Volatile organic compounds (VOCs) emitted from materials collected from buildings affected by microorganisms

In this study mould damaged materials, including carpet, concrete, gypsum board, insulation, plastic, sand and wood, from 20 different buildings with moisture problems were collected. To study emissions from these materials both conventional methods for sampling, such as collection on Tenax TA, were used as well as complementary methods for sampling a wider spectrum of compounds, such as more volatile VOCs, amines and aldehydes. Analysis was carried out using gas chromatography and high-performance liquid chromatography. Mass spectrometry was used for identification of compounds. Alcohols and ketones were almost exclusively emitted from the materials after they had been wet for a week. Acids were also emitted in large quantities from wet gypsum board and plastic. No primary or secondary amines could be identified, but two tertiary amines, trimethylamine and triethylamine, were emitted from sand contaminated by Bacillus. The most common moulds found were Penicillium and Aspergillus. A multivariate method (partial least squares, PLS) was used to investigate the emission patterns from the materials. Materials with bacterial growth had a different VOC profile to those with only mould growth.     

Microbial secondary metabolites in school buildings inspected for moisture damage in Finland, The Netherlands and Spain

Secondary metabolites produced by fungi and bacteria are among the potential agents that contribute to adverse health effects observed in occupants of buildings affected by moisture damage, dampness and associated microbial growth. However, few attempts have been made to assess the occurrence of these compounds in relation to moisture damage and dampness in buildings. This study conducted in the context of the HITEA project (Health Effects of Indoor Pollutants: Integrating microbial, toxicological and epidemiological approaches) aimed at providing systematic information on the prevalence of microbial secondary metabolites in a large number of school buildings in three European countries, considering both buildings with and without moisture damage and/or dampness observations. In order to address the multitude and diversity of secondary metabolites a large number of more than 180 analytes was targeted in settled dust and surface swab samples using liquid chromatography/mass spectrometry (LC/MS) based methodology. While 42%, 58% and 44% of all samples collected in Spanish, Dutch and Finnish schools, respectively, were positive for at least one of the metabolites analyzed, frequency of detection for the individual microbial secondary metabolites - with the exceptions of emodin, certain enniatins and physcion - was low, typically in the range of and below 10% of positive samples. In total, 30 different fungal and bacterial secondary metabolites were found in the samples. Some differences in the metabolite profiles were observed between countries and between index and reference school buildings. A major finding in this study was that settled dust derived from moisture damaged, damp schools contained larger numbers of microbial secondary metabolites at higher levels compared to respective dust samples from schools not affected by moisture damage and dampness. This observation was true for schools in each of the three countries, but became statistically significant only when combining schools from all countries and thus increasing the sample number in the statistical analyses.     

室内人造板材制品释放挥发性有机化合物研究

通过对浸渍纸层压木质地板、实木地板、实木复合地板、竹地板、胶合板、细木工板6种共39个人造板材中的挥发性有机物进行定性研究,确定了家用人造板材制品释放的主要挥发性有机物种类,以及人造板材制品中芳香族化合物的主要来源.通过对5间购入新家具的室内环境空气中甲醛、苯、甲苯和总挥发性有机化合物(TVOC)的定量分析,确定了人造板材制品释放挥发性有机化合物的污染水平.研究表明,人造板材释放的挥发性有机化合物以烯烃、芳香族、酯类化合物为主,其中芳香族化合物主要来源于胶合板和细木工板,室内人造板材制品的使用可以使室内环境空气中挥发性有机化合物的质量浓度显著提高.     

DNPH衍生化采样-溶剂解析-高效液相色谱法同时测定木制品中25种醛酮化合物

建立了DNPH衍生化采样-溶剂解析-高效液相色谱测定木制品中醛酮化合物的方法。采样时需在2,4-二硝基苯肼吸附管前串联一只SEP-PAK脱臭氧小柱;采样体积应≤10 L,流量≤400 m L/min。该法对25种醛(酮)化合物对应的衍生物分离效果良好,在0.005~3 mg/L范围内线性良好,相关系数R2≥0.999 6,回收率为85.3%~113.5%,精密度为2.67%~4.56%。采样量为10 L时,25种醛(酮)化合物的检出限和定量限分别≤0.16和0.50μg/m3。     

Use of headspace SPME-GC-MS for the analysis of the volatiles produced by indoor molds grown on different substrates

An automated headspace solid phase microextraction method followed by GC-MS analysis was used to evaluate and compare the in vitro production of microbial volatile organic compounds (MVOCs) on malt extract agar, plasterboard and wallpaper. Five fungal strains were isolated from the walls of water-damaged houses and identified. In addition, four other common molds were studied. In general, MVOC production was the highest on malt extract agar. On this synthetic medium, molds typically produced 2-methylpropanol, 2-methylbutanol and 3-methylbutanol. On wallpaper, mainly 2-ethylhexanol, methyl 2-ethylhexanoate and compounds of the C8-complex such as 1-octene-3-ol, 3-octanone, 3-octanol and 1,3-octadiene were detected. The detection of 2-ethylhexanol and methyl 2-ethylhexanoate indicates an enhanced degradation of the substrate by most fungi. For growth on plasterboard, no typical metabolites were detected. Despite these metabolite differences on malt extract agar, wallpaper and plasterboard, some molds also produced specific compounds independently of the used substrate, such as trichodiene from Fusarium sporotrichioides and aristolochene from Penicillium roqueforti. Therefore, these metabolites can be used as markers for the identification and maybe also mycotoxin production of these molds. All five investigated Penicillium spp. in this study were able to produce two specific diterpenes, which were not produced by the other species studied. These two compounds, which remain unidentified until now, therefore seem specific for Penicillium spp. and are potentially interesting for the monitoring of this fungal genus. Further experiments will be performed with other Penicillium spp. to study the possibility that these two compounds are specific for this group of molds.     

Quantitative PCR analysis of fungi and bacteria in building materials and comparison to culture-based analysis

Prolonged moisture on building materials can lead to microbial growth on them. Microbes can emit spores, metabolites and structural parts into the indoor air and thus, cause adverse health effects of people living and working in these buildings. So far, culture methods have been used for assessment of microbial contamination of building materials. In this work, we used quantitative PCR (qPCR) for the detection of selected fungal and bacterial groups in 184 building materials of different types and compared the results with culture-based analysis. Nine either commonly found species, genera or groups of fungi, or those considered as moisture damage indicators, and one bacterial genus, Streptomyces, were determined using qPCR. Fungi and mesophilic actinomycetes were also cultivated using standard media and conditions of the routine analysis. The bacterial genus Streptomyces and the fungal group Penicillium/Aspergillus/Paecilomyces were the most prevalent microbial groups in all building material types, followed by Stachybotrys chartarum and Trichoderma viride/atroviride/koningii. The highest prevalences, concentrations and species diversity was observed on wooden materials. In general, the results of the two methods did not correlate well, since concentrations of fungi and streptomycetes were higher and their occurrence more prevalent when determined by qPCR compared to culture-based results. However, with increasing concentrations, the correlation generally increased. The qPCR assay did not detect Aspergillus versicolor and Acremonium strictum as often as culture.     

A two-column method for long-term monitoring of non-methane hydrocarbons (NMHCs) and oxygenated volatile organic compounds (o-VOCs)

A method has been developed for concurrent analysis of C2-C7 hydrocarbons and C2-C5 oxygenated volatile organic compounds (o-VOCs) including alcohols, aldehydes, ketones and ethers. A multi-bed, Peltier-cooled adsorbent trap, consisting of Carboxen 1000 and Carbopack B, was used to acquire one sample per hour. Upon injection the sample was split in an approximately 50:50 ratio between a 50 m aluminium oxide (Al2O3) porous layer open tubular (PLOT) column and a 10 m LOWOX column. Eluents from each column were then analysed using flame ionisation detection (FID). Regular calibration of the system was performed using a standard cylinder mixture at the parts per billion by volume (ppbV) level for non-methane hydrocarbons (NMHCs) and a permeation tube method for the oxygenated species. The system is fully automated with NMHC detection limits between 1 and 10 parts per trillion by volume (pptV) and o-VOC detection limits between 10 and 40 pptV.     

Remediation of mould damaged building materials--efficiency of a broad spectrum of treatments

We compared the efficiency of some commercially available products and methods used for remediation of mould-contaminated building materials. Samples of gypsum board and pinewood were artificially contaminated with toxin-producing isolates of Stachybotrys chartarum and Aspergillus versicolor, respectively, then, ten different remediation treatments were applied according to the manufacturers' instructions. Microbial and chemical analyses of the infested materials were carried out both immediately before and after treatment, after six weeks of drying at room temperature, and after another six weeks of remoistening. The aim of the study was to determine whether the investigated methods could inhibit the mould growth and destroy some selected mycotoxins produced by the moulds. None of the decontamination methods tested could completely eliminate viable moulds. Some methods, especially boron based chemicals, ammonium based chemicals, and oxidation reduced the contents of mycotoxins produced by S. chartarum (satratoxin G and H, verrucarol), whereas the one which uses an ammonium based chemical reduced the amount of sterigmatocystin produced by A. versicolor with statistical significance. No remediation treatment eliminated all the toxins from the damaged materials. These results emphasize the importance to work preventively with moisture safety throughout the construction processes and management to prevent mould growth on building materials.     

空气或废气中挥发性醛、酮的气相色谱法测定

本文研究采用了空气或废气中挥发性醛、酮类化合物在常温下经２，４二硝基苯肼（ＤＮＰＨ）的酸性饱和溶液吸收，分别形成各自的腙，用ＣＳ２萃取后，经气相色谱法（ＧＣＦＩＤ）以３％ＳＥ３０／ＣｈｒｏｍｏｓｏｒｂＷＨＰ８０１００目为固定相和载体，分离测定，对空气或废气中的甲醛、乙醛、丙烯醛、丁醛、丙酮、丁酮、甲基异丁基酮等的测定，获得较满意的结果。     

A systematic indoor air quality audit approach for public buildings

Good indoor air quality (IAQ) in buildings provides a comfortable and healthy environment for the occupants to work, learn, study, etc. Therefore, it is important to ascertain the IAQ status in the buildings. This study is aimed to establish and demonstrate the comprehensive IAQ audit approach for public buildings, based on Portugal national laws. Four public buildings in Portugal are used to demonstrate the IAQ audit application. The systematic approach involves the measurement of physical parameters (temperature, relative humidity, and concentration of the suspended particulate matter), monitoring of the concentrations of selected chemical indicators [carbon dioxide (CO₂), carbon monoxide, formaldehyde, ozone, and total volatile organic compounds], and the measurements of biological indicators (bacteria and fungi). In addition, air exchange rates are measured by the concentration decay method using metabolic CO₂ as the tracer gas. The comprehensive audits indicated some situations of common IAQ problems in buildings, namely: (1) insufficient ventilation rate, (2) too high particle concentration; and (3) poor filtration effectiveness and hygienic conditions in most of the air handling units. Accordingly, a set of recommendations for the improvement of IAQ conditions were advised to the building owner/managers.     

城市大气环境中醛酮类化合物污染状况及变化规律

2003年对郑州市城市环境空气中醛酮类化合物的污染状况及变化规律进行了初步调查研究.结果表明:大气环境中醛酮类污染物的质量浓度范围为未检出～167 μg/m3,主要污染物为甲醛、乙醛和丙酮;醛酮类污染物含量在不同季节的变化趋势是:夏季>春季>冬季;醛酮类污染物主要来源于大气中有机物的光化学反应,甲醛与乙醛、甲醛与丙酮有...     

浅析气象因子对大气中低分子醛酮类有机物的影响

对广州市大气中低分子醛酮类有机污染物进行采样监测,并同步观测气象条件,分析气象因子与大气中低分子醛酮类有机物之间的相关性。结果表明：常规气象因子（温度、湿度、气压、风速等）对大气环境中醛酮类有机污染物的浓度有一定的影响。     

Study of odor compounds in gaseous effluents generated during production of poultry feather and viscera meal using headspace solid phase microextraction

This work reports the screening and characterization of odor compounds in gaseous effluents generated during the production of poultry feather and viscera meal, the by-products of the poultry meat industry. Chemical analysis was carried out by solid phase microextraction in the headspace (HS-SPME) mode. Exhaust air of thermal processing of poultry feather and viscera were sampled online from a bench-scale digester, condensed, and collected in sampling flasks. Both volatile and semivolatile organic compounds present in the condensed gases were extracted under agitation at constant temperature. The extracts were analyzed with a gas chromatograph coupled to a mass spectrometric detector (GC/MSD). The identification of compounds was carried out by comparing the mass spectra obtained with those from the Wiley library and quantification was accomplished through authentic analytical standards. For the determination of the best extraction conditions and analysis, extraction fibers of different coatings and polarities were tested: divinylbenzene/carboxen/polydimethyilsiloxane (DVB/CAR/PDMS), carbowax/divinylbenzene (CW/DVB), and polydimethylsiloxane (PDMS) and chromatography columns of different polarities: DB-WAX (polar) and DB-5 (nonpolar). The best extraction conditions and analysis of the compounds of interest were obtained by the use of the SPME fiber with DVB/CAR/PDMS coating and analysis by GC/MSD with polar capillary column. Several carboxylic acids were identified, as well as mercaptans, amines, and aldehydes of great environmental importance.     

Occupational exposure to rubber vulcanization products during repair of rubber conveyor belts in a brown coal mine

Several hundred chemical compounds were found in workroom environments in the rubber industry, but most of the published exposure data relate to the production of tyres; information from the "non-tyre" sections are very limited, if any. This study was carried out to identify chemical substances and measure their air concentrations in the repair shop of a brown coal mine in which damaged rubber conveyor belts were repaired. GC-MS and HPLC analysis of stationary air samples resulted in identification of aliphatic and aromatic hydrocarbons to C12, PAHs, alcohols, phenols, ketones, heterocyclic nitrogen and sulfur compounds. Quantitative evaluation of occupational exposure included determination of organic compound vapours collected on charcoal (GC-MSD), polycyclic aromatic hydrocarbons (HPLC), N-nitrosoamines and other amines (GC-NPD) and DNPH derivatives of aldehydes (HPLC) in the breathing zone of workers representing all job titles. The concentrations of investigated compounds were very low. Carcinogenic substances: N-nitrosoamines, benzene, PAHs were not present in workroom air in concentrations exceeding limits of detection of the analytical methods being applied; concentrations of methylisobutylketone, tetrachloroethylene, naphtha, aromatic hydrocarbons, phthalates and aldehydes were much lower than the respective occupational exposure limit values. The results indicate much lower exposure than that reported in the production of tyres and other fabricated rubber products.     

Stabilities of 58 volatile organic compounds in fused-silica-lined and SUMMA polished canisters under various humidified conditions

Fused-silica-lined (FSL) canisters and SUMMA polished (SUMMA) canisters were compared for the recoveries and the stabilities of 58 volatile organic compounds (VOCs) at low ppbv (volume/volume) levels under various humidified conditions using a three-stage preconcentration method followed by GC-MS analysis. The target VOCs included non-polar VOCs (e.g. halogenated hydrocarbons and aromatic hydrocarbons) and polar VOCs (e.g. alcohols, ketones, esters, ethers, nitriles and thiols). The three-stage preconcentration method was initially optimized for simultaneous analysis of non-polar and polar VOCs because determination of canister stability is dependent on the accuracy of analytical measurements. The method showed good linearity over the concentration range from 1 to 25 ppbv for all target analytes, and the correlation coefficients were higher than 0.9974. The method detection limits ranged from 0.023 to 0.39 ppbv. The test mixtures loaded in both type of canisters (n = 3) had concentrations of 1.7-2.5 ppbv per compound at ambient pressure under various humidified conditions (%RH = 1.6, 8.0, 27, 39, 53 and >99% with excess water present). All canister samples were initially analyzed on day 0 (after 6-12 h). The effect of competitive adsorption of water vapor and polar VOCs on active sites of interior surface was remarkably observed for SUMMA canisters. Polar VOCs had a greater requirement for water vapor to be present. The RH percentages that ensured good recovery on day 0 were RH > 8% for non-polar VOCs and RH > 27% for polar VOCs (except alcohols under the condition of RH > 99%). All thiols were not recovered from SUMMA canisters under all conditions. FSL canisters showed good recoveries of more than 86% for all VOCs under all conditions on day 0 (except alcohols under the condition of RH > 99%). The recoveries of alcohols in both canisters under the condition of RH > 99% displayed relatively low recoveries in the range 25-76% because of the partitioning effect into condensed water. The canister samples under the conditions of RH 8.0, 27, 53 and > 99% were analyzed for the stability test on days 3, 7, 14 and 28 after loading. All non-polar VOCs were reasonably stable in the FSL canisters under all examined conditions over 28 days. However, several polar VOCs that have relatively lower vapor pressure, e.g. MIBK, butyl acetate and alcohols except ethanol, showed unstable characteristics under relatively dry conditions (RH 8 and 27%) during 28 days. RH > 53% was needed to ensure good stabilities of all analytes except thiols with the recoveries of > 80% over 28 days for both canisters. Although the FSL canister showed good recoveries of more than 86% for thiols on day 0, drastic degradations were observed after day 3 and they were not detected after day 14.     

Determination of carbonyls using liquid chromatography-mass spectrometry with atmospheric pressure chemical ionization

A liquid chromatographic method for the determination of aldehydes and ketones based on mass spectrometric detection is described. Recently developed modular derivatizing agents are employed for analysis. These hydrazine reagents, e.g. 4-dimethylamino-6-(4-methoxy-1-naphthyl)-1,3,5-triazine-2-hydrazine (DMNTH), react with the carbonyl compounds with the formation of the respective hydrazones, which are separated by HPLC-MS with atmospheric pressure chemical ionization in the positive mode. Electrospray ionization may also be used for analysis. Particular focus is directed on various calibration approaches, including external calibration with standard solutions and internal calibration with a hydrazone standard of cyclobutanone, an aldehyde not likely to occur in real samples. A second approach for internal calibration is based on the 13C2-labelled acetaldehyde hydrazone standard. Different calibration approaches may then be used for the analysis of real samples. Limits of detection range from 2 x 10(-8) to 5 x 10(-8) mol L-1 for a series of hydrazones, including hydrazones of saturated aldehydes with alkyl chain lengths from 1 to 7 carbon atoms, and hydrazones of selected unsaturated and aromatic aldehydes as well as ketone hydrazones.     

Solubilities of hydrophobic compounds in aqueous-organic solvent mixtures

Solubilities of several hydrophobic organic substances (paradichlorobenzene, endrin, naphthalene, and dibutyl phthalate) in aqueous solutions containing up to 0.10 mole fraction of common alcohols and ketones, were measured by gas chromatography. The solubilities are significantly increased by the alcohols and ketones. The results are interpreted in terms of the association of n molecules of alcohol or ketone with each hydrophobic organic molecule. Values of n and the equilibrium constant for this association are reported for each hydrophobic organic-alcohol and organic-ketone combination. The implications of these results for the disposal of toxic wastes by landfilling is discussed.     

Multi-component analysis of polar water pollutants using sequential solid-phase extraction followed by LC-ESI-MS

A multi-component screening analysis method for polar to medium-polar water pollutants was developed. Sample clean-up and group separation are performed by sequential solid-phase extraction (SSPE) using automated SPE with C18 and polymeric sorbent materials. Analyses are performed by liquid chromatography electrospray ionization mass spectrometry (LC-ESI-MS) using a single-quadrupole instrument. More than 90 priority compounds of environmental interest--comprising the most important chemical and substance classes: phenols, carboxylic acids, aromatic sulfonates, aromatic amines, pharmaceuticals, surfactants, dyes, and pesticides--have been chosen for the experiments. The compounds are divided by the SSPE procedure into 3 different polarity classes. The extraction recoveries were determined in the 3 fractions for every single substance, and were for most of the analytes in the range of 50-100%. A mixture of hexane-dichloromethane was used for the elution of nonpolar compounds like alkylphenols from C18. Methanol and acetone are well suited for the elution of more polar substances. The limits of detection (LODs) were determined for all compounds. Effluents from municipal and industrial wastewater treatment plants (WWTPs) treating waste water from textile industries; and the corresponding receiving waters (rivers and lakes) have been analysed with the developed method. Urban and industrial pollution was observed in rivers and streams in the area north of Milan, Italy. In the water samples different phenols (nitrophenols, bisphenol A, nonylphenol), alkylphenol ethoxylate surfactants, their metabolites with endocrine disrupting potential, aromatic sulfonates, linear alkylbenzenesulfonate surfactants, dyes, pesticides, pharmaceuticals, and a dichlorobenzidine compound were identified.     

Volatile Organic Compounds in the Area of Madrid: A Chemometrical Approach

Multivariate techniques have been applied to the set of dataobtained after one year sampling of volatile organic compounds(VOCs), including volatile aldehydes in the area of Madrid inorder to evaluate the possible correspondence among groups ofanalysed compounds, as far as modelling of different emissionsources in relation to location and season. The measurements were carried out at four sites in Madrid, characteristic for urban and suburban areas. Additionally, as reference, a rural area 100 km far from the city was considered. Results of correlation analysis, factor and cluster analysis are presented.Higher correlations were found between variables related withtraffic emissions. Factor analysis results showed two mainsignificant variables related to anthropogenic and biogenicemissions respectively. In relation to cluster analysis, samples were grouped according to sampling site and seasonal variations.     

Performance evaluation of a sorbent tube sampling method using short path thermal desorption for volatile organic compounds

Air sampling, using sorbents, thermal desorption and gas chromatography, is a versatile method for identifying and quantifying trace levels of volatile organic compounds (VOCs). Thermal desorption can provide high sensitivity, appropropriate choices of sorbents and method parameters can accommodate a wide range of compounds and high humidity, and automated short-path systems can minimize artifacts, losses and carry-over effects. This study evaluates the performance of a short-path thermal desorption method for 77 VOCs using laboratory and field tests and a dual sorbent system (Tenax GR, Carbosieve SIII). Laboratory tests showed that the method requirements for ambient air sampling were easily achieved for most compounds, e.g., using the average and standard deviation across target compounds, blank emissions were < or = 0.3 ng per sorbent tube for all target compounds except benzene, toluene and phenol; the method detection limit was 0.05 +/- 0.08 ppb, reproducibility was 12 +/- 6%, linearity, as the relative standard deviation of relative response factors, was 16 +/- 9%, desorption efficiency was 99 +/- 28%, samples stored for 1-6 weeks had recoveries of 87 +/- 9%, and high humidity samples had recoveries of 102 +/- 12%. Due to sorbent, column and detector characteristics, performance was somewhat poorer for phenol groups, ketones, and nitrogen containing compounds. The laboratory results were confirmed in an analysis of replicate samples collected in two field studies that sampled ambient air along roadways and indoor air in a large office building. Replicates collected under field conditions demonstrated good agreement except for very low concentrations or large (> 41 volume) samples of high humidity air. Overall, the method provides excellent performance and satisfactory throughput for many applications.