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.     

Determination of germanium in urine and its usefulness for biomonitoring of inhalation exposure to inorganic germanium in the occupational setting

The present study aimed to assess whether urinary germanium concentration can be used as a biomarker of inhalation exposure to airborne dust from metallic germanium (Ge) or GeO2 in the occupational setting. A novel hydride generation-based method coupled with fow-injection graphite furnace atomic absorption spectrometry (HG/FI-GFAAS) was developed for the determination of urinary germanium. It was found that urinary germanium concentration could be reliably determined by a standard additions method after thorough digestion of the urine and careful pH adjustment of the digest. The limit of detection (LOD) in urine for the HG/FI-GFAAS method was 0.25 microg Ge L(-1). In Belgian control male subjects, the urinary germanium concentration was below this LOD. In 75 workers currently exposed to inorganic germanium compounds, respirable and inhalable concentrations of germanium in the aerosols were measured on Monday and Friday at the job sites using personal air samplers. Spot-urine samples were collected on the same days before and after the work shift. The germanium concentrations of respirable dust correlated very well with those of inhalable dust and represented 20% of the inhalable fraction. Workers exposed to metallic Ge dust were on average ten times less exposed to germanium than those whose exposure involved GeO2 (3.4 versus 33.8 microg Ge m(-3)). This difference was reflected in the urinary germanium concentrations (3.4 versus 23.4 microg Ge g(-1) creatinine). Regression analysis showed that the concentration of germanium in the inhalable fraction explained 42% of the post-shift urinary germanium concentration either on Monday or on Friday, whereas in a subgroup of 52 workers mainly exposed to metallic germanium dust 57% (r = 0.76) of the Monday post-shift urinary germanium was explained. Urinary elimination kinetics were studied in seven workers exposed to airborne dust of either metallic Ge or GeO2. The urinary elimination rate of germanium was characterised by half-times ranging from 8.2 to 18.1 h (on average 12 h 46 min). The present study did not allow discrimination between the germanium species to which the workers were exposed, but it showed fast urinary elimination kinetics for inhalation exposure to dust of metallic Ge and GeO2. It pointed out that urine samples taken at the end of the work shift can be used for biological monitoring of inorganic germanium exposure in the occupational setting.     

Assessment of workers' exposure to palladium in a catalyst production plant

Airborne particulate matter was collected and biomonitoring of workers was performed by sampling blood, urine and hair of 84 exposed subjects, 17 occasionally exposed employees, 21 controls from administrative offices and 25 unexposed people (external controls). Determination of Pd was performed using Quadrupole and High Resolution Inductively Coupled Plasma Mass Spectrometry. The Production of Catalysts Department and the Refining Service presented the highest levels of Pd in airborne matter collected by means of an area sampler. The highest level of soluble Pd (1.66 microg m(-3)) was found in the Production of Catalysts Department. The highest concentration of Pd in airborne matter, collected by means of personal devices (7.90 microg m(-3)) was found in the Refining Service. Hair showed a clear distribution pattern among departments, with values ranging from 0.60 to 5.54 microg g(-1). Administrative workers presented blood levels of Pd between 2 and 500 times higher than external controls. Only urine levels correlated with the measurements of airborne Pd collected with personal devices. A very strong association between airborne Pd collected by personal devices and Pd levels in hair (r(2)= 0.569, with p< or = 0.01) and urine (r(2)= 0.684, with p< or = 0.01) was found. On the basis of these findings: (i) blood results appear to be an unsuitable biological marker for occupational exposure to Pd; (ii) urine could be considered as a satisfactorily responsive bio-marker for occupational monitoring; and (iii) hair cannot be considered a good index of time-related exposure.     

Characterisation of workers' exposure in a Russian nickel refinery

In support of a feasibility study of reproductive and developmental health among females employed in the Monchegorsk (Russia) nickel refinery, personal exposure and biological monitoring assessments were conducted. The inhalable aerosol fraction was measured and characterised by chemical speciation and particle-size distribution measurements. Unexpected findings were that: (i), pyrometallurgical working environments had significant levels of water-soluble nickel; (ii), significant exposure to cobalt occurred for the nickel workers; (iii), particles of size corresponding to the thoracic and respirable fractions appeared to be virtually absent in most of the areas surveyed. The water-soluble fraction is judged to be primarily responsible for the observed urinary nickel and cobalt concentrations. It is concluded relative to current international occupational-exposure limits for nickel in air, and because of the high nickel concentrations observed in urine, that the Monchegorsk nickel workers are heavily exposed. The implication of this finding for follow-up epidemiological work is alluded to.     

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.     

土壤中挥发性有机污染物现场快速监测技术应用进展

在总结我国突发性环境事故发生现状的基础上,提出了我国环境现场快速监测工作缺少规范化管理,以及标准监测技术方法不完善等问题。探讨了土壤中挥发性有机污染物快速监测技术的研究进展,重点讨论了检测管,手持式气体检测器,便携式气相色谱(配置光离子化检测器、氢火焰离子化检测器或串/并联检测器)及便携式气相色谱-质谱等技术在快速检测土壤中挥发性有机污染物方面的性能特点与应用情况,并对我国建立土壤中挥发性有机污染物现场快速监测标准方法提出了建议。     

Environmental and Biological Assessment of Exposure to Benzene in Petroleum Workers

Occupational exposure to benzene was measured in two gasoline marketing terminals and five major refineries in Singapore. A total of 280 workers were monitored over two years. This assessment was carried out with two primary objectives: (1) To find out the extent of occupational exposure to benzene in the petroleum industry in Singapore, (2) To identify suitable biomarkers for monitoring of low levels of benzene exposure. The exposure was measured in five different categories of petroleum and petrochemical workers, i.e., truck drivers, despatch assistant, process operators, oil movements operators and laboratory technicians. The results revealed wide variations in exposure, from 0.01 to 13.6 ppm for personal time weighted average (TWA) exposure over the whole workshift. The exposure of truck drivers appeared to be the highest, with geometric mean (GM) of 1.98 ppm (ranged from 0.25 to 13.6 ppm). The average benzene exposure for process operators was relative low with a GM of 0.04 ppm. Lowest benzene exposure was found in the laboratory technicians, with a GM of 0.02 ppm. As cigarette smoking is known to affect metabolism of benzene, data analyses on the relationships with environmental exposure were conducted only on the 190 nonsmokers. The results showed that urinary trans, trans-muconic acid (ttMA), unmetabolized benzene in urine (UBZ) and benzene in blood (BBZ) were better biomarkers for low level benzene exposure as compared to urinary phenolic metabolites in urine, such as hydroquinone, phenol and catechol.     

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.     

Uranium bioassay and radioactive dust measurements at some uranium processing sites in Egypt--health effects

The safety of radiation workers in the uranium mining industry requires close and continuous monitoring of their working conditions. In this study, external radiation surveillance, radioactive dust monitoring and the bioassay of uranium were carried out in some processing sites. As dust represents one of the most important sources of radiation exposure in mills and mines, dust monitoring and bioassays were performed for a sample of workers on the production lines. The concentration of uranium in air ranged from 22.6 x 10(-7) to 11.1 x 10(-5) Bq cm-3, and the exposure levels ranged from 1 to 80 microSv h-1. Laser fluorimetric determination of uranium in urine samples showed concentrations in the range 8.4-29.2 micrograms L-1. Renal function parameters, such as serum creatinine and urea, and hematological parameters were determined in an attempt to correlate them with radiation exposure and the health status of the workers. Urine specimens collected from workers at the ore crushing and separation site showed elevated concentrations of uranium (up to 29.2 micrograms L-1) and a strong correlation between these concentrations and the registered serum creatinine. The mean uranium excretion in the investigated group was more than 20 times the occupational exposure decision level for urine uranium of 0.8 microgram L-1.     

Changes in urinary catecholamines in response to noise exposure in workers at Sarcheshmeh Copper Complex, Kerman, Iran

Noise is one of the most harmful agents in the workplace. In addition to the adverse effects of noise on the auditory system, as a stressor it may cause increased blood pressure, cardiovascular disease, anxiety, and impaired secretion of hormones. The purpose of this study was to evaluate changes in urinary catecholamines in workers exposed to industrial noise. This is an experimental study of the workers at the smelter section of Sarcheshmeh Copper Industries done on two separate days. During the first day, urine samples from 20 workers who did not use any hearing protection device, were collected during an 8-h work shift and on the second day the same was done but they were asked to use earplugs. Also 20 people were selected as a control group from people who were not exposed to noise at work. Urinary catecholamine levels were measured with ELISA kits. The mean urinary epinephrine and norepinephrine levels in the workers (without earplugs) was respectively 8.69 and 35.56 μg/8h on the first day and on the second day (with earplugs) dropped to 6.45 and 30.95 μg/8h. Noise reduction by earplugs led to almost significant reductions in urinary epinephrine (p?=?0.05) and significant reductions in norepinephrine (p?=?0.02). The results showed that with noise reduction the urinary excretion of stress hormones, especially norepinephrine significantly decreases and workers are probably less prone to stress-related disorders.     

Air concentrations and urinary metabolites of polycyclic aromatic hydrocarbons among paving and remixing workers

The exposure of paving workers to polycyclic aromatic hydrocarbons (PAH) during stone mastic asphalt (SMA) paving and remixing was evaluated. The effects on the workers' PAH exposure were also evaluated during the use of an industrial by-product, coal fly ash (CFA), instead of limestone as the filler in the SMA. The PAH exposure was measured by personal air sampling and by analysing the levels of urinary naphthols, phenanthrols and 1-hydroxypyrene (1-OHP) in the workers' pre- and post-shift urine samples. The respiratory PAH exposure of the paving workers (geometric mean (GM) 5.7 microg m(-3)) was about ten-fold that of the traffic controllers (GM 0.43 microg m(-3)). The levels of PAH metabolites were significantly higher (p < 0.05) in the post-shift urine samples than in the pre-shift urine samples, and the levels of metabolites in the post-shift urine of paving workers were significantly higher than in that of the controls (p < 0.01). Urinary 1-naphthol correlated well with the airborne concentrations of the two- to three-ring PAHs (r = 0.544, p = 0.003) and naphthalene (r = 0.655, p < 0.001), when non-smoking paving workers were tested. A good correlation was observed between urinary 1-OHP and the airborne concentrations of the four- to six-ring PAHs (r = 0.524, p = 0.003) as well as total PAHs (r = 0.575, p = 0.001). The concentrations of 1-OHP and phenanthrols in the urine of the pavers were significantly higher (p < 0.01) during remixing than during SMA paving. The CFA in the asphalt had no effect on the airborne PAH exposure or on the concentrations of the PAH metabolites in the paving workers' urine.     

Detection criteria and preventive measures for occupational disease in the mines of Almaden (Spain)

This research focuses on the metallurgy and underground mining job positions in the historic mines of Almaden (Spain). We introduce a preventive methodology for hydrargyrism in work environments known by the name of Methodology for Operational Units Action Levels for Health Indicators (MUONAIS). The methodology allows critical levels to be established using environmental and clinical–biological indicators. The prevention plan concentrated on 15 job positions in the metallurgy department that employed more than 100 workers between the years 1986 and 1997. The development of this preventive methodology managed to keep workers’ mercury levels below 60 μg/l in blood and 200 μg/l in urine, values that present no negative effects on human health. MUONAIS has proven very effective in protecting workers’ health. During this period, some cases of micro-mercurialism were detected, yet were completely reversible, allowing us to affirm that the terrible disease of hydrargyrism was totally eradicated.     

Manganese air exposure assessment and biological monitoring in the manganese alloy production industry

One hundred workers carried personal air sampling equipment during three days to assess exposure to inhalable and respirable Mn. A novel four-step chemical fractionation procedure developed for the speciation of Mn in workroom aerosols was applied for selected aerosol filters. Blood and urine samples were analysed for Mn. The geometric mean (GM) concentrations of inhalable (n = 265) and respirable (n = 167) Mn determined in all filters were 254 microg m(-3) and 28 microg m(-3) respectively. Only 10.6% (95% CI 8.9-12.5) respirable Mn was found in the inhalable fraction when inhalable and respirable samples collected in parallel were considered (n = 153 pairs). There was a high correlation (Pearson's r = 0.70; p < 0.001) between respirable and inhalable Mn. The largest amounts of Mn in the inhalable aerosol fraction were found as Mn0 and Mn2+ (47.4%), whereas 28% was practically "insoluble". The associations between B-Mn and aerosol concentrations of Mn were weak, but an association was found between U-Mn and respirable Mn; Pearson's r being 0.38 between "soluble" respirable Mn and U-Mn. No significant association was found between the "insoluble" components (probably SiMn) and Mn in biological samples.     

Volatile hydrocarbon emissions from vehicles and vertical ventilations in the Hsuehshan traffic tunnel, Taiwan

The concentrations of 56 volatile organic hydrocarbons (VOCs) were measured simultaneously in the southbound bore, the northbound bore and the exhaust air shafts of the Hsuehshan tunnel near Yilan, Taiwan during 2007 and 2008. A total of 60 integrated air samples were collected using stainless steel canisters and analyzed using GC/FID and GC/MS. The highest temperature and lowest relative humidity were observed at the exit of the tunnel owing to the accumulation in the tunnel of waste heat that was exhausted from vehicles. The five most abundant species in all samples were ethylene, acetylene, isopentane, propylene, and toluene. The exit/entrance ratios of total non-methane hydrocarbon (NMHC) concentration were 7.8 and 4.8 for the southbound and northbound bores, respectively. Furthermore, the most abundant species of emission rate (ER) is toluene (21.93-42.89 mg s(-1)), followed by isopentane, ethylene, propylene and 1-butene, with ER ranging from 2.50 to 9.31 mg s(-1) for the three shafts. The ozone formation potential (OFP)/total NMHC ratios in three exhaust air shafts show that the reactivities of these emissions are similar to those of vehicle emissions.     

淄博化工园区大气有机污染应急监测与管理对策

针对工业聚集区内多种恶臭混杂的情况,以淄博化工园区为例,研究了大气有机污染突发事件中有机物的应急监测方法,并提出了治理对策。利用便携式气相色谱-质谱联用仪,对重点企业事先监测,掌握各企业特征污染物,作为应急监测查找污染源头的依据;现场分析受污染空气中的化合物组成及浓度,通过查询、比对各企业特征污染物,确认责任排污企业。提出了末端监测处罚治理与对重点污染企业推行清洁生产相结合,应急监测与有机污染物在线监测相结合,建立企业污染源特征组分数据库,加强企业无组织排放监测与监管等治理大气有机污染的建议。     

Assessment of non-occupational exposure to polycyclic aromatic hydrocarbons through personal air sampling and urinary biomonitoring

Non-occupational inhalation and ingestion exposure to polycyclic aromatic hydrocarbons (PAHs) has been studied in 8 non-smoking volunteers through personal air sampling and urinary biomonitoring. The study period was divided into 4 segments (2 days/segment), including weekdays with regular commute and weekends with limited traffic related exposures; each segment had a high or low PAH diet. Personal air samples were collected continuously from the subjects while at home, at work, and while commuting to and from work. All urine excretions were collected as individual samples during the study. In personal air samples, 28 PAHs were measured, and in urine samples 9 mono-hydroxylated metabolites (OH-PAHs) from 4 parent PAHs (naphthalene, fluorene, phenanthrene and pyrene) were measured. Naphthalene was found at higher concentrations in air samples collected at the subjects' residences, whereas PAHs with four or more aromatic rings were found at higher levels in samples taken while commuting. Urinary OH-PAH biomarker levels increased following reported high inhalation and/or dietary exposure. On days with a low PAH diet, the total amount of inhaled naphthalene during each 24-hour period was well correlated with the amount of excreted naphthols, as was, to a lesser extent, fluorene with its urinary metabolites. During days with a high dietary intake, only naphthalene was significantly correlated with its excreted metabolite. These findings suggest that this group of non-occupational subjects were exposed to naphthalene primarily through indoor air inhalation, and exposed to other PAHs such as pyrene mainly through ingestion.     

温室气体光声光谱检测系统的建立及效果分析

“双碳”目标下,温室气体在线长期稳定监测技术是全面掌握温室气体排放及其环境、气候效应,并预测未来变化趋势的重要保障。为了实时在线监测工业生产现场等环境温室气体浓度及其变化趋势,及时采取相应措施,在分析光声光谱信号产生机理及多组分气体混合监测原理的基础上,根据温室气体的主要成分,分析其吸收光谱特性,基于光声光谱的多组分温室气体的定性和定量监测技术,搭建温室气体光声光谱在线监测实验平台,分析监测器内部噪声和环境温度、湿度等外部影响因素,并通过现场测试,分析试验数据,应用吸附法降低内外部因素的影响。结果表明,对称安装传声器和非共振式光声腔能有效削弱外部噪声对测试结果的影响;空气净化器能降低空气中水蒸气和其他气体对测试结果的影响;低、高浓度混合气体监测结果偏差均小于0.5,与GC测试结果偏差小于10%。应用光声光谱技术的环境温室气体监测技术监测范围宽,选择性好,且监测精度达10^-6,适用于环境温室气体浓度在线监测。     

塔里木油田环境空气质量状况及评价

根据塔里木油田１９９３－１９９６年环境空气监测数据，对其环境空气质量状况进行了分析和评价。     

Diatoms as indicators in the Environmental Monitoring and Assessment Program-Surface Waters (EMAP-SW)

As a part of the U.S. Environmental Protection Agency's Environmental Monitoring and Assessment Program-Surface Waters (EMAP-SW), sedimentary diatom assemblages were studied from 66 lakes in the northeastern U.S.A. to evaluate the applicability of diatoms for this nation-wide monitoring program. Sediment cores were collected from the study lakes and diatoms were analyzed from the top (present-day) and bottom (pre-industrial) sediment samples. Canonical correspondence analysis (CCA) was used to examine which environmental variables correlate most closely with the distributions of diatom taxa in the top (surface) samples. Forward selection and Monte Carlo permutation tests showed that diatom species distributions were significantly related to total lakewater phosphorus (TP), pH, chloride, Secchi depth, and lake size and maximum depth. We developed weighted-averaging calibration and regression models for inferring TP (r ²=0.62), chloride (r ²=0.61), pH (r ²=0.86), and Secchi depth (r ²=0.62). An index of overall lake disturbance was also developed. Our diatom data indicate that marked changes have occurred in the study lakes since pre-industrial times as a result of anthropogenic activity.     

有机硫自动分析仪在石化园区环境空气监测中的应用

有机硫化物是环境空气典型恶臭物质,因环境浓度低和化学稳定性差,其定性定量分析是公认的难题。研究筛选5台市场主流有机硫自动分析仪,在石化园区开展实测以考察仪器在复杂环境下的适用性。结果表明:各仪器能对环境空气中有机硫物质持续有效监测,多数仪器所测甲硫醇、甲硫醚、二甲二硫醚和二硫化碳浓度的时间变化趋势较一致,其中D和E仪器的4种有机硫监测数据均呈显著相关,其相关系数分别为0.67、0.80、0.67和0.70(P0.01)。不同仪器测得有机硫数据呈正偏态分布,但浓度分布区间差异较大,表明部分仪器对污染物的富集、脱附和检测等环节仍需改进。D和E仪器监测的有机硫浓度明显升高时,监测点位附近的GC-FID/PID测得总挥发性有机物浓度较其他时段升高,且周边区域异味投诉量增加,说明这2台仪器监测数据能较好地反映该园区有机硫化物的污染特征。研究可为石化园区有机硫自动监测仪的设备选型提供依据。