Chin.J.Geochem.(2010)29:152156 DOI: 10.

1007/s11631-010-0152-4

Evolution of isotopic compositions in groundwater of the area between the Gulf of Oman and the Arabian Gulf
Ahmed Murad*
Department of Geology-Faculty of Sciences, UAE University, P.O.Box: 17551, Al-Ain, United Arab Emirates * Corresponding author, E-mail: ahmed.murad@uaeu.ac.ae

Received April 1, 2009; May 4, 2009 Science Press and Institute of Geochemistry, CAS and Springer-Verlag Berlin Heidelberg 2010 Abstract The stable isotopes of oxygen and hydrogen have been implemented to assess the recharge mechanisms in an area in the UAE bounded to the northwestern part of the Gulf of Oman and the southeastern part of the Arabian Gulf. The conversion of stable isotopes to deuterium excess was utilized as a supportive tool to understand the process of groundwater recharge. The concluding results of this study showed that the origin of moisture is the Mediterranean Sea. The precipitation is the main source of recharge, in which the precipitation having undergone evaporation before recharge occurs. The comparison between regression line for data collected in 1996 and regression line for samples collected in 2006 suggests that the precipitation water which recharged the groundwater, was diluted with groundwater and this dilution is observed from decreasing of the deuterium excess of collected groundwater samples with increasing isotopes of oxygen. The dilution of groundwater with the recharge water suggests modern-day recharge as it is seen from high deuterium excess that exceeded the deuterium excess of LMWL and was close to MMWL. Key words primary evaporation; deuterium excess; recharge; Arabian Gulf; Mediterranean Sea

1 Introduction
Groundwater resources in the northern part of the United Arab Emirates (UAE), which is bounded between the southeast Arabian Gulf and the northwest Gulf of Oman (Fig. 1), are limited and affected negatively due to misuses of groundwater for agricultural and domestic uses. The arid climate of the study area accompanied with a low amount of recharge to major aquifers is the main challenge to water resources in the region. The mean annual precipitation in the study area is 155 mm (Garamoon, 1996; Al Wahedi, 1997) and the mean annual class-A pan evaporation and potential evapotranspiration can reach 1990 and 3320 mm, respectively (MAFcurrently MEW, 1993b). The annual flood of the region is about 1.4106 m3, while the annual recharge is 9.57106 m3 (MAF currently MEW, 1993a; Al Asam, 1998). Severe decline in water level has resulted from heavy groundwater abstraction which deteriorates the aquifers in the study area. Stable isotopes of oxygen and hydrogen are commonly used to study the origin and chemical evolution of groundwater (Clark and Fritz, 1997;
www.gyig.ac.cn www.springerlink.com

Vengosh et al., 2007). The measurements of stable isotopes of oxygen and hydrogen of the water are excellent tracers for recharge of surface water to groundwater, particularly in areas where there are shallow water tables (Herczeg et al., 1992; Chambers et al., 1996). Stable isotopes of water are influenced by the atmospheric processes and during groundwater recharge (Gupta and Deshpande, 2005). In order to visualize the isotope data, local meteoric water lines (LMWL) for each area must be established. The slope of 8 of global meteoric water line (GMWL) corresponds to equilibrium fractionation of D and 18O at 25, whereas the intercept of 10 arises due to kinetic evaporation of ocean water at an average humidity of approximately 85% (Clark and Fritz, 1997). Evaporation of water leads to modification of the isotopic compositions of oxygen and hydrogen due to diffusion-induced fractionation during evaporation process (Simmons et al., 2002; Cappa et al., 2003). Different processes such as evaporation, mixing between different water groups and water-rock interactions, may lead to deviate samples from a slope of 8 on 18O and D plot (Clark and Fritz, 1997; Vengosh et al., 2007). The deuterium excess (d-excess) reflects the conditions that lead to kinetic isotope fractionation between

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water and vapor during primary evaporation in the oceans (Dansgaard, 1964). The d-excess is used to characterize the recharge sources where the slope is equal to 8 (Gat and Issar, 1974). The ultimate objectives of this study were to determine the origin source of groundwater recharge in the study area and investigate the effect of travel moisture from the source on the isotopic signatures of oxygen and hydrogen in groundwater.

limestone that underlain the gravel deposits (Electrowatt, 1981). The gravels can transport a large quantity of water with a moderate hydraulic gradient because of their high horizontal hydraulic conductivity (Al Wahedi, 1997). The aquifer recharged from a catchment of 475 km2 in area (Rizk et al., 2007) with an average elevation of 1050 m above sea level (Abu Al Enien, 1996).

Fig. 2. Geologic map of the study area (after Rizk et al., 2007).

3 Methodology
Fig. 1. Map showing the location of the study area.

2 Geological and hydrogeological settings

The study area called Wadi Al Bih lies within Ras El Khamiah Emirate in the northern part of the UAE and is characterized by thin surface soil layer, scarce vegetation and high runoff (Electrowatt, 1981). The investigated area is part of the Ruus Al Jibal Massif of the Hajar Supergroup, which is composed of a sequence of shallow-marine limestones and dolomites with minor quartz sandstone (Fig. 2) (Glennie et al., 1973). The Hajar Supergroup is divided into three subgroups which are the Ruus Al Jibal, Elphinstone and Munsandam subgroups (Glennie et al., 1974). The Ruus Al Jibal is a broad block-faulted region of N and N-NE trends (Hunting, 1979a, b). The age of these subgroups is from Permian to Lower Cretaceous. Geologically, the study area mainly consists of dolomite with some fine-grained limestone and contain karst fractures (Hudson, 1960). The limestone succession in the study area is well-exposed, easily accessible, and provides information about the relative sea level change which will help to understand the sequence stratigraphy of the adjacent platform (Glennie et al., 1974; Farrant et al., 2006). The carbonate aquifer of the study area is composed of the upper unconfined alluvial gravels and the lower confined fractured Hagil Formation. The upper gravels consist mainly of uncemented, coarse, and very permeable alluvial carbonate gravels, while the lower fractured Hagil Formation contains fractured

Isotope analyses of oxygen and hydrogen were conducted at the Atomic Energy Authority of Egypt on 14 selected groundwater samples (Fig. 3) and one surface water sample was analyzed for comparison purposes. Groundwater samples were collected from the study area during April-June 2006. The isotopic measurements of 18O and D are reported with respect to the International Standard Vienna Standard Mean Ocean Water (VSMOW) and expressed in per mil (). Both local meteoric water line (LMWL) and Mediterranean meteoric water line (MMWL) were employed in the 18O and D plot to determine the source of the moisture. The stable isotopes of oxygen and hydrogen were converted to deuterium excess (d-excess) to show the extent of the movement of the vapor. The deuterium excess for groundwater samples is defined to be D-8 18O (Dansgaard, 1964). In addition, the deuterium excess will be used as an index of evaporation rate (Pang et al., 2004).

4 Results and discussion

The stable isotope data for the groundwater samples collected from the study area are presented in Table 1. The 18O and D values of the groundwater samples collected from the study area do not vary widely, ranging from -3.4 to -3.9 and -9.8 to -13.5 for 18O and D, respectively. The variation of 18O is mainly absent, while the D variations are fairly small, indicating the common origin of ground-

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water. The collected surface water has a value of 0.8 and 14 for 18O and D, respectively. The isotopic measurements of oxygen and hydrogen for surface water are heavier than those of groundwater samples as the surface water exposed to the sun which accelerates the evaporation rate (Fetter, 2001). The resulting linear relationship between 18O and D for groundwater samples included in this study is D=3 18O0.3 (Fig. 4).

for more contact and exchange with the atmosphere. The intercept of -0.3, on the other hand, is lower than 15 of the LMWL, which exhibits that the moisture traveled over long distance before reaching the Arabian Gulf area, and while it traveled, it underwent different degrees of evaporation as is seen from the slope and intercept of the groundwater samples.

Fig. 4. D-18O regression line for the groundwater samples collected Fig. 3. Map showing the location of groundwater samples. from the study area. Red square point indicates surface water samples.

Table 1. D, O and d-excess for the groundwater samples collected from the study area
Sample ID 1 2 3 4 5 6 7 8 9 10 11 12 13 14 D -12.3 -13.5 -10.7 -11.6 -12.3 -13.2 -11.8 -11 -10.8 -11.2 -10.1 -11.3 -9.8 -10.1 O -3.8 -3.9 -3.4 -3.5 -3.7 -3.8 -3.8 -3.7 -3.8 -3.7 -3.7 -3.8 -3.5 -3.9
18

18

d-excess 18.1 17.7 16.5 16.4 17.3 17.2 18.6 18.6 19.6 18.4 19.5 19.1 18.2 21.1

The plot of isotopic compositions of groundwater in the study area are generally above the local meteoric water line (LMWL) (D=8 18O+15) of UAE and scatter around the Mediterranean meteoric water line (MMWL) (D=8 18O+20). This distribution pattern suggests that the source of precipitation in the region is the Mediterranean Sea at high elevation as the isotopic compositions of groundwater are lighter than the LMWL of UAE. The shift in 18O-D pairs away to the left of LMWL results from the evaporation of the raindrops (Friedman et al., 1962; Barnes and Allison, 1988). It is found that the slope and intercept of the regression line are lower than those of LMWL, in which the slope of the best fit line to all data is 3 and the intercept is -0.3. The lower slope of collected groundwater samples implies primary evaporation during precipitation as moisture traveled from the Mediterranean Sea to the region, thus allowing time

The precipitation water originated from the Mediterranean Sea does not stay long enough on the surface because of quick infiltration of precipitation through loose, coarse, and very permeable alluvial gravels. This will not allow precipitation water to evaporate more on the surface prior to recharge. In order to understand the recharge mechanisms of the study area, current regression line (D=3 18O0.3) for samples collected in 2006 has been compared with published regression line for samples collected in 1996 for the study area by Rizk et al. (2007) (D=2.9 18O4.3). The slope of 3 is comparable to the value of 2.9, indicating the process of primary evaporation for groundwater samples before recharge affected groundwater in both periods at almost the same rate of evaporation. However, the y-intercept is slightly different, reflecting different degrees of evaporation prior to groundwater recharge. The similarity between the slopes of two regression lines for 1996 and 2006 confirmed the fact that the recharged water diluted the groundwater at each event of precipitation, suggesting modern-day recharge. In addition, the isotopic signatures of surface water samples are isolated and far away from those of the groundwater samples, supporting the fact that recharged water diluted the groundwater, in which the isotopic signatures of oxygen and hydrogen are lighter than those of the surface water. Another way of expressing the isotope data is to use deuterium excess which is a number that reflects the deviation of a given sample from the meteoric

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water line (Simmons et al., 2002). The calculated deuterium of the study area ranges from 16.4 to 21.1, which clearly showed the variations of deuterium excess are mostly narrow, confirming the common origin. It is noticed that the values of deuterium excess for collected groundwater samples are higher than those of LMWL (15), and also these values are close to 20 which is the d-excess of MMWL. This suggests that the Mediterranean Sea is the main source of moisture for the region. In addition, dilution of the groundwater with precipitated water could increase deuterium excess (Yuan and Miyamoto, 2008), which might indicate modern recharge. The existing groundwater mixed with different average isotope values of precipitation which has undergone evaporation to different extents before recharge. This is evident in an approximate decrease in deuterium excess with increasing 18O (Fig. 5).

References
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Fig. 5. The d-excess vs. 18O plot for collected groundwater samples.

5 Conclusions
It appears that primary evaporation significantly affected the isotope hydrology of groundwater in the area in UAE bounded between the southeastern part of the Arabian Gulf and the northwestern part of the Gulf of Oman. The original moisture has undergone evaporation while it travels before precipitating in the study area as rainfall. This is seen from the slope of groundwater samples that are located above the LMWL. The distribution of the samples between LMWL and MMWL and close to MMWL suggests that the Mediterranean Sea is the main source of precipitation. The regression equation of this study has been compared with the regression equation established for collected data in 1996 and it is found that at each precipitation event evaporated raindrops will dilute the groundwater. The evidence of mixing and dilution of groundwater is seen from decreasing of the deuterium excess of collected groundwater samples with increasing 18O. The dilution of groundwater with precipitated water suggests modern recharge as is observed from high deuterium excess.

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