/naphthalene series, and light hydrocarbon (C3-C5) in oil samples from all water coolers in the refinery fluid catalytic cracking (FCC) unit were analyzed by gas chromatography-mass spectrometry (GC/MS). Gasoline, diesel, and poor oil could be distinguished in terms of benzene and naphthalene distribution. The three similar types of gasolines could be distinguished by the volatile hydrocarbons especially C3-C4. The classification model for the spill of gasoline, diesel, and poor oil in circulating water was constructed by the partial least squares discriminant analysis algorithm with a 100% correct classification rate at the concentration more than 10 ppm. The gasoline spills in the circulating backwater of the refinery were successfully recognized by the classification model. This method enables the rapid prediction of oil spill type in refinery circulating water, and a similar method by installing online instrument and software potentially can be used for monitoring the circulating water in real time.

Exposure to Crude Oil-Related Volatile Organic Compounds Associated with Lung Function Decline in a Longitudinal Panel of Children.

BACKGROUND: Children in the affected area were exposed to large amounts of volatile organic compounds (VOCs) from the Hebei Spirit oil spill accident. OBJECTIVES: We investigated the lung function loss from the exposure to VOCs in a longitudinal panel of 224 children 1, 3, and 5 years after the VOC exposure event. METHODS: Atmospheric estimated concentration of total VOCs (TVOCs), benzene, toluene, ethylbenzene, and xylene for 4 days immediately after the accident were calculated for each village (n = 83) using a modeling technique. Forced expiratory volume in 1 s (FEV1) as an indicator of airway status was measured 1, 3, and 5 years after the exposure in 224 children 4~9 years of age at the exposure to the oil spill. Multiple linear regression and linear mixed models were used to evaluate the associations, with adjustment for smoking and second-hand smoke at home. RESULTS: Among the TVOCs (geometric mean: 1319.5 mg/m3·4 d), xylene (9.4), toluene (8.5), ethylbenzene (5.2), and benzene (2.0) were dominant in the order of air concentration level. In 224 children, percent predicted FEV1 (ppFEV1), adjusted for smoking and second-hand smoke at home, was 100.7% after 1 year, 96.2% after 3 years, and 94.6% after 5 years, and the loss over the period was significant (p < 0.0001). After 1 and 3 years, TVOCs, xylene, toluene, and ethylbenzene were significantly associated with ppFEV1. After 5 years, the associations were not significant. Throughout the 5 years' repeated measurements in the panel, TVOCs, xylene, toluene, and ethylbenzene were significantly associated with ppFEV1. CONCLUSIONS: Exposure to VOCs from the oil spill resulted in lung function loss among children, which remained significant up to 5 years after the exposure.

Assessing the effect of BTEX on blood and spirometry parameters staff in a petroleum refinery.

This study aimed to investigate the impact of BTEX compound on blood and spirometry parameters of staff in the Abadan petroleum refinery (Iran). In 80 staff was examined in terms of BTEX exposure (40 exposed and 40 non-exposed). In this study, the air sampling was carried out according to the NIOSH 1,501 method and an automated hematology analyzer was used to analyze all blood samples to evaluate blood parameters and using a Micro Direct automated computerized spirometer. Spss20 software was used to interpret the performance. According to the obtained results, total BTEX concentrations with the recommended standard level showed that, toluene, ethylbenzene, and xylenes, concentrations in Abadan Oil Refining Company Workers' breathing zone were lower than the TLV-TWA recommended by ACGIH. However, the average concentration of benzene was higher than the allowable limit. Therefore, in this study the effect of benzene on the blood and respiratory parameters of the workers was evaluated, the comparison of the blood and respiratory parameters between the groups of exposed and unexposed workers did not reveal any statistical difference between the groups (p > 0.001). The results showed no statistically significant connection between mean blood and spirometry parameters and benzene exposure. Also, based on results the effect of benzene problems needs to be prevented in employees with adequate engineering and management controls and periodic inspection.

Health risk assessment of volatile organic compounds (VOCs) in a refinery in the southwest of Iran using SQRA method.

Oil industries, such as oil refineries, are important sources of volatile organic compound production. These compounds have significant health effects on human health. In this study, a health risk assessment is carried out on volatile organic compounds (VOCs) in the recovery oil plant (ROP) unit of a refinery in southwest Iran. It was performed using the SQRA method including respiratory risk for chronic daily intake (CDI) of VOCs and cancer risk and non-cancer risk indices. Five locations in the area of oil effluents and five locations in the refinery area (control samples) were considered for evaluation. The sampling was done according to the standard NIOSH-1501 and SKC pumps. The gas chromatography/flame ionization detector (GC/FID) method was used to extract VOCs. The cancer slope factor (CSF) and respiratory reference dose (RFC) were calculated in addition to the respiratory risk (CDI). The end result shows that a significant difference was observed between the concentrations of volatile organic compounds in the two groups of air (P < 0.05). The SQRA risk assessment showed that the risk levels of benzene for workers in the pit area were very high (4-5). Health hazard levels were also evaluated as high levels for toluene (2-4) and moderate levels for xylene and paraxylene (1-3). The cancer risk assessment of volatile organic compounds recorded the highest level of cancer risk for benzene in the range of petroleum effluents (>1). Also, a non-cancer risk (HQ) assessment revealed that benzene had a significant health risk in the range of oil pits (2-3). Based on the results, petroleum industries, including refineries, should conduct health risk assessment studies of volatile organic compounds. The units that are directly related to the high level of VOCs should be considered sensitive groups, and their employees should be under special management to reduce the level of exposure to these compounds and other hazardous compounds.

Associations between airborne crude oil chemicals and symptom-based asthma.

RATIONALE: The 2010 Deepwater Horizon (DWH) oil spill response and cleanup (OSRC) workers were exposed to airborne total hydrocarbons (THC), benzene, toluene, ethylbenzene, o-, m-, and p-xylenes and n-hexane (BTEX-H) from crude oil and PM2.5 from burning/flaring oil and natural gas. Little is known about asthma risk among oil spill cleanup workers. OBJECTIVES: We assessed the relationship between asthma and several oil spill-related exposures including job classes, THC, individual BTEX-H chemicals, the BTEX-H mixture, and PM2.5 using data from the Gulf Long-Term Follow-up (GuLF) Study, a prospective cohort of 24,937 cleanup workers and 7,671 nonworkers following the DWH disaster. METHODS: Our analysis largely focused on the 19,018 workers without asthma before the spill who had complete exposure, outcome, and covariate information. We defined incident asthma 1-3 years following exposure using both self-reported wheeze and self-reported physician diagnosis of asthma. THC and BTEX-H were assigned to participants based on measurement data and work histories, while PM2.5 used modeled estimates. We used modified Poisson regression to estimate risk ratios (RR) and 95% confidence intervals (CIs) for associations between spill-related exposures and asthma and a quantile-based g-computation approach to explore the joint effect of the BTEX-H mixture on asthma risk. RESULTS: OSRC workers had greater asthma risk than nonworkers (RR: 1.60, 95% CI: 1.38, 1.85). Higher estimated THC exposure levels were associated with increased risk in an exposure-dependent manner (linear trend test p < 0.0001). Asthma risk also increased with increasing exposure to individual BTEX-H chemicals and the chemical mixture: A simultaneous quartile increase in the BTEX-H mixture was associated with an increased asthma risk of 1.45 (95% CI: 1.35,1.55). With fewer cases, associations were less apparent for physician-diagnosed asthma alone. CONCLUSIONS: THC and BTEX-H were associated with increased asthma risk defined using wheeze symptoms as well as a physician diagnosis.

Isolation and characterization of phytochemicals from ethyl acetate fraction of Solanum nigrum using GC-MS.

Solanum nigrum plant has rich therapeutic potential and different developed countries utilize this plant as a chief element for oriental medicinal practice including cancer therapy. The current study determines the isolation and purification of S. nigrum bioactive constituents through column chromatography from ethyl acetate extract of the plant followed by the Gas Chromatography-Mass Spectroscopy (GC-MS) to analyze the isolated compounds Different gradient elutions followed by thin layer chromatography of collected fractions were done and structural analysis of the isolated compounds was performed following GCMS analysis, More specifically the compounds were identified as 1, 2 benzene dicarboxylic acid, diisooctyl ester (95%) and as Bis (2-Ethylhexyl) phthalate (84%) along with 3 hydroxy 4 carboxy 2 methyl 6 pyridine (58%) with reference to chemical abstract service which may be responsible for its pharmacological properties. According to the best information available, no documented information exists regarding GC-MS based identification of the isolated chemical compounds from the S. nigrum. Present findings will help in exploring the therapeutic potential of 1, 2 benzene dicarboxylic acid, diisooctyl ester (95%), Bis (2-Ethylhexyl) phthalate (84%) and 3 hydroxy 4 carboxy 2 methyl 6 pyridine (58%) will be helpful in the development of new composites in pharmaceutical fields.

Occupational Benzene Exposure in the Norwegian Offshore Petroleum Industry, 2002-2018.

PURPOSE: Workers on offshore petroleum installations are at risk of being exposed to benzene which is carcinogenic to humans. The present study aimed to assess the time trend of full-shift benzene exposure from 2002 to 2018 in order to characterize benzene exposure among laboratory technicians, mechanics, process operators, and industrial cleaners, and to examine the possible determinants of benzene exposure. METHODS: A total of 924 measurements of benzene exposure from the Norwegian petroleum offshore industry were included. The median sampling duration was 680 min, ranging from 60 to 940 min. The overall geometric mean (GM) and 95% confidence interval, time trends, and determinants of exposure were estimated using multilevel mixed-effects tobit regression analyses. Time trends were estimated for sampling duration below and above 8 h, both overall and for job groups. The variability of exposure between installation and workers was investigated in a subset of data containing worker identification. RESULTS: The overall GM of benzene exposure was 0.004 ppm. When adjusting for job group, design of process area, season, wind speed, and sampling duration, industrial cleaners had the highest exposure (GM = 0.012). Laboratory technicians, mechanics, and process operators had a GM exposure of 0.004, 0.003, and 0.004 ppm, respectively. Overall, the measured benzene exposure increased by 7.6% per year from 2002 to 2018. Mechanics had an annual increase of 8.6% and laboratory technicians had an annual decrease of 12.6% when including all measurements. When including only measurements above 8 h, mechanics had an increase of 16.8%. No statistically significant time trend was found for process operators. Open process area, high wind speed, and wintertime were associated with reduced exposure level. CONCLUSIONS: An overall increase in measured exposure was observed from 2002 to 2018. The increase may reflect changes in measurement strategy from mainly measuring on random days to days with expected exposure. However, the time trend varied between job groups and was different for sampling duration above or below 8 h. Industrial cleaners had the highest exposure of the four job groups while no differences in exposure were observed between laboratory technicians, mechanics, and process operators. The design of the process area, job group, wind speed, and season were all significant determinants of benzene exposure.

Evaluating the relationship between the respiratory exposure to the benzene with the primary damages of deoxyribonucleic acid and total antioxidant capacity in one of the oil companies in Iran.

Benzene is a carcinogenic chemical substance which causes the injuries and damages through producing the free radicals in DNA (deoxyribonucleic acid) and the antioxidants are the agents which reduce the impacts of DNA damages by inhibiting the free radicals. This study was conducted aiming at determination of primary damages of DNA and level of plasma oxidative stress markers resulting from the respiratory exposure to the benzene found in petroleum compounds among the workers at loading platforms of a petroleum products distribution center. This study was an analytical (case control) research conducted among the workers in a working shift serving at the loading platforms of petroleum products. The exposure group included the workers with a history of contact with benzene and the control group was composed of the persons with no history of exposure to benzene. To investigate the level of the personnel's exposure to benzene, NIOSH-1501 method was utilized; to analyze the samples taken from the air, GC mass (gas chromatography-mass spectrometry) was applied; and to determine the average of DNA primary damages, comet assay was used. Total antioxidant capacity was determined by a photometric method. Results indicated that tail length (TL), tail density (TD), tail momentum (TM), percentage of tail in the DNA (%DNA), and %TAC in control group were 78.59, 8.35, 1.20, 10.05, and 25.58 and in the exposure group were 59.21, 75.74, 57.74, 3.5, and 16.58, respectively. The previously mentioned results showed a decrease in the TL, %DNA, and %TAC values among the workers already exposed to benzene while an increase in the TD and TM values of the same group compared to the control non-exposed group. In comparing the averages between two studied groups, all study variables had statistically meaningful difference (p < 0.05). More studies are recommended to be conducted on using the methods which identify the special places of breakage and damage in DNA chain due to the exposure to benzene and consequently prevent the complications and consequences.

Occupational exposure to gasoline in gasoline station male attendants promotes M1 polarization in macrophages.

Several studies have reported the toxicological implications of exposure to petroleum hydrocarbon fumes in animal models. There is little documentation on the effect of such exposure on oxidative stress levels and immune response. To our knowledge, no documentation of M1 polarization in macrophages in gasoline station male attendants. Therefore, this study aimed to evaluate the harmful effects of gasoline vapors in 62 male attendants (16-70 years) compared to 29 age- and sex-matched-unexposed controls. The attendants were recruited from Damietta governorate gasoline stations. Gasoline exposure induced a significant increase in tumor necrosis factor-α (TNF-α) level (p < 0.05) as well as a slight but non-significant increase in the activity of acidic mammalian chitinase (AMCase) (p > 0.05). Further TNF-α/AMCase ratio was significantly increased (p < 0.01) in sera of the attendants when compared to those of the healthy controls. Also, the total leucocytic and lymphocytic counts were significantly increased (p < 0.01 and p < 0.001, respectively). On contrary, neutrophils to lymphocytes ratio (NLR) and platelets to lymphocytes ratio (PLR) were significantly decreased (p < 0.05 and p < 0.001, respectively). In addition, significant reduction in hemoglobin (Hb) concentration, plasma glutathione reduced form (GSH), and catalase, as well as superoxide dismutase (SOD) activities in red blood cells were observed in the exposed attendants. As a result, malondialdehyde (MDA), nitric oxide (NO) levels, and NO/AMCase ratio were significantly increased (p < 0.05). In conclusion, this study inferred that prolonged gasoline exposure can mediate immune activation, especially M1 macrophages polarization, possibly via oxidative stress-mediated mechanism.

Evaluation of potential human health risks from exposure to volatile organic compounds in contaminated urban groundwater in the Sava river aquifer, Belgrade, Serbia.

The oil pollutant in the Sava River aquifer in the residential area of Belgrade, Serbia was investigated in order to analyze the extent, origin and spatial distribution of the pollution, with the aim to estimate potential human health risks from exposure to the compounds detected. Analytical methods indicated that the dominant compounds in this oil pollutant were gasoline range organic compounds. Benzene, toluene, ethylbenzene and xylenes (BTEX) were identified as compounds of concern and quantified by headspace gas chromatography. The concentrations of benzene measured at all sampling points were higher than the remediation value while the maximum concentrations of BTEX quantified were among the highest concentrations of these compounds reported in the petroleum-contaminated aquifers in the world. The assessment of the human health risks from exposure to BTEX-covered industrial scenario for adult receptors and residential scenario for adult receptors and children. The exposure routes analyzed were dermal contact with and ingestion of contaminated water, considering both cancer and non-cancer effects. The analysis of the lifetime incremental cancer risk indicated the potential for adverse health effects for human exposure at the investigated location, and because of that it was interpreted as an unacceptable risk level or risks of high priority which required immediate consideration for remedial measures at this location. A complete set of mitigation measures was proposed including: groundwater decontamination treatment, installation of filters for tap water, development of the system for monitoring of BTEX in the groundwater and development of the emergency response capacities at this location.

Use of statistical modeling for BTEX prediction in cases of crude oil spill in seawater.

Cases of oil spillage and leakage in marine environments are increasing, and generating a need to quickly assess the presence of these contaminants in seawater. This work aims to estimate the concentrations of benzene, toluene, ethylbenzene and xylenes (BTEX) dissolved in seawater in cases of oil spillage using experimental factorial planning. The study factors were oil °API and oil/seawater contact time after spillage. The models obtained were able to satisfactorily estimate BTEX concentrations, with accuracy greater than 99.3% within the ranges studied, with R² correlation coefficients ranging from 0.992 to 0.997. The models presented forecast efficiency higher than 88%, with low relative errors, ranging from 0.1% to 12%. The concentrations of benzene dissolved in seawater found experimentally with only one hour of spillage, for the two types of oils studied, were higher than allowed by Brazilian legislation, demonstrating real environmental risk in cases of spillage of these types of oil into the sea. These results can corroborate the development of a risk assessment in oil spills within the studied ranges and serve as a useful analytical tool for emergencies.

[Detection of Residual Solvents in Commercial Supplements Using Headspace (HS)-GC-MS].

In order to understand the actual state of residual solvents contained in commercial supplements, we performed a simultaneous analysis of residual solvents by headspace (HS)-GC-MS with reference to the Japanese Pharmacopoeia's "Residual Solvents", for 29 products selected from among commercial supplements (e.g., revitalizers, weight loss pills) that are deeply colored or contain coating agents and extract powder. As a result, benzene (class 1) was detected in eight black-colored supplements, and hexane (class 2B) was also detected in one of those products. On the other hand, methanol (class 2A) was detected in four products containing coating agents and extract powders, such as citrus peel extract. None of these residual solvents exceeded the concentration limits set by the Japanese Pharmacopoeia. Benzene was detected at 1.7 µg/g, which was near the concentration limit, in some products. As raw materials used for the manufacture of the black-colored supplements from which benzene was detected commonly included activated carbon, we analyzed the residual solvents contained in activated carbon commercially available for use as food additive and in food production and medicine. As a result, benzene was detected at high concentrations in activated carbon made from hemp (approximately 29 µg/g) and bamboo (approximately 140 µg/g).

Ultrafine Ru species within confined space: An efficient adsorbent for ultra-deep desulfurization of benzene.

The ultra-deep adsorptive desulfurization (ppb level) of benzene remains a challenging subject with the need to construct efficient adsorbent systems. Herein, a kind of ruthenium-based adsorbent functionalized with bimetallic Ru-Al was rationally designed using Al2O3 as support (denoted as 0.8%Ru-1.2%Al/Al2O3). It was found that the co-anchoring of Ru and Al species endows the Ru-based adsorbent unique adsorption capability, which is able to completely eliminate sulfur compounds in benzene, and exhibiting a much higher breakthrough sulfur capacity than that of the 0.8%Ru/Al2O3. Remarkably, under the industrial experiment conditions, 0.8%Ru-1.2%Al/Al2O3 exhibited excellent long-term stability for more than 1200 h, showing the potential for industrial application. Various characterization techniques, including BET, XRD, SEM, TEM, TPD-MS, TPR and XPS, were used to investigate the correlation between the adsorption performance and the microstructure of the adsorbents. Over 0.8%Ru-1.2%Al/Al2O3, the ultra-thin aluminum additive is beneficial to improve the dispersion of Ru species, which therefore exhibits desirable desulfurization efficiency. Moreover, the enhanced performance is also correlated to the presence of the suitable Ru active centers generated from the selective coverage by Al species. It leads to an optimal exposure of the Ru active centers, which would facilitate the interaction of S-Ru and the improvement of the desulfurization activity.

Distribution Characteristics of Volatile Organic Compounds and Contribution to Ozone Formation in a Coking Wastewater Treatment Plant.

Ozone pollution, which can be caused by photochemical reactions, has become a serious problem. The ozone formation potential (OFP) is used to describe the photochemical reactivity. Volatile organic compounds (VOCs) are main precursors of ozone formation, and wastewater treatment plants (WWTPs) are important sources of VOCs. Therefore, it is necessary to study the concentration level and OFP of VOCs from WWTPs. In this work, a coking WWTP with anaerobic-oxic-oxic (A/O/O) processes in Shaoguan city, Guangdong province, China, was selected to investigate the characteristics of VOCs at wastewater treatment areas and office areas. The OFP of VOCs was estimated by the maximum incremental reactivity (MIR) coefficient method. Results showed that 17 VOCs were detected, and the total concentration of VOCs was the highest at the raw water tank (857.86 µg m-3). The benzene series accounted for 69.0%-86.9% and was the main component of VOCs in the WWTP. Based on OFP data, the top six VOCs contributing most to the OFP were m-xylene, toluene, p-xylene, o-xylene, styrene, and benzene. This study provides field data and information on the environmental risk of VOCs for coking companies and environmental departments. We found that the priority control sources of VOCs were wastewater treatment units because of their larger OFP contributions.