Chemical characterization of combustion engine exhaust and assessment of helicopter deck operator occupational exposures on an offshore frigate class ship.

Diesel engine exhaust (DE) consists of a complex mixture of gases and aerosols, originating from sources such as engines, turbines, and power generators. It is composed of a wide range of toxic compounds ranging from constituents that are irritating to those that are carcinogenic. The purposes of this work were to characterize DE originating from different engine types on a ship operating offshore and to quantify the potential exposure of workers on the ship's helicopter deck to select DE compounds. Sampling was conducted on a Norwegian Nansen-class frigate that included helicopter operations. Frigate engines and generators were fueled by marine diesel oil, while the helicopter engine was fueled by high flash point kerosene-type aviation fuel. Exhaust samples were collected directly from the stack of the diesel engine and one of the diesel generator exhaust stacks, inside a gas turbine exhaust stack, and at the exhaust outlet of the helicopter. To characterize the different exhaust sources, non-targeted screening of volatile and semi-volatile organic compounds was performed for multiple chemical classes. Some of the compounds detected at the sources are known irritants, such as phthalic anhydride, 2,5-dyphenyl-p-benzoquinone, styrene, cinnoline, and phenyl maleic anhydride. The exhaust from the diesel engine and diesel generator was found to contain the highest amounts of particulate matter and gaseous compounds, while the gas turbine had the lowest emissions. Personal exposure samples were collected outdoors in the breathing zone of a helicopter deck operator over nine working shifts, simultaneously with stationary measurements on the helicopter deck. Elemental carbon, nitrogen dioxide, and several volatile organic compounds are known to be present in DE, such as formaldehyde, acrolein, and phenol were specifically targeted. Measured DE exposures of the crew on the helicopter deck were variable, but less than the current European occupational exposure limits for all compounds, except elemental carbon, in which concentration varied between 0.5 and 37 µg/m3 over nine work shifts. These findings are among the first published for this type of working environment.

Atmospheric Chemistry of Methyl Isocyanide-An Experimental and Theoretical Study.

The reaction of CH3NC with OH radicals was studied in smog chamber experiments employing PTR-ToF-MS and long-path FTIR detection. The rate coefficient was determined to be kCH3NC+OH = (7.9 ± 0.6) × 10-11 cm3 molecule-1 s-1 at 298 ± 3 K and 1013 ± 10 hPa; methyl isocyanate was the sole observed product of the reaction. The experimental results are supported by CCSD(T*)-F12a/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ quantum chemistry calculations showing the reaction to proceed primarily via electrophilic addition to the isocyanide carbon atom. On the basis of the quantum chemical data, the kinetics of the OH reaction was simulated using a master equation model revealing the rate coefficient to be nearly independent of pressure at tropospheric conditions and having a negative temperature dependence with kOH = 4.2 × 10-11 cm3 molecule-1 s-1 at 298 K. Additional quantum chemistry calculations on the CH3NC reactions with O3 and NO3 show that these reactions are of little importance under atmospheric conditions. The atmospheric fate of methyl isocyanide is discussed.

Cardiorespiratory fitness associates negatively with arterial stiffness in a cohort of industrial workers followed up for 4 years.

OBJECTIVE: Previously we have found increased carotid-to-femoral pulse wave velocity (cfPWV) among shift workers compared to day workers in industry, and a decline in maximal oxygen uptake (V̇O2max) in all 86 workers. METHODS: Utilizing all available measurements in 2018, 2021 and 2022, this study investigated associations between V̇O2max and measures of arterial stiffness. Using a mixed model approach, we analysed the cross-sectional association between all V̇O2max (outcome) and measures of arterial stiffness (covariates). RESULTS: We observed a significant association between V̇O2max and cfPWV of -1.59 (95%CI -3.03, -0.16), augmentation pressure (AP) and augmentation index (Aix) of -0.32 (95%CI -0.58, -0.06) and -0.12 (95%CI -0.23, -0.005), respectively. CONCLUSIONS: We found a significant negative association between cardiorespiratory fitness and measures of arterial stiffness. The former and present results pose challenges for shift workers' future macro and microvascular health.

The Prolonged Effect of Shift Work and the Impact of Reducing the Number of Nightshifts on Arterial Stiffness-A 4-Year Follow-Up Study.

AIM: To assess changes in blood pressure (BP) and arterial stiffness among 84 rotating shift and 25 dayworkers (control subjects) at two industrial plants during a 4-year follow-up, and to assess changes in outcome variables among shift workers at the two plants after a reduction in the number of night shifts during the last year of follow-up in one of the plants. METHODS: We collected demographic data using a questionnaire, examined systolic and diastolic blood pressure (sBP, dBP), central systolic and diastolic aorta pressure (cSP, cDP), augmentation pressure (AP), central pulse pressure (cPP), and pulse wave velocity (PWV). We registered sleep quality. The last 4-14 months of follow-up one plant implemented a 12-week shift plan reducing the total number of night shifts and consecutive night shifts from 16.8 to 14 and from 7.2 to 4. To assess differences in change of outcomes between study groups we applied linear mixed models. RESULTS: The dayworkers were older, more hypertensive, reported less sleep disturbance, and smoked/snuffed less than the shift workers did. The adjusted annual increase in PWV was 0.34 m/s (95%CI, 0.22, 0.46) among shift workers and 0.09 m/s (95%CI, -0.05, 0.23) in dayworkers, yielding a significant difference of change of 0.25 m/s (95%CI, 0.06, 0.43). No significant differences were found between the two groups of shift workers in any cardiovascular disease (CVD) outcome during the last year of follow-up. CONCLUSIONS: Shift work in industry is associated with arterial stiffness, reflecting an increased risk of future CVD. No significant changes in arterial stiffness were identified as a consequence of a small reduction in the number of night shifts and consecutive night shifts.

Monitoring photooxidation-induced dynamic changes in the volatile composition of extended shelf life bovine milk by PTR-MS.

Exposure of milk to light leads to photooxidation and the development of off-flavours. To follow these reactions, semi-skimmed (1.5% fat) and whole (3.8% fat) extended shelf life (ESL) bovine milk samples were exposed to fluorescent light for up to 20 h at room temperature, and the volatiles in the samples' headspace were measured in real time using proton-transfer-reaction mass spectrometry (PTR-MS). Compounds tentatively identified as methanethiol, acetone/propanal, pentanal/octanal/nonanal/1-octen-3-ol, hexanal, diacetyl, dimethyl disulphide, heptanal and benzaldehyde displayed dynamic release profiles relating to the changes occurring in milk upon exposure to light.