Automatic δD and δ18O analyses of multi-water samples using H2- and CO2-water equilibration methods with a common equilibration set-up

doi:10.1016/0883-2889(89)90100-7

International Journal of Radiation Applications and Instrumentation. Part A. Applied Radiation and Isotopes

Volume 40, Issue 9, 1989, Pages 801-805

https://doi.org/10.1016/0883-2889(89)90100-7 Get rights and content

Abstract

An automatic CO₂-water equilibration set-up originally designed for δ¹⁸O measurement of water samples was employed for δD analysis using the lately established H₂-water equilibration method without any modification of the instrument. No special skill is needed and the time required for both δD and δ¹⁸O analyses of 24 waters was only 15 h. Long-term reproducibilities were ± 1.5 and ±0.16% for δD and δ¹⁸O analyses, respectively. This method is very suitable for multi-water analyses.

References (24)

C.A.M. Brenninkmeijer et al.
An automated system for isotopic equilibration of CO₂ and H₂O for ¹⁸O analysis of water
Chem. Geol.
(1987)
H. Craig
Isotopic standards for carbon and oxygen and correction factors for mass-spectrometric analysis of carbon dioxide
Geochim. Cosmochim. Acta
(1957)
S. Epstein et al.
Variation of ¹⁸O content of waters from natural sources
Geochim. Cosmochim. Acta
(1953)
I. Friedman
Deuterium content of natural waters and other substances
Geochim. Cosmochim. Acta
(1953)
J. Horita
Hydrogen isotope analysis of natural waters using an H₂-water equilibration method: a special implication to brines
Chem. Geol.
(1988)
G. Nief et al.
Mass spectrometric analysis of simple hydrogen compounds
Adv. Mass Spectrom.
(1959)
W. Roether
Water-CO₂ exchange set-up for the routine ¹⁸oxygen assay of natural waters
Int. J. Appl. Radiat. Isot.
(1970)
J. Bigeleisen et al.
Conversion of hydrogenic materials to hydrogen for isotopic analysis
Anal. Chem.
(1952)
F. Buzek
A rapid procedure for preparing oxygen-18 determination in water samples
Isotopenpraxis
(1983)
H. Chiba et al.
Automatic Measurement of Oxygen Isotope Ratio of Water Samples
(1985)

M.L. Coleman et al.

Reduction of water with zinc for hydrogen isotope analysis

Anal. Chem.

(1982)

I. Friedman et al.

Compilation of Stable Isotope Fractionation Factors of Geochemical Interest

(1977)

Cited by (123)

Dual clumped (Δ<inf>47</inf>-Δ<inf>48</inf>) isotope data for amorphous carbonates and transformation products reveal a novel mechanism for disequilibrium clumped isotope effects
2023, Geochimica et Cosmochimica Acta
Amorphous precursors to minerals have been observed in laboratory materials and in nature, including across diverse phyla. These metastable phases allow for the incorporation of cations at higher concentrations than classical crystallization pathways, thus, their chemistry and behavior have implications in an array of disciplines. Currently, little is known about the isotopic composition of the anion in amorphous carbonates and how isotopic values evolve during transformation into a mineral. Here, we examined the evolution of isotopic values in amorphous carbonates and mineral transformation products to identify the potential origins of disequilibrium isotopic compositions in carbonate minerals that form from an amorphous precursor. We measured dual carbonate clumped isotopes (¹³C¹⁸O¹⁶O - Δ₄₇; ¹²C¹⁸O¹⁸O - Δ₄₈), bulk stable isotope ratios (δ¹³C, δ¹⁸O), and chemical and structural data throughout the transformation of amorphous calcium magnesium carbonate (ACMC) into high Mg-calcite (HMC) over 1 year, with crystallization occurring in solutions from 10 to 60 °C. The Δ₄₇, Δ₄₈, and δ¹⁸O values evolved significantly during transformation, indicating dissolution of ACMC and reprecipitation of HMC. After crystallization, the Δ₄₇ and Δ₄₈ values achieved a disequilibrium steady state, while δ¹⁸O values continued to evolve. For the fully crystallized HMC samples, the low temperature samples formed at 10 °C had the greatest extent of oxygen isotope disequilibrium (measured value – equilibrium value = −39‰); conversely; the greatest clumped isotope disequilibrium was observed in high temperature samples formed at 40 and 60 °C (0.068‰ for Δ₄₇, 0.072‰ for Δ₄₈). These results are consistent with a new potential mechanism of disequilibrium clumped isotope values in carbonate minerals. Specifically, the dissolution of ACMC during transformation causes disequilibrium oxygen and clumped isotope values in the dissolved inorganic carbon (DIC) pool. The extent of isotopic disequilibrium in DIC during transformation is temperature dependent, and is recorded by the forming mineral. Isotopic results may also reflect mixing effects, as scanning electron microscopy (SEM) showed ACMC and HMC existing simultaneously during transformation, indicating that ACMC likely progressively dissolves and reprecipitates as the DIC pool isotopically evolves. This may result in heterogeneous isotopic values in HMC. In total, these data suggest a highly dynamic localized environment could exist in biomineralizing organisms and abiotic systems that utilize amorphous precursors to form carbonate minerals, potentially resulting in isotopic values that are not representative of formation temperature.
Determination of groundwater origins and vulnerability based on multi-tracer investigations: New contributions from passive sampling and suspect screening approach
2023, Science of the Total Environment
Knowledge about groundwater origins and their interactions with surface water is fundamental to assess their vulnerability. In this context, hydrochemical and isotopic tracers are useful tools to investigate water origins and mixing. More recent studies examined the relevance of contaminants of emerging concern (CECs) as co-tracers to distinguish sources contributing to groundwater bodies. However, these studies focused on known and targeted CECs a priori selected regarding their origin and/or concentrations. This study aimed to improve these multi-tracer approaches using passive sampling and qualitative suspect screening by exploring a larger variety of historical and emerging concern contaminants in combination with hydrochemistry and water molecule isotopes. With this objective, an in-situ study was conducted in a drinking water catchment area located in an alluvial aquifer recharged by several water sources (both surface and groundwater sources). CECs determined by passive sampling and suspect screening allowed to provide in-depth chemical fingerprints of groundwater bodies by enabling the investigation of >2500 compounds with an increased analytical sensitivity. Obtained cocktails of CECs were discriminating enough to be used as chemical tracer in combination with hydrochemical and isotopic tracers. In addition, the occurrence and type of CECs contributed to a better understanding of groundwater-surface water interactions and highlighted short-time hydrological processes. Furthermore, the use of passive sampling with suspect screening analysis of CECs lead to a more realistic assessment and mapping of groundwater vulnerability.
Increasing intrusion of high salinity water alters the mariculture activities in Zhanjiang Bay during the past two decades identified by dual water isotopes
2022, Journal of Environmental Management
The decrease of river runoff caused by the intensified human activities (e.g. artificial dams) and increasing intrusion of high salinity water in the coastal bays have become a worldwide environmental problem. However, the mixing can hardly be identified by traditional method with temperature and salinity due to the complicated water sources in the coastal area. Thus, it is difficult to quantify the impact of intrusion of high salinity water on coastal ecological environment. Here, seasonal dual water isotopes (δD and δ¹⁸O), hydrographic parameters, and nutrients were investigated in a typical semi-enclosed mariculture bay in South China Sea (SCS), to quantify the intrusion of high salinity water and its impact on the water environment. The results showed that salinity in the bay has increased significantly (18%) over the past two decades due to the decrease of runoff and dredging activity. Zhanjiang Bay is mainly affected by the seawater from the SCS in outer bay, and the seawater from the outer bay (89%) was significantly higher than that of freshwater (7%) in summer, despite the increase in freshwater input from the river during this period. In winter, the intrusion of high salinity water increased (accounting for 94%) due to the decrease of runoff input. However, the contribution of groundwater was similar in summer (4%) and winter (5%). The estimation results from the relationship of δ¹⁸O-salinity and δD-salinity showed that the intrusion of high salinity water has increased significantly for the past two decades (increased by 23%). This resulted in the area suitable for oyster breeding is decreasing, and the oyster breeding activities have been gradually moving to the inner bay. Moreover, the nutrients in Zhanjiang Bay were mainly originated from freshwater input in summer (54%–90%), while it changed to the SCS input from the outer bay in winter (40%–97%). This study suggests that the intrusion of high salinity water significantly increases the salinity, and seriously retains the pollutants of freshwater in the bay, which poses a great threat to the oyster breeding activities in the semi-enclosed bay.
Unravelling 30 ka recharge history of an intensely exploited multi-tier aquifer system in North West India through isotopic tracers – Implications on deep groundwater sustainability
2022, Science of the Total Environment
Northwest part of India is an agriculturally active region experiencing rapid rise in food production and steep decline in groundwater levels. The freshwater requirement is mostly met by regional aquifers which are inherently heterogeneous and undergoing extensive human inducted perturbations. These factors pose great challenge in planning sustainable groundwater management. In this study, environmental isotopes (²H, ¹⁸O, ¹³C, ³H and ¹⁴C) were applied to understand the regional recharge mechanism during the last 30 ka and hydrogeological controls impacting the aquifer dynamics and inter-aquifer connectivity of the Ghaggar River basin. Rayleigh distillation modeling indicates that major groundwater recharge is through monsoonal rains while rainfall during other seasons is lost either through evaporation or surface runoff. The evaporation loss is estimated to be 1.5 to 10% and more pronounced in the southern part of the study area. Regional recharge from Siwalik foothills contributes to groundwater up to a depth of 250 m below ground level (bgl). The lumped parameter modeling (LPM) using ³H data estimated groundwater ages 34.7 ± 12.1 and 95.8 ± 11.3 years for shallow and deep aquifers respectively. Radiocarbon dating indicates presence of paleogroundwater (0.4 to 28.6 ka before present, BP) in the deeper aquifer of central part of the study area. Interpretation of the paleowater and paleoprecipitation isotope data in conjunction with available paleogeomorphologic information suggests two different recharge phases. Phase I extending from ~28.6 to 10.1 ka, showed ~48–61% contribution from isotopically depleted perennial river system. Phase II spanning from ~12.5 to 0.4 ka BP showed insignificant contribution from river recharge, which can be attributed to the decreased strength of the perennial river flows. The research methodology proposed in this study will be beneficial in improving the understanding of groundwater storage and its variability with changes in regional climatic conditions.
Groundwater mixing in shallow aquifers stressed by land cover/land use changes under hyper-arid conditions
2021, Journal of Hydrology
The impact of land cover/land use (LCLU) changes on surface runoff and groundwater contamination have been widely investigated, yet their impact on groundwater mixing is still poorly understood. The stress on resources in the Nile Delta triggered a vast migration of urban, agricultural, and industrial activities to its desert fringes exposing the Quaternary alluvial aquifers to contamination and introducing new sources of recharge. Here, we integrated remote sensing, chemical, and isotopic data with multivariate statistical analysis to identify groundwater sources and the mixing dynamics in response to LCLU changes. LCLU analysis indicated an increase of agricultural and urban areas from 84 km² to 470.5 km² between 1972 and 2018. These changes introduced new recharge sources including wastewater and irrigation return. Three major water sources were defined including: (1) modern precipitation (cluster 3 and Miocene aquifer; δ¹⁸O: −4.59 to −0.47‰, and δ²H: −34.4 to 3.1‰) with an estimated annual recharge of 11–13.5 × 10⁶ m² and 5.1–6.2 × 10⁶ m² for El-Gafra and El-Watan catchments, respectively, (2) old Nile water (subcluster 1.1; δ¹⁸O: −0.87 to −0.53‰, and δ²H: 1 to 3.7), and (3) modern Nile water (cluster 2; δ¹⁸O: 0.49 to 2.71‰, and δ²H: 10.5 to 24.4‰). Moreover, three mixed groups were defined including: (1) a mixture of modern precipitation, wastewater and irrigation return (cluster 4; δ¹⁸O: −1.02 to 0.37‰, and δ²H: −9.3 to 6.4‰), (2) a mixture of old Nile waters and modern precipitation (subcluster 1.3; δ¹⁸O: −1.74 to −1.38‰, and δ²H: −6.8 to −2.3‰), and (3) a mixture of more than two sources with wide ranges of isotopic and chemical compositions (subclusters 1.2 and 1.4). These findings provide a good basis for further studies of groundwater mixing and assessment of contamination sources in shallow aquifers stressed by LCLU changes in hyper-arid environments.
Deterioration mechanism of alkali-activated materials in sulfuric acid and the influence of Cu: A micro-to-nano structural, elemental and stable isotopic multi-proxy study
2021, Cement and Concrete Research
In this study, a multi-proxy approach combining ²⁹Si, ²⁷Al and ¹H MAS-NMR, FEG-EPMA, XANES at the Cu K-edge and XRD analytics with hydrochemical tools such as ICP-OES analyses, oxygen-isotope signatures, and thermodynamic modelling was applied to K-silicate-activated metakaolin specimens - with and without CuSO₄·5H₂O addition - exposed to sulfuric acid at pH = 2 for 35 days. The results revealed a multistage deterioration mechanism governed by (i) acid diffusion, (ii) leaching of K-A-S-H, (iii) microstructural damage related to precipitation of expansive (K,Ca,Al)-sulfate-hydrate phases (iv) complete dissolution of the K-A-S-H framework, (v) and formation of silica gel in the outermost corroded regions. Copper ions were mainly located in layered spertiniite-chrysocolla-like phases in the as-cured materials. The results demonstrate an overall negative effect of Cu addition on chemical material durability, implying that the reported higher durability of Cu-doped AAM in biocorrosion environments can be best explained by bacteriostatic effects.

View all citing articles on Scopus

View full text

Automatic δD and δ18O analyses of multi-water samples using H2- and CO2-water equilibration methods with a common equilibration set-up

Abstract

Chem. Geol.

Geochim. Cosmochim. Acta

Geochim. Cosmochim. Acta

Geochim. Cosmochim. Acta

Chem. Geol.

Adv. Mass Spectrom.

Int. J. Appl. Radiat. Isot.

Conversion of hydrogenic materials to hydrogen for isotopic analysis

Anal. Chem.

A rapid procedure for preparing oxygen-18 determination in water samples

Isotopenpraxis

Automatic Measurement of Oxygen Isotope Ratio of Water Samples

Reduction of water with zinc for hydrogen isotope analysis

Anal. Chem.

Compilation of Stable Isotope Fractionation Factors of Geochemical Interest

Automatic δD and δ¹⁸O analyses of multi-water samples using H₂- and CO₂-water equilibration methods with a common equilibration set-up