Universally Applicable Model for the Quantitative Determination of Lake Sediment Composition Using Fourier Transform Infrared Spectroscopy

ABSTRACT: Fourier transform infrared spectroscopy (FTIRS) can provide detailed information on organic and minerogenic constituents of sediment records. Based on a large number of sediment samples of varying age (0�340 000 yrs) and from very diverse lake settings in Antarctica, Argentina, Canada, Macedonia/Albania, Siberia, and Sweden, we have developed universally applicable calibration models for the quantitative determination of biogenic silica (BSi; n = 816), total inorganic carbon (TIC; n = 879), and total organic carbon (TOC; n = 3164) using FTIRS. These models are based on the differential absorbance of infrared radiation at specific wavelengths with varying concentrations of individual parameters, due to molecular vibrations associated with each parameter. The calibration models have low prediction errors and the predicted values are highly correlated with conventionally measured values (R = 0.94�0.99). Robustness tests indicate the accuracy of the newly developed FTIRS calibration models is similar to that of conventional geochemical analyses. Consequently FTIRS offers a useful and rapid alternative to conventional analyses for the quantitative determination of BSi, TIC, and TOC. The rapidity, cost-effectiveness, and small sample size required enables FTIRS determination of geochemical properties to be undertaken at higher resolutions than would otherwise be possible with the same resource allocation, thus providing crucial sedimentological information for climatic and environmental reconstructions.

Fourier transform infrared spectroscopy, a new method for rapid determination of total organic and inorganic carbon and biogenic silica concentration in lake sediments

Abstract We demonstrate the use of Fourier transform infrared spectroscopy (FTIRS) to make quantitative measures of total organic carbon (TOC), total inorganic carbon (TIC) and biogenic silica (BSi) concentrations in sediment. FTIRS is a fast and costeffective technique and only small sediment samples are needed (0.01 g). Statistically significant models were developed using sediment samples from northern Sweden and were applied to sediment records from Sweden, northeast Siberia and Macedonia. The correlation between FTIRS-inferred values and amounts of biogeochemical constituents assessed conventionally varied between r = 0.84–0.99 for TOC, r = 0.85– 0.99 for TIC, and r = 0.68–0.94 for BSi. Because FTIR spectra contain information on a large number of both inorganic and organic components, there is great potential for FTIRS to become an important tool in paleolimnology.

Enhanced (1)G(4) emission in NaLaF4: Pr3+, Yb3+ and charge transfer in NaLaF4: Ce3+, Yb3+ studied by fourier transform luminescence spectroscopy

A high resolution luminescence study of NaLaF4: 1%Pr3+, 5%Yb3+ and NaLaF4: 1%Ce3+, 5%Yb3+ in the UV to NIR spectral range using a InGaAs detector and a fourier transform interferometer is reported. Although the Pr3+(P-3(0) -> (1)G(4), Yb3+(F-2(7/2) -> F-2(5/2)) energy transfer step takes place, significant Pr3+ (1)G(4) emission around 993, 1330 and 1850 nm is observed. No experimental proof for the second energy transfer step in the down-conversion process between Pr3+ and Yb3+ can be given. In the case of NaLaF4: Ce3+, Yb3+ it is concluded that the observed Yb3+ emission upon Ce3+ 5d excitation is the result of a charge transfer process instead of down-conversion. (C) 2010 Elsevier B.V. All rights reserved.

Biogeochemical variability during the past 3.6 million years recorded by FTIR spectroscopy in the sediment record of Lake El'gygytgyn, Far East Russian Arctic

Abstract. A number of studies have shown that Fourier transform infrared spectroscopy (FTIRS) can be applied to quantitatively assess lacustrine sediment constituents. In this study, we developed calibration models based on FTIRS for the quantitative determination of biogenic silica (BSi; n = 420; gradient: 0.9–56.5 %), total organic carbon (TOC; n = 309; gradient: 0–2.9 %), and total inorganic carbon (TIC; n = 152; gradient: 0–0.4 %) in a 318 m-long sediment record with a basal age of 3.6 million years from Lake El’gygytgyn, Far East Russian Arctic. The developed partial least squares (PLS) regression models yield high cross-validated (CV) R2 CV = 0.86–0.91 and low root mean square error of crossvalidation (RMSECV) (3.1–7.0% of the gradient for the different properties). By applying these models to 6771 samples from the entire sediment record, we obtained detailed insight into bioproductivity variations in Lake El’gygytgyn throughout the middle to late Pliocene and Quaternary. High accumulation rates of BSi indicate a productivity maximum during the middle Pliocene (3.6–3.3 Ma), followed by gradually decreasing rates during the late Pliocene and Quaternary. The average BSi accumulation during the middle Pliocene was �3 times higher than maximum accumulation rates during the past 1.5 million years. The indicated progressive deterioration of environmental and climatic conditions in the Siberian Arctic starting at ca. 3.3 Ma is consistent with the first occurrence of glacial periods and the finally complete establishment of glacial–interglacial cycles during the Quaternary.

Independent measurement of biogenic silica in sediments by FTIR spectroscopy and PLS regression

We present an independent calibration model for the determination of biogenic silica (BSi) in sediments, developed from analysis of synthetic sediment mixtures and application of Fourier transform infrared spectroscopy (FTIRS) and partial least squares regression (PLSR) modeling. In contrast to current FTIRS applications for quantifying BSi, this new calibration is independent from conventional wet-chemical techniques and their associated measurement uncertainties. This approach also removes the need for developing internal calibrations between the two methods for individual sediments records. For the independent calibration, we produced six series of different synthetic sediment mixtures using two purified diatom extracts, with one extract mixed with quartz sand, calcite, 60/40 quartz/calcite and two different natural sediments, and a second extract mixed with one of the natural sediments. A total of 306 samples—51 samples per series—yielded BSi contents ranging from 0 to 100 %. The resulting PLSR calibration model between the FTIR spectral information and the defined BSi concentration of the synthetic sediment mixtures exhibits a strong cross-validated correlation ( R2cv = 0.97) and a low root-mean square error of cross-validation (RMSECV = 4.7 %). Application of the independent calibration to natural lacustrine and marine sediments yields robust BSi reconstructions. At present, the synthetic mixtures do not include the variation in organic matter that occurs in natural samples, which may explain the somewhat lower prediction accuracy of the calibration model for organic-rich samples.