Benzene In Air Research Articles

The potential of biochar as sorptive media for removal of hazardous benzene in air

Airborne benzene is hazardous even at sub-ppm levels. Therefore, an effective strategy is required for its removal, such as the use of a sorbent with large adsorption capacity or high breakthrough volume. To meet the goal, the performance for the removal of benzene was assessed by loading benzene at 5 Pa inlet partial pressure against seven types of biowaste-derived biochar: (1) paper mill sludge, (2) conventional biochar with magnetic properties, (3) biochar composites with carbon nanotubes (CNTs), (4) gasification biochar from mixed feedstock, (5) gasification biochar from a single feedstock, (6) modified gasification biochar, and (7) activated carbon (AC) as a reference. The 298 K maximum adsorption capacities (mg g−1), when measured at a benzene inlet pressure of 5 Pa (or 50 ppm in ultrapure nitrogen) and flow rate of 50 mL atm min−1, varied widely for different biochars, from 0.35 (MS: Swine manure + plastic mulch film waste) to 144 mg g−1 (XC-1: biochar from mixed feedstock); their 10% breakthrough volumes (BTV) were in the range of 0.22–492 L g−1, respectively. The experimental data (capacity vs. benzene outlet partial pressure) could be fitted to either two or three linearized Langmuir isotherms with distinctive sorption mechanisms ((1) a retrograde region (Type III isotherm: 0 to ∼0.2 Pa), (2) an intermediate pressure region (0.2 and 2.0 Pa), and (3) a higher pressure region (>2 Pa)) which was also confirmed similarly by Freundlich, Dubinin–Radushkevich, and Elovich fitting. About 65% of the maximum capacity was achieved in the retrograde region. The strongest biochar sorbent, XC-1, showed similar performance as activated carbon to prove its feasibility toward air quality management (AQM) applications.

Spatiotemporal variation, ozone formation potential and health risk assessment of ambient air VOCs in an industrialized city in Iran

Volatile organic compounds (VOCs) are common air pollutants that are primarily emitted by motor vehicles and through industrial activity and can have a significant impact on air quality and adversely affect human health. The aim of this study was to characterize benzene, toluene, xylenes and styrene (BTXS) in the ambient air of Tabriz, a city in northwestern Iran, and describe their spatiotemporal variations, ozone formation potential (OFP) and provide a health risk assessment. The measured concentrations of BTXS ranged from 0.46 to 69.32 μg/m3. Diurnal variation showed a significant difference between the morning and evening concentrations, in which the evening values were primarily higher. Spatial analysis showed that the maximum levels of BTXS occurred in the industrial zone. The estimated OFP values ranged from 26 to 418 and 16 to 725 in winter and summer, respectively. In addition, the mean T/B ratio was 1.84, indicating the combustion of fuel in motor vehicles as the main source of VOCs. The hazard ratio of target pollutants was lower than the limits recommended by the USEPA and WHO; however, the estimated lifetime cancer risk for benzene was 7.82 × 10−6, which exceeds the threshold of 1 × 10−6.

Identification of gene expression predictors of occupational benzene exposure.

BackgroundPreviously, using microarrays and mRNA-Sequencing (mRNA-Seq) we found that occupational exposure to a range of benzene levels perturbed gene expression in peripheral blood mononuclear cells.ObjectivesIn the current study, we sought to identify gene expression biomarkers predictive of benzene exposure below 1 part per million (ppm), the occupational standard in the U.S.MethodsFirst, we used the nCounter platform to validate altered expression of 30 genes in 33 unexposed controls and 57 subjects exposed to benzene (<1 to ≥5 ppm). Second, we used SuperLearner (SL) to identify a minimal number of genes for which altered expression could predict <1 ppm benzene exposure, in 44 subjects with a mean air benzene level of 0.55±0.248 ppm (minimum 0.203ppm).ResultsnCounter and microarray expression levels were highly correlated (coefficients >0.7, p<0.05) for 26 microarray-selected genes. nCounter and mRNA-Seq levels were poorly correlated for 4 mRNA-Seq-selected genes. Using negative binomial regression with adjustment for covariates and multiple testing, we confirmed differential expression of 23 microarray-selected genes in the entire benzene-exposed group, and 27 genes in the <1 ppm-exposed subgroup, compared with the control group. Using SL, we identified 3 pairs of genes that could predict <1 ppm benzene exposure with cross-validated AUC estimates >0.9 (p<0.0001) and were not predictive of other exposures (nickel, arsenic, smoking, stress). The predictive gene pairs are PRG2/CLEC5A, NFKBI/CLEC5A, and ACSL1/CLEC5A. They play roles in innate immunity and inflammatory responses.ConclusionsUsing nCounter and SL, we validated the altered expression of multiple mRNAs by benzene and identified gene pairs predictive of exposure to benzene at levels below the US occupational standard of 1ppm.

Coupling of a High-Resolution Ambient Pressure Drift Tube Ion Mobility Spectrometer to a Commercial Time-of-flight Mass Spectrometer.

Ion mobility spectrometry provides information about molecular structures of ions. Hence, high resolving power allows separation of isomers which is of major interest in several applications. In this work, we couple our high-resolution ion mobility spectrometer (IMS) with a resolving power of Rp = 100 to a time-of-flight mass spectrometer (TOF-MS). Besides, the benefit of an increased resolving power such an IMS-MS also helps analyzing and understanding the ionization processes in IMS. Usually, the coupling between IMS and TOF-MS is realized by synchronizing data acquisition of the IMS and MS resulting in two-dimensional data containing ion mobility and mass spectra. However, due to peak widths of less than 100μs in our high-resolution IMS, this technique is not practicable due to significant peak broadening during the ion transfer into the MS and an insufficient data acquisition rate of the MS. Thus, a novel but simple interface between the IMS and MS has been designed which minimizes ion losses, allows recording of ion mobility at full IMS resolving power, and enables a shuttered transmission of ions into the MS. The interface is realized by replacing the Faraday plate used in IMS by a Faraday grid that is shielded by two additional aperture grids. For demonstration, positive product ions of benzene, toluene, and m-xylene in air are investigated. The IMS is equipped with a radioactive 3H source. Besides the well-known product ions M+ and M·NO+, a dimer ion is also observed for benzene and toluene, consisting of two molecules and three further hydrogen atoms. Graphical Abstract ᅟ.

Biological monitoring of low level exposure to benzene in an oil refinery: Effect of modulating factors

The aim of the study was to investigate the effect of various factors that modulate the metabolism of benzene, including smoking habits, metabolic genotype of GST and co-exposure to toluene, on the levels of three biomarkers, i.e. urinary benzene (UB), S-phenylmercapturic acid (SPMA) and t,t-muconic acid (t,t-MA), in 146 refinery workers exposed to low levels of air benzene (AB) in the range <1.5–529.2 μg/m3 (mean value 32.6 μg/m3).The study confirmed the validity of SPMA as a good biomarker of benzene exposure even at low levels of exposure. It was also confirmed that cigarette smoking is the main confounding factor when assessing biological monitoring data of occupational exposure to AB. Our data indicate that the GSTT1, but not the GSTM1 genotype, significantly increases the urinary levels of SPMA, even at low levels of exposure. It is not known, though, whether subjects with a GSTT1 “null” genotype may be more susceptible to the effects of benzene. Finally, environmental toluene appears to inhibit the metabolism of benzene to SPMA even at low concentrations, also resulting in an underestimation by SPMA levels of the actual exposure of workers to benzene.

Metal-Organic Frameworks for the Capture of Trace Aromatic Volatile Organic Compounds

Summary Air pollution, typically haze is getting worse in the urban areas of many countries worldwide. The development of advanced materials for the removal of air pollutants is of great significance for protecting public health. We herein present two promising metal-organic frameworks (MOFs) that show high capture capacities for aromatic volatile organic compounds even at low pressure and high temperature, e.g. benzene uptakes of 1.65 and 0.71 mmol g −1 at 0.12 kPa and 80°C. Breakthrough experiments verify their excellent performance in capturing trace benzene in humid air, also showing them to be comparable with some benchmark materials, including Carboxen 1000, PAF-1, MIL-101(Cr), and so on. Furthermore, the capture performance is well interpreted by the single-crystal structures of guest-loaded phases, where distinct adsorption sites, multiple synergistic host-guest and guest-guest interactions, and adaptive local flexibility are disclosed.

Efficient removal of benzene in air at atmospheric pressure using a side-on type 172nm Xe2 excimer lamp.

The photochemical removal of benzene was studied in air at atmospheric pressure using a side-on type 172nm Xe2 excimer lamp with a wide irradiation area. After 1.5min photoirradiation, C6H6 (1000ppm) in air was completely converted to HCOOH, CO, and CO2 at a total flow rate of 1000mL/min. The initial decomposition rate of C6H6 was determined to be 1.18min-1. By using a flow system, C6H6 (200ppm) was completely removed at a total flow rate of 250mL/min. The conversion of C6H6 and the energy efficiency in the removal of C6H6 changed in the 31-100% and 0.48-1.2g/kWh range, respectively, depending on the flow rate, the O2 concentration, and the chamber volume. On the basis of kinetic model simulation, dominant reaction pathways were discussed. Results show that the O(3P) + C6H6 reaction plays a significant role in the initial stage of the C6H6 decomposition. Important experimental parameters required for further improvement of the C6H6 removal apparatus using a 172 excimer lamp were discussed based on model calculations.

A type of novel glass for indoor air cleaning under visible-light

Since the pollution of indoor air has significant effects on health, it is meaningful if decorative glass inside can purify indoor air. Types of glass were prepared by coating them with modified nano titanium dioxides (nano-TiO2) and N, F and Fe ions were used as modification agents. Orthogonal experimental method was adopted in the preparation. Finally, a type of novel glass able to purify indoor air was found. The air cleaning performance of the glass was evaluated by the degradation of benzene in air. Optimal preparation conditions for the glass were determined. High initial benzene concentration and velocity had positive effect on the degradation efficiency. The enhanced photocatalytic activity was attributed to the nano crystallite size, element doping and proper preparation temperature. Additionally, the glass with optimized doping element was found to display a good self-cleaning ability, which was estimated by comparing the contact angle of water dropped on the glass surface. The glass also showed high durability and transmittance, which met the requirements of practical utilization.

Air pollution control: The evaluation of TerphApm@MWCNTs as a novel heterogeneous sorbent for benzene removal from air by solid phase gas extraction

Benzene is one of the most harmful VOCs pollutions which its control emission is a vital purpose in industries and environment. A new and efficient method based on solid phase gas extraction (SPGE) with Schiff base immobilized on MWCNTs (TerphApm@MWCNTs) as a novel sorbent was used for benzene removal from artificial air after loaded in Robson quartz tubes (RGT). The TerphApm@MWCNTs were synthesized and purified via heat treatment at 60 °C as a new heterogeneous sorbent. In bench scale set up, a system was designed and developed for standard gas generation of benzene in air with difference concentrations, and then was passed through RGT by SKC pump at optimized flow rate. Benzene volatile was absorbed on the TerphApm@MWCNTs and desorbed from it at 80 °C before determined by GC/FID. The important factors such as, temperature, humidity, benzene concentration, amount of adsorbent and flow rate were optimized. The recovery and capacity of benzene capture with 20 mg of TerphApm@MWCNTs were obtained 98% and 492 mg g−1 (25 °C). The flow rate and temperature had highly impact on the removal efficiency and adsorption capacity. According to results, the unique characterization of TerphApm@MWCNTs can be considered as a best adsorbent for benzene removal from air as compare to MWCNTs, SWCNTs, and NAC.

Managing Exposure to Benzene and Total Petroleum Hydrocarbons at Two Oil Refineries 1977-2014.

Air concentrations of and inhalation exposure to total petroleum hydrocarbons (TPH) and benzene was monitored separately at two oil refineries from 1977 to 2014. Prevention policies and control measures that may explain changes were surveyed. The aim was to evaluate how the application of of Occupational Health and Safety Assessment Series OHSAS 18001.04 principles as well as Environmental protection Agency EPA and European Oil Company Organisation for Environment, Health and Safety CONCAWE practices have influenced air concentrations. Benzene air concentrations declined in 11 of 17 units, six of which were associated with declining exposures. Benzene air concentrations declined across all units on average by 46%. This amounts to an average yearly decline of 1.7%. TPH air concentrations declined in 10 of 17 units, seven of which were associated with declining exposures. The average decline in TPH air concentrations was 49%, corresponding to 1.3% per year. As a result, average working day exposure in 10 of 17 units have declined significantly and today, benzene and TPH exposure in most units are well below 10% of the current Occupational Exposure Limit (OEL8h:s). A decline in air concentrations have coincided with consistent implementation of control measures. Such measures include on-line monitoring of leaks; benzene recovery; floating container roofs; improved valves and seals; hermetic pumps; recovery of loading gases and instalment of torches in terminals; cutback in coke combustion; a new production line spanning directly from the dock to aromatics production; and recovery of loading gases in the doc. Other tools in exposure management include personal leak monitors, on-line measurements, monitoring campaigns, risk assessment, and availability and user training of protective equipment. However, improvements are still needed. Hydrocarbon or benzene air concentrations have not declined in 8 of 17 units, in some of which concentrations exceed 10% of the relevant OEL8h value. In addition, for benzene even 10% of the current OEL, 0.1 ppm, might still possess a risk. With this in mind, methods to estimate exposure at the refineries need to be improved to enable measuring benzene concentrations <0.1 ppm. Shut downs of the refinery have been associated with peaks in exposure concentrations. Consequently, effort should be placed on safe working methods pertaining to shutdowns. Also, the connection and detachment of hoses continues to be problematic from the point of view of controlling exposure.

BTEX compounds identification by means of gas sensors arrays

BTEX compounds can cause a threat to environment and human health. For this reason measurement devices are needed for rapid identification of such pollutants. The paper presents the results of recognition of mixtures of benzene, toluene, ethylbenzene and xylenes in humid air by means of two gas sensor arrays and linear discriminant analysis. Measurements were conducted during stabilization/solidification processes of contaminated soils. High classification ratios were obtained for both arrays (I: 88%–94%; II: 94%–96%). Improvement of identification was achieved when two copies of every sensor were included in analysis – classification rates reached 97.1–100%.

Effect of Food Containing High Fe (Iron) Intake to Urinary trans, trans-muconic Acid (tt-ma) Levels on Workers exposed to Benzene

Glue is one of important material in the footwear manufacture which is contained benzene. Benzene vapour can enter body through the respiratory tract easily. Benzene is going to metabolism by CYP 2E 1 in the liver to form trans, trans muconic acid (tt-MA) and going to excrete simultaneously with urine. Before formed tt-MA, benzene is oxidized to an epoxy benzene and benzene oxepin which are electrophilic. It can cause cancer by DNA adduct. The increase of the rate of benzene metabolism can increase tt-MA formation and reduce the risk of DNA adducts. Benzene metabolism can be enhanced by increasing Fe intake. The study aims to analyze the effect of high dietary intake of Fe with the concentration of urinary trans, trans-muconic acid (tt-MA) in the shoe worker. Pre-experimental study with one group pretest posttest design was conducted and 19 subjects of this study recruited who had fulfilled the inclusion criteria.Worker characteristics ( age, sex, and residence), nutritional status (body mass index), activity pattern ( exposure time, exposure frequency and smoking habit), Fe absorption inhibitor consumption and benzene air level were identified. Urinary tt-MA measurement performed twice, before and after intervention. The intervention was giving meal containing high Fe for 56 hours (3 times/day). Weighing leftovers and recall Fe absorption inhibitor consumption was conducted in the end of every meal time. The study result showed that Fe intake from meat had effect on alteration of urinary tt-MA level (p a).

Comparison of personal air benzene and urine t,t-muconic acid as a benzene exposure surrogate during turnaround maintenance in petrochemical plants.

Previous studies have shown that biomarkers of chemicals with long half-lives may be better surrogates of exposure for epidemiological analyses, leading to less attenuation of the exposure-disease association, than personal air samples. However, chemicals with short half-lives have shown inconsistent results. In the present study, we compared pairs of personal air benzene and its short-half-life urinary metabolite trans,trans-muconic acid (t,t-MA), and predicted attenuation bias of theoretical exposure-disease association. Total 669 pairs of personal air benzene and urine t,t-MA samples were taken from 474 male workers during turnaround maintenance operations held in seven petrochemical plants. Maintenance jobs were classified into 13 groups. Variance components were calculated for personal air benzene and urine t,t-MA separately to estimate the attenuation of the theoretical exposure-disease association. Personal air benzene and urine t,t-MA showed similar attenuation of the theoretical exposure-disease association. Analyses for repeated measurements showed similar results, while in analyses for values above the limits of detection (LODs), urine t,t-MA showed less attenuation of the theoretical exposure-disease association than personal air benzene. Our findings suggest that there may be no significant difference in attenuation bias when personal air benzene or urine t,t-MA is used as a surrogate for benzene exposure.

Environmental and biological monitoring of exposures to VOCs in a petrochemical complex in Iran.

Exposure to volatile organic compounds (VOCs) can cause cancers in human. This study aimed to measure the concentration of four VOCs including benzene, styrene, ethylbenzene, and phenol in ambient air of a petrochemical complex in Iran. Also, their urinary metabolites including phenol, mandelic acid (MA), and phenylglyoxylic acid (PGA) in the workers were monitored. Urine samples were collected before and after the 8-h workshift according to the NIOSH methods. They were analyzed by a gas chromatograph coupled with a flame ionization detector (GC-FID). High levels of the ambient VOCs were detected in the units of recovery and olefin. The levels of ethylbenzene and phenol were less than the guidelines suggested by NIOSH and ACGIH. However, in some cases, the amounts of benzene and styrene were higher than the guidelines. Excellent positive correlations were observed between VOCs exposure and their urinary metabolites (r 2 > 0.90), except for benzene (r 2 = 0.26). Our finding verified that urinary biomarkers can be applied as bioindicators for ambient exposure to VOCs. There is a risk of exposure to high levels of the pollutants in some of the sites, and it is necessary to adopt some preventive measures to reduce health risk.

Influence of sample temperature and environmental humidity on measurements of benzene in ambient air by transportable GC-PID

Abstract. Calibration of in situ analysers of air pollutants is usually done with dry standards. In this paper, the influence of sample temperature and environmental humidity on benzene measurements by gas chromatography coupled with a photoionisation detector (GC-PID) is studied. Two reference gas mixtures (40 and 5 µg m−3 nominal concentration benzene in air) were subjected to two temperature cycles (20/5/20 °C and 20/35/20 °C) and measured with two identical GC-PIDs. The change in sample temperature did not produce any significant change in readings. Regarding ambient humidity, the chromatographs were calibrated for benzene with dry gases and subjected to measure reference standards with humidity (20 and 80 % at 20 °C). When measuring a concentration of 0.5 µg m−3 benzene in air, the levels of humidity tested did not produce any significant interference in measurements taken with any of the analysers. However, when measuring a concentration of 40 µg m−3, biases in measurements of 18 and 21 % for each respective analyser were obtained when the relative humidity of the sample was 80 % at 20 °C. Further tests were carried out to study the nature of this interference. Results show that humidity interference depends on both the amount fractions of water vapour and benzene. If benzene concentrations in an area are close to its annual limit value (5 µg m−3), biases of 2.2 % can be expected when the absolute humidity is 8.6 g cm−3 – corresponding to a relative humidity of 50 % at 20 °C. This can be accounted for in the uncertainty budget of measurements with no need for corrections. If benzene concentrations are above the annual limit value, biases become higher. Thus, in these cases, actions should be taken to reduce the humidity interference, as an underestimation of benzene concentrations may cause a mismanagement of air quality in these situations.

Assessment of Commercial Active Ceramic Tiles on Benzene Degradation for the Pollution Control of Indoor Atmospheric Buildings

Volatile Organic Compounds (VOCs) constitutes an important class of air pollutants, and benzene is one of the main contaminants of indoor air pollution. Among the methods for the treatment of environments with a high VOCs concentration is the photocatalytic oxidation by TiO2 (anatase) ceramic coated surfaces. The effectiveness of VOCs photodegradation studies using active ceramic tiles made in laboratory is well reported in the literature. However, this has not been reported using commercial tiles, although active ceramics are sold for such a function. In this context, this study proposed the assessment of commercial active ceramic tiles capacity in the photocatalytic degradation of benzene in indoor air. The development of this work arose from two questions: a) if the commercial active ceramic tiles are efficient in the VOCs degradation as the manufacturers claim; b) if they are able to degrade VOCs in indoor building environments. Experiments were conducted in laboratory’s scale, using an adapted simulation chamber. The volatilized benzene entered in contact with the commercial ceramic tile under fluorescent light and ultraviolet (UV) light of 365 nm. Samples of the chamber internal air were collected by adsorption on polydimethylsiloxane fibres in headspace technique (SPME-HS). The evaluation of the benzene degradation occurred by gas chromatography analysis with mass spectrometry (GC-MS). The characterization of commercial active ceramic samples occurred by techniques of X-Ray Diffraction Powder (XRD), and Scanning Electron Microscopy (SEM) with Energy Dispersive Spectrometry (EDS). Results showed that, under the experimental conditions, the commercial active ceramic tile was not capable of the benzene photocatalytic oxidation. The ceramic characterization detected very low quantity of TiO2 on ceramic samples, being this fact attributed as the main responsible for the ceramic photocatalytic inactiveness.

Evidence for non-linear metabolism at low benzene exposures? A reanalysis of data

The presence of a high-affinity metabolic pathway for low level benzene exposures of less than one part per million (ppm) has been proposed although a pathway has not been identified. The variation of metabolite molar fractions with increasing air benzene concentrations was suggested as evidence of significantly more efficient benzene metabolism at concentrations <0.1 ppm The evidence for this pathway is predicated on a rich data set from a study of Chinese shoe workers exposed to a wide range of benzene concentrations (not just “low level”). In this work we undertake a further independent re-analysis of this data with a focus on the evidence for an increase in the rate of metabolism of benzene exposures of less than 1 ppm.The analysis dataset consisted of measurements of benzene and toluene from personal air samplers, and measurements of unmetabolised benzene and toluene and five metabolites (phenol hydroquinone, catechol, trans, trans-muconic acid and s-phenylmercapturic acid) from post-shift urine samples for 213 workers with an occupational exposure to benzene (and toluene) and 139 controls. Measurements from control subjects were used to estimate metabolite concentrations resulting from non-occupational sources, including environmental sources of benzene. Data from occupationally exposed subjects were used to estimate metabolite concentrations as a function of benzene exposure. Correction for background (environmental exposure) sources of metabolites was achieved through a comparison of geometric means in occupationally exposed and control populations. The molar fractions of the five metabolites as a function of benzene exposure were computed.A supra-linear relationship between metabolite concentrations and benzene exposure was observed over the range 0.1–10 ppm benzene, however over the range benzene exposures of between 0.1 and 1 ppm only a modest departure from linearity was observed. The molar fractions estimated in this work were near constant over the range 0.1–10 ppm. No evidence of high affinity metabolism at these low level exposures was observed. Our reanalysis brings in to question the appropriateness of the dataset for commenting on low dose exposures and the use of a purely statistical approach to the analysis.

Non-parametric estimation of low-concentration benzene metabolism

Two apparently contradictory findings in the literature on low-dose human metabolism of benzene are as follows. First, metabolism is approximately linear at low concentrations, e.g., below 10 ppm. This is consistent with decades of quantitative modeling of benzene pharmacokinetics and dose-dependent metabolism. Second, measured benzene exposure and metabolite concentrations for occupationally exposed benzene workers in Tianjin, China show that dose-specific metabolism (DSM) ratios of metabolite concentrations per ppm of benzene in air decrease steadily with benzene concentration, with the steepest decreases below 3 ppm. This has been interpreted as indicating that metabolism at low concentrations of benzene is highly nonlinear. We reexamine the data using non-parametric methods. Our main conclusion is that both findings are correct; they are not contradictory. Low-concentration metabolism can be linear, with metabolite concentrations proportional to benzene concentrations in air, and yet DSM ratios can still decrease with benzene concentrations. This is because a ratio of random variables can be negatively correlated with its own denominator even if the mean of the numerator is proportional to the denominator. Interpreting DSM ratios that decrease with air benzene concentrations as evidence of nonlinear metabolism is therefore unwarranted when plots of metabolite concentrations against benzene ppm in air show approximately straight-line relationships between them, as in the Tianjin data. Thus, an apparent contradiction that has fueled heated discussions in the recent literature can be resolved by recognizing that highly nonlinear, decreasing DSM ratios are consistent with linear metabolism.

An efficient analytical method for determination of S-phenylmercapturic acid in urine by HPLC fluorimetric detector to assessing benzene exposure.

Benzene is an important occupational and environmental contaminant, naturally present in petroleum and as by-product in the steel industry. Toxicological studies showed pronounced myelotoxic action, causing leukemic and others blood cells disorders. Assessing of benzene exposure is performed by biomarkers as trans, trans-muconic acid (AttM) and S-phenylmercapturic acid (S-PMA) in urine. Due to specificity of S-PMA, this biomarker has been proposed to asses lower levels of benzene in air. The aim of this study was to validate an analytical method for the quantification of S-PMA by High-Performance Liquid Chromatography with fluorometric detector. The development of an analytical method of S-PMA in urine was carried out by solid phase extraction (SPE) using C-18 phase. The eluated were submitted to water bath at 75°C and nitrogen to analyte concentration, followed by alkaline hydrolysis and derivatization with monobromobimane. The chromatography conditions were reverse phase C-18 column (240mm, 4mm and 5μm) at 35°C; acetonitrile and 0.5% acetic acid (50:50) as mobile phase with a flow of 0.8mL/min. The limits of detection and quantification were 0.22μg/L and 0.68μg/L, respectively. The linearity was verified by simple linear regression, and the method exhibited good linearity in the range of 10-100μg/L. There was no matrix effect for S-PMA using concentrations of 40, 60, 80 and 100μg/L. The intra- and interassay precision showed coefficient of variation of less than 10% and the recovery ranged from 83.4 to 102.8% with an average of 94.4%. The stability of S-PMA in urine stored at -20°C was of seven weeks. The conclusion is that this method presents satisfactory results per their figures of merit. This proposed method for determining urinary S-PMA showed adequate sensitivity for assessment of occupational and environmental exposure to benzene using S-PMA as biomarker of exposure.

MnO2-nanowire@NiO-nanosheet core-shell hybrid nanostructure derived interfacial Effect for promoting catalytic oxidation activity

Nanostructure-derived interfacial effect plays a great role in enhancing catalytic activities. Herein, a MnO2 nanowires@NiO nanosheets core-shell hybrid nanostructure was successfully prepared by uniformly decorating NiO nanosheets on the one-dimensional MnO2 nanowires. The physi-chemical properties of the MnO2 and MnO2@NiO were characterized by using XRD, BET, SEM, H2-TPR and XPS techniques. Compared to the single MnO2 nanowires, the MnO2@NiO nanocomposite with better low-temperature reducibility and more active surface oxygen species exhibited much better performance in complete oxidation of benzene, giving the temperatures for 100% benzene conversion of 320°C under the conditions of 1000ppm benzene in air and space velocity of 120,000mLg−1h−1 while the value over pure MnO2 was 380°C. The novel hetero-interface constructed between MnO2 and NiO core-shell nanostructures might make a great contribution on this significantly promoting effect.