A preliminary investigation of hydrogeochemistry ...

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ISSN 0974-5904, Volume 07, No. 02

April 2014, P.P. 456-466

A preliminary investigation of hydrogeochemistry, metals and saturation indices of minerals in Nakdong surface water and adjacent deltaic groundwater using WATEQ4F geochemical model S. VENKATRAMANAN 1, S. Y. CHUNG1*, N. P ARK2, T. RAMKUMAR3 AND G .GNANACHANDRASAMY3 1

Institute of Environmental Geosciences, Department of Earth & Environmental Sciences, Pukyong National University, 599-1 Daeyeon-dong Nam-gu, Busan 608-737, Korea 2 Department of Civil Engineering, Dong-A University, 840 Hadan-dong Saha-gu, Busan 604-717, Korea 3 Department of Earth Sciences, Annamalai University, Annamalai Nagar-608 502, Tamilnadu, India Email: [email protected], [email protected]

Abstract: A preliminary investigation of hydrogeochemistry, metals and mineral saturation indices were carried out in Nakdong surface water and adjacent deltaic groundwater in Busan, Korea in order to assess their suitability in relation to domestic and agricultural uses. Further, this study was conducted to bring out the relationship and the behavior of different Saturation Indices (SI) of carbonate, sulphate and oxide minerals. One surface water and two groundwater samples were collected, and hydrogeochemical nature was investigated by analyzing the major cations (Ca, Mg, Na, K) and anions (Cl, HCO3, SO4, NO3, F) with some metals (Fe, Mn, Cu, Zn, Sr). Piper diagram showed that water samples fell in the field of mixed Ca-HCO3 type followed by Na-Cl water types. Hydrogeochemical processes controlling water chemistry were water–rock interaction rather than evaporation or precipitation. In Wilcox diagram, water samples fell in low to very high sodium and salinity hazards indicating the suitability for agricultural purpose. Geochemical model, WATEQ4F was used to calculate the Saturation index (SI) of minerals. The SIs of carbonate, sulphate and oxide minerals represented undersaturated and equilibria state. Interpretation of geochemical data suggested that weathering, ion exchange reactions, and SI were the dominant factors that determined the major ionic compositions of groundwater in the study area. Keywords: Hydrogeochemistry, Saturation index, Piper diagram, Gibbs diagram, Wilcox classification, Nakdong River, Korea. 1.

Introduction:

Water is an essential and vital component for our lifesupport system. By the way, the contamination of surface water and groundwater in the world is continuously increasing mainly by anthropogenic origins. The purpose of this research is to investigate the spatial changes of water quality in river and deltaic regions. Rivers included in previous studies are the Seine River in France [27], the Thames River in the UK [16], the Struma River in Bulgaria [2], the Aliakmon River in northern Greece [39], the water bodies of Newfoundland and Labrador in Canada [12], the Lake Tahoe basin in the USA, the Han River in Korea [6], the Amu Darya River in Central Asia [9], the Bagmati River in Nepal [23]. Palar River Basin India [11], Mamundiyar River Basin Tamil Nadu, India [10], Thirumanimuttar River basin, Tamilnadu, India [44], and Gadilam River basin, Tamilnadu, India [34]. The drastic increases in population, modern land use applications (agricultural and industrial), and demands

for water supply have globally accelerated the development of groundwater resources in terms of both its quality and quantity. Even though urban aquifers are important to the supply of drinking water, they are often perceived to be irrelevant to drinking water supply, and leading toward crisis in terms of drinking water scarcity. The contamination of the aquifers has continuously increased, and portability of groundwater has decreased [13]. The quality of water is of vital concern for mankind, since it is directly linked with human welfare. Poor quality of water adversely affects the plant growth and human health [20, 21, 24, 41, 42, 43, 47, and 48]. Groundwater quality data give important clues to the geologic history of rocks and indications of groundwater recharge, movement and storage [46]. The knowledge of hydrochemistry is essential to determine the origin of chemical composition of groundwater [50]. Calculation of mineral saturation index (SI) and thermodynamic equilibrium studies were initiated by [14] to understand the possible reactant and product

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S. VENKATRAMANAN , S. Y. CHUNG, N. P ARK, T. RAMKUMAR AND G .GNANACHANDRASAMY

minerals, and the equilibrium state of groundwater and the surrounding materials. A systematic use of computers for studying the hydrogeochemical systems was initiated by [17-19]. Recently, a considerable number of algorithms and programs for calculating chemical equilibrium by using computer have been developed. They introduce two ways in simulating physico-chemical water rock interactions: (a) computation by the equilibrium constants of chemical reactions, and (b) calculation by the method of free energy minimization. Many researchers have used the saturation indices of silicate, carbonate and fluoride minerals as an indicator to understand the weathering processes from aquifer matrix [7, 35, 44]. The purpose of the present study is to determine the

hydrogeochemistry of surface water and groundwater in Nakdong River and adjacent delta and to classify the water in order to evaluate its suitability for domestic and agricultural uses. WATEQ4F geochemical model was used for calculating the saturation index of the minerals. 2.

Study area:

The study area is located at the downstream of the Nakdong River (Fig.1), which is the longest river in Korea. The length of the Nakdong River is 525km, and the total watershed area is 24,000 km2. The river has the 8 main tributaries. The river is connected to the East China Sea. Flood frequently happens in the study area during summer, and many sediments and organics deposit in the study area.

South Korea Monitoring Site GW1

SW1

GW2 Nakdong River

Fig1: Location map of the study area The delta deposits are about 60~90 m deep, and composed of backfill, upper clay, sand, lower clay and gravel in sequence. It is estimated that sediments on gravel began to deposit from the late Pleistocene Epoch, i.e., the end of 4th glacial period [29, 38]. Basal gravel bed indicates an unconformity between delta sediments and bedrock. The bedrock consists of granite, andesite or rhyolite. The thickness of upper clay ranges 5~10 m, sand 10~40 m, lower clay 10~30 m, and gravel 5~40 m, respectively. The upper clay is relatively soft and loose, but lower clay is relatively stiff and dense. An unconfined aquifer of sand layer and a confined aquifer of gravel layer co-exist in the study area. The industrial

complex is located near the right side of the Nakdong River in the study area, and many factories are managed at the upstream of the Nakdong River. Many rice paddies and greenhouses of fruits and vegetables are also managed in the delta as well as its upstream area. Many houses, roads and airport are also located in the deltaic region. Thus, some contaminants such as nitrate, phosphate, and some inorganic and organic materials occasionally come into the Nakdong River, even though the city controls contamination sources very well. The mouth of the Nakdong River is connected to East China Sea. By the way, the barrages were constructed at the river mouth to prevent seawater intrusion in 1987. Thus,

International Journal of Earth Sciences and Engineering ISSN 0974-5904, Vol. 07, No. 02, April, 2014, pp. 456-466

A Preliminary investigation of hydro geochemistry, metals and saturation index of minerals in Nakdong surface water and adjacent deltaic groundwater using WATEQ4F geochemical model

the influence of seawater has been very limited in the study area since 1987. 3.

Material and Methods:

To assess the water chemistry of the study area, one surface water and two groundwater samples were collected during the period of autumn (October) in the study area. Three monitoring stations were selected for collecting samples such as SW1, GW1 and GW2. The distance between GW1 and GW2 is 2.5 km, and that between GW1 and SW1 is 2 km. Then, it was sealed and brought to the laboratory for analysis and stored properly (4°C) before analysis. Standard procedures were followed for the analysis of groundwater and surface water samples [1]. Some references were measured in the field using portable instruments: Therm Orion 250A+, U.S.A. for pH, Kasahara TR-5Z, Japan for turbidity and TOA CM-14P, Japan for electrical conductivity (EC) and total dissolved solids (TDS). Alkalinity was measured with titration method using 0.02 N H2SO4 in the field. Major cations and heavy metals were determined by Atomic Absorption Spectrometer (AAS, PerkinElmer 400) and Inductively Coupled Plasma Mass Spectrometer (ICP-MS, Agilent 7500 CE). Major anions were analyzed by Ion chromatography (Water 431). Hardness was expressed as the equivalent of the calcium carbonate (CaCO3), and calculated by the equation,

HT  2.5Ca  4.1Mg . All concentration values were expressed in milligram per liter unless otherwise indicated. Analytical grade chemicals were used throughout the study without further purification. To prepare all reagents and calibration standards, double distilled water was used. Aquachem Ver.4 Software was used for the generation of hydrogeochemical plots. In this study, aqueous speciation computed with WATEQ4F [3] was used to define possible saturation index in the aquifer system and to assess the state of equilibrium between groundwater and minerals. 4.

Results and discussion:

4.1. Water chemistry: The chemical composition of the groundwater samples of the study is given in Table1 and Fig.2. The general dominance of anion was in the order of Cl > HCO3 > SO4 > NO3. Groundwater was a little alkaline in nature, and EC values were higher at monitoring well GW1 compared to GW2 and SW1. HCO3 in the study area was higher (959 mg/L, GW1) due to weathering of carbonate minerals of the study area. The concentration of Cl was higher in groundwater (15,865 mg/L) compared to the surface water due to residual saline water, industrial and domestic activities, and dry

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climatic condition [4, 33, 36, 45]. The distance between sampling stations and Sea of China is about 13 km. Chemical and electrical factories, airport, houses, and restaurants are located at the study area. SO4 was higher in GW2 (44 mg/L) indicating the results of water-rock interaction and human influences [8, 28]. NO3 was noted in GW2 (6.8 mg/L) indicating leaching of organic substances from weathered soil. The general dominance of cations was in the order of Na > Mg > Ca > K. For cations, Na was higher in GW1 (9,014 mg/L) representing the influences of seawater intrusion and anthropogenic sources. K was a little high in all samples due to its lower geochemical mobility. Ca and Mg were very high in GW1 (754.8 and 1,114 mg/L) as the results of industrial and agricultural activities. The agricultural activities include rice farming, vegetable and fruit cultivations. F was a little shown in GW1, and originated from the parent rock, granite and andesite. Further concentration has been brought about due to semi-arid climate of the region and long residence time of groundwater in the aquifer [49]. The geology of the study area consists of the Cretaceous sedimentary rocks, igneous intrusive rocks, and Quaternary alluvial deposits. The influence of local lithology and soil aided by other factor like small quantity of freshwater exchange due to the semi-arid climate (average daily temperature 25°C and average daily rainfall of 2 mm) was responsible for higher concentration of fluoride in the groundwater of the region. Higher concentration of fluoride was noted in granite, andesite followed by rhyolite due to presence of dominant fluoride-bearing minerals like apatite, hornblende, and biotite which has enhanced the fluoride concentration. The order of abundance of heavy metals was followed by Sr > Mn > Zn > Fe > Cu. The concentrations of heavy metals in the study area were shown within the permissible limits of Korean drinking water standard except Sr (strontium). The high concentration of Sr (28.5 mg/L) was originated from seawater intrusion [26]. The study area was influenced by transgression and regression of seawater several times before the Holocene Epoch. The geological relation between sedimentary deposits and the basement of bedrock is unconformity. The bedrock was formed in the late Cretaceous Period, and the sediment deposits were estimated to be formed from the late Tertiary Period. Thus, it is thought that the groundwater quality was affected by the old saline water during transgressive activities, and that the groundwater showed high concentration of Sr. 4.2. Water types: The major ion chemistry of water is examined by using Piper [31] trilinear diagram to identify chemical evolution in groundwater. The Piper diagram consists of


459


two lower triangular fields and a central diamondshaped field. The triangular fields are plotted separately with epm values of cations (Ca+Mg) alkali earth, (Na+K) alkali, HCO3 weak acid, and (SO4+Cl) strong acid. Water facies can be identified by plotting in the central diamond-shaped field as the classifications made by [24]. Hydrogeochemical facies is a useful tool for determining the flow pattern and environmental history of groundwater masses (Fig.3). Groundwater samples fall in the Na-Cl (GW1), Ca-Na-Mg-HCO3-SO4 (GW2) and Ca-Na-Mg-HCO3-SO4-Cl (SW1) facies. The enrichment of HCO3 in anion indicates the transformation of hard calcium bicarbonate type to alkaline mixed bicarbonate type along the flow path which favors higher mobility of fluoride ions (>1.5

mg/L) into the groundwater system. The similar facies were identified at stations GW2 and SW1, due to groundwater recharged from surface water during the study period [30, 40]. 4.3. Mechanisms chemistry:

controlling

the

groundwater

The reaction between water and aquifer minerals has a significant role on the characteristics of groundwater quality [5]. General chemistry of groundwater is regulated by diverse processes and various mechanisms controlling the aquifer system. Because the study area experienced dry and semi-arid climatic condition, evaporation might contribute to groundwater chemistry in the study region.

Table1: Statistics of water chemistry (all values in mg/L except pH and EC) Parameters

Min - Max

Average

St. Dev.

Ca

12.63 - 754.8

262.00

381.73

Mg

4.05 - 1114.4

375.74

572.17

Na

11.7 - 9014.0

3014.66

4647.07

Cl

12.01 - 5865.0

5298.33

8184.91

HCO3

37 - 959

355.33

467.83

SO4

5 - 44

22.00

17.87

TDS

117.2 - 4700

5026

8377.9

EC

167.5 - 1000

7179.8

11969

K

3.1 - 230.48

80.19

116.43

Fe

0 - 0.13

0.08

0.06

Mn

0.006 - 7.836

2.62

4.04

Cu

0 - 0.082

0.04

0.00

Zn

0.006 - 0.274

0.14

0.00

Sr

0.168 - 28.46

9.64

14.58

F

0 - 0.27

0.09

0.14

NO3

0.3 - 6.8

2.93

3.06

pH

7.2-7.7

7.53

0.289



460

Box and Whisker Plot GW1 1000.0

Box and Whisker Plot GW2

Legend 10.0 Max.

100.0

Legend

75 percentile

Max.

Median

10.0 1.0

1.0

75 percentile

25 percentile

Median

Min.

25 percentile Min.

0.1

Concentrations (meq/l)

Concentrations ()

0.1

0.0

0.0

0.0

0.0

0.0

0.0

0.0 0.0

0.0

0.0

0.0

Na

Ca

Mg

Cl HCO3SO4 Fe Mn Parameters

Cu

Zn

Sr

K

F

NO3

Na

Ca

Mg

Cl HCO3SO4 Fe Mn Parameters

Cu

Zn

Sr

K

F

NO3

Box and Whisker Plot SW1 1

Legend Max. 75 percentile Median

0

25 percentile Min.

Concentrations (meq/l)

Box and Whisker Plot GW2 0

Legend Max.

0

75 percentile Median

0

25 percentile 0

Na

Ca

Mg

Cl HCO3SO4 K F NO3 Parameters

Fe

Mn

Cu

Zn

Min.

Sr

Fig2: Box and Whisker plots of chemical components in groundwaters and surface water Gibbs plot was employed in this study to understand and differentiate the influences of rock–water interaction, evaporation, and precipitation on water chemistry [15]. Fig. 3 illustrates that SW1 and GW2 falls in water–rock interaction field, and GW1 plotted on evaporation zone, which indicating the interaction between rock chemistry and the percolating water into the subsurface.

Piper Plot Legend Legend 80

D B C

80

60

60

40

40

20

D

B C

20

Mg

SO4

80

80

60

60

40

20

Na+K

HCO3

80

60

40

20

20

D 40

60

80

Ca

40

B C

B C

20

D Cl

Fig3: Hydrogeochemical facies of groundwater and surface water

Mg

Cl HCO3SO4 Fe Mn International Cu Zn Journal Sr of Earth K Sciences F NO3 and Engineering Parameters ISSN 0974-5904, Vol. 07, No. 02, April, 2014, pp. 456-466

GW1 GW2 SW1

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4.4. Evaporation: The process of evaporation is not only a common phenomenon in surface water and groundwater system. Na/Cl ratio is widely used to find out the evaporation process in groundwater. Evaporation will increase the concentration of TDS in water, but the Na/Cl ratio remains the same. It is one of good evidences for evaporation process. If evaporation is the dominant process, Na/Cl ratio should be constant although EC rises [22, 33]. Na/Cl versus EC scatter diagram of the groundwater samples (Fig.5) shows that its trend line is inclined, and Na/Cl ratio decreases with increasing salinity (EC) which seems to be the removal of sodium by ion exchange reaction. This observation indicates that evaporation may not be the major geochemical process controlling the chemistry of water in this study region, and ion exchange reaction can be predominant over evaporation. Gibbs diagrams (Fig.4) justify that evaporation is not a dominant process in this present study. 4.5. Irrigation quality: Excessive sodium in water produces the undesirable effects such as the change of soil properties and the reduction of soil permeability [25]. Hence, for considering the suitability for irrigation, Na concentration needs to be assessed. The degree of the participation of irrigation water in cation exchange reaction can be indicated by Sodium Adsorption Ratio (SAR). Na replacing adsorbed Ca2+ and Mg2+ is a hazard because it reduces the permeability of soil. SAR is defined as: SAR=Na+/√Ca2+ + Mg2+/2 where the concentrations are reported in meq/L. Wilcox plot of SAR versus EC shows the rating of irrigation water (Fig.6). Na and salinity hazard are two important parameters, which can indicate suitability of water for irrigation purposes. The classification of irrigation water based on SAR [37] represents that both SW1 and GW2 fall in C1S1 category (Fig.6). They can be used for salt tolerant to semi-tolerant crops under favorable drainage conditions. However, GW1 falls in C4S4 category, and it can be used only for irrigation with high sodium and salinity hazards.

Fig4: Mechanism controlling the water chemistry of the study area



462

using the computerized geochemical model WATEQ4F [32]. The saturation state of the water samples is defined by the SI as the following:

Fig5: Relationship between EC and Na/Cl in the water

Fig6: Wilcox diagram for the irrigation status of groundwater and surface water 4.6. Saturation index (SI) by WATEQ4F geochemical modeling: The aqueous speciation, chemical composition, distribution, and saturation state of three water samples with respect to various mineral phases were calculated

Positive values of SI indicate that water is supersaturated with respect to mineral phase. Negative values indicate undersaturation, and zero indicates equilibrium. The characterization of the thermodynamic state for the observed calculations shows which processes were performed in the aquifer system. The replacement of minerals is likely for water composition that is supersaturated with respect to one mineral while undersaturated with respect to another. All these reactions would tend to move an observed water composition from the predicted mixing curve toward equilibrium at SI = 0. Saturation index of carbonate minerals is mainly based on the HCO3 concentration in water. Bicarbonate derived by the pressure of weathering or from other source remains in the aqueous medium trying to equilibrate with different ions like Ca2+, Mg2+ or both to attain saturation with different minerals like Calcite, Aragonite, Dolomite, Magnesite, Strontianite, Rhodochrosite, Smithsonite, Siderite, Azurite and Malachite. SIs of Carbonate minerals (Fig.7) show undersaturation to saturation state in all water samples. The saturation state of Carbonate minerals are in the following order: Azurite > Malachite > Dolomite > Smithsonite > Strontianite > Rhodochrosite > Magnesite > Siderite > Aragonite > Calcite. The calculated values of SI for sulphate minerals (Fig.8) of the water samples shows undersaturation to equilibrium state in all wells. This represents that water-rock interaction play a vital role for the groundwater of the study area. The saturation state of sulphate minerals are in the following order: Brochantite > Antlerite > Jarosite > Epsomite > Anhydrite > Gypsum. Saturation index of oxide minerals (Fig.9) like Pyrolusite > Manganite > Ferrihydrite > Brusite > Tenorite > Zincite > Goethite.



SI of Carbonate Minerals (Log IAP/KT)

463

20

0 Aragonite Calcite Dolomite Magnesite Strontianite Rhodochrosite Smithsonite Siderite Azurite Malachite

-20

-40

-60 SW1

GW1

GW2

Stations

SI of Sulphate Minerals (Log IAP/KT)

Fig7: Saturation index of carbonate minerals

20

0 Anhydrite Epsomite

-20

Gypsum -40

Jarosite Celestite

-60

Antlerite -80

Brochantite

-100 SW1

GW1

GW2

Stations

SI of Oxide Minerals (Log IAP/KT)

Fig8: Saturation index of sulphate minerals

20

Brusite 0

Pyrolusite Zincite Ferrihydrite

-20

Goethite Manganite -40 Cuprite Tenorite -60 SW1

GW2

GW1

Stations

Fig9: Saturation index of oxide minerals 5.

Conclusion:

The results of this study provide an outline of the geochemical processes controlling the water chemistry in the study area. The hydrogeochemical types of water can be divided into two major groups. The first group includes mixed Na-Cl and Ca-Na-Mg-HCO3-SO4 followed by, Ca-Na-Mg-HCO3-SO4-Cl types, revealing the influences of seawater and anthropogenic activity. The concentrations of TDS in water samples are >1,000 mg/L, i.e., saline water. The relative concentrations of

the major ions occur in the order of Na > Mg > Ca > K, Cl > HCO 3> SO4 > NO3, and metals Sr > Mn > Zn > Fe>Cu. In the study area, water-rock interaction and anthropogenic activity are the major hydrogeochemical processes responsible for the formation of major ions in groundwater. Higher concentration of strontium in some groundwater can be resulted from the seawater influence. Saturation index of minerals indicates undersaturated and equilibria state of carbonate, sulphate and oxide minerals during the study period. In general, water chemistry is determined by lithological



influences by complex weathering process or ion exchange along with influence of ions from anthropogenic impact. The information presented in this study will be helpful for the sustainable management of groundwater resources in relation with water chemistry, and enables planners and policymakers to evolve a strategy to solve similar problems. 6.

Acknowledgement:

This research was supported by a grant (Code: 13AWMP-B066761-01) from AWMP Program funded by Ministry of Land, Infrastructure and Transport of Korean government. The authors express deep gratitude to two anonymous referees and editor for their constructive comments and suggestions which lead to significant improvements to the manuscript. 7.

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