Molecular signatures of dissolved organic matter in a tropical karst system

Karst areas are widespread landforms present on all continents, formed by the dissolution of carbonate or evaporite host rock. Little is known about the composition and nature of dissolved organic matter (DOM) as it moves through karst systems, although karst DOM has been recognized as important for a range of natural processes. Microbial communities living in karst systems are some of the most diverse and intriguing on the planet, and their metabolism and life cycle can give clues related to the development of a host of different life forms. Karst areas are also of interest due to their mostly subterranean hydrology, and the repercussions of these processes on local carbon cycles. We illustrate some of the processes acting on DOM in karst waters through the analysis of soil, drip and cave pool waters at the tropical site of Yok Balum Cave, in southern Belize. Water samples were analyzed using ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS), a technique that enables the resolution of single molecular formulae within a DOM spectrum. We perform multivariate statistics to detect trends in the data and identify provenance of detected molecular components. In addition to karst waters, four aliquots of a powdered stalagmite sample from the same cave system are analyzed. Our results show a clear gradient between the soil and the cave system. We hypothesize that both sorption on mineral surfaces and microbial reworking are responsible for the observed trend in DOM composition. The stalagmite extracts show an anomalous DOM pattern, which may be due to a variety of factors, including microbial activity on the stalagmite surface and different affinities of compounds to incorporation in the carbonate. The goal of this study was to follow the molecular transformations of DOM on its journey from the surface to the cave, and to provide a molecular basis for the establishment of stalagmite DOM proxies in karst systems

До питання конституційної правосуб’єктності українського народу

Розглядаються поняття сутності, характеру і змісту конституційної право­суб’єктності українського народу.Рассматриваются понятия сущности, характера и содержания конституционной правосубъектности украинского народа.The article deals with the notion, subject matter, character and content of constitutional legal standing of Ukrainian people

An Abrupt Aging of Dissolved Organic Carbon in Large Arctic Rivers

Permafrost thaw in Arctic watersheds threatens to mobilize hitherto sequestered carbon. We examine the radiocarbon activity (F14C) of dissolved organic carbon (DOC) in the northern Mackenzie River basin. From 2003‐2017, DOC‐F14C signatures (1.00 ± 0.04; n = 39) tracked atmospheric 14CO2, indicating export of “modern” carbon. This trend was interrupted in June 2018 by the widespread release of aged DOC (0.85 ± 0.16, n = 28) measured across three separate catchment areas. Increased nitrate concentrations in June 2018 lead us to attribute this pulse of 14C‐depleted DOC to mobilization of previously frozen soil organic matter. We propose export through lateral perennial thaw zones occurred at the base of the active layer weakened by preceding warm summer and winter seasons. Although we are not yet able to ascertain the broader significance of this “anomalous” mobilization event, it highlights the potential for rapid and large‐scale release of aged carbon from permafrost

A novel approach for construction of radiocarbon-based chronologies for speleothems

Robust chronologies are crucial for the correct interpretation of climate proxy records and for detailed reconstructions of palaeoclimate. Stalagmites have garnered strong interest as recorders of past climate in part due to their amenability to U-series dating. However, many stalagmites are not dateable using this technique due to low 238U and/or high detrital Th concentrations (e.g., many tropical cave systems (Adkins et al., 2013)), and occasionally these issues affect stalagmites across wide geographical regions (e.g., large parts of Australia (Green et al. 2013)) complicating the use of stalagmites in these areas. Radiocarbon (14C) offers an alternative method of dating stalagmites, but issues associated with the ‘dead carbon fraction’ (DCF) have historically hindered this approach. Here, a novel 14C-based method for dating stalagmites is presented and discussed. The technique calculates a best-fit growth rate between a time-series of stalagmite 14C data and known atmospheric 14C variability. The new method produces excellent results for stalagmites that satisfy four requirements: i) the absence of long-term secular variability in DCF (i.e., stalagmite DCF varies around a mean value with no long-term trend), ii) stalagmite growth rate does not vary significantly (the technique identifies stalagmites with substantial growth rate variability), iii) the stalagmite record is long enough that measurable 14C decay has occurred, and iv) one ‘anchor’ point exists where the calendar age is known. The model produces good results for a previously U–Th dated stalagmite from Heshang Cave, China, and is then applied to an undated stalagmite from southern Poland. The new method will not replace high-precision U–Th measurements, because the precision of the technique is difficult to quantify. However, it provides a means for dating certain stalagmites undateable by conventional U–Th methods and for refining coarse U–Th chronologies

Alkylpyrroles in kerogen pyrolysates : evidence for abundant macromolecularly-bound tetrapyrrole pigments

Porphyrins and related compounds are well known biological markers often applied in geochemistry

Alkylpyrroles in a kerogen pyrolysate: Evidence for abundant tetrapyrrole pigments

C1-C6 alkylated pyrroles were identified as major constituents of the flash pyrolysate of a kerogen from the Miocene Monterey Formation (California, USA) using gas chromatography with an N-selective detector and gas chromatography-mass spectrometry. The major alkylpyrroles identified are 2,3,4-trimethylpyrrole; 3-ethyl-4-methylpyrrole; 2,3-dimethyl-4-ethylpyrrole; 2,4-dimethyl-3-ethylpyrrole; and 3-ethyl-2,4,5-trimethylpyrrole. The alkyl substitution patterns of the alkylpyrroles strongly suggest an origin from tetrapyrrole pigments. Evidence for this hypothesis was provided by flash pyrolysis of the tetrapyrrole pigments chlorophyll-a, protoporphyrin-IX dimethyl ester, and bilirubin, which yielded alkylpyrroles with a similar isomer distribution. Quantitative pyrolysis using a polymer internal standard of both the kerogen and the tetrapyrrole pigments revealed that ca. 5% of the kerogen consists of macromolecularly bound tetrapyrrole pigments or that this fraction contains ca. 5% insoluble tetrapyrrole salts. These results show that in specific cases tetrapyrrole pigments can contribute significantly to the sedimentary organic matter