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

Heidke, Inken; Hoffmann, Thorsten

doi:10.5194/bg-15-5831-2018

Cited by 8 publications

(27 citation statements)

References 43 publications

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“…The methods used for dating of the stalagmite samples, the analysis of trace elements and stable isotopes as well as the calculation of the drip rate for the cave drip water samples and the growth rate of the stalagmite are described in detail in Mischel et al (2017) and references therein. The method used here for the analysis of lignin oxidation products in speleothems and cave drip water is described in detail in Heidke et al (2018). In the following paragraph, only a brief description will be given.…”

Section: Methodsmentioning

confidence: 99%

“…For the drip water stable isotope and trace element data, the uncertainty is very small and therefore not shown here, but it is provided in Mischel et al (2017). For the drip water LOP data, the uncertainty was calculated as described in Heidke et al (2018), and for the stalagmite LOP data, the calculation of the uncertainty is described in section 3.2.…”

Section: Methodsmentioning

confidence: 99%

“…The resulting lignin oxidation products (LOPs) were again extracted via SPE and then analysed via ultrahigh-performance liquid chromatography (UHPLC) coupled to heated electrospray ionisation (HESI) high resolution mass spectrometry (HRMS) using a Dionex Ultimate 3000 UHPLC system and a Q-Exactive Orbitrap mass spectrometer (Thermo Fisher Scientific). Further details of the method can be found in Heidke et al (2018).…”

Section: Analysis Of Lopsmentioning

confidence: 99%

“…with ∆X batch k and ∆X representing the standard deviations of the respective mean values and ∆x representing the uncertainty of a single sample analysis as described in Heidke et al (2018). The smoothed and original data for Σ8 can be compared in The mean Σ8 concentration in the whole stalagmite was 51 ± 15 ng • g −1 .…”

Section: Lops In Stalagmite Samplesmentioning

confidence: 99%

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

Heidke

Scholz

Hoffmann

2019

Preprint

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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.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Analysis Of Lopsmentioning

confidence: 99%

Section: Lops In Stalagmite Samplesmentioning

confidence: 99%

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

Heidke

Scholz

Hoffmann

2019

Preprint

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“…A recent study showed that trace concentrations of lignin oxidation products can be quantified in dripwater and speleothems (Heidke et al, 2018). In addition, in a Holocene stalagmite from the Herbstlabyrinth, Germany, the LOP concentrations and C/V and S/V ratios were found to co-vary with environmental changes and correlate with other proxies, such as P, U and Ba concentrations as well as δ 13 C values (Heidke et al, 2019).…”

Section: Introductionmentioning

confidence: 92%

Lignin oxidation products in soil, dripwater and speleothems from four different sites in New Zealand

Heidke¹,

Hartland²,

Scholz³

et al. 2020

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Abstract. Lignin oxidation products (LOPs) are widely used as vegetation proxies in climate archives, such as sediment and peat cores. The total LOP concentration, Σ8, provides information on the abundance of vegetation, while the ratios C / V and S / V of the different LOP groups also provide information on the type of vegetation. Recently, LOP analysis has been successfully applied to speleothem archives. However, there are many open questions concerning the transport and microbial degradation of LOPs on their way from the soil into the cave system. These processes could potentially alter the original source-dependent LOP signals, in particular the C / V and S / V ratios, and thus complicate their interpretation in terms of past vegetation changes. We analyzed LOPs in leaf litter and different soil horizons as well as dripwater and flowstone samples from four different cave sites from different vegetation zones in New Zealand using ultrahigh performance liquid chromatography coupled to high resolution mass spectrometry. We test whether the original source-dependent LOP signal of the overlying vegetation is preserved and can be recovered from flowstone samples and investigate how the signal is altered by the transport from the soil to the cave. The LOP concentrations range from mg/g in the soil to ng/g in the flowstones. Our results demonstrate that, from the soil to the flowstone, the C / V and S / V ratios both increase, while the total lignin content, Σ8, strongly decreases. This shows that the LOP signal is strongly influenced by both transport and degradation processes. Nevertheless, the relative LOP signal from the overlying soil at the different cave sites is preserved in the flowstone. We emphasize that for the interpretation of C / V and S / V ratios in terms of past vegetation changes, it is important to compare only samples of the same type (e.g., speleothem, dripwater or soil) and to evaluate only relative variations.

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Development of a Method for Anodic Degradation of Lignin for the Analysis of Paleo‐Vegetation Proxies in Speleothems

et al. 2022

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Here we present an electrochemical method for the anodic oxidation and subsequent degradation of lignin in speleothems to utilize the resulting lignin oxidation products (LOPs) as paleo‐vegetation markers. LOPs were analyzed using an ultra‐high performance liquid chromatography (UHPLC) system coupled to a high‐resolution mass spectrometer (HRMS). The method presented here achieved comparable or even higher LOP concentrations than established CuO and CuSO4 oxidation methods. The method represents a new tool for the analysis and reconstruction of paleo‐vegetation and has the potential to be applied to other climate archives.

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

Cited by 8 publications

References 43 publications

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

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

Lignin oxidation products in soil, dripwater and speleothems from four different sites in New Zealand

Development of a Method for Anodic Degradation of Lignin for the Analysis of Paleo‐Vegetation Proxies in Speleothems

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