Speleothem calcite farmed in situ: Modern calibration of δO and δC paleoclimate proxies in a continuously-monitored natural cave system

Understanding the relationships between speleothem stable isotopes (δ¹³C δ¹⁸O) and in situ cave forcing mechanisms is important to interpreting ancient stalagmite paleoclimate records. Cave studies have demonstrated that the δ¹⁸O of inorganically precipitated (low temperature) speleothem calcite is systematically heavier than the δ¹⁸O of laboratory-grown calcite for a given temperature. To understand this apparent offset, rainwater, cave drip water, groundwater, and modern naturally precipitated calcite (farmed in situ) were grown at multiple locations inside Hollow Ridge Cave in Marianna, Florida. High resolution micrometeorological, air chemistry time series and ventilation regimes were also monitored continuously at two locations inside the cave, supplemented with periodic bi-monthly air gas grab sample transects throughout the cave.Cave air chemistry and isotope monitoring reveal density-driven airflow pathways through Hollow Ridge Cave at velocities of up to 1.2 m s⁻¹ in winter and 0.4 m s⁻¹ in summer. Hollow Ridge Cave displays a strong ventilation gradient in the front of the cave near the entrances, resulting in cave air that is a mixture of soil gas and atmospheric CO₂. A clear relationship is found between calcite δ¹³C and cave air ventilation rates estimated by proxies pCO₂ and ²²²Rn. Calcite δ¹³C decreased linearly with distance from the front entrance to the interior of the cave during all seasons, with a maximum entrance-to-interior gradient of Δδ¹³C_CaCO3 = −7‰. A whole-cave “Hendy test” at multiple contemporaneous farming sites reveals that ventilation induces a +1.9 ± 0.96‰ δ¹³C offset between calcite precipitated in a ventilation flow path and calcite precipitated on the edge or out of flow paths. This interpretation of the “Hendy test” has implications for interpreting δ¹³C records in ancient speleothems. Calcite δ¹³C_CaCO3 may be a proxy not only for atmospheric CO₂ or overlying vegetation shifts but also for changes in cave ventilation due to dissolution fissures and ceiling collapse creating and plugging ventilation windows.Farmed calcite δ¹⁸O was found to exhibit a +0.82 ± 0.24‰ offset from values predicted by both theoretical calculations and laboratory-grown inorganic calcite. Unlike δ¹³C_CaCO3, oxygen isotopes showed no ventilation effects, i.e. Δδ¹⁸O_CaCO3 appears to be a function of growth temperature only although we cannot rule out a small effect of (unmeasured) gradients in relative humidity (evaporation) accompanying ventilation. Our results support the findings of other cave investigators that water-calcite fractionation factors observed in speleothem calcite are higher that those measured in laboratory experiments. Cave and laboratory calcite precipitates may differ mainly in the complex effects of kinetic isotope fractionation. Combining our data with other recent speleothem studies, we find a new empirical relationship for cave-specific water-calcite oxygen isotope fractionation across a range of temperatures and cave environments:

1000lnα=16.1(10³T^-1)-24.6     

Can sedimentary leaf waxes record D/H ratios of continental precipitation? Field, model, and experimental assessments

D/H ratios of leaf waxes (δD_wax) derived from terrestrial plants and preserved in lake sediments can provide important information on past continental hydrology. Ideally, δD_wax can be used to reconstruct precipitation D/H ratios (δD_P) which is a well-established paleoclimate proxy. However, many other factors, such as vegetation and relative humidity (RH), also affect δD_wax variation. How the combination of these factors affects sedimentary δD_wax is unclear. Here, we use a transect of 32 lake surface sediments across large gradients of precipitation, relative humidity, and vegetation composition in the southwestern United States to study the natural factors affecting sedimentary δD_wax. δD values of C₂₈n-alkanoic acids show significant correlation with δD_P values (R² = 0.76) with an apparent isotopic enrichment of ∼99 ± 8‰, indicating that sedimentary δD_wax values track overall δD_P variation along the entire transect. Leaf waxes produced by plants grown under controlled conditions (RH = 80%, 60%, 40%) show a small increase in D/H ratios as RH decreases, consistent with prediction from the Craig-Gordon model. However, the isotopic effect of RH on δD_wax along the natural transect is partially countered by the opposing influence of vegetation changes. The correlation between δD_wax and δD_P values is significantly higher (R² = 0.84) in the drier portions of the transect than in the wetter regions (R² = 0.64). This study suggests that D/H ratios of sedimentary leaf waxes can be used as a proxy for precipitation δD variations, with particularly high fidelity in dry regions, although more studies in other regions will be important to further test this proxy.     

Microbial carbon cycling in oligotrophic regional aquifers near the Tono Uranium Mine, Japan as inferred from δC and ΔC values of in situ phospholipid fatty acids and carbon sources

Microorganisms are ubiquitous in deep subsurface environments, but their role in the global carbon cycle is not well-understood. The natural abundance δ¹³C and Δ¹⁴C values of microbial membrane phospholipid fatty acids (PLFAs) were measured and used to assess the carbon sources of bacteria in sedimentary and granitic groundwaters sampled from three boreholes in the vicinity of the Tono Uranium Mine, Gifu, Japan. Sample storage experiments were performed and drill waters analyzed to characterize potential sources of microbial contamination. The most abundant PLFA structures in all waters sampled were 16:0, 16:1ω7c, cy17:0, and 18:1ω7c. A PLFA biomarker for type II methanotrophs, 18:1ω8c, comprised 3% and 18% of total PLFAs in anoxic sedimentary and granitic waters, respectively, sampled from the KNA-6 borehole. The presence of this biomarker was unexpected given that type II methanotrophs are considered obligate aerobes. However, a bacterium that grows aerobically with CH₄ as the sole energy source and which also produces 56% of its total PLFAs as 18:1ω8c was isolated from both waters, providing additional evidence for the presence of type II methanotrophs. The Δ¹⁴C values determined for type II methanotroph PLFAs in the sedimentary (−861‰) and granite (−867‰) waters were very similar to the Δ¹⁴C values of dissolved inorganic carbon (DIC) in each water (∼−850‰). This suggests that type II methanotrophs ultimately derive all their carbon from inorganic sources, whether directly from DIC and/or from CH₄ produced by the reduction of DIC. In contrast, δ¹³C values of type II PLFAs in the sedimentary (−93‰) and granite (−60‰) waters indicate that these organisms use different carbon assimilation schemes in each environment despite very similar δ¹³C_CH4 values (∼−95‰) for each water. The δ¹³C_PLFA values (−28‰ to −45‰) of non-methanotrophic bacteria in the KNA-6 LTL water do not clearly distinguish between heterotrophic and autotrophic metabolisms, but Δ¹⁴C_PLFA values indicate that >65% of total bacteria filtered from the KNA-6 LTL water are heterotrophs. Ancient Δ¹⁴C values (∼−1000‰) of some PLFAs suggest that many heterotrophs utilize ancient organic matter, perhaps from lignite seams within the sedimentary rocks. The more negative range of δ¹³C_PLFA values determined for the KNA-6 granitic water (−42‰ to −66‰) are likely the result of a microbial ecosystem dominated by chemolithoautotrophy, perhaps fuelled by abiogenic H₂. Results of sample storage experiments showed substantial shifts in microbial community composition and δ¹³C_PLFA values (as much as 5‰) during 2-4 days of dark, refrigerated, aseptic storage. However, water samples collected and immediately filtered back in the lab from freshly drilled MSB-2 borehole appeared to maintain the same relative relationships between δ¹³C_PLFA values for sedimentary and granitic host rocks as observed for samples directly filtered under artesian flow from the KNA-6 borehole of the Tono Uranium Mine.     

Can pyrolysis-GC/MS be used to estimate the degree of thermal alteration of black carbon?

Very little is known about the macromolecular properties of biomass combustion residues referred to as black carbon (BC). Pyrolysis-gas chromatography–mass spectrometry (Py-GC/MS) was performed on: (i) peat from Spain at 400–1200 °C to investigate the effect of charring on pyrolysis fingerprint and (ii) natural charcoal from Laos in order to link molecular information to published chemical and reactivity parameters. Confirming earlier Py-GC/MS studies, the BC in the artificially charred peat and the natural charcoal produced predominantly benzene, toluene, C₂-benzenes, PAHs and benzonitriles. Furthermore, some charcoal samples produced significant amounts of phenols, methoxyphenols, carbohydrate markers, n-alkanes and n-alkenes upon pyrolysis, reflecting non-charred and weakly charred biomass. A series of pyrolysis product ratios related to the degree of dealkylation of the pyrolysis products (benzene/toluene, naphthalene/C₁-naphthalenes, C₁-naphthalenes/C₂-naphthalenes, benzofuran/C₁-benzofurans and benzonitrile/C₁-benzonitrile) increased with increasing artificial charring (peat) and, for the natural charcoal, these ratios were in accordance with established chemical and reactivity parameters related to charring intensity from other methods: proportion of aromatic C obtained from solid state ¹³C nuclear magnetic resonance spectroscopy (NMR), the proportion of charred material as estimated from NMR in conjunction with a molecular mixing model (NMR–MMM) and the resistance to acid dichromate oxidation. The alkyl side chains of aromatic pyrolysis products are probably inherited from short chain aliphatic C chains that cross link the predominantly aromatic building blocks of BC, and these linkages seem to disappear with increasing charring intensity. Thus, the degree of thermal alteration of BC can be discerned from the pyrolysis fragmentation pattern.     

Can shells of freshwater mussels (Unionidae) be used to estimate low summer discharge of rivers and associated droughts?

This paper examines if shell oxygen isotope ratios (δ¹⁸O_ar) of Unio sp. can be used as a proxy of past discharge of the river Meuse. The proxy was developed from a modern dataset for the reference time interval 1997–2007, which showed a logarithmic relationship between discharge and measured water oxygen isotope ratios (δ¹⁸O_w). To test this relationship for past time intervals, δ¹⁸O_ar values were measured in the aragonite of the growth increments of four Unio sp. shells; two from a relatively wet period and two from a very dry time interval (1910–1918 and 1969–1977, respectively). Shell δ¹⁸O_ar records were converted into δ¹⁸O_w values using existing water temperature records. Summer δ¹⁸O_w values, reconstructed from δ¹⁸O_ar of 1910–1918, showed a similar range as the summer δ¹⁸O_w values for the reference time interval 1997–2007, whilst summer reconstructed δ¹⁸O_w values for the time interval 1969–1977 were anomalously high. These high δ¹⁸O_w values suggest that the river Meuse experienced severe summer droughts during the latter time interval. δ¹⁸O_w values were then applied to calculate discharge values. It was attempted to estimate discharge from the reconstructed δ¹⁸O_w values using the logarithmic relationship between δ¹⁸O_w and discharge. A comparison of the calculated summer discharge results with observed discharge data showed that Meuse low-discharge events below a threshold value of 6 m³/s can be detected in the reconstructed δ¹⁸O_w records, but true quantification remains problematic.     

The Water Framework Directive: Can more information be extracted from groundwater data? A case study of Seewinkel,Burgenland, eastern Austria

Water protection is one of the most important goals in environmental protection. The Clean Water Act in the USA and the Water Framework Directive (WFD) in Europe are the legal frameworks to facilitate the achievement of this goal. The question is raised of whether more information can be extracted from WFD-related groundwater data. To answer it, a methodology has been developed that is easy to use and could be implemented into official practice. A case study is presented in which the groundwater data of a sodic area in Austria (Seewinkel) is assessed. Eighteen parameters in groundwater sampled from 23 wells (1991–2011) were analyzed. With basic statistics, trend-, cluster-, Wilks’ λ and spatial sampling density analysis, local phosphorus and boron phenomena were described, along with the determining role of sulphate, groundwater flow, and the oxygen gradient in the area. As a final step, the spatial sampling density was determined. Regarding the current set of parameters, all the sampling sites are necessary and only in the case of certain parameters (Ca²⁺, Mg²⁺, K⁺, NO₃ ^?, pH) could one sampling site be abandoned. The methodology applied brings a new perspective to exploring groundwater data collected according to the requirements of the WFD.     

In situ and laboratory investigation of the alteration of Boom Clay (Oligocene) at the air–geological barrier interface within the Mol underground facility (Belgium): Consequences on kerogen and bitumen compositions

The Boom Clay formation (Oligocene) is studied as a reference host rock for methodological studies on deep geological disposal of radioactive waste. During excavation of galleries within the Clay formation (HADES underground research facility, Mol, Belgium), the physico-chemical conditions are significantly modified as an air–clay interface is created. In order to study the long-term impact of the air–clay contact on the organic matter contained in the Boom Clay, two types of samples were studied: (1) a reference series of clay samples having been in contact with the atmosphere of the HADES gallery for increasing times up to several years and (2) unaltered clay samples submitted to artificial oxidation in a ventilated oven at 80 °C. The evolution of geochemical data of the two series was compared using Rock-Eval pyrolysis, GC–MS and size exclusion chromatography. The organic matter of the unaltered clays sampled in the HADES galleries is dominated by type III kerogen (terrestrial) with some contribution of type II (marine) and is thermally immature. The evolution of geochemical parameters during air alteration for the two series are very similar. They show progressive oxidation of kerogen accompanied by the release of bitumen enriched in low molecular weight constituents. Molecular analysis evidences the presence of a complex mixture of aliphatic and aromatic O-bearing compounds, inherited from the degradation of kerogen as well as from the clay catalyzed oxidation of the bitumen. These results show that (1) air oxidation is a major process in the in situ alteration of the organic matter of Boom Clay within the HADES galleries, (2) laboratory oxidation experiments at 80 °C yield similar results as in situ air alteration of Boom Clay and (3) artificial air oxidation may be used to assess the long term exposure of the organic matter to air.     

‘Unionising’ the new spaces of the new economy? Alternative labour organising in India’s IT Enabled Services-Business Process Outsourcing industry

This paper explores the lived experiences and aspirational social constructions of call centre work and employment in India’s high profile IT Enabled Services-Business Process Outsourcing (ITES-BPO) industry; the ways in which they differ from those previously documented amongst call centre workers in the Global North (specifically the UK); and the consequences of that geographical reconfiguration of offshored call centre work for the replicability in India of workplace collective bargaining strategies successfully developed in some UK call centres. These issues are analysed using new empirical evidence from a regional survey of 511 non-unionised ITES-BPO workers and 42 in-depth interviews in India’s National Capital Region. Based on this analysis, the paper then discusses the operation, outcomes and ongoing challenges faced by the newly formed ‘Union for ITES Professionals’ (UNITES Pro) in developing an alternative occupational organising model better suited to the particular needs, motivations and preferences of India’s young, mobile, call centre workers. The empirical analysis presented in the paper is located, therefore, within wider debates on the role of geographical context in shaping possibilities for organising white-collar service workers at different ends of global service chains in the new economy.