The Global Meteoric Water Line (GMWL) describes the global annual average relationship between hydrogen and oxygen isotope (oxygen-18 [18O] and deuterium [2H]) ratios in natural meteoric waters. The GMWL was first developed in 1961 by Harmon Craig, and has subsequently been widely used to track water masses in environmental geochemistry and hydrogeology.
When working on the global annual average isotopic composition of 18O and 2H in meteoric water, geochemist Harmon Craig observed a correlation between these two isotopes, and subsequently developed and defined the equation for GMWL: [2]
Where δ18O and δ2H (aka δD) are the ratio of heavy to light isotopes (e.g. 18O/16O, 2H/1H).
The relationship of δ18O and δ2H in meteoric water is caused by mass dependent fractionation of oxygen and hydrogen isotopes between evaporation from ocean seawater and condensation from vapor. [3] As oxygen isotopes (18, 16O) and hydrogen isotopes (2, 1H) have different masses, they behave differently in the evaporation and condensation processes, and thus result in the fractionation between 18O and 16O as well as 2H and 1H. Equilibrium fractionation causes the isotope ratios of δ18O and δ2H to vary between localities within the area. The fractionation processes can be influenced by a number of factors including: temperature, latitude, continentality, and most importantly, humidity. [3] [4]
Craig observed that δ18O and δ2H isotopic composition of cold meteoric water from sea ice in the Arctic and Antarctica are much more negative than that in warm meteoric water from the tropic. [2] A correlation between temperature (T) and δ18O was proposed later [6] in the 1970s. Such correlation is then applied to study surface temperature change over time. [7] The δ18O of ancient meteoric water, preserved in ice cores, can also be collected and applied to reconstruct paleoclimate. [8] [9]
A meteoric water line can be calculated for a given area, named as local meteoric water line (LMWL), and used as a baseline within that area. Local meteoric water line can differ from the global meteoric water line in slope and intercept. Such deviated slope and intercept is a result largely from humidity. In 1964, the concept of deuterium excess d (d = δ2H - 8δ18O) [3] was proposed. Later, a parameter of deuterium excess as a function of humidity has been established, as such the isotopic composition in local meteoric water can be applied to trace local relative humidity, [10] study local climate and used as a tracer of climate change. [6]
In hydrogeology, the δ18O and δ2H of groundwater are often used to study the origin of groundwater [11] and groundwater recharge. [12]
It has been shown that, even taking into account the standard deviation related to instrumental errors and the natural variability of the amount-weighted precipitations, the LMWL calculated with the EIV (error in variable regression) [13] method has no differences on the slope compared to classic OLSR (ordinary least square regression) or other regression methods. [14] However, for certain purposes such as the evaluation of the shifts from the line of the geothermal waters, it would be more appropriate to calculate the so-called "prediction interval" or "error wings" related to LMWL. [13]
Deuterium (hydrogen-2, symbol 2H or D, also known as heavy hydrogen) is one of two stable isotopes of hydrogen; the other is protium, or hydrogen-1, 1H. The deuterium nucleus, called a deuteron, contains one proton and one neutron, whereas the far more common 1H has no neutrons. Deuterium has a natural abundance in Earth's oceans of about one atom of deuterium in every 6,420 atoms of hydrogen. Thus deuterium accounts for about 0.0156% by number (0.0312% by mass) of all hydrogen in the ocean: 4.85×1013 tonnes of deuterium – mainly as HOD (or 1HO2H or 1H2HO) and only rarely as D2O (or 2H2O) – in 1.4×1018 tonnes of water. The abundance of 2H changes slightly from one kind of natural water to another (see Vienna Standard Mean Ocean Water).
Isotope analysis is the identification of isotopic signature, abundance of certain stable isotopes of chemical elements within organic and inorganic compounds. Isotopic analysis can be used to understand the flow of energy through a food web, to reconstruct past environmental and climatic conditions, to investigate human and animal diets, for food authentification, and a variety of other physical, geological, palaeontological and chemical processes. Stable isotope ratios are measured using mass spectrometry, which separates the different isotopes of an element on the basis of their mass-to-charge ratio.
In the study of past climates ("paleoclimatology"), climate proxies are preserved physical characteristics of the past that stand in for direct meteorological measurements and enable scientists to reconstruct the climatic conditions over a longer fraction of the Earth's history. Reliable global records of climate only began in the 1880s, and proxies provide the only means for scientists to determine climatic patterns before record-keeping began.
Vienna Standard Mean Ocean Water (VSMOW) is an isotopic standard for water, that is, a particular sample of water whose proportions of different isotopes of hydrogen and oxygen are accurately known. VSMOW is distilled from ocean water and does not contain salt or other impurities. Published and distributed by the Vienna-based International Atomic Energy Agency in 1968, the standard and its essentially identical successor, VSMOW2, continue to be used as a reference material.
Isotope hydrology is a field of geochemistry and hydrology that uses naturally occurring stable and radioactive isotopic techniques to evaluate the age and origins of surface and groundwater and the processes within the atmospheric hydrologic cycle. Isotope hydrology applications are highly diverse, and used for informing water-use policy, mapping aquifers, conserving water supplies, assessing sources of water pollution, investigating surface-groundwater interaction, refining groundwater flow models, and increasingly are used in eco-hydrology to study human impacts on all dimensions of the hydrological cycle and ecosystem services.
Kinetic fractionation is an isotopic fractionation process that separates stable isotopes from each other by their mass during unidirectional processes. Biological processes are generally unidirectional and are very good examples of "kinetic" isotope reactions. All organisms preferentially use lighter isotopes, because "energy costs" are lower, resulting in a significant fractionation between the substrate (heavier) and the biologically mediated product (lighter). For example, photosynthesis preferentially takes up the light isotope of carbon 12C during assimilation of atmospheric CO2. This kinetic isotope fractionation explains why plant material (and thus fossil fuels, which are derived from plants) is typically depleted in 13C by 25 per mil (2.5%) relative to most inorganic carbon on Earth.
A paleothermometer is a methodology that provides an estimate of the ambient temperature at the time of formation of a natural material. Most paleothermometers are based on empirically-calibrated proxy relationships, such as the tree ring or TEX86 methods. Isotope methods, such as the δ18O method or the clumped-isotope method, are able to provide, at least in theory, direct measurements of temperature.
An isotopic signature is a ratio of non-radiogenic 'stable isotopes', stable radiogenic isotopes, or unstable radioactive isotopes of particular elements in an investigated material. The ratios of isotopes in a sample material are measured by isotope-ratio mass spectrometry against an isotopic reference material. This process is called isotope analysis.
Oxygen isotope ratio cycles are cyclical variations in the ratio of the abundance of oxygen with an atomic mass of 18 to the abundance of oxygen with an atomic mass of 16 present in some substances, such as polar ice or calcite in ocean core samples, measured with the isotope fractionation. The ratio is linked to ancient ocean temperature which in turn reflects ancient climate. Cycles in the ratio mirror climate changes in the geological history of Earth.
An isoscape is a geologic map of isotope distribution. It is a spatially explicit prediction of elemental isotope ratios (δ) that is produced by executing process-level models of elemental isotope fractionation or distribution in a geographic information system (GIS).
The environmental isotopes are a subset of isotopes, both stable and radioactive, which are the object of isotope geochemistry. They are primarily used as tracers to see how things move around within the ocean-atmosphere system, within terrestrial biomes, within the Earth's surface, and between these broad domains.
Oxygen-18 is a natural, stable isotope of oxygen and one of the environmental isotopes.
Meteoric water, derived from precipitation such as snow and rain, includes water from lakes, rivers, and ice melts, all of which indirectly originate from precipitation. The journey of meteoric water from the atmosphere to the Earth's surface is a critical component of the hydrologic cycle. While a significant portion of this water reaches the sea through surface flow, a considerable amount gradually infiltrates the ground, continuing its descent to the zone of saturation and becoming an integral part of groundwater in aquifers.
In geochemistry, paleoclimatology and paleoceanography δ18O or delta-O-18 is a measure of the deviation in ratio of stable isotopes oxygen-18 (18O) and oxygen-16 (16O). It is commonly used as a measure of the temperature of precipitation, as a measure of groundwater/mineral interactions, and as an indicator of processes that show isotopic fractionation, like methanogenesis. In paleosciences, 18O:16O data from corals, foraminifera and ice cores are used as a proxy for temperature.
The Dole effect, named after Malcolm Dole, describes an inequality in the ratio of the heavy isotope 18O to the lighter 16O, measured in the atmosphere and seawater. This ratio is usually denoted δ18O.
Magmatic water, also known as juvenile water, is an aqueous phase in equilibrium with minerals that have been dissolved by magma deep within the Earth's crust and is released to the atmosphere during a volcanic eruption. It plays a key role in assessing the crystallization of igneous rocks, particularly silicates, as well as the rheology and evolution of magma chambers. Magma is composed of minerals, crystals and volatiles in varying relative natural abundance. Magmatic differentiation varies significantly based on various factors, most notably the presence of water. An abundance of volatiles within magma chambers decreases viscosity and leads to the formation of minerals bearing halogens, including chloride and hydroxide groups. In addition, the relative abundance of volatiles varies within basaltic, andesitic, and rhyolitic magma chambers, leading to some volcanoes being exceedingly more explosive than others. Magmatic water is practically insoluble in silicate melts but has demonstrated the highest solubility within rhyolitic melts. An abundance of magmatic water has been shown to lead to high-grade deformation, altering the amount of δ18O and δ2H within host rocks.
Isotopic analysis by nuclear magnetic resonance allows the user to quantify with great precision the differences of isotopic contents on each site of a molecule and thus to measure the specific natural isotope fractionation for each site of this molecule. The SNIF-NMR analytical method was developed to detect the (over) sugaring of wine and enrichment of grape musts, and is mainly used to check the authenticity of foodstuffs and to control the naturality of some aromatic molecules. The SNIF-NMR method has been adopted by the International Organisation of Vine and Wine (OIV) and the European Union as an official method for wine analysis. It is also an official method adopted by the Association Of Analytical Chemists (AOAC) for analysis of fruit juices, maple syrup, vanillin, and by the European Committee for Standardization (CEN) for vinegar.
Clumped isotopes are heavy isotopes that are bonded to other heavy isotopes. The relative abundance of clumped isotopes (and multiply-substituted isotopologues) in molecules such as methane, nitrous oxide, and carbonate is an area of active investigation. The carbonate clumped-isotope thermometer, or "13C–18O order/disorder carbonate thermometer", is a new approach for paleoclimate reconstruction, based on the temperature dependence of the clumping of 13C and 18O into bonds within the carbonate mineral lattice. This approach has the advantage that the 18O ratio in water is not necessary (different from the δ18O approach), but for precise paleotemperature estimation, it also needs very large and uncontaminated samples, long analytical runs, and extensive replication. Commonly used sample sources for paleoclimatological work include corals, otoliths, gastropods, tufa, bivalves, and foraminifera. Results are usually expressed as Δ47 (said as "cap 47"), which is the deviation of the ratio of isotopologues of CO2 with a molecular weight of 47 to those with a weight of 44 from the ratio expected if they were randomly distributed.
Hydrogen isotope biogeochemistry (HIBGC) is the scientific study of biological, geological, and chemical processes in the environment using the distribution and relative abundance of hydrogen isotopes. Hydrogen has two stable isotopes, protium 1H and deuterium 2H, which vary in relative abundance on the order of hundreds of permil. The ratio between these two species can be called the hydrogen isotopic signature of a substance. Understanding isotopic fingerprints and the sources of fractionation that lead to variation between them can be applied to address a diverse array of questions ranging from ecology and hydrology to geochemistry and paleoclimate reconstructions. Since specialized techniques are required to measure natural hydrogen isotopic composition (HIC), HIBGC provides uniquely specialized tools to more traditional fields like ecology and geochemistry.
Isotopic reference materials are compounds with well-defined isotopic compositions and are the ultimate sources of accuracy in mass spectrometric measurements of isotope ratios. Isotopic references are used because mass spectrometers are highly fractionating. As a result, the isotopic ratio that the instrument measures can be very different from that in the sample's measurement. Moreover, the degree of instrument fractionation changes during measurement, often on a timescale shorter than the measurement's duration, and can depend on the characteristics of the sample itself. By measuring a material of known isotopic composition, fractionation within the mass spectrometer can be removed during post-measurement data processing. Without isotope references, measurements by mass spectrometry would be much less accurate and could not be used in comparisons across different analytical facilities. Due to their critical role in measuring isotope ratios, and in part, due to historical legacy, isotopic reference materials define the scales on which isotope ratios are reported in the peer-reviewed scientific literature.
