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.     

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.     

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.     

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.     

Penetration patterns of monomeric and polymeric 1,6-hexamethylene diisocyanate monomer in human skin

We investigated penetration patterns of monomeric and polymeric 1,6-hexamethylene diisocyanate (HDI), experimentally and as part of commercial products, in excised full-thickness human skin at 5, 10, 30, or 60 min after exposure. We observed that both monomeric and polymeric HDI were readily absorbed into the skin and that the clearcoat composition affects the penetration rate of the individual isocyanates. The short-term absorption rates for HDI monomer, biuret, and isocyanurate were determined and used to estimate the exposure time required to reach a body burden equal to the American Conference of Governmental Industrial Hygienists (ACGIH) inhalation threshold limit value (TLV) or Oregon State occupational exposure limit (OEL). Oregon is the only government entity in the United States to promulgate a short-term exposure limit (STEL) for HDI-based polyisocyanates biuret and isocyanurate. Based on these absorption rates for a slow-drying clearcoat after 10 min (1.33 μg cm(-2) h(-1)) or 60 min (0.219 μg cm(-2) h(-1)), we calculated that 6.5 and 40 min dermal exposure, respectively, is required to achieve a dose of HDI equivalent to the ACGIH TLV. For biuret, the time to achieve a dose equivalent to the Oregon OEL for slow-drying clearcoat was much shorter (<31 min) than that for fast-drying clearcoat (618 min). Isocyanurate had the shortest skin absorption times regardless of clearcoat formulation (14 s-1.7 min). These results indicate that the dose received through dermal exposure to HDI-containing clearcoats has a significant potential to exceed the dose equivalent to that received through inhalation exposure at established regulatory limits. A critical need exists to monitor dermal exposure quantitatively in exposed workers, to use proper protective equipment to reduce dermal exposure, and to re-evaluate regulatory exposure limits for isocyanates.     

Determination of isocyanates, aminoisocyanates and amines in air formed during the thermal degradation of polyurethane

An air sampling method for the determination of isocyanates, aminoisocyanates and amines formed during the thermal degradation of polyurethane (PUR) is presented. The method is based on the collection of air samples using impinger flasks containing di-n-butylamine (DBA) in toluene with a glass fibre filter in series. Isocyanates are derivatized with DBA to urea derivatives, and amines are derivatized in a subsequent work-up procedure with ethyl chloroformate (ET) to carbamate esters. Amine, aminoisocyanate and isocyanate derivatives were characterized using liquid chromatography-time of flight mass spectrometry (LC-TOFMS) and liquid chromatography-chemiluminescent nitrogen detection (LC-CLND). Quantification was performed by LC-MS, monitoring molecular ions [MH]+ in the electrospray mode. The instrumental detection limits for amines, aminoisocyanates and isocyanates were in the ranges 30-40, 2-3 and 3-70 fmol, respectively. Thermal degradation products of PUR were observed in high concentrations during welding in district heating pipes and PUR-coated metal sheets. Eleven isocyanates, three amines and five aminoisocyanates were identified. The concentrations of isocyanates, aminoisocyanates and amines in samples collected in the smoke close to the welding spot were in the ranges 150-650, 4-290 and 1-70 ppb, respectively. In samples collected in the breathing zone, isocyanates and aminoisocyanates were observed in the ranges 9-120 and 4-19 ppb, respectively. The compounds were present in both gas and particle phases. Volatile compounds dominated in the gas phase, whereas less volatile compounds dominated in the particle phase. The method presented makes it possible to sample and determine amines and aminoisocyanates, in addition to isocyanates. The need to monitor these compounds is clearly illustrated by the high concentrations found during the thermal degradation of PUR.     

Soil heterogeneity effects on acid flushing of lead-contaminated soil

A compact model for evaluation of acid flushing of heavy-metal-contaminated soil in a small-scale on-site treatment plant is proposed. The model assumes that the soil was re-packed in a container after excavation resulting in a soil structure with heterogeneous and random physical and chemical properties. To evaluate the effects of heterogeneity on the efficiency of contaminant removal by acid flushing, a numerical analysis of lead transport in the heterogeneous soil medium was performed. The model examines cation exchange and surface complexation reactions involving three cations (Ca, Pb, and H) and one anion (Cl) in both dissolved and exchangeable forms, two Pb surface complexes (SOPbCl and SOPbOH), and one Cl surface complex (SOH₂Cl). The transport of these species during flushing with acid in a synthetically generated two-dimensional heterogeneous soil was simulated in the model. Results indicated that the flushing fluid preferentially followed pathways with large permeability. The heterogeneous cation exchange capacity (CEC) distribution and surface complexation sites had a significant effect on the transport of dissolved species. Because the CEC was set to a relatively low value, Pb was adsorbed mainly as surface complexes (SOPbCl and SOPbOH). Simulation results suggest that blocks of low hydraulic conductivity located in the upper part of the model domain greatly impede solute transport. Ponding conditions did not significantly affect the efficiency of decontamination. The model and its results are useful in the design of small-scale treatment plants for acid flushing.     

Evaluation of the NIOSH draft method 5525 for determination of the total reactive isocyanate group (TRIG) for aliphatic isocyanates in autobody repair shops. National Institute for Occupational Safety and Health

This paper evaluates the performance of the NIOSH draft method 5525 for analysis of monomeric and TRIG aliphatic isocyanates in autobody repair shops. It was found that an optimized pH gradient enhanced noticeably the resolution and, therefore, identification of aliphatic isocyanates. Samples proved to be very stable for at least a year when stored at -13 degrees C in the freezer, and no major stability problems were found for the MAP reagent. The detector response factor RSD for selected MAP ureas was 40% in the fluorescence (FLD), 3% in the UV at 254 nm (UV254), and 1% in the UV at 370 nm (UV370). The mean FLD/UV254 and UV254/UV370 detector response ratios of standards were 31.7 (RSD = 37.8) and 17.1 (RSD = 5.4), respectively. The FLD/UV254 ratio in bulks varied from 0.41 to 1.97 times the HDI monomer ratio. The mean UV254/UV370 ratio in bulks was 16.1 (range 14.1 to 19.2, N = 38). Mean (range) recovery of 92 (91.2-93.2)% was found for the N3300 (isocyanurate) spiked on 25 mm quartz fiber filters in the range 0.07 to 2.2 microg NCO ml(-1). Mean (range) recovery for impingers was 100.7 (91.7-106.0)% for N3300 in the concentration range of 0.018 to 2.5 microg NCO ml(-1) and 81.0 (76.1-89.1)% for IPDI in the concentration range of 0.016 to 1.87 microg NCO ml(-1). Analytical method precision was 3.4% and mean bias 7.4% (range = 0-25%). The NIOSH draft method 5525 provides flexibility, enhanced sensitivity and specificity, powerful resolution, and very small compound-to-compound variability in the UV254, resulting in a more reliable identification and quantification of aliphatic isocyanates.     

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.     

Analysis of volatile organic compounds (VOCs) in sediments using in situ SPME sampling

A new method of determining the composition of sediment/soil gases and their volatile organic compound (VOC) content is described. VOCs were collected in situ from intertidal sediments in the Menai Strait and surrounding areas. The sampling was performed using a portable sampler comprising a funnel coupled to a SPME fibre. Gases were extracted from the sediments using a small vacuum pump pulling 100 mL min(-1) at atmospheric pressure. Sixty one different compounds were detected in the samples, and their fluxes and concentrations were determined. The compounds were classified into groups: halogenated, sulfur containing compounds, aldehydes, BTEXs (benzene, toluene, ethyl benzene and xylene) and aliphatic hydrocarbons. Results of principal component analysis (PCA) showed that the chemical composition of extracted gas was influenced primarily by sediment type. Muddy anoxic sediments were dominated by halogenated and sulfur containing compounds and sandy sediments had more aldehydes and BTEXs.     

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.     

Efficiency evaluation of sewage treatment plants with different technologies in Delhi (India)

Physical, chemical and microbiological efficiencies of Sewage Treatment Plants (STPs) located in Delhi's watershed in context of different treatment technologies employed in these plants have been determined. There were in all seventeen STPs treating domestic wastewater which were studied over a period of 12 months. These STPs were based on Conventional Activated sludge process (ASP), Extended aeration (Ex. Aeration), physical, chemical and biological removal treatment (BIOFORE) and oxidation pond treatment process. Results suggests that except "Mehrauli" STP which was based on Extended aeration process and "Oxidation pond", effluents from all other STPs exceeded FC standard of 10(3) MPN/100 ml for unrestricted irrigation criteria set by National river conservation directorate (NRCD). Actual integrated efficiency (IE(a)) of each STP was evaluated and compared with the standard integrated efficiency (IE(s)) based upon physical, biological and microbiological removal efficiencies depending upon influent sewage characteristics. The best results were obtained for STPs employing extended aeration, BIOFORE and oxidation pond treatment process thus can be safely used for irrigation purposes.     

Harmonized Nordic strategies for isocyanate monitoring in workroom atmospheres

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 Fr?ya, 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.     

A method for measuring dermal exposure to multifunctional acrylates

UV-curable acrylates are used increasingly for coating wood surfaces in the furniture industry. One of the active components, tripropylene glycol diacrylate (TPGDA), is known to be both an allergen and irritant to the skin. Methods to measure dermal exposure to skin irritants and allergens, such as acrylates, are insufficient for exposure assessment and there is none for this compound. The aim of this investigation was to develop a skin and surface sampling method, based on tape stripping, and a gas chromatographic method for quantitative analysis for assessing occupational skin exposure to multifunctional acrylates. Twelve adhesives were tested for their efficiency to remove TPGDA and UV-coating from a glass surface, the skin of guinea pigs and human volunteers employing the tape-stripping method in order to find the best performing tape. Variables that affect removal efficiency such as the applied dose and its retention time on the skin, tape adhesion time on the skin, and the number of strippings required to detect the contaminant from the skin were studied. Fixomull tape performed the best during sampling and analysis and had the most consistent removal efficiencies for the studied substances. The average removal efficiency with a single stripping at the 2 microliters TPGDA exposed skin sites was 85% (RSD = 14.1), and for UV-resin exposed sites 63% (RSD = 20.2). The results indicated that this method can be used for measuring dermal exposure to multifunctional acrylates efficiently, accurately, and economically. This method provides a sensitive and powerful tool for the assessment of dermal exposure to multifunctional acrylates both from the skin and from other contaminated surfaces in occupational field settings.     

Evaluation of efficiency of aircraft liquid waste treatment and identification of daily inspection indices: a case study in Changchun, China

Evaluation of the efficiency of aircraft liquid waste treatment has previously been conducted to prevent pollution of the environment. The current study aimed to provide a set of practical methods for efficient airport sanitary supervision. Aircraft liquid waste was collected at Longjia International Airport, Changchun from multiple flights. The efficiency of liquid waste treatment as well as the water quality of the wastewater processed via a second-stage wastewater facility were examined by measuring a number of physical, chemical, and biological indices. Our results indicated that treatment solely via resolvable sanitizing liquid was not sufficient. Although the contents of first-class pollutants all met the requirements of the standard criteria, the contents of a number of second-class pollutants did not satisfy these criteria. However, after further treatment via a second-stage wastewater facility installed at the airport, all indices reached second-grade requirements of the discharge standard. We suggest that daily inspection and quarantine indices at airports should include the suspension content, biological oxygen demands after 5 days, chemical oxygen demand total organic carbon content, amino nitrogen content, total phosphorous content, and the level of fecal coliforms.     

基于燃煤电厂超低排放的汞分布特性研究

为掌握超低排放改造后烟气处理装置对汞分布的影响,选择6台有代表性的超低排放火电机组进行现场测试。通过对火电机组入炉煤、炉渣、飞灰、脱硫石膏、末端烟气等样品的测试,得出不同燃烧产物中汞的分布:底渣和湿除出水的汞含量极微;电除尘底灰中的汞所占比重相对较大,平均汞含量占燃烧产物中总汞的比例可达57.97%。依据质量平衡原理,计算出不同超低排放改造工艺路线对汞的协同脱除效率为87.26%~95.60%,并分析了不同污染控制设备对汞排放的影响。     

Treatment technologies for PAH-contaminated sites: a critical review

To reduce environmental and human health risks of contaminated sites, having a comprehensive knowledge about the polycyclic aromatic hydrocarbon (PAH) removal processes is crucial. PAHs are contaminants which are highly recognized to pose threats to humans, animals, and plants. PAHs are hydrophobic and own two or more benzene rings, and hence are resistant to structural degradation. There are various techniques which have been developed to treat PAH-contaminated soil. Four distinct processes to remove PAHs in the contaminated soil, thought to be more effective techniques, are presented in this review: soil washing, chemical oxidation, electrokinetic, phytoremediation. In a surfactant-aided washing process, a removal rate of 90% was reported. Compost-amended phytoremediation treatment presented 58–99% removal of pyrene from the soil in 90 days. Chemical oxidation method was able to reach complete conversion for some PAHs. In electrokinetic treatment, researchers have achieved reliable results in removal of some specific PAHs. Researchers’ innovations in novel studies and advantages/disadvantages of the techniques are also investigated throughout the paper. Finally, it should be noted that an exclusive method or a combination of methods by themselves are not the key to be employed for remediation of every contaminated site but the field characteristics are also essential in selection of the most appropriate decontamination technique(s). The remedy for selection criteria is based on PAH concentrations, site characteristics, costs, shortcomings, and advantages.     

Determination of alkylamine permeation through protective gloves using aliphatic amine pads

A quantitative study of alkylamine permeation through a glove material using Permea-Tec aliphatic amine pads, used for the detection of chemical breakthrough of protective clothing, was performed for triethylamine following a microwave-extraction process and gas chromatographic analysis. Triethylamine exhibited > 99% adsorption on the pads at a spiking level of 729 ng (1.0 ml). Triethylamine showed recoveries from 63 to 90% (RSD < or = 5%) over the range 0.2-1.0 ml (146-729 ng) applied to pads. The ASTM F739 standard and direct permeability testing procedures were used to determine breakthrough times for five protective glove materials using triethylamine as a challenge chemical. Breakthrough times for six protective gloves were determined ranging from 40 s to > 4 h. The quantitative concentration of triethylamine on the pads following permeation through the gloves was also determined, ranging from 101 to 103 ng cm-2 (382-386 ng per pad).     

Tape-stripping as a method for measuring dermal exposure to resin acids during wood pellet production

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.