Coupled abiotic-biotic cycling of nitrous oxide in tropical peatlands

Atmospheric nitrous oxide (N2O) is a potent greenhouse gas thought to be mainly derived from microbial metabolism as part of the denitrification pathway. Here, we report that in unexplored peat soils of Central and South America, N2O production can be driven by abiotic reactions (> 98 %) highly competitive to their enzymatic counterparts. Extracted soil iron positively correlated with in-situ abiotic N2O production determined by isotopic tracers. Moreover, we found that microbial N2O reduction accompanied abiotic production, essentially closing a coupled abiotic-biotic N2O cycle. Anaerobic N2O consumption occurred ubiquitously (pH 6.4-3.7), with proportions of diverse clade II N2O-reducers increasing with consumption rates. Our findings show denitrification in tropical peat soils is not a purely biological process, but rather a 'mosaic' of abiotic and biotic reduction reactions. We predict hydrological and temperature fluctuations differentially affect abiotic and biotic drivers and further contribute to the high N2O flux variation in the region.

The DIC carbon isotope evolutions during CO2 bubbling: implications for ocean acidification laboratory culture

Ocean acidification increases pCO2 and decreases pH of seawater and its impact on marine organisms has emerged as a key research focus. In addition to directly measured variables such as growth or calcification rate, stable isotopic tracers such as carbon isotopes have also been used to more completely understand the physiological processes contributing to the response of organisms to ocean acidification. To simulate ocean acidification in laboratory cultures, direct bubbling of seawater with CO2 has been a preferred method because it adjusts pCO2 and pH without altering total alkalinity. Unfortunately, the carbon isotope equilibrium between seawater and CO2 gas has been largely ignored so far. Frequently, the dissolved inorganic carbon (DIC) in the initial seawater culture has a distinct 13C/12C ratio which is far from the equilibrium expected with the isotopic composition of the bubbled CO2. To evaluate the consequences of this type of experiment for isotopic work, we measured the carbon isotope evolutions in two chemostats during CO2 bubbling and composed a numerical model to simulate this process. The isotopic model can predict well the carbon isotope ratio of dissolved inorganic carbon evolutions during bubbling. With help of this model, the carbon isotope evolution during a batch and continuous culture can be traced dynamically improving the accuracy of fractionation results from laboratory culture. Our simulations show that if not properly accounted for in experimental or sampling design, many typical culture configurations involving CO2 bubbling can lead to large errors in estimated carbon isotope fractionation between seawater and biomass or biominerals, consequently affecting interpretations and hampering comparisons among different experiments. Therefore, we describe the best practices on future studies working with isotope fingerprinting in the ocean acidification background.

Chemical and Isotopic Tracers for Characterization of the Groundwater in the Heterogeneous System: Case from Chichaoua-Imin’tanout (Morocco)

The geological and hydrogeological approach of the structure of the basin OuladBouSbaâ led to the definition of the geometry of the main aquifers. In general, the profiles show the complexity of the geological configuration. The filling of the depression of OuladBouSbaâ is from the Eo-Cretacian. At this level, the aquifer is recharged by direct water infiltration. The quaternary, Eocene, and Cenomanian-Turonian formations constitute the main aquifers. Horizontal as well as vertical heterogeneity lead to a higher diversification of aquifer characteristics. To define the origins and understand the groundwater flows in this complex zone, we used a multi-tracer approach with the analysis of major elements and the isotopes of δ2H and δ18O. The chemical composition is mainly governed by the interaction with the rock with low electrical conductivity except in areas around domestic landfills. Geochemical results analyzing groundwater in the Piper diagram show two distinct chemical facies: the sulfated calcium and magnesium, and the hyper-chloride calcium. The levels of δ18O range from −7.60 to −4.25 while those of δ2H vary between −53.07 and −27.03. Analyses of signature isotopes differentiate two groups. The first contains high levels of heavy isotopes (highest levels of δ2H and δ18O) having therefore been submitted to evaporation. The second with lower levels of δ2H and δ18O did not undergo evaporation. The first one belongs to the unconfined free aquifer while the second corresponds to the captive aquifer.

An updated version of the global interior ocean biogeochemical data product, GLODAPv2.2021

The Global Ocean Data Analysis Project (GLODAP) is a synthesis effort providing regular compilations of surface-to-bottom ocean biogeochemical bottle data, with an emphasis on seawater inorganic carbon chemistry and related variables determined through chemical analysis of seawater samples. GLODAPv2.2021 is an update of the previous version, GLODAPv2.2020 (Olsen et al., 2020). The major changes are as follows: data from 43 new cruises were added, data coverage was extended until 2020, all data with missing temperatures were removed, and a digital object identifier (DOI) was included for each cruise in the product files. In addition, a number of minor corrections to GLODAPv2.2020 data were performed. GLODAPv2.2021 includes measurements from more than 1.3 million water samples from the global oceans collected on 989 cruises. The data for the 12 GLODAP core variables (salinity, oxygen, nitrate, silicate, phosphate, dissolved inorganic carbon, total alkalinity, pH, CFC-11, CFC-12, CFC-113, and CCl4) have undergone extensive quality control with a focus on systematic evaluation of bias. The data are available in two formats: (i) as submitted by the data originator but updated to World Ocean Circulation Experiment (WOCE) exchange format and (ii) as a merged data product with adjustments applied to minimize bias. For this annual update, adjustments for the 43 new cruises were derived by comparing those data with the data from the 946 quality controlled cruises in the GLODAPv2.2020 data product using crossover analysis. Comparisons to estimates of nutrients and ocean CO2 chemistry based on empirical algorithms provided additional context for adjustment decisions in this version. The adjustments are intended to remove potential biases from errors related to measurement, calibration, and data handling practices without removing known or likely time trends or variations in the variables evaluated. The compiled and adjusted data product is believed to be consistent with to better than 0.005 in salinity, 1 % in oxygen, 2 % in nitrate, 2 % in silicate, 2 % in phosphate, 4 µmol kg−1 in dissolved inorganic carbon, 4 µmol kg−1 in total alkalinity, 0.01–0.02 in pH (depending on region), and 5 % in the halogenated transient tracers. The other variables included in the compilation, such as isotopic tracers and discrete CO2 fugacity (fCO2), were not subjected to bias comparison or adjustments. The original data, their documentation, and DOI codes are available at the Ocean Carbon Data System of NOAA NCEI (https://www.ncei.noaa.gov/access/ocean-carbon-data-system/oceans/GLODAPv2_2021/, last access: 7 July 2021). This site also provides access to the merged data product, which is provided as a single global file and as four regional ones – the Arctic, Atlantic, Indian, and Pacific oceans – under https://doi.org/10.25921/ttgq-n825 (Lauvset et al., 2021). These bias-adjusted product files also include significant ancillary and approximated data and can be accessed via https://www.glodap.info (last access: 29 June 2021). These were obtained by interpolation of, or calculation from, measured data. This living data update documents the GLODAPv2.2021 methods and provides a broad overview of the secondary quality control procedures and results.

The Blood Lactate/Pyruvate Equilibrium Affair

The Lactate Shuttle hypothesis is supported by a variety of techniques including mass spectrometry analytics following infusion of carbon labeled isotopic tracers. However, there has been controversy over whether lactate tracers measure lactate (L) or pyruvate (P) turnover. Here we review the analytical errors, use of inappropriate tissue and animal models, failure to consider L and P pool sizes in modeling results, inappropriate tracer and blood sampling sites, and failure to anticipate roles of heart and lung parenchyma on L:P interactions. With support from magnetic resonance spectroscopy (MRS) and immunocytochemistry we conclude that carbon-labeled lactate tracers can be used to quantitate lactate fluxes.

Understanding long-term groundwater flow at Pahute Mesa and vicinity, Nevada National Security Site, USA, from naturally occurring geochemical and isotopic tracers

Recently collected naturally occurring geochemical and isotopic groundwater tracers were combined with historic data from the Pahute Mesa area of the Nevada National Security Site (NNSS), Nevada, USA, to provide insights into long-term regional groundwater flow patterns, mixing and recharge. Pahute Mesa was the site of 85 nuclear detonations between 1965 and 1992, many of them deeply buried devices that introduced radionuclides directly into groundwater. The dataset examined included major ions and field measurements, stable isotopes of hydrogen (δ2H), oxygen (δ18O), carbon (δ13C) and sulfur (δ34S), and radioisotopes of carbon (14C) and chloride (36Cl). Analysis of the patterns of groundwater 14C data and the δ2H and δ18O signatures indicates that groundwater recharge is predominantly of Pleistocene age, except for a few localized areas near major ephemeral drainages. Steep gradients in sulfate (SO4) and chloride (Cl) define a region near the western edge of the NNSS where high-concentration groundwater flowing south from north of the NNSS merges with dilute groundwater flowing west from eastern Pahute Mesa in a mixing zone that coincides with a groundwater trough associated with major faults. The 36Cl/Cl and δ34S data suggest that the source of the high Cl and SO4 in the groundwater was a now-dry, pluvial-age playa lake north of the NNSS. Patterns of groundwater flow indicated by the combined data sets show that groundwater is flowing around the northwest margin of the now extinct Timber Mountain Caldera Complex toward regional discharge areas in Oasis Valley.

Pyrite Framboid Formation Chemistry

Pyrite forms mainly through two routes: (1) the reaction between FeS species and polysulfides, and (2) the reaction of FeS species and H2S. Both of these reactions produce framboidal pyrite, and the mechanisms have been confirmed both kinetically and through the use of isotopic tracers. Aqueous Fe2+ does not appear to react directly with aqueous polysulfide species to produce pyrite, and the S-S bond in aqueous S2(-II) is normally split by aqueous Fe2+ to produce aqueous FeS and sulfur. The FeS moiety involved in pyrite formation may be provided by aqueous FeS or =FeS groups on solid surfaces. The reaction with surface =FeS occurs with any iron mineral in a sulfidic environment, including the relatively scarce iron sulfide minerals, mackinawite and greigite, nanoparticulate FeS, and pyrite itself. The reaction with surface =FeS sites on pyrite is a major route for pyrite crystal growth. The extreme insolubility of pyrite is one of the fundamental reasons for its particular involvement in framboid formation as well as for the ubiquity of framboids.