Bench-scale and field-scale evaluation of catechol 2,3-dioxygenase specific primers for monitoring BTX bioremediation

The objective of this work was to test a molecular genetic method for in situ monitoring of aerobic benzene, toluene, and xylene (BTX) biodegrading microorganisms. Catechol 2,3-dioxygenase (C23DO) genes occur in bacteria that biodegrade benzene, toluene, xylenes, phenol, biphenyl, and naphthalene. A competitive quantitative polymerase chain reaction (QC-PCR) technique using a single set of primers specific for an entire subfamily of C23DO genes was recently developed. To determine whether bacteria containing these C23DO genes actually exist in environments contaminated by BTX, aerobic microcosms containing previously uncontaminated soil were amended with different aromatic hydrocarbons and DNA extracts were analyzed by QC-PCR for C23DO genes. Anaerobic microcosms were established to confirm that oxygen was also necessary for the enrichment of C23DO genes. Field testing was done at two sites undergoing monitored natural attenuation. In microcosm experiments naphthalene, m-xylene, and p-xylene strongly enriched for C23DO genes while benzene, toluene, and o-xylene produced only transient, weakly detectable genes. In the field study, C23DO genes were detected in groundwater samples contaminated with either xylenes or naphthalene. The results of this study demonstrated that molecular genetic techniques can provide an accurate and rapid method to detect microorganisms capable of aromatic hydrocarbon biodegradation. Such a technique would be useful for monitoring the effectiveness of aeration technologies and for documenting microbial processes for monitored natural attenuation.     

An overview of environmental and toxicological aspects of aromatic hydrocarbons. II. Toluene

The salient aspects of the exposure to toluene were reviewed via an initial examination of the production, use, occurrence and disposition of toluene, as well as populations at potential risk. Special note should be taken as to the increasing use of toluene as a "safe" replacement for benzene in solvent applications and its increasing use in many consumer products. There is a broad potential for exposure by industrial workers and the general public (via vehicle exhausts and consumer products). The effects on humans and animals as well as the genetic effects of toluene were also reviewed following an initial consideration for its absorption and elimination. The narcotic and neurotoxic properties of toluene represent the main recognized health hazards to humans.     

Exhaust ventilation in attached garages improves residential indoor air quality

Previous research has shown that indoor benzene levels in homes with attached garages are higher than homes without attached garages. Exhaust ventilation in attached garages is one possible intervention to reduce these concentrations. To evaluate the effectiveness of this intervention, a randomized crossover study was conducted in 33 Ottawa homes in winter 2014. VOCs including benzene, toluene, ethylbenzene, and xylenes, nitrogen dioxide, carbon monoxide, and air exchange rates were measured over four 48‐hour periods when a garage exhaust fan was turned on or off. A blower door test conducted in each garage was used to determine the required exhaust fan flow rate to provide a depressurization of 5 Pa in each garage relative to the home. When corrected for ambient concentrations, the fan decreased geometric mean indoor benzene concentrations from 1.04 to 0.40 μg/m³, or by 62% (P<.05). The garage exhaust fan also significantly reduced outdoor‐corrected geometric mean indoor concentrations of other pollutants, including toluene (53%), ethylbenzene (47%), m,p‐xylene (45%), o‐xylene (43%), and carbon monoxide (23%) (P<.05) while having no impact on the home air exchange rate. This study provides evidence that mechanical exhaust ventilation in attached garages can reduce indoor concentrations of pollutants originating from within attached garages.     

寒地污水厂曝气池VOCs逸散速率研究

本文以寒冷地区某城市污水处理厂曝气池作为研究对象,应用数学模型计算曝气池中苯系物(苯,甲苯,二甲苯)和氯代烃(三氯甲烷,四氯化碳,三氯乙烯,四氯乙烯)的逸散速率。计算结果表明寒冷地区污水处理厂苯系物和氯代烃在冬季的逸散速率最高。苯、甲苯、二甲苯、三氯甲烷、四氯化碳、三氯乙烯和四氯乙烯在冬季的逸散速率分别为5.22、0.37、0.46、1.46、1.18、18.92和2.22g/s。污水处理厂曝气池苯系物和氯代烃的排放标准满足《大气污染物综合排放标准(GB16297-1996)》。     

Spatial modelling of gaseous emissions from two municipal solid waste dump sites

This paper reports the spatial modelling of gaseous emissions from two municipal solid waste dump sites to determine exposure to landfill gases. The AERMOD modelling software and the Mexican Biogas Model were used, with information from nearby meteorological stations for the period 2015–2016. It was observed that, at one of the dump sites, gas emissions reach populated areas, but in concentrations too low to be detected by the olfactory pathway (benzene <5 µg/m³, toluene and xylene <50 µg/m³). At the second dump site, concentrations are greater; there are no population settlements close by. The highest concentrations of benzene, toluene, xylene and hydrogen sulphide are found within, or around, the dump sites, reaching levels greater than 38 μg/m³ for benzene, 770 μg/m³ for toluene and 237 μg/m³ for xylene.     

Effect of ethanol on BTEX biodegradation kinetics: aerobic continuous culture experiments

The use of ethanol as an automotive fuel oxygenate represents potential economic and air-quality benefits. However, little is known about how ethanol may affect the natural attenuation of petroleum product releases. Chemostat experiments were conducted with four pure cultures (representing archetypes of the known aerobic toluene degradation pathways) to determine how ethanol affects benzene, toluene, ethylbenzene, and xylene (BTEX) biodegradation kinetics. In all cases, the presence of ethanol decreased the metabolic flux of toluene (measured as the rate of toluene degradation per cell). This negative effect was counteracted by an ethanol-supported increase in biomass, which is conducive to faster degradation rates. When the influent total organic carbon (TOC) of the toluene-ethanol mixture was kept constant, the metabolic flux of toluene was proportional to its relative contribution to the influent TOC. This empirical relationship was used to derive a mathematical model that simulated effluent benzene concentrations as a function of the influent mixed-substrate composition, the dilution rate, and Monod kinetic coefficients. Under carbon-limiting conditions (1 mg/L influent benzene), the data and model simulations showed an increase in benzene removal efficiency when ethanol was fed at low concentrations (ca. 1 mg/L) because its positive effect on cell growth outweighed its negative effect on the metabolic flux of benzene. High ethanol concentrations, however, had a negative effect, causing oxygen limitation and increasing effluent benzene concentrations to higher levels than when benzene was fed alone. The slower BTEX degradation rates expected at sites with high ethanol concentrations (e.g., at gasohol-contaminated sites) could result in longer BTEX plumes and a greater risk of exposure.     

Indoor levels of volatile organic compounds at Florentine museum environments in Italy

Indoor Air Quality monitoring in cultural institutions is of particular concern to protect these places and the cultural heritage content. An indoor monitoring campaign was performed in three museums in Florence (Italy) to determine the occurrence and levels of volatile organic compounds (VOCs). VOCs of interest included BTEX (benzene, toluene, ethylbenzene, xylenes), terpenes, aldehydes, organic acids, and cyclic volatile methyl siloxanes (cVMS). The most abundant VOCs in all samples analyzed were BTEX, which were strictly related to the traffic source, followed by siloxanes and terpenes. Among BTEX, toluene was always the most abundant followed by xylenes, ethylbenzene, and benzene. cVMS in exhibition rooms with the presence of visitors showed higher values compared to samples collected when the museums were closed. Terpenes showed not only the influence of vegetation-biogenic sources surrounding a museum but could also be related to the wood used for the construction of showcases and furniture and the use of cleaning products. Data obtained also showed the presence of organic acids and aldehydes whose source can be traced back to exhibits themselves and wood-based furniture. Assessing the levels of organic acids in museums is important because, over time, it can cause deterioration of the artifacts.     

Mass concentrations of BTEX inside air environment of buses in Changsha,China

In order to estimate the mass concentrations of benzene (B), toluene (T), ethylbenzene (E) and xylenes (X) inside air environment of buses and to analyze the influencing factors of the BTEX pollution levels, 22 public buses were investigated in Changsha, China. The interior air was collected through activated charcoal adsorption tubes and then the air samples were analyzed with thermally desorbed gas chromatograph. The mass concentrations ranged from 21.3 to 106.4 μg/m³ for benzene, from 53.5 to 266.0 μg/m³ for toluene, from 19.6 to 95.9 μg/m³ for ethylbenzene and from 46.9 to 234.8 μg/m³ for xylenes. Their mean values were 68.7, 179.7, 62.5 and 151.8 μg/m³, respectively. The rates of buses tested where the interior concentrations exceeded the limit levels of Chinese Indoor Air Quality Standard were 45.5% for toluene and 13.6% for xylenes. The BTEX levels increased when in-car temperature or relative humidity rose, and decreased when car age or travel distance increased. The BTEX concentrations were higher in leather trims buses than in non-leather trims ones, in air-conditioned buses than in non-air-conditioned ones, and in high-grade buses than in low-grade ones. According to the analysis of multiple linear regression equation, car age and in-car temperature were two most important factors influencing the BTEX pollution levels in the cabins of public buses.     

Biodegradation of monoaromatic hydrocarbons in aquifer columns amended with hydrogen peroxide and nitrate

The ability of indigenous microorganisms to degrade benzene, toluene, ethylbenzene and xylenes (BTEX) in laboratory scale flow-through aquifer columns was tested separately with hydrogen peroxide (110 mg/l) and nitrate (330 mg/l as NO₃⁻) amendments to air-saturated influent nutrient solution. The continuous removal of individual components from all columns relative to the sterile controls provided evidence for biodegradation. In the presence of hydrogen peroxide, the indigeneous microorganisms degraded benzene and toluene (> 95%), meta- plus para-xylene (80%) and ortho-xylene (70%). Nitrate addition resulted in 90% removal of toluene and 25% removal of ortho-xylene. However, benzene, ethylbenzene, meta- and para-xylene concentrations were not significantly reduced after 42 days of operation. Following this experiment, low dissolved oxygen (< 1 mg/l) conditions were initiated with the nitrate-amended column influent in order to mimic contaminated groundwater conditions distal from a nutrient injection well. Toluene continued to be effectively degraded (> 90%), and more than 25% of the benzene, 40% of the ethylbenzene, 50% of the meta- plus para-xylenes and 60% of the ortho-xylene were removed after several months of operation.     

A comparative study of VOCs in Singapore and European office buildings

This study compares the characteristics of volatile organic compounds (VOCs) and the associated factors affecting them within European (EU) and Singapore buildings. Generally, concentrations of target VOCs determined in the two types of buildings were within health and comfort guidelines. This study found that concentrations of 2-methylpentane and n-heptane were significantly higher in the EU buildings, while those of n-tetradecane, 2-ethyl 1-hexanol, benzene, toluene, m/p-xylene, benzaldehyde and naphthalene significantly higher in Singapore buildings. Area specific emission rates of the methylpentane isomers, n-heptane and isoprene were significantly higher in the EU buildings, while those of 2-ethyl 1-hexanol, benzene, toluene and naphthalene were significantly higher in Singapore buildings. Lower ventilation rates within Singapore buildings caused relatively higher concentrations of m/p-xylenes and benzaldehyde despite no differences in emission rates between the two types of buildings. Elevated levels of 2-ethyl 1-hexanol in Singapore buildings are due to the higher air velocities and relative humidity indoors. There were no differences in 1,1,1-trichloroethane and 2-propanone levels, suggesting similar use of consumer products and occupant densities relating these two VOCs. Higher emission rates of methylpentane isomers and heptane were associated with the use of adhesives and solvents related to internal surfaces while higher emission rates for isoprene in the EU buildings were associated with environmental tobacco smoke (ETS). Higher levels of benzene, toluene and naphthalene in ETS-free Singapore buildings were associated with human-related activities.     

Air pollution in the microenvironment of parked new cars

Potential health effects of material emissions in new motor vehicles are of great public concern in China. To estimate the pollution levels, air samples were taken from 802 new cars parked in a well-ventilated underground parking garage in Beijing, China. These vehicles were all manufactured in and after 2003, and represented three different price ranges. For comparison, 20 older vehicles (manufactured before 2003) were also examined. Monitoring items included benzene, toluene, xylene, and formaldehyde. Preliminary results indicate that 82% of the vehicles studied had toluene levels exceeding the Chinese National Indoor Air Quality Standard. For benzene, xylene, and formaldehyde, the rates of noncompliance were 75%, 25%, and 24%, respectively. For all the pollutants, newer vehicles had higher concentrations than older ones. There seems a connection between the types of interior materials used in the passenger cabins and the concentrations of certain air pollutants.     

Abbau aromatischer Kohlenwasserstoffe und Metabolitenbildung im Grundwasserleiter eines ehemaligen Gaswerkstandorts

Hydrochemical investigations were performed at a contaminated site in the area of a former gasplant at Düsseldorf, Germany, between October, 1995 and November, 1996. The changes of the biodegradation processes in the aquifer during the remediation of groundwater and soil were monitored. The organic contaminants present in the groundwater were mainly BTEX (benzene, toluene, ethylbenzene, xylenes) and low moleuclar weight PAH (plycyclic aromatic hydrocarbons). At the beginning of the remediation activities, natural degradation of the contaminants occurred with sulfate reduction as the prevailing terminal electron accepting process. Due to oxygen input into the aquifer during soil removal the biodegradation process was disturbed and the concentrations of aromatic hydroarbons and sulfate rose significantly. The aromatic acids occuring as metabolites of the aromatic hydrocarbons reacted specifically to the changes in the degradation processes.     

By‐products formation in catalytic combustion of aromatic compounds over a pt‐based catalyst

By‐products formation in the catalytic combustion of different aromatic compounds has been experimentally investigated. A commercial Pt‐based catalyst, in the shape of a short monolith, has been employed. Toluene, styrene, o‐xylene and cumene have been tested at low concentrations for conversions in the range 5–50%. The results confirm the formation of benzene in the combustion of toluene and styrene, as previously observed by other researchers, but in a very small amount; testing cumene, significant amounts of acetone have been found in the outlet flow. Some hypothesis about the reaction mechanism are put forward.     

关于TVOC中甲苯、二甲苯的讨论

TVOC作为空气质量的重要衡量指标之一,对身体健康有危害,而苯系物是TVOC中的主要物质,本文统计了部分装饰装修工程TVOC中甲苯、二甲苯的含量,试图找出其中的比例关系,更准确地定义了TVOC。     

Seasonal and diurnal variations of volatile organic compounds (VOCs) in the atmosphere of Hong Kong

Ambient VOCs samples were collected at three locations (PolyU campus (PU), Kwun Tong (KT), Hok Tsui (HT)) in Hong Kong during the periods of November 2000-February 2001 and June 2001-August 2001. Also the concentrations of VOCs in Cross Harbor tunnel in Hong Kong were obtained in order to determine the vehicular sources of VOCs. Toluene was the most abundant VOC detected in Hong Kong. At the PU station, which is close to a main road, the concentrations of most VOCs were higher in summer than in winter. However, at the background location HT, the concentrations of all VOCs except tetrachloroethene were higher in winter than in summer. Regional physical dispersion/transportation and mixing depth may be the reasons for higher VOC concentrations in winter at HT. The BTEX (benzene:toluene:ethylbenzene:xylene) ratios of PU and KT during winter period were (1.9:10.1:1.0:1.8) and (1.9:10.4:1.0:1.5), and (0.9:8.3:1.0:2.2) and (0.8:29.6:1.0:1.8) for summer season, respectively. The xylene/ethylbenzene (X/E) ratio was used to assess the relative age of the air parcels in this study. The concentrations of VOCs in the atmosphere in Hong Kong were mainly affected by direct emissions from vehicles, evaporation of fuels, photochemical reactions and few industrial emissions. The BTEX ratio in the tunnel was 2:10.4:1:3.2. The BTEX ratios at PU and KT during the winter period were similar to that in tunnel (except for xylenes). The X/E ratio in the tunnel was higher than that in the ambient air. This indicated that the freshly emitted xylenes in the tunnel decayed at different rates from OH-oxidation in the atmosphere. Good BTEX correlations (r>0.8) were found at PU and KT in winter (**P<0.01). Vehicular exhaust was the dominant source at PU and KT stations, and less evaporation of fuel or additive occurred at low temperature in winter. Diurnal variations of mean BTEX concentrations at the roadside monitoring station (PU) showed two peaks associated with traffic density and vehicle type.     

Enumeration of aromatic oxygenase genes to evaluate monitored natural attenuation at gasoline-contaminated sites

Monitoring groundwater benzene, toluene, ethylbenzene, and xylene (BTEX) concentrations is the typical method to assess monitored natural attenuation (MNA) and bioremediation as corrective actions at gasoline-contaminated sites. Conclusive demonstration of bioremediation, however, relies on converging lines of chemical and biological evidence to support a decision. In this study, real-time PCR quantification of aromatic oxygenase genes was used to evaluate the feasibility of MNA at two gasoline-impacted sites. Phenol hydroxylase (PHE), ring-hydroxylating toluene monooxygenase (RMO), naphthalene dioxygenase (NAH), toluene monooxygenase (TOL), toluene dioxygenase (TOD), and biphenyl dioxygenase (BPH4) genes were routinely detected in BTEX-impacted wells. Aromatic oxygenase genes were not detected in sentinel wells outside the plume indicating that elevated levels of oxygenase genes corresponded to petroleum hydrocarbon contamination. Total aromatic oxygenase gene copy numbers detected in impacted wells were on the order of 10(6)-10(9)copies L(-1). PHE, RMO, NAH, TOD, and BPH4 gene copies positively correlated to total BTEX concentration. Mann-Kendall analysis of benzene concentrations was used to evaluate the status of the dissolved BTEX plume. The combination of trend analysis of contaminant concentrations with quantification of aromatic oxygenase genes was used to assess the feasibility of MNA as corrective measures at both sites.     

Actual car fleet emissions estimated from urban air quality measurements and street pollution models.

A method to determine emissions from the actual car fleet under realistic driving conditions has been developed. The method is based on air quality measurements, traffic counts and inverse application of street air quality models. Many pollutants are of importance for assessing the adverse impact of the air pollution, e.g. NO2, CO, lead, VOCs and particulate matter. Aromatic VOCs are of special great concern due to their adverse health effects. Measurements of benzene, toluene and xylenes were carried out in central Copenhagen since 1994. Significant correlation was observed between VOCs and CO concentrations, indicating that the petrol engine vehicles are the major sources of VOC air pollution in central Copenhagen. Hourly mean concentrations of benezene were observed to reach values of up to 20 ppb, what is critically high according to the WHOs recommendations. Based on inverse model calculation of dispersion of pollutants in street canyons, an average emission factor of benzene for the fleet of petrol fuelled vehicles was estimated to be 0.38 g/km in 1994 and 0.11 in 1997. This decrease was caused by the reduction of benzene content in Danish petrol since summer 1995 and increasing percentage of cars equipped with three-way catalysts. The emission factors for benzene for diesel-fuelled vehicles were low.     

Long-term observations on the influence of groundwater level variations on BTEX concentrations in groundwater

A long-term study on natural attenuation and remediation in soil and groundwater at the former military base Schäferhof-Süd (Niedersachsen) was performed at a former gasoline filling station. At this locality, a large residual source of benzene, toluene, ethylbenzene, xylenes (BTEX) and additional petroleum hydrocarbons is present in the soil. BTEX-concentrations in the groundwater and their correlation with groundwater level variations were monitored for three years. Within the monitoring period, a very dry summer was recorded, which caused the groundwater level to drop by 1.7 m and the BTEX concentrations to increase from 240 µg/l to 1300 µg/l at the site of contamination. The microbial degradation of BTEX was documented by data on consumption of electron acceptors (oxygen, nitrate or sulphate) and production of reduced products (Fe(II), methane). The degradation is further supported by the detection of metabolites. Therefore, the increasing BTEX concentrations were not a consequence of limited biological degradation.     

Determination of exposure to benzene, toluene and xylenes in Turkish primary school children by analysis of breath and by environmental passive sampling

Benzene, toluene, m/p-xylene and o-xylene (BTX) are toxic volatile organic compounds and ubiquitous air pollutants. Smoking and consumer products are indoor sources of BTX, whereas traffic and industrial activities are primary sources contributing to outdoor levels of BTX. The aim of this study was to characterize exposure of children to BTX by personal air sampling using diffusive samplers and by analysis of end-exhaled air. For this study, 101 children of 10-11 years of age were recruited from four primary schools in Southern Turkey during the warm season (May 2008). Two schools were situated in a residential area near primary and secondary iron and steel works (Payas) and two schools were located in a non-industrialized city (Iskenderun). The children and their parents were visited at home for an interview and to identify possible sources of BTX in the residence. Median concentrations of benzene determined by diffusive samplers were higher in Payas (4.1 μg/m³) than in Iskenderun (2.7 μg/m³, p < 0.001). For toluene, no differences were observed, whereas for xylene isomers air concentrations tended to be lower for children living in Payas. The median end-exhaled air concentrations were 8.2, 29, 3.8, and 5.7 pmol/L for benzene, toluene, m/p-xylene and o-xylene, respectively (Payas), and 6.9, 25, 4.9, and 6.0 pmol/L, respectively (Iskenderun). Concentrations of toluene in end-exhaled air were 50% higher in children living with household members who smoked indoors (p < 0.05) and benzene in end-exhaled air was more than 3-fold higher for those children who were exposed to tobacco smoke inside a vehicle (p < 0.001). End-exhaled concentrations of benzene were also higher in children living in a residence with an attached garage (p < 0.05). These exposure modifying factors were not identified when using the results obtained with diffusive samplers.     

Modeling the competitive effect of ammonium oxidizers and heterotrophs on the degradation of MTBE in a packed bed reactor

A mathematical model was used to study effects on the degradation of methyl tert-butyl ether (MTBE) in a packed bed reactor due to the presence of contaminants such as ammonium, and the mix of benzene, toluene, ethylbenzene and xylenes (BTEX). It was shown that competition between the slower growing MTBE degraders and the co-contaminant oxidizers prevented MTBE's degradation when oxygen was limited. In this event, the co-contaminant oxidizers out-competed the MTBE degraders in the reactor's biofilm. However, if the oxygen supply was sufficient, MTBE would be fully degraded after the zone where the co-contaminants were oxidized. The results of the model further indicate that contradicting findings in the literature about the effects of BTEX on the degradation of MTBE are mainly due to differences in the study methodologies. Effects such as short-term toxicity of BTEX and the lack of steady-state conditions may also add to contradictions among reports.