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Spectroradiometric measurements of direct solar irradiance traceable to the SI were performed by three spectroradiometer systems during a 3-week campaign in September 2022 at the Izaña Atmospheric Observatory (IZO) located on the island of Tenerife, Canary Islands, Spain. The spectroradiometers provided direct spectral irradiance measurements in the spectral ranges 300 to 550 nm (QASUME), 550 to 1700 nm (QASUME-IR), 300 to 2150 nm (BiTec Sensor, BTS), and 316 to 1030 nm (Precision Solar Spectroradiometer, PSR), with relative standard uncertainties of 0.7 %, 0.9 %, and 1 % for QASUME/QASUME-IR, the PSR, and the BTS respectively. The calibration of QASUME and QASUME-IR was validated prior to this campaign at Physikalisch-Technische Bundesanstalt (PTB) by measuring the spectral irradiance from two spectral irradiance sources, the high-temperature blackbody BB3200pg as a national primary standard and the tuneable laser facility TULIP. The top-of-atmosphere (ToA) solar irradiance spectra from the spectroradiometers were retrieved from direct solar irradiance measurements using zero-air-mass extrapolation during cloud-free conditions, which were then compared to the TSIS-1 Hybrid Solar Reference Spectrum (HSRS). These ToA solar spectra agreed to within 1 % for spectral ranges longer than 400 nm (for QASUME also at shorter wavelengths) in the spectral regions free of significant trace gas absorption and were well within the combined uncertainties over the full investigated spectral range. Using the results from the comparison with QASUME, the relative standard uncertainty of the TSIS-1 HSRS ToA solar spectrum in the spectral range 308 to 400 nm could be reduced from its nominal 1.3 % to 0.8 %, representing the relative standard uncertainty of the QASUME ToA solar spectrum in this spectral range. The spectral aerosol optical depth (AOD) retrieved from the solar irradiance measurements of these spectroradiometers using the TSIS-1 HSRS as the reference ToA solar spectrum agreed to within 0.01 in optical depth in nearly all common spectral channels of two narrowband filter radiometers belonging to the Global Atmosphere Watch Precision Filter Radiometer (GAW-PFR) network and Aerosol Robotic Network (AERONET). This study shows that it is now possible to retrieve spectral AOD over the extended spectral range from 300 to 1700 nm using solar irradiance measurements traceable to the SI using laboratory-calibrated spectroradiometers with similar quality to that from traditional Langley-based calibrated instruments. The main improvement to previous investigations is the recent availability of the high-spectral-resolution TSIS-1 HSRS with very low uncertainties, which provides the top-of-atmosphere reference for the spectral atmospheric transmission measurements obtained from ground-based solar irradiance measurements.

Metalworking fluids (MWFs) are widely used to cool and lubricate metal workpieces during processing to reduce heat and friction. Extending a MWF's service life is of importance from both economical and ecological points of view. Knowledge about the effects of processing conditions on the aging behavior and reliable analytical procedures are required to properly characterize the aging phenomena. While so far no quantitative estimations of ageing effects on MWFs have been described in the literature other than univariate ones based on single parameter measurements, in the present study we present a simple spectroscopy-based set-up for the simultaneous monitoring of three quality parameters of MWF and a mathematical model relating them to the most influential process factors relevant during use. For this purpose, the effects of MWF concentration, pH and nitrite concentration on the droplet size during aging were investigated by means of a response surface modelling approach. Systematically varied model MWF fluids were characterized using simultaneous measurements of absorption coefficients µ a and effective scattering coefficients µ' s . Droplet size was determined via dynamic light scattering (DLS) measurements. Droplet size showed non-linear dependence on MWF concentration and pH, but the nitrite concentration had no significant effect. pH and MWF concentration showed a strong synergistic effect, which indicates that MWF aging is a rather complex process. The observed effects were similar for the DLS and the µ' s values, which shows the comparability of the methodologies. The correlations of the methods were R 2 = 0.928 and R c = 0.927, as calculated by a partial least squares regression (PLS-R) model. Furthermore, using µ 2 , it was possible to generate a predictive PLS-R model for MWF concentration (R P = 0.890, R a , it was possible to generate a predictive PLS-R model for MWF concentration (R 2 is possible with good accuracy (R² c = 0.803, R² 2 P -PLS-R model, the predictive capability of the µ' s -PLS-R model for pH was refined (10 wt%: R² c = 0.998, R² P = 0.732). With prior knowledge of the MWF concentration using the µ a -PLS-R model, the predictive capability of the µ' s -PLS-R model for pH was refined (10 wt%: R² c = 0.998, R² p = 0.997). This highlights the relevance of the combined measurement of µ a and µ' s . Recognizing the synergistic nature of the effects of MWF concentration and pH on the droplet size is an important prerequisite for extending the service life of an MWF in the metalworking industry. The presented method can be applied as an in-process analytical tool that allows one to compensate for ageing effects during use of the MWF by taking appropriate corrective measures, such as pH correction or adjustment of concentration.