Occupational chronic exposure to organic solvents XII. O-cresol excretion after toluene exposure

Summary Thirty-five printing workers were investigated according to their external and internal exposure to toluene. The concentration of toluene in the air of the working place was determined using stationary air sampling and gas chromatography. To determine the levels of toluene in blood as well as the concentrations of o-cresol, hippuric acid, and phenol in urine, biological specimens were collected at the end of exposure. The parameters were determined by gas chromatography and gas chromatography/mass spectrometry. According to our results, o-cresol concentrations higher than 5.3 mg per litre of post-shift urine might indicate an external exposure higher than the present MAK-value of 200 ppm.     

Propylene glycol monomethyl ether (PGME) occupational exposure

An analytical method was developed for the determination of free and conjugated PGME-α in urine. The method involves a solid-phase extraction on LC-18 columns and a GC/FID analysis after derivatization with trimethysilylimidazole. The assay was linear (least-squares regression coefficient 0.996), specific, reproducible (intraassay variability 10%, interassay variability 10%), and allowed a high level of PGME recovery (more than 90%). The assay was applied to the analysis of urine samples from three workers who were occupationally exposed to PGME to estimate their exposure. The highest value of PGME concentration in urine was 7.78 mg/l. Air concentrations of PGME ranged between 20 and 40 ppm. A statistically significant correlation was found between measurements of external exposure and PGME in urine. An important fraction of PGME in urine was found to be conjugated. Received: 6 July 1999 / Accepted: 27 December 1999     

Propylene glycol monomethyl ether occupational exposure. 3. Exposure of human volunteers

OBJECTIVE: Propylene glycol monomethyl ether (PGME) is a widely used additive in industrial and consumer products (paints, inks, diluents, cleaning products, cosmetics.). The aim of the present study was to determine uptake and disposition of PGME alpha-isomer in humans. METHOD: Six healthy male volunteers were exposed to PGME-alpha vapour (15, 50 and 95 ppm) with and without respiratory protection for 6 h including a 30-min break. Free PGME and total PGME (free and conjugated) were analysed in urine. The analytical method involved hydrolysis with HCl (only for the analysis of total PGME in urine), a solid phase extraction on LC-18 columns and a gas chromatograph-flame ionisation detector (GC/FID) analysis after derivatisation with trimethylsilylimidazole. RESULTS: End-exposure levels of free PGME in urine were found to reach 1.3 (+/-0.3), 4.4 (+/-1.6) and 7.9 (+/-2.5) mg/l for 15, 50 and 95-ppm exposure, respectively, without respiratory protection. End-exposure levels of total PGME in urine were found to reach 2.5 (+/-0.8), 6.2 (+/-1.6) and 10.3 (+/-2.3) mg/l for 15, 50 and 95-ppm exposure respectively. Levels of free PGME were also monitored in exhaled air (0.4 (+/-0.1), 1.4 (+/-0.4) and 2.9 (+/-0.9) ppm at the end of 15, 50 and 95-ppm exposure, respectively) and in blood (2.0 (+/-0.9), 4.9 (+/-2.3) and 11.8 (+/-2.4) mg/l at the end of 15, 50 and 95-ppm exposure, respectively). PGME is rapidly excreted in urine and in exhaled air; the half-lives were calculated to be approximately 3.5 h in urine and 10 min in exhaled air. PGME was below detection limits in breath (<0.1 ppm), in blood (<1 mg/l) and in urine (<1 mg/l) after dermal-only exposure to vapour. CONCLUSIONS: This study has demonstrated the relatively high pulmonary uptake compared with the dermal uptake. It has also shown the rapid excretion in urine (3.5 h) and in expired air (10 min). With regard to metabolism, this study has established the presence of conjugated PGME in urine.     

Urinary elimination of nickel and cobalt in relation to airborne nickel and cobalt exposures in a battery plant

Objective To estimate the relationship between Ni concentrations in the ambient air and in the urine, at a battery plant using nickel hydroxide. Methods Workers occupationally exposed to a mixture of nickel hydroxide, metallic cobalt and cobalt oxyhydroxide dust were studied during two consecutive workdays. Air levels of Ni and Co in total dust were determined by personal sampling in the breathing zone. Both metals in air were sampled by Teflon binder filters and analyzed by inductively coupled plasma absorption emission spectrophotometry. Urine was collected from 16 workers immediately before and after the work shift. Urinary Ni and Co concentrations were measured by electrothermal atomic absorption spectrometry. Results A poor correlation was seen between Co in the air and in post-shift urine (r = 0.491; P < 0.01), and no correlation was found between Ni in the air and in post-shift urine (r = 0.272; P = 0.15), probably due to the use of respiratory protection. The subjects were exposed to higher levels of Ni than Co (Ni (mg/m³) = −0.02 + 7.41 Co (mg/m³), r = 0.979, P < 0.0001). Thus, exposure to Co at 0.1 mg/m³ should produce a Ni level of 0.7 mg/m³. According to section XIII of the German list of MAK and BAT Values, a relationship between exposure to Co and urinary Co excretion, Co (μg/l) = 600 Co (mg/m³), has been established and the relationship between soluble or insoluble Ni salts in the air and Ni in urine was as follows: Ni (μg/l) = 10 + 600 Ni (mg/m³) or Ni (μg/l) = 7.5 + 75 Ni (mg/m³). Assuming nickel hydroxide to be soluble and to be insoluble, the Ni concentrations corresponding to Ni exposure at 0.7 mg/m³ were calculated as 430 and 60 μg Ni/l, respectively. Similarly, exposure to Co at 0.1 mg/m³ should result in Co urinary concentrations of 60 μg Co/l. On the other hand, a good correlation was found between Co and Ni in post-shift urine (Ni (μg/l) = 9.9 + 0.343 Co (μg/l), r = 0.833, P < 0.0001). On the basis of this relationship, the corresponding value found in our study was 0.343 × 60 μg Co/l + 9.9 = 30.5 μg Ni/l. This value was close to that calculated by the equation for a group of insoluble compounds, but about 14 times lower than that calculated by the equation for a group of soluble compounds. Conclusions Our results suggest that exposure to nickel hydroxide yields lower urine nickel concentrations than the very soluble nickel salts, and that the grouping of nickel hydroxide might be reevaluated. Therefore, to evaluate conclusively the relationship between nickel hydroxide dust in the air and Ni in post-shift urine, further studies are necessary.     

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.     

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     

Occupational chronic exposure to organic solvents

Summary Seventeen persons (2 women and 15 men), who were exposed to glycolethers in a varnish production plant, were examined according to their external and internal solvent exposure. The workers in the production plant (n =12) were exposed to average concentrations of ethoxyethanol, ethoxyethyl acetate, butoxyethanol, 1-methoxypropanol-2, 2-methoxypropyl-1-acetate and xylene of 2.8; 2.7; 1.1; 7.0; 2.8 and 1.7 ppm. In the air of the store (n = 3) and in the laboratory (n = 2) only minor concentrations of xylene respectively xylene and ethoxyethyl acetate could be measured. Internal exposure was estimated by measuring butoxyethanol (BE) in blood as well as ethoxyacetic acid (EAA) and butoxyacetic acid (BAA) in urine samples. Urine samples were taken pre- and post-shift. As expected, the highest values were found in the varnish production. The average post shift concentrations of BE, EAA and BAA were 121.3 g/l; 167.8 and 10.5 mg/l. The relatively high concentrations of EAA and BAA in pre-shift samples can be explained by the long half-lives of these metabolites. According to our findings most of the glycolethers were taken up through the skin. Comparing our results with those reported in the literature we think that a future tolerable limit value for the concentration of ethoxyacetic acid in urine should be in the order of 100 to 200 mg/l.     

Biological surveillance of workers exposed to dimethylformamide and the influence of skin protection on its percutaneous absorption

Summary Two studies were carried out among workers exposed to dimethylformamide (DMF) in an acrylic fiber factory. The first study involved 22 exposed workers and 28 control workers. Blood was examined at the beginning and at the end of a working week for the presence of biological signs of liver dysfunction. Pre- and post-shift urine samples were also collected during 1 week for determination of N-methylformamide (NMF) concentration. The airborne concentration of DMF was determined at different work places during the same period. On prevention of direct skin contact with DMF solution a significant correlation was found on a group basis between the concentration of DMF vapor and the NMF concentration in post-shift urine samples. When the concentration of NMF in post-shift urine samples from a group of workers does not exceed 30 mg/g creatinine, then their integrated exposure is probably below 60 mg/m³ × h (10 mg/m3 for 6 h). This exposure appears to be safe with regard to the risk of liver damage but does not necessarily preclude episodes of alcohol intolerance in some workers.During a second study, NMF concentrations in pre- and post-shift urine samples were followed-up in seven workers during three weeks when different personal protective devices were used. In an acrylic fiber factory, skin absorption was found to be more important than inhalation in the overall exposure to the solvent when no personal protective devices were used. The use of impermeable gloves with long sleeves appears to be the best method of preventing skin absorption of DMF. Silicone or glycerol barrier creams are less effective and should not be recommended.Part of this work was presented at the First International Congress on Toxicology in Toronto 1977     

Ambient monitoring and biomonitoring of workers exposed to N-methyl-2-pyrrolidone in an industrial facility

Objectives: The exposure of seven workers and three on-site study examiners to N-methyl-2-pyrrolidone (NMP) was studied in an adhesive bonding compound and glue production facility. Methods: Airborne NMP was analysed by personal and stationary sampling on activated charcoal tubes. NMP and its main metabolites, 5-hydroxy-N-methyl-2-pyrrolidone (5-HNMP) and 2-hydroxy-N-methylsuccinimide (2-HMSI), were analysed in pre-shift and post-shift spot urine samples by gas chromatography-mass spectrometry. The workers were examined with respect to irritation of the eyes, the mucous membranes and the skin, and health complaints before and after the work-shift were recorded. Results: The time-weighted average concentration of NMP in most work areas varied between 0.2 and 3.0 mg/m³. During the manual cleaning of stirring vessels, valves and tools, 8-h TWA exposures of up to 15.5 mg/m³ and single peak exposures of up to 85 mg/m³ were observed. NMP and its metabolites were detected in two pre-shift urine specimens. NMP and 5-HNMP concentrations in post-shift urine samples of five workers and three on-site study examiners were below 125 μg/g creatinine and 15 mg/g creatinine, respectively, while two vessel-cleaning workers showed significantly higher urinary NMP concentrations of 472 and 711 μg/g creatinine and 5-HNMP concentrations of 33.5 and 124 mg/g creatinine. 2-HMSI was detectable in four post-shift samples (range: 1.6–14.7 mg/g creatinine). The vessel cleaner with the highest NMP exposure reported irritation of the eyes, the upper respiratory tract and headaches. Conclusions: The results of this study indicate a relatively low overall exposure to NMP in the facility. An increased uptake of NMP occurred only during extensive manual vessel cleaning. Health complaints associated with NMP exposure were recorded in one case and might be related to an excessive dermal exposure due to infrequent and inadequate use of personal protective equipment.     

Occupational chronic exposure to organic solvents

Summary Twenty persons occupationally exposed to methanol were examined according to their methanol levels in blood and urine and their formic acid excretion. An 8-h exposure to a methanol concentration of 93 ml/m³ (geometric mean) in the air at the working area caused average methanol levels in blood and urine of (8.9 ± 14.7) mg/l and (21.8 ± 20.0) mg/l, respectively, and a mean formic acid excretion of (29.9 ± 28.6) mg/l. These average concentrations for the exposed group showed statistically significant increases compared to those of a control group. For the methanol workers we succeeded in] correlating their methanol levels in blood and urine. When considering the possible application of these parameters for biological monitoring, difficulties were encountered, especially for the individual case from the overlapping range in the concentrations of exposed and unexposed persons for each of the applied parameters. This range is minimum for the methanol concentration in urine. About 80% of the urinary levels from the methanol workers lies above the upper limit within the control group range. Based on our results a rough estimate shows the corresponding methanol content in urine to be about 40 mg/l for an 8-h exposure at 200 ml/m³ (German MAK value).     

二硫化碳接触工人尿2-硫代噻唑烷-4-羧酸排泄规律的研究

目的　探讨二硫化碳 (CS2 )接触工人尿 2 硫代噻唑烷 4 羧酸 (TTCA)的排泄规律 ,为制定CS2 短时接触生物监测提供实验依据。方法　将受试对象分为 3组进行实验 :(1) 14名非CS2 接触者在某CS2 车间暴露 2h后收集不同时段尿液 ,分析其TTCA浓度变化 ;(2 )某CS2 车间 15名CS2 接触工人三班倒休息 4 8h后上班 ,连续收集 3d班前、班中、班末尿 ,分析其TTCA浓度变化 ;(3)收集 4 0名长期接触CS2 工人班末尿 ,分析其TTCA浓度变化与工人接触CS2 的 8h时间加权平均浓度 (PC TWA)的关系。结果　第 1组研究结果显示 ,接触CS2 4h后 (此时已停止接触 2h)尿中TTCA含量达到最高值 [(1.0 3± 0 .72 )mg/gCr];第 2组研究结果显示 ,班前尿TTCA含量极低 [(0 .37± 0 .2 8)mg/gCr],与班中尿 [上班后 4h(1.2 3± 0 .71)mg/gCr]及班末尿 [(1.31± 0 .78)mg/gCr]比较 ,差异有显著性 (P <0 .0 1) ,而班中尿TTCA值与班末尿相比 ,差异无显著性 (P >0 .0 5 ) ;第 3组研究结果显示 ,班末尿TTCA值与工人PC TWA之间有直线关系 [Y(TTCAmg/gCr) =1.16 36X(CS2 mg/m3) - 5 .4 116 ]。结论　班末尿TTCA值可作为CS2 接触工人的生物监测指标。     

Occupational chronic exposure to organic solvents XVII. Ambient and biological monitoring of workers exposed to xylenes

Ambient-air and biological monitoring of occupational xylene exposure were carried out on 2 groups of workers (13 and 10 men, respectively) exposed to a mixture of xylenes during the production of paints or during spraying. Methods: Personal ambient-air monitoring was performed for one complete work shift. Blood and urine samples were collected directly at the end of the shift. Biological monitoring was based on the determination of the concentration of xylenes in blood and on the quantification of the sum of the three methylhippuric acids in urine. Results: Average xylene ambient-air concentrations were 29 ppm (production) and 8 ppm (spraying), ranging from 5 to 58 ppm and from 3 to 21 ppm, respectively. The concentrations of xylenes in blood ranged from 63 to 715 μg/l and from 49 to 308 μg/l, with average values being 380 and 130 μg/l, respectively. Accordingly, the workers engaged in paint production also excreted more methylhippuric acids in their urine (average 1221 mg/l, range 194–2333 mg/l) than did the sprayers (average 485 mg/l, range 65–1633 mg/l). Discussion: Our results as well as a literature review indicate that occupational xylene exposure on average barely exceeds the threshold limit value of 100 ppm as proposed by both American and German institutions. Biological monitoring based on the determination of xylenes in blood and of methylhippuric acids in urine provides sufficient sensitivity and specificity for occupational health surveillance. The results also confirm the current limit values (BAT values) proposed by the Deutsche Forschungsgemeinschaft for xylenes in blood (1500 μg/l) and methylhippuric acids in urine (2000 mg/l). Received: 27 May 1998 / Accepted: 3 September 1998     

Occupational chronic exposure to organic solvents XVI. Ambient and biological monitoring of workers exposed to toluene

Object Ambient air and biological monitoring of an occupational toluene exposure was carried out on a group of 33 workers. Method The biological monitoring of the workers was based on determination of the concentration of toluene in blood and on quantification of the urinary metabolites o-cresol and hippuric acid. All blood and urine samples were collected post-shift. Results The average toluene concentration in the workplace air was 65?ppm, ranging from 13 to 151?ppm. An average concentration of toluene in blood of 911?μg/l was found, corresponding to an average urinary concentration of 2.9?mg/l (2.3?mg/g creatinine) o-cresol and 2.4?g/l (1.9?g/g creatinine) hippuric acid. Both urinary metabolites can be correlated with the concentration of toluene in ambient air and blood, respectively. Conclusions The results of our study indicate that the determination of the urinary o-cresol excretion represents a diagnostically specific and sensitive parameter for the estimation of an individual toluene uptake. In contrast, monitoring of the concentration of hippuric acid in urine cannot be recommended for assessment of individual exposure. To set up a biological tolerance value (BAT) for o-cresol, a urinary concentration of 3?mg/l o-cresol should be in accordance with the current MAK value of 50?ppm toluene.     

Proposal for single and mixture biological exposure limits for sevoflurane and nitrous oxide at low occupational exposure levels

OBJECTIVES: Assessment of individual exposures to sevoflurane plus nitrous oxide (N(2)O) by biological monitoring of unmodified analytes in post-shift urine of exposed personnel. METHODS: Anaesthetics in urine and breathing area were monitored in 124 subjects in 11 operating theatres. Passive samplers were collected after 2.5-7 h of exposure, at the same time as post-shift urinary samples, to evaluate the individual time-weighted average (TWA) exposures to sevoflurane and N(2)O. A static headspace sampler coupled with a gas chromatograph mass spectrometer was used for analytical determinations (sensitivity sufficient to reveal biological/environmental exposures of 0.1 microg/l(urine) and 50 ppb for sevoflurane, and 1 microg/l(urine) and 80 ppb for N(2)O). RESULTS: Median (range) post-shift urinary and environmental values were 1.2 microg/l(urine) (0.1-5.0) and 0.4 ppm (0.05-3.0) for sevoflurane ( n=107) and 10.9 microg/l(urine) (0.5-74.9) and 8.6 ppm (0.2-123.4) for N(2)O ( n=121) (all low-exposure range). At log-log regression, urinary levels closely correlated with environmental data (sevoflurane, r(2)=0.7538; N(2)O, r(2)=0.8749). Biological equivalent limits (BELs) based on National Institute for Occupational Safety and Health (NIOSH) TWA exposure limits, calculated as means of regression slope and y-intercept, were 3.6 microg/l(urine) for sevoflurane (corresponding to 2 ppm) and 22.3 microg/l(urine) for N(2)O (corresponding to 25 ppm). Individual "mixture BELs", which we calculated by applying the American Conference of Governmental Industrial Hygienists (ACGIH) threshold limit value (TLV) mix formula to biomarker values and using the obtained NIOSH-based BELs as a reference, closely correlated with mixture TLVs (rho=0.816, Lin's concordance test). CONCLUSIONS. We propose urinary sevoflurane as a new, specific, internal dose biomarker for routine biological monitoring of personal exposures among operating-theatre personnel, and use of reliable "mixture BELs" to provide safer levels of internal exposure for workers exposed to mixtures of sevoflurane and N(2)O, and conceivably also to other mixtures of toxicants with possible additive effects.     

Accumulation of carbon disulphide metabolites

Summary Biological monitoring for carbon disulphide (CS₂) exposure performed using the iodine-azide test (IAT) and 2-thiothiazolidine-4-carboxylic acid (TTCA) test in urinalysis of workers with high exposure to CS₂ (112–142 mg/m³, n = 34), workers with low exposure (4–7 mg/m³, n = 16), and non-exposed university workers (n =10). Pre-shift and post-shift urine specimens were collected on three consecutive days in the exposed and for only one day in the non-exposed. According to the findings the specificity and the sensitivity seem to be low for the IAT and high for the TTCA test. Contrary to a previous report all pre-shift urine samples showed negative IATs. The TTCA test was positive in pre-shift urine even after 32 to 63.5 h without exposure, and values tended to increase during consecutive days of exposure in highly exposed workers.The possible health implications of these findings should be further investigated.     

Respiratory Symptoms and Pulmonary Function among Chinese Rice-granary Workers

Abstract

The authors conducted a cross-sectional study of 474 rice-granary workers and 235 non-granary worker controls in a rural area near Shanghai, the People's Republic of China. Responses to a respiratory-symptom questionnaire and pre- and post-shift spirometry were obtained for all subjects. Area sampling was performed for total and vertically elutriated (≤15 μm)dust levels. Total dust levels were high, ranging from 6.6 mg/m³ to 59.8 mg/m³, with vertical elutriated dust concentrations ranging from 2.0 to 10.4 mg/m³. The granary workers reported significantly more respiratory symptoms, induding chronic cough, sputum production, chronic bronchitis, grain fever (ODTS), and nasal and skin irritation. Grain dust and tobacco smoking were more than additivc for the prevalence of chronic cough and chronic bronchitis. Meter adjusting for confounders, the granary workers had lower mean FEV₁/FVC values both pre- and post-shift, indicating an association between chronic grain-dust exposure and chronic airway obstruction. The results suggest that exposure to rice dust can induce pulmonary responses similar to those observed with exposures to other types of grains.     

<Emphasis Type="Italic">N</Emphasis>-Nitrosodiethanolamine urinary excretion in workers exposed to aqueous metalworking fluids

Objective This work was intended to clarify the extent of exposure of workers occupationally exposed to N-nitrosodiethanolamine (NDELA), a carcinogenic nitrosamine, while working with aqueous metalworking fluids (MWFs) formulated with ("nitrite-formulated") or without ("nitrite-free") nitrite and to study the relationships between the nitrite and NDELA content of the MWFs as well as between the concentration of NDELA in MWFs and in urine.Method Pre-shift and post-shift urine samples from 100 workers directly exposed to MWFs in 15 factories were analysed for NDELA with chemiluminescent detection (TEA) according to a previously described analytical procedure. The method was also applied to eight indirectly exposed workers and to 48 unexposed subjects. The NDELA and concentrations in 84 fluids used by the workers were also determined.Results No detectable NDELA could be observed in the control group. The mean post-shift NDELA excretion in workers exposed to "nitrite-formulated" and "nitrite-free" MWFs were 44.6 and 0.4 µg/l, with maxima of 277 and 2.7 µg/l, respectively. According to the correlation between the nitrite and NDELA concentrations in "nitrite-free" MWFs, there is a low probability of fluids exceeding 5 mg/l NDELA when the nitrite content does not exceed 20 mg/l. The NDELA concentrations in the fluids and urine were found to be highly correlated, particularly after correction for creatinine (r=0.917 in post-shift samples). Cutaneous contact probably contributes, at least in part, to the overall body uptake of NDELA.Conclusion Due to clear evidence of urinary NDELA excretion in workers exposed to contaminated MWFs, and despite a lack of knowledge of the human risk following NDELA exposure, levels of NDELA in MWFs should be kept as low as possible. NDELA fluid concentrations of less than 1 mg/l must be considered as the objective to be attained, even if the limit of 5 mg/l is temporarily satisfactory and consistent with a nitrite limit of 20 mg/l that is easy to verify with inexpensive colorimetric tests. "Nitrite-formulated" fluids, still sometimes used, should be prohibited. Meanwhile, the material safety data sheets (MSDS) of commercially available products should be clearly labelled to indicate their nitrite content.     

Biological monitoring of cobalt exposure,based on cobalt concentrations in blood and urine

Summary Cobalt exposure level and its concentrations in blood and urine were determined for 175 hard metal workers. For control data, the cobalt concentrations in blood and urine were measured for 20 office workers. The exposed workers had significantly higher cobalt concentrations in both blood and urine. The relationships between exposure level and cobalt concentrations in blood and urine were linear and positive. The results clearly showed that the cobalt concentration in the blood or urine can be used as an exposure indicator. With cobalt exposure of 100 g/m³, the cobalt concentration was 0.57 to 0.79 g/dl in blood and 59 to 78 g/l in urine with 95% confidence limits. In workers using respirators, the cobalt concentrations in the blood and urine decreased to 2/5 and 1/8, respectively, of those not using respirators.     

Occupational chronic exposure to organic solvents

Summary A study was carried out among 20 workers employed in a printing, office at three different work places (methanol concentration: 85, 101, and 134 ppm) to determine whether the concentration of formic acid in blood or urine and the methanol content of alveolar air permit the estimation of methanol exposure.For this purpose blood, urine, and end expiratory air were collected at the beginning and the end of the shift. For comparison formic acid concentrations were determined in the morning and in the afternoon in blood and urine of 36 and 15 control persons, respectively.The concentration of formic acid in blood increased significantly from 3.2 ± 2.4 mg/l before to 7.9 ± 3.2 mg/l after the shift in the exposed workers (mean increase 4.7 ± 3.8 mg/l). The corresponding concentrations in urine were 13.1 ± 3.9 mg/l and 20.2 ± 7 mg/l, respectively, with a mean increase of 7.1 ± 5.3 mg/l. This difference is also significant. On the contrary, in the control groups there was a small but significant decrease of formic acid concentration in blood from 5.6 ±4.5 mg/l in the morning to 4.9 ± 4.2 mg/l in the afternoon. In urine, the formic acid concentrations in the morning (11.9 ± 6.4 mg/l) and in the afternoon (11.7 ±5.6 mg/l) were not significantly different. The increase of formic acid concentration in blood during the shift is the most useful parameter for monitoring methanol exposed persons. In contrast determinations of methanol concentrations in the ambient air or in the exhaled air are only crude estimates.(Direktor: Prof. Dr. G. Lehnert)     

Serum and urinary aluminium levels of workers in the aluminium industry

We have measured serum aluminium and urinary aluminium/creatinine ratios in 235 aluminium workers and 44 controls to examine the association between occupational exposure to airborne aluminium and aluminium absorption. Serum and urine samples were taken before and after a 3- to 5-day work shift. Occupational exposure was estimated from aluminium measurements of respirable and total particulates in air. Median exposure values were 25 and 100 μg m⁻³, respectively. Serum aluminium and urinary aluminium/creatinine ratios did not change significantly during the shift; however, both pre-shift and post-shift serum aluminium and urinary aluminium/creatinine ratios were increased in the exposed group. Occupational exposure was associated with serum aluminium increments of 1.32μg l.⁻¹ (P = 0.01) pre-shift, and 0.96μg l.⁻¹ (P = 0.08) post-shift. Greater and more significant differences were seen between exposed and controls for the urinary aluminium/creatinine ratios [5.67 μg g⁻¹ (P < 0.01) pre-shift; 8.01 μg g⁻¹ (P < 0.01) post-shift]. Urinary aluminium/creatinine ratios were greater in plants with higher aluminium exposures. These results are consistent with the systemic absorption of aluminium from occupational exposure and suggest the presence of a sensitive uptake process for airway aluminium.