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.     

气相色谱-质谱法快速筛查气态制冷剂产品中的热点管控类卤代烃

建立了利用气相色谱-质谱法快速筛查气态制冷剂产品中的10种热点管控类卤代烃的分析方法。采用气密性微量注射器对气态制冷剂样品进行取样,刺透瓶盖隔垫加入到顶空瓶中,自动进样;以GS-GasPro(多孔层开管,60 m×0.32 mm)为色谱柱,采用电子轰击离子源,全扫描模式采集。测试结果显示:目标物的体积分数在0.50%~100.00%范围内,相对响应因子的相对标准偏差(RSD)均小于20%;线性相关系数r均在0.999以上;检出限(3.143倍标准偏差)为0.01%~0.05%。对实际样品进行加标回收,回收率为79.5%~102%,测定值RSD为0.5%~3.1%。该方法可为快速、准确、批量筛查气态制冷剂产品中的多种热点管控类卤代烃提供技术支撑。     

Peak exposures in aluminium potrooms: instrument development and field calibration

Aluminium smelter potrooms are unique in that workplace exposures to hydrogen fluoride (HF), sulfur dioxide (SO2), and particulate matter occur simultaneously for some tasks. The peak exposures to these contaminants are of increasing interest in discovering the etiology of respiratory health effects. While a variety of direct-reading instruments are available for sulfur dioxide and particulate matter, only a few exist for hydrogen fluoride. The sensors in these HF instruments have a cross-sensitivity to sulfur dioxide making it difficult to monitor HF in an environment that also contains SO2. To overcome this problem, we assessed the simultaneous use of two electrochemical instruments: one with a SO2 sensor that does not respond to HF and the second with a hydrogen fluoride sensor that responds to both HF and SO2 in a 1 : 1 ratio, termed 'total acid gas'. The difference in the response between the two instruments should indicate the HF concentration: [HF + SO2] minus SO2 equals HF. The performance characteristics of this sampling train were evaluated in the laboratory through the generation of both HF and SO2 with permeation tubes. The response and recovery times for the SO2 only instrument were acceptable (6 and 15 s, respectively), but the "total acid gas" instrument exhibited both slow response and slow recovery approaching three and six min. The association between the traditional integrated filter sampling method and the direct-reading instrument for SO2 is 0.80 (Spearman's rho). The use of the digital filter strengthens the association between the HF direct-reading instrument and the integrated samples from 0.41 to 0.68.     

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.     

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.     

Mass, surface area and number metrics in diesel occupational exposure assessment

While diesel aerosol exposure assessment has traditionally been based on the mass concentration metric, recent studies have suggested that particle number and surface area concentrations may be more health-relevant. In this study, we evaluated the exposures of three occupational groups-bus drivers, parking garage attendants, and bus mechanics-using the mass concentration of elemental carbon (EC) as well as surface area and number concentrations. These occupational groups are exposed to mixtures of diesel and gasoline exhaust on a regular basis in various ratios. The three groups had significantly different exposures to workshift TWA EC with the highest levels observed in the bus garage mechanics and the lowest levels in the parking ramp booth attendants. In terms of surface area, parking ramp attendants had significantly greater exposures than bus garage mechanics, who in turn had significantly greater exposures than bus drivers. In terms of number concentrations, the exposures of garage mechanics exceeded those of ramp booth attendants by a factor of 5-6. Depending on the exposure metric chosen, the three occupational groups had quite different exposure rankings. This illustrates the importance of the choice of exposure metric in epidemiological studies. If these three occupational groups were part of an epidemiological study, depending on the metric used, they may or may not be part of the same similarly exposed group (SEG). The exposure rankings (e.g., low, medium, or high) of the three groups also changes with the metric used. If the incorrect metric is used, significant misclassification errors may occur.     

沧州市滨海盐碱区土壤盐渍化特征

分层采集不同时期沧州市滨海盐碱区的土样,采用流动分析仪测定各土样的总含盐量及主要盐分离子,分析土壤的盐渍化特征.结果表明:该地区为硫酸盐-氯化物型盐渍化土壤,土壤中氯化钠、氯化镁和氯化钙为氯化物的主要组成部分,硫酸盐类主要为硫酸钠、硫酸镁和硫酸钙.该地区不同采样时期间、不同地区间和不同土层间土壤盐渍化状态均存在极显著差异.除碳酸根+碳酸氢根外,钾离子、钠离子、镁离子、氯离子、钙离子、硅酸根离子和硫酸根离子均为表征该地区土壤盐渍化状态的主要盐分离子.     

Development of a field method for measuring manganese in welding fume

Workers who perform routine welding tasks are potentially exposed to fume that may contain manganese. Manganese may cause respiratory problems and is implicated in causing the occurrence of Parkinson-like symptoms. In this study, a field colorimetric method for extracting and measuring manganese in welding fume was developed. The method uses ultrasonic extraction with an acidic hydrogen peroxide solution to extract welding fume collected on polyvinyl chloride filters. Commercially available pre-packaged reagents are used to produce a colored solution, created by a reaction of manganese(ii) with 1-(2-pyridylazo)-2-naphthol. Absorbance measurements are then made using a portable spectrophotometer. The method detection limit and limit of quantification (LOQ) were 5.2 microg filter(-1) and 17 microg filter(-1), respectively, with a dynamic range up to 400 microg filter(-1). When the results are above the LOQ for the colorimetric method, the manganese masses are equivalent to those measured by the International Organization for Standardization Method 15202-2, which employs a strong acid digestion and analysis using inductively coupled plasma-optical emission spectrometry.     

The determination of chlorofluorocarbons and extractives in the expanded and disposable polystyrene ware

Residual chlorofluorocarbons (CFCs) and water-extractive residues in expanded polystyrene ware were determined because of the threat to environmental and public health arising from the ozone depleting potential of CFCs and the leaching of toxic monomers and oligomers into food and drink. Chlorofluorocarbon in expanded polystyrene ware was analysed using headspace gas chromatography in the flame ionization mode, and confirmed by gas chromatography-mass spectrometry. The amount of extractive residue leached from this type of polymeric material was determined using an aqueous medium simulating categories of food and beverages. A wide range of concentrations of CFC-12 (dichlorodifluorocarbon) was detected in the styrofoam ware. It fluctuated between a low of 32 ppm and a high of 35471 ppm in two different samples of styrofoam plates. Similarly, the highest and lowest levels of extractive residue detected in two different styrofoam plates were 54 ppm and 0.5 ppm respectively. CFC-22 or HCFC (chlorodifluorocarbon) was absent from these expanded polystyrene ware. The continued use of chlorofluorocarbons as a blowing agent will further exert a deleterious effect on the stratospheric ozone layer. Though the level of water extractive residue from these expanded polystyrene ware was relatively safe, public health could be further safe-guarded through improvmeents in raw material selection and mode of production.     

Increased metal concentrations in exhaled breath condensate of industrial welders

It was the aim of this study to evaluate the effect of different devices on the metal concentration in exhaled breath condensate (EBC) and to prove whether working conditions in different welding companies result in diverse composition of metallic elements. The influence of two collection devices (ECoScreen, ECoScreen2) on detection of metallic elements in EBC was evaluated in 24 control subjects. Properties of ECoScreen and a frequent use can alter EBC metal content due to contamination from metallic components. ECoScreen2 turned out to be favourable for metal assessment. Concentrations of iron, nickel and chromium in EBC sampled with ECoScreen2 were compared between non-exposed controls and industrial welders. Metal concentrations in EBC were higher in 36 welders recruited from three companies. Exposure to welding fumes could be demonstrated predominantly for increased iron concentrations. Concentrations of iron and nickel differed by working conditions, but chromium could not be detected in EBC.     

Impact of agglomeration and different dispersions of titanium dioxide nanoparticles on the human related in vitro cytotoxicity and genotoxicity

The published results on nanoparticles cytotoxicity and genotoxicity such as titanium dioxide nanoparticles (TiO(2) NPs) are inconsistent, and often conflicting and insufficient. Since different parameters may have impact on the toxicity results, there is need to lay stress on detailed characterization of NPs and the use of different testing conditions for assessment of NPs toxicity. In order to investigate whether dispersion procedures influence NP cytotoxicity and genotoxicity, we compared two protocols giving TiO(2) NP dispersions with different stability and agglomeration states. Detailed primary and secondary characteristics of both TiO(2) NP dispersions in culture media were carried out before toxicological testing; TK6 human lymphoblast cells, EUE human embryonic epithelial cells and Cos-1 monkey kidney fibroblasts were used to assess cytotoxicity (by trypan blue exclusion, proliferation activity and plating efficiency assays) and genotoxicity (by the comet assay). DNA strand breaks were detected by the alkaline comet assay. DNA oxidation lesions (especially 8-oxo-7,8-dihydroguanine, 8-oxoG) were measured with a modified comet assay including incubation with specific repair enzyme formamidopyrimidine DNA glycosylase (FPG). The TiO(2) NPs dispersion with large agglomerates (3 min sonication and no serum in stock solution) induced DNA damage in all three cell lines, while the TiO(2) NPs dispersed with agglomerates less than 200 nm (foetal serum in stock solution and sonication 15 min) had no effect on genotoxicity. An increased level of DNA oxidation lesions detected in Cos-1 and TK6 cells indicates that the leading mechanism by which TiO(2) NPs trigger genotoxicity is most likely oxidative stress. Our results show that the dispersion method used can influence the results of toxicity studies. Therefore at least two different dispersion procedures should be incorporated into assessment of cyto- and genotoxic effects of NPs. It is important, when assessing the hazard associated with NPs, to establish standard testing procedures and thorough strategies to consider the diverse conditions relevant to possible exposures.     

Continuous, intermittent and passive sampling of airborne VOCs

Long sampling periods are often advantageous or required for measuring air quality and characterizing exposures. However, sampling periods exceeding 8 to 24 h using thermally desorbable adsorbent tube (TDT) samplers for the measurement of airborne volatile organic compounds (VOCs) face several challenges, including maintaining stable and low flow rates, and avoiding breakthrough of the adsorbent. These problems may be avoided using intermittent sampling; however, the literature contains few if any reports that have evaluated this technique in environmental, occupational or other applications. The purpose of this study is to evaluate continuous, intermittent and passive sampling methods using both laboratory and real-world tests. Laboratory tests compared continuous and intermittent (active) samplers in a controlled dynamic test gas generation system. Field tests used side-by-side active and passive samplers in an office, home workshop and four smokers' homes. All samples were analyzed for a wide range of VOCs by GC-MS. In most instances, intermittent sampling yielded better reproducibility (duplicate precision of 10 +/- 6%) than continuous low-flow sampling (18 +/- 5%), in part due to difficulty maintaining low flows. Concentrations obtained using intermittent sampling agreed with those for continuous sampling, with downward biases resulting primarily from errors in flow rate measurements. In the field, more VOC species were detected using active rather than passive sampling. Passive measurements were 12% lower than continuous measurements, a difference attributed to declining uptake rates at higher concentrations over the 3 to 4 d sampling period. Overall, most measurements obtained using the three sampling methods agreed within 20% for a wide range of concentrations (0.1 to 230 microg m(-3)). Both passive and intermittent sampling approaches are suitable for long sampling periods, but intermittent sampling provides greater flexibility with respect to sampling period, and permits the use of multi-bed adsorbents that can capture a wider range of VOCs.     

Ozone facilitated dechlorination of 2-chloroethanol and impact of organic solvents and activated charcoal

The ozone-initiated oxidation of 2-chloroethanol was followed by monitoring the consumption of the halogenated organic substrate. Gas chromatographic analysis of the ozonated products showed an increase in conversion from about 1 % after 3 h of ozone treatment to about 22 % after 12 h. The yields of major ozonated products identified and quantified namely acetaldehyde, acetic acid, and chloride ion increased proportionately as a function of ozone treatment time. The percent conversion of 2-chloroethanol in the presence of acetic acid or ethyl acetate were found to be higher than those under solvent-free conditions with similar products obtained. The use of activated charcoal during the ozonolyis of 2-chloroethanol showed a significant increase in the percent conversion of the substrate compared to solvent free ozonation. Based on the experimental findings, the overall mechanism for the reaction between 2-chloroethanol and ozone is described.     

Stabilize lead and cadmium in contaminated soils using hydroxyapatite and potassium chloride

Combination of hydroxyapatite (HAP) and potassium chloride (KCl) was used to stabilize lead and cadmium in contaminated mining soils. Pot experiments of chilli (Capsicum annuum) and rape (Brassica rapachinensis) were used to evaluate the stabilization efficiency. The results were the following: (1) the optimal combination decreased the leachable lead by 83.3 and 97.27 %, and decreased leachable cadmium by 57.82 and 35.96% for soil HF1 and soil HF2, respectively; (2) the total lead and cadmium concentrations in both plants decreased 69 and 44 %, respectively; (3) The total lead and cadmium concentrations in the edible parts of both vegetables also decreased significantly. This study reflected that potassium chloride can improve the stabilization efficiency of hydroxyapatite, and the combination of hydroxyapatite and potassium chloride can be effectively used to remediate lead and cadmium contaminated mining soil.     

吹扫捕集- GC/MS法测定水中卤代烃的质量控制指标研究

采用吹扫捕集-气相色谱/质谱联用法,通过实际样品测试及全国多家实验室测定数据统计两种方法,针对水中三氯甲烷、四氯化碳、溴仿、二氯甲烷、1,2-二氯乙烷、1,1-二氯乙烯、三氯乙烯、四氯乙烯等8种卤代烃的平行样测定相对偏差、空白加标回收率及实际样品加标回收率等3个指标,研究了每种卤代烃的质控指标评价标准,提出其平行样测定...     

Protein adducts as biomarkers of exposure to aromatic diisocyanates in workers manufacturing polyurethane (PUR) foam

This work was undertaken to investigate the usefulness of diisocyanate-related protein adducts in blood samples as biomarkers of occupational exposure to toluene diisocyanate (TDI; 2,4- and 2,6-isomers) and 4,4'-methylenediphenyl diisocyanate (MDI). Quantification of adducts as toluene diamines (TDAs) and methylenedianiline (MDA) was performed on perfluoroacylated derivatives by gas chromatography-mass spectrometry (GC-MS/MS) in negative chemical ionisation mode. TDI-derived adducts were found in 77% of plasma and in 59% of globin samples from exposed workers manufacturing flexible polyurethane foam. The plasma levels ranged from 0.003 to 0.58 nmol mL(-1) and those in globin from 0.012 to 0.33 nmol g(-1). The 2,6-isomer amounted to about two-thirds of the sum concentration of TDA isomers. MDI-derived adducts were detected in 3.5% of plasma and in 7% of globin samples from exposed workers manufacturing rigid polyurethane foam. A good correlation was found between the sum of TDA isomers in urine and that in plasma. The relationship between globin adducts and urinary metabolites was ambiguous. Monitoring TDI-derived TDA in plasma thus appears to be an appropriate method for assessing occupational exposure. Contrary to TDI exposure, adducts in plasma or globin were not useful in assessing workers' exposure to MDI. An important outcome of the study was that no amine-related adducts were detected in globin samples from TDI- or MDI-exposed workers, alleviating concerns that TDI or MDI might pose a carcinogenic hazard. Further studies are nevertheless required to judge whether diisocyanates per se could be such a hazard.     

Airborne exposure to wheat allergens: optimised elution for airborne dust samples

Well-validated methods for measuring airborne occupational allergens are essential for effective control and reduction of allergen exposures. For wheat flour allergens, specific immunoassays are available, but there is a need for optimisation and standardization of sample processing procedures. Wheat flour allergen elution and storage were studied using airborne dust samples collected in bakeries with a new parallel sampler. Forty-eight series of 9 parallel filters were subjected to extraction procedures varying in elution medium, shaking method, extraction vial, and centrifugation speed. Wheat allergens were measured with enzyme immunoassays, and the effect of various procedures evaluated by mixed regression analyses. The stability of the eluted allergens was assessed after storage for 20 days and 4 months at -20 degrees C, in the presence or absence of casein in the medium. Only the type of elution medium had significant effects on allergen recovery: addition of Tween-20 resulted in 3- to 100-fold increased levels, an effect that was most pronounced at low concentrations. Allergen levels in extracts were stable for at least 4 months at -20 degrees C, irrespective of the presence of casein in the medium. Addition of Tween-20 to the elution medium is essential for optimal extraction of wheat allergen. The recommended procedure further includes the use of conventional polystyrene tubes, simple shaking methods, and centrifugation after extraction. Wheat dust extracts in PBS-Tween can be stored frozen for at least 4 months, and addition of a stabilising protein is not required.     

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.     

Characterization of airborne trace metal and trace organic species from coal gasification

Fugitive emissions from a slagging fixed-bed coal-gasification pilot plant were analyzed by flameless atomic absorption spectrophotometry, gas chromatography, and mass spectrometry for trace metal and trace organic species. Analysis of the size distributions of airborne particulate matter inside the plant showed an abundance of large metal-containing particles; outdoor distributions in the vicinity of the plant resembled the indoor distributions, suggesting the importance of the gasifier in influencing ambient air quality. This conclusion was further supported by identification of similar organic compounds inside and outside the plant. Trace element enrichment factors based on the earth's crustal composition were greater than those based on the composition of the lignite used in the gasifier, showing the importance of characterizing the proper source material when inverstigating chemical fraction during aerosol formation. Enrichments in the present study were much greater than those found in previous sampling during aborted start-up and cleaning procedures, where normal operating temperatures had not yet been reached. Both studies showed evidence of enrichment factors which decreased with increasing particle size. Although much of the airborne mass was associated with large particles having low respirability, the high concentrations of some metals indoors suggests that further assessment of potential occupational exposures is warranted.     

Characteristics and origin of the hydrogen sulphide spring water from the Split spa (Southern Croatia)

The objective of this paper is to study the hydrological characteristics and origin of the hydrogen sulphide spring water from the Split spa in Southern Croatia in 1987, 1988 and 2003. This paper presents the results of monitoring the content of chlorides and hydrogen sulphide as well as the temperature of the hydrogen sulphide spring water. Since the hydrogen sulphide content during the dry periods significantly differs from the hydrogen sulphide content during rainy periods, this paper also compares the results obtained for those two periods. Under the influence of great quantities of rainfall during cold periods (winter and the beginning of spring) the ratio between seawater and surface water changes and thus the reduction of chlorides and other minerals occurs. The lowered temperature also reduces hydrogen sulphide which can disappear completely. The concentration of 12‰ chlorides (76–94.4% days/year) and 12 mg/L hydrogen sulphide (66.7–88.9% days/year) has been taken as a limit value between water with a normal typical content and water in cold rainy periods. According to the monitoring results it can be concluded that hydrogen sulphide spring water consists of seawater and hydrogencarbonate surface water with a fairly constant content during dry periods while the hydrogencarbonate content increases during rainy periods.