The brominated flame retardants (BFRs), pentabromotoluene (PBT), pentabromoethylbenzene (PBEB) and hexabromobenzene (HBB), exhibit physical-chemical properties similar to other persistent organic pollutants, and have been in use as flame retardants for several decades. Data on these BFRs in diverse environmental samples can be found in studies from the 1970s and 1980s, as well as in recent years, though very little in the years in between. Due to a lack of data, the cause for the apparent re-emergence of these BFRs in recent studies is unclear, and could reflect changes in production volumes, accumulation of transformation products from BFR precursors, improved analytical techniques or simply a re-emergence in concern. Very little data are available on their environmentally relevant partitioning properties, which could help to explain the occurrence and fate of these BFRs. In this study we analysed for the presence of HBB, PBT, and PBEB in diverse environmental samples from potential Norwegian BFR source zones. Additionally, environmental partitioning properties of these BFRs as well as brominated benzenes were estimated and validated using experimental data for brominated benzenes. Of the three BFRs, HBB was identified in detectable quantities at most source zones, PBEB only near a metal recycling factory, and PBT only in a few additional locations from where PBEB was detected. Data from this study show that HBB is likely widely distributed, as verified both by chemical analysis and estimated properties. Measured HBB levels in wastewater treatment plants indicate that the treatment practices used in the study locations are not effective at lowering HBB levels, perhaps due to association with low density suspended solids (e.g. microplastics).
Resin acids are constituents of natural and technical products of widespread use. Exposure is known to cause health effects in the airways and on the skin. Liquid chromatography/positive ion electrospray-mass spectrometry (HPLC/pos ESI-MS) was investigated for determination of 7-oxodehydroabietic (7-OXO), dehydroabietic (DHAA) and abietic acid (AA) in wood dust-containing air samples as a derivatisation-free alternative to the GC/FID HSE method 83/2, developed by the Health and Safety Executive UK. The resin acid 7-OXO was measured as a marker for oxidised resin acids, which are known to be the main contact allergens in colophonium. The found detection limits were 0.42 ng m(-3) for 7-OXO, 5.2 ng m(-3) for DHAA and 9.4 ng m(-3) for AA, respectively, which are considerably lower than with the GC/FID method (24, 115 and 89 ng m(-3)). The two methods correlated well, although consistently and significantly lower concentrations of 7-OXO were detected with LC/MS. The higher concentration of this compound with MDHS 83/2 is suggested to be an artefact from the derivatisation step in the presence of soluble wood dust remains.
The purpose of the current study was to investigate spatial and seasonal variation of dioxin and dioxin-like PCB (dl-PCB) content in herring sampled along the northern Baltic Sea coast and map out risk zones for dioxins and dl-PCBs. We further aimed to investigate relationships between congener distribution (pattern) and sampling location and season. The results showed that there were distinct geographical differences in concentrations of dioxins, dibenzofurans and dl-PCBs along the Swedish coast, from the Bothnian Bay to north Baltic Proper, with the highest levels detected in the southern Bothnian Sea. The majority of the locations showed concentrations above the prescribed maximum for dioxin residues (4 TEQ pg g–1 wet weight [w.w.]). If all the edible parts of the fish (muscle, subcutaneous fat and skin) are considered, the estimated concentrations exceeded the prescribed maximum level in the whole study area for herring collected during spring–summer. Concentrations in herring caught during spring–summer compared to concentrations in herring sampled in the autumn indicated seasonal variation. The pattern analysis showed a variation in relative congener concentration at the different sampling locations (spring–summer). Pattern differences were also noticed between seasons.
New sampling methods are needed to simplify and enable frequent monitoring of workers' exposure to polycyclic aromatic hydrocarbons (PAHs). The sampler needs to fulfil some key operational requirements for occupational exposure assessments: (i) be usable as a personal sampler; (ii) work over 8 h exposure time; (iii) sequester PAHs both in gas and particle phase, (iv) yield reliable estimates of air concentrations. Here, a new smaller design of the traditional polyurethane foam (PUF) passive air sampler (PAS) (i.e. a 'mini-PUF') was introduced and assessed against these requirements in sites with elevated PAH concentrations. The exposure times were 2 weeks and 8 hours. The obtained sampling rates (R-values) were not significantly different between gas phase (0.4-3.3 m(3) day(-1), 0.3-2.3 L min(-1)) and particle associated PAHs (0.5-1.9 m(3) day(-1), 0.4-1.3 L min(-1)). The accuracy in estimating air concentrations was within +/-25% from the active sampler for half of the PAHs for the mini-PUF under 8 h exposures. Significant correlations (p < 0.003) were found between personally deployed mini-PUFs and a co-deployed personal active sampling method. This together with the low costs and ease-of-use of the mini-PUF encourage application in exposure assessments.
Growth of different microorganisms is often related to dampness in buildings. Both fungi and bacteria produce complicated mixtures of volatile organic compounds that include hydrocarbons, alcohols, ketones, sulfur- and nitrogen-containing compounds etc. Microbially produced substances are one possible explanation of odour problems and negative health effects in buildings affected by microbial growth. A mixture of five fungi, Aspergillus versicolor, Fusarium culmorum, Penicillium chrysogenum, Ulocladium botrytis and Wallemia sebi were grown on three different humid building materials (pinewood, particle board and gypsum board) and on one synthetic medium. Six different sampling methods were used, to be able to collect both non-reactive volatile organic compounds and reactive compounds such as volatile amines, aldehydes and carboxylic acids. Analysis was performed using gas chromatography, high-performance liquid chromatography and ion chromatography, mass spectrometry was used for identification of compounds. The main microbially produced metabolites found on pinewood were ketones (e.g. 2-heptanone) and alcohols (e.g. 2-methyl-1-propanol). Some of these compounds were also found on particle board, gypsum board and the synthetic medium, but there were more differences than similarities between the materials. For example, dimethoxymethane and 1,3,5-trioxepane and some nitrogen containing compounds were found only on particle board. The metabolite production on gypsum board was very low, although some terpenes (e.g. 3-carene) could be identified as fungal metabolites. On all materials, except gypsum board, the emission of aldehydes decreased during microbial growth. No low molecular weight carboxylic acids were identified.
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.
The purpose of this study was to develop a sensitive and specific method for quantifying dermal exposure to the resin acids 7-oxodehydroabietic acid (7-OXO), dehydroabietic acid (DHAA), abietic acid (AA), and pimaric acid (PA). In addition the method was evaluated in occupational settings during production of wood pellets. Tape-strips were spiked with the substances to evaluate the recovery of the acids from the tape. The removal efficiency of the tape was assessed by tape-stripping a specified area on a glass plate spiked with resin acids. The recovery of the acids from human skin in vivo was evaluated by applying acids in methanol onto the skin of volunteers. Occupational dermal exposure to the resin acids was assessed by tape-stripping the skin of workers involved in the production of wood pellets. The resin acids were analyzed by liquid chromatography mass spectrometry (LC-MS). The limit of detection was 15 pg (7-OXO), 150 pg (DHAA), 285 pg (AA) and 471 pg (PA) per injection. The recovery from spiked tapes was in general 100%. The removal efficiency of the tape was 48-101%. Recovery tests from human skin in vivo showed a mean recovery of 27%. Quantifiable amounts of resin acids were observed on four different skin areas with an increase in exposure during a work shift. This study shows that occupational dermal exposure to resin acids can be assessed by tape-stripping and quantified by LC-MS.
The dermal exposure to the suspected allergenic monoterpenes [small alpha]-pinene, [small beta]-pinene and [capital Delta](3)-carene was assessed with a patch sampling technique. The patch used was made of activated charcoal sandwiched between two layers of cotton cloth. Patches were fastened at 12 different spots on a sampling overall and at the front of a cap to estimate the potential exposure of the body. Fastening two patches on a cotton glove, one patch representing the dorsal side and one patch representing the palm of the hand respectively, assessed the exposure on the hands. Sampling was carried out during collecting of pine and spruce boards in sawmills and during sawing of pine wood pieces in joinery shops respectively. The potential dermal exposure of the total body was 29.0-1 890 mg h(-1) with a geometric mean (GM) of 238 mg h(-1) during sawing. During collecting the GM was estimated to 100 mg h(-1) with a range of 12.2-959 mg h(-1). The hands had a mean exposure of 9.24 mg h(-1) during sawing and 3.25 mg h(-1) during collecting respectively. The good correlation between the mass of contamination on the individual body parts and the potential body exposure indicates that sampling can be performed on one body part to give a good estimation of the potential body exposure. Monoterpenes were detected at patches fastened underneath the protective clothing indicating a contamination of the skin of the worker. The patch used may overestimate the dermal exposure.
This article addresses problems that complicate attempts to compare methods when several factors may be associated with an effect, but it is not known which factors are relevant. Chemicals that may contribute to 'sick building syndrome' (SBS), and thus should be sampled in investigations of SBS, are not currently known. A study was undertaken to compare the utility of three adsorbents (Carbopack B, Chromosorb 106 and Tenax TA) for detecting differences in personal chemical exposure to volatile organic compounds in indoor air, between persons with and without SBS symptoms (cases and controls). On the basis of office workers' responses to a questionnaire, 15 cases and 15 controls were chosen. They simultaneously carried diffusive samplers with adsorbents during a week at work, and the acquired samples were analysed by gas chromatography/mass spectrometry (GC/MS). The adsorbents were then compared in terms of their ability to separate cases and controls in partial least square discriminant analysis (PLS-DA) models. This method of comparison takes into account detected differences in chemical exposure between cases and controls measured with the different adsorbents. Tenax TA gave the best PLS-DA models for separating cases and controls, but a combination of measurements with Tenax TA and Carbopack B gave better PLS-DA models than models based on measurements from either adsorbent alone. Adding measurements from Chromosorb 106 did not improve the results.
A diffusive sampler for NO2, Willems badge, was validated in laboratory experiments and field tests. The collecting reagent for NO2 in the sampler is triethanolamine, and the analysis is based on a modified colorimetric method, the
Saltzman method. The analysis was performed by a flow injection analysis (FIA) technique. The sampling rate for the sampler was determined to be 40.0 ml min−1. There was no effect of NO2 concentration or relative humidity on sampling rate, and the influence of sampling time was found to be small. The detection limit was 4 mg m−3 for a 24 h
sample. The capacity is high enough to allow sampling of 150 mg m−3 for 7 days, which is twice the recommended Swedish short-term (24 h) guideline value as a 98-percentile over 6 months. In field tests, the sampler performedwell, even at wind speeds higher than 2 m s−1, and at low temperatures. The overall uncertainty of the method was 24%. The sensitivity and capacity of the method also make it suitable for personal sampling for 2–8 h in working environments.
A small-scale field trial in Umeå, Sweden with Ogawa samplers and a chemiluminescence instrument indicated that the NO(2) concentration was underestimated with respect to the reference monitor, if calculated according to the manufacturer's Ogawa sampling protocol. By co-locating Ogawa samplers and reference monitors at six sites in two Swedish cities, uptake rates were determined for NO(2) and NO(x) better applicable to the Swedish conditions and climate. The concentrations of NO(2) and NO(x) calculated according to the instruction manual of the sampler and using the field-determined uptake rates were compared with values derived from chemiluminescence monitors for each week over which samples were taken. When calculated according to the manufacturer's suggested protocol, the Ogawa sampler underestimated the NO(2) concentrations by 9.1% on average for all samples (N = 53), with respect to the reference monitor. In contrast, NO(x) concentrations were overestimated by a mean value of 15% for all samples (N = 45). By using the field determined uptake rates for the calculation of NO(2) and NO(x) a better estimation of the concentrations was obtained. The ratio between concentrations determined with the Ogawa samplers and chemiluminescence monitors was then 1.02 for all measurements of NO(2) and 1.00 for NO(x). Precision, expressed as the mean coefficient of variation, was 6.4% for six, 6-replicate measurements of NO(2) and 3.7% for five, 6-replicate measurements of NO(x).
Exposure measurements should be performed as close as possible to the nose and mouth for a more correct assessment of exposure. User-friendly sampling equipment, with a minimum of handling before, during and after measurement, should not affect ordinary work. In diffusive (passive) sampling, no extra equipment as sampling pumps is needed, making the measurements more acceptable to the user. The diffusive samplers are normally attached on a shoulder, on a breast-pocket or on the lapel. There are, however, difficulties if true breathing-zone sampling is to be performed, since available diffusive samplers normally cannot be arranged close to the nose/mouth. The purpose of this work was to study the performance of a miniaturized tube type diffusive sampler attached to a headset for true breathing-zone sampling. The basis for this miniaturization was the Perkin Elmer ATD tube. Both the size of the tube and the amount of adsorbent was decreased for the miniaturized sampler. A special tube holder to be used with a headset was designed for the mini tube. The mini tube is thermally desorbed inside a standard PE tube. The new sampler was evaluated for the determination of styrene, both in laboratory experiments and in field measurements. As reference method, diffusive sampling with standard Perkin Elmer tubes, thermal desorption and gas chromatographic (GC) analysis was used. The sampling rate was determined to 0.356 mL min-1 (CV 9.6%) and was not significantly affected by concentration, sampling time or relative humidity.
Eleven organophosphorus compounds (OPs) that are used as plasticizers and flame retardants were analysed in duplicate samples of indoor air from 17 domestic and occupational environments. Solid-phase extraction (SPE) columns were used as adsorbents and analysis was performed using GC with a nitrogen phosphorus selective detector. The total amounts of OPs in the air samples ranged between 36 and 950 ng m(-3); tris(chloropropyl) phosphate (TCPP) and tris(2-chloroethyl) phosphate (TCEP) being the most abundant (0.4 to 730 ng m(-3)), followed by tributyl phosphate (0.5-120 ng m(-3)). Public buildings tended to have about 3-4 times higher levels of OPs than domestic buildings. The relative amounts of individual OPs varied between the sites and generally reflected the building materials, furniture and consumer products used in the sampled environments. Potential sources of these compounds include, inter alia, acoustic ceilings, upholstered furniture, wall coverings, floor polish and polyvinylchloride floor coverings. A correlation was observed between the TCEP concentrations in the air in the sampled environments and previously reported concentrations in dust, but no such correlation was seen for the heavier and less volatile tris(2-butoxyethyl) phosphate (TBEP). Based on estimated amounts of indoor air inhaled and dust ingested, adults and children in the sampled environments would be exposed to up to 5.8 mu g kg(-1) day(-1) and 57 mu g kg(-1) day(-1) total OPs, respectively.
The levels and relative proportions of 11 organophosphorus flame retardants and plasticizers (OPs), some of which are reportedly toxic to aquatic organisms, were investigated in human breast milk and samples of fish and mussels from Swedish lakes and coastal areas in order to assess spatial differences in environmental exposure and spatial and temporal differences in human exposure. Some of the biota samples were collected at locations with known potential sources of OPs, but most were collected in background locations. Tris-2-chloroisopropyl phosphate (TCPP) and triphenyl phosphate (TPP) dominated in the biota with levels ranging from 170 to 770 ng g-1 for TCPP in perch and between 21 and 180 ng g-1 for TPP. In milk samples, TCPP (median 45 ng g-1) and tributyl phosphate (median 12 ng g(-1)) were the most frequently occurring OPs. Among samples of fish from background locations, the concentrations and profiles of most OPs were quite similar, indicating that their sources were diffuse. However, in fish from sample locations near known sources, there were marked differences in OP concentrations and profiles. Fish from a stream receiving surface water from Arlanda airport displayed high levels of OPs (10 200 ng g-1) that are commonly used in aircraft hydraulic fluids. Fish collected at points 1 or 2 km downstream of sewage treatment plants showed significantly higher levels of tris(2-butoxyethyl) phosphate (TBEP), one of the most typically abundant OP in effluents from such plants. In the milk samples obtained from women in different towns no distinct differences were detected in OP concentrations or profiles. However, the levels of TBEP tended to be higher in milk collected 10 years ago than in milk collected more recently. However, human exposure to OPs through eating fish or to breastfeeding babies seems to be of minor importance in relation to other potential sources, such as indoor dust inhalation and ingestion.
As a complement to traditional exposure assessment, monitoring deposition of aerosols can be a simple and quick screening method for identifying deposited aerosols. In this presentation examples of screening studies, based on wipe sampling in combination with adequate analytical techniques, are described. These screening methods are rapid, simple and easy to carry out. The examples given in this presentation show a broad applicability and the methods are proven useful for assessing aerosol distribution in the workplace as well as to identify target spots for more extensive assessment of a worker's exposure situation.
The Nordic Network on Isocyanates (NORDNI) is financed by the Nordic Council of Ministers and is under the administration of Prof. Yngvar Thomassen and co-workers. National Institute of Occupational Health, Norway. The aim of NORDNI is to establish a broad network between the Nordic National Institutes of Occupational Health working within the field of isocyanate exposure and strategies for sampling and determination of isocyanates in workroom atmospheres. This viewpoint article summarizes the resolutions that were established at the 1st NORDNI consensus meeting arranged in Frøya, Norway, 31st August-2nd September, 2001. The consensus platform from the 1st NORDNI meeting was presented at the 4th International Symposium on Modern Principles of Air Monitoring, Lillehammer, Norway, 3-7 February, 2002.
Solution (31)phosphorus NMR spectroscopy and sequential fractionation were used to follow diagenetic changes in phosphorus forms during decomposition of settling seston in Lake Nordborg, a shallow eutrophic lake in Denmark. In a decomposition experiment, seston released >60% of their total phosphorus during similar to 50 days incubation, although seston collected during summer contained more phosphorus and released it over a longer period compared to seston collected during spring. Seston decomposition increased concentrations of potentially bioavailable polyphosphate and phosphodiesters, but also promoted the formation of refractory phosphorus forms that might be buried permanently in the sediment. Combining these results with in situ measurements of phosphorus concentrations in lake water and sediment traps revealed that the release from settling seston plays only a minor role in the accumulation of phosphorus in the hypolimnion of Lake Nordborg.
In order to encourage more exposure measurements to be performed, a formic acid gas-phase biosensor has been developed for this purpose. In the present paper, an enzyme based biosensor has been validated with respect to analyte selectivity and on-site use. To ensure that the sampler developed measures the compound of interest the biosensor was exposed to three near structural homologues to formic acid, i.e. acetic acid, methanol and formaldehyde. These vapours were generated with and without formic acid and the only compound that was found to have an effect on the performance of the biosensor, albeit a small one, was acetic acid. The field test was performed in a factory using formic acid-containing glue for glulam products. In parallel to the measurements with the biosensor a well defined reference method was used for sampling and analysing formic acid. It was found that the biosensor worked satisfactorily in this environment when used in a stationary position. It was also shown that the biosensor could determine formic acid vapour concentrations down to 0.03 mg m−3.
A systematic investigation on interferences in the determination of unsaturated aldehydes and ketones using the 2,4-dinitrophenylhydrazine (DNPH) method is described. Acrolein, crotonaldehyde, methacrolein and 1-buten-3-one are derivatized with DNPH in the presence of an acidic catalyst to form the respective hydrazones. The unstable hydrazones react with excess reagent to form adducts. These are identified by high-performance liquid chromatography (HPLC)-mass spectrometry and spectroscopic techniques after cryogenic fraction collection of the adducts. The quantification of the unsaturated carbonyls with the DNPH method remains difficult. N-Methyl-4-hydrazino-7-nitrobenzofurazan (MNBDH) was used as an alternative reagent for this purpose. As with DNPH, the formation of a side product is observed. In contrast to DNPH, the alteration of the pH immediately after sampling leads to only one reaction product, which is stable and storable in solution at 4 degrees C for 2 days.
In the study reported here semipermeable membrane devices (SPMDs) were used to sample 28 PAHs and 19 PCBs in the gas phase in 15 single-family houses located in an area where domestic wood burning is widespread. Eight of the households used wood burning appliances whereas the others used other systems for residential heating. Most of the studied compounds were found in the houses: the PAHs at levels that were similar to or slightly higher than published SPMD-sampled levels for background or urban sites in Sweden, and the PCBs at levels that were somewhat lower than those recently found in both indoor and outdoor urban locations. A principal component analysis revealed that wood-burning heating systems may contribute to PAHs in indoor air. The sources may be emissions indoors or penetration from outdoors. The convenience of SPMD technology facilitates its use for semi-quantitative screening and monitoring of various persistent organic compounds indoors in dwellings and working environments.
Diffusive samplers for monitoring of air quality are user-friendly devices that can normally be operated by the user himself. Hence these samplers are suitable for self-assessment. Practical and work organisational aspects of self-assessment of chemical exposure were studied in different occupational settings. It was found that the diffusive sampler used in these studies, the Perkin-Elmer tube in combination with thermal desorption, worked well for the purpose and could be correctly handled by the individuals using it. The results from self-assessments agreed well with expert measurements carried out by an occupational hygienist. However, in order to obtain a sustainable system of self-assessment strong organizational support is needed.
A diffusive sampling method for determination of methyl isocyanate in air has been developed. A glass fibre filter impregnated with 1-(2-methoxyphenyl)piperazine in a commercially available diffusive sampling device was used to collect methyl isocyanate and the derivative formed was analysed with LC-MS/MS. The sampling rate was determined to be 15.6 ml min(-1), with a relative standard deviation of 7.3%. The sampler was validated for sampling periods from 15 min to 8 h, for relative humidities from 20% to 80% and for concentrations from I to 46 microg m(-3). A field validation was also made and the diffusive sampling results showed no difference compared to a pumped reference method. The impregnated filters have to be stored apart from the diffusive sampler housing and loaded into the sampler prior to each sampling.
Given the increasing interest in using peat bogs as archives of atmospheric metal deposition, the lack of validated sample preparation methods and suitable certified reference materials has hindered not only the quality assurance of the generated analytical data but also the interpretation and comparison of peat core metal profiles from different laboratories in the international community. Reference materials play an important role in the evaluation of the accuracy of analytical results and are essential parts of good laboratory practice. An ombrotrophic peat bog reference material has been developed by 14 laboratories from nine countries in an inter-laboratory comparison between February and October 2002. The material has been characterised for both acid-extractable and total concentrations of a range of elements, including Al, As, Ca, Cd, Cr, Cu, Fe, Hg, Mg, Mn, Na, Ni, P, Pb, Ti, V and Zn. The steps involved in the production of the reference material (i.e. collection and preparation, homogeneity and stability studies, and certification) are described in detail.
Cladosporium is one of the most common airborne molds found in indoor and outdoor environments. Cladosporium spores are important aeroallergens, and prolonged exposure to elevated spore concentrations can provoke chronic allergy and asthma. To accurately quantify the levels of Cladosporium in indoor and outdoor environments, two real-time PCR systems were developed in this study. The two real-time PCR systems are highly specific and sensitive for Cladosporium detection even in a high background of other fungal DNAs. These methods were employed to quantify Cladosporium in aerosols of five different indoor environments. The investigation revealed a high spore concentration of Cladosporium (10(7) m(-3)) in a cow barn that accounted for 28-44% of the airborne fungal propagules. In a countryside house that uses firewood for heating and in a paper and pulp factory, Cladosporium was detected at 10(4) spores m(-3), which accounted for 2-6% of the fungal propagules in the aerosols. The concentrations of Cladosporium in these three indoor environments far exceeded the medical borderline level (3000 spores m(-3)). In a power station and a fruit and vegetable storage, Cladosporium was found to be a minor component in the aerosols, accounted for 0.01-0.1% of the total fungal propagules. These results showed that monitoring Cladosporium in indoor environments is more important than in outdoor environments from the public health point of view. Cladosporium may not be the dominant fungi in some indoor environments, but its concentration could still be exceeding the threshold value for clinical significance. The methods developed in this study could facilitate accurate detection and quantification of Cladosporium for public health related risk assessment.