Using fugacity to predict volatile emissions from layered materials with a clay/polymer diffusion barrier

Structural insulated panels (SIPs) have significant environmental and energy advantages. However, the tight structure that results may cause degraded indoor air quality and the potential release of volatile organic compounds (VOCs) from these layered materials must be considered. A physically based model for predicting VOC emissions from multi-layer materials is described. Fugacity is used to eliminate the concentration discontinuities at the interface between layers. This avoids an obstacle associated with numerically simulating mass transfer in composite materials. The numerical model is verified for a double-layer system by comparing predicted concentrations to those obtained with a previously published analytical model. In addition, hexanal emissions from multi-layer SIPs are simulated to demonstrate the usefulness of the fugacity approach. Finally, the multi-layer model is used to investigate the impact that clay/polyurethane nanocomposite diffusion barriers can have on VOC emissions. Indoor gas-phase concentrations can be greatly reduced with a barrier layer on the surface, thereby minimizing the environmental impact of SIPs.     

室内环境中挥发性有机物释放过程的数学模型

根据组成结构,将室内环境中释放挥发性有机物(VOCs)的建筑装饰材料划分为单层干材料、单层湿材料、多层组合材料等类型,总结了这三种材料的VOCs释放特征、传输过程和数学模型研究现状,分析了模型的特点和适用范围,指出了模型研究发展的趋势,对应用中模型的选择提出了指导性建议.     

Exposure of population and microenvironmental distributions of volatile organic compound concentrations in the EXPOLIS study

Determination of volatile organic compounds (VOCs) formed one part of the EU-EXPOLIS project in which the exposure of European urban populations to particles and gaseous pollutants was studied. The EXPOLIS study concentrated on 30 target VOCs selected on the basis of environmental and health significance and usability of the compounds as markers of pollution sources. In the project, 201 subjects in Helsinki, 50 in Athens, 50 in Basel, 50 in Milan and, 50 in Oxford and 50 in Prague were selected for the final exposure sample. The microenvironmental and personal exposure concentrations of VOCs were the lowest in Helsinki and Basel, while the highest concentrations were measured in Athens and Milan; Oxford and Prague were in between. In all cities, home indoor air was the most significant exposure agent. Workplace indoor air concentrations measured in this study were generally lower than the home indoor concentrations and home outdoor air played a minor role as an exposure agent. When estimating the measured personal exposure concentrations using the measured concentrations and time fractions spent at home indoors, at home outdoors, and at the workplace, it could be concluded that these three microenvironments do not fully explain the personal exposure. Other important sources for personal exposure must be encountered, the most important being traffic/transportation and other indoor environments not measured in this study.     

Levels and source apportionment of volatile organic compounds in southwestern area of Mexico City

Thirteen volatile organic compounds (VOCs) were quantified at three sites in southwestern Mexico City from July 2000 to February 2001. High concentrations of different VOCs were found at a Gasoline refueling station (GS), a Condominium area (CA), and at the University Center for Atmospheric Sciences (CAS). The most abundant VOCs at CA and CAS were propane, n-butane, toluene, acetylene and pentane. In comparison, at GS the most abundant were toluene, pentane, propane, n-butane, and acetylene. Benzene, a known carcinogenic compound had average levels of 28, 35 and 250 ppbC at CAS, CA, and GS respectively. The main contributing sources of the measured VOCs at CA and CAS were the handling and management of LP (Liquid Propane) gas, vehicle exhaust, asphalt works, and use of solvents. At GS almost all of the VOCs came from vehicle exhaust and fuel evaporation, although components of LP gas were also present. Based on the overall results possible abatement strategies are discussed.     

Transient analysis of volatile organic compound concentrations for estimating emission rates

While emission rates of volatile organic compounds (VOCs) have been obtained for building materials, furnishings and processes in chambers, field measurements are more difficult. Procedures to estimate emission rates using transient analysis of VOC concentrations are described and applied in a two-story classroom/office building. The analysis employs semi-real-time VOC concentrations determined with a portable GC/FID and simultaneous air change rate measurements using tracer gas decay. The results of the analysis yield consistent values of emission rates for building materials ranging from 0.20 to 0.40 mg m⁻² h⁻¹ when normalized by floor area. Occupancy-related emissions were more difficult to estimate and covered a wider range from roughly 0.1 to 1.5 mg m⁻² h⁻¹. The test data were also analyzed in an attempt to determine sink parameters, but these efforts were not particularly successful. Furthermore, in these tests, the inclusion of sink effects did not significantly impact the estimated emission rates. While this paper offers a transient analysis approach that may lead to improved field estimates of VOC emission rates, it is not presented as a definitive methodology. Nevertheless, transient analysis has potential for use in other buildings, but simultaneous air change rate measurements are critical in its application in estimating VOC emission rates in the field.     

The diffusion and sorption of volatile organic compounds through kaolinitic clayey soils

Laboratory experiments to estimate the effective molecular diffusion coefficient (D(e)) and sorption coefficient (K(d)) for volatile organic compounds through natural clayey soils were conducted using diffusion testing apparatus. The compounds tested were methyl ethyl ketone (MEK), toluene and trichloroethylene (TCE). The D(e) and K(d) values were determined by a curve fitting procedure. The compound losses, and the effects of porous disks used in the apparatus were significant. The transport of MEK was faster than that of TCE and toluene because of the lower sorption to the soils. The D(e) values of all the compounds were of the order of 10(-10) m(2)/s and smaller than the diffusion coefficient in pure aqueous solution at infinite dilution (D(0)), due to the tortuosity of the samples. The effects of the sample thickness on the parameter determination were not significant. Comparison to the K(d) values estimated from batch sorption tests and from organic carbon content (f(oc))-based predictions showed that the diffusion test results were intermediate between those from the other two methods. The diffusion tests use compacted soil samples and should be more relevant to in situ conditions, but the reliability of the tests is affected by large compound losses that cause uncertainties in their interpretation. It is recommended that more than one method be used to assess K(d) values.     

Visualization and localization of bromotoluene distribution in Hedera helix using NanoSIMS

Some plants are known as indoor air purifiers. A large number of studies report kinetic purification results for an extensive panel of plants, i.e. the pollutant concentration (volatile organic compounds, as known as VOC, most of the time) is continuously monitored by gas chromatography. However, only a few papers describe the mechanisms involved in such processes. This study deals with the use of secondary ion mass spectrometry imaging as an efficient tool to locate atmospheric pollutant as bromotoluene within the Hedera helix plant (leaf, roots) and the substrate on which it was previously grown. Hedera helix plants have been placed in a pollution chamber with control of the exposure parameters. Plant and soil samples excised were transferred into a fixative solution of glutaraldehyde and paraformaldehyde for a few days, were dehydrated using ethanol and were embedded with resin. Cross sections were made from the pale brown solids obtained. Then, a device using a cathodic pulverization device capable of depositing a few nanometers of gold atoms over the sample was used to make the surface electronically conductive for the NanoSIMS. Hence, polluted and unpolluted samples of Hedera helix and substrates were obtained following a careful procedure that allowed for the discrimination between polluted and nonpolluted ones. Nanoscale spatial resolution was an invaluable tool (NanoSIMS) to achieve this, and proved that VOCs, such as bromotoluene, were actually trapped by plants such as Hedera helix.     

Spatial gradients and source apportionment of volatile organic compounds near roadways

Concentrations of 55 volatile organic compounds (VOCs) (C₂–C₁₂) are reported near a highway in Raleigh, NC. Thirty-minute samples were collected at eight locations, ranging from approximately 10–100 m perpendicular from the roadway. The highest concentrations of VOCs were generally measured closest to the roadway, and concentrations decreased exponentially with increasing distance from the roadway. The highest mean concentration for individual VOCs were for ethylene (3.10 ppbv) (mean concentration at x = 13 m), propane (2.27 ppbv), ethane (1.91 ppbv), isopentane (1.54 ppbv), toluene (0.95 ppbv), and n-butane (0.89 ppbv). Concentrations at the nearest roadway location (x = 13 m) were generally between 2.0 and 1.5 times those from the farthest roadway location (x = 92 m). The data were apportioned into four source categories using the EPA Chemical Mass Balance Model (CMB8.2): motor vehicle exhaust, compressed natural gas, propane gas, and evaporative gasoline. The majority of the VOCs resulted from motor vehicle exhaust (67 ± 12%) (% of total VOC at x = 13 m ± S.D.). Compressed natural gas, propane gas, and evaporative gasoline accounted for approximately 15%, 7% and 1% of the total VOC emissions, respectively, at x = 13 m.     

活性炭吸附室内空气中挥发性有机化合物

活性炭吸附室内空气中挥发性有机化合物的１０％穿透时间与气相浓度及挥发性有机化合物的种类有关,通过对苯、甲苯和丙酮的实验研究,得出了由高浓度估算室内低浓度时炭床１０％穿透时间的经验公式ｔｂ,１＝ｔｂ,ｈ（Ｃ０,１／Ｃ０,ｈ）＾ａ,其中ａ值是与炭床性能及挥发性有机化合物种类有关的参数,可通过实验确定。     

二氧化钛/碳纳米管/壳聚糖薄膜的制备及对苯的降解性能

研究了光催化降解挥发性有机化合物过程中催化剂二氧化钛/碳纳米管/壳聚糖薄膜的制备以及该催化剂对苯的光催化性能。首先采用溶胶-凝胶法制备纳米复合材料二氧化钛/碳纳米管,然后利用壳聚糖作为交联剂,制得二氧化钛/碳纳米管/壳聚糖复合材料催化薄膜。通过傅立叶红外光谱(FT-IR)、X射线衍射(XRD)透射电镜扫描(TEM)和紫外-可见光漫反射(UV-Vis)等技术分析了复合材料薄膜的组成、结构、形貌和对光的吸收性能,然后使用该催化剂对室内常见的污染物苯进行降解,并在同样的实验条件下,使用催化剂二氧化钛(P25)/壳聚糖对苯进行降解,对两者催化性能进行对比,结果表明,二氧化钛/碳纳米管/壳聚糖对苯有更强的吸附能力和更高的催化活性。     

Influence of dissolved humic substances on the mass transfer of organic compounds across the air-water interface

The effect of dissolved humic substances (DHS) on the rate of water-gas exchange of two volatile organic compounds was studied under various conditions of agitation intensity, solution pH and ionic strength. Mass-transfer coefficients were determined from the rate of depletion of model compounds from an apparatus containing a stirred aqueous solution with continuous purging of the headspace above the solution (dynamic system). Under these conditions, the overall transfer rate is controlled by the mass-transfer resistance on the water side of the water-gas interface. The experimental results show that the presence of DHS hinders the transport of the organic molecules from the water into the gas phase under all investigated conditions. Mass-transfer coefficients were significantly reduced even by low, environmentally relevant concentrations of DHS. The retardation effect increased with increasing DHS concentration. The magnitude of the retardation effect on water-gas exchange was compared for Suwannee River fulvic and humic acids, a commercially available leonardite humic acid and two synthetic surfactants. The observed results are in accordance with the concept of hydrodynamic effects. Surface pressure forces due to surface film formation change the hydrodynamic characteristics of water motion at the water-air interface and thus impede surface renewal.     

Nitration and hydroxylation of benzene in the presence of nitrite/nitrous acid in aqueous solution

This paper studies the nitration and hydroxylation of benzene in the presence of nitrite/nitrous acid in aqueous solution, both in the dark upon addition of hydrogen peroxide and under 360 nm irradiation. In both cases the detected transformation intermediates were phenol (P), nitrobenzene (NB), 2-nitrophenol (2NP) and 4-nitrophenol (4NP). P and NB directly form from benzene, and the initial formation rate of P is at least an order of magnitude higher than that of NB. In our experiments nitrophenols arise from P nitration, as can be inferred by their time evolution and isomer ratio (2NP:4NP=60:40, 3NP below detection limit). Nitrophenols may also form upon hydroxylation of NB, but in a different ratio (2NP:3NP:4NP=45:30:25). The detection of 3NP is thus a marker for the hydroxylation of NB, since this isomer is not formed in P nitration processes. The formation rates of P and NB increase with decreasing pH, both in the presence of HNO₂ + H₂O₂ in the dark (which produce HOONO) and in the presence of NO₂⁻/HNO₂ under irradiation. In the former case the pH dependence reflects the formation rate of HOONO. In the case of the irradiation experiments the pH effect can be accounted for by the higher molar absorbivity and photolysis quantum yield of nitrous acid when compared with nitrite. Interestingly, benzene does not react with HNO₂ alone in the dark. An important feature of benzene nitration in the presence of NO₂⁻/HNO₂ under irradiation is that the process is not inhibited by the addition of hydroxyl scavengers, differently from the case of phenol nitration. This finding indicates that nitrite irradiation might lead to the nitration of certain aromatic compounds in natural waters even in the presence of natural hydroxyl scavenging agents, which are usually thought to limit the environmental role of many photochemical processes.     

Source apportionment and source/sink relationships of PAHs in the coastal atmosphere of Chicago and Lake Michigan

Multivariate statistical techniques were used to investigate source apportionment and source/sink relationships for polycyclic aromatic hydrocarbons (PAHs) in the urban and adjacent coastal atmosphere of Chicago/Lake Michigan in 1994–1995. The PAH signatures for the atmospheric particle phase, surface water particle phase and sediments indicate that atmospheric deposition is the major source of PAHs to the sediments and water column particulate phase of Lake Michigan. The PAH signature for the atmospheric gas phase and water dissolved phase indicate an intimate linkage between the lake and its overlying atmosphere. A modified factor analysis-multiple regression model was successfully applied to the source apportionment of atmospheric PAHs (gas+particle). Coal combustion accounted for 48±5% of the ΣPAH concentration in both the urban and adjacent coastal atmosphere, natural gas combustion accounted for 26±2%, coke ovens accounted for 14±3%, and vehicle emissions (gas+diesel) accounted for 9±4%. Each is an identified source category for the region. These results are consistent with the mix of fossil fuel combustion sources and ratios of indicator PAHs.     

Levels of chemical and microbiological pollutants in the vicinity of a waste incineration plant and human health risks: temporal trends

In 2007, a program was initiated to monitor air levels of volatile organic compounds (VOCs) and bioaerosols in the vicinity of a municipal solid waste incinerator (MSWI) (Tarragona, Catalonia, Spain). To investigate the temporal trends of chemical and microbiological pollutants, four 6-monthly campaigns were performed. Air samples were collected at different distances and directions from the facility, as well as in reference sites. In general terms, the concentrations of microbiological agents were very similar to those found in urban zones worldwide. The seasonal evaluation of the results showed higher levels of gram-negative bacteria in winter, contrasting with the increase of the airborne amount of total bacteria in summer. On the other hand, the concentrations of VOCs (mean range: 7.6-18.2 μgm⁻³) were typical of suburban zones. The current exposure to those compounds should not mean additional health risks for the population living nearby.     

Comparison of the substrate effect on voc emissions from water based varnish and latex paint

BACKGROUND, AIMS AND SCOPE: The building materials are recognised to be major contributors to indoor air contamination by volatile organic compounds (VOCs). The improvement of the quality of the environment within buildings is a topic of increasing research and public interest. Legislation in preparation by the European Commission may induce, in the near future, European Union Member States to solicit the industries of paints, varnishes and flooring materials for taking measures, in order to reduce the VOC emissions resulting from the use of their products. Therefore, product characterisation and information about the influence of environmental parameters on the VOC emissions are fundamental for providing the basic scientific information required to allow architects, engineers, builders, and building owners to provide a healthy environment for building occupants. On the other hand, the producers of coating building materials require this information to introduce technological alterations, when necessary, in order to improve the ecological quality of their products, and to make them more competitive. Studies of VOC emissions from wet materials, like paints and varnishes, have usually been conducted after applying the material on inert substrates, due to its non-adsorption and non-porosity properties. However, in real indoor environments, these materials are applied on substrates of a different nature. One aim of this work was to study, for the first time, the VOC emissions from a latex paint applied on concrete. The influence of the substrate (uncoated cork parquet, eucalyptus parquet without finishing and pine parquet with finishing) on the emissions of VOC from a water-based varnish was also studied. For comparison purposes, polyester film (an inert substrate) was used for both wet materials. METHODS: The specific emission rates of the major VOCs were monitored for the first 72 h of material exposure in the atmosphere of a standardized test chamber. The air samples were collected on Tenax TA and analysed using thermal desorption online with gas chromatography provided with both mass selective detection and flame ionisation detection. A double exponential model was applied to the VOC concentrations as a function of time to facilitate the interpretation of the results. RESULTS AND DISCUSSION: The varnish, which was introduced in the test chamber 23 h after the application of the last layer of material, emitted mainly glycolethers. Only primary VOCs were emitted, but their concentrations varied markedly with the nature of the substrate. The higher VOC concentrations were observed for the parquets of cork and eucalyptus, which indicated that they have a much higher porosity and, therefore, a higher power of VOC adsorption than the finished pine parquet (and polyester film). The paint was introduced in the chamber just after its application. Only primary VOCs were emitted (esters, phthalates, glycolethers and white spirit) but some compounds, like 2-(2-butoxyethoxy)ethanol and diethylphthalate, were only observed for paint/polyester, which suggested that they were irreversibly adsorbed by the paint/concrete. Compared with the inert substrate, the rate of VOC emissions was lower for concrete in the wet-stage (first hours after the paint application) but slightly higher later (dry-stage) as a consequence of desorption. CONCLUSIONS: As to varnish, the substrates without finishing, like cork and eucalyptus parquets, displayed a higher power of adsorption of VOCs than the pine parquet with finishing, probably because they have a higher porosity. As concerns paint, the total masses of VOCs emitted were lower for concrete than for polyester, indicating that concrete reduces the global VOC emissions from the latex paint. Concrete is seen to have a strong power of adsorption of VOCs. Some compounds, namely 2-(2-butoxyethoxy)ethanol, diethylphthalate and TEXANOL (this partially), were either irreversibly adsorbed by the concrete or desorbed very slowly (at undetected levels). A similar behaviour had not been reported for gypsum board, a paint substrate studied before. RECOMMENDATIONS AND OUTLOOK: The present data suggest that concrete may be a recommendable substrate for paint in an indoor environment. As the nature of the substrate conditions the rate and nature of VOC emissions from wet materials, it must be explicit when emissions from composite materials are reported, in order to allow comparisons and labelling of the product in terms of indoor air quality.     

Marine and farmed fish on the Polish market: comparison of the nutritive value and human exposure to PCDD/Fs and other contaminants

Chemical analyses were performed in nine fish species that are popular on the Polish market. These included Baltic fish (cod, herring, salmon), fish farmed in Poland (carp, trout), marine fish imported from China (Alaska pollock, sole), and farmed fish imported from Vietnam and China (sutchi catfish, tilapia). The nutritional composition (amino acid, micro- and macronutrients, fat-soluble vitamins - A₁, D₃, E) and certain contaminants (organochlorine pesticides, OCPs; indicator polychlorinated biphenyl, PCB₆; polychlorinated dibenzo-paradioxins and polychlorinated dibenzofurans, PCDD/Fs; dioxin-like polychlorinated biphenyls, dl-PCBs; organotin compounds, OCTs; dyes, malachite green and crystal violet; veterinary drug residues, nitrofurans and chloramphenicol; toxic metals, Cd, Pb, Hg) in the muscle tissues of fish were determined. It was confirmed that the fish species analyzed were excellent sources of amino acids, and were rich in phosphorous and selenium. Baltic Sea fish (salmon, herring), fish farmed in Poland (carp and trout), and tilapia were also rich in vitamin D₃.Traces of OCP, PCB₆, OCT, dyes, veterinary drug residues, and heavy metals were detected in concentrations which do not pose a threat to consumers at the current rate of fish consumption in Poland. However, the problem might arise from the content of PCDD/Fs and dl-PCBs in fatty Baltic fish. The fish species analyzed, differed in their nutritional values and degrees of contamination. We suggest that for optimum health and safety, it is advisable that consumers include a variety of different fish species in their diets.     

Copper and cadmium effects on growth and extracellular exudation of the marine toxic dinoflagellate Alexandrium catenella: 3D-fluorescence spectroscopy approach

In this study, metal contamination experiments were conducted to investigate the effects of copper and cadmium on the growth of the marine toxic dinoflagellate Alexandrium catenella and on the production of dissolved organic matter (Dissolved Organic Carbon: DOC; Fluorescent Dissolved Organic Matter: FDOM). This species was exposed to increasing concentrations of Cu²⁺ (9.93 × 10⁻¹⁰–1.00 × 10⁻⁷ M) or Cd²⁺ (1.30 × 10⁻⁸–4.38 × 10⁻⁷ M), to simulate polluted environments. The drastic effects were observed at pCu²⁺ = 7.96 (Cu²⁺: 1.08 × 10⁻⁸ M) and pCd²⁺ = 7.28 (Cd²⁺: 5.19 × 10⁻⁸ M), where cyst formation occurred. Lower levels of Cu²⁺ (pCu²⁺ > 9.00) and Cd²⁺ (pCd²⁺ > 7.28) had no effect on growth. However, when levels of Cu²⁺ and Cd²⁺ were beyond 10⁻⁷ M, the growth was totally inhibited. The DOC released per cell (DOC/Cell) was different depending on the exposure time and the metal contamination, with higher DOC/Cell values in response to Cu²⁺ and Cd²⁺, comparatively to the control. Samples were also analyzed by 3D-fluorescence spectroscopy, using the Parallel Factor Analysis (PARAFAC) algorithm to characterize the FDOM. The PARAFAC analytical treatment revealed four components (C1, C2, C3 and C4) that could be associated with two contributions: one, related to the biological activity; the other, linked to the decomposition of organic matter. The C1 component combined a tryptophan peak and a characteristic humic substances response, and the C2 component was considered as a tryptophan protein fluorophore. The C3 and C4 components were associated to marine organic matter production.