Occupational chronic exposure to organic solvents

Summary Two groups of workers occupationally exposed to glycol ethers in a varnish production plant or the ceramic industry were examined. For 19 persons the external and internal exposure was assessed on the Monday and Tuesday after an exposure-free weekend. In the varnish production area the concentrations of 2-ethoxy-ethanol (EE) 2-ethoxyethyl acetate (EEAc), and 2-butoxyethanol (BE) in air averaged 2.9, 0.5, and 0.5 ppm, respectively, on the Monday, and 2.1, 0.1, and 0.6 ppm, respectively, on the Tuesday. At the same workplaces the mean urinary 2-ethoxyacetic acid (EAA) and 2-butoxyacetic acid (BAA) concentrations were 53.2 and 0.2 mg/l on Monday preshift and 53.8 and 16.4 mg/l on Tuesday postshift. The results show that glycol ethers are very well absorbed through the skin. Therefore biological monitoring is indispensable. To study the kinetics of the toxic metabolite, 17 persons were examined for their excretion of EAA in urine during an exposure-free weekend. The median values of the calculated half-times were 57.4 and 63.4 h, respectively, which are longer than the values presented in literature until now. According to our calculations the limit value should not exceed 50 mg EAA per liter of urine, which is the current German biological tolerance value (BAT value) for EAA in urine. The maximum concentration value at the work place (MAK value) for EE and EEAc in air should be revised. Finally, the subjects from the varnish production plant as well as a group of reference persons were studied for cytogenetic effects of glycol ethers (sister chromatid exchange, micronucleus test). Such effects could not be detected.     

Free and total urinary 2-butoxyacetic acid following dermal and inhalation exposure to 2-butoxyethanol in human volunteers

Objectives: To assess excretion kinetics of free and total (free + conjugated) 2-butoxyacetic acid (BAA) following dermal and inhalation exposure to butoxyethanol (BE). Methods: Six male volunteers were dermally exposed for 4 h to a 50% aqueous solution of BE on an area of 40 cm² of the volar forearm. Six other male volunteers were exposed by inhalation (mouth only) to 93 mg m^–3 BE for 30 min. As biological indices of exposure, BE in blood and total and free BAA in urine were measured. Results: Following inhalation exposure, the 24-h cumulative excretion of free and total BAA in urine amounted to 5.5 ± 2.7 and 12.8 ± 4.0 mg, respectively. After dermal exposure, 147.1 ± 61.0 and 346 ± 52 mg, respectively, of free and total BAA were excreted in urine up to 48 h after the onset of exposure. The proportion of conjugated BAA in single urine samples increased after dermal exposure in time from 45±30% in the first collection period to 92±2% after 48 h. The elimination half-life of total BAA following dermal exposure was longer than that of free BAA (5.1 ± 0.6 and 3.8 ± 0.4 h, respectively). The interindividual variation in the cumulative excreted amount after inhalatory exposure was higher (49%) for free BAA than for total BAA (31%). The average dermal flux amounted to 3.5 mg cm^–2 h^–1 independently of whether free or total BAA was used for the calculation, and, again, the interindividual variation in the estimated fluxes was higher for free BAA than for total BAA (41% and 15%, respectively). Conclusion: The interindividual variation in the extent of conjugation is large, and the degree of conjugation increases with time. Due to lower interindividual variability, total BAA is superior to free BAA as a biomarker of exposure.     

Gas chromatographic determination of methoxyacetic and ethoxyacetic acid in urine

Methoxyacetic acid (MAA) and ethoxyacetic acid (EAA), the major metabolites of, respectively, ethylene glycol monomethyl ether and ethylene glycol monoethyl ether and their acetates, are determined by gas chromatography after extraction from urine and methylation using 2-furoic acid (2-FA) as an internal standard. The mean recoveries (n = 30) from urine of MAA, EAA, and 2-FA are 31.4 +/- 7.0%, 62.5 +/- 13.4%, and 58.4 +/- 8.7%, respectively. The recoveries decreased (p less than 0.001), however, as the total amount of acids increased. Standard curves for MAA and EAA in urine are presented. The detection limits of MAA and EAA are 0.15 and 0.07 mg/l. Intra-assay variation for MAA and EAA was 6.0 +/- 2.5% and 6.4 +/- 2.8% and inter-assay variation was 6.2 +/- 2.2% and 8.9 +/- 2.4%. When volunteers were exposed to air containing ethylene glycol monoethyl ether (20 mg/m3), urinary concentration of EAA rose significantly one hour after the exposure period (2.39 +/- 1.03 v less than or equal to 0.07 mg/l, t = 5.2, p less than 0.005).     

Gas chromatographic determination of methoxyacetic and ethoxyacetic acid in urine.

Methoxyacetic acid (MAA) and ethoxyacetic acid (EAA), the major metabolites of, respectively, ethylene glycol monomethyl ether and ethylene glycol monoethyl ether and their acetates, are determined by gas chromatography after extraction from urine and methylation using 2-furoic acid (2-FA) as an internal standard. The mean recoveries (n = 30) from urine of MAA, EAA, and 2-FA are 31.4 +/- 7.0%, 62.5 +/- 13.4%, and 58.4 +/- 8.7%, respectively. The recoveries decreased (p less than 0.001), however, as the total amount of acids increased. Standard curves for MAA and EAA in urine are presented. The detection limits of MAA and EAA are 0.15 and 0.07 mg/l. Intra-assay variation for MAA and EAA was 6.0 +/- 2.5% and 6.4 +/- 2.8% and inter-assay variation was 6.2 +/- 2.2% and 8.9 +/- 2.4%. When volunteers were exposed to air containing ethylene glycol monoethyl ether (20 mg/m3), urinary concentration of EAA rose significantly one hour after the exposure period (2.39 +/- 1.03 v less than or equal to 0.07 mg/l, t = 5.2, p less than 0.005).     

Correspondence between occupational exposure limit and biological action level values for alkoxyethanols and their acetates

Objectives: The Finnish occupational exposure limit (OEL) values for alkoxyethanols and their acetates were lowered in 1996. A reevaluation of the correspondence between the new OEL value and the biological action level (BAL) was thus needed. This study was conducted in silkscreen printing enterprises, where 2-alkoxyethanols and their acetates are mainly used as solvents. The air/urine correlations between 2-methoxyethylacetate, 2-ethoxyethylacetate, 2-butoxyethanol, 2-butoxyethylacetate, and 2-methoxyacetic (MAA), 2-ethoxyacetic (EAA), and 2-butoxyacetic acid (BAA) were evaluated on an individual and time-related basis at four different enterprises. Methods: Inhalation exposure to alkoxyalcohols and their acetates was monitored with diffusion badges (n = 38) for an entire work week. Urinary excretion of alkoxyacetic acids immediately after the shift and at 14–16 h after exposure (n = 112) was analyzed by a gas chromatograph equipped with a flame-ionization detector. Results: Inhalation exposure to 2-methoxyethylacetate at 0.5 cm³/m³ corresponded to MAA excretion of 3 mmol/mol creatinine in urine at 14 to 16 hours after exposure. The next-morning urinary EAA excretion of 37 mmol/mol creatinine corresponded to an 8-h 2-ethoxyethylacetate exposure of 2 cm³/m³ when all collected data were included. This average EAA excretion was 69% of the German BAT value and only 34% of the American biological exposure index (BEI) value. Urinary EAA excretion was 30–40% lower at the beginning of the work week than at the end of the work week. On the other hand, EAA excretion was 10–20% higher than that measured at 14–16 h after exposure. Urinary BAA excretion of 75 mmol/mol creatinine in postshift urine corresponded to an 8-h 2-butoxyethanol and 2-butoxyethylacetate exposure of 5 cm³/m³. This BAA excretion was 87% of the German BAT value. Conclusion: According to these results, it seems that the BAL for MAA and EAA should be 3 and 50 mmol/mol creatinine as measured at 14–16 h after exposure, respectively. The BAL value for BAA seems to be 70 mmol/mol creatinine in postshift samples. These recommendations are valid only if samples are collected at the end of the work week. Received: 29 January 1997 / Accepted: 2 July 1997     

Biological monitoring of workers exposed to low levels of 2-butoxyethanol

Objectives: (1) To assess the value of urinary butoxyacetic acid (BAA) measurement for the monitoring of workers exposed to low concentration of 2-butoxyethanol (BE); (2) to evaluate the in vivo effect of low occupational BE exposure on the erythrocyte lineage; and (3) to test the possible influence of genetic polymorphism for cytochrome P450 2E1 (CYP 2E1) on urinary BAA excretion rate. Methods: Thirty-one male workers exposed to BE in a beverage package production plant were examined according to their external (BE) and internal (BAA) solvent exposure. The effect of this exposure on erythrocyte lineage [red blood cell numeration (RBC), hemoglobin (Hb), hematocrit (Htc), mean corpuscular volume (MCV), mean corpuscular hemoglobin (MCH), mean corpuscular hemoglobin concentration (MCHC), haptoglobin (Hp), reticulocyte numeration (Ret) and osmotic resistance (OR)], hepatic [aspartate aminotransferase (GOT), alanine aminotransferase (GPT)] and renal [plasmatic creatinine, urinary retinol binding protein (RBP)] parameters was also investigated. DNA purified from whole blood was used for CYP 2E1 genotyping. Results: Average airborne concentration of BE was 2.91 mg/m³ (0.59 ppm) with a standard deviation of 1.30 mg/m³ (0.27 ppm). There was a relatively good correlation between external and internal exposure estimated by measuring BAA in post-shift urine samples (average 10.4 mg/g creatinine; r=0.55;P=0.0012). Compared with a matched control group (n=21) exposed workers had a statistically significant decrease (3.3%;P=0.03) in Hct while MCHC was increased (2.1%;P=0.02). No significant difference was observed either in other erythroid parameters or in hepatic and renal biomarkers. One exposed individual exhibited a mutant allele with increased cytochrome P450 oxidative activity which coincided with a very low urinary BAA excretion. Conclusions: Single determination of BAA in post-shift urine samples can be used to assess exposure to low levels of BE. A slight but significant effect on erythroid parameters suggesting membrane damage was observed in exposed workers. The influence of the genetic polymorphism for CYP 2E1 deserves further investigation for the interpretation of urinary BAA measurements. Received: 6 December 1996 / Accepted: 21 February 1997     

Gaschromatographic determination of butoxyacetic acid after hydrolysis of conjugated metabolites in urine from workers exposed to 2-butoxyethanol

For the gaschromatographic determination of total butoxyacetic acid (BAA), i.e., free plus conjugated BAA in urine, we studied the acid hydrolysis condition to cleave the conjugate. The optimum condition for hydrolysis was chosen to be 60 min boiling of the mixture of 1 ml twofold diluted urine and 1.2 ml hydrochloric acid. For the biological monitoring of workers exposed to 2-butoxyethanol (BE), we applied our acid hydrolysis method to the urine from 6 workers exposed to the solvent for 7 days and determined total BAA as well as free BAA and conjugated BAA, which was calculated as the difference between the concentrations of free and conjugated BAA. The percentages of conjugated BAA vs. total BAA varied from 44.4% to 92.2% (mean value 71.1 %) among 6 individual workers over 7 days and decreased gradually over the consecutive work days. In the latter half of the work week, free BAA comparatively accounted for the larger portion of urinary BAA. Significant correlations were found between urinary BAA concentrations and BE levels in the breathing-zone air (TWA). The correlation coefficients of urinary concentrations of total or conjugated BAA vs. BE levels was higher than that of free BAA concentrations vs. BE levels. Hence, the determination of total BAA in urine is a suitable test for the biological monitoring of BE exposure, because of the simplicity in procedures and the good agreement with BE exposure levels.     

Serum bile acid concentrations as a liver function test in workers occupationally exposed to organic solvents

Summary Liver injury has long been associated with occupational exposure to a wide variety of chemicals. The controversial data existing in relation to hepatotoxicity of organic solvents might be explained as a consequence of the different exposures or it may well be that the tests used for evaluating liver function might not be sensitive enough to detect any mild changes at an early stage. To study liver function during exposure to solvent mixtures, we determined serum bile acid (SBA) concentrations as compared with conventional liver function tests in a selected group of workers (n = 30) occupationally exposed to a mixture of organic solvents (mostly toluene, xylene, acetone, n-butylacetate, n-butanol, ethylacetate) and in a reference group (n = 20). The mean levels of liver enzyme activities and bilirubin concentrations in the two groups were similar, whereas mean SBA levels increased in the exposed group (8.0 ± 6.0 mol/l vs 2.8 ± 1.4 mol/l) and the difference as compared with the controls was significant (P < 0.01). In 73% of the exposed workers, SBA levels were higher than 5.6 mol/l (the cut-off value) as compared with 5% of the controls. These results demonstrate the higher sensitivity in detecting liver dysfunction achieved with the SBA test as compared with conventional hepatic function tests. As increased SBA concentrations are considered to reflect an impairment of anion transport across the liver, higher SBA levels in the group of workers exposed to organic solvents might be explained as a slight and early sign of liver dysfunction. Therefore, SBA determination in biological monitoring of workers exposed to potentially hepatotoxic chemicals might be proposed.     

Synthetic Musk Toxicity to Early Life Stages of Zebrafish (<Emphasis Type="Italic">Danio rerio</Emphasis>)

Synthetic musk substances have been found in a number of environmental samples. Some of these chemicals have been detected in concentrations above 1 g/L in water, which raises concern about possible effects on aquatic life. The toxicity of four synthetic musks, 4-tert-butyl-2,6-dimethyl-3,5-dinitrophenylethanone (musk ketone), 1-tert-butyl-3,5-dimethyl-2,4,6-trinitrobenzene (musk xylene), 1-(5,6,7,8-tetrahydro-3,5,5,6,8,8-hexamethyl-2-naphthalenyl)ethanone (AHTN, tonalide) and 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-[g]-2-benzopyrane (HHCB, galaxolide), were studied in zebrafish by the use of two different early life-stage methods. In the first method, specific developmental characteristics during the first 48 hours were studied. In the second method, hatching and survival times were studied on eggs and larvae. The results on heart rate in the first test gave the following LOECs: musk ketone 10 g/L, musk xylene and AHTN 33 g/L, and HHCB showed no effect up to 1000 g/L. In the study of survival time, LOEC for musk ketone was 100 g/L, for musk xylene 33 g/L, and AHTN gave no effect on survival time up to 100 g/L. The LOECs for musk ketone, musk xylene, and AHTN in this study are in the range of what has been measured in sewage effluents and recipients, and consequently these substances may have adverse impact on wild fish.     

Occupational exposure to organic solvents during paint stripping and painting operations in the aeronautical industry

Summary The exposure of workers to methylene chloride and phenol in an aeronautical workshop was measured during stripping of paint from a Boeing B 747. Methylene chloride exposure was measured during two work days by personal air sampling, while area sampling was used for phenol. During paint stripping operations, methylene chloride air concentrations ranged from 299.2 mg/m³ (83.1 ppm) to 1888.9 mg/m³ (524.7 ppm). The exposures to methylene chloride calculated for an 8-h work day ranged from 86 mg/m³ (23.9 ppm) to 1239.5 mg/m³ (344.3 ppm). In another aeronautical workshop, exposure to organic solvents, especially ethylene glycol monoethyl-ether acetate (EGEEA), was controlled during the painting of an Airbus A 320. The external exposure to solvents and EGEEA was measured by means of individual air sampling. The estimation of internal exposure to EGEEA was made by measuring its urinary metabolite, ethoxyacetic acid (EAA). Both measurements were made during the course of 3 days. The biological samples were taken pre-and post-shift. During painting operations, methyl ethyl ketone, ethyl acetate, n-butyl alcohol, methyl isobutyl ketone, toluene, n-butyl acetate, ethylbenzene, xylenes and EGEEA were detected in working atmospheres. For these solvents, air concentrations ranged from 0.1 ppm to 69.1 ppm. EGEEA concentrations ranged from 29.2 mg/m³ (5.4 ppm) to 150.1 mg/m³ (27.8 ppm). For biological samples, the average concentrations of EAA were 108.4 mg/g creatinine in pre-shift and 139.4 mg/g creatinine in post-shift samples. Despite the fact that workers wore protective respiratory equipment during paint spraying operations, EEA urinary concentrations are high and suggest that percutaneous uptake is the main route of exposure for EGEEA. The introduction of new paint stripping processes in the aeronautical industry could help to reduce future exposure to methylene chloride.     

Improved method to measure urinary alkoxyacetic acids

OBJECTIVES: To simplify the current preparation of samples, and to improve the specificity and reliability of the conventional analytical methods to measure urinary alkoxyacetic acids. METHODS: Samples containing alkoxyacetic acids including methoxy, ethoxy, and butoxyacetic acids (MAA, EAA, and BAA) were acidified with HCl and extracted with a mixed solvent of methylene chloride and isopropyl alcohol, then analysed by gas chromatography/mass spectrometry (GC/MS). RESULTS: Optimal results were obtained when pH was 1.05-1.45, the ratio of methylene chloride and isopropyl alcohol was 2:1, and when extraction time was 10 minutes. Over the concentration range 0.3-200 micrograms/ml, MAA, EAA, and BAA could be determined with a pooled coefficient of variation (nine concentrations, six replicate samples) of 5.55%, 6.37%, and 6.41%, respectively. Urine samples were stable for at least 5 months and 3 freeze-thaw cycles at -20 degrees C. The limits of detection of MAA, EAA, and BAA were 0.055, 0.183, and 0.009 microgram/ml, respectively. The matrix effect of urine samples was negligible for MAA and EAA, but were marginally significant for BAA. The average recoveries of alkoxyacetic acids were 99%-101%. In urine samples MAA from 15 exposed workers showed a strong linear correlation (r = 0.999, slope = 1.01) between the new GC/MS method and Sakai's GC method. CONCLUSIONS: The simplified non-derivatisation pretreatment of samples coupled with GC/MS can provide a specific, sensitive, simple, safe, and reliable method for the biological monitoring of occupational exposure of ethylene glycol ethers.

 

     

Tetrachloroethene in exhaled air of persons living near polution sources

Summary Exhaled air was analyzed for tetrachloroethene (PER) in teachers and 4–5-year-old pupils of a kindergarten situated near a factory, and in residents of an old folks' home situated near a former chemical waste dump. The PER concentrations were higher in the exhaled air of children living near the factory (mean 24 g/m³, n=6) than in control children (mean 2.8 g/m³, n=11). In the old folks' home, the PER concentrations in the exhaled air of people living on the first floor were higher (mean 7.8 g/m³, n=10) than in the exhaled air of the people living on the second floor and higher (mean 1.8 g/m³, n=19). From the results of this study, it is clear that in environmental exposure to tetrachloroethene, biological monitoring of exhaled air is a simple, efficient, effective and convenient method of assessing total ambient exposure of both young and aged subjects.     

Cytotoxicity of 2-butoxyethanol and its oxidation products in vitro

Glycol ethers belong to a group of solvents with a wide spectrum of applications, particularly because of their compatibility to both hydrophilic and lipophilic systems. Especially ethylene glycol monobutyl ether (2-butoxy ethanol, BE) is widely used as a key ingredient in many industrial and consumer cleaning products. From cases of acute BE intoxication in humans it is known that it causes severe toxicity, including coma, metabolic acidosis, hypokalemia and hemoglobinuria. It is currently unknown whether the toxicity is related to BE itself or its oxidation products, butoxyacetaldehyde (BAL) and butoxyacetic acid (BAA). By use of an established kidney epithelial cell line from the proximal tubule (opossum kidney cells), the effects of BE, BAL and BAA on cell viability and the organization of the intracellular cytoskeleton of the cells were investigated and combined with gas chromatographic and mass spectrometric determinations. The experiments were performed with (i) freshly used BE, (ii) BE that had been stored at room temperature for 3 months after use in the original packing and containing 0.5% BAL, (iii) BAL with a purity of 73.5% after catalytic oxidative dehydration of BE with a heated copper meshwork, and (iv) BAA as the final oxidation product of BE. Kidney epithelial cells were unable to oxidize BE via BAL to BAA directly, but formation of BAA after the addition of BAL was observed with a turnover rate of approximately 45%. The tests for cytotoxicity showed no acute toxic effect for freshly used BE and BAA, whereas stored BE containing 0.5% BAL and synthesized BAL caused a dose-dependent decrease of viable cells within 24 h. The EC₅₀ (i.e. the concentration causing a 50% loss in cell viability) was 1 mg/mL for stored BE and 15 7g/mL for BAL. Calculations taking the actual BAL content of stored BE and BAL into account demonstrated that the cytotoxic effects seem to be mainly related to BAL and not to by-products such as butyraldehyde or n-butanol. In accordance with the tests for cytotoxicity were the cytoskeletal alterations of the three-dimensional stress fiber network. Stored BE and synthesized BAL caused a disruption and/or depolymerization of the stress fiber network which points to massive alterations of the intracellular ional milieu. The present study provides evidence that BE and BAA possess only a minor toxic potential, whereas BAL as the corresponding reactive intermediate has marked toxic effects. Thus, the aldehyde might be responsible for the toxic effects observed in studies in vitro and after human intoxication.     

Percutaneous absorption of neat and aqueous solutions of 2-butoxyethanol in volunteers

Objectives To study the influence of the presence of water on the dermal absorption of 2-butoxyethanol (BE) in volunteers.Methods Six male volunteers were dermally exposed to 50%, 90% or neat w/w BE for 4 h on the volar forearm over an area of 40 cm². An inhalation exposure with a known input rate and duration served as a reference dosage. The dermal absorption parameters were calculated from 24-h excretion of total (free + conjugated) butoxyacetic acid (BAA) in urine and BE in blood, measured after both inhalation and dermal exposure. Results The dermal absorption of BE from aqueous solutions was markedly higher than that of neat BE. The time-weighted average dermal fluxes were calculated from the urine and blood data and expressed in milligrammes per square centimetre per hour. The dermal fluxes obtained from cumulative 24-h excretion of BAA amounted to 1.34±0.49, 0.92±0.60 and 0.26±0.17 mg cm^–2 h^–1 for 50%, 90% and neat BE, respectively. The dermal fluxes calculated from the BE blood data amounted to 0.92±0.34 and 0.74±0.25 mg cm^–2 h^–1 for 50% and 90% BE, respectively. The permeation rates into the blood reached a plateau between 60 and 120 min after the start of exposure, indicating achievement of steady-state permeation. The apparent permeability coefficient K_p, was 1.75±0.53×10^–3 and 0.88±0.42×10^–3 cm h^–1 for 50% and 90% BE, respectively. Conclusion The percutaneous absorption of BE from aqueous solution increased markedly when compared with neat BE. Even water content as low as 10% led to an approximate fourfold increase in the permeation rates. These findings are important for the health risk assessment of occupational exposure to BE, since BE is commonly used in mixtures that contain water. Exposure to aqueous solutions of 50% and 90% of BE may result in substantial skin absorption: if a 60-min skin contact of 1,000 cm² is assumed, dermal uptake would be four-times higher than the pulmonary uptake of an 8-h occupational exposure at a TLV of 100 mg m^–3. This clearly justifies the skin notation for BE. For the purpose of biological monitoring, both BE in blood and BAA in urine were shown to be reliable indicators of exposure.     

Current external and internal exposure to naphthalene of workers occupationally exposed to polycyclic aromatic hydrocarbons in different industries

Objectives: External and internal exposure to naphthalene was examined in the most important industries that are typically concerned with polycyclic aromatic hydrocarbon (PAH)-induced diseases (cancer). Furthermore, a control collective from the general population was investigated. Methods: External naphthalene was determined by personal air sampling (n=205). The internal exposure was examined by urinary metabolites 1-naphthol and 2-naphthol (n=277). Results: Highest median concentrations of naphthalene in air were found in converter infeed (93.2 g/m³) and coal-tar distillation (35.8 g/m³). Moderate and low levels were determined in coking plants (14.5 g/m³) and in the production of refractories (6.1 g/m³) and graphite electrodes (0.7 g/m³). Biological monitoring revealed concentrations of the sum of both metabolites [(1+2)-NOL] in smokers to be increased by 1.6–6.4 times compared with that in non-smokers at the same workplaces. Among non-smokers we found high median (1+2)-NOL levels in converter bricklayers (120.1 g/l), in coal-tar distillation workers (56.0 g/l) and in coking plant workers (29.5 g/l). (1+2)-NOL concentrations around 10 g/l were found in the production of refractories and graphite electrodes. There was a rough coherency between external and internal naphthalene exposure. In the controls, median (1+2)-NOL concentrations were 10.9 g/l in non-smokers urine and 40.3 g/l in smokers urine samples. Conclusions: Actual conditions of occupational hygiene at the workplaces investigated in this comprehensive study are better than those that current limit values of 50,000 g/m³ (TLV, TRK) seem to induce. It has become obvious that tobacco smoking is a crucial confounding factor in biological monitoring of naphthalene-exposed humans, making interpretation of occupationally increased naphthol excretions very difficult at low exposure levels.     

Air and biological monitoring of solvent exposure during graffiti removal

Objective: The principal aim of the study was to estimate the level of exposure to organic solvents of graffiti removers, and to identify the chemicals used in different cleaning agents. A secondary objective was to inform about the toxicity of various products and to optimise working procedures. Methods: Exposure to organic solvents was determined by active air sampling and biological monitoring among 38 graffiti removers during an 8-h work shift in the Stockholm underground system. The air samples and biological samples were analysed by gas chromatography. Exposure to organic solvents was also assessed by a questionnaire and interviews. Results: Solvents identified were N-methylpyrrolidone (NMP), dipropylene glycol monomethyl ether (DPGME), propylene glycol monomethyl ether (PGME), diethylene glycol monoethyl ether (DEGEE), toluene, xylene, pseudocumene, hemimellitine, mesitylene, ethylbenzene, limonene, nonane, decane, undecane, hexandecane and γ-butyrolactone. The 8-h average exposures [time-weighted average (TWA)] were below 20% of the Swedish permissible exposure limit value (PEL) for all solvents identified. In poorly ventilated spaces, e.g. in elevators etc., the short-term exposures exceeded occasionally the Swedish short-term exposure limit values (STEL). The blood and urine concentrations of NMP and its metabolites were low. Glycol ethers and their metabolites (2-methoxypropionic acid (MPA), ethoxy acetic acid (EAA), butoxy acetic acid (BAA), and 2-(2-methoxyethoxy) acetic acid (MEAA)) were found in low concentrations in urine. There were significant correlation between the concentrations of NMP in air and levels of NMP and its metabolites in blood and urine. The use of personal protective equipment, i.e. gloves and respirators, was generally high. Conclusions: Many different cleaning agents were used. The average exposure to solvents was low, but some working tasks included relatively high short-term exposure. To prevent adverse health effects, it is important to inform workers about the health risks and to restrict the use of the most toxic chemicals. Furthermore, it is important to develop good working procedures and to encourage the use of personal protection equipment. Received: 20 October 1999 / Accepted: 4 March 2000     

Reduced exposure to organic solvents by use of water-based paint systems in car repair shops

Objective The objective of this study was to determine to what extent the substitution of solvent-based paint by water-based paint has reduced potential exposure to organic solvents for spray painters in car repair shops.Methods Full-shift personal air sampling (n=79) was carried out over 3 consecutive days in eight car repair shops. Blood samples on the Monday morning (n=26) and at the end of the shift on the Wednesday (n=26), were analysed for organic solvents by headspace techniques.Results Toluene was the organic solvent detected at the highest geometric mean concentration in air samples when solvent-based paint systems were used (0.8 ppm), whereas xylene was found at the highest level when water-based systems were used (0.25 ppm). Toluene, isopropanol, acetone and butyl acetate were detected at higher concentrations when solvent-based paint was used than when water-based paint was employed. The additive factor, based on Norwegian limit values, was three-times higher for the painters using solvent-based paint (0.15) than for those using water-based paint (0.05). On Wednesday after shift the geometric mean of toluene in blood was significantly higher for the painters using solvent-based paint (0.044 g/ml) than for the painters using water-based paint (0.007 g/ml). There was a significant correlation between toluene in personal air samples and toluene in blood samples taken at the end of the shift on the same day.Conclusions When solvent-based paint systems were used the additive factor for organic solvent exposure was three-times higher than when water-based systems were employed. The exposure levels of the organic solvents were well below the Norwegian limit values. The significant correlation between the toluene concentration in air and blood samples indicated that the uptake of organic solvents was correspondingly reduced. At the levels of organic solvents presently described the risk of acute and chronic health effects caused by organic solvents is low.     

A new HPLC fluorimetric method to monitor urinary delta-aminolevulinic acid (ALA-U) levels in workers exposed to lead

Summary A new sensitive HPLC method for the determination of urinary delta-aminolevulinic acid (ALA-U) was used to evaluate the relationship between blood-lead (Pb-B) and ALA-U levels in male workers exposed to lead. The differences between the ALA-U levels determined by this method (ALAU-HP) and by a colorimetric method (ALA-U-CL) are discussed. The HPLC method gave values similar to the ALA-U-CL values at high ALA-U level. However, at low blood-lead levels (58 ± 22 g/l, n = 23), the mean ALA-U-HP level corrected by urinary creatinine level was one-third of the corrected ALA-UCL level (0.83 ± 0.14 and 2.4 ± 0.5 mg/g creatinine, respectively). A significant increase of the mean corrected ALA-U-HP level was observed at 162 ± 22 g/l Pb-B (P < 0.05, n = 26), while that of ALA-UCL was observed at 245 ± 30 g/l Pb-B (P < 0.01, n = 37). The regression equation based on the logistic model fitted well to the relationship data between the Pb-B level and the percentage of the subjects with corrected ALA-U-HP above the cut-off point (1.12 mg/g creatinine) and the expected Pb-B level for 50% response was 270 g/l Pb-B, while it did not fit well to the relationship data between Pb-B level and the percentage of the subjects with corrected ALAU-CL above the cut-off point (3.5 mg/g creatinine). The maximum responses for the two sets of corrected ALA-U levels were both observed at 625 ± 25 g/l. The corrected ALA-U level by HPLC method seems to be a useful indicator for biological monitoring of exposure to lead at low levels (< 400 g/l Pb-B = health-based biological limit, WHO) as well as high ones.     

Contaminant levels in harbor seals from the northeastern United States

The concentrations of polychlorinated biphenyls (PCBs), organochlorine pesticides, polycyclic aromatic hydrocarbons (PAHs), polychlorinated dibenzofurans (PCDF), polychlorinated dibenzo-p-dioxins (PCDD), and mercury (Hg) were determined in blubber and liver tissues of harbor seals (Phoca vitulina) collected along the northeast coast of the U.S. Average PCB concentrations in seal blubber (sum of congeners) were 12.0 g/g (wet weight) with a range of 7.30 to 24.3 g/g in 1980 and 6.66 g/g (wet weight) with a range of 2.61 to 11.3 g/g in 1990–1992. Comparisons between blubber data from this study and previous work indicated that the concentration of PCBs along the northeast coast of the U.S. may have decreased over the past twenty years.The average p,p-DDE concentrations in seal blubber were 10.9 g/g (wet weight) in 1980 with a range of 6.95 to 21.9 g/g and 4.12 g/g (wet weight) with a range of 1.83 to 7.84 g/g in 1990–1992. Only trace amounts of PCDFs and PCDDs were found in a few blubber samples; levels in most tissues were below detection (3–5 pg/g) (wet weight). Trace amounts (<30 ng/g) of phenanthracene, anthracene, and alkylated MW-178 compounds were found in some seal samples; all other PAH compounds were below the detection level (5–15 ng/g).Toxic equivalents (TEQ) of selected coplanar and mono-ortho PCB congeners and relative toxic equivalents (RTE) (pg total TEQ/g total PCB) were calculated, using recently proposed dioxin toxic equivalent factors (Ahlborg et al. 1994). The TEQs ranged from 41 to 315, and the RTEs ranged from 2.25 to 16.3. The RTEs for seal blubber indicated that the present values were in the midrange of those reported in the literature. Toxic equivalents calculated on the basis of the concentrations of the coplanar PCBs, PCDDs, and PCDFs indicated that coplanar PCBs, rather than PCDDs and PCDFs, may pose a more important toxic threat to harbor seals.Mercury levels in liver tissue averaged 70.0 g/g (wet weight) and 44.1 g/g (wet weight) in the 1991 and 1980 samples, respectively, and are similar to those found in relatively polluted waters of the British Isles.     

Short-term exposure of zooplankton to the synthetic pyrethroid,fenvalerate, and its effects on rates of filtration and assimilation of the alga,Chlamydomonas reinhardii

In acute tests of toxicity, two cladocerans,Daphnia galeata mendotae andCeriodaphnia lacustris, and the calanoid,Diaptomus oregonensis, were more sensitive to fenvalerate thanDaphnia magna, the organism used in standard laboratory bioassays. The 48-hr EC₅₀s for each species/stage in order of increasing sensitivity were adultD. magna — 2.52 g/L;D. magna (48-hr old) — 0.83 g/L; adultD. galeata mendotae — 0.29 g/L; adultC. lacustris — 0.21 g/L;D. galeata mendotae (48-hr old) — 0.16 g/L; adultDiaptomus oregonensis — –0.12 g/L. No toxicity was observed when these organisms were exposed to a range of concentrations of the emulsifiable concentrate without fenvalerate (the EC blank).Rates of filtration of the¹⁴C-labelled alga,Chlamydomonas reinhardii byD. galeata mendotae, C. lacustris andD. oregonensis were decreased significantly at sublethal concentrations of fenvalerate after only 24-hr exposure.Ceriodaphnia lacustris showed the greatest sensitivity with rates of filtration significantly decreased at 0.01 g fenvalerate/ L. Concentrations of fenvalerate 0.05 g/L resulted in decreased rates of filtration byD. galeata mendotae. A concentration of 0.10 g fenvalerate/ L caused rates of filtration to increase inD. oregonensis. whereas 0.05 and 0.5 g/L resulted in a decrease in these rates.Rates of assimilation of algae byD. galeata mendotae, C. lacustris andD. oregonensis exposed to similar concentrations of fenvalerate were decreased at concentrations 0.05 g fenvalerate/L. Changes in rates of assimilation were not as sensitive a parameter of toxicity as changes in rates of filtration. The EC blank had no significant effects on rates of filtration or assimilation for all three species.