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.

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.

Evaluating the feasibility of air environment management system for VOCs through 'VOCs specification' of petroleum refining industry.

The chemical industry releases various types of volatile organic compounds (VOCs) into the atmosphere, and the concentration of VOCs emitted from chimneys is regulated worldwide. However, some VOCs such as benzene are highly carcinogenic, while others such as ethylene and propylene may cause secondary air pollution, owing to their high ozone-generating ability. Accordingly, the US EPA(United State, Environment Protect Agency) introduced a fenceline monitoring system that regulates the concentration of VOCs at the boundary of a facility, away from the chimney source. This system was first introduced in the petroleum refining industry, which simultaneously emits benzene, affecting the local community because of its high carcinogenicity, and ethylene, propylene, xylene, and toluene, which have a high photochemical ozone creation potential (POCP). These emissions contribute to air pollution. In Korea, the concentration at the chimney is regulated; however, the concentration at the plant boundary is not considered. In accordance with the EPA regulations, Korea's petroleum refining industries were identified and the limitations of the Clean Air Conservation Act were studied. The average concentration of benzene at the research facility examined in this study was 8.53 µg/m3, which complied with the benzene action level of 9 µg/m3. However, this value was exceeded at some points along the fenceline, in proximity to the benzene-toluene-xylene (BTX) manufacturing process. The composition ratios of toluene and xylene were 27% and 16%, respectively, which were higher than those of ethylene or propylene. These results suggest that reduction measures in the BTX manufacturing process are necessary. This study shows that legal regulations should enforce reduction measures through continuous monitoring at the fenceline of petroleum refineries in Korea.Implications: Although volatile organic compounds(VOCs) are essential in various industrial sites, they adversely affect the health of people in the near community. Benzene is highly carcinogenic, so it is dangerous if exposed continuously. In addition, there are various types of VOCs, which combine with atmospheric ozone to generate smog. Globally, VOCs are managed as Total VOCs. However, through this study, VOCs have priority, and in the case of the petroleum refining industry, it is suggested that VOCs should be preemptively measured and analyzed to be regulated. In addition, it is necessary to minimize the impact on the local community by regulating the concentration at the fenceline beyond the chimney measurement.

Technique for order preference by similarity to ideal solution (TOPSIS): a MCDM approach for selecting suitable solvent considering biochemical profiles and in vitro antibacterial efficacy of petioles of betel leaf (Piper betle L.).

Petioles of betel leaf (BLP) are the major industrial by-products of betel leaf industries sold at throwaway prices or used as cattle feed. The present work was taken up to evaluate suitable solvent based on yield, antioxidant, and antimicrobial properties to isolate extract of BLP using the Shannon entropy-TOPSIS method. Four solvents were chosen for the extraction process: hexane, toluene + ethanol (2:1), acetone, and ethanol. The findings showed that ethanol-based BLP extract had the highest TPC value, measuring 2193.71 ± 0.17 mg of gallic acid equivalence/g of dry extract, while acetone-based extracts had the highest TFC value, measuring 8.03 mg of quercetin equivalent/g of dry extract. Radical scavenging activities like DPPH (IC50 = 52.44 µg/mL), ABTS (IC50 = 62.41 µg/mL), and FRAP (8.03 mg QE/g of dry extract) were found best for acetone extract. The antibacterial study of the extracts revealed that acetone extract was more sensitive to Gram-positive and Gram-negative bacterial strains followed by ethanol, toluene + ethanol, and hexane extracts. Among five foodborne bacteria, B. subtilis showed the highest susceptibility against all extracts. GC-MS analysis showed that acetoxychavicol acetate (31.27%) (PubChem ID: 119,104), germacrene D (7.24%) (PubChem Id: 531,750), isoxylic acid (22.56%) (PubChem ID: 11,892), and cis-1,2-indandiol (43.92%) (PubChem ID: 20,758) are four major compounds among 22 components. TOPSIS analysis revealed that acetone extract had the highest relative closeness value (0.71) followed by ethanol (0.65), toluene + ethanol (0.53), and hexane (0.32). These results indicate that acetone extract of BLP can be considered an alternative to synthetic active ingredients in the future. These results indicated that TOPSIS method has computational robustness for selecting a solvent comparing yield, antioxidant, and antimicrobial activities of extract of a plant part.

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.

Decontamination of water co-polluted by copper, toluene and tetrahydrofuran using lauric acid.

Co-contamination by organic solvents (e.g., toluene and tetrahydrofuran) and metal ions (e.g., Cu2+) is common in industrial wastewater and in industrial sites. This manuscript describes the separation of THF from water in the absence of copper ions, as well as the treatment of water co-polluted with either THF and copper, or toluene and copper. Tetrahydrofuran (THF) and water are freely miscible in the absence of lauric acid. Lauric acid separates the two solvents, as demonstrated by proton nuclear magnetic resonance (1H NMR) and Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy (ATR-FTIR). The purity of the water phase separated from 3:7 (v/v) THF:water mixtures using 1 M lauric acid is ≈87%v/v. Synchrotron small angle X-Ray scattering (SAXS) indicates that lauric acid forms reverse micelles in THF, which swell in the presence of water (to host water in their interior) and ultimately lead to two free phases: 1) THF-rich and 2) water-rich. Deprotonated lauric acid (laurate ions) also induces the migration of Cu2+ ions in either THF (following separation from water) or in toluene (immiscible in water), enabling their removal from water. Laurate ions and copper ions likely interact through physical interactions (e.g., electrostatic interactions) rather than chemical bonds, as shown by ATR-FTIR. Inductively coupled plasma-optical emission spectrometry (ICP-OES) demonstrates up to 60% removal of Cu2+ ions from water co-polluted by CuSO4 or CuCl2 and toluene. While lauric acid emulsifies water and toluene in the absence of copper ions, copper salts destabilize emulsions. This is beneficial, to avoid that copper ions are re-entrained in the water phase alongside with toluene, following their migration in the toluene phase. The effect of copper ions on emulsion stability is explained based on the decreased interfacial activity and compressional rigidity of interfacial films, probed using a Langmuir trough. In wastewater treatment, lauric acid (a powder) can be mixed directly in the polluted water. In the context of groundwater remediation, lauric acid can be solubilized in canola oil to enable its injection to treat aquifers co-polluted by organic solvents and Cu2+. In this application, injectable filters obtained by injecting cationic hydroxyethylcellulose (HEC +) would impede the flow of toluene and copper ions partitioned in it, protecting downstream receptors. Co-contaminants can be subsequently extracted upstream of the filters (using pumping wells), to enable their simultaneous removal from aquifers.

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.

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.

Highly efficient decomposition of toluene using a high-temperature plasma-catalysis reactor.

Plasma-catalysis technologies (PCTs) have the potential to control the emissions of volatile organic compounds, although their low-energy efficiency is a bottleneck for their practical applications. A plasma-catalyst reactor filled with a CeO2/γ-Al2O3 catalyst was developed to decompose toluene with a high-energy efficiency enhanced by the elevating reaction temperature. When the reaction temperature was raised from 50 °C to 250 °C, toluene conversion dramatically increased from 45.3% to 95.5% and the energy efficiency increased from 53.5 g/kWh to 113.0 g/kWh. Conversely, the toluene conversion using a thermal catalysis technology (TCT) exhibited a maximum of 16.7%. The activation energy of toluene decomposition using PCTs is 14.0 kJ/mol, which is far lower than those of toluene decomposition using TCTs, which implies that toluene decomposition using PCT differs from that using TCT. The experimental results revealed that the Ce3+/Ce4+ ratio decreased and Oads/Olatt ratio increased after the 40-h evaluation experiment, suggesting that CeO2 promoted the formation of the reactive oxygen species that is beneficial for toluene decomposition.

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.

Ecotoxicity tests with Allium cepa to determine the efficiency of rice husk ash in the treatment of groundwater contaminated with benzene, toluene, ethylbenzene, and xylene.

The validation of adsorption treatment based on toxicity assays aims to assess the actual environmental impact caused by effluents after treatment. This study describes the use of rice husk ash as adsorbent and evaluates the efficiency of adsorption treatment to remediate groundwater contaminated with benzene, toluene, ethylbenzene, and xylene (BTEX). The synthetic effluent was prepared with standard benzene, toluene, ethylbenzene, and xylene solutions. Adsorption was assessed at treatment times 0, 60, 120, and 240 min. Compounds were quantified by gas chromatography with flame ionization detector. The treatment was validated based on ecotoxicity assays using Allium cepa as indicator organism. For the treatment times stipulated, samples containing 25, 50, and 100% of BTEX were used. The dilutions were carried out with drinking water according to Fiskesjö (1985). The relative growth index (RGI), root inhibition index (Ii), and germination index (GI) confirmed the efficiency of the treatment approach tested. The best adsorption time for an initial BTEX concentration of 3.378 mg/L was 60 min. Critical level (EC50) and critical concentration that induced phytotoxic effect on A. cepa germination was observed only for the undiluted effluent.

Forensic source attribution for toluene in environmental samples.

The formation of toluene by microbiological processes can confound environmental investigations relating to petroleum releases. This is because toluene is a constituent of petroleum and can move readily within wetland environments, and analysis for toluene in relation to a petroleum release can lead to incorrect assignment of detected biogenic toluene as related to the release. No legally defensible method of distinguishing biogenic and petrogenic origins of detectible concentrations of toluene have been demonstrated to date. Using example petrogenic samples and samples of peat from 2 wetland environments, a poor bog and a poor fen, the present study demonstrates the use of an established ASTM International analytical methodology that was originally designed for arson analysis for the determination of the origin of toluene. Environmental forensic data-interpretation methods such as chromatogram inspection and diagnostic ratios are shown to be capable of readily distinguishing biogenic and petrogenic origins of toluene. Environ Toxicol Chem 2018;37:729-737. © 2017 SETAC.

Assessment of Surface Water Contamination from Coalbed Methane Fracturing-Derived Volatile Contaminants in Sullivan County, Indiana, USA.

There is a growing concern over the contamination of surface water and the associated environmental and public health consequences from the recent proliferation of hydraulic fracturing in the USA. Petroleum hydrocarbon-derived contaminants of concern [benzene, toluene, ethylbenzene, and xylenes (BTEX)] and various dissolved cations and anions were spatially determined in surface waters around 15 coalbed methane fracking wells in Sullivan County, IN, USA. At least one BTEX compound was detected in 69% of sampling sites (n = 13) and 23% of sampling sites were found to be contaminated with all of the BTEX compounds. Toluene was the most common BTEX compound detected across all sampling sites, both upstream and downstream from coalbed methane fracking wells. The average concentration of toluene at a reservoir and its outlet nearby the fracking wells was ~2× higher than other downstream sites. However, one of the upstream sites was found to be contaminated with BTEX at similar concentrations as in a reservoir site nearby the fracking well. Calcium (~60 ppm) and sulfates (~175 ppm) were the dominant cations and anions, respectively, in surface water around the fracking sites. This study represents the first report of BTEX contamination in surface water from coalbed methane hydraulic fracturing wells.

Elucidating the fate of a mixed toluene, DHM, methanol, and i-propanol plume during in situ bioremediation.

Organic pollutants such as solvents or petroleum products are widespread contaminants in soil and groundwater systems. In-situ bioremediation is a commonly used remediation technology to clean up the subsurface to eliminate the risks of toxic substances to reach potential receptors in surface waters or drinking water wells. This study discusses the development of a subsurface model to analyse the performance of an actively operating field-scale enhanced bioremediation scheme. The study site was affected by a mixed toluene, dihydromyrcenol (DHM), methanol, and i-propanol plume. A high-resolution, time-series of data was used to constrain the model development and calibration. The analysis shows that the observed failure of the treatment system is linked to an inefficient oxygen injection pattern. Moreover, the model simulations also suggest that additional contaminant spillages have occurred in 2012. Those additional spillages and their associated additional oxygen demand resulted in a significant increase in contaminant fluxes that remained untreated. The study emphasises the important role that reactive transport modelling can play in data analyses and for enhancing remediation efficiency.

Lab-based investigation of enhanced BTEX attenuation driven by groundwater table fluctuation.

Groundwater fluctuation is often overlooked and lack of study in the field contaminant hydrogeology. Hydraulic force from fluctuating groundwater tables leads to dissolution and subsequent enhanced advective transport of petroleum (e.g. BTEX) in contaminated subsurface system. A laboratory investigation of effect of the groundwater table fluctuation (GTF) on BTEX transport, taking toluene as a typical compound, in a typical representative model of aquifers subjected to a daily water-table fluctuation was undertaken in this work. Results showed that toluene in effluent degraded significantly with cycles of GTF, and the attenuation rates differed in porous media types with higher value for fine-coarse sand media (13.7 mg L-1 d-1) and lower for fine sand-clay media (2.8 mg L d-1). Hydraulic and hydrochemical evidences inferred that toluene attenuation was controlled mainly by flushing effect in the initial GTF cycle stages, followed by dissolution and mixing action in the later stages. Meanwhile, adsorption was found to take effects in toluene behavior throughout the whole GTF process, particularly obvious in fine sand-clay media with its toluene attenuation rate of only 2.8 mg L d-1.

Occurrence and distribution of monocyclic aromatic hydrocarbons (BTEX) and the impact on macrobenthic community structure in Lagos lagoon, Nigeria.

The widespread distribution of petroleum products arising from the rapid growth of the petroleum industry in Nigeria has resulted in the pollution of the environment through oil spills involving leakages from tankers, pipelines, tank farms, and dumping of waste petroleum products. The impacts and distribution of major toxic components (benzene, toluene, ethylbenzene, and xylene (BTEX)) of petroleum products in water and sediment samples collected from sampling stations in the Lagos lagoon was investigated over a 2-year period (February 2009-July 2010). The distribution of benthic communities in the different sampling stations of the Lagos lagoon was assessed. The determination of hydrocarbon levels in the samples showed that the levels of total hydrocarbon content (THC) in the water samples around the Atlas Cove and Apapa were high with values ranging from 2.03 to 31.38 mg/l and 4.04 to 22.89 mg/l, respectively. The highest value of total BTEX in the lagoon sediment was also recorded in the Apapa station (450.53 µg/kg), where oil depots and tank farm facilities are located. The study of the macrobenthic community structure showed that the species richness ranged from 1.57 to 2.02 in the reference station, Unilag, while in the Atlas Cove, Iddo, and Apapa stations, it ranged from 1.80 to 2.89, 1.95 to 3.03, and 1.86 to 2.95, respectively. The highest number of organisms (183) was recorded in the reference stations, while the least number (46) was recorded in Apapa. The main hydrocarbon pollution indicator species identified in the impacted aquatic stations were Nais eliguis and Heteromastus filiformis. The levels of hydrocarbon observed in the aquatic environment showed that there is widespread contamination as a result of petroleum product importation, storage, and distribution. The assessment of the monocyclic aromatic hydrocarbon and benthic community will therefore provide important tools for early detection, diagnosis, and management of hydrocarbon pollution in the Lagos lagoon.

Toluene removal by sequential adsorption-plasma catalytic process: Effects of Ag and Mn impregnation sequence on Ag-Mn/γ-Al2O3.

A series of Ag-Mn/γ-Al2O3 were prepared under different Ag/Mn impregnation sequence and tested in the sequential adsorption-plasma catalytic removal of toluene. When Mn was impregnated first, the resulting catalyst, Ag-Mn(F)/γ-Al2O3, had longer breakthrough time, gave less emission of toluene, had higher CO2 selectivity, and had better carbon balance and COx yield compared to catalysts prepared via other impregnation sequences. After 120 min of NTP treatment, the carbon balance of Ag-Mn(F)/γ-Al2O3 was 91%, with 87% as COx contributions. A Brunauer-Emmett-Teller (BET) analysis and X-ray photoelectron spectroscopy (XPS) results show that, the impregnation sequence impacts the BET surface area and the ratio and existing state of Ag on the surface of the catalysts. The longer breakthrough time when using Ag-Mn(F)/γ-Al2O3 as catalyst is attributed to the large amount of Ag(+) on the surface. Ag(+) is a new active site for toluene adsorption. When Ag was impregnated first (Ag(F)-Mn/γ-Al2O3) or Ag and Mn co-impregnated (Ag-Mn-C/γ-Al2O3), the predominant specie was Ag(+). Both Ag(0) and Ag(+) species were detected on Ag-Mn(F)/γ-Al2O3. Ag(0) cooperation with MnOx may promote the migration of surface active oxygen. This would facilitate the oxidation of adsorbed toluene with CC bond already weakened by Ag(+) and would result in higher CO2 selectivity and better carbon balance as seen in the Ag-Mn(F)/γ-Al2O3 system.

BTX in urban areas of eastern Spain: a focus on time variations and sources.

Seasonal and daily cycles of BTX were studied in a non-industrialized city (Alicante) and an urban area near an oil refinery plant (Castellón) in order to evaluate the influence of different sources on time variations. Lower levels were observed in summer than in winter at both locations due to higher dispersion conditions and photochemical removal of BTX during the summer season. Daily patterns showed seasonal differences and were controlled by traffic emissions and the evolution of the mixing layer height, with no influence of the petroleum refinery plant in the city of Castellón. The results of the conditional bivariate probability function suggest that the influence of this source on BTX concentrations was limited to point impacts. At both sites, benzene exhibited a different behavior from toluene and xylenes, most likely due to its significantly lower chemical reactivity.

Analyzing tree cores to detect petroleum hydrocarbon-contaminated groundwater at a former landfill site in the community of Happy Valley-Goose Bay, eastern Canadian subarctic.

This research examines the feasibility of analyzing tree cores to detect benzene, toluene, ethylbenzene, and m, p, o-xylene (BTEX) compounds and methyl tertiary-butyl ether (MTBE) in groundwater in eastern Canada subarctic environments, using a former landfill site in the remote community of Happy Valley-Goose Bay, Labrador. Petroleum hydrocarbon contamination at the landfill site is the result of environmentally unsound pre-1990s disposal of households and industrial solid wastes. Tree cores were taken from trembling aspen, black spruce, and white birch and analyzed by headspace-gas chromatography-mass spectrometry. BTEX compounds were detected in tree cores, corroborating known groundwater contamination. A zone of anomalously high concentrations of total BTEX constituents was identified and recommended for monitoring by groundwater wells. Tree cores collected outside the landfill site at a local control area suggest the migration of contaminants off-site. Tree species exhibit different concentrations of BTEX constituents, indicating selective uptake and accumulation. Toluene in wood exhibited the highest concentrations, which may also be due to endogenous production. Meanwhile, MTBE was not found in the tree cores and is considered to be absent in the groundwater. The results demonstrate that tree-core analysis can be useful for detecting anomalous concentrations of petroleum hydrocarbons, such as BTEX compounds, in subarctic sites with shallow unconfined aquifers and permeable soils. This method can therefore aid in the proper management of contamination during landfill operations and after site closures.

Integration of decentralized torrefaction with centralized catalytic pyrolysis to produce green aromatics from coffee grounds.

The aim of this work was to integrate decentralized torrefaction with centralized catalytic pyrolysis to convert coffee grounds into the green aromatic precursors of terephthalic acid, namely benzene, toluene, ethylbenzene, and xylenes (BTEX). An economic analysis of this bioproduct system was conducted to examine BTEX yields, biomass costs and their sensitivities. Model predictions were verified experimentally using pyrolysis GC/MS to quantify BTEX yields for raw and torrefied biomass. The production cost was minimized when the torrefier temperature and residence time were 239°C and 34min, respectively. This optimization study found conditions that justify torrefaction as a pretreatment for making BTEX, provided that starting feedstock costs are below $58 per tonne.