The isotopic ratios O/O and O/O in molecular oxygen and their significance in biogeochemistry

Recently, a new method has been introduced for the estimation of photosynthetic oxygen production from the triple isotope composition (δ¹⁷O and δ¹⁸O) of dissolved O₂ in the ocean and of air O₂ in ice cores. This method is based on the deviations (¹⁷Δ) from mass dependent respiratory fractionation, the major process affecting the isotopic composition of air O₂. To apply this method, the slope in the ¹⁷O/¹⁶O vs. ¹⁸O/¹⁶O relationship used for ¹⁷Δ calculation must be known with high accuracy. Using numerical simulations and closed system experiments, we show how the respiratory slope is manifested in the ¹⁷Δ of O₂ in situations where respiration is the only process affecting oxygen isotopic composition (kinetic slope), and in systems in steady state between photosynthesis and respiration (steady state slope). The slopes of the fractionation line in these two cases are different, and the reasons of this phenomenon are discussed. To determine the kinetic respiratory slope for the dominant O₂ consumers in aquatic systems, we have conducted new experiments using a wide range of organisms and conditions and obtained one universal value (0.5179 ± 0.0006) in ln(δ¹⁷O + 1) vs. ln(δ¹⁸O + 1) plots. It was also shown that the respiratory fractionations under light and dark are identical within experimental error. We discuss various marine situations and conclude that the kinetic slope 0.518 should be used for calculating ¹⁷Δ of dissolved O₂. In contrast, a steady state fractionation slope should be used in global mass balance calculations of triple isotope ratios of O₂ in air records of ice cores.     

Long-term deforestation in NW Spain: linking the Holocene fire history to vegetation change and human activities

The Holocene fire regime is thought to have had a key role in deforestation and shrubland expansion in Galicia (NW Spain) but the contribution of past societies to vegetation burning remains poorly understood. This may be, in part, due to the fact that detailed fire records from areas in close proximity to archaeological sites are scarce. To fill this gap, we performed charcoal analysis in five colluvial soils from an archaeological area (Campo Lameiro) and compared the results to earlier studies from this area and palaeo-ecological literature from NW Spain. This analysis allowed for the reconstruction of the vegetation and fire dynamics in the area during the last ca 11 000 yrs. In the Early Holocene, Fabaceae and Betula sp. were dominant in the charcoal record. Quercus sp. started to replace these species around 10 000 cal BP, forming a deciduous forest that prevailed during the Holocene Thermal Maximum until ～5500 cal BP. Following that, several cycles of potentially fire-induced forest regression with subsequent incomplete recovery eventually led to the formation of an open landscape dominated by shrubs (Erica sp. and Fabaceae). Major episodes of forest regression were (1) ～5500–5000 cal BP, which marks the mid-Holocene cooling after the Holocene Thermal Maximum, but also the period during which agropastoral activities in NW Spain became widespread, and (2) ～2000–1500 cal BP, which corresponds roughly to the end of the Roman Warm Period and the transition from the Roman to the Germanic period. The low degree of chronological precision, which is inherent in fire history reconstructions from colluvial soils, made it impossible to distinguish climatic from human-induced fires. Nonetheless, the abundance of synanthropic pollen indicators (e.g. Plantago lanceolata and Urtica dioica) since at least ～6000 cal BP strongly suggests that humans used fire to generate and maintain pasture.     

The use of the exponent K(q) function to delimit homogeneous regions in regional frequency analysis of extreme annual daily rainfall

The regional frequency analysis of extreme annual rainfall data is a useful methodology in hydrology to obtain certain quantile values when no long data series are available. The most crucial step in the analysis is the grouping of sites into homogeneous regions. This work presents a new grouping criterion based on some multifractal properties of rainfall data. For this purpose, a regional frequency analysis of extreme annual rainfall data from the Maule Region (Chile) has been performed. Daily rainfall data series of 53 available stations have been studied, and their empirical moments scaling exponent functions K(q) have been obtained. Two characteristics parameters of the K(q) functions (γ_max and K(0)) have been used to group the stations into three homogeneous regions. Only five sites have not been possible to include into any homogenous regions, being the local frequency analysis of extreme daily rainfall the most appropriate method to be used at these locations. Copyright © 2014 John Wiley & Sons, Ltd.     

Pre‐Alpine discordant granitic dikes in the metamorphic core of the Betic Cordillera: tectonic implications

Pegmatite dikes bearing andalusite crosscut foliation S₂ in Alpujarride gneisses and schists. Post‐S₂ andalusite is transposed by a foliation S₃, defined by fibrolite, which affects the dikes. The dikes represent highly differentiated granitic magmas with low REE and Zr contents and a positive Eu anomaly. U‐Pb SHRIMP dating of magmatic zircons provided Pan‐African ages (cores) and late Variscan ages (rims). However, U‐rich rims also provided metamorphic Alpine ages, supporting a polyorogenic tectonometamorphic history for pre‐Mesozoic Alpujarride rocks.     

The multi-component Hekla Ö Tephra,Iceland: a complex widespread mid-Holocene tephra layer

Large Plinian eruptions from Hekla volcano, Iceland, produce compositionally zoned tephra used as key markers in tephrochronology. However, spatial variations in chemical composition of a tephra layer may complicate its identification. An example is the 5950–6180 cal a bp Hekla Ö tephra layer, which shows compositional spread from rhyolite, dacite and andesite to basalt. In soil sections north of Hekla, the SiO₂ content of the tephra glass reaches 76 wt% in the lowest unit of the Hekla Ö deposit and decreases to 62–63 wt% in the uppermost unit. Intermingled within the whole deposit are basalt tephra grains having 46–47 wt% SiO₂. The composition of the basalt glass includes primitive basalt and a more evolved basalt (MgO >6 and <6 wt%, respectively). Together with literature data, the Hekla Ö tephra and the so-called T-Tephra/Hekla-T are most likely from contemporaneous eruptions of different vents on the Hekla volcanic system, forming a single important marker tephra (Hekla ÖT) deposited over 80% of Iceland. Identification is complicated by its spatial compositional heterogeneity, such as systematic decrease in SiO₂ content from the east to the west of Hekla volcano. Consequently, an individual tephra layer from a large explosive eruption can have different composition at different locations. © 2020 John Wiley & Sons, Ltd.     

Crustal segments in the North Patagonian Massif,Patagonia: An integrated perspective based on Sm–Nd isotope systematics

New insights on the Paleozoic evolution of the continental crust in the North Patagonian Massif are presented based on the analysis of Sm–Nd systematics. New evidence is presented to constrain tectonic models for the origin of Patagonia and its relations with the South American crustal blocks. Geologic, isotopic and tectonic characterization of the North Patagonian Massif and comparison of the Nd parameters lead us to conclude that: (1) The North Patagonian Massif is a crustal block with bulk crustal average ages between 2.1 and 1.6 Ga T_DM (Nd) and (2) At least three metamorphic episodes could be identified in the Paleozoic rocks of the North Patagonian Massif. In the northeastern corner, Famatinian metamorphism is widely identified. However field and petrographic evidence indicate a Middle to Late Cambrian metamorphism pre-dating the emplacement of the ca. 475 Ma granitoids. In the southwestern area, are apparent 425–420 Ma (?) and 380–360 Ma metamorphic peaks. The latter episode might have resulted from the collision of the Antonia terrane; and (3) Early Paleozoic magmatism in the northeastern area is coeval with the Famatinian arc. Nd isotopic compositions reveal that Ordovician magmatism was associated with attenuated crust. On the southwestern border, the first magmatic recycling record is Devonian. Nd data shows a step by step melting of different levels of the continental crust in the Late Palaeozoic. Between 330 and 295 Ma magmatism was likely the product of a crustal source with an average 1.5 Ga T_DM (Nd). Widespread magmatism represented by the 295–260 Ma granitoids involved a lower crustal mafic source, and continued with massive shallower-acid plutono volcanic complexes which might have recycled an upper crustal segment of the Proterozoic continental basement, resulting in a more felsic crust until the Triassic. (4) Sm–Nd parameters and detrital zircon age patterns of Early Paleozoic (meta)-sedimentary rocks from the North Patagonian Massif and those from the neighboring blocks, suggest crustal continuity between Eastern Sierras Pampeanas, southern Arequipa-Antofalla and the northeastern sector of the North Patagonian Massif by the Early Paleozoic. This evidence suggests that, at least, this corner of the North Patagonian Massif is not allochthonous to Gondwana. A Late Paleozoic frontal collision with the southwestern margin of Gondwana can be reconcilied in a para-autochthonous model including a rifting event from a similar or neighbouring position to its post-collision location. Possible Proterozoic or Early Paleozoic connections of the NPM with the Kalahari craton or the western Antartic blocks should be investigated.     

Air–sea CO2 fluxes in the north-eastern shelf of the Gulf of Cádiz (southwest Iberian Peninsula)

An intra-annual investigation of the fugacity of CO₂ (fCO₂) has been conducted in surface waters of the north-eastern shelf of the Gulf of Cádiz (SW Iberian Peninsula) in four cruises made in 2006 and 2007. Intra-annual variability of fCO₂ was assessed and is discussed in terms of mixing, temperature and biology. In the study area of the shelf, thermodynamic control over fCO₂ predominates from early May to late November, and this is opposite and similar in magnitude to the net biological effect. However, biological control over fCO₂ predominates during winter. The results suggest that surface waters in the coastal area are under-saturated with respect to atmospheric CO₂ during most of the year; therefore they represent a sink for atmospheric CO₂ between November and May (? 1.0 mmol m^? 2 day^? 1), but a weak source in June (1.3 mmol m^? 2 day^? 1). In contrast, the coastal ecosystems studied (the lower estuary of Guadalquivir Estuary and Bay of Cádiz) acted as a weak sink for atmospheric CO₂ during February (? 1.3 mmol m^? 2 day^? 1) and as a source between May and November (2.6 mmol m^? 2 day^? 1). The resulting mean annual CO₂ flux in the north-eastern shelf of the Gulf of Cádiz was ? 0.07 mol m^? 2 year^? 1 (? 0.2 mmol m^? 2 day^? 1), indicating that the area acts as a net sink on an annual basis.     

Severe soil erosion during a 3‐day exceptional rainfall event: combining modelling and field data for a fallow cereal field

Exceptional rainfall events cause significant losses of soil, although few studies have addressed the validation of model predictions at field scale during severe erosive episodes. In this study, we evaluate the predictive ability of the enhanced Soil Erosion and Redistribution Tool (SERT‐2014) model for mapping and quantifying soil erosion during the exceptional rainfall event (~235 mm) that affected the Central Spanish Pyrenees in October 2012. The capacity of the simulation model is evaluated in a fallow cereal field (1.9 ha) at a high spatial scale (1 × 1 m). Validation was performed with field‐quantified rates of soil loss in the rills and ephemeral gullies and also with a detailed map of soil redistribution. The SERT‐2014 model was run for the six rainfall sub‐events that made up the exceptional event, simulating the different hydrological responses of soils with maximum runoff depths ranging between 40 and 1017 mm. Predicted average and maximum soil erosion was 11 and 117 Mg ha^?1 event^?1, respectively. Total soil loss and sediment yield to the La Reina gully amounted to 16.3 and 9.0 Mg event^?1. These rates are in agreement with field estimations of soil loss of 20.0 Mg event^?1. Most soil loss (86%) occurred during the first sub‐event. Although soil accumulation was overestimated in the first sub‐event because of the large amount of detached soil, the enhanced SERT‐2014 model successfully predicted the different spatial patterns and values of soil redistribution for each sub‐event. Further research should focus on stream transport capacity. Copyright © 2014 John Wiley & Sons, Ltd.