Comparative application of solid-phase microextraction fibre assemblies and semi-permeable membrane devices as passive air samplers for semi-volatile chlorinated organic compounds. A case study on the landfill "Grube Antonie" in Bitterfeld, Germany

Solid phase microextraction (SPME) fibres coated with Carbowax/divinylbenzene and semi-permeable membrane devices (SPMDs) of standard configuration were used to obtain time-weighted average (TWA) field air concentrations of selected chlorinated semi-volatile compounds on a landfill, where large amounts of lindane by-products were deposited, together with other hazardous chemical residues in the past. Additionally, spot sampling with SPME fibres was performed to identify the emission hotspot and sampling rates were determined/predicted for the substances of interest. Both samplers yield comparable TWA air concentrations of lindane and its isomers and of DDT with its metabolites and gain in certainty about the landfill as remaining source of air pollution with these compounds in the region. Both SPME fibres and SPMDs (respective their modifications) can be recommended as sampling tools in process studies and larger air monitoring programmes. However, further calibration studies and field tests are necessary to obtain reliable sampling rates for a wider range of semi-volatile compounds.     

Interaction of volatile organic compounds with indoor materials—a small-scale screening method

Indoor air pollution caused by volatile organic compounds (VOCs) may affect the health and well-being of inhabitants. Uptake and release of these compounds by and from indoor materials alter their concentrations in indoor air: uptake will lower peak concentrations, whereas subsequent (slow) release at lower concentration levels will prolong the presence of VOCs in indoor air. An experimental set-up has been implemented where indoor materials are placed as a “membrane” separating two air compartments. Both compartments – consisting of Field and Laboratory Emission Cells FLECs – are constantly flushed with air, one air stream containing a mixture of 20 VOCs, and concentrations in both compartments are measured after 1 h. Ten materials usually covering extensive surfaces indoors were consecutively exposed to the vapour mixture at concentration levels typically found in indoor environments. Under the chosen experimental conditions, five of these materials exhibited a permeability high enough that VOCs could be detected on the other side. Mass transport of VOCs into and through indoor materials has therefore been confirmed by experiment. The set-up allows for a quick screening of indoor materials with respect to their sorption capacity and permeability.     

Sensory and chemical characterization of VOC emissions from building products: impact of concentration and air velocity

The emissions from five commonly used building products were studied in small-scale test chambers over a period of 50 days. The odor intensity was assessed by a sensory panel and the concentrations of selected volatile organic compounds (VOCs) of concern for the indoor air quality were measured. The building products were three floor coverings: PVC, floor varnish on beechwood parquet and nylon carpet on a latex foam backing; an acrylic sealant, and a waterborne wall paint on gypsum board. The impacts of the VOC concentration in the air and the air velocity over the building products on the odor intensity and on the emission rate of VOCs were studied. The emission from each building product was studied under two or three different area-specific ventilation rates, i.e. different ratios of ventilation rate of the test chamber and building product area in the test chamber. The air velocity over the building product samples was adjusted to different levels between 0.1 and 0.3 m s^-1. The origin of the emitted VOCs was assessed in order to distinguish between primary and secondary emissions. The results show that it is reasonable after an initial period of up to 14 days to consider the emission rate of VOCs of primary origin from most building products as being independent of the concentration and of the air velocity. However, if the building product surface is sensitive to oxidative degradation, increased air velocity may result in increased secondary emissions. The odor intensity of the emissions from the building products only decayed modestly over time. Consequently, it is recommended to use building products which have a low impact on the perceived air quality from the moment they are applied. The odor indices (i.e. concentration divided by odor threshold) of primary VOCs decayed markedly faster than the corresponding odor intensities. This indicates that the secondary emissions rather than the primary emissions, are likely to affect the perceived air quality in the long run. Some of the building products continued to affect the perceived air quality despite the concentrations of the selected VOCs resulted in odor indices less than 0.1. Therefore, odor indices less than 0.1 as an accept criterion cannot guarantee that a building product has no impact on the perceived air quality.     

Reducing Indoor Air Formaldehyde Concentrations

Urea-formaldehyde resin bonded partlcleboard, medium density fiberboard and plywood paneling are used as flooring, wall paneling, for cabinet work and in furniture, and are present In almost every office, home and public building. If large quantities of these products are used In poorly ventilated spaces, high manufacturing quality control is necessary to avoid problems of latent formaldehyde release. Indoor air formaldehyde concentrations depend on the nature of the product, the product surface to air volume (loading) factor, temperature, humidity, age and product emission rates. Standard test methods are now available for measuring product emission rates that make It possible to predict the performance of UF-bonded pressed wood materials If use conditions and environmental parameters are known. Recent modifications In adhesive and board manufacturing parameters have made It possible to reduce formaldehyde emission significantly, and UF-bonded wood products are now capable of meeting indoor air quality standard levels of 0.1 ppm under almost all customary loading conditions.     

Relevance study of bare and coated zero valent iron nanoparticles for lindane degradation from its by-product monitorization

Zero-valent iron nanoparticles (NZVI) as well as polymer–stabilized nanoparticles were synthesized and used for lindane (γ-hexachlorocyclohexane) degradation in aqueous solution. To study the effectiveness of the different coated nanoparticles, simple and rapid analytical methods have been developed to measure and to detect lindane and its by-products. For the monitorization of lindane degradation solid-phase extraction (SPE) was used, while volatile by-products formation measurement was carried out by headspace-solid phase microextraction (HS–SPME) followed by GC/MS. The SPE–GC/MS method provides low detection limits (0.2 μg L⁻¹), high recovery (above 95%) and it is a valuable tool for kinetic studies of the degradation process for each polymer used, while HS–SPME–GC/MS has proved to be an effective tool for the extraction and evaluation of volatile degradation by-products.     

The Altitude: A Fundamental Parameter in the Use of Air Quality Standards

Organic vapors are emitted to the indoor air from a variety of consumer products and building materials. The U.S. EPA Is evaluating the emission characteristics from such sources using small environmental test chambers. Emission rate data are presented, and the effect of temperature and air exchange rate are discussed. Models are used to account for the Impact of chamber concentration and “wall effects” on emission rates. Indoor concentrations of specific organlcs emitted from a silicone caulk are estimated from the chamber test data.     

A Simple Technique for Measuring Mean H2S Concentration

Lead acetate impregnated ceramic tiles are useful devices for determining H₂S levels in the outdoor air. The exposure of tiles in simple shelters and for an overnight period is effective in an areawide sampling program to determine: (1) whether a significant H₂S source exists, (2) the source location, (3) the area affected, and (4) the relative intensity pattern.

On the basis of an overnight exposure, tiles can “see” a mean H₂S concentration range of 0.003 to 0.3 ppm. The lower level of sensitivity is near 0.03 ppm X hr. Hence, tiles offer a way to verify whether hourly air quality standards are being exceeded.

Tiles can be qualitatively evaluated against: experience, known effects, or by ranking against each other. Tiles can be semi-quantitatively evaluated by visual grading against painted standards developed by exposing tiles of particular manufacture to known H₂S dosages.     

Volatility of propoxur from different surface materials commonly found in homes

The purpose of this study was to determine the volatilization rates of propoxur from different surface materials commonly found in homes, and to conduct field measurements under ventilated and non-ventilated conditions. Since it is known that temperature, humidity and constant air flow most significantly affect volatility, various surface materials were sprayed using a constant amount of propoxur under the controlled conditions of an exposure chamber. Acetonitrile was used to desorb both XAD-2 resin that collected airborne propoxur and surface materials containing propoxur residue. HPLC was used to analyze propoxur concentrations. Based on multiple regression models, temperature most significantly affected volatility, followed by humidity. Volatilization rates of propoxur were highest from quartz surfaces and lowest from glass. Interaction was most readily found on glass surfaces based on humidity-air flow and humidity-temperature factors. In field applications, propoxur was sprayed in a room under two conditions with ventilation and without in order to measure the concentrations of propoxur in the air and on a quartz surface. Findings showed both airborne and settled concentrations peaked after a half hour then decreased under both conditions, both more sharply in the ventilated room. Under both conditions, no propoxur was detected on the quartz surface after three and a half hours but airborne concentrations remained detectable after thirty-three and one half hours. We conclude that to maintain good air quality, ventilation is important and special care must be taken when spraying insecticides on different surfaces.     

Measurements of carbonyls in a 13-story building

BACKGROUND, AIM AND SCOPE: Formaldehyde and acetaldehyde are emitted by many mobile and stationary sources and secondary aldehydes are intermediates in the photo-oxidation of organic compounds in the atmosphere. These aldehydes are emitted indoors by many materials such as furniture, carpets, heating and cooling systems, an by smoking. Carbonyls, mainly formaldehyde and acetaldehyde, have been studied because of their adverse health effects. In addition, formaldehyde is a suspected carcinogen. Therefore, the concentrations of formaldehyde and acetaldehyde were determined to assess the inhalation exposure doses to carbonyls for people who work in a 13-story building and in order to evaluate the cancer hazard. METHODS: Carbonyl compounds in indoor and outdoor air were measured at a 13-story building located in Mexico City. The mezzanine, fifth and tenth floors, and the third level-parking garage were selected for sampling. Samples were collected in two sampling periods, the first from April 20 to 29, 1998 and the second from December 1 to 20, 1998. Carbonyls were sampled by means of DNHP-coated cartridges at a flow rate of 1 l min(-1) from 9:00 to 19:00 hours, during 2-hour time intervals and analyzed by HPLC with hours, during 2-hour time intervals and analyzed by HPLC with UV/VIS detection. RESULTS: Mean carbonyl concentrations were highest in the 3rd level-parking garage, with the formaldehyde concentration being the highest ranging from 108 to 418 microg m(-3). In working areas, the highest carbonyl arithmetic mean concentrations (AM) were observed on the 5th floor. Acetone and formaldehyde concentrations were highest in April ranging from 161 to 348 microg m(-3) (AM = 226) and from 157 to 270 microg m(-3) (AM = 221), respectively. Propionaldehyde and butyraldehyde were present in smaller concentrations ranging from 2 to 25 and 1 to 28 microg m(-3), respectively, considering all the samples. Mean indoor/outdoor ratios of carbonyls ranged from 1.8 to 9.6. A reduction of inhalation exposure doses of 41% and 45% was observed in the fifth floor air after the air conditioning systems had been repaired. Formaldehyde and acetaldehyde concentrations were higher in smoking environments. CONCLUSION: Indoor carbonyl concentrations were significantly greater than outdoor concentrations. Tobacco smoke seems to be the main indoor source of formaldehyde. After the air conditioning system was maintained and repaired (as was recommended), an important reduction in the emission of formaldehyde and acetaldehyde was achieved on all floors, except for the 3rd level parking garage, thereby reducing the inhalation exposure doses. RECOMMENDATION: The results obtained in this research demonstrated that maintenance of air conditioning systems must be carried out regularly in order to avoid possible adverse effects on health. Additionally, it is mandatory that isolated smoking areas, with air extraction systems, be installed in every public building.     

Occurrence of organic and inorganic biocides in the museum environment

In the museum environment organic and inorganic chemicals can be found, which originate from both outside and inside the building. Many of the contaminants may cause adverse effects on works of art and human health, but in the past, pollution research in museums has focused on the protection of artifacts, while the risk assessment for humans has been neglected. Especially, the application of biocides leads to a conflict of interest: on the one hand cultural assets have to be protected against microorganisms, insects and rodents while on the other hand it is essential to provide healthy conditions for museum staff and visitors. It has recently been shown that the release of organic indoor pollutants from building products is one of the main reasons for deterioration of artifacts. In this work, we present the results of screening measurements on biocides in different locations of German museums. The major components that could be identified were DDT, PCP, lindane, methoxychlor, naphthalene, chlorinated naphthalenes, 1,4-dichlorobenzene, PCBs and arsenic. It is demonstrated that the application of chlorinated organic compounds and arsenic for preventive conservation is one of the prime reasons for indoor pollution in museums and provides a potential for exposure. However, the concentrations in air, dust and material are widely different and a health risk for humans has to be evaluated case by case.     

Using the chemical mass balance model to estimate VOC source contributions in newly built timber frame houses: a case study

Basing on the material emission data obtained in a test chamber, chemical mass balance (CMB) was used to assess the source apportionment of volatile organic compound (VOC) concentrations in three newly built timber frame houses. CMB has been proven to be able to discriminate the source contributions for two contrasted environmental conditions (with and without ventilation). The shutdown of the ventilation system caused an increase in the VOC concentrations due to the increased contribution of indoor surface materials like the door material and furniture explaining together over 65% of total VOCs. While the increase in formaldehyde concentration is mainly due to furniture (contribution of 70%), the increase in α-pinene concentration is almost exclusively attributable to the emission of door material (up to 84%). The apportionment of VOC source contributions appears as highly dependent on the position of source materials in the building (surface materials or internal materials) and the ventilation conditions explaining that the concentrations of compounds after the shutdown of ventilation system do not increase in equivalent proportion. Knowledge of indoor sources and its contributions in real conditions may help in the selection of materials and in the improvement of construction operations to reduce the indoor air pollution.     

In vitro studies of copper release from powder particles in synthetic biological media

The aim of this paper is to provide quantitative data on copper release from powder particles of different copper materials, including artificial copper patina, Cu(2)O and metallic Cu, when exposed to different synthetic biological media to simulate an inhalation scenario and/or skin contact. Generated data may contribute in risk assessment of potential health effects following exposure to and handling of various copper materials. All tests were performed in vitro to determine total copper concentrations, release rates of total copper, and to elucidate its time-dependence. The copper release process was interpreted in terms of specific surface area, surface morphology-, and composition. All powder materials show a time-dependent release process with total copper release rates less than 3 microg/cm(2) per hour at steady state conditions, for all media investigated. The importance of using relevant test media when simulating different interstitial lung conditions and difficulties encountered when comparing powder particles of essentially different properties are thoroughly discussed.     

Ceramic tiles with black pigment made from stainless steel plant dust: Physical properties and long-term leaching behavior of heavy metals

Stainless steel plant dust is a hazardous by-product of the stainless steelmaking industry. It contains large amounts of Fe, Cr, and Ni, and can be potentially recycled as a raw material of inorganic black pigment in the ceramic industry to reduce environmental contamination and produce value-added products. In this paper, ceramic tiles prepared with black pigment through recycling of stainless steel plant dust were characterized in terms of physical properties, such as bulk density, water absorption, apparent porosity, and volume shrinkage ratio, as well as the long-term leaching behavior of heavy metals (Cr, Ni, Pb, Cd, and Zn). The results show that good physical properties of ceramic tiles can be obtained with 8% pigments addition, sample preparation pressure of 25 MPa, and sintering at 1200 ºC for 30 min. The major controlling leaching mechanism for Cr and Pb from the ceramic tiles is initial surface wash-off, while the leaching behavior of Cd, Ni, and Zn from the stabilized product is mainly controlled by matrix diffusion. The reutilization process is safe and effective to immobilize the heavy metals in the stainless steel plant dust.

Implications: Stainless steel plant dust is considered as a hazardous material, and it can be potentially recycled for black pigment preparation in the ceramic industry. This paper provides the characteristics of the ceramic tiles with black pigment through recycling stainless steel plant dust, and the long-term leaching behavior and controlling leaching mechanisms of heavy metals from the ceramic tile. The effectiveness of the treatment process is also evaluated.     

Modelling and field application of the Chemcatcher passive sampler calibration data for the monitoring of hydrophobic organic pollutants in water

Passive sampling of dissolved pollutants in water has been gaining acceptance for environmental monitoring. Previously, an integrative passive sampler consisting of a C18 Empore disk receiving phase saturated with n-octanol and fitted with low density polyethylene membrane, was developed and calibrated for the measurement of time weighted average (TWA) concentrations of hydrophobic pollutants in water. In this study, the exchange kinetics were modelled to obtain a better understanding of the mechanism of the accumulation process and to enable the measurement of TWA concentrations of hydrophobic pollutants in the field. An empirical relationship that enables the calculation of in situ sampling rates of chemicals using performance reference compounds was derived and its application was demonstrated in a field study in which TWA aqueous concentrations estimated from sampler data for target analytes were compared with TWA concentrations obtained from spot samples of water collected regularly during the sampler deployment period.     

Application of System Dynamics technique to simulate the fate of persistent organic pollutants in soils

Persistent organic pollutants (POPs) are within the most dangerous pollutants released into the environment by human activities. Due to their resistance to degradation (chemical, biological or photolytic), it is critical to assess the fate and environmental hazards of the exchange of POPs between different environmental media.System Dynamics enables to represent complex systems and analyze their dynamic behavior. It provides a highly visual representation of the structure of the system and the existing relationships between the several parameters and variables, facilitating the understanding of the behavior of the system. In the present study the fate of γ-hexachlorocyclohexane (lindane) in a contaminated soil was modeled using the Vensim® simulation software.Results show a gradual decrease in the lindane content in the soil during a simulation period of 10 years. The most important route affecting the concentrations of the contaminant was the biochemical degradation, followed by infiltration and hydrodynamic dispersion. The model appeared to be highly sensitive to the half-life of the pollutant, which value depends on environmental conditions and directly affects the biochemical degradation.     

PCB and dioxin-like PCB in indoor air of public buildings contaminated with different PCB sources--deriving toxicity equivalent concentrations from standard PCB congeners

Data on dioxin-like PCB in indoor air of buildings with PCB-containing materials and on possible correlation between toxicity equivalent concentrations (TEQ) and levels of non-dioxin-like standard PCB is sparse. As part of a larger survey on indoor-air contamination with PCB, the connection between the concentration of standard PCB congeners and the dioxin-like toxicity expressed as TEQ was investigated. Indoor air samples (n=8) were collected in four public buildings with known PCB sources and total PCB levels in the range from 715 to 2250 ng/m3 and analyzed for the six non-dioxin-like standard PCB (congeners 28, 52, 101, 138, 153, 180), the twelve dioxin-like PCB congeners according to WHO and the 17 2,3,7,8-substituted PCDD/PCDF congeners. In three buildings where PCB were used as flame retardant coatings of acoustic ceiling tiles, PCB 101 had the maximum level among the six standard PCB, while in the building with permanent elastic sealants as PCB source, congeners 28 and 52 dominated the pattern by far. In the case of permanent elastic sealants as PCB source (n=3) a total PCB concentration of 1000 ng/m3 corresponded to a total TEQ level of 0.3-0.6 pg/m3. In contrast, in rooms with acoustic ceiling tiles as PCB source, 1.8-4.7 pg TEQ/m3 per 1000 ng total PCB/m3 were found. Linear regression analysis between PCB and TEQ indicated that PCB 118 might be used to calculate the total TEQ of dioxin-like PCB and PCDD/PCDF. By means of such a correlation it is possible to estimate TEQ by extrapolation from the results of less sophisticated analytical methods. It is tentatively recommended to use PCB 118 for screening purposes or re-evaluation of standard PCB indoor-air measurements. If only the six non-dioxin-like PCB standard congeners are available, a regression algorithm using the sum of PCB 101, 138, 153 and 180 might be used instead.     

Reactions between ozone and building products: Impact on primary and secondary emissions

Reactions of ozone on common building products were studied in a dedicated emission test chamber system. Fourteen new and unused products were exposed to 100–160 ppb of ozone at 23 °C and 50% RH during 48 h experiments. Ozone deposition velocities calculated at steady state were between 0.003 cm s⁻¹ (alkyd paint on polyester film) and 0.108 cm s⁻¹ (pine wood board). All tested product showed modified emissions when exposed to ozone and secondary emissions of several aldehydes were identified. Carpets and wall coverings emitted mainly C₅–C₁₀ n-aldehydes, typical by-products of surface reactions. Linoleum, polystyrene tiles and pine wood boards also showed increased emissions of formaldehyde, benzaldehyde and hexanal associated with reduced emissions of unsaturated compounds suggesting the occurrence of gas-phase reactions. The ozone removal on the different tested products was primarily associated with surface reactions. The relative contribution of gas-phase reactions to the total ozone removal was estimated to be between 5% and 30% for pine wood boards depending on relative humidity (RH) and on the incoming ozone concentration and 2% for polystyrene tiles. On pine wood board, decreasing ozone deposition velocities were measured with increasing ozone concentrations and with RH increasing in the range 30–50%.     

Photocatalytic oxidation of gaseous chlorinated organics over titanium dioxide

The photocatalytic oxidation of high levels of volatile chlorinated organic compounds in gas phase has been studied using a specially designed photoreactor. The influence of light intensity, initial water vapour concentration, temperature, inlet contaminant concentration and flow rate on destruction efficiency has been investigated. The performance of the titanium catalyst was strongly affected by the presence of water in the air stream. Experiments have been most successfully conducted at room temperature, low initial contaminant concentrations, low flow rates and high light intensities. Several by-products have been detected performing photocatalytic degradation of trichloroethylene (TCE) and tetrachloroethylene (PCE). No catalyst deactivation was observed.     

Solar driven nitrous acid formation on building material surfaces containing titanium dioxide: A concern for air quality in urban areas?

The photoenhanced uptake of nitrogen dioxide (NO₂) to the surface of commercially available self-cleaning window glass has been studied under controlled laboratory conditions. This material is one of an array of modern building products which incorporate titanium dioxide (TiO₂) nanoparticles and are finding increasing use in populated urban areas. Amongst the principal drivers for the use of these materials is that they are thought to facilitate the irreversible removal of pollutants such as NO₂ and organic molecules from the atmosphere and thus act to remediate air quality. While it appears that TiO₂ materials do indeed remove organic molecules from built environments, in this study we show that the photoenhanced uptake of NO₂ to one example material, self-cleaning window glass, is in fact accompanied by the substantial formation (50–70%) of gaseous nitrous acid (HONO). This finding has direct and serious implications for the use of these materials in urban areas. Not only is HONO a harmful respiratory irritant, it is also readily photolysed by solar radiation leading to the formation of hydroxyl radicals (OH) together with the re-release of NO_x as NO. The net effect of subsequent OH initiated chemistry can then be the further degradation of air quality through the formation of secondary pollutants such as ozone and VOC oxidation products. In summary, we suggest that a scientifically conceived technical strategy for air quality remediation based on this technology, while widely perceived as universally beneficial, could in fact have effects precisely opposite to those intended.