Analysis of nitrogen-based explosives with desorption atmospheric pressure photoionization mass spectrometry.

RATIONALE: Fast methods that allow the in situ analysis of explosives from a variety of surfaces are needed in crime scene investigations and home-land security. Here, the feasibility of the ambient mass spectrometry technique desorption atmospheric pressure photoionization (DAPPI) in the analysis of the most common nitrogen-based explosives is studied. METHODS: DAPPI and desorption electrospray ionization (DESI) were compared in the direct analysis of trinitrotoluene (TNT), trinitrophenol (picric acid), octogen (HMX), cyclonite (RDX), pentaerythritol tetranitrate (PETN), and nitroglycerin (NG). The effect of different additives in DAPPI dopant and in DESI spray solvent on the ionization efficiency was tested, as well as the suitability of DAPPI to detect explosives from a variety of surfaces. RESULTS: The analytes showed ions only in negative ion mode. With negative DAPPI, TNT and picric acid formed deprotonated molecules with all dopant systems, while RDX, HMX, PETN and NG were ionized by adduct formation. The formation of adducts was enhanced by addition of chloroform, formic acid, acetic acid or nitric acid to the DAPPI dopant. DAPPI was more sensitive than DESI for TNT, while DESI was more sensitive for HMX and picric acid. CONCLUSIONS: DAPPI could become an important method for the direct analysis of nitroaromatics from a variety of surfaces. For compounds that are thermally labile, or that have very low vapor pressure, however, DESI is better suited.

Post-mortem analysis of lactate concentration in diabetics and metformin poisonings.

Lactate is produced in carbohydrate metabolism under anaerobic conditions. Lactic acidosis occurs when the production of lactate exceeds its removal. In post-mortem (PM) context, the lactic acidosis is difficult to interpret due to unknown pathophysiological factors prior to death and PM changes that may affect the lactate levels. We evaluated 1865 medico-legal autopsy cases where the quantitation of glucose, lactate, and ketone bodies was performed as a part of the cause of death (CoD) investigation. Lactate was shown to ascend in a logarithmic manner as the PM interval increased until a plateau was achieved approximately after 8-10 days PM, and the elevation was caused mainly by PM changes. The lactate level was higher than the mean in cases where the CoD was diabetes mellitus type 2 (DM2) or metformin poisoning. Although there was a correlation between metformin and lactate levels, our findings suggest the DM2 and its complications were the cause for elevated lactate levels rather than metformin, since the lactate levels were similar in DM2-associated deaths where no metformin was detected. Elevated lactate levels in PM samples rather referred to metabolic disturbances often caused by DM2. An assay to detect D-lactate in PM samples was described.

Prospective study on shoulder symptoms among kitchen workers in relation to self-perceived and observed work load.

OBJECTIVES: To study the occurrence of shoulder symptoms among professional kitchen workers, and whether reduction in self-perceived and observed physical work load decreases future symptoms. METHODS: In this prospective study conducted in 2002-2005 in municipal kitchens in Finland, changes during a 1-year follow-up in the physical strenuousness of work tasks were self-assessed by 376 female workers (substudy I). Changes in exposure to manual lifting and awkward upper arm posture during the follow-up were also observed by experts in 69 kitchens with 183 workers (substudy II). Information on shoulder symptoms was collected with questionnaires at baseline and at follow-up. The risk of shoulder symptoms at follow-up related to changes in exposure was estimated with logistic regression. RESULTS: The 3-month prevalence of shoulder pain was 34% at baseline and 41% at follow-up. Reduction during follow-up in work tasks perceived as the most strenuous physically (ie, receiving and storing raw food) led to a significantly reduced risk of future shoulder pain with an adjusted odds ratio (OR) of 0.41 (95% CI 0.17 to 0.98) and trouble caused by the pain with an OR of 0.34 (0.14 to 0.83). The observed reduction in lifting was also associated with a lower risk for future shoulder symptoms. CONCLUSIONS: Reduction in lifting showed beneficial protective effects on the shoulder. Although more risk factor and intervention studies are needed to estimate the health impacts of kitchen work, special attention should be paid to work tasks that include lifting when assessing risk and designing preventive measures.

A randomised controlled trial on whether a participatory ergonomics intervention could prevent musculoskeletal disorders.

OBJECTIVES: To examine the efficacy of a participatory ergonomics intervention in preventing musculoskeletal disorders among kitchen workers. Participatory ergonomics is commonly recommended to reduce musculoskeletal disorders, but evidence for its effectiveness is sparse. METHODS: A cluster randomised controlled trial among the 504 workers of 119 kitchens in Finland was conducted during 2002-2005. Kitchens were randomised to an intervention (n = 59) and control (n = 60) group. The duration of the intervention that guided the workers to identify strenuous work tasks and to seek solutions for decreasing physical and mental workload, was 11 to 14 months. In total, 402 ergonomic changes were implemented. The main outcome measures were the occurrence of and trouble caused by musculoskeletal pain in seven anatomical sites, local fatigue after work, and sick leave due to musculoskeletal disorders. Individual level data were collected by a questionnaire at baseline and every 3 months during the intervention and 1-year follow-up period. All response rates exceeded 92%. RESULTS: No systematic differences in any outcome variable were found between the intervention and control groups during the intervention or during the 1-year follow-up. CONCLUSIONS: The intervention did not reduce perceived physical work load and no evidence was found for the efficacy of the intervention in preventing musculoskeletal disorders among kitchen workers. It may be that a more comprehensive redesign of work organisation and processes is needed, taking more account of workers' physical and mental resources.

Perceived competence in computer use as a moderator of musculoskeletal strain in VDU work: an ergonomics intervention case.

Musculoskeletal strain and other symptoms are common in visual display unit (VDU) work. Psychosocial factors are closely related to the outcome and experience of musculoskeletal strain. The user-computer relationship from the viewpoint of the quality of perceived competence in computer use was assessed as a psychosocial stress indicator. It was assumed that the perceived competence in computer use moderates the experience of musculoskeletal strain and the success of the ergonomics intervention. The participants (n = 124, female 58%, male 42%) worked with VDU for more than 4 h per week. They took part in an ergonomics intervention and were allocated into three groups: intensive; education; and reference group. Musculoskeletal strain, the level of ergonomics of the workstation assessed by the experts in ergonomics and amount of VDU work were estimated at the baseline and at the 10-month follow-up. Age, gender and the perceived competence in computer use were assessed at the baseline. The perceived competence in computer use predicted strain in the upper and the lower part of the body at the follow-up. The interaction effect shows that the intensive ergonomics intervention procedure was the most effective among participants with high perceived competence. The interpretation of the results was that an anxiety-provoking and stressful user-computer relationship prevented the participants from being motivated and from learning in the ergonomics intervention. In the intervention it is important to increase the computer competence along with the improvements of physical workstation and work organization.

Atmospheric pressure photoionization-mass spectrometry and atmospheric pressure chemical ionization-mass spectrometry of neurotransmitters.

A group of five neurotransmitters with different properties was analyzed using atmospheric pressure photoionization (APPI) and atmospheric pressure chemical ionization-mass spectrometry (APCI-MS). The sensitivity of the techniques for the analytes was tested in six solvents and in positive and negative ion modes. APPI was found to be superior in sensitivity for all the compounds in both positive and negative ion modes. In positive ion mode, water/methanol/formic acid was found to be the best solvent, whereas in negative ion mode, water/methanol/ammonium hydroxide performed best. Detection limits using APPI were between 2.5-250 fmol, depending on the compound. The sensitivity was best for the neurosteroids dehydroepiandrosterone and beta-estradiol, and acetylcholine (LOD 2.5-10 fmol).

Utilization of a multimembrane inlet and a cyclic sudden sampling introduction mode in membrane inlet mass spectrometry.

Sudden sampling introduction into a membrane inlet mass spectrometer (MIMS) considerably improves the selectivity of the membrane inlet and is therefore applicable even for compounds with low permeabilities through a silicone membrane. In this study the basics of cyclic non-steady-state sudden increase sample injection were studied using a three-membrane inlet and a portable sector double-focusing mass spectrometer. The operational parameters of the inlet system providing the most efficient enrichment of volatile organic compounds (VOCs) in air were defined. Simulation of the diffusion process following sudden sample introduction into the three-membrane inlet was also carried out. Experimental testing of the three-membrane inlet system with the cyclic sudden sample injection mode for benzene, toluene, styrene, and xylene in air was performed. The simulation and the experimental results demonstrated that, when this mode is used, the VOCs/nitrogen relative enrichment factor of samples introduced into the mass spectrometer equipped with a three-membrane inlet is increased by a factor of approximately 10(5) compared with a direct introduction method. This effect may be used to decrease detection limits of compounds obtained with mass spectrometry to decrease matrix flow through the inlet at the same detection limits.

Work related and individual predictors for incident neck pain among office employees working with video display units.

AIMS: To investigate work related and individual factors as predictors for incident neck pain among office employees working with video display units (VDUs). METHODS: Employees in three administrative units of a medium sized city in Finland (n = 515) received mailed questionnaires in the baseline survey in 1998 and in the follow up survey in 1999. Response rate for the baseline was 81% (n = 416); respondents who reported neck pain for less than eight days during the preceding 12 months were included into the study cohort as healthy subjects (n = 232). The follow up questionnaire 12 months later was completed by 78% (n = 180). Incident neck cases were those reporting neck pain for at least eight days during the preceding 12 months. RESULTS: The annual incidence of neck pain was 34.4% (95% CI 25.5 to 41.3). Poor physical work environment and poor placement of the keyboard increased the risk of neck pain. Among the individual factors, female sex was a strong predictor. Smoking showed a tendency for an increased risk of neck pain. There was an interaction between mental stress and physical exercise, those with higher mental stress and less physical exercise having especially high risk. CONCLUSION: In the prevention of neck disorders in office work with a high frequency of VDU tasks, attention should be given to the work environment in general and to the more specific aspects of VDU workstation layout. Physical exercise may prevent neck disorders among sedentary employees.

Purge-and-membrane mass spectrometry, a screening method for analysis of VOCs from soil samples.

Purge-and-membrane mass spectrometry (PAM-MS) is a combination of dynamic headspace sampling and membrane extraction. A new and simple purge-and-membrane sampler is introduced and its basic testing results for the analysis of VOCs in soil samples are reported. Soil moisture had no effect on desorption times in the case of sand, but the desorption times increased when the content of organic matter in the soil sample (garden soil) increased. The longest desorption times were measured with dry garden soil samples. For both types of samples, minor differences in desorption peak areas were observed between 10 and 20% moisture. Detection limits of the VOCs varied in the range 2-150 microg/kg, depending on the soil type. Good linearity (correlation coefficient > 0.990) was observed in the range 0.5-50 mg/kg. Aging of the spiked soil samples had only a slight effect on desorption peak areas for samples stored at 5 degrees C up to two weeks, but after six months of storing, differences were observed between dry sand and moistened garden soil. In both cases, peak areas were diminished. On average, 46% of compounds could be desorbed from the aged sand and 86% from the aged garden soil. The modified vapor fortification method was used in preparing standard soil samples, which were analyzed by static headspace gas chromatography (HSGC) and PAM-MS. Some authentic soil samples were also analyzed using both of these techniques. Many of the vapor fortification samples and the authentic samples were also analyzed in another laboratory by HSGC. The agreement between the methods and the laboratories was generally good.

Interobserver repeatability and validity of an observation method to assess physical loads imposed on the upper extremities.

Interobserver repeatability and validity were assessed for a new semiquantitative, time-based observation method for the estimation of physical loads imposed on the upper extremities. Six risk factors of upper extremity disorders were included in the method: repetitive use of hand, use of hand force, pinch grip, non-neutral wrist posture, elevation of upper arm, local mechanical pressure. Two occupational health nurses were trained to use the method. They observed 127 work cycles at a food-processing plant and a paper mill. The method was validated against expert observations from the video, continuous recordings of myoelectric activity (EMG) of forearm muscles, and wrist posture measured with goniometers. Interobserver repeatability was good or moderate for repetitive use of hand, hand force, pinch grip (range kappa = 0.58-0.71 on the right; 0.60-0.61 on the left side). Interobserver repeatability was moderate or poor for non-neutral wrist posture, elevation of the upper arm and local mechanical pressure. Validity ranged from moderate to good for repetitive use of hand, use of hand force, pinch grip and non-neutral wrist posture when expert observation was used as reference standard. When observations were validated against force estimations (EMG) and wrist goniometer data, validity was poor. In the absence of generally accepted reference values, arbitrarily chosen limits were used for the proportional duration of some physical load factors. Studies should be carried out to assess the limits that best differentiate between safe and hazardous jobs.

Optimization of capillary electrophoretic-electrospray ionization-mass spectrometric analysis of catecholamines.

The capillary electrophoretic-mass spectrometric analysis (CE-MS) of catecholamines was optimized with coaxial sheath flow interface and electrospray ionization (ESI). The parameters studied included the sheath liquid composition and its flow rate, separation conditions in ammonium acetate buffer together with the ESI and cone voltages as mass spectrometric parameters. In addition, the effect of ESI voltage on injection as well as the siphoning effect were considered. The optimized conditions were a sheath liquid composition of methanol-water (80:20 v/v) with 0.5% acetic acid, with a flow rate of 6 microL/min. The capillary electrophoretic separation parameters were optimized with 50 mM ammonium acetate buffer, pH 4.0, to +25 kV separation voltage together with a pressure of 0.1 psi. The most intensive signals were obtained with an ESI voltage of +4.0 kV and a cone voltage of +20 V. The nonactive ESI voltage during injection as well as avoidance of the siphoning effect increased the sensitivity of the MS detection considerably. The use of ammonium hydroxide as the CE capillary conditioning solution instead of sodium hydroxide did not affect the CE-MS performance, but allowed the conditioning of the capillary between analyses to be performed in the MS without contaminating the ion source.

Analysis of residual solvents in pharmaceuticals with purge-and-membrane mass spectrometry.

A method using purge-and-membrane mass spectrometry (PAM-MS) was developed for the analysis of residual solvents in pharmaceutical products. The method combines dynamic headspace and membrane inlet mass spectrometry. The limits of detection for the compounds studied, benzene, toluene, chloroform, 2-pentene and 2-methyl- and 3-methylpentane, were 0.05-0.1 mg/kg. In quantitative analysis the method showed good linearity (r(2) > 0.998) and acceptable within-day (RSD = 7.9-18%) and between-day (RSD = 6.8-10%) repeatability. The PAM-MS method combined with the custom-made Solver program was compared with a method using purge-and-trap gas chromatography/mass spectrometry (P&T-GC/MS) for identification of residual solvents from authentic samples. The results showed that PAM-MS/Solver provides reliable identification of the main volatile organic compounds (VOCs) in the pharmaceuticals, but VOCs with low concentrations (below 0.5 mg/kg) were better identified by P&T-GC/MS. Other advantages of the PAM-MS method were short analysis times and non-requirement for pre-treatment of samples.

Determination of mono- and sesquiterpenes in water samples by membrane inlet mass spectrometry and static headspace gas chromatography.

A membrane inlet mass spectrometric (MIMS) method is presented and compared with a static headspace gas chromatographic method (HSGC) for the determination of terpenes in water. The MIMS method provides a very simple and fast analysis of terpenes in water, detection limits being relatively low, from 0.2 mug l(-1) for monoterpenes to 2 mug l(-1) for geraniol. The analysis of terpenes by the HSGC (equipped with flame ionization detector, FID) method is more time-consuming and the detection limits (2 mug l(-1) for monoterpenes to 100 mug l(-1) for geraniol) are higher than with MIMS. However, the HSGC method has the advantage of determining individual mono- and sesquiterpene compounds, whereas MIMS provides only separation of different classes of terpenes. Both methods were applied to the analysis of mono- and sesquiterpenes in several condensation water samples of pulp and paper mills.

Determination of phenolic compounds in water using membrane inlet mass spectrometry.

Two membrane inlet mass spectrometric (MIMS) methods for determining phenolic compounds in water are described and compared, namely direct analysis and analysis after acetylation of the phenolic compounds. Direct analysis of phenolic compounds in water is a very simple and rapid method and detection limits are relatively low (from 30 mug 1(-1) for phenol to 1000 mug 1(-1) for 4-nitrophenol). Analysis of phenolic compounds after aqueous acetylation is also a very simple and rapid method, and the detection limits are even two orders of magnitude lower than in the direct analysis. For example the detection limit of phenol acetate is 0.5 mug 1(-1) and that of 4-nitrophenol is 10 mug 1(-1). The acetylation method was also tested in the analysis of phenolic compounds from contaminated surface water samples.

Comparison of different methods for the determination of volatile organic compounds in water samples.

The aim of this work was to compare the characteristics of three methods, membrane inlet mass spectrometry (MIMS), purge-and-trap gas chromatography-mass spectrometry (P&T) and static headspace gas chromatography (HSGC), for the determination of volatile organic compounds in water samples as used in routine analysis. The characteristics examined included linear dynamic ranges, detection limits of selected environmentally hazardous volatile organic compounds (e.g. toluene, benzene and trichloroethene) in water, required analysis time and reproducibility of the analytical methods. The MIMS and P&T methods had the lowest detection limits for all the tested compounds, ranging from 0.1 to 5 mug 1(-1). Linear dynamic ranges using the MIMS method were about four orders of magnitude and using the P&T method about two orders of magnitude. Detection limits of the HSGC method were 10-100 times higher than those of the other two methods, but the linear dynamic ranges were larger, even up to six orders of magnitude. The analysis time per sample was shortest for the MIMS method, from 5 to 10 min, and ranged around from 35 to 45 min for the HSGC and P&T methods. The reproducibilities of the methods were of the same order of magnitude, in the range of 1-13%. Agreement between the analytical results obtained for spiked samples and for environmental water samples by the three different methods was very good.

Quantitative Determination of Semivolatile Organic Compounds in Solution Using Trap-and-Release Membrane Inlet Mass Spectrometry.

This paper discusses the use of trap-and-release membrane inlet mass spectrometry (T&R-MIMS) for the quantitative determination of semivolatile organic compounds in real samples. We found that the T&R-MIMS technique is particular sensitive to relatively polar, semivolatile organic compounds. For example, the detection limits for the acids acetylsalicylic acid and phenoxyacetic acid were lowered by a factor of 100 as compared with those possible with standard MIMS, and caffeine was detectable only with the T&R-MIMS method. The detection limits were in the parts-per-billion range, and the dynamic range was 3 orders of magnitude. As a practical example of the application of the T&R-MIMS technique, we used it for the quantitative analysis of caffeine in ground coffee and tea leaves. Good agreement between T&R-MIMS and HPLC determinations was found, and the reproducibility of the whole analytical system for caffeine determination (extraction procedure and T&R-MIMS determination) was within 10% as relative standard deviation. However, for coffee, a large background from the essential oils prevented low-level work, such as the determination of residual caffeine in decaffeinated coffee. Obviously, the analysis of many complex matrixes will require the use of tandem mass spectrometry.

The effect of appraisers in estimating metabolic rate with the Edholm scale.

A study was made of the appraisers' effect on the estimation of metabolic rate with the Edholm scale and a table of the ISO 7243 heat stress standard. The appraisers, five experienced and five inexperienced persons, estimated the metabolic rate of three different work tasks from videotapes. Analysis of variance indicated significant ( [Formula: see text] ) differences in the appraisers' recordings of the activities. The appraisers were grouped according to the similarity of the estimated values they gave. The groups thus contained both experienced and inexperienced appraisers, and it was not possible to classify the appraisers into experienced and inexperienced groups according to their earlier experience. The metabolic rates according to the Edholm scale were higher than according to the ISO 7243 table. The differences in metabolic rates given by the individual observers varied from 38 to 118 W/m(2). The variations in the estimation of metabolic rates were greater when the Edholm scale was used. This variation caused considerable variation also in the predicted mean vote, PMV index. It is recommended that the appraisers be selected carefully, because it is not possible to know whether a randomly selected appraiser is an 'average' or an 'extreme' appraiser without a test. Before conducting extensive field surveys where several appraisers estimate the metabolic rates, it would be useful to arrange training in order to calibrate the levels of the Edholm scale as well as ISO method among the appraisers because training clearly unified the estimation.

Prevalence of epicondylitis and elbow pain in the meat-processing industry.

To determine the etiologic role of strenuous manual tasks in relation to epicondylitis, three clinical cross-sectional examinations were performed on meatcutters (N = 102), sausage makers (N = 125), packers (N = 150), and workers in nonstrenuous tasks (N = 332). The workers in strenuous jobs reported elbow symptoms 1.6-1.8 times as often as those in nonstrenuous jobs. Female sausage makers also showed epicondylar tenderness more often than the women in nonstrenuous jobs. In all the cross-sectional examinations combined, seven cases (0.8%) of epicondylitis were detected in both the strenuous and nonstrenuous jobs. A control for the possible sources of bias (leaving the company, changing task, being on sick leave) did not suggest a marked loss of potential cases of epicondylitis. A major role of strenuous tasks in the etiology of epicondylitis was not shown. However, because the number of clinical cases was small, the power of the study was low.