Abstract: Catalytic oxidation of benzene assisted by ozone, on alumina, silica, and boehmite-supported Ni/Pd catalysts was investigated at 353 K to assess the influence of the support on the reaction. Three bimetallic Ni/Pd nanosized samples with loading 4.7% of Ni and 0.17% of Pd supported on SiO2, AlOOH and Al2O3 were synthesized by the extractive-pyrolytic method. The phase composition was characterized by means of XRD and the surface area and pore size were estimated using Brunauer–Emmett–Teller (BET) and Barrett–Joyner–Halenda (BJH) methods. At the beginning of the reaction, catalysts were significantly deactivated due to the accumulation of intermediates on the catalyst surface and after 60 minutes it turned stable. Ni/Pd/AlOOH catalyst showed the highest steady-state activity in comparison with the Ni/Pd/SiO2 and Ni/Pd/Al2O3 catalysts. Their activity depends on the ozone decomposition potential of the catalysts because of generating oxidizing active species. The sample with the highest ozone decomposition ability which correlated to the surface area of the support oxidizes benzene to the highest extent.
Abstract: Air travel, and the use of airports, has experienced proliferative growth in the past few decades, resulting in the concomitant release of air pollutants. Air pollution needs to be monitored because of the known relationship between exposure to air pollutants and increased adverse effects on human health. This study monitored a group of volatile organic compounds (VOCs); specifically BTEX (viz. benzene, toluene, ethyl-benzene and xylenes), as many are detrimental to human health. Through the use of passive sampling methods, the spatial variability of BTEX within an international airport was investigated, in order to determine ‘hotspots’ where occupational exposure to BTEX may be intensified. The passive sampling campaign revealed BTEXtotal concentrations ranged between 12.95–124.04 µg m-3. Furthermore, BTEX concentrations were dispersed heterogeneously within the airport. Due to the slow wind speeds recorded (1.13 m.s-1); the hotspots were located close to their main BTEX sources. The main hotspot was located over the main apron of the airport. Employees working in this area may be chronically exposed to these emissions, which could be potentially detrimental to their health.
Abstract: Mesoporous materials are very commonly used as adsorbent materials for removing phenolic compounds. However, the adsorption mechanism of these compounds is still poorly controlled. However, understanding the interactions mesoporous materials/adsorbed molecules is very important in order to optimize the processes of liquid phase adsorption. The difficulty of synthesis is to keep an orderly and cubic pore structure and achieve a homogeneous surface modification. The grafting of Si(CH3)3 was chosen, to transform hydrophilic surfaces hydrophobic surfaces. The aim of this work is to study the kinetics and thermodynamics of two volatile organic compounds VOC phenol (PhOH) and P hydroxy benzoic acid (4AHB) on a mesoporous material of type MCM-48 grafted with an organosilane of the Trimethylchlorosilane (TMCS) type, the material thus grafted or functionalized (hereinafter referred to as MCM-48-G). In a first step, the kinetic and thermodynamic study of the adsorption isotherms of each of the VOCs in mono-solution was carried out. In a second step, a similar study was carried out on a mixture of these two compounds. Kinetic models (pseudo-first order, pseudo-second order) were used to determine kinetic adsorption parameters. The thermodynamic parameters of the adsorption isotherms were determined by the adsorption models (Langmuir, Freundlich). The comparative study of adsorption of PhOH and 4AHB proved that MCM-48-G had a high adsorption capacity for PhOH and 4AHB; this may be related to the hydrophobicity created by the organic function of TMCS in MCM-48-G. The adsorption results for the two compounds using the Freundlich and Langmuir models show that the adsorption of 4AHB was higher than PhOH. The values obtained by the adsorption thermodynamics show that the adsorption interactions for our sample with the phenol and 4AHB are of a physical nature. The adsorption of our VOCs on the MCM-48 (G) is a spontaneous and exothermic process.
Abstract: An optimum technic has been developed for extracting volatile organic compounds which contribute to the aroma of lime fruit (Citrus aurantifolia). The volatile organic compounds of healthy and infested lime fruit with California red scale Aonidiella aurantii were characterized using headspace solid phase microextraction (HS-SPME) combined with gas chromatography (GC) coupled flame ionization detection (FID) and gas chromatography with mass spectrometry (GC-MS) as a very simple, efficient and nondestructive extraction method. A three-phase 50/30 μm PDV/DVB/CAR fibre was used for the extraction process. The optimal sealing and fibre exposure time for volatiles reaching equilibrium from whole lime fruit in the headspace of the chamber was 16 and 4 hours respectively. 5 min was selected as desorption time of the three-phase fibre. Herbivorous activity induces indirect plant defenses, as the emission of herbivorous-induced plant volatiles (HIPVs), which could be used by natural enemies for host location. GC-MS analysis showed qualitative differences among volatiles emitted by infested and healthy lime fruit. The GC-MS analysis allowed the initial identification of 18 compounds, with similarities higher than 85%, in accordance with the NIST mass spectral library. One of these were increased by A. aurantii infestation, D-limonene, and three were decreased, Undecane, α-Farnesene and 7-epi-α-selinene. From an applied point of view, the application of the above-mentioned VOCs may help boost the efficiency of biocontrol programs and natural enemies’ production techniques.
Abstract: The catalytic oxidation of CO and volatile organic compounds (VOCs) is considered as one of the most efficient ways to reduce harmful emissions from various chemical industries. The effectiveness of gold-based catalysts for many reactions of environmental significance was proven during the past three decades. The aim of this work was to combine the favorable features of Au and Cu-Ce mixed oxides in the design of new catalytic materials of improved efficiency and economic viability for removal of air pollutants in waste gases from formaldehyde production. Supported oxides of copper and cerium with Cu: Ce molar ratio 2:1 and 1:5 were prepared by wet impregnation of g-alumina. Gold (2 wt.%) catalysts were synthesized by a deposition-precipitation method. Catalysts characterization was carried out by texture measurements, powder X-ray diffraction, temperature programmed reduction and electron paramagnetic resonance spectroscopy. The catalytic activity in the oxidation of CO, CH3OH and (CH3)2O was measured using continuous flow equipment with fixed bed reactor. Both Cu-Ce/alumina samples demonstrated similar catalytic behavior. The addition of gold caused significant enhancement of CO and methanol oxidation activity (100 % degree of CO and CH3OH conversion at about 60 and 140 oC, respectively). The composition of Cu-Ce mixed oxides affected the performance of gold-based samples considerably. Gold catalyst on Cu-Ce/γ-Al2O3 1:5 exhibited higher activity for CO and CH3OH oxidation in comparison with Au on Cu-Ce/γ-Al2O3 2:1. The better performance of Au/Cu-Ce 1:5 was related to the availability of highly dispersed gold particles and copper oxide clusters in close contact with ceria.
Abstract: The identification and evaluation of organic and inorganic pollutants were performed in a flexographic facility in Novi Sad, Serbia. Air samples were collected and analyzed in situ, during 4-hours working time at five sampling points by the mobile gas chromatograph and ozonometer at the printing of collagen casing. Experimental results showed that the concentrations of isopropyl alcohol, acetone, total volatile organic compounds and ozone varied during the sampling times. The highest average concentrations of 94.80 ppm and 102.57 ppm were achieved at 200 minutes from starting the production for isopropyl alcohol and total volatile organic compounds, respectively. The mutual dependences between target hazardous and microclimate parameters were confirmed using a multiple linear regression model with software package STATISTICA 10. Obtained multiple coefficients of determination in the case of ozone and acetone (0.507 and 0.589) with microclimate parameters indicated a moderate correlation between the observed variables. However, a strong positive correlation was obtained for isopropyl alcohol and total volatile organic compounds (0.760 and 0.852) with microclimate parameters. Higher values of parameter F than Fcritical for all examined dependences indicated the existence of statistically significant difference between the concentration levels of target pollutants and microclimates parameters. Given that, the microclimate parameters significantly affect the emission of investigated gases and the application of eco-friendly materials in production process present a necessity.
Abstract: This work studies the effect of chemical composition
on the activity and selectivity of γ–alumina supported CuO/
MnO2/Cr2O3 catalysts toward deep oxidation of CO, dimethyl ether
(DME) and methanol. The catalysts were prepared by impregnation
of the support with an aqueous solution of copper nitrate, manganese
nitrate and CrO3 under different conditions. Thermal, XRD and TPR
analysis were performed. The catalytic measurements of single
compounds oxidation were carried out on continuous flow equipment
with a four-channel isothermal stainless steel reactor. Flow-line
equipment with an adiabatic reactor for simultaneous oxidation of all
compounds under the conditions that mimic closely the industrial
ones was used. The reactant and product gases were analyzed by
means of on-line gas chromatographs.
On the basis of XRD analysis it can be concluded that the active
component of the mixed Cu-Mn-Cr/γ–alumina catalysts consists of at
least six compounds – CuO, Cr2O3, MnO2, Cu1.5Mn1.5O4,
Cu1.5Cr1.5O4 and CuCr2O4, depending on the Cu/Mn/Cr molar ratio.
Chemical composition strongly influences catalytic properties, this
influence being quite variable with regards to the different processes.
The rate of CO oxidation rapidly decrease with increasing of
chromium content in the active component while for the DME was
observed the reverse trend. It was concluded that the best
compromise are the catalysts with Cu/(Mn + Cr) molar ratio 1:5 and
Mn/Cr molar ratio from 1:3 to 1:4.
Abstract: Pt/γ-Al2O3 membrane catalysts were prepared via an
evaporative-crystallization deposition method. The obtained Pt/γ-
Al2O3 catalyst activity was tested after characterization (SEM-EDAX
observation, BET measurement, permeability assessment) in the
catalytic oxidation of selected volatile organic compound (VOC) i.e.
propane, fed in mixture of oxygen. The VOC conversion (nearly
90%) obtained by varying the operating temperature showed that
flow-through membrane reactor might do better in the abatement of
VOCs.
Abstract: The quality and condition of perishable products
delivered to the market and their subsequent selling prices are
directly affected by the care taken during harvesting and handling.
Mechanical injury, in fact, occurs at all stages, from pre-harvest
operations through post-harvest handling, packing and transport to
the market. The main implications of this damage are the reduction of
the product’s quality and economical losses related to the shelf life
diminution. For most perishable products, the shelf life is relatively
short and it is typically dictated by microbial growth related to the
application of dynamic and static loads during transportation. This
paper presents the correlation between vibration levels and
microbiological growth on strawberries and woodland strawberries
and detects the presence of volatile organic compounds (VOC) in
order to develop an intelligent logistic unit capable of monitoring
VOCs using a specific sensor system. Fresh fruits were exposed to
vibrations by means of a vibrating table in a temperature-controlled
environment. Microbiological analyses were conducted on samples,
taken at different positions along the column of the crates. The values
obtained were compared with control samples not exposed to
vibrations and the results show that different positions along the
column influence the development of bacteria, yeasts and filamentous
fungi.
Abstract: The volatile organic compounds - BTEX (Benzene, Toluene, Ethylbenzene, and Xylene) petroleum derivatives, have high rates of toxicity, which may carry consequences for human health, biota and environment. In this directon, this paper proposes a method of treatment of these compounds by using corona discharge plasma technology. The efficiency of the method was tested by analyzing samples of BTEX after going through a plasma reactor by gas chromatography method. The results show that the optimal residence time of the sample in the reactor was 8 minutes.
Abstract: The paper deals with the development of portable aerosol concentrator and its application for the determination of nitrites and nitrates. The device enables the continuous trapping of pollutants in the air. An extensive literature search has been elaborated which aims at the development of samplers and the possibilities of their application in the continuous determination of volatile organic compounds. The practical part of the paper is focused on the development of the portable aerosol concentrator. The device using the Aerosol Enrichment Unit has been experimentally verified and subsequently realized. It operates on the principle of equilibrium accumulation of pollutants from the gaseous phase using absorption liquid polydisperse aerosol. The device has been applied for monitoring nitrites and nitrates in the air. The chemiluminescence detector was used for detection; the achieved detection limit for nitrites was 28 ng/m3 and for nitrates 78 ng/m3.
Abstract: Group contribution methods such as the UNIFAC are
very useful to researchers and engineers involved in synthesis,
feasibility studies, design and optimization of separation processes.
They can be applied successfully to predict phase equilibrium and
excess properties in the development of chemical and separation
processes. The main focus of this work was to investigate the
possibility of absorbing selected volatile organic compounds (VOCs)
into polydimethylsiloxane (PDMS) using three selected UNIFAC
group contribution methods. Absorption followed by subsequent
stripping is the predominant available abatement technology of
VOCs from flue gases prior to their release into the atmosphere. The
original, modified and effective UNIFAC models were used in this
work. The thirteen selected VOCs that have been considered in this
research are: pentane, hexane, heptanes, trimethylamine, toluene,
xylene, cyclohexane, butyl acetate, diethyl acetate, chloroform,
acetone, ethyl methyl ketone and isobutyl methyl ketone. The
computation was done for solute VOC concentration of 8.55x10-8
which is well in the infinite dilution region. The results obtained in
this study compare very well with those published in literature
obtained through both measurements and predictions. The phase
equilibrium obtained in this study show that PDMS is a good
absorbent for the removal of VOCs from contaminated air streams
through physical absorption.
Abstract: There has been a growing interest in utilizing surfactants in remediation processes to separate the hydrophobic volatile organic compounds (HVOCs) from aqueous solution. One attractive process is cloud point extraction (CPE), which utilizes nonionic surfactants as a separating agent. Since the surfactant cost is a key determination of the economic viability of the process, it is important that the surfactants are recycled and reused. This work aims to study the performance of the co-current vacuum stripping using a packed column for HVOCs removal from contaminated surfactant solution. Six types HVOCs are selected as contaminants. The studied surfactant is the branched secondary alcohol ethoxylates (AEs), Tergitol TMN-6 (C14H30O2). The volatility and the solubility of HVOCs in surfactant system are determined in terms of an apparent Henry’s law constant and a solubilization constant, respectively. Moreover, the HVOCs removal efficiency of vacuum stripping column is assessed in terms of percentage of HVOCs removal and the overall liquid phase volumetric mass transfer coefficient. The apparent Henry’s law constant of benzenz , toluene, and ethyl benzene were 7.00×10-5, 5.38×10-5, 3.35× 10-5 respectively. The solubilization constant of benzene, toluene, and ethyl benzene were 1.71, 2.68, 7.54 respectively. The HVOCs removal for all solute were around 90 percent.
Abstract: Ground-level tropospheric ozone is one of the air
pollutants of most concern. It is mainly produced by photochemical
processes involving nitrogen oxides and volatile organic compounds
in the lower parts of the atmosphere. Ozone levels become
particularly high in regions close to high ozone precursor emissions
and during summer, when stagnant meteorological conditions with
high insolation and high temperatures are common.
In this work, some results of a study about urban ozone
distribution patterns in the city of Badajoz, which is the largest and
most industrialized city in Extremadura region (southwest Spain) are
shown. Fourteen sampling campaigns, at least one per month, were
carried out to measure ambient air ozone concentrations, during
periods that were selected according to favourable conditions to
ozone production, using an automatic portable analyzer.
Later, to evaluate the ozone distribution at the city, the measured
ozone data were analyzed using geostatistical techniques. Thus, first,
during the exploratory analysis of data, it was revealed that they were
distributed normally, which is a desirable property for the subsequent
stages of the geostatistical study. Secondly, during the structural
analysis of data, theoretical spherical models provided the best fit for
all monthly experimental variograms. The parameters of these
variograms (sill, range and nugget) revealed that the maximum
distance of spatial dependence is between 302-790 m and the
variable, air ozone concentration, is not evenly distributed in reduced
distances. Finally, predictive ozone maps were derived for all points
of the experimental study area, by use of geostatistical algorithms
(kriging). High prediction accuracy was obtained in all cases as
cross-validation showed. Useful information for hazard assessment
was also provided when probability maps, based on kriging
interpolation and kriging standard deviation, were produced.
Abstract: This work considered the thermodynamic feasibility
of scrubbing volatile organic compounds into biodiesel in view of
designing a gas treatment process with this absorbent. A detailed
vapour – liquid equilibrium investigation was performed using the
original UNIFAC group contribution method. The four biodiesels
studied in this work are methyl oleate, methyl palmitate, methyl
linolenate and ethyl stearate. The original UNIFAC procedure was
used to estimate the infinite dilution activity coefficients of 13
selected volatile organic compounds in the biodiesels. The
calculations were done at the VOC mole fraction of 9.213x10-8. Ethyl
stearate gave the most favourable phase equilibrium. A close
agreement was found between the infinite dilution activity coefficient
of toluene found in this work and those reported in literature.
Thermodynamic models can efficiently be used to calculate vast
amount of phase equilibrium behaviour using limited number of
experimental data.
Abstract: The aim of this study was to compare the solubility of selected volatile organic compounds in water and silicon oil using the simple static headspace method. The experimental design allowed equilibrium achievement within 30 – 60 minutes. Infinite dilution activity coefficients and Henry-s law constants for various organics representing esters, ketones, alkanes, aromatics, cycloalkanes and amines were measured at 303K. The measurements were reproducible with a relative standard deviation and coefficient of variation of 1.3x10-3 and 1.3 respectively. The static determined activity coefficients using shaker flasks were reasonably comparable to those obtained using the gas liquid - chromatographic technique and those predicted using the group contribution methods mainly the UNIFAC. Silicon oil chemically known as polydimethysiloxane was found to be better absorbent for VOCs than water which quickly becomes saturated. For example the infinite dilution mole fraction based activity coefficients of hexane is 0.503 and 277 000 in silicon oil and water respectively. Thus silicon oil gives a superior factor of 550 696. Henry-s law constants and activity coefficients at infinite dilution play a significant role in the design of scrubbers for abatement of volatile organic compounds from contaminated air streams. This paper presents the phase equilibrium of volatile organic compounds in very dilute aqueous and polymeric solutions indicating the movement and fate of chemical in air and solvent. The successful comparison of the results obtained here and those obtained using other methods by the same authors and in literature, means that the results obtained here are reliable.
Abstract: Smoke from domestic wood burning has been
identified as a major contributor to air pollution, motivating detailed
emission measurements under controlled conditions. A series of
experiments was performed to characterise the emissions from wood
combustion in a fireplace and in a woodstove of two common species
of trees grown in Spain: Pyrenean oak (Quercus pyrenaica) and
black poplar (Populus nigra). Volatile organic compounds (VOCs) in
the exhaust emissions were collected in Tedlar bags, re-sampled in
sorbent tubes and analysed by thermal desorption-gas
chromatography-flame ionisation detection. Pyrenean oak presented
substantially higher emissions in the woodstove than in the fireplace,
for the majority of compounds. The opposite was observed for
poplar. Among the 45 identified species, benzene and benzenerelated
compounds represent the most abundant group, followed by
oxygenated VOCs and aliphatics. Emission factors obtained in this
study are generally of the same order than those reported for
residential experiments in the USA.
Abstract: Abstract–Indoor air (VOCs) samples were collected
simultaneously from variety of indoors (e.g. living rooms, baby-s
rooms) and outdoor environments which were voluntarily selected
from the houses in which pregnant residents live throughout Ankara.
This is the first comprehensive study done in Turkey starting from
prenatal period and continued till the babies had one year old. VOCs
levels were measured over 76 homes. Air samples were collected in
Tenax TA sorbent filled tubes with active sampling method and
analyzed with Thermal Desorber and Gas Chromatography/Mass
spectrometry (TD-GC/MS). At the first sampling period in the baby-s
rooms maximum concentration of toluene was measured about
240.77μg.m-3 and in the living rooms maximum concentration of
naphthalene was 180.24μg.m-3. At the second sampling period in the
baby-s rooms maximum concentration of toluene was measured
about 144.97μg.m-3 and in the living rooms maximum concentration
of naphthalene was 247.89μg.m-3. Concentration of TVOCs in the
first period was generally higher than the second period.
Abstract: This work proposes an optical fiber system (OF) for
sensing various volatile organic compounds (VOCs) in human breath
for the diagnosis of some metabolic disorders as a non-invasive
methodology. The analyzed VOCs are alkanes (i.e., ethane, pentane,
heptane, octane, and decane), and aromatic compounds (i.e., benzene,
toluene, and styrene). The OF displays high analytical performance
since it provides near real-time responses, rapid analysis, and low
instrumentation costs, as well as it exhibits useful linear range and
detection limits; the developed OF sensor is also comparable to a
reference methodology (gas chromatography-mass spectrometry) for
the eight tested VOCs.
Abstract: Air emissions from waste treatment plants often
consist of a combination of Volatile Organic Compounds (VOCs)
and odors. Hydrogen sulfide is one of the major odorous gases
present in the waste emissions coming from municipal wastewater
treatment facilities. Hydrogen sulfide (H2S) is odorous, highly toxic
and flammable. Exposure to lower concentrations can result in eye
irritation, a sore throat and cough, shortness of breath, and fluid in
the lungs. Biofiltration has become a widely accepted technology for
treating air streams containing H2S. When compared with other nonbiological
technologies, biofilter is more cost-effective for treating large
volumes of air containing low concentrations of biodegradable compounds.
Optimization of biofilter media is essential for many reasons such as:
providing a higher surface area for biofilm growth, low pressure drop,
physical stability, and good moisture retention. In this work, a novel
biofilter media is developed and tested at a pumping station of a
municipality located in the United Arab Emirates (UAE). The
media is found to be very effective (>99%) in removing H2S
concentrations that are expected in pumping stations under steady
state and shock loading conditions.