Trasmission and Reflection (ATR)Far-Infrared Spectroscopy Applied in the Analysis of Cultural Heritage Materials

FIR spectroscopy is an alternative way of collecting spectra of many inorganic pigments and corrosion products found on art objects, which is not normally observed in the MIR region. Most FIR spectra are traditionally collected in transmission mode but as a real novelty it is now also possible to record FIR spectra in ATR (Attenuated Total Reflectance) mode. In FIR transmission we employ polyethylene (PE) for preparation of pellets by embedding the sample in PE. Unfortunately, the preparation requires heating of the PE in order to produces at transparent pellet. This will affect compounds with low melting points, especially those with structurally incorporated water. Another option in FIR transmission is the use of thin films. We test the use of polyethylene thin film (PETF), both commercial and laboratory-made PETF. ATR collection of samples is possible in both the MIR and FIR region on solid, powdery or liquid samples. Changing from the MIR to the FIR region is easy as it simply requires the change of detector and beamsplitter (which can be performed within a few minutes). No preparation of the sample is necessary, which is a huge advantage over the PE transmission method. The most obvious difference, when comparing transmission with ATR, is the distortion of band shape (which appears asymmetrical in the lower wavenumber region) and intensity differences. However, the biggest difference can be the shift of strong absorbing bands moving to lower wavenumbers in ATR mode. The sometimes huge band shift necessitates the collection of standard library spectra in both FIR transmission and ATR modes, provided these two methods of collecting are to be employed for analyses of unknown samples. Standard samples of 150 pigment and corrosion compounds are thus collected in both FIR transmission and ATR mode in order to build up a digital library of spectra for comparison with unknown samples. XRD, XRF and Raman spectroscopy assists us in confirming the purity or impurity of our standard samples. 24 didactic test tables, with known pigment and binder painted on the surface of a limestone tablet, are used for testing the established library and different ways of collecting in ATR and transmission mode. In ATR, micro samples are scratched from the surface and examined in both the MIR and FIR region. Additionally, direct surface contact of the didactic tablets with the ATR crystal are tested together with water enhanced surface contact. In FIR transmission we compare the powder from our test tablet on the laboratory PETF and embedded in PE. We also compare the PE pellets collected using a 4x beam condenser, focusing the IR beam area from 8 mm to 2 mm. A few samples collected from a mural painting in a Nepalese temple, corrosion products collected from archaeological Chinese bronze objects and samples from a mural paintings in an Italian abbey, are examined by ATR or transmission spectroscopy.

High-resolution summer temperature reconstruction from Lake Silvaplana based on in-situ reflectance spectroscopy

Annually laminated (varved) sediments of proglacial Lake Silvaplana (46 ̊27’N, 9 ̊48’E, 1791 m a.s.l., Engadine, eastern Swiss Alps) provide an excellent archive for quantitative high-resolution (seasonal – annual) reconstruction of high- and lowfrequency climate signals back to AD 1580. The chronology of the core is based on varve counting, Cs-137, Pb-210 and event stratigraphy. In this study we present a reconstruction based on in-situ reflectance spectroscopy. In situ reflectance spectroscopy is known as a cost- and time-effective non destructtive method for semi-quantitative analysis of pigments (e.g., chlorines and carotenoids) and of lithoclastic sediment fractions. Reflectance-dependent absorption (RDA) was measured with a Gretac Macbeth spectrolino at 2 mm resolution. The spectral coverage ranges from 380 nm to 730 nm at 10 nm band resolution. In proglacial Lake Silvaplana, 99% of the sediment is lithoclastic prior to AD 1950. Therefore, we concentrate on absorption features that are characteristic for lithoclastic sediment fractions. In Lake Silvaplana, two significant correlations that are stable in time were found between RDA typical for lithoclastics and meteorological data: (1) the time series R 570 /R 630 (ratio between RDA at 570 nm and 630 nm) of varves in Lake Silvaplana and May to October temperatures at nearby station of Sils correlate highly significantly (calibration period AD 1864 – 1951, r = 0.74, p < 0.01 for 5ptsmoothed series; RMSE is 0.28 ̊C, RE = 0.41 and CE = 0.38), and (2) the minimum reflectance within the 690nm band (min690) data correlate with May to October (calibration period AD 1864 – 1951, r = 0.68, p < 0.01 for 5pt-smoothed series; RMSE = 0.22 ̊C, RE = 0.5, CE = 0.31). Both proxy series (min690nm and R 570 /R 630 values) are internally highly consistent (r = 0.8, p < 0.001). In proglacial Lake Silvaplana the largest amount of sediment is transported by glacial meltwater. The melting season spans approximately from May to October, which gives us a good understanding of the geophysical processes explaining the correlations between lithoclastic proxies and the meteorological data. The reconstructions were extended back to AD 1580 and show a broad corresponddence with fully independent reconstructions from tree rings and documentary data.

hyDRaCAT Spectral Reflectance Library: Hyperspectral Field Spectroscopy and Field Spectro-Goniometry of Siberian and Alaskan Tundra

hyDRaCAT Spectral Reflectance Library for tundra provides the surface reflectance data and the bidirectional reflectance distribution function (BRDF) of important Arctic tundra vegetation communities at representative Siberian and Alaskan tundra sites. The aim of this dataset is the hyperspectral and spectro-directional reflectance characterization as basis for the extraction of vegetation parameters, and the normalization of BRDF effects in off-nadir and multi-temporal remote sensing data. The spectroscopic and field spectro-goniometric measurements were undertaken on the YAMAL2011 expedition of representative Siberian vegetation fields and on the North American Arctic Transect NAAT2012 expedition of Alaskan vegetation fields both belonging to the Greening-of-the-Arctic (GOA) program. For the field spectroscopy each 100 m2 vegetation study grid was divided into quadrats of 1 × 1 m. The averaged reflectance of all quadrats represents the spectral reflectance at the scale of the whole grid at the 10 × 10 m scale. For the surface radiometric measurements two GER1500 portable field spectroradiometers (Spectra Vista Corporation, Poughkeepsie, NY, USA) were used. The GER1500 measures radiance across the wavelength range of 350-1,050 nm, with sampling intervals of 1.5 nm and a radiance accuracy of 1.2 × 10**-1 W/cm**2/nm/sr. In order to increase the signal-to-noise ratio, 32 individual measurements were averaged per one target scan. To minimize variations in the target reflectance due to sun zenith angle changes, all measurements at one study location have been performed under similar sun zenith angles and during clear-sky conditions. The field spectrometer measurements were carried out with a GER1500 UV-VIS spectrometer The spectrogoniometer measurements were carried out with a self-designed spectro-goniometer: the Manual Transportable Instrument platform for ground-based Spectro-directional observations (ManTIS, patent publication number: DE 10 2011 117 713.A1). The ManTIS was equipped with the GER1500 spectrometer allowing spectro-directional measurements with up to 30° viewing zenith angle by full 360° viewing azimuth angles. Measurements in central Yamal (Siberia) at the research site 'Vaskiny Dachi' were carried out in the late summer phenological state from August 12 2011 to August 28 2011. All measurements in Alaska along the North South transect on the North Slope were taken between 29 June and 11 July 2012, ensuring that the vegetation was in the same phenological state near peak growing season.