Comparison of quantification of selenocyanate and thiocyanate in cultured mammalian cells between HPLC-fluorescence detector and HPLC-inductively coupled plasma mass spectrometer.

The simultaneous detection of cyanide (CN), thiocyanate (SCN), and selenocyanate (SeCN) by a HPLC-fluorescence detector (FLD) with the post-column König reaction was recently reported. SCN and SeCN are also detectable by HPLC-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) because sulfur and selenium can be detected, respectively, without any pre- or post-treatment. ICP-MS has high sensitivity for selenium and sulfur detection and is robust to sample matrices. In this study, we compared HPLC-FLD with the post-column König reaction and HPLC-ICP-MS in terms of SCN and SeCN detection sensitivity and linearity. The limit of detection (LOD) for SCN indicated that HPLC-FLD with the post-column König reaction was 354 times more sensitive than HPLC-ICP-MS. Likewise, the LOD for SeCN indicated that HPLC-FLD was 51 times more sensitive than HPLC-ICP-MS. These results demonstrated that HPLC-FLD was a more suitable technique for SeCN and SCN detection than HPLC-ICP-MS. We previously reported that SeCN was generated in selenite-exposed mammalian cells to detoxify excess selenite. HPLC-FLD with the post-column König reaction enabled good separation and detection for quantifying SCN and SeCN in mammalian cell lines exposed to selenite. The intracellular SCN and SeCN concentrations determined by this technique suggested differences in the metabolic capacity for selenite to form SeCN among the cell lines. In addition, since the amount of intracellular SCN and SeCN were significantly decreased by pretreatment of myeloperoxidase (MPO) inhibitors, SCN and SeCN were resulted from the interaction of sulfur and selenium with endogenous CN, respectively, generated with MPO.

High Concentrations of Atmospheric Isocyanic Acid (HNCO) Produced from Secondary Sources in China.

Isocyanic acid (HNCO) is a potentially toxic atmospheric pollutant, whose atmospheric concentrations are hypothesized to be linked to adverse health effects. An earlier model study estimated that concentrations of isocyanic acid in China are highest around the world. However, measurements of isocyanic acid in ambient air have not been available in China. Two field campaigns were conducted to measure isocyanic acid in ambient air using a high-resolution time-of-flight chemical ionization mass spectrometer (ToF-CIMS) in two different environments in China. The ranges of mixing ratios of isocyanic acid are from below the detection limit (18 pptv) to 2.8 ppbv (5 min average) with the average value of 0.46 ppbv at an urban site of Guangzhou in the Pearl River Delta (PRD) region in fall and from 0.02 to 2.2 ppbv with the average value of 0.37 ppbv at a rural site in the North China Plain (NCP) during wintertime, respectively. These concentrations are significantly higher than previous measurements in North America. The diurnal variations of isocyanic acid are very similar to secondary pollutants (e.g., ozone, formic acid, and nitric acid) in PRD, indicating that isocyanic acid is mainly produced by secondary formation. Both primary emissions and secondary formation account for isocyanic acid in the NCP. The lifetime of isocyanic acid in a lower atmosphere was estimated to be less than 1 day due to the high apparent loss rate caused by deposition at night in PRD. Based on the steady state analysis of isocyanic acid during the daytime, we show that amides are unlikely enough to explain the formation of isocyanic acid in Guangzhou, calling for additional precursors for isocyanic acid. Our measurements of isocyanic acid in two environments of China provide important constraints on the concentrations, sources, and sinks of this pollutant in the atmosphere.

High levels of isocyanic acid in smoke generated during hot iron cauterization.

Pyrolysis of nitrogen containing biofuels generates isocyanic acid (ICA) and we here studied if ICA also is present in cauterization smoke. Air sampling was performed when animal technicians that had developed airway symptoms worked with dehorning. Tissue heated in a laboratory model was used to mimic cauterization. ICA in air at the workplace exceeded 10 times the national exposure limit. In the laboratory, the ICA generated per mg tissue from heated hair, horn and nail was 13.9 ± 7.8, 24.0 ± 4.1 and 32.0 ± 2.9 µg, respectively. Three workers were medically examined and two were diagnosed with asthma and a third had severe airway problem that resembled asthma. The study shows that high levels of ICA are generated during cauterization of nitrogen-containing tissue. If this could trigger airway symptoms deserves to be investigated further.

Identification of the biliary selenium metabolite and the biological significance of selenium enterohepatic circulation.

Although selenium (Se) is mainly excreted in urine, it has been reported that an unknown Se metabolite is excreted in bile. When we administered selenomethionine (SeMet), selenocyanate or selenite to rats, a common biliary selenometabolite was detected 10 min after administration. The amount of the selenometabolite originating from SeMet was less than that originating from the two inorganic Se compounds, selenocyanate and selenite, suggesting that the transformation from the methylated organic selenocompound, i.e., SeMet, was less efficient than that from the inorganic Se compounds. The common biliary selenometabolite was concretely identified as selenodiglutathione (GSSeSG) by two types of mass spectrometry, i.e., LC-inductively coupled mass spectrometry (ICP-MS) and LC-ESI-Q/TOF. The bile-drained rats had lower urinary Se levels than the sham-operated rats. In addition, the Se amounts in urine plus bile of the bile-drained rats were comparable to the Se amount in the urine of the sham-operated rats. These results suggest that the biliary selenometabolite, GSSeSG, was reabsorbed in the gut and finally excreted in urine. Enterohepatic circulation occurs to maintain Se status in the body.

Sources of isocyanic acid (HNCO) indoors: a focus on cigarette smoke.

The sources and sinks of isocyanic acid (HNCO), a toxic gas, in indoor environments are largely uncharacterized. In particular, cigarette smoke has been identified as a significant source. In this study, controlled smoking of tobacco cigarettes was investigated in both an environmental chamber and a residence in Toronto, Canada using an acetate-CIMS. The HNCO emission ratio from side-stream cigarette smoke was determined to be 2.7 (±1.1) × 10-3 ppb HNCO/ppb CO. Side-stream smoke from a single cigarette introduced a large pulse of HNCO to the indoor environment, increasing the HNCO mixing ratio by up to a factor of ten from background conditions of 0.15 ppb. Although there was no evidence for photochemical production of HNCO from cigarette smoke in the residence, it was observed in the environmental chamber via oxidation by the hydroxyl radical (1.1 × 107 molecules per cm3), approximately doubling the HNCO mixing ratio after 30 minutes of oxidation. Oxidation of cigarette smoke by O3 (15 ppb = 4.0 × 1017 molecules per cm3) and photo-reaction with indoor fluorescent lights did not produce HNCO. By studying the temporal profiles of both HNCO and CO after smoking, it is inferred that gas-to-surface partitioning of HNCO acts as an indoor loss pathway. Even in the absence of smoking, the indoor HNCO mixing ratios in the Toronto residence were elevated compared to concurrent outdoor measurements by approximately a factor of two.

Isocyanic acid (HNCO) and its fate in the atmosphere: a review.

Isocyanic acid (HNCO) has recently been identified in ambient air at potentially concerning concentrations for human health. Since its first atmospheric detection, significant progress has been made in understanding its sources and sinks. The chemistry of HNCO is governed by its partitioning between the gas and liquid phases, its weak acidity, its high solubility at pH above 5, and its electrophilic chemical behaviour. The online measurement of HNCO in ambient air is possible due to recent advances in mass spectrometry techniques, including chemical ionization mass spectrometry for the detection of weak acids. To date, HNCO has been measured in North America, Europe and South Asia as well as outdoors and indoors, with mixing ratios up to 10s of ppbv. The sources of HNCO include: (1) fossil fuel combustion such as coal, gasoline and diesel, (2) biomass burning such as wildfires and crop residue burning, (3) secondary photochemical production from amines and amides, (4) cigarette smoke, and (5) combustion of materials in the built environment. Then, three losses processes can occur: (1) gas phase photochemistry, (2) heterogenous uptake and hydrolysis, and (3) dry deposition. HNCO lifetimes with respect to photolysis and OH radical oxidation are on the order of months to decades. Consequently, the removal of HNCO from the atmosphere is thought to occur predominantly by dry deposition and by heterogeneous uptake followed by hydrolysis to NH3 and CO2. A back of the envelope calculation reveals that HNCO is an insignificant global source of NH3, contributing only around 1%, but could be important for local environments. Furthermore, HNCO can react due to its electrophilic behaviour with various nucleophilic functionalities, including those present in the human body through a reaction called protein carbamoylation. This protein modification can lead to toxicity, and thus exposure to high concentrations of HNCO can lead to cardiovascular and respiratory diseases, as well as cataracts. In this critical review, we outline our current understanding of the atmospheric fate of HNCO and its potential impacts on outdoor and indoor air quality. We also call attention to the need for toxicology studies linking HNCO exposure to health effects.

Artifacts and Common Errors in Protein Gel Electrophoresis.

In spite of taking precautions, some common mistakes creep into well-planned gel electrophoresis experiments. This occurs commonly in relation to calculating the cross-linking factor of a gel, polymerization temperature and time for a polyacrylamide gel, inducing aggregates in samples for electrophoresis, titrating the running buffer in electrophoresis, proper sample preparation, amount of protein to be loaded on a gel, sample buffer-to-protein ratios, incompletely removing phosphate-buffered saline from cells prior to cell lysis, and over-focusing of IPG strip in two-dimensional gel electrophoresis. In addition, subtle artifacts can have significant deleterious effects on carefully planned and executed experiments. Proteases that act at room temperature upon proteins in the sample buffer prior to heating, cleavage of the Asp-Pro bond upon prolonged heating of proteins at high temperatures, contamination of sample or sample buffer with keratin, leaching of chemicals from disposable plastic ware, and contamination of urea with ammonium cyanate are some of the common reasons for artifacts in gel electrophoresis. Taking proper heed to all these factors can greatly help generate good experimental results.

Comparison of air samplers for determination of isocyanic acid and applicability for work environment exposure assessment.

Isocyanic acid (ICA) is one of the most abundant isocyanates formed during thermal decomposition of polyurethane (PUR), and other nitrogen containing polymers. Hot-work, such as flame cutting, forging, grinding, turning and welding may give rise to thermal decomposition of said polymers potentially forming significant amounts of ICA. A newly launched dry denuder sampler for airborne isocyanates using di-n-butylamine (DBA) demonstrated build-up of background ICA-DBA over time. Build-up of background ICA-DBA was not observed when stored at inert conditions (Ar atmosphere) for 84 days. Thus, freshly prepared denuders were used. The sampling efficiency of ICA using freshly prepared denuder samplers (0.2 L min-1), impinger + filter samplers (0.5 L min-1) using DBA and 1-(2-methoxyphenyl) piperazine (2MP)-impregnated filter cassette samplers (1 L min-1) was investigated. PTR-MS measurements of ICA were used as a quantitative reference. Dynamically generated standard ICA atmospheres covered the range 5.6 to 640 ppb at absolute humidities (AH) 4.0 and 16 g m-3. Recovered ICA was found to be 73-115% (denuder), 89-115% (impinger + filter) and 62-100% (2MP filter cassette). The method limit of detection (LOD) was equal to an amount of ICA of 24 ng (denuder), 8.9 ng (impinger + filter) and 9.4 ng (2MP filter cassette). The PTR-MS LOD for ICA was 1.8 and 2.8 ppb in atmospheres with an AH of 4 and 16 g m-3. Denuder samplers were used for personal (n = 176) and stationary (n = 31) air sampling during hot-work at six industrial sites (n = 23 workers). ICA was detected above method LOD in 66% and 58% of the personal and stationary samples, respectively. ICA workroom air concentrations were determined to be 1.8-320 ppb (median 12 ppb) (personal samples), and 1.5-44 ppb (median 6.6 ppb) (stationary samples).

Contribution of post-harvest agricultural paddy residue fires in the N.W. Indo-Gangetic Plain to ambient carcinogenic benzenoids, toxic isocyanic acid and carbon monoxide.

In the north west Indo-Gangetic Plain (N.W.IGP), large scale post-harvest paddy residue fires occur every year during the months of October-November. This anthropogenic perturbation causes contamination of the atmospheric environment with adverse impacts on regional air quality posing health risks for the population exposed to high concentrations of carcinogens such as benzene and toxic VOCs such as isocyanic acid. These gases and carbon monoxide are known to be emitted from biomass fires along with acetonitrile. Yet no long-term in-situ measurements quantifying the impact of this activity have been carried out in the N.W. IGP. Using high quality continuous online in-situ measurements of these gases at a strategic downwind site over a three year period from 2012 to 2014, we demonstrate the strong impact of this anthropogenic emission activity on ambient concentrations of these gases. In contrast to the pre-paddy harvest period, excellent correlation of benzenoids, isocyanic acid and CO with acetonitrile (a biomass burning chemical tracer); (r≥0.82) and distinct VOC/acetonitrile emission ratios were observed for the post-paddy harvest period which was also characterized by high ambient concentrations of these species. The average concentrations of acetonitrile (1.62±0.18ppb), benzene (2.51±0.28ppb), toluene (3.72±0.41ppb), C8-aromatics (2.88±0.30ppb), C9-aromatics (1.55±0.19ppb) and CO (552±113ppb) in the post-paddy harvest periods were about 1.5 times higher than the annual average concentrations. For isocyanic acid, a compound with both primary and secondary sources, the concentration in the post-paddy harvest period was 0.97±0.17ppb. The annual average concentrations of benzene, a class A carcinogen, exceeded the annual exposure limit of 1.6ppb at NTP mandated by the National Ambient Air Quality Standard of India (NAAQS). We show that mitigating the post-harvest paddy residue fires can lower the annual average concentration of benzene and ensure compliance with the NAAQS. Calculations of excessive lifetime cancer risk due to benzene amount to 25 and 10 per million inhabitants for children and adults, respectively, exceeding the USEPA threshold of 1 per million inhabitants. Annual exposure to isocyanic acid was close to 1ppb, the concentration considered to be sufficient to enhance risks for cardiovascular diseases and cataracts. This study makes a case for urgent mitigation of post-harvest paddy residue fires as the unknown synergistic effect of multi-pollutant exposure due to emissions from this anthropogenic source may be posing grave health risks to the population of the N.W. IGP.

A fluorescence-based method for cyanate analysis in ethanol/water media: correlation between cyanate presence and ethyl carbamate formation in sugar cane spirit.

UNLABELLED: Based on the fluorescence properties of 2,4-(1H,3H)-quinazolinedione, a product of the reaction between cyanate and 2-aminobenzoic acid, a simple, sensitive, selective, and reproducible method for the cyanate analysis in aqueous ethanolic media is proposed. In this method, λ(exc) and λ(em) are 310 and 410 nm, respectively, and the limits of detection and quantification are 2.2 × 10(-7) and 6.7 × 10(-7) mol/L, respectively. Under optimal conditions (pH = 4.5, 40% ethanol), a concentration of 5.0 × 10(-6) mol/L cyanate can be determined in a single measurement, at a 95% level of confidence, with an uncertainty of ± 0.13 × 10(-6) mol/L. Cyanide, thiocyanate, chloride, nitrate, and sulfate ions, as well as urea and urethane in concentrations 1 × 10(3) higher than that of cyanate do not interfere with the measurement. The methodology was applied to cyanate analyses in the different fractions of the sugarcane distillate and the data strongly suggest a correlation between the presence of urea in wine, and the cyanate and ethyl carbamate concentrations in the spirit. PRACTICAL APPLICATION: Based on the fluorescence properties of the reaction product between cyanate and 2-aminobenzoic acid, a method for assaying cyanate was devised. This procedure applied to the sugarcane distillate showed for the first time a correlation between cyanate presence and ethyl carbamate (EC) formation in the different fractions of the product. Therefore, the proposed methodology can be used to predict in freshly distillate sugar cane spirits the potential total concentration of EC to be formed. Therefore, these data could be used to advise about the necessity of implementing a procedure to reduce spirit EC concentration before the product reaches the market.

Real-time emission factor measurements of isocyanic acid from light duty gasoline vehicles.

Exposure to gas-phase isocyanic acid (HNCO) has been previously shown to be associated with the development of atherosclerosis, cataracts and rheumatoid arthritis. As such, accurate emission inventories for HNCO are critical for modeling the spatial and temporal distribution of HNCO on a regional and global scale. To date, HNCO emission rates from light duty gasoline vehicles, operated under driving conditions, have not been determined. Here, we present the first measurements of real-time emission factors of isocyanic acid from a fleet of eight light duty gasoline-powered vehicles (LDGVs) tested on a chassis dynamometer using the Unified Driving Cycle (UC) at the California Air Resources Board (CARB) Haagen-Smit test facility, all of which were equipped with three-way catalytic converters. HNCO emissions were observed from all vehicles, in contrast to the idealized laboratory measurements. We report the tested fleet averaged HNCO emission factors, which depend strongly on the phase of the drive cycle; ranging from 0.46 ± 0.13 mg kg fuel(-1) during engine start to 1.70 ± 1.77 mg kg fuel(-1) during hard acceleration after the engine and catalytic converter were warm. The tested eight-car fleet average fuel based HNCO emission factor was 0.91 ± 0.58 mg kg fuel(-1), within the range previously estimated for light duty diesel-powered vehicles (0.21-3.96 mg kg fuel(-1)). Our results suggest that HNCO emissions from LDGVs represent a significant emission source in urban areas that should be accounted for in global and regional models.

The applicability of proton transfer reaction-mass spectrometry (PTR-MS) for determination of isocyanic acid (ICA) in work room atmospheres.

A method is presented for the real-time quantitative determination of isocyanic acid (ICA) in air using proton transfer reaction-mass spectrometry (PTR-MS). Quantum mechanical calculations were performed to establish the ion-polar molecule reaction rate of ICA and other isocyanates. The PTR-MS was calibrated against different ICA air concentrations and humidity conditions using Fourier transform-infrared spectroscopy (FT-IR) as quantitative reference. Based on these experiments a simple humidity dependant model was derived for correction of the PTR-MS response for ICA. The corrected PTR-MS data was linearly correlated (R(2) > 0.99) with the data acquired by FT-IR. The PTR-MS instrumental limit of detection (LOD) for ICA was 2.3 ppb. Humid atmospheres resulted in LODs of 3.4 and 7.8 ppb, at an absolute humidity (AH) of 4.0 and 15.5 g m(-3), respectively. Furthermore, off-line sampling using denuder and impinger samplers using di-n-butylamine (DBA) as derivatization reagent was compared with PTR-MS measurements in a dynamically generated standard ICA atmosphere. Denuder (n = 4) and impinger (n = 4) sampling subsequent to liquid chromatography mass spectrometry (LC-MS) determination compared to corrected PTR-MS data resulted in recoveries of 79.6 (8.1% RSD) and 99.9 (9.3% RSD) %, respectively. Measurements of ICA from thermally decomposed cured 1,6-hexamethylene diisocyanate (HDI)-paint was performed using PTR-MS and denuder (n = 3) sampling. The relation between the average ICA responses using denuders (34.4 ppb) and PTR-MS (42.6 ppb) was 80.6%, which coincided well with the relative recovery obtained from the controlled laboratory experiments using dynamically generated ICA atmospheres (79.6%). The variability in ICA air concentration during the welding process (170% RSDPTR-MS) illustrated the need for real-time measurements.

Analysis of gold(I/III)-complexes by HPLC-ICP-MS demonstrates gold(III) stability in surface waters.

Understanding the form in which gold is transported in surface- and groundwaters underpins our understanding of gold dispersion and (bio)geochemical cycling. Yet, to date, there are no direct techniques capable of identifying the oxidation state and complexation of gold in natural waters. We present a reversed phase ion-pairing HPLC-ICP-MS method for the separation and determination of aqueous gold(III)-chloro-hydroxyl, gold(III)-bromo-hydroxyl, gold(I)-thiosulfate, and gold(I)-cyanide complexes. Detection limits for the gold species range from 0.05 to 0.30 µg L(-1). The [Au(CN)2](-) gold cyanide complex was detected in five of six waters from tailings and adjacent monitoring bores of working gold mines. Contrary to thermodynamic predictions, evidence was obtained for the existence of Au(III)-complexes in circumneutral, hypersaline waters of a natural lake overlying a gold deposit in Western Australia. This first direct evidence for the existence and stability of Au(III)-complexes in natural surface waters suggests that Au(III)-complexes may be important for the transport and biogeochemical cycling of gold in surface environments. Overall, these results show that near-µg L(-1) enrichments of Au in environmental waters result from metastable ligands (e.g., CN(-)) as well as kinetically controlled redox processes leading to the stability of highly soluble Au(III)-complexes.

Chromatographic determination of nanomolar cyanate concentrations in estuarine and sea waters by precolumn fluorescence derivatization.

Recent studies suggest that cyanate (OCN(-)) is a potentially important source of reduced nitrogen (N) available to support the growth of aquatic microbes and, thus, may play a role in aquatic N cycling. However, aquatic OCN(-) distributions have not been previously described because of the lack of a suitable assay for measuring OCN(-) concentrations in natural waters. Previous methods were designed to quantify OCN(-) in aqueous samples with much higher reduced N concentrations (micromolar levels) than those likely to be found in natural waters (nanomolar levels). We have developed a method to quantify OCN(-) in dilute, saline environments. In the method described here, OCN(-) in aqueous solution reacts with 2-aminobenzoic acid to produce a highly fluorescent derivative, 2,4-quinazolinedione, which is then quantified using high performance liquid chromatography. Derivatization conditions were optimized to simultaneously minimize the reagent blank and maximize 2,4-quinazolinedione formation (>90% reaction yield) in estuarine and seawater matrices. A limit of detection (LOD) of 0.4 nM was achieved with only minor matrix effects. We applied this method to measure OCN(-) concentrations in estuarine and seawater samples from the Chesapeake Bay and coastal waters from the mid-Atlantic region. OCN(-) concentrations ranged from 0.9 to 41 nM. We determined that OCN(-) concentrations were stable in 0.2 µm filtered seawater samples stored at -80 °C for up to nine months.

Isocyanate exposure control in motor vehicle paint spraying: evidence from biological monitoring.

AIMS: The purpose of this work was to assess the changes in control of exposure to hexamethylene diisocyanate based paints used in vehicle spraying after a Health & Safety Executive (HSE) national project. METHODS: Paint sprayers and managers from motor vehicle repair (MVR) bodyshops across the UK, were invited to one of 32 Safety and Health Awareness Days (SHADs) to increase their understanding of the hazards, and practical ways of controlling of exposure to isocyanate based paints. Exposure measurement based on biological monitoring was offered, free of charge, to each of the roughly 4000 participants and used to assess the effectiveness of controls and methods of working. Results are compared with pre and post SHAD measurements. RESULTS: Urine samples were received from 995 paint sprayers. Hexamethylene diamine (HDA) levels in urine, indicative of exposure to hexamethylene diisocyanate (HDI), were significantly lower (Mann-Whitney, p<0.0001) than had been seen in a wider population from previous HSE inspections and routine sampling. Where a sprayer's urinary HDA was above the quantification limit they were asked to send another sample after reviewing and improving exposure control measures. The results from these repeat samples were significantly lower than the original results. There was no difference in the exposures of sprayers using air-fed half-mask face-pieces compared with visor type air-fed breathing apparatus, or between spray booths and rooms. CONCLUSIONS: The analysis of HDA in urine is a useful technique for assessing exposure to isocyanates in paint sprayers. The simplicity of this approach has allowed wide-scale use of biological monitoring in an industry dominated by small and micro businesses. Biological monitoring of exposure has enabled individual companies, and sprayers, to check that their control measures are working. This study showed overall lower levels of HDA in paint sprayers following SHADs. These lower levels have been maintained across a wider population of UK paint sprayers over the succeeding years. Whilst there may be many reasons for the reduction in exposure, the weight of evidence suggests that the key messages about exposure control measures, delivered through the SHADs and other means, were influential.

Assessment of exposure to TDI and MDI during polyurethane foam production in Poland using integrated theoretical and experimental data.

The aim of this study was to develop an optimal strategy for the assessment of inhalation exposure to isocyanates such as TDI and MDI in the production of polyurethane foam by integration of theoretical and experimental data. ECETOC TRA and EASE predictive models were used to determine the estimated levels of exposure to isocyanates. The results of our study suggest that both applications EASE and ECETOC TRA can be used as a screening 1st Tier tool in this case study. PROC12 ECETOC TRA category can be linked to exposure on TDI during polyurethane foam manufacturing because it is working properly and exceeds 90th percentile measured concentration with factor 3 and the maximum measured value with factor 1, 5. The value estimated by using category PROC2 is underestimated so this category should not be linked to this scenario. At the same time, the applications of EASE overstate the expected concentrations although the scenario "Use in closed process" seems to underestimate the exposure at the "lower end". For MDI the both models estimate exposure in a conservative manner.

Biomonitoring Hexamethylene diisocyanate (HDI) exposure based on serum levels of HDI-specific IgG.

OBJECTIVES: Isocyanate chemicals essential for polyurethane production are widely used industrially, and are increasingly found in consumer products. Asthma and other adverse health effects of isocyanates are well-documented and exposure surveillance is crucial to disease prevention. Hexamethylene diisocyanate (HDI)-specific serum immunoglobulin G (IgG) was evaluated as an exposure biomarker among workers at a US Air Force Air Logistics Center, which includes a large aircraft maintenance facility. METHODS: HDI-specific IgG (HDI-IgG) titers in serum samples (n = 74) were measured using an enzyme-linked immunosorbent assay based upon the biuret form of HDI conjugated to human albumin. Information on personal protective equipment (PPE), work location/tasks, smoking, asthma history, basic demographics, and HDI skin exposure was obtained through questionnaire. RESULTS: HDI-specific serum IgG levels were elevated in n = 17 (23%) of the workers studied. The prevalence and/or end-titer of the HDI-IgG was significantly (P < 0.05) associated with specific job titles, self-reported skin exposure, night-shift work, and respirator use, but not atopy, asthma, or other demographic information. The highest titers were localized to specific worksites (C-130 painting), while other worksites (generator painting) had no or few workers with detectable HDI-IgG. CONCLUSIONS: HDI-specific immune responses (IgG) provide a practical biomarker to aid in exposure surveillance and ongoing industrial hygiene efforts. The strategy may supplement current air sampling approaches, which do not assess exposures via skin, or variability in PPE use or effectiveness. The approach may also be applicable to evaluating isocyanate exposures in other settings, and may extend to other chemical allergens.

Identification and determination of selenosulfate and selenocyanate in flue gas desulfurization waters.

In this work, 13 selenium species in flue gas desulfurization (FGD) waters from coal-fired power plants were separated and quantified using anion-exchange chromatography coupled to inductively coupled plasma mass spectrometry. For the first time, we identified both selenosulfate (SeSO(3)(2-)) and selenocyanate (SeCN(-)) in such waters, using retention time matching and confirmation by electrospray mass spectrometry. Besides selenite and selenate, selenosulfate was the most frequently occurring selenium species. It occurred in most samples and constituted a major fraction (up to 63%) of the total selenium concentration in waters obtained from plants employing inhibited oxidation scrubbers. Selenocyanate occurred in about half of the tested samples, but was only a minor species (up to 6% of the total selenium concentration). Nine additional Se-containing compounds were found in FGD waters, but they remain unidentified at this point.

Development of a sampling patch to measure dermal exposures to monomeric and polymeric 1,6-hexamethylene diisocyanate: a pilot study.

The purpose of this study was to develop and evaluate a patch sampler to monitor dermal exposures to monomeric and polymeric 1,6-hexamethylene diisocyanate (HDI) in the automotive refinishing industry. Different patch materials were used to construct the patches, and patches impregnated with a derivatizing solution were compared with those that were not impregnated. We observed that impregnated felt patches measured significantly more HDI monomer (p = 0.04) than non-impregnated patches in a controlled experiment. Both impregnated and non-impregnated patches were compared with the tape-strip method by monitoring three spray painters' dermal exposure to monomeric and polymeric HDI. Isocyanurate was the predominant species measured by all three sampler types with detectable levels in >86% of samples. Overall, tape-strips of exposed skin measured lower levels of monomeric and polymeric HDI than impregnated patch samplers at the same sampling site on the skin. Unlike tape-strips, impregnated patches are not as prone to evaporative or reactive losses or losses due to rapid penetration into the skin. Further investigations are warranted to evaluate these and other methods to measure dermal exposure to workers under occupational conditions to better understand the relationship between dermal exposure and internal dose.