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.     

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.     

Correlation of urinary nickel excretion with observed 'total' and inhalable aerosol exposures of nickel refinery workers

An investigation of the relationship between observed nickel aerosol exposures and urinary nickel excretion was undertaken at a Scandinavian nickel refinery. The goal of the study was to assess the impact of nickel aerosol speciation, the use of particle size-selective sampling instrumentation and adjustment of urinary levels for creatinine excretion on the usefulness of urinary nickel excretion as a marker for exposure. Urinary nickel measurements and paired 'total' and inhalable aerosol exposure measurements were collected each day for one week from refinery workers in four process areas. The mean observed urinary nickel concentration was 12 micrograms L-1 (11 micrograms of Ni per g of creatinine). The strongest relationships between urinary excretion and aerosol exposure were found when urinary nickel levels were adjusted for creatinine excretion and when exposure to only soluble forms of nickel aerosol was considered. No significant difference was observed between measures of 'total' and inhalable aerosol in the ability to predict urinary excretion patterns. In the light of these results, it is recommended that consideration be given to the chemical species distribution of nickel aerosol in the use of urinary nickel measurements as a screening tool for cancer risk in occupationally-exposed populations.     

The assessment of biomarkers in sentinel cattle for monitoring vanadium exposure

Various potential biomarkers were sampled for vanadium every 3-4 months from Bos indicus beef cattle farmed extensively immediately adjacent (high exposure (HE) group) and two km away (low exposure (LE) group) from a vanadium processing plant, respectively. Vanadium intake (mg vanadium kg(-1) bwt d(-1)) was modelled using environmental and physiological data as inputs. The vanadium intake ranged from 0.57 to 5.44 mg vanadium kg(-1) bwt d(-1) in the HE group and 0.41 to 2.61 mg vanadium kg(-1) bwt d(-1) in the LE group over a five-year period of monitoring. Samples collected from live sentinel animals over the five-year period included caudal coccygeal vertebrae, tail-switch hair, milk, urine, faeces, rib-bone biopsies and a wide range of blood clinical pathology and haematological parameters. The data was analysed for differences in response between the HE and LE groups. Where differences were found, a linear mixed-effects regression model was fitted to model the relationship between the exposure dose and the response variable. The model included the effects of age, duration of exposure and response, and allowed the prediction of the exposure dose given these inputs. Moreover, forty-two adult cattle were slaughtered over the five years. A wide range of tissue samples, rumen content and whole blood were taken from the cattle at slaughter for vanadium determination. In live animals, a difference in response was found between the HE group and LE group with respect to serum albumin (n = 36), monocyte (n = 36) and thrombocyte (n = 36) counts, and hair (n = 2) and faeces (n = 34) vanadium concentrations. No difference in vanadium concentrations could be shown for urine (n = 36), the traditional occupational health biomarker. Regression models are described for serum albumin, monocyte counts, faeces and hair, which showed the most promise as biomarkers. Average concentrations of vanadium in the tissues of slaughtered cattle ranged from 0.08 to 2.94 mg kg(-1) (wet-weight basis) and rumen content contained 16.67 mg kg(-1). Significant correlations were found between the exposure dose (end-dose) just prior to slaughter and the concentrations of vanadium in the coccygeal vertebrae, liver, diaphragm and rib-bone in descending order of magnitude. Other tissues showed poor correlation to the end-dose. Tissue levels of vanadium in healthy cattle include a much wider range than is currently reflected in the literature. The best tissue from slaughter animals for assessing chronic vanadium exposure is probably the liver.     

Submicrometer elemental carbon as a selective measure of diesel particulate matter in coal mines

A monitoring method for diesel particulate matter was published as Method 5040 by the National Institute for Occupational Safety and Health (NIOSH). Organic and elemental carbon are determined by the method, but elemental carbon (EC) is a better exposure measure. The US Mine Safety and Health Administration (MSHA) proposed use of NIOSH 5040 for compliance determinations in metal and nonmetal mines. MSHA also published a rulemaking for coal mines, but no exposure standard was provided. A standard based on particulate carbon is not considered practical because of coal dust interference. Interference may not be a problem if an appropriate size-selective sampler and EC exposure standard are employed. Submicrometer dust concentrations found in previous surveys of nondieselized, underground coal mines were relatively low. If a large fraction of the submicrometer dust is organic and mineral matter, submicrometer EC concentrations would be much lower than submicrometer mass concentrations. Laboratory and field results reported herein indicate the amount of EC contributed by submicrometer coal dust is minor. In a laboratory test, a submicrometer EC concentration of 31 microg m(-3) was found when sampling a respirable coal dust concentration over three times the US compliance limit (2 mg m(-3)). Laboratory results are consistent with surveys of nondieselized coal mines, where EC results ranged from below the method limit of detection to 18 microg m(-3) when size-selective samplers were used to collect dust fractions having particle diameters below 1.5 microm-submicrometer EC concentrations were approximate 7 microg m(-3). In dieselized mines, submicrometer EC concentrations are much higher.     

Characteristics and assessment of phthalate esters in urban dusts in Guangzhou city, China

Phthalate esters (PAEs) were examined in indoor and outdoor dust samples from the subtropical city of Guangzhou, China. The ∑(16)PAEs concentrations ranged from 121 to 3,223 μg g(-1) dust, with the median concentration of 840 μg g(-1) dust. Significantly higher concentrations of PAEs in dust samples were found in offices where electrical and electronic devices, carpet pads, and office furniture were widely used. Of the 16 PAEs, diisobutyl phthalate (DiBP), di-n-butyl phthalate (DnBP), and di(2-ethylhexyl) phthalate (DEHP) dominated the PAEs in indoor and outdoor dust samples, and accounted for >96.8% and >93.1% of the ∑(16)PAEs concentrations, respectively. The median daily inhalation exposure of ∑(16)PAEs were 3.53 and 0.247 μg kg(-1) body weight day(-1), and at the 95(th) percentile were 7.62 and 0.530 μg kg(-1) body weight day(-1), up on the measured concentrations and estimated dust ingestion rates, respectively, for toddles and adults. The ubiquitous distribution of PAEs as noted in this study suggests the need for detailed assessment of PAEs concentrations using more sites and to further investigate the factors influencing PAEs exposure in China.     

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.     

Carbon disulfide at a Chinese viscose factory external and internal exposure assessment

This article presents the results of carbon disulfide exposure measurements in a Chinese viscose rayon factory. The objectives of the study were to identify the external exposure levels at a large factory and to investigate the 2-thiothiazolidine-4-carboxylic acid (TTCA) concentrations in the urine of the subjects who were exposed to carbon disulfide in the working place atmosphere. The metabolism of carbon disulfide in the exposed subjects was also studied in order to demonstrate the best points in time for the internal exposure sampling. The measurement of the amount of personal exposure to carbon disulfide in the air of the workplace was performed by GC-FPD; the presence of TTCA in the workers urine was analyzed by use of a modified HPLC method. The kinetics of TTCA excretion was studied by analyses at different time-points both during and after exposure to carbon disulfide in the subjects. A total of 155 personal samples were obtained. The carbon disulfide concentration in the staple viscose hall was 13.72 +/- 1.12 mg m-3 in terms of the geometric mean +/- geometric standard deviation, and was 20.05 +/- 1.33 mg m-3 in the filament spinning hall. The TTCA values in the subjects who worked in the staple spinning hall were 1.18 +/- 0.43 mg g-1 creatinine and 1.07 +/- 0.38 mg g-1 creatinine for subjects working in the filament spinning hall. The best time for TTCA sampling is at the end of the working shift, the TTCA excretion was stable for a period of 4-12 h after exposure of the subjects to the carbon disulfide. It might be that the Chinese have different anthropometric characteristics; a sampling bias may therefore appear among different races.     

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.     

Biological monitoring of wood dust exposure in nasal lavage by high-performance liquid chromatography

A high-performance liquid chromatography (HPLC) method for biomonitoring of occupational wood dust exposure based on nasal lavage as a biomonitoring matrix was developed. Gallic acid (GA) was chosen as the indicator compound for oak dust exposure. From the chromatographic profile of ash dust, four peaks were chosen as indicator compounds. Phenolic indicator compounds were analysed by HPLC. Personal dust samples and corresponding nasal lavage samples were collected from 16 workers exposed to oak dust and six to ash dust. The dust concentrations in the workers' breathing zone varied between 0.7 and 13.8 mg m(-3). The indicators revealed the nature of the wood dust inhaled. For the workers who did not use respirators, the correlation between the dust and corresponding indicator compound in their nasal lavage was significant; r2 = 0.59 (n = 12) for oak dust and r2 = 0.58 (n = 6) for ash dust, respectively. Further, the correlation for oak dust workers who used respirators was r = 0.67 (n = 4). Nasal lavage sampling and HPLC analysis of polyphenol indicator compounds are promising tools for measuring wood dust exposure. Although further validation is necessary, determination of the individual dose may prove invaluable in prospective epidemiological studies.     

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.     

Environmental and biological monitoring of methyl ethyl ketone (MEK)

This study was conducted to evaluate the usefulness of various biological parameters for monitoring of workers exposed to methyl ethyl ketone (MEK). Fifty male workers from a large magnetic videotape factory participated in this study. Personal air samples were collected using 3M organic vapor monitors and analysed for MEK by gas chromatography with flame ionisation detector (FID). 10 mL of urine; blood (1 mL) and exhaled air were also collected at the end of an 8-hour workshift. The headspace GC method was applied for measurement of urinary and blood MEK. MEK in expired air was analysed directly by using a GC/FID.The correlation coefficients (r) between environmental MEK and all other biological parameters measured show significant positive relationships. The r for environmental MEK and urine MEK was 0.84; for blood 0.73 and for breath 0.64. The correlation coefficients between blood and urine was 0.72; blood and breath was 0.88 and urine and breath 0.60. These findings suggest that measurements of unmetabolised MEK in blood, exhaled air and urine can be used for biological monitoring of MEK exposure. Nevertheless, laboratory methodological assessment is in favour of measuring urinary MEK as it is non-invasive and does not have to be analysed immediately after collection.     

Urinary 8-hydroxy-2'-deoxyguanosine in inhabitants chronically exposed to arsenic in groundwater in Cambodia

Arsenic concentrations in hair and urine, and urinary levels of 8-hydroxy-2'-deoxyguanosine (8-OHdG), a marker of oxidative DNA damage, were examined for inhabitants of the Mekong Basin in Kratie Province, Cambodia. Also, the arsenic levels of tube-well water were determined. Total arsenic concentrations in tube-well water ranged from <1 to 886 microg L(-1), and 44.8% of these exceeded the WHO drinking water guideline of 10 microg L(-1). Elevated levels of arsenic were observed in the human hair and urine, and also a significant positive correlation was observed between the concentrations in hair and urine. These results suggest that the inhabitants are chronically exposed to arsenic through drinking the tube-well water. Levels of urinary 8-OHdG were higher for the subjects with higher arsenic levels in hair and urine, suggesting that induction of oxidative DNA damage was caused by chronic exposure to arsenic in tube-well water for the inhabitants in Kratie Province. To our knowledge, this is the first report on the oxidative DNA damage caused by chronic exposure to arsenic in groundwater for the inhabitants in Cambodia.     

Determination of N-acetyl-S-(N-methylcarbamoyl)cysteine (AMCC) in the general population using gas chromatography-mass spectrometry

Carbamoylation of glutathione, peptides and DNA is thought to be one of the most important reactions occurring in an organism after exposure to nitrosoureas, methylformamides or isocyanates. The carcinogenic effects of carbamoylation are not yet fully clarified. Although carbamoylation is known to occur after occupational exposure, it has never been reported in the general population. To clarify the situation, we investigated the levels of N-acetyl-S-(N-methylcarbamoyl)cysteine (AMCC) in urine samples from persons without occupational exposure using a sensitive and specific method (gas chromatography-mass spectrometry, GC-MS). AMCC is the degradation product of N-methylcarbamoylated glutathione. The clean-up procedure of urine samples includes two liquid-liquid extraction steps and solid phase extraction using a cation-exchange resin to separate AMCC from other urinary components. N,N-Dimethylpropionic acid amide (DMPA) is used as internal standard. During the preparation of the samples, AMCC is converted to ethyl-N-methylcarbamate (EMC) in the presence of anhydrous potassium carbonate (K2CO3) and ethanol. The reliability and accuracy of this method have been proven in detail. The relative standard deviation for the within-series imprecision for three different concentrations was determined to be between 10.9% and 14.3%, while the relative standard deviation for the between-day imprecision was between 11.3% and 14.8%. The mean recovery for AMCC was determined to be between 79.2% and 85.6%. The limit of detection for the simultaneous measurement of two fragment masses was 30 micrograms L-1. Using this GC-MS method, we analysed urine samples from 42 individuals of the general population in order to determine their urinary excretion of AMCC. It was identified in 40 samples. The mean concentration was 40 micrograms L-1. AMCC can be formed in two ways. The first possibility is the dietary intake of isothiocyanates, especially methyl isothiocyanate, which is a component of wine and cruciferous vegetables (such as cabbage, turnips and cress). During the metabolism of isothiocyanates in humans, the sulfur is partly exchanged for oxygen resulting in the formation of the corresponding isocyanate derivatives. The other possibility is the physiological formation of AMCC. In humans, this may occur via a two step process: carbamoylation and methylation, or vice versa. However, as AMCC was identified in about 95% of urine samples, and the standard deviation for the level of AMCC excreted was low, physiological formation seems to be the more probable pathway.     

Exposure and inhalation risk assessment in an aluminium cast-house

To date the exposure, absorption and respiratory health effects of cast-house workers have not been described since most studies performed in the aluminium industry are focused on exposure and health effects of potroom personnel. In the present study, we assessed the external exposure and the absorbed dose of metals in personnel from the aluminium cast house. This was combined with an evaluation of respiratory complaints and the lung function of the personnel. 30 workers from an aluminium casting plant participated and 17 individuals of the packaging and distribution departments were selected as controls. The exposure was assessed by the quantification of total inhalable fume with metal fraction and by the determination of urinary aluminium, chromium, beryllium, manganese and lead concentration. Carbon monoxide (CO), carbon dioxide (CO2), aldehydes and polyaromatic hydrocarbons and man-made mineral fibres concentration were assessed as well. In order to evaluate their respiratory status each participant filled out a questionnaire and their lung function was tested by forced spirometry. Total inhalable fume exposure was maximum 4.37 mg m(-3). Exposure to the combustion gases, man-made mineral fibres and metal fume was well below the exposure limits. Beryllium could not be detected in the urine. The values of aluminium, manganese and lead in the urine were all under the respective reference value. One individual had a urinary chromium excretion above the ACGIH defined biological exposure index (BEI) of 30 microg g(-1) creatinine. There was no significant difference in any of the categories of the respiratory questionnaire and in the results of the spirometry between cast house personnel and referents (Chi-square, all p > 0.05). Exposure in cast houses seem to be acceptable under these conditions. However, peak exposure to fumes cannot be excluded and the potential risk of chromium and beryllium exposure due to the recycling of aluminium requires further attention.     

Influence of reagent purity on the ion chromatographic determination of bromate in water using 3,3'-dimethoxybenzidine as a prochromophore for photometric detection

Variable availability of the purified dihydrochloride salt of 3,3'-dimethoxybenzidine (DMB; ortho-dianisidine) led us to investigate the effects of reagent purity on the analytical results obtained when this reagent is used in the photometric determination of the disinfection byproduct bromate. After analyte ions are separated by ion chromatography, a solution of DMB (post-column reagent) is added to the eluate and the DMB is oxidized, thereby producing a chromophore detected by its absorbance. Although some commercial products of undefined grade performed well, others did not. Variability was also observed between lots of purified material. Sensitivity at low concentrations (< 5 micrograms L-1 BrO3-) varied by a factor of up to 10. In some cases, the lower limit of detection for photometric detection was greater than that obtained using conductivity detection, as high as 5-7 micrograms L-1 BrO3-. An impurity or several impurities are suspected to be responsible for deviations from linearity at low analyte concentrations. This investigation underscores the need for ensuring reagent purity in environmental analyses. Ideally, chemical manufacturers will meet the needs of analytical chemists who test potable water and begin producing a high grade material in sufficient quantities to meet monitoring requirements. The establishment of third-party standards for a spectrophotometric grade of DMB.2HCl would be helpful in ensuring that a variety of manufacturers could supply products of uniformly high quality that would be suitable for the measurement of bromate in public drinking water supplies.     

Fragmentation of extracellular DNA by long-term exposure to radiation from uranium in aquatic environments

Persistent harmful scenarios associated with disposal of radioactive waste, high-background radiation areas and severe nuclear accidents are of great concern regarding consequences to both human health and the environment. Of particular concern is the extracellular DNA in aquatic environments contaminated by radiological substances. Strand breaks induced by radiation promote decrease in the transformation efficiency for extracellular DNA. The focus of this study is the quantification of DNA damage following long-term exposure (over one year) to low doses of natural uranium (an alpha particle emitter) to simulate natural conditions, since nothing is known about alpha radiation induced damage to extracellular DNA. A high-resolution Atomic Force Microscope was used to evaluate DNA fragments. Double-stranded plasmid pBS as a model for extracellular DNA was exposed to different amounts of natural uranium. It was demonstrated that low concentrations of U in water (50 to 150 ppm) produce appreciable numbers of double strand breaks, scaling with the square of the average doses. The importance of these findings for environment monitoring of radiological pollution is addressed.     

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 and biological monitoring of bar and restaurant workers before and after the introduction of a smoking ban

The aims were to assess the impact of a total smoking ban on the level of airborne contaminants and the urinary cotinine levels in the employees in bars and restaurants. In a follow up design, 13 bars and restaurants were visited before and after the implementation of a smoking ban. Ninety-three employees in the establishments were initially included into the study. The arithmetic mean concentration of nicotine and total dust declined from 28.3 microg m(-3) (range, 0.4-88.0) and 262 microg m(-3) (range, 52-662), respectively, to 0.6 microg m(-3) (range, not detected-3.7) and 77 microg m(-3) (range, not detected-261) after the smoking ban. The Pearson correlation coefficient between airborne nicotine and total dust was 0.86 (p < 0.001; n = 48). The post-shift geometric mean urinary cotinine concentration declined from 9.5 microg g(-1) creatinine (cr) (95% CI 6.5-13.7) to 1.4 microg g(-1) cr (95% CI 0.8-2.5) after the ban (p < 0.001) in 25 non-snuffing non-smokers. A reduction from 1444 microg g(-1) cr (95% CI 957-2180) to 688 microg g(-1) cr (95% CI 324-1458) was found (p < 0.05) in 29 non-snuffing smokers. The urinary cotinine levels increased from 11.7 microg g(-1) cr (95% CI 7.0-19.6) post-shift to 21.9 microg g(-1) cr (95% CI 13.3-36.3) (p < 0.01) in the next morning in 24 non-snuffing non-smokers before the smoking ban. A substantial reduction of airborne nicotine and total dust was observed after the introduction of a smoking ban in bars and restaurants. The urinary cotinine levels were reduced in non-smokers. The decline found in smokers may suggest a reduction in the amount of smoking after intervention. In non-smokers cotinine concentrations were higher based on urine sampled the morning after a shift than based on urine sampled immediately post-shift.     

Road pavers' occupational exposure to asphalt containing waste plastic and tall oil pitch

Waste plastic (WP) and tall oil pitch (T), which are organic recycled industrial by-products, have been used as a binder with bitumen in stone mastic asphalt (SMA) and asphalt concrete (AC). We compared the exposure over one workday in 16 road pavers participating in a survey at four paving sites, using mixes of conventional asphalt (SMA, AC) or mixes containing waste material (SMA-WPT, AC-WPT). The concentrations of 11 aldehydes in air were 515 and 902 microg m(-3) at the SMA-WPT and AC-WPT worksites, being 3 and 13 times greater than at the corresponding worksites laying conventional asphalt. Resin acids (2-42 microg m(-3)), which are known sensitizers, were detected only during laying of AC-WPT. The emission levels (microg m(-3)) of total particulates (300-500), bitumen fumes (60-160), bitumen vapour (80-1120), naphthalene (0.59-1.2), phenanthrene (0.21-0.32), pyrene (<0.015-0.20), benzo(a)pyrene (<0.01) and the sum of 16 PAHs (polycyclic aromatic hydrocarbons, 1.28-2.00) were similar for conventional and WPT asphalts. The dermal deposition of 16 PAHs on exposure pads (on workers' wrist) was low in all pavers (0.7-3.5 ng cm(-2)). Eight OH-PAH biomarkers of naphthalene, phenanthrene and pyrene exposures were quantified in pre- and post-shift urine specimens. The post-shift concentrations (mean +/- SD, micromol mol(-1) creatinine) of 1- plus 2-naphthol; 1-,2-,3-,4- plus 9-phenanthrol; and 1-hydroxypyrene were, respectively, for asphalt workers: 18.1+/- 8.0, 2.41 +/- 0.71 and 0.66+/- 0.58 (smokers); 6.0+/- 2.3, 1.70+/- 0.72 and 0.27+/- 0.15 (non-smokers); WPT asphalt workers: 22.0+/- 9.2, 2.82+/- 1.11 and 0.76+/- 0.18 (smokers); 6.8+/- 2.6, 2.35+/- 0.69 and 0.46+/- 0.13 (non-smokers). The work-related uptake of PAHs was low in all pavers, although it was significantly greater in smokers than in non-smokers. The WPT asphalt workers complained of eye irritation and sore throat more than the pavers who had a much lower exposure to aldehydes and resin acids.