In situ and time-resolved infrared detection of the reactivity induced by electrons in polymer films.

The real time and in situ analysis of chemical reactions such as polymerization reactions, polymer degradation, and oxidation of polymers is of utmost importance. Surprisingly, only few experimental tools allowing this are available. To bridge this gap, we have developed a new experimental setup coupling a 60 keV electron gun with an infrared spectrometer operating in the mid-IR region (800-4000 cm-1) and associated with the rapid scan mode. The measurements are performed using the infrared reflection absorption spectroscopy approach. We worked here with 0.5-25 ms pulses for which the dose per pulse ranges from 4 to 200 kGy. Combining pulse electrons with rapid scan analysis enables performing experiments with a time resolution of 80 ms (and above). Therefore, this new platform can, for instance, give direct insights into reaction mechanisms at stake during the degradation of polymers. First results on a bisphenol A polycarbonate irradiated under vacuum enabling the validation of this new setup and also the recording of time-resolved spectra are presented. Reaction mechanisms are then proposed.

The effect of myoglobin crowding on the dynamics of water: an infrared study.

Solutions containing 8 and 32 wt% myoglobin are studied by means of infrared spectroscopy, as a function of temperature (290 K and lower temperatures), in the mid- and far-infrared spectral range. Moreover, ultrafast time-resolved infrared measurements are performed at ambient temperature in the O-D stretching region. The results evidence that the vibrational properties of water remain the same in these myoglobin solutions (anharmonicity, vibrational relaxation lifetime…) and in neat water. However, the collective properties of the water molecules are significantly affected by the presence of the protein: the orientational time increases, the solid-liquid transition is affected in the most concentrated solution and the dynamical transition of the protein is observed, from the point of view of water, even in the least concentrated solution, proving that the water and myoglobin dynamics are coupled.

Water radiolysis in exchanged-montmorillonites: the H2 production mechanisms.

The radiolysis of water confined in montmorillonites is studied as a function of the composition of the montmorillonite, the nature of the exchangeable cation, and the relative humidity by following the H2 production under electron irradiation. It is shown that the main factor influencing this H2 production is the water amount in the interlayer space. The effect of the exchangeable cation is linked to its hydration enthalpy. When the water amount is high enough to get a basal distance higher than 1.3 nm, then a total energy transfer from the montmorillonite sheets to the interlayer space occurs, and the H2 production measured is very similar to the one obtained in bulk water. For a basal distance smaller than 1.3 nm, the H2 production increases with the relative humidity and thus with the water amount. Lastly, electron paramagnetic resonance measurements evidence the formation of a new defect induced by ionizing radiation. It consists of a hydrogen radical (H2 precursor) trapped in the structure. This implies that structural hydroxyl bonds can be broken under irradiation, potentially accounting for the observed H2 production.

A trapped water network in nanoporous material: the role of interfaces.

The infrared spectra of water confined in well controlled pore glasses were recorded as a function of the pore size ranging from 8 to 320 nm and in the 30-4000 cm(-1) spectral range using the ATR technique. The experiments prove that even in the large pores, the water network is significantly perturbed. The energy of the connectivity (or hindered translation) band (around 150 cm(-1)) is found to increase when the pore size decreases, indicating that confinement increases the H-bonding between neighbouring water molecules. Moreover, a drastic decrease of the FWHM of the connectivity band was observed upon confinement. This can be related to some ordering induced by the rigid walls of the pores. Furthermore, the partial filling of pores causes a significant modification to the water network, resembling heating of the trapped liquid and suggesting a role played by the water/air interface.

Uranium carcinogenicity in humans might depend on the physical and chemical nature of uranium and its isotopic composition: results from pilot epidemiological study of French nuclear workers.

OBJECTIVE: To study the cancer risk related to protracted, low-dose exposure to different industrial uranium compounds, paying attention to their isotopic composition and solubility. METHODS: Two thousand and ninety-seven workers employed at the AREVA NC uranium processing plant (France) were followed up for mortality from 1960 to 2006. Historical exposure to uranium and other carcinogenic chemical and physical pollutants was assessed on the basis of the plant-specific job-exposure matrix. For each type of uranium, Cox regression models stratified on sex and calendar period, and adjusted for socioeconomic status and potentially confounding co-exposures were used to estimate hazard ratios (HRs) for mortality from lung cancer (53 deaths) and lymphatic and hematopoietic tissue malignancies (21 deaths). RESULTS: We observed that exposure to reprocessed uranium entails increasing risks of mortality from lung cancer and lymphatic and hematopoietic malignancies (the most significant HR being respectively 1.14 (95% CI: 1.00-1.31) and 1.20 (95% CI: 1.01-1.43) per unit of a time-lagged log-transformed continuous exposure scores), and that the HRs tend to increase with decreasing solubility of the compounds. CONCLUSION: Our results suggest that uranium carcinogenicity may depend on isotopic composition and solubility of uranium compounds. This study is the first to show the carcinogenic effect of slowly soluble reprocessed uranium on two uranium target organs. This finding is consistent with data from epidemiological and experimental studies on similar compounds but need to be confirmed in the more powerful dose-response analysis.

Mortality among workers monitored for radiation exposure at the French nuclear fuel company.

A cohort of 9,285 nuclear workers employed at the French company AREVA NC specializing in the nuclear fuel cycle was established. Vital status, causes of death, employment characteristics and annual exposure to ionizing radiation were reconstructed for each individual over the time period 1977-2004. Standardized mortality ratios (SMRs) were computed using national mortality rates as an external reference. Tests for trends in mortality with duration of employment and cumulative external dose were performed. The all-cause and all-cancer mortality was significantly lower than expected from the French population. No significant excess among cancer sites studied was observed. Significant positive trends with cumulative dose were observed for colon and liver cancer and for respiratory diseases. Isolated significant trends should be carefully interpreted and considered in line with the large number of trend tests performed.

Solid-state NMR characterization of a controlled-pore glass and of the effects of electron irradiation.

Controlled-pore glasses (CPGs) are silica-based materials which provide an adequate model system for a better understanding of the radiation chemistry of glasses, especially under nanoscopic confinement. This paper presents a characterization of a nanoporous CPG before and after electron irradiation using multinuclear solid-state magnetic resonance (NMR). 1H MAS NMR has been used for studying the surface proton sites and it is observed that the irradiation leads to a dehydration of the material. Accordingly, concerning the silicon sites near the surface, the observed variation of the Q4, Q3 and Q2 species from 1H-29Si CPMAS spectra shows an increase of the surface polymerization under irradiation, implying in majority a Q2 to Q3/Q4 conversion mechanism. Similarly, 1H-17 O CPMAS measurements exhibit an increase of Si-O-Si groups at the expenses of Si-OH groups. In addition, modifications of the environment of the residual boron atoms are also put in evidence from 11B MAS and MQMAS NMR These data show that MAS NMR methods provide sensitive tools for the characterization of these porous glasses and of the tiny modifications occurring under electron irradiation.

Mortality risk in the French cohort of uranium miners: extended follow-up 1946-1999.

OBJECTIVES: This paper presents the risk of death from lung cancer and from other causes of death for the French cohort of uranium miners through 1999 and estimates associations with radon exposure. METHODS: The cohort includes men employed as uranium miners for at least 1 year between 1946 and 1990. For each miner, vital status and cause of death were obtained from the national registry, and radon exposure was reconstructed for each year. Standardised mortality ratios were computed with national mortality rates as references. Exposure-risk relationships were estimated by Poisson regression, with a linear excess relative risk (ERR) model and a 5-year lag. RESULTS: The cohort included 5086 miners and 153 063 person-years of exposure. The mean duration of follow-up was 30.1 years. In all 4140 miners exposed to radon, the average cumulative exposure was 36.6 working level months (WLM). There were 1411 deaths of miners <85 years of age. The miners did not differ significantly in overall mortality from the general male population. The analysis confirmed an excess risk of lung cancer death (n = 159; SMR = 1.43; 95% CI: 1.22 to 1.68), which increased significantly with cumulative radon exposure (ERR per 100 WLM = 0.71; 95% CI: 0.29 to 1.35). The ERR per unit exposure was much higher after 1955, when the accuracy of exposure measurement improved substantially (ERR per 100 WLM = 2.00; 95% CI: 0.91 to 3.65). A significant excess of kidney cancer deaths was observed (n = 20; SMR = 2.0; 95% CI: 1.22 to 3.09), which was not associated with cumulative radon exposure. No excess was observed for other causes of death, except silicosis (n = 23; SMR = 7.12; 95% CI: 4.51 to 10.69). CONCLUSIONS: The analysis confirmed the excess risk of death from lung cancer associated with low radon exposure. An excess risk of death from kidney cancer was also observed, apparently not associated with cumulative radon exposure.

External radiation exposure and mortality in a cohort of French nuclear workers.

OBJECTIVE: To analyse the effect of external radiation exposure on the mortality of French nuclear workers. METHODS: A cohort of 29 204 workers employed between 1950 and 1994 at the French Atomic Energy Commission (Commissariat à l'Energie Atomique (CEA)) or at the General Company of Nuclear Fuel (COmpagnie GEnérale des MAtières nucléaires (Cogema, now Areva NC)) was followed up for an average of 17.8 years. Standardised mortality ratios (SMRs) were computed with reference to French mortality rates. Dose-effect relationship were analysed through trend tests and Poisson regression, with linear and log-linear models. RESULTS: The mean exposure to X and gamma radiation was 8.3 mSv (16.9 mSv for exposed worker population). A total of 1842 deaths occurred between 1968 and 1994. A healthy worker effect was observed, the number of deaths in the cohort being 59% of the number expected from national mortality statistics. Among the 21 main cancer sites studied, a statistically significant excess was observed only for skin melanoma, and an excess of borderline statistical significance was observed for multiple myeloma. A dose-effect relationship was observed for leukaemia after exclusion of chronic lymphoid leukaemia (CLL). The relative risk observed for non-CLL leukaemia, n = 20, was 4.1 per 100 mSv (90% CI 1.4 to 12.2), linear model and 2.2 per 100 mSv (90% CI 1.2 to 3.3), log-linear model. Significant dose-effect relationship were also observed for causes of deaths associated with alcohol consumption: mouth and pharynx cancer, cirrhosis and alcoholic psychosis and external causes of death. CONCLUSION: The risk of leukaemia increases with increasing exposure to external radiation; this is consistent with published results on other nuclear workers cohorts.

French population exposure to radon, terrestrial gamma and cosmic rays.

In France, natural sources account for most of the population exposure to ionising radiation. This exposure varies widely with area. Radon and gamma-ray exposure data come from national measurement campaigns; cosmic doses were calculated from city altitude. These data were corrected for season of measurement, housing characteristics and population density to study their relationship with health indicators. The crude average of indoor radon concentrations was 89 Bq m(-3), and the average corrected for season and housing characteristics was 83 Bq m(-3) (range over districts: 19-297). Weighting by district population density yielded a national average of 63 Bq m(-3). Gamma-ray dose rates averaged 55 nSv h(-1) (23-96) indoors and 46 nSv h(-1) (25-85) outdoors; corrections did not change the means. Corrected cosmic annual doses averaged 0.28 mSv (0.27-0.38). These corrections estimated the radiation exposure of the French population more accurately and represented its distribution well, thereby allowing its study as a cofactor in ecological studies.

Gas phase infrared spectroscopy of selectively prepared ions.

The first example of direct structural characterization of polyaromatic ions by coupling a Fourier transform ion cyclotron resonance mass spectrometer with an infrared free-electron laser is presented. Measurement of the IR spectra of selectively prepared ionic reactive intermediates is allowed by the association of the high peak power and wide tunability of the laser with the flexibility of the spectrometer, where several mass selection and ion reaction steps can be combined, as demonstrated in the case of iron cation complexes of hydrocarbons. The present experimental setup opens the way to understanding chemical reaction paths.