Characterization of thermally generated aerosols from polyurethane foam

Isocyanates constitute a group of highly reactive chemicals used on a large scale for the production of flexible polyurethane (PUR) foam. Exposure to isocyanates is known to produce irritation of the mucous membranes and the eyes. Isocyanates also have strong sensitizing properties and may cause occupational asthma. It is therefore important to monitor isocyanate emissions at workplaces. To obtain information for the improvement of isocyanate samplers and for health risk assessments of exposure, the emitted aerosol from two types of flexible PUR foam subjected to thermal degradation was characterized. Particle size distribution and toluene diisocyanate (TDI) concentration in the emitted aerosols were measured. Thermal degradation of flexible PUR foam at temperatures from 250 to 300 degrees C produced an aerosol with a geometric mean particle diameter of 30-50 nm. Between 5% and 9% of the PUR foam was emitted as TDI, and 2% to 6% of TDI monomers were found in the particle phase under the experimental conditions used. The 2,6-TDI isomer was more abundant in the gas phase than in the particle phase.     

Biological monitoring of aromatic diisocyanates in workers exposed to thermal degradation products of polyurethanes

Exposure to diisocyanates was assessed by biological monitoring among workers exposed to the thermal degradation products of polyurethanes (PURs) in five PUR-processing environments. The processes included grinding and welding in car repair shops, milling and turning of PUR-coated metal cylinders, injection moulding of thermoplastic PUR, welding and cutting of PUR-insulated district heating pipes during installation and joint welding, and heat-flexing of PUR floor covering. Isocyanate-derived amines in acid-hydrolysed urine samples were analysed as perfluoroacylated derivatives by gas chromatography mass spectrometry in negative chemical ionisation mode. The limits of quantification (LOQs) for the aromatic diamines 2,4- and 2,6-toluenediamine (2,4- and 2,6-TDA) and 4,4'-methylenedianiline (4,4'-MDA) were 0.25 nmol l(-1), 0.25 nmol l(-1) and 0.15 nmol l(-1), respectively. The LOQ for the aliphatic diamines hexamethylenediamine (HDA), isophoronediamine (IpDA) and 4,4'-diaminodicyclohexyl methane (4,4'-DDHM) was 5 nmol l(-1). TDA and MDA were detected in urine samples from workers in car repair shops and MDA in samples from workers welding district heating pipes. The 2,4-TDA isomer accounted for about 80% of the total TDA detected. No 2.6-TDA was found in the urine of non-exposed workers. The highest measured urinary TDA and MDA concentrations were 0.79 nmol mmol(-1) creatinine and 3.1 nmol mmol(-1) creatinine, respectively. The concentrations found among non-exposed workers were 0.08 nmol mmol(-1) creatinine for TDA and 0.05 nmol mmol(-1) creatinine for MDA (arithmetic means). Exposure to diisocyanates originating from the thermal degradation of PURs are often intermittent and of short duration. Nevertheless, exposure to aromatic diisocyanates can be identified by monitoring diisocyanate-derived amines in acid-hydrolysed urine samples.     

Airborne thermal degradation products of polyurethene coatings in car repair shops

A methodology for workplace air monitoring of aromatic and aliphatic, mono- and polyisocyanates by derivatisation with di-n-butylamine (DBA) is presented. Air sampling was performed using midget impinger flasks containing 10 ml of 0.01 mol l(-1) DBA in toluene and a glass-fibre filter in series after the impinger flask, thereby providing the possibility of collecting and derivatising isocyanates in both the gas and particle phases. Quantification was made by LC-MS, monitoring the molecular ions [MH]+. Air samples taken with this method in car repair shops showed that many different isocyanates are formed during thermal decomposition of polyurethane (PUR) coatings. In addition to isocyanates such as hexamethylene (HDI), isophorone (IPDI), toluene (TDI) and methylenediphenyl diisocyanate (MDI), monoisocyanates such as methyl (MIC), ethyl (EIC), propyl (PIC), butyl (BIC) and phenyl isocyanate (PhI) were found. In many air samples the aliphatic monoisocyanates dominated. During cutting and welding operations, the highest levels of isocyanates were observed. In a single air sample from a welding operation in a car repair shop, the highest concentrations found were: MIC, 290; EIC, 60; PIC, 20; BIC, 9; PhI, 27; HDI, 105; IPDI, 39; MDI, 4; and 2,4-TDI and 2,6-TDI 140 microg m(-3). Monitoring the particle size distribution and concentration during grinding, welding and cutting operations showed that ultrafine particles (< 0.1 microm) were formed at high concentrations. Isocyanates with low volatility were mainly found in the particle phase, but isocyanates with a relatively high volatility such as TDI, were found in both the particle and gas phases.     

Determination of technical grade isocyanates used in the production of polyurethane plastics

A method for determination of technical grade isocyanates used in the production of polyurethane (PUR) is presented. The isocyanates in technical grade products were characterised as di-n-butylamine (DBA) derivatives using LC-MS and LC-chemiluminescent nitrogen detection (CLND) and the total isocyanate content was compared to a titration assay. For collection of isocyanates in air, an impinger-filter sampling technique with DBA as derivatisation reagent was used. Characterised DBA and nonadeuterium labelled DBA derivatives of isocyanates in technical products were used as calibration standards and internal standards, respectively, in the analysis of air samples. Three workplaces were studied where PUR products were produced either by spraying or by moulding. In both technical products and in air samples, a number of monomeric, oligomeric and prepolymeric isocyanates of e.g. methylenebisphenyl diisocyanate (MDI) and hexamethylene diisocyanate (HDI) were characterised. Several of these have not previously been described in workplace atmospheres. In the technical isocyanate products, between 69 and 102% of the NCO content determined by titration was accounted for by LC-CLND. Quantifications of a wide range of isocyanates in air samples were performed with correlation coefficients in the range 0.988-0.999 (n= 8) and the instrumental detection limits were 0.7-25 pg. At the two workplaces where MDI- and HDI isocyanurate-based products were sprayed, the isocyanate composition in the air reflected the composition in the technical product. At the workplace where a MDI-based product was used in a moulding process, only the monomeric isocyanates were found in the air. The advantage of using characterised technical grade isocyanates as analytical standards was clearly demonstrated and the possibility of using index compounds when monitoring isocyanate exposure is discussed.     

Relationship between environmental exposure to toluene,xylene and ethylbenzene and the expired breath concentrations for gasoline service workers

This study evaluated the relationship between the breath concentrations of, and personal exposure to, toluene, xylene and ethylbenzene of thirty workers from ten gasoline stations. Personal exposure air samples and workplace samples were collected simultaneously. Each subject provided a sample of exhaled breath after his or her personal exposure air was sampled. Twenty-five personal air, 17 workplace and 30 breath samples were collected in this study. Results indicated that breath concentrations of toluene and xylene were significantly correlated with personal monitoring concentrations. Furthermore, multiple regression analysis showed that exhaled toluene levels were highly influenced by personal toluene concentrations and the amount of personal gasoline sold (r2 = 0.762), while exhaled xylene levels depended on wind speed and personal xylene exposure concentrations (r2 = 0.665). Exhaled ethylbenzene levels were too low to present a relationship between concentrations and personal exposure levels. The exhaled toluene, xylene and ethylbenzene concentrations ranged from 4.3 to 41.8, 0.9 to 13.9, and 0.2 to 6.5 ppb, and the corresponding personal monitoring concentrations ranged from 60.3 to 572.3, 16.4 to 156.6, and 10.7 to 136.6, respectively. The average number of symptoms per person, according to neurotoxic questionnaire 16 (abbreviated as Q16) was 4.1 and six workers showed over six symptoms in Q16. This study suggests that exhaled toluene and xylene levels are suitable for use as biological exposure indices even at the ppb-level of exposure. Gasoline service workers are exposed to high levels of volatile organic compounds (VOCs) and the potential threats to their neurological systems deserve further investigation.     

Indoor air pollution evaluation with emphasize on HDI and biological assessment of HDA in the polyurethane factories

Today, many raw materials used in factories may have a dangerous effect on the physiological system of workers. One of them which is widely used in the polyurethane factories is diisocyanates. These compounds are widely used in surface coatings, polyurethane foams, adhesives, resins, elastomers, binders, and sealants. Exposure to diisocyanates causes irritation to the skin, mucous membranes, eyes, and respiratory tract. Hexamethylene diamine (HDA) is metabolite of hexamethylene diisocyanate (HDI). It is an excretory material by worker’s urine who is exposed to HDI. Around 100 air samples were collected from five defined factories by midget impinger which contained dimethyl sulfoxide absorbent as a solvent and tryptamine as reagent. Samples were analyzed by high-performance liquid chromatography with EC\UV detector using NIOSH 5522 method of sampling. Also, 50 urine samples collected from workers were also analyzed using William’s biological analysis method. The concentration of HDI into all air samples were more than 88 xxxμg/m³, and they have shown high concentration of pollutant in the workplaces in comparison with NIOSH standard, and all of the workers’ urine were contaminated by HDA. The correlation and regression test were used to obtain statistical model for HDI and HDA, which is useful for the prediction of diisocyanates pollution situation in the polyurethane factories.     

An FTIR investigation of isocyanate skin absorption using in vitro guinea pig skin

Isocyanates may cause contact dermatitis, sensitization and asthma. Dermal exposure to aliphatic and aromatic isocyanates can occur in various exposure settings. The fate of isocyanates on skin is an important unanswered question. Do they react and bind to the outer layer of skin or do they penetrate through the epidermis as unreacted compounds? Knowing the kinetics of these processes is important in developing dermal exposure sampling or decontamination strategies, as well as understanding potential health implications such exposure may have. In this paper the residence time of model isocyanates on hairless guinea pig skin was investigated in vitro using attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectrometry. Model isocyanates tested were octyl isocyanate, polymeric hexamethylene diisocyanate isocyanurate (pHDI), polymeric isophorone diisocyanate isocyanurate (pIPDI) and methylenediphenyl diisocyanate (MDI). Isocyanates in ethyl acetate (30 microL) were spiked directly on the skin to give 0.2-1.8 micromol NCO cm(-2) (NCO = -N=C=O), and absorbance of the isocyanate group and other chemical groups of the molecule were monitored over time. The ATR-FTIR findings showed that polymeric isocyanates pHDI and pIPDI may remain on the skin as unreacted species for many hours, with only 15-20% of the total isocyanate group disappearing in one hour, while smaller compounds octyl isocyanate and MDI rapidly disappear from the skin surface (80+% in 30 min). Isocyanates most likely leave the skin surface by diffusion predominantly, with minimal reaction with surface proteins. The significance of these findings and their implications for dermal exposure sampling and isocyanate skin decontamination are discussed.     

Exposure to airborne isocyanates and other thermal degradation products at polyurethane-processing workplaces

The thermal degradation products of polyurethanes (PURs) and exposure to isocyanates were studied by stationary and personal measurements in five different occupational environments. Isocyanates were collected on glass fibre filters impregnated with 1-(2-methoxyphenyl)piperazine (2MP) and in impingers containing n-dibutylamine (DBA) in toluene. connected to a glass fibre postfilter. The derivatives formed were analysed by liquid chromatography: 2MP derivatives with UV and electrochemical detection and DBA derivatives with mass spectrometric detection. The release of aldehydes and other volatile organic compounds into the air was also studied. In a comparison of the two sampling methods, the 2MP method yielded about 20% lower concentrations for 4,4'-methylenediphenyl diisocyanate (MDI) than did the DBA method. In car repair shops, the median concentration of diisocyanates (given as NCO groups) in the breathing zone was 1.1 microg NCO m(-3) during grinding and 0.3 microg NCO m(-3) during welding, with highest concentrations of 1.7 and 16 pg NCO m(-3), respectively. High concentrations of MDI, up to 25 and 19 microg NCO m(-3), respectively, were also measured in the breathing zone during welding of district heating pipes and turning of a PUR-coated metal cylinder. During installation of PUR-coated floor covering, small amounts of aliphatic diisocyanates were detected in the air. A small-molecular monoisocyanate, methyl isocyanate, and isocyanic acid were detected only during welding and turning operations. The diisocyanate concentrations were in general higher near the emission source than in the workers' breathing zone. A sampling strategy to evaluate the risk of exposure to isocyanates is presented.     

Quantitative determination of hexamethylene diisocyanate (HDI), 2,4-toluene diisocyanate (2,4-TDI) and 2,6-toluene diisocyanate (2,6-TDI) monomers at ppt levels in air by alkaline adduct coordination ionspray tandem mass spectrometry

Occupational exposures to isocyanates can lead to occupational asthma. Once sensitized, some workers could react to isocyanate monomers at concentrations below 1% of the Permissible Exposure Limit of 5 ppb in air. Currently available methods are not sufficiently sensitive to adequately evaluate isocyanates present at these levels in workplace air. This article describes a novel method for isocyanate determination allowing the ultratrace quantification in workplace air of hexamethylene diisocyanate, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate monomers. Sampling is performed during a complete workshift at a flow rate of 1 L min(-1) with a cassette containing a 1-(2-methoxyphenyl)piperazine-impregnated 25 mm filter. Analysis is performed using liquid chromatography hyphenated with coordination ionspray tandem mass spectrometry. The analytical method's linearity was measured for a concentration range varying from the limit of detection of 0.04-0.13 ng mL(-1), depending on the monomer, up to approximately 32 ng mL(-1) for every isocyanate monomer, all with correlation coefficients (R(2)) greater than 0.999. The analytical method's lower limit of quantification combined with an adapted sampling strategy allow the quantification of isocyanate monomers down to 0.04 ppt for an 8 h work shift when a lithium adduct is used, which is more than 300 times lower than the most sensitive method currently available. This novel method can be used to confirm the very low level of isocyanate monomers for the safe reassignment of sensitized workers and it is also useful for charting the isocyanate dispersion tail in workplace environments.     

Perfluorinated organic compounds in human blood serum and seminal plasma: a study of urban and rural tea worker populations in Sri Lanka

Concentrations and accumulation of 13 fluorinated organic compounds (FOCs) in human sera and seminal plasma were measured in an Asian developing country, Sri Lanka. Six of the FOCs, PFOS (perfluorooctanesulfonate), PFHS (perfluorohexanesulfonate), PFUnA (perfluoroundecanoic acid), PFDA (perfluorodecanoic acid), PFNA (perfluorononanoic acid) and PFOA (perfluorooctanoic acid), were detected in all of the sera samples. Measurable quantities of two main perfluorosulfonates, PFOS and PFHS, were found in all seminal plasma samples. The detection frequency of the predominant perfluoroalkylcarboxylate, PFOA, in seminal plasma was >70%. Accumulation of PFOS in sera was significantly positively correlated with PFOA, PFHS and PFNA. Positive linear regressions were also found between PFNA and PFUnA and PFNA and PFDA suggesting that these compounds may have a similar origin of exposure and accumulation. Significantly positive associations were observed for partitioning of both PFOS and PFNA between sera and seminal plasma. The accumulation of FOCs was not significantly different in sera from Colombo (urban population) and Talawakele (rural conventional tea workers). However, the Haldummulla population (rural organic tea workers) had relatively lower exposure to FOCs compared to the other two groups, urban and rural conventional tea workers. Concentrations of FOCs in Sri Lanka were similar to those reported for industrialized countries suggesting that human exposure to such chemicals is widespread even in developing countries. The novel finding of FOCs in human seminal plasma implies that further studies are needed to determine whether long-term exposure in humans can result in reproductive impairments.     

Exposure of garbage truck drivers and maintenance personnel at a waste handling centre to polycyclic aromatic hydrocarbons derived from diesel exhaust

Exposure to diesel exhaust was evaluated in summer and winter by measuring vapour and particle phase polycyclic aromatic hydrocarbons (PAHs). Fifteen PAHs were simultaneously determined from the air samples obtained from truck drivers collecting household waste and maintenance personnel at a waste handling centre. The major compounds analysed from the personal air samples of exposed workers were naphthalene, phenanthrene and fluorene. The total PAH exposure (sum of 15 PAHs) of garbage truck drivers ranged from 71 to 2,660 ng m(-3) and from 68 to 900 ng m-3 in the maintenance work. The exposure of garbage truck drivers to benzo[a]pyrene (B[a]P) ranged from the mean of 0.03 to 0.3 ng m(-3) whereas no B[a]P in control samples or in those collected from maintenance workers was detected. A statistically significant difference in diesel-derived PAH exposure between the garbage truck drivers and the control group in both seasons (in summer p = 0.0022, degrees of freedom (df) 70.5; and in winter p < 0.0001, df = 80.4) was observed. Also, a significant difference in PAH exposure between the garbage truck drivers and the maintenance workers (in summer p < 0.0001, df = 50.1; and in winter p < 0.0001, df = 44.2) was obtained.     

Biological responses of workplace particles and their association with adverse health effects on miners

Epidemiological research has demonstrated the relationship between exposure to quartz dust and an elevated risk of pneumoconiosis and possible elevated risk of cancer. The current study was designed to evaluate the biological responses of workplace particles containing crystalline silica using an in vitro cell test. Respirable particle samples were sampled from four tin mines, where the standardized mortality ratio (SMR) for pneumoconiosis was 51.6 and SMR for lung cancer was 2.2 in dust-exposed miners. Alveolar macrophages (AM) are considered as the target cells for primary dust effects. The samples were then measured at 15, 30, 60 and 120 microg particle per 10(6) AM for cytoxicity with the release of glucuronidase, lactate dehydrogenase, for reactive oxygen damage with H(2)O(2) release, and for ability to induce fibrosis using the secretion of tumor necrosis factor-alpha (TNF-alpha). Pure quartz (DQ12) and corundum were used as controls. The results showed the samples from tin mines caused a higher cytoxicity when compared to corundum, yet lower when compared to quartz. However, reactive oxygen species release (148-177 nmol/3 x 10(5) AM in high concentration of 120 microg/10(6) AM) induced by the samples were significantly higher than that induced by quartz (57 nmol/3 x 10(5) AM) and corundum (62 nmol/3 x 10(5) AM). Furthermore, particle samples induced higher TNF-alpha secretion than corundum, the samples from Limu tin mine induced much higher TNF-alpha levels than that induced by DQ12 quartz. The results from the in vitro tests help elucidate the degree of hazard of dust particles in tin mines. The in vitro reaction patterns of AM also constitute a powerful tool to monitor biological and pathogenic responses of humans following dust particle exposure.     

Polycyclic aromatic hydrocarbons with molecular weight 302 in PM 2.5 at two industrial sites in South China

Daytime and nighttime PM(2.5) samples were collected between August 5 and 16, 2009 and between January 24 and February 4, 2010 in an industrial complex site (site A) and an electronic waste recycling site (site B) to determine the seasonal and diurnal variations of 19 individual polycyclic aromatic hydrocarbons (PAHs) with molecular weight 302 (MW302) including four highly carcinogenic dibenzopyrene (DBP) isomers dibenzo[a,l]pyrene (DBalP), dibenzo[a,e]pyrene (DBaeP), dibenzo[a,i]pyrene (DBaiP), and dibenzo[a,h]pyrene (DBahP). This is the first report on DBP isomers in air particles from South China. The total concentration of PAH MW302 isomers ranged from 1.65 to 3.60 ng m(-3) in summer and 3.82 to 9.81 ng m(-3) in winter. The strongest peaks in the chromatograms of the MW302 isomers were naphtha[2,1-a]pyrene (N21aP), dibenzo[j,l]fluoranthene (DBjlF), naphtha[1,2-b]fluoranthene (N12bF), naphtha[1,2-k]fluoranthene (N12kF) and dibenzo[a,e]fluoranthene (DBaeF), constituting 52.0 to 55.4% of the total MW302 isomers. All the MW302 isomers showed notable seasonal variations. Most of the MW302 isomers in site B showed distinctive diurnal variations with higher concentrations occurring in the night. Taking into account both concentration and potency equivalence factors (PEFs), the strongest carcinogen in the analyzed samples was DBaiP, and the ratios of sum carcinogenic potency of four highly carcinogenic DBP isomers to benzo[a]pyrene (BaP) was about 0.94 in winter to 1.89 in summer, indicating the importance of DBP isomers for the risk assessment. Health risk assessment indicated that on average, 1 in 100 000 residents in the two industrial sites may have an increased risk of cancer due to PAH exposure.     

Solvent-free sampling with di-n-butylamine for monitoring of isocyanates in air

The solvent-free sampler for airborne isocyanates consisted of a polypropylene tube with an inner wall coated with a glass fibre filter, coupled in series with a 13 mm glass fibre filter. The filters were impregnated with reagent solution containing equimolar amounts of di-n-butylamine (DBA) and acetic acid. Air sampling was performed with an air flow of 0.2 l min(-1). The formed isocyanate-DBA derivatives were determined using liquid chromatography and tandem mass spectrometry. The sampler was investigated in regard to collection principle and extraction of the formed derivatives with good results. The possibility to store the sampler before sampling and to perform long-term sampling was demonstrated. Field extraction of the sampler was not necessary, as there was no difference between immediately extracted samples and stored ones (2 days). In comparative studies, the sampler was evaluated against a reference method, impinger-filter sampling with DBA as reagent. The ratios between the results obtained with the sampler and the reference in a test chamber at a relative humidity (RH) of 45% was in the range of 83-109% for isocyanates formed during thermal decomposition of PUR. At RH 95%, the range was 72-101% with the exception of isocyanic acid. In two field evaluations, the ratios for fast curing 2,4'- and 4,4'-methylene bisphenyl diisocyanate (MDI) was in the range 81-113% and for the 3-ring MDI the range was 54-70%. For the slower curing 1,6-hexamethylene diisocyanate (HDI) and HDI isocyanurate, the ratios were in the range 78-145%. In conclusion, the solvent-free sampler is a convenient alternative in most applications to the more cumbersome impinger-filter sampler.     

Analysis of HO-PCBs and PCP in blood plasma from individuals with high PCB exposure living on the Chukotka Peninsula in the Russian Arctic

A trace analytical method is presented for the analysis of hydroxylated polychlorinated biphenyl metabolites (HO-PCBs) and pentachlorophenol (PCP) in human plasma. The described methodology is a modification of a previously validated method used for PCB and organochlorine pesticide analysis. The modified method enables the combined analysis of phenolic and neutral halogenated compounds. A tandem Florisil column is used for separating the HO-PCBs and PCP from the neutral fraction, instead of the more common chemical partitioning. In the same step the neutral fraction is purified for GC analysis. The extraction of the HO-PCBs and PCP was found to be highly dependent on sufficient acidification of the sample and the polarity of the extracting solvent. Analysis of plasma samples gave recovery rates for (13)C(6)-PCP and (13)C(12)-4-HO-CB 187 of 64 and 72%, respectively. The limit of detection ranged between 2-20 pg g(-1) plasma for the HO-PCBs and 5 pg g(-1) plasma for PCP. No matrix interferences were observed in the chromatograms. In plasma samples (n = 15) from the native Chukchi people in Uelen (Russian Arctic), a population with high PCB exposure, the median ratio of sum HO-PCBs to sum PCBs was as high as 0.4 and the sum HO-PCBs and PCBs were significantly correlated (r(2) > 0.7, p < 0.01). The median sum HO-PCBs (10 congeners) was 5920 pg g(-1) plasma with 4-HO-CB 107 as the dominating congener (median: 1670 pg g(-1) plasma). The median PCP level was measured at 642 pg g(-1) plasma.     

Mixing ratios of carbonyls and BTEX in ambient air of Kolkata, India and their associated health risk

Mixing ratios of 15 carbonyls and BTEX (benzene, toluene, ethyl benzene, xylenes) were measured for the first time in ambient air of Kolkata, India at three sites from March to June 2006 and their photochemical reactivity was evaluated. Day and nighttime samples were collected on weekly basis. Formaldehyde was the most abundant carbonyl (mean concentration ranging between 14.07 microg m(-3) to 26.12 microg m(-3) over the three sites) followed by acetaldehyde (7.60-18.67 microg m(-3)) and acetone (4.43-10.34 microg m(-3)). Among the high molecular weight aldehydes, nonanal showed the highest concentration. Among the mono-aromatic VOCs, mean concentration of toluene (27.65-103.31 microg m(-3)) was maximum, closely followed by benzene (24.97-79.18 microg m(-3)). Mean formaldehyde to acetaldehyde (1.4) and acetaldehyde to propanal ratios (5.0) were typical of urban air. Based on their photochemical reactivity towards OH. radical, the concentrations of the VOCs were scaled to formaldehyde equivalent, which showed that the high molecular weight carbonyls and xylenes contribute significantly to the total OH-reactive mass of the VOCs. Due to the toxic effect of the VOCs studied, an assessment for both cancer risk and non-cancer hazard due to exposure to the population were calculated. Integrated life time cancer risk (ILTCR) due to four carcinogens (benzene, ethyl benzene, formaldehyde and acetaldehyde) and non-cancer hazard index for the VOCs at their prevailing level were estimated to be 1.42E-04 and 5.6 respectively.     

Assessment of sorbent impregnated PUF disks (SIPs) for long-term sampling of legacy POPs

Two field studies were conducted for one year using sorbent-impregnated polyurethane foam (SIP) disks for PCB and PBDE air sampling. SIP disks were introduced by Shoeib et al. (2008) as an alternative passive air sampling medium to the polyurethane foam (PUF) disk and have the advantage of a higher holding capacity for organic chemicals. The first study on SIP disks confirmed their application for measuring volatile perfluorinated compounds (PFCs) and their ability to maintain time-integrated (linear) air sampling. In this study, the suitability of the SIP disks for long-term sampling of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and hexachlorobenzene (HCB) was assessed. SIP disks were deployed at a rural site in the UK and harvested after periods ranging from 35-350 days. Atmospheric POP concentrations were monitored with a high-volume air sampler during the deployment period. Linear uptake was observed for all monitored PCBs and PBDEs over the full exposure time. Air-sampler equilibrium was observed for HCB after 6 months. In a second field study, SIP disks were deployed for one year at 10 sites on a latitudinal transect in the UK and Norway, at which air sampling has been undertaken previously with different passive air sampling media since 1994. The estimated concentrations and spatial distributions derived from the SIP disks were largely in agreement with previously reported data.     

Quantitative monitoring of dermal and inhalation exposure to 1,6-hexamethylene diisocyanate monomer and oligomers

Respiratory sensitization and occupational asthma are associated with exposure to 1,6-hexamethylene diisocyanate (HDI) in both monomeric and oligomeric forms. The monomer and polymers of diisocyanates differ significantly in their rates of absorption into tissue and their toxicity, and hence may differ in their contribution to sensitization. We have developed and evaluated a liquid chromatography/mass spectrometry (LC-MS) method capable of quantifying HDI and its oligomers (uretidone, biuret, and isocyanurate) in air, tape-stripped skin, and paint samples collected in the automotive refinishing industry. To generate analytical standards, urea derivatives of HDI, biuret, and isocyanurate were synthesized by reaction with 1-(2-methoxyphenyl)piperazine and purified. The urea derivatives were shown to degrade on average by less than 2% per week at -20 degrees C over a 2 month period in occupational samples. The average recovery of HDI and its oligomers from tape was 100% and the limits of detection were 2 and 8 fmol microl(-1), respectively. Exposure assessments were performed on 13 automotive spray painters to evaluate the LC-MS method and the sampling methods under field conditions. Isocyanurate was the most abundant component measured in paint tasks, with median air and skin concentrations of 2.4 mg m(-3) and 4.6 microg mm(-3), respectively. Log-transformed concentrations of HDI (r = 0.79, p < 0.0001) and of isocyanurate (r = 0.71, p < 0.0001) in the skin of workers were correlated with the log-transformed product of air concentration and painting time. The other polyisocyanates were detected on skin for less than 25% of the paint tasks. This LC-MS method provides a valuable tool to investigate inhalation and dermal exposures to specific polyisocyanates and to explore relative differences in the exposure pathways.     

Assessment of dermal exposure to benzene and toluene in shoe manufacturing by activated carbon cloth patches

OBJECTIVES: The aim of this investigation was to use activated carbon cloth (ACC) patches to study the probability and extent of dermal exposure to benzene and toluene in a shoe factory. METHODS: Inhalation and dermal exposure loading were measured simultaneously in 70 subjects on multiple days resulting in 113 observations. Dermal exposure loading was assessed by ACC patches attached to likely exposed skin areas (e.g. the palm of the hand and abdomen). A control patch at the chest and an organic vapor monitor (OVM) were used to adjust the hand and abdomen patches for the contribution from the air through passive absorption of benzene and toluene on the ACC patches. Systemic exposure was assessed by quantification of unmetabolized benzene (UBz) and toluene (UTol) in urine. RESULTS: Mean air concentrations for the study population were 1.5 and 7.5 ppm for benzene and toluene, respectively. Iterative regression analyses between the control patch, OVM and the dermal patches showed that only a small proportion of the ACC patches at the hand had likely benzene (n = 4; mean 133 microg cm(-2) h(-1)) or toluene (n = 5; mean 256 microg cm(-2) h(-1)) contamination. Positive patches were exclusively observed among subjects performing the task of gluing. Significant dermal exposure loading to the abdomen was detected only for toluene (n = 2; mean 235 microg cm(-2) h(-1)). No relation was found between having a positive hand or abdomen ACC patch and UBz or UTol levels. In contrast a strong association was found between air levels of benzene (p = 0.0016) and toluene (p < 0.0001) and their respective urinary levels. CONCLUSIONS: ACC patches are shown to be a useful technique for quantifying the probability of dermal exposure to organic solvents and to provide estimates of the potential contribution of the dermal pathway to systemic exposure. Using ACC patches we show that dermal exposure to benzene and toluene in a shoe manufacturing factory is probably rare, and when it occurred exposures were relatively low and did not significantly contribute to systemic exposure.     

Brominated flame retardants in plasma samples from three different occupational groups in Norway

Brominated flame retardants (BFRs) are widely used in plastics, textile coatings, electrical appliances and printed circuit boards to prohibit the development of fires. In order to investigate how exposure to BFRs is related to specific occupations, samples were obtained from Norwegian individuals working at an electronics dismantling facility, in the production of printed circuit boards, or as laboratory personnel. Nine BFRs were quantified in the plasma samples: 2,4,4'-tribromodiphenyl ether (BDE-28), 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), 2,2',4,4',6-pentabromodiphenyl ether (BDE-100), 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153), 2,2',4,4',5,6'-hexabromodiphenyl ether (BDE-154), 2,2',3,4,4',5',6-heptabromodiphenyl ether (BDE-183), 2,4,6-tribromophenol (TriBP) and tetrabromobisphenol A (TBBP-A). The BFRs were extracted from plasma using solid-phase extraction (SPE). The plasma lipids were decomposed by treatment with concentrated sulfuric acid directly on the SPE column, prior to the elution of the BFRs. Following diazomethane derivatization, the samples were analysed by gas chromatography-electron capture mass spectrometry. The subjects working at the electronics dismantling plant had significantly higher plasma levels of TBBP-A and BDE-153 compared to the other groups, and the heptabrominated congener BDE-183 was only detected in plasma from this group. TriBP was generally the most abundant BFR present, and the plasma concentrations were in the range 0.17-81 ng g-1 lipids. BDE-47 was the dominant BDE congener in all the individual samples and the levels were in the range 0.43-14.6 ng g-1 lipids. The total amounts of the seven BDEs were 8.8, 3.9 and 3.0 ng g-1 lipids for the group of electronics dismantlers, circuit board producers and laboratory personnel, respectively. Generally, large variations in the individual concentration levels were found within the groups, especially in the group of electronics dismantlers, where the relative standard deviations for BDE concentrations were in the range 23-164%. The levels of BFRs were not correlated to age or the level of 2,2',4,4',5,5'-hexachlorobiphenyl (CB-153). The present work indicates that the population in Norway is exposed to several BFRs, probably with food as a major source. The elevated level of higher brominated BDEs and TBBP-A in the plasma from the workers at the dismantling plant suggests an additional occupational exposure for these individuals. Thus, human exposure to BFRs seems to originate from a combination of different sources; however, further studies investigating plasma samples from a larger number of individuals are necessary for a more complete assessment of human exposure pathways to these environmental contaminants.