VOC amounts in ambient areas of a high-technology science park in Taiwan: their reciprocal correlations and impact on inhabitants

Introduction  

This study presents bihourly, seasonal, and yearly concentration changes in volatile organic compounds (VOCs) in the inlet and effluent water of the wastewater treatment plant (WWTP) of a high-technology science park (HTIP) in Taiwan, with the VOC amounts at different sites correlated geologically.     

Degradation of 1,2-dichloroethane from wash water of ion-exchange resin using Fenton’s oxidation

Background, aim, and scope  

Chlorinated volatile organic compounds (CVOCs), widely used in industry as solvents and chemical intermediates in the production of synthetic resins, plastics, and pharmaceuticals, are highly toxic to the environment and public health. Various studies reported that Fenton’s oxidation could degrade a variety of chlorinated VOCs in aqueous solutions. In acidic conditions, ferrous ion catalyzes the decomposition of H₂O₂ to form a powerful ^•OH radical. In this study, wastewater from wash of ion-exchange resin containing typical CVOC, 1,2-dichloroethane, was treated using Fenton’s oxidation. To reduce environmental load and processing costs of wastewater, Fenton process as a simple and efficient treatment method was applied to degrade 1,2-dichloroethane of wash water.     

Speciation of volatile organic compounds from poultry production

Volatile organic compounds (VOCs) emitted from poultry production are leading source of air quality problems. However, little is known about the speciation and levels of VOCs from poultry production. The objective of this study was the speciation of VOCs from a poultry facility using evacuated canisters and sorbent tubes. Samples were taken during active poultry production cycle and between production cycles. Levels of VOCs were highest in areas with birds and the compounds in those areas had a higher percentage of polar compounds (89%) compared to aliphatic hydrocarbons (2.2%). In areas without birds, levels of VOCs were 1/3 those with birds present and compounds had a higher total percentage of aliphatic hydrocarbons (25%). Of the VOCs quantified in this study, no single sampling method was capable of quantifying more than 55% of compounds and in several sections of the building each sampling method quantified less than 50% of the quantifiable VOCs. Key classes of chemicals quantified using evacuated canisters included both alcohols and ketones, while sorbent tube samples included volatile fatty acids and ketones. The top five compounds made up close to 70% of VOCs and included: 1) acetic acid (830.1 μg m^?3); 2) 2,3-butanedione (680.6 μg m^?3); 3) methanol (195.8 μg m^?3); 4) acetone (104.6 μg m^?3); and 5) ethanol (101.9 μg m^?3). Location variations for top five compounds averaged 49.5% in each section of the building and averaged 87% for the entire building.     

Quantitative analysis of volatile organic compounds (VOCs) in atmospheric particles

There are a number of difficulties associated with the quantitative analysis of volatile organic compounds (VOCs) in atmospheric particles. Therefore, majority of the previous studies on VOCs associated with particles have been qualitative. Air samples were collected in Izmir, Turkey to determine ambient particle and gas phase concentrations of several aromatic, oxygenated and halogenated VOCs. Samples were quantitatively analyzed using thermal desorption–gas chromatography/mass spectrometry. Gas-phase concentrations ranged between 0.02 (bromoform) and 4.65 μg m⁻³ (toluene) and were similar to those previously measured at the same site. Particle-phase concentrations ranged from 1 (1,3-dichlorobenzene) to 933 pg m⁻³ (butanol). VOCs were mostly found in gas-phase (99.9±0.25%). However, the particulate VOCs had comparable concentrations to those reported previously for semivolatile organic compounds. The distribution of particle-phase VOCs between fine (d_p<2.5 μm) and coarse (2.5 μm<d_p<10 μm) fractions was also investigated. It was found that VOCs were mostly associated with fine particles.     

Evaluating threats to an endangered species by proxy: air pollution as threat to the blue swallow (<Emphasis Type="Italic">Hirundo atrocaerulea</Emphasis>) in South Africa

Background, aim, and scope  

The blue swallow (Hirundo atrocaerulea) is one of the most threatened bird species in southern Africa. Among terrestrial birds, its plumage is known to be the most water repellent, an adaptation to foraging on the wing in dense fog. Despite this unique adaptation, the nesting success of the blue swallow at the Blue Swallow Natural Heritage Site (BSNHS) is lower during years with high incidence of fog. As the phenomenon is not observed at other nesting sites, we hypothesized that this is due to changes in the air chemistry at the BSNHS. In the immediate proximity of the BSNHS, plantations of exotic trees (e.g., pines and eucalypts), rich in volatile organic compounds (VOCs), are dominant features. In addition, air pollution from the Johannesburg area is transported with the surface winds and mix with VOCs released from exotic trees. Together with the high humidity and high elevation, these conditions may result in the formation of sulphonates. Sulphonates are strong detergents, and the presence of these in the fog could lead to decreased water repellence of the plumage. This study was performed in order to determine the occurrence and distribution of sulphonates in the BSNHS and to compare these with sulphonates formed in other locations in South Africa. Because the blue swallow is endangered, pine needles were used as proxy to detect formation of sulphonates.     

Biogenic VOC emissions from fresh leaf mulch and wood chips of Grevillea robusta (Australian Silky Oak)

The emissions of VOC from freshly cut and shredded Grevillea robusta (Australian Silky Oak) leaves and wood have been measured. The VOC emissions from fresh leaf mulch and wood chips lasted typically for 30 and 20 h respectively, and consisted primarily of ethanol, (E)-2-hexenal, (Z)-3-hexen-1-ol and acetaldehyde. The integrated emissions of the VOCs were 0.38±0.04 g kg⁻¹ from leaf mulch, and 0.022±0.003 g kg⁻¹ from wood chips. These emissions represent a source of VOCs in urban and rural air that has previously been unquantified and is currently unaccounted for. These VOCs from leaf mulch and wood chips will contribute to both urban photochemistry and secondary organic aerosol formation. Any CH₄ emissions from leaf mulch and wood chips were <1×10⁻¹¹ g g dry mass⁻¹ s⁻¹.     

Identification of volatiles from Pinus silvestris attractive for Monochamus galloprovincialis using a SPME-GC/MS platform

Introduction

A myriad of volatile organic compounds (VOCs) released by terrestrial vegetation plays an important role in environmental sciences. A thorough chemical identification of these species at the molecular level is essential in various fields, ranging from atmospheric chemistry to ecology of forest ecosystems. In particular, the recognition of VOCs profiles in a context of plant?Cinsect communication is a key issue for the development of forest protection tools.

Purpose

This work was aimed at the development of a simple, robust and reliable method for the identification of volatiles emitted from plant materials, which can attract or deter pest insects. Specifically, volatiles emitted from the bark of Pinus sylvestris were studied, which might attract the black pine sawyer beetle Monochamus galloprovincialis??a serious pest of the tree and a vector of a parasitic nematode Bursaphelenchus xylophius.

Method

The volatiles from bark samples were collected using a solid-phase micro-extraction technique, and subsequently analysed by gas-chromatography/mass-spectrometry (GC/MS). The characterisation of the volatile fraction was based on the comparison with data in mass spectral libraries, and in most cases, with the available authentic standards. The identified compounds were screened against the available entomological data to select insect attractors.

Results

The identified components included terpenes (??-pinene, ?-3-carene, and para-cymenene), oxygenated terpenes (??-terpineol and verbenone), sesquiterpenes (??-longipinene, longifolene, E-??-farnesene, ??-cadinene and pentadecane), and diterpenes (manoyl oxide and (+)-pimaral). Of these, longifolene and (+)-pimaral are of particular interest as plausible attractors for the M. galloprovincialis beetle that might find application in the construction of insect bait traps.     

Temperature and air velocity effects on ethanol emission from corn silage with the characteristics of an exposed silo face

Volatile organic compounds (VOCs) from agricultural sources are believed to be an important contributor to tropospheric ozone in some locations. Recent research suggests that silage is a major source of VOCs emitted from agriculture, but only limited data exist on silage emissions. Ethanol is the most abundant VOC emitted from corn silage; therefore, ethanol was used as a representative compound to characterize the pattern of emission over time and to quantify the effect of air velocity and temperature on emission rate. Ethanol emission was measured from corn silage samples removed intact from a bunker silo. Emission rate was monitored over 12 h for a range in air velocity (0.05, 0.5, and 5 m s^?1) and temperature (5, 20, and 35 °C) using a wind tunnel system. Ethanol flux ranged from 0.47 to 210 g m^?2 h^?1 and 12 h cumulative emission ranged from 8.5 to 260 g m^?2. Ethanol flux was highly dependent on exposure time, declining rapidly over the first hour and then continuing to decline more slowly over the duration of the 12 h trials. The 12 h cumulative emission increased by a factor of three with a 30 °C increase in temperature and by a factor of nine with a 100-fold increase in air velocity. Effects of air velocity, temperature, and air-filled porosity were generally consistent with a conceptual model of VOC emission from silage. Exposure duration, temperature, and air velocity should be taken into consideration when measuring emission rates of VOCs from silage, so emission rate data obtained from studies that utilize low air flow methods are not likely representative of field conditions.     

Biogenic C5 VOCs: release from leaves after freeze–thaw wounding and occurrence in air at a high mountain observatory

During investigations of the formation of volatile organic compounds (VOCs) in leaves, we observed C5 VOCs during leaf drying, senescence, and following freeze–thaw damage. VOCs were quantified by proton-transfer-reaction mass spectrometry (PTR-MS). In freeze-damaged leaves, VOC products were verified with a gas chromatography PTR-MS system, showing that a variety of plants produced 1-penten-3-ol and 1-penten-3-one with smaller amounts of 2(Z)-penten-1-ol and pentenals; similar VOCs have been detected in soybean seed homogenates (Gardner et al., J. Agric. Food Chem. 44 (1996) 882). Most plants wounded in this way also released hexenals and hexanal, and clover also released methylbutanals. The formation of the C5 products was oxygen–dependent, consistent with the involvement of the enzyme lipoxygenase, and pentenone appeared to form independent of an alcohol dehydrogenase reaction; the latter is apparently disrupted by the freeze–thaw treatment. In parallel with these laboratory experiments, on-line PTR-MS measurements of ambient air were conducted at the Sonnblick Observatory in the Austrian Alps (3106 m a.s.l.). Following a hard freeze in central Austria, substantial amounts of C5 VOCs, ranging from 300 pptv to 6 ppbv and including 1-penten-3-ol, methylbutanals and probably pentenone, were detected at this site for several days peaking after midnight. Factor analysis supported their biogenic origin. We speculate that these VOCs were derived from freeze-damaged local vegetation by processes similar to those seen in laboratory freezing studies. If confirmed, these results suggest that leaf-freezing events in forests will give rise to the release of substantial levels of reactive C5 and C6 VOCs that can contribute to regional tropospheric chemistry.     

VOC concentration profiles in an ozone non-attainment area: A case study in an urban and industrial complex metroplex in southern Taiwan

VOCs are important precursors of the atmospheric ozone formation species. This study investigated the airborne concentrations of 52 VOCs at two air quality monitoring stations, Daliao and Tzouying, during wintertime in southern Taiwan. Airborne VOCs samples were taken in stainless steel canisters four times per day and analyzed via gas chromatography/mass spectrometry. Maximum increment reactivity (MIR) was used to evaluate the ozone formation potential in this ozone non-attainment region. Toluene, propane, isopentane, propene, n-butane, n-pentane and isoprene contributed 78–79% of the 52 VOCs in Daliao. Toluene, 1-butene, isopentane, propene, propane, n-undecane, and n-butane contributed 71–77% of the 52 VOCs in Tzouying. The VOCs concentrations were higher in Daliao due to the high toluene emissions from a paint plant and a solvent plant in the nearby industrial district. The 24-h VOC concentrations averaged 25 ppb higher in Tzouying than in Daliao. The ozone formation potential of airborne VOCs was 1687–2730 and 1717–2261 μg-O₃/g-VOCs in Daliao and Tzouying, respectively. Ozone concentrations in Tzouying were 44 ppb higher than in Daliao during the 1200–1600 sampling period.     

NORMACAT project: normalized closed chamber tests for evaluation of photocatalytic VOC treatment in indoor air and formaldehyde determination

Background, aim

The aims of the NORMACAT project are: to develop tools and unbiased standardized methods to measure the performance and to validate the safety of new materials and systems integrating photocatalysis, to develop new photocatalytic media with higher efficiency and to give recommendations aimed at improving the tested materials and systems.

Method

To achieve this objective, it was necessary to design standardized test benches and protocols to assess photocatalytic efficiency of materials or systems used in the treatment of volatile organic compounds (VOCs) and odour under conditions close to applications. The tests are based on the validation of robust analytical methods at the parts per billion by volume level that not only follow the disappearance of the initial VOCs but also identify the secondary species and calculate the mineralization rates.

Results

The first results of inter-laboratory closed chamber tests, according to XP B44-013 AFNOR standard, are described. The photocatalytic degradation of mixtures of several defined pollutants under controlled conditions (temperature, relative humidity, initial concentration) was carried out in two independent laboratories with the same photocatalytic device and with various analytical procedures. Comparison of the degradation rate and of the mineralization efficiency allowed the determination of the clean air delivery rate in both cases. Formaldehyde was the only by-product detected during photocatalytic test under standardized experimental conditions. The concentration of transient formaldehyde varied according to the initial VOC concentration. Moreover the photocatalytic reaction rate of formaldehyde in mixture with other pollutants was analysed. It was concluded that formaldehyde concentration did not increase with time.

Conclusion??perspective

This type of experiment should allow the comparison of the performances of different photoreactors and of photocatalytic media under controlled and reproducible conditions against mixtures of pollutants including formaldehyde.     

Analysis of ozone and VOCs measured in Shanghai: A case study

Shanghai Meteorological Administration has established a volatile organic compounds (VOCs) laboratory and an observational network for VOCs and ozone (O₃) measurements in the city of Shanghai. In this study, the measured VOCs and O₃ concentrations from 15 November (15-Nov) to 26 November (26-Nov) of 2005 in Shanghai show that there are strong day-to-day and diurnal variations. The measured O₃ and VOCs concentrations have very different characterizations between the two periods. During 15-Nov to 21-Nov (defined as the first period), VOCs and O₃ concentrations are lower than the values during 22-Nov to 28-Nov (defined as the second period). There is a strong diurnal variation of O₃ during the second period with maximum concentrations of 40–80 ppbv at noontime, and minimum concentrations at nighttime. By contrast, during the first period, the diurnal variation of O₃ is in an irregular pattern with maximum concentrations of only 20–30 ppbv. The VOC concentrations change rapidly from 30–50 ppbv during the first period to 80–100 ppbv during the second period. Two chemical models are applied to interpret the measurements. One model is a regional chemical/dynamical model (WRF-Chem) and another is a detailed chemical mechanism model (NCAR MM). Model analysis shows that the meteorological conditions are very different between the two periods, and are mainly responsible for the different chemical characterizations of O₃ and VOCs between the two periods. During the first period, meteorological conditions are characterized by cloudy sky and high-surface winds in Shanghai, resulting in a higher nighttime planetary boundary layer (PBL) and faster transport of air pollutants. By contrast, during the second period, the meteorological conditions are characterized by clear sky and weak surface winds, resulting in a lower nighttime PBL and slower transport of air pollutants. The chemical mechanism model calculation shows that different VOC species has very different contributions to the high-ozone concentrations during the second period. Alkane (40 ppbv) and aromatic (30 ppbv) are among the highest VOC concentrations observed in Shanghai. The analysis suggests that the aromatic is a main contributor for the O₃ chemical production in Shanghai, with approximately 79% of the O₃ being produced by aromatic. This analysis implies that future increase in VOC (especially aromatic) emissions could lead to significant increase in O₃ concentrations in Shanghai.     

A sensitive diffusion sampler for the determination of volatile organic compounds in ambient air

We developed a diffusive sampling device (DSD-voc) for volatile organic compounds (VOCs) which is suitable for collection of low level VOCs and analysis with thermal desorption. This sampling device is composed of two parts, an exposure part made of a porous polytetrafluoroethylene (PTFE) filter, and an analysis part made of stainless-steel tubing. The DSD-voc collects VOCs through the mechanism of molecular diffusion. Collection is controlled by moving the adsorbent from the exposure part to the analysis part by changing the posture of the DSD-voc. Adsorbates in the DSD-voc were analyzed by GC/MS with a thermal desorption cold trap injector (TCT). The TCT has the advantage of being able to accept the entire quantity of VOCs. We connected a condenser between the DSD-voc and the trap tube to prevent moisture from freezing in the trap tube when the sampler was packed with strong adsorbent. We also examined the desorption efficiency for VOCs from several types of adsorbents (Carboxen^TM 1000, Carbosieve^TM G, Carbosieve S III, Carbotrap^TM B, and activated carbon) over a wide range of temperatures. Carboxen 1000 was suitable for the determination of VOCs with a low boiling point range, from CFC12 to hexane, while Carbotrap B was suitable for VOCs from hexane to 1,4-dichlorobenzene. The limits of detection with Carboxen 1000 and Carbotrap B were 0.036–0.046 and 0.0035–0.014 ppb, respectively, for a sampling duration of 24 h. Coefficients of variation for concentrations of major VOCs ranged from 3.8 to 14%. It is possible to estimate atmospheric VOCs at sub-parts per billion (sub-ppb), with high sensitivity, by using both adsorbents in combination.     

The effect of the increase in urban temperature on the concentration of photochemical oxidants

An atmospheric dispersion model, where the inputs of meteorological field were calculated using a meteorological model, was used to reproduce the observed air pollution conditions for the typical fine day in summer period, especially the concentration of the photochemical oxidants. As well, the effects of an increase in the urban temperature and VOC emissions on the concentration of photochemical oxidants were also considered. The following conclusions were drawn.The observed air pollution levels were well modeled by the atmospheric dispersion model using in this study, although modeled NO levels were slightly lower than the observed levels. An analysis of the temperature data showed that a 1 °C increase in temperature leads to a maximal photochemical oxidant concentration of 5.3 ppb, which is an increase of 11%. Additionally, the effect on the photochemical oxidant concentration due to an increase in the vegetation-derived VOCs was more than double the effect due to an increase in the photochemical reactions. It was found that the temperature and photochemical oxidant concentration were linearly related up to a temperature increase of 3 °C. When the temperature increases up to 3 °C, the concentration of photochemical oxidants increases by 19 ppb. An analysis of the effect of vegetation-derived VOCs on photochemical oxidant concentrations showed that, the concentration of photochemical oxidants was 30 ppb higher in the afternoon by the effect of vegetation-derived VOCs, so even in metropolitan areas with relatively little vegetation, vegetation-derived VOCs have a strong impact on photochemical oxidant concentrations.     

Use of thermal desorption–gas chromatography–mass spectrometry (TD–GC–MS) on identification of odorant emission focus by volatile organic compounds characterisation

Volatile organic compounds (VOCs) from several different municipal solid wastes’ treatment plants in Mallorca (Spain) have been analysed by thermal desorption–gas chromatography–mass spectrometry (TD–GC–MS). Ambient (immission) air was collected during February and March 2011 by active sampling onto sorbents Tenax™ TA and Carboxen™ 1000. The study presents the chemical characterisation of 93 volatile organic compounds (VOCs) from an overall set of 84 immission air samples. 70 VOCs were positively identified.The linear fit for all 93 external standard calibration, from 10 mg L⁻¹ to 150 mg L⁻¹ (n = 4), was within the range 0.974 < r² < 0.998. Limits of detection of the method (LOD) for all the standards were within the range 1.1–4,213 pg, as the absolute standard amount spiked into sorbent tubes in 1 μL standard mixture (dissolved in methanol).Overall results stated systematic correlation between waste’s nature and VOCs’ air composition. Organic wastes show main contribution of terpenes, waste water sludge residues’ of reduced sulphured compounds (RSCs) and municipal solid wastes show contribution of a wide sort of VOCs. The use of a chemometric approach for variable’s reduction to 12 principal components enables evaluation of similarities and dissimilarities between facilities. PCA clearly related samples to its corresponding facility on the basis of their VOCs composition and the ambient temperature.     

Variability-lifetime relationship of VOCs observed at the Sonnblick Observatory 1999—estimation of HO-densities

An extensive dataset of VOC measurements was collected at the Sonnblick Observatory, Austria (3106 m) in Fall/Winter 1999/2000, showing high mixing ratios of anthropogenic and biogenic VOCs at this high altitude site due to upward mixing of air masses (Geophys. Res. Lett. 2F (2001) 507). Here we give an interpretation of proton-transfer-reaction (PTR-MS) mass scans obtained in November 1999 based on fragmentation data, GC-PTR-MS analysis and the variability-lifetime relationship, described by the power law, σ(ln(x))=Aτ^−b. The variability-lifetime plot of anthropogenic VOCs gave a proportionality factor A of 1.40 and a,b exponent (sink term) of 0.44 and allowed an estimate of average HO-densities on the order of (1.5±0.4)×10⁵ molecules cm⁻³. Additionally we were able to indirectly determine a diurnal HO-profile with peak values of (1.3±0.5)×10⁶ molecules cm⁻³ around midday. HO-reaction rate coefficients for higher aldehydes (heptanal to nonanal) were estimated due to photochemical losses during a stagnant air episode (27 November) and from the variability-lifetime relationship. Combining long term PTR-MS analysis of VOCs and the variability-lifetime method provides a valuable tool for assessing the dominant cause of the variability in VOC concentrations. This information is essential in understanding the sources and photochemical processing of VOCs detected in ambient air at field measurement sites.     

Compound specific carbon and hydrogen stable isotope analyses of volatile organic compounds in various emissions of combustion processes

This study presents carbon (δ¹³C) and hydrogen (δD) isotope values of volatile organic compounds (VOCs) in various emission sources using thermal desorption–gas chromatography–isotope ratio mass spectrometry (TD–GC–irMS). The investigated VOCs ranged from C6 to C10. Samples were taken from (i) car exhaust emissions as well as from plant combustion experiments of (ii) various C3 and (iii) various C4 plants. We found significant differences in δ values of analysed VOCs between these sources, e.g. δ¹³C of benzene ranged between (i) −21.7 ± 0.2‰, (ii) −27.6 ± 1.6‰ and (iii) −16.3 ± 2.2‰, respectively and δD of benzene ranged between (i) −73 ± 13‰, (ii) −111 ± 10‰ and (iii) −70 ± 24‰, respectively. Results of VOCs present in investigated emission sources were compared to values from the literature (aluminium refinery emission). All source groups could be clearly distinguished using the dual approach of δ¹³C and δD analysis. The results of this study indicate that the correlation of compound specific carbon and hydrogen isotope analysis provides the potential for future research to trace the fate and to determine the origin of VOCs in the atmosphere using thermal desorption compound specific isotope analysis.     

Natural radionuclides in trees grown on a uranium mill tailings waste pile

Objective  

The purpose of the study was to investigate natural radionuclide uptake and allocation by trees.     

Improving the prediction of ammonium nitrogen removal through struvite precipitation

Purpose  

Both an optimization statistical model and a chemical thermodynamic equilibrium computer model were proposed to develop, improve, and optimize struvite precipitation process.     

Sensitivity of ozone concentrations to diurnal variations of surface emissions in Mexico City: A WRF/Chem modeling study

Sensitivity of ozone (O₃) concentrations in the Mexico City area to diurnal variations of surface air pollutant emissions is investigated using the WRF/Chem model. Our analysis shows that diurnal variations of nitrogen oxides (NO_x = NO + NO₂) and volatile organic compound (VOC) emissions play an important role in controlling the O₃ concentrations in the Mexico City area. The contributions of NO_x and VOC emissions to daytime O₃ concentrations are very sensitive to the morning emissions of NO_x and VOCs. Increase in morning NO_x emissions leads to decrease in daytime O₃ concentrations as well as the afternoon O₃ maximum, while increase in morning VOC emissions tends to increase in O₃ concentrations in late morning and early afternoon, indicating that O₃ production in Mexico City is under VOC-limited regime. It is also found that the nighttime O₃ is independent of VOCs, but is sensitive to NO_x. The emissions of VOCs during other periods (early morning, evening, and night) have only small impacts on O₃ concentrations, while the emissions of NO_x have important impacts on O₃ concentrations in the evening and the early morning.This study suggests that shifting emission pattern, while keeping the total emissions unchanged, has important impacts on air quality. For example, delaying the morning emission peak from 8 am to 10 am significantly reduced the morning peaks of NO_x and VOCs, as well as the afternoon O₃ maxima. It suggests that without reduction of total emission, the daytime O₃ concentrations can be significantly reduced by changing the diurnal variations of the emissions of O₃ precursors.