Deuterium Distribution in Crude Oil

Abstract

The aim of this paper is to rehabilitate informative potential of using deuterium as a natural tracer in geofluids investigations and to illustrate how the deuterium concentration from geological fluid links the micro-scale effects to the macro-scale processes.

Research on the deuterium concentration of crude oils formerly has highlighted the role of deuterium as a natural tracer during diagenesis. We discuss how the deuterium abundance in oil and water from sedimentary basins provides information on dynamics of hydrocarbons reservoirs.

We can obtain qualitative and quantitative information about the dynamics of fluids from deposit by deuterium concentration monitoring from geofluids (gas-oil-water).     

Groundwater of the Crimean peninsula: a first systematic study using stable isotopes

ABSTRACT

Karst springs in the Main Range of the Crimean Mountains and the Crimean Piedmont show a restricted range of values (δ¹⁸O?=?–10.5 to –8.0 ‰, δ²H?=?–72 to –58 ‰), somewhat more negative than the weighted mean of meteoric precipitation. This suggests preferential recharge at higher elevations during winter months. Groundwater tapped by boreholes splits in three groups. A first group has isotopic properties similar to those of the springs. The second group shows significantly lower values (δ¹⁸O?=?–13.3 to –12.0 ‰, δ²H?=?–95 to –82 ‰), suggesting recharge during colder Pleistocene times. The third group has high isotope values (δ¹⁸O?=?–2.5 to +1.0 ‰, δ²H?=?–24 to –22 ‰); the data points are shifted to the right of the Local Meteoric Water Line, suggesting water–rock exchange processes in the aquifer. These boreholes are located in the Crimean Plains and discharge mineralized (ca. 25 g L^?1) thermal (65°C) water from a depth of 1600–1800 m. Groundwater associated with mud volcanoes on the Kerch peninsula have distinct isotope characteristics (δ¹⁸O?=?–1.6 to +9.4 ‰, δ²H?=?–30 to –18 ‰). Restricted δ²H variability along with variable and high δ¹⁸O values suggest water–rock interactions at temperatures exceeding 95 °C.     

Analysis of isotopic signals in the Danube River water at Tulln,Austria, based on daily grab samples in 2012

Results of stable isotope measurements (δ²H, δ¹⁸O) of daily grab samples, taken from the Danube River at Tulln (river km 1963) during 2012, show seasonal and short-term variations depending on the climatic/hydrological conditions and changes in the catchment area (temperature changes, heavy rains and snow melt processes). Isotope ratios in river water clearly reflect the isotopic composition of precipitation water in the catchment area since evaporation influences play a minor role. Average δ²H and δ¹⁸O values in 2012 are?78‰ and?11.0‰, respectively, deuterium excess averages 10‰. The entire variation amounts to 1.8‰ in δ¹⁸O and 15‰ in δ²H. Quick changes of the isotopic composition within a few days emphasise the necessity of daily sampling for the investigation of hydrological events, while monthly grab sampling seems sufficient for the investigation of long-term hydro-climatic trends. ³H results show peaks (half-width 1–2 days, up to about 150 TU) exceeding the regional environmental level of about 9 TU, probably due to releases from nuclear power plants.     

Benefits of Important Industrial Tracer Applications in the GDR

Tracers can be used to label substances or objects in order to discriminate between them, to follow their movement, to record changes of concentration and distribution between phases, etc. The main advantages of tracer investigations are the contactless recording of signals without influencing the observed process (also under rigorous operation conditions), the high detection sensitivity, the large number of available tracer nuclides (problems of all branches of industry can be solved) and the fact that tracer investigation can be carried out on operating production units, so that they provide valuable checks of the validity of design and process data. The cost-to-benefit ratio can be as low as 1:50. In the following some selected examples of tracer applications carried out by the staff of the Central Institute of Isotope and Radiation Research and their benefits will be presented.     

Spatial and temporal variability of stable isotopes and biological parameters for the Danube River in Serbia

This paper presents the results of hydrological, physicochemical, biological, and isotopic investigations of the Danube River along the stretch through Serbian territory conducted during four campaigns in September and November 2007, September 2008 and April 2009. The stable isotope values exhibited significant changes both in the Danube (?10.7 to?9.5‰ for δ¹⁸O and?73.7 to?67.1 ‰ for δ²H) and in its tributaries (?9.1 to?8.5‰ for δ¹⁸O and?69.4 to?59.4‰ for δ²H) depending on the time of survey, which could be partly attributed to the influences of seasonal effects. Results emphasise the dominant role of tributaries inflows from aquifers along the Danube. The very narrow range of δ¹³C_POC (from?28.9 to?27.4 ‰) was associated with relatively high C/N ratios (C/N>9), and together with δ¹⁵N_TPN values, the date suggested that, in early spring, a major fraction of particulate organic matter was derived from allochthonous matter. An orthogonal varimax rotation of the principal components analysis identified four latent factors (‘mineral related’, ‘biological’, ‘hardness’, and ‘soil inlets’) which are responsible for the data structure covering 79% of the observed variations among the variables studied. A reliable grouping of samples with respect to the season was found.     

Hydrochemistry and boron isotopes as natural tracers in the study of groundwaters from North Chianan Plain,Taiwan

In this paper, hydrochemistry and boron isotopes are successfully applied to elucidate hydrogeological processes by the use of natural tracers. The hydrochemical analysis identifies four end-members in the hydrochemical evolution of groundwater from the North Chianan plain groundwater district. A few groundwater contain extraordinary chlorine concentrations of up to 48,000 mg l^?1. However, the hydrochemistry of groundwater only reveals that high saline water is a dominant factor in groundwater hydrochemistry. It is thought that these groundwater experienced precipitation of carbonates during seawater evaporation that did not involve the precipitation of gypsum. Boron isotopes are very efficient tracers in determining the source of salinisation. The boron isotopes reveal the results of mixing of evaporated seawater and water–sediment interaction. In general, the boron isotope ratio of the groundwater is controlled by a two-end-member mixing system, which is composed of evaporated seawater (isotopically heavy) and fresh surface water (isotopically light). Due to a long lagoonal period in the coastal plain, the groundwaters in the downstream area generally have high Cl/B ratios and relatively heavy boron isotope ratios while those in the upstream area are composed of low Cl/B and light boron isotopes. However, there is not a resolvable mixing trend between the Cl/B ratio and the isotopic composition of boron. It is probably obscured by a highly variable boron isotope ratio in fresh surface water and through fractionation associated with water–rock interaction. Both factors would decrease the boron isotope ratio but one effect cannot be distinguished from the other.     

The Origin and Evolution of Some Mineral Water Sources Estimated from Their Deuterium Content

In this paper are discussed the origin and the evolution of several mineral water sources from some places of Romania, on the basis of deuterium content variations of water which take place in time and their correlation with the total salt content.     

Natural abundances of 15N and 13C in leaves of some N2-fixing and non-N2-fixing trees and shrubs in Syria

A survey study was conducted on man-made plantations located at two different areas in the arid region of Syria to determine the variations in natural abundances of the ¹⁵N and ¹³C isotopes in leaves of several woody legume and non-legume species, and to better understand the consequence of such variations on nitrogen fixation and carbon assimilation. In the first study area (non-saline soil), the δ¹⁵N values in four legume species (Acacia cyanophylla,?1.73 ‰ Acacia farnesiana,?0.55 ‰ Prosopis juliflora,?1.64 ‰; and Medicago arborea,+1.6 \textperthousand) and one actinorhizal plant (Elaeagnus angustifolia,?0.46 to?2.1 ‰) were found to be close to that of the atmospheric value pointing to a major contribution of N₂ fixing in these species; whereas, δ¹⁵N values of the non-fixing plant species were highly positive. δ¹³C ‰; in leaves of the C3 plants were found to be affected by plant species, ranging from a minimum of?28.67 ‰; to a maximum of?23 ‰. However, they were relatively similar within each plant species although they were grown at different sites. In the second study area (salt affected soil), a higher carbon discrimination value (Δ¹³C ‰) was exhibited by P. juliflora, indicating that the latter is a salt tolerant species; however, its δ¹⁵N was highly positive (+7.03 ‰) suggesting a negligible contribution of the fixed N₂. Hence, it was concluded that the enhancement of N₂ fixation might be achieved by selection of salt-tolerant Rhizobium strains.     

Bladder wrack (Fucus vesiculosus) as a multi-isotope bio-monitor in an urbanized fjord of the western Baltic Sea

The spatial variations in the elemental and stable carbon, nitrogen, and sulphur isotope composition of bladder wrack (Fucus vesiculosus) growing along the shore line of the semi-enclosed urbanized Kiel Fjord (western Baltic Sea) was investigated at more than 60 sites. The analyses of the carbon-nitrogen-sulphur (CNS) stoichiometry and C and N stable isotope signature of F. vesiculosus displayed substantial differences between the north-western and the south-eastern parts of the Kiel Fjord. Different size classes displayed in part differences in C:N and C:S ratios, and the carbon isotope composition, reflecting the impact of the boundary conditions during growth. Whereas the sulphur isotope composition was controlled by the assimilation of seawater sulphate, the carbon isotope composition reflected the difference in the composition of surface waters. The δ¹⁵N values of the organic tissue tend to be an integrated monitor of anthropogenic impacts on the fjord. Results are compared to the composition of surface waters.     

Pleistocene age paleo-groundwater inferred from water-stable isotope values in the central part of the Baltic Artesian Basin

A new data set of δ²H and δ¹⁸O in the groundwater from the central part of the Baltic Artesian Basin is presented. The hydrogeological section is subdivided into stagnation, slow exchange and active exchange zones. Na–Ca–Cl brine found at the deepest part – the stagnation zone – is characterized by δ¹⁸O values above ?5?‰ and δ²H values approaching ?40?‰ with respect to Vienna Standard Mean Ocean Water. The slow exchange zone where waters of mostly intermediate salinity reside is characterized by δ¹⁸O values around ?11.7?‰ and δ²H values around ?85.3?‰. Mean δ¹⁸O and δ²H values of the fresh groundwater in the active water exchange zone are ?11.1 and ?79.9?‰, respectively. Characteristically, the groundwater in the active and slow exchange zone is isotopically more depleted compared with the precipitation values observed, and the depletion increases with depth down to the level where strongly enriched brines are encountered.     

Spatial and temporal characteristics of stable isotopes in the Tarim River Basin

By using 233 isotope samples, we investigated the spatial and temporal variations of δ¹⁸O and δ²H in precipitation and surface water, and the contribution of different water sources in the rivers within the Tarim River Basin (TRB), which receives snow/glacier meltwater, groundwater, and rainfall. Our study revealed a similar seasonal pattern of precipitation δ¹⁸O and δ²H at both the north and south edges of the basin, indicating the dominant effect of westerly air masses in the summer and the combined influence of westerly and polar air masses during the winter, although the southern part showed more complex precipitation processes in the summer. River water in the basin has relatively large temporal variations in both δ¹⁸O and δ²H showing a distinct seasonal pattern with lower isotope values in May than in September. Higher d-excess values throughout the year in the Aksu river and the Tizinafu river suggest that water may be intensively recycled in the mountains of the TRB. Based on isotopic hydrograph separation, we found that groundwater is the main water source that discharges the entire basin although individual rivers vary.     

Application of stable isotopes and hydrochemical analysis in groundwater aquifers of Argolis Peninsula (Greece)

The present study examines the isotopic and hydrochemical composition of 18 inland spring waters and 3 coastal karstic spring waters, covering the period between October 2005 and March 2008. The stable isotopes (¹⁸O, ²H) processing has revealed the absence of significant evaporation phenomena and that the origin of fresh water samples is meteoric. Using ¹⁸O values in rainfall waters, an average line of isotopic depletion with altitude has been constructed, extracting a rate of?0.45‰/100 m as typical for the study area. Furthermore, the mean altitude of recharge of the springs has been estimated by plotting the groundwater sampling points on a δ¹⁸O versus altitude diagram. Hydrochemistry results have shown that the dissolution of carbonate, flysch and ophiolitic formations defines the hydrochemical characteristics of groundwater. Moreover, seawater intrusion in the coastal area is significantly high, causing the water in the three karstic springs to be brackish.     

Identifying local and regional groundwater in basins: chemical and stable isotopic attributes of multivariate classification of hydrochemical data,the Lower Virgin River Basin,Nevada, Arizona and Utah,U.S.A

In the Basin and Range Province of the Southwestern U.S.A., deep carbonate groundwater has been suggested as a significant source to many overlying basin-fill alluvial aquifer systems. Notwithstanding, testing this hypothesis is limited by obtaining data from such considerable depths and complex geology.

This study uses δ²H and δ¹⁸O data from springs, rivers, and wells tapping shallow basin-fill groundwater to test the hydrochemical interpretation of deep regional carbonate groundwater flow into the basin-fill aquifers. Stable isotopic and major ion attributes of hydrochemical facies suggest basin-fill alluvial groundwater of the Lower Virgin River Basin is a mixture of precipitation recharge within the Lower Virgin River Basin or the Clover and Escalante Desert Basin northwards, and the deep carbonate flow. The data support the conclusions that in the Lower Virgin River Basin, deep carbonate groundwater is an important source to the alluvial aquifer system and likely accounts for approximately 50% of the alluvial aquifer groundwater. Na⁺, K⁺, and SO₄^2– increase in the basin-fill alluvial groundwaters outside the Virgin River floodplain appears to be related with upwelling of deep regional groundwater, and indicating that the chemical character of the basin-fill alluvial groundwaters are related to the deeper flow systems.     

Insights from stable isotopes of water and hydrochemistry to the evolutionary processes of groundwater in the Subei lake basin,Ordos energy base,Northwestern China

ABSTRACT

Changes in groundwater evolutionary processes due to aquifer overexploitation show a world-wide increase and have been of growing concern in recent years. The study aimed to improve the knowledge of groundwater evolutionary processes by means of stable water isotopes and hydrochemistry in a representative lake basin, Ordos energy base. Groundwater, precipitation, and lake water collected during four campaigns were analysed by stable isotopes and chemical compositions. Results showed that temperature effect predominated the isotope fractionation in precipitation, while evaporation and inadequate groundwater recharge were the key factors explaining high salinity and isotopic enrichment in lake water. Additionally, the Kuisheng Lake was a preferential area of groundwater recharge, while the Subei Lake received less sources from underlying aquifer due to the combined effects of low permeable zone and upstream groundwater captured by the production wells. The homogeneous isotope signatures of groundwater may be ascribed to the closely vertical hydraulic connectivity between the unconfined and the confined aquifers. Isotopically enriched groundwater pumping from well field probably promoted isotopic depletion in groundwater depression cone. These findings not only provide the conceptual framework for the inland basin, but also have important implications for sustainable groundwater management in other groundwater discharge basins with arid climate.     

Sulphur and Oxygen Isotopes in Sulphates in Natural Waters: (1) Surface Waters of Relatively Unpolluted Terrains

Abstract

The paper presents a whole-year study (1990) of an unique area in S-E Poland with numerous small rivers and streams carrying clean waters. We report the results of δ¹⁸O of waters and δ³⁴S of the sulphates sampled 4 times in 1990 from 20 rivers of the study area. The observations clearly show the impact of biological activity on the oxygen and sulphur isotopic compositions in sulphates. Attempts have been made to interpret the correlation between δ³⁴S and δ¹⁸O in sulphates. The highest correlation coefficient has been noticed for samples collected in April, whereas the lowest in August. The conclusion of this study is that the river sulphates are predominantly produced outside the river environment. We have distinguished three major sources of sulphates: (1) ones produced in the aquifer from which waters are discharged, (2) those produced in soils and marshes of forest environment, and (3) ones on anthropogenic origin.