The Ratio 1660/1690 cm−1 Measured by Infrared Microspectroscopy Is Not Specific of Enzymatic Collagen Cross-Links in Bone Tissue

In postmenopausal osteoporosis, an impairment in enzymatic cross-links (ECL) occurs, leading in part to a decline in bone biomechanical properties. Biochemical methods by high performance liquid chromatography (HPLC) are currently used to measure ECL. Another method has been proposed, by Fourier Transform InfraRed Imaging (FTIRI), to measure a mature PYD/immature DHLNL cross-links ratio, using the 1660/1690 cm−1 area ratio in the amide I band. However, in bone, the amide I band composition is complex (collagens, non-collagenous proteins, water vibrations) and the 1660/1690 cm−1 by FTIRI has never been directly correlated with the PYD/DHLNL by HPLC. A study design using lathyritic rats, characterized by a decrease in the formation of ECL due to the inhibition of lysyl oxidase, was used in order to determine the evolution of 1660/1690 cm−1 by FTIR Microspectroscopy in bone tissue and compare to the ECL quantified by HPLC. The actual amount of ECL was quantified by HPLC on cortical bone from control and lathyritic rats. The lathyritic group exhibited a decrease of 78% of pyridinoline content compared to the control group. The 1660/1690 cm−1 area ratio was increased within center bone compared to inner bone, and this was also correlated with an increase in both mineral maturity and mineralization index. However, no difference in the 1660/1690 cm−1 ratio was found between control and lathyritic rats. Those results were confirmed by principal component analysis performed on multispectral infrared images. In bovine bone, in which PYD was physically destructed by UV-photolysis, the PYD/DHLNL (measured by HPLC) was strongly decreased, whereas the 1660/1690 cm−1 was unmodified. In conclusion, the 1660/1690 cm−1 is not related to the PYD/DHLNL ratio, but increased with age of bone mineral, suggesting that a modification of this ratio could be mainly due to a modification of the collagen secondary structure related to the mineralization process

Properties of Sarychev sulphate aerosols over the Arctic

Aerosols from the Sarychev Peak volcano entered the Arctic region less than a week after the strongest SO2 eruption on June 15 and 16, 2009 and had, by the second week in July, spread out over the entire Arctic region. These predominantly stratospheric aerosols were determined to be sub-micron in size and inferred to be composed of sulphates produced from the condensation of SO2 gases emitted during the eruption. Average (500 nm) Sarychev-induced stratospheric optical depths over the Polar Environmental Atmospheric Research Laboratory (PEARL) at Eureka, Nunavut, Canada were found to be between 0.03 and 0.05 during the months of July and August, 2009. This estimate, derived from sunphotometry and integrated lidar backscatter profiles was consistent with averages derived from lidar estimates over Ny-Ålesund (Spitsbergen). The Sarychev SOD e-folding time at Eureka, deduced from lidar profiles, was found to be approximately 4 months relative to a regression start date of July 27. These profiles initially revealed the presence of multiple Sarychev plumes between the tropopause and about 17 km altitude. After about two months, the complex vertical plume structures had collapsed into fewer, more homogeneous plumes located near the tropopause. It was found that the noisy character of daytime backscatter returns induced an artifactual minimum in the temporal, pan-Arctic, CALIOP SOD response to Sarychev sulphates. A depolarization ratio discrimination criterion was used to separate the CALIOP stratospheric layer class into a low depolarization subclass which was more representative of Sarychev sulphates. Post-SAT (post Sarychev Arrival Time) retrievals of the fine mode effective radius (reff,f) and the logarithmic standard deviation for two Eureka sites and Thule, Greenland were all close to 0.25 μm and 1.6 respectively. The stratospheric analogue to the columnar reff,f average was estimated to be reff,f(+) = 0.29 μm for Eureka data. Stratospheric, Raman lidar retrievals at Ny-Ålesund, yielded a post-SAT average of reff,f(+) = 0.27 μm. These results are ~ 50% larger than the background stratospheric-aerosol value. They are also about a factor of two larger than modeling values used in recent publications or about a factor of five larger in terms of (per particle) backscatter cross section