scholarly journals Quantification of lignin oxidation products as vegetation biomarkers in speleothems and cave drip water

2018 ◽  
Vol 15 (19) ◽  
pp. 5831-5845 ◽  
Author(s):  
Inken Heidke ◽  
Denis Scholz ◽  
Thorsten Hoffmann
Keyword(s):  
Organic Matter ◽  
Sample Size ◽  
Water Samples ◽  
Solid Phase ◽  
Oxidation Products ◽  
Drip Water ◽  
Cave Drip Water ◽  
Lignin Oxidation ◽  
The Individual ◽  
Sensitive Method

Abstract. Here we present a sensitive method to analyze lignin oxidation products (LOPs) in speleothems and cave drip water to provide a new tool for paleo-vegetation reconstruction. Speleothems are valuable climate archives. However, compared to other terrestrial climate archives, such as lake sediments, speleothems contain very little organic matter. Therefore, very few studies on organic biomarkers in speleothems are available. Our new sensitive method allows us to use LOPs as vegetation biomarkers in speleothems. Our method consists of acid digestion of the speleothem sample followed by solid-phase extraction (SPE) of the organic matter. The extracted polymeric lignin is degraded in a microwave-assisted alkaline CuO oxidation step to yield monomeric LOPs. The LOPs are extracted via SPE and finally analyzed via ultrahigh-performance liquid chromatography (UHPLC) coupled to electrospray ionization (ESI) and high-resolution Orbitrap mass spectrometry (HRMS). The method was applied to stalagmite samples with a sample size of 3–5 g and cave drip water samples with a sample size of 100–200 mL from the Herbstlabyrinth-Advent Cave in Germany. In addition, fresh plant samples, soil water, and powdered lignin samples were analyzed for comparison. The concentration of the sum of eight LOPs (Σ8) was in the range of 20–84 ng g−1 for the stalagmite samples and 230–440 ng L−1 for the cave drip water samples. The limits of quantification for the individual LOPs ranged from 0.3–8.2 ng per sample or 1.5–41.0 ng mL−1 of the final sample solution. Our method represents a new and powerful analytical tool for paleo-vegetation studies and has great potential to identify the pathways of lignin incorporation into speleothems.

scholarly journals Quantification of lignin oxidation products as vegetation biomarkers in speleothems and cave drip water

2018 ◽  
Author(s):  
Inken Heidke ◽  
Denis Scholz ◽  
Thorsten Hoffmann
Keyword(s):  
Organic Matter ◽  
Sample Size ◽  
Water Samples ◽  
Solid Phase ◽  
Oxidation Products ◽  
Drip Water ◽  
Cave Drip Water ◽  
Lignin Oxidation ◽  
The Individual ◽  
Sensitive Method

Abstract. Here we present a sensitive method to analyse lignin oxidation products (LOPs) in speleothems and cave drip water to provide a new tool for paleo vegetation reconstruction. Speleothems are valuable climate archives. However, compared to other terrestrial climate archives, such as lake sediments, speleothems contain very little organic matter. Therefore, very few studies on organic biomarkers in speleothems are available. Our new sensitive method allows to use LOPs as vegetation biomarkers in speleothems. Our method consists of acid digestion of the speleothem sample followed by solid phase extraction (SPE) of the organic matter. The extracted polymeric lignin is degraded in a microwave assisted alkaline CuO oxidation step to yield monomeric LOPs. The LOPs are extracted via SPE and finally analysed via ultrahigh-performance liquid chromatography (UHPLC) coupled to electrospray ionisation (ESI) and high-resolution orbitrap mass spectrometry (HRMS). The method was applied to stalagmite samples with a sample size of 3–5 g and cave drip water samples with a sample size of 100–200 mL from the Herbstlabyrinth-Advent-Cave in Germany. In addition, fresh plant samples, soil water and powdered lignin samples were analysed for comparison. The concentration of the sum of eight LOPs (Σ8) was in the range of 20–84 ng g−1 for the stalagmite samples and 230–440 ng L−1 for the cave drip water samples. The limits of quantification for the individual LOPs ranged from 0.3–8.2 ng per sample. Our method represents a new and powerful analytical tool for paleo vegetation studies and has great potential to identify the pathways of lignin incorporation into speleothems.

scholarly journals Lignin oxidation products as a potential proxy for vegetation and environmental changes in speleothems and cave drip water – a first record from the Herbstlabyrinth, central Germany

2019 ◽  
Vol 15 (3) ◽  
pp. 1025-1037
Author(s):  
Inken Heidke ◽  
Denis Scholz ◽  
Thorsten Hoffmann
Keyword(s):  
Environmental Changes ◽  
Seasonal Pattern ◽  
First Record ◽  
Oxidation Products ◽  
Central Germany ◽  
Drip Water ◽  
Cave Drip Water ◽  
Lignin Oxidation ◽  
Climate Proxies ◽  
Vegetation And Climate

Abstract. Here, we present the first quantitative speleothem record of lignin oxidation products (LOPs), which has been determined in a Holocene stalagmite from the Herbstlabyrinth Cave in central Germany. In addition, we present LOP results from 16 months of drip water monitoring. Lignin is only produced by vascular plants and therefore has the potential to be an unambiguous vegetation proxy and to complement other vegetation and climate proxies in speleothems. We compare our results with stable isotope and trace element data from the same sample. In the stalagmite, LOP concentrations show a similar behavior to P, Ba and U concentrations, which have previously been interpreted as vegetation proxies. The LOP S∕V and C∕V ratios, which are usually used to differentiate between angiosperm and gymnosperm and woody and non-woody vegetation, show complex patterns suggesting additional influencing factors, such as transport and microbiological effects. The drip water from a fast drip site shows a seasonal pattern of LOPs with low LOP concentrations in winter and higher LOP concentrations in summer. These results indicate the potential of LOPs as a new proxy for vegetational and environmental changes in speleothems but also demonstrate the complexity and the current limitations of our understanding of the transport of lignin from the soil into the cave and the speleothems.

An improved method for fluorescence analysis of dissolved organic matter in cave drip water

2014 ◽  
Vol 8 (4) ◽  
pp. 595-598 ◽  
Author(s):  
Xiuli Li ◽  
Chaoyong Hu ◽  
Jin Liao ◽  
Liangliang Bao ◽  
Qixi Mao
Keyword(s):  
Organic Matter ◽  
Dissolved Organic Matter ◽  
Fluorescence Analysis ◽  
Improved Method ◽  
Drip Water ◽  
Cave Drip Water

scholarly journals Lignin oxidation products as a vegetation proxy in stalagmite and drip water samples from the Herbstlabyrinth, Germany

2019 ◽  
Author(s):  
Inken Heidke ◽  
Denis Scholz ◽  
Thorsten Hoffmann
Keyword(s):  
Vascular Plants ◽  
Seasonal Pattern ◽  
Water Monitoring ◽  
Oxidation Products ◽  
Trace Element Data ◽  
Central Germany ◽  
Drip Water ◽  
Lignin Oxidation ◽  
Climate Proxies ◽  
Vegetation And Climate

Abstract. Here we present the first quantitative record of lignin oxidation products (LOPs) in a Holocene stalagmite from the Herbstlabyrinth Cave in central Germany, as well as LOP results from 16 months of drip water monitoring. Lignin is only produced by vascular plants and is therefore an unambiguous vegetation proxy, which can help to better interpret other vegetation and climate proxies in speleothems. We compared our results with stable isotope and trace element data from the same samples. The drip water monitoring reveals a seasonal pattern of LOPs in a fast drip site with low LOP concentrations in winter and higher LOP concentrations in summer, which is opposite to the behaviour of the drip rate, Mg2+ and PO3−4 concentrations. In the stalagmite, LOP concentrations are correlated or show a similar behaviour to P, Ba and U concentrations. The LOP ratios C/V and S/V, which are usually used to differentiate between angiosperm and gymnosperm and woody and non-woody lignin sources, are anticorrelated to the LOP concentrations and show a similar behaviour to δ13C and Mg concentrations. These results highlight the potential of LOPs as a new, highly specific vegetation proxy in speleothems, but also demonstrate current limitations in our understanding of the transport of lignin from the soil into the cave and the speleothems.

Fluorescence technique for the characterization of natural organic matter in river water

2002 ◽  
Vol 46 (9) ◽  
pp. 117-125 ◽  
Author(s):  
U.K. Ahmad ◽  
Z. Ujang ◽  
Z. Yusop ◽  
T.L. Fong
Keyword(s):  
Organic Matter ◽  
River Water ◽  
Natural Organic Matter ◽  
Water Samples ◽  
Solid Phase ◽  
Complex Nature ◽  
Fluorescence Technique ◽  
Excitation Spectra ◽  
The Impact

The complex nature of natural organic matter (NOM), and the impact of this matter on drinking water quality have necessitated the characterization studies of NOM. A fluorescence technique for the characterization of NOM in Malaysian river water is reported. Water samples from several river sampling sites were collected and concentrated using a low-pressure reverse osmosis (LPROM). Solid phase extraction (SPE) using C18 extraction cartridges were used to fractionate the water samples into humic and non-humic fractions. To differentiate and classify various types of humic substances, fluorescence was applied in emission, excitation and in synchronous-scan modes. A synchronous spectral profile was found to be able to differentiate humic and fulvic acids better than the emission or excitation spectra. Synchronous excitation spectra showed different spectral patterns for the water samples due to different origin. All water samples showed the presence of both fulvic and humic acids.

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