Journal Pre-proofs

Research papers

Chemical signature detection of groundwater and geothermal waters for evi-

dence of crustal deformation along fault zones

Priyadarshini Singh, Saumitra Mukherjee

PII: S0022-1694(19)31194-1
DOI: https://doi.org/10.1016/j.jhydrol.2019.124459
Reference: HYDROL 124459

To appear in: Journal of Hydrology

Received Date: 2 September 2019

Revised Date: 9 December 2019
Accepted Date: 10 December 2019

Please cite this article as: Singh, P., Mukherjee, S., Chemical signature detection of groundwater and geothermal
waters for evidence of crustal deformation along fault zones, Journal of Hydrology (2019), doi: https://doi.org/
10.1016/j.jhydrol.2019.124459

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Chemical signature detection of groundwater and geothermal waters for

evidence of crustal deformation along fault zones

Priyadarshini Singh and Saumitra Mukherjee*

Affiliations: School of Environmental Sciences, Jawaharlal Nehru University, New Delhi,

INDIA

*
Corresponding Author: Prof. Saumitra Mukherjee

Professor of Geology, Remote Sensing and Space Sciences

School of Environmental Sciences

Jawaharlal Nehru University

New Delhi-110067

India

Contact information: Remote Sensing Applications Laboratory *

School of Environmental Sciences

Jawaharlal Nehru University, New Delhi - 110067, INDIA

Email: saumitra@mail.jnu.ac.in; saumitramukherjee3@gmail.com

Phone: +91-11-26704312, 9313908512 (Mobile)

Fax: +91-11-26704312

Website: http://www.jnu.ac.in/Faculty/smukherjee

1
ABSTRACT

Common crustal igneous and high grade metamorphic rocks contain peroxy defects which

remain dormant until the rock experiences stress upon deformation. Stress activated peroxy

defects form highly reactive oxygen species (ROS) at the rock-water interface observed in

both terrestrial and extraterrestrial rock samples. The ROS complex is formed upon rock fluid

interaction when groundwater combines with the ROS to produce hydrogen peroxide giving

an indirect measure of the underlying rock stress and crustal deformation along active faults.

The average concentration of hydrogen peroxide from the Sohna thermal spring water falling

along the active Sohna fault and geothermal field was measured to be ~ 0.53 ± 0.014 mg/l.

Similar average concentration was also recorded from borewell sample north of the spring (~

0.56 ± 0.017 mg/l) within the same geothermal field. Lower concentration of hydrogen

peroxide was recorded within samples collected from hard rock aquifers outside the

geothermal field and the active fault zone (~0.138 ± 0.095 mg/l). The detailed analysis

suggests that the presence of hydrogen peroxide is largely dependent on the circulation

pattern through the interconnected fractures/joints within the quartzite bedrock lying adjacent

to the fault plane. Laboratory analysis results also show high hydrogen peroxide

concentration within two borewell samples falling adjacent to the epicentre of a shallow

microtremor event within the hard rock region falling alongside a lineament along the Delhi

hard rock mega fold. Rock water interaction post stress activation of peroxy defects and

formation of ROS has therefore been inferred to be responsible for the formation of hydrogen

peroxide at the rock water interface within these zones. This pilot study provides scientific

field evidence that hydrogen peroxide concentrations within groundwaters might offer

prospects for seismic stress estimation and crustal deformation along seismically active

zones.

2
Keywords: peroxy defects, positive hole, hydrogen peroxide, seismic stress, earthquake

prediction, geothermal spring

1.0 Introduction

The build-up of tectonic stress leads to earthquakes upon crustal deformation (Chlieh et al.,

2004; Hamling et al., 2014). Monitoring of stress induced deformation of subsurface

bedrocks along active fault zones and convergent plate boundaries have been under

consideration for detecting premonitory earthquake signals (Royden et al., 1997; Scheuber

and Gonzalez, 1999; Wang et al., 2001). Several case studies across the globe searching for

such premonitory signals for earthquake prediction have reported anomalous changes in the

concentration of terrestrial gases such as radon, helium, argon, hydrogen as well as ionic

concentrations of groundwater, springwater and soil air within seismically active regions

(Barberio et al., 2017; Igarashi et al., 1995; Inan et al., 2012; Hirose et al., 2011; Claesson et

al., 2004; Ghose et al., 1994; Skelton et al., 2014). An investigation correlating

hydrogeochemical changes within a tectonically active region thus can elucidate the link

between seismic stress and crustal rock deformation (Bolognesi, 1997; Andrén et al., 2016;

Wästeby et al., 2014).

Observations report that during the process of igneous rock formation, water gets

incorporated into the rock’s mineral grains in the form of hydroxyl ions upon crystallisation

from water laden magmas, even within anhydrous mineral grains (Takeuchi et al., 2005).

Upon cooling, H2O gets incorporated into the anhydrous mineral grains (quartz, feldspars

etc.) into such an electronic rearrangement which enables a distribution of single OH-, OH-

pairs and sometimes larger OH- clusters. Further through redox conversion, peroxy links

(O3X-OO-XO3) are formed which are mostly found in all igneous and high grade

metamorphic rocks (equation 1) (Takeuchi et al., 2005).

O3X – OH HO – YO3 ↔ O3X/OO\YO3 + H2 (1)

3
 Where X,Y = Si4+, Al3+ etc

These peroxy links break when the rock experiences stress, upon which O2- coverts into O-.

This O- represents a hole or a defect electron in a matrix of O2- known as a positive hole (h•

or p-hole) (Freund and Sornette, 2007; Balk et al., 2009; Freund et al., 2006; Freund and

Freund, 2015). The transfer of charge takes place when a neighbouring electron from O2- fills

the hole, itself turning into O- (equation 2) leading to the breakage of peroxy links or positive

hole pairs (PHP) representing a dormant state of positive holes (equation 3)

Peroxy link + O2¯ ↔ loosely bound e’ + O¯= h• (2)

O3X/OO\YO3 + [XO4]n¯ ↔ O3X/O•O/YO3 + [XO4](n-1)- (3)

When igneous and high-grade metamorphic rocks experience stress due to crustal

deformation, activation of PHPs lead to the production of currents when positive charge

carriers flow from the stressed rock volume into the unstressed rock volume. The flow of

current rises with increase in stress on the unstressed rock volume (Freund and Sornette,

2007). Laboratory simulations have shown that these positive holes can travel along stress

gradients with speeds of ~100 m/s and over distances of meters. In the field, these positive

holes are estimated to propagate in kilometres causing the rock mass to transmit current and

behave like a battery (Freund et al., 2006; Freund and Freund; 2015; Freund, 2002; 2007;

Grant et al., 2011). Further, these simulations suggest that once the positive holes reach the

rock water interface, oxidation of water to hydrogen peroxide takes place when the circuit is

complete achieved by connecting a copper wire from the stressed end to the unstressed end of

the rock (Balk et al., 2009). When the potential difference is large the positive hole (h•) turns

into a highly reactive oxygen radical (•O chemically equivalent to O-) which oxidizes H2O to

H2O2 according to equations (4-6) (Balk et al., 2009).

4
 O¯surface + H2O  OH¯surface + •OH (4)

H3O+ + e¯  H2O + ½ H2 (5)

•OH + •OH  H2O2 (6)

This H2O2 has been measured at nM scales in laboratory simulations involving the

application of stress through steel pistons on a block of Gabbro (Balk et al., 2009). It was

observed that the battery current started to flow as soon as a manually operated hydraulic

press was loaded onto the rock. The current increased rapidly reaching a maximum of ~10

nA at less than 20 MPa, corresponding to <10% of the compressive strength of the rock. The

ends of the rock mass were dipped in pools of water. Hydrogen Peroxide concentration was

measured upon the passage of current. It was inferred that the stressed rock volume behaves

as an anode from where h• charge carriers flow out (Balk et al., 2009). The concentration of

peroxy defects in typical rock-forming minerals and, hence, the number of h• charge carriers

in a given volume of rock, are still poorly understood but it is estimated that the average

peroxy concentration in igneous and high-grade metamorphic rocks is 100 ppm (Batllo et al.,

1990) with every km3 having the potential to produce about 1013 C km−3, equivalent to a

battery current of about 106 A flowing for 6 months.

A study also reported the biogeochemical dark production of hydrogen peroxide in the

groundwaters of an alluvial aquifer adjacent to the Colorado River near Rifle, CO (Yuan et

al., 2017). In the study, the generation of highly reactive oxygen species (such as OH¯

radical) at the oxic anoxic boundaries was inferred to be associated with a cascade of redox

reactions involving the interconversion between metal species such as Iron.

Studies have also shown that besides terrestrial rock samples, freshly crushed basaltic soil

and rock samples from Martian and lunar crusts formed highly reactive radical species on the

surfaces of the crushed samples once the rocks underwent severe mechanical stress upon

grinding (Balk et al., 2009). These radical species produced ROS such as hydrogen peroxide

5
(H2O2), hydroxyl radical (•OH) and superoxide ion (•O2-) once the crushed rock was

immersed in water (Hurowitz et al., 2007). Grant et al., 2011 also reported disappearance of

European toad species Bufo Bufo from their spring mating and spawning grounds five days

before the occurrence of a 6.3 L’Aquila earthquake in April, 2006. The toads reappeared only

after all the aftershocks ceased to occur after the primary earthquake. This behaviour was also

inferred to have occurred as the toads picked up these chemical clues such as release of H2O2

and other oxidized products from the water. Further, hydrogen gas production has been

associated with occurrence of small and large magnitude earthquakes (King, 1986; Sato,

1986) formed when freshly exposed rock surfaces react with water (Ito et al., 1999).

The present study was therefore conducted by sampling geothermal spring and hard rock

aquifers lying along fault zones and regions with microtremor epicentral clusters within

major fault intersection zone to search for presence and anomalous changes in hydrogen

peroxide concentration as an indirect measure of crustal deformation and rock stress. Further,

this study also attempts to validate through hydrochemical analysis of aquifers and spring

samples along faults and fracture zones that a fairly qualitative estimation of rock stress and

crustal deformation can be achieved by measuring the concentration of H2O2 and with other

physico-chemical parameters.

2.0 Study Area

2.1 Seismotectonics of the region.

The study region is located within the states of Haryana and Delhi traversing along zones

with a dense network of small and large active faults, fractures and lineaments (Fig.1 & 2)

falling within seismic zone IV, categorized as high damage risk zone prone with the MSK

(Medvedev-Sponheuer-Karnik) shaking intensity of 8 and above. Ancient and current

seismicity records indicate that the Mahendragarh Dehradun Subsurface Fault (MDSSF), axis

of Delhi-Sargodha Ridge (DSR) and Aravalli-Delhi Fold axis are seismically most active

6
zones within the north-western Indian region (Shukla et al., 2007, Prakash and Srivastava,

2012).

Fig. 1. Seismic Hazard map of Haryana and Delhi (Study area falls within seismic zone IV

(high damage risk zone)

7
 Fig. 2. Study Area with sampling locations and prominent faults and lineaments (map

prepared from digitization of BHUVAN geoportal and Seisat 9 map of seismotectonic

atlas of India (Dasgupta et al., 2000))

This seismicity is attributed to bending of the upper crust prior to underthrusting below the

Himalayas at the Eurasian and Indian convergent plate boundary (Molnar et al., 1973). The

seismic epicentral location maps of the region (Fig. 3) show that several clusters of

microtremor events ranging in magnitude between Mw 2-3 are located at the boundary of

Rohtak and Sonipat districts in Haryana as well as in some parts of the national capital region

of Delhi. The microtremor clusters for the seismic events occurring from 2000-2015 fall at

the intersection of the MDSSF and axis of DSR (Delhi Lahore Fault). These clusters indicate

8
that frequent microtremor events occur (< 3 magnitude) in this region which is mainly

attributed to the activation of different faults at one time or another.

Fig. 3. Seismicity of Delhi and adjoining areas during year 2000-2015 showing clustered

events along Mahendragarh-Dehradun Subsurface Fault (MDSSF) and Delhi Sargodha Ridge

(DSR): The spatial interpolation maps were prepared by Inverse Distance Weighted

interpolation technique on the spatial analyst tool of ArcGIS 10.1.

2.2 Geology and geomorphology of the study region

The seismic microtremor clusters fall within two geomorphic zones consisting of a hard rock

region falling in the districts of Gurugram, Faridabad and a part of Delhi and within the

9
alluvial region falling in the districts of Rohtak, Sonipat and Jhajjhar. The geology of the area

is characterized by the Precambrian metasediments of the Delhi Supergroup with widespread

occurrence of quartzites, schists, siliceous limestones, slates and phyllites (Cinti et al., 2009;

Singh, 1996).

Fig. 4. Geological map of the study area

The alluvial region comprises of polycyclic sequence of silt-clay with gravel and fine to

medium grained sand along with a few patches of aeolian windblown sand scattered within

the alluvial plain. The subsurface also contains a complex system of several interconnected

faults and lineaments as depicted in the geological map of the region (Fig. 4).

10
 Fig. 5. Geomorphology of the hard rock region within the study area

The hard rock outcrop of the Delhi fold belt within the study area encompassing Delhi,

Gurugram and Faridabad districts contains numerous lineaments and fractures (Fig. 5). A

distinct N-S oriented seismogenic fault known as the Sohna fault associated with the

Himalayan orogenic movement runs from Sohna to the Delhi Ridge existing below the

alluvium in the vicinity of a thermal spring (Fig. 5 & 6) (Sharma et al., 2003).

11
 Fig. 6. Study Area showing the epicentre locations along with major lineaments

2.2.1 Geology of Sohna geothermal spring

The geothermal field and thermal spring fall within the tectonic depression formed by the

downward faulting of a central block lying between two anticlinal ridges belonging to the

Delhi belt. (Fig. 6).The spring is located at an altitude of ~200 m from the mean sea level at

the hinge region of the synformal fold within a tectonic depression (Pandey and Negi, 1995;

Thussu, 2001). The temperature data suggests that the geothermal field extends over an area

of ~3900 m2 (Deb and Ray, 1971). The water emanates out of a fissure within the Pre-

Cambrian quartzite bedrock. The region to the north and east of the spring is occupied by

alluvium whereas the southern and western parts are covered by Alwar Quartzite of the Delhi

supergroup. The alluvium on the east of the spring comprises of aquifers made up of sand

with some silt and clay. On the west of the spring the alluvium consists of gravel, sand, silt

and clay and is devoid of good aquifers (Fig. 7) (Deb and Ray, 1971).

12
 Fig. 7. Geological Map of the region of Sohna thermal spring (box in inset)

The quartzites of the anticlinal ridges are highly jointed and compacted with the joints

occurring in two sets; one lying perpendicular to the bedding plane and the other lying

parallel. The unique pattern of joints within the bed rock gives rise to rectangular blocks of

quartzites providing passageways for the circulating water (Deb and Ray, 1971; Chaudhary et

al., 1996). The water table of the region follows the topography with the wells lying close to

the ridge to be of deeper origin. The fractures and joints within the quartzite bedrock

constitute the water bearing zone whereas the rest of the hard rock region has a poor capacity

to store and transmit water (Bajpai and Mahanta, 2003).

The water circulation drains from the western alluvium travelling through the pattern of

fractures and joints till the hinge region after which it finally issues out through a fissure as a

spring (Fig. 8). The circulation pattern of the water therefore is inferred to be the main factor

influencing the changes in the geochemistry of the spring water.

13
 Fig. 8. Generalized schematic representation of the hydrogeological setup and the thermal

spring water circulation (modified after Deb & Ray, 1971) along the segment A-B marked

in Fig. 7.

The quartzite bedrock of the geothermal field has a provenance dominated by evolved

granitic rocks and consists of intercalations of muscovite schist, kyanite schist and phyllite

(Tripathi and Rajamani, 2003). Quartzite is an intermediate to high grade metamorphic rock

formed when quartz-rich sandstone is exposed to high temperatures and pressures often along

tectonic boundaries. It is non-foliated, medium grained and almost entirely composed of

quartz mineral (Chatterjee, 1974). Schist as well is produced by medium to high grade

metamorphism consisting of mineral grains of quartz, feldspar, muscovite, biotite and chlorite

(Tripathi and Rajamani, 2003). Phyllite, on the other hand is a fine grained, low grade

metamorphic rock composed of mineral grains of muscovite, chlorite, biotite along with

graphite and iron oxides (Chatterjee, 1974).

3.0 Methodology

3.1. Sampling

14
The investigation was initiated by surveying the region through maps (seismotectonic maps,

geological maps, geomorphological maps) depicting the features and terrain of the area in

order to delineate zones for collection of water samples. Representative samples were then

collected from aquifers at appropriate locations falling in the alluvial region within the

seismic epicentral clusters as well as the region falling within the Sohna geothermal field and

surrounding hard rock area.

Sampling was done in the premonsoon season (April, 2015) as well in the postmonsoon

season (December, 2015) from borewells and handpumps. The polypropylene sampling

bottles were initially rinsed 2-3 times with the water being sampled. To get a fresh

representative sample of the aquifer, the handpumps were initially pumped for 50 strokes to

remove stagnant water within the iron pipes minimizing the impact of contamination. In case

of borewells, the water was allowed to run for approximately ten minutes before collecting

the sample. For the hard rock region outside the geothermal field, 16 groundwater samples

were collected in the premonsoon season and 27 samples were collected in the postmonsoon

season surrounding the Delhi Fold axis and the hard rock Aravalli outcrops at Sohna (Fig. 1).

Two samples each were collected from the geothermal spring water and the borewell 100 m

north of the spring. One sample each was also collected from the alluvium to the west and

east of the Sohna spring falling outside the geothermal field. In the alluvial region, 32

samples were collected in the premonsoon season and 20 samples were collected in the

postmonsoon season from the aquifers along the linear transect as well as within the zone of

the seismic epicentral clusters. Temperature, pH, Electrical Conductivity (EC) and Total

Dissolved Solids (TDS) measurements were done on field using thermometer and

multiparameter handheld probe (thermo Fischer multi-parameter TESTR 35 series). The

samples collected for cation analysis were preserved using conc. HNO3 (pH<2). Post

collection, the samples were filtered using 0.45 μm millipore filter paper and stored at 4°C

15
until analysis was done. The location for each sampling point was recorded by Garmin global

positioning system (GPS) (Fig. 1). Thermal camera image of the exposed fractured hard rock

was captured by FLIR-Thermal Camera (Model C-2) to obtain the relative radiative

temperatures of the exposed hard rock. The samples for the analysis of hydrogen peroxide

concentration were collected in amber high density polypropylene (HDPE) bottles which

were kept airtight and immediately stored at 4°C after sample collection. Samples were

collected in duplicates to increase the accuracy of the measured concentration of hydrogen

peroxide. Filtration of the collected samples was avoided to prevent exposure to light.

3.2. Hydrochemical analysis

Samples were analysed for major ions (Na+, K+, Ca2+, Mg2+, HCO3-, SO42-, Cl-) and total Iron

and Silica in the laboratory using the standard methods (APHA, 1995) and methodology

outlined by Diatloff & Rengel, 2001. The methodology used as well as the detection limits

have been tabulated in supplementary table 5. Samples were analysed for sulphate and

hydrogen peroxide using UV/visible spectrophotometer (Lambda 35, Perkin Elmer); Sodium,

Potassium and Calcium using flame photometer (Elico CL-378); Magnesium and Iron using

Atomic Absorption Spectrometer and Chloride and Alkalinity (HCO3 + CO3) by titration

technique. The data generated from the analysis is tabulated in Supplementary tables 1-4.

The hydrogen peroxide concentration was measured the same day in the laboratory using a

simple and rapid spectrophotometric method based on the liberation of iodine in an acidic

medium (pH 2-3) equivalent to the hydrogen peroxide present in solution (equation 8) (Sunil

and Narayana, 2008).

H2O2 + 2H+ + 2I¯  I2 + 2H2O (8)

16
The method involves the liberation of iodine which bleaches the blue colour of toluidine blue

reagent (absorption maximum at 628 nm) into a colourless species. Standard stock solution of

hydrogen peroxide was prepared by dilution of 30% reagent grade hydrogen peroxide

(Sigma-Aldrich). Standards of known concentrations of hydrogen peroxide ranging from 2 -

14 μM were prepared by dilution of the stock solution which was standardized using

titrimetric method (Jeffery et al., 1995). Other reagents used for the analysis consisted of 2%

potassium iodide, 0.01% toluidine blue indicator, 2M hydrochloric acid and 2M sodium

acetate solution.

The standard curve was generated by measuring the absorbance values of solutions with

varying hydrogen peroxide concentrations at a wavelength of 628 nm against the reagent

blank. The decrease in absorbance compared to the reagent blank is directly proportional to

the concentration of hydrogen peroxide.

The mineral phases of the rock and soil samples collected from the Sohna thermal spring site

were analysis using X-Ray Diffraction technique. The samples were crushed and grinded

using a pulveriser and passed through 200 μm mesh size. The samples were then loaded on

PANalytical X’Pert PRO. The generated data was processed on X’Pert HighScore Software

version 1.0a for identifying the mineralogical composition. The 2°Theta peaks of the XRD

diffractogram were matched using the standards provided in Lindholm, 1987.

4.0 Results and Discussion

4.1 Hydrochemical parameters

The statistical summary of the physicochemical parameters analysed for the hard rock aquifer

samples and the alluvial aquifer samples in the premonsoon and postmonsoon season is

tabulated in Table 1.

17
 Parameter Premonsoon (Hard- Postmonsoon Premonsoon Postmonsoon

Rock) (Hard-Rock) (Alluvium) (Alluvium)

pH 6.59±0.55 7.15±0.3 7.34±0.34 7.29±0.39

EC 1233.13±624.61 1368.94±573.48 2062.31±1486.98 1715.05±1194.96

HCO3- 299.61±122.75 368.93±80.81 264.75±145.5 368.51±135.61

Cl- 281.52±211.11 236.75±156.22 359.42±367.31 319.97±320.43

NO3- 38.48±46.97 41.57±38.55 31.66±32.28 31.69±41.59

PO43- 0.43±0.12 0.43±0.13 0.53±0.19 0.20±0.13

SO42- 50.79±43.86 60.98±52.48 81.52±82.86 120.86±66.99

Na+ 102.13±53.02 230.61±57.9 79±55.01 144.06±108.05

K+ 5.28±3.81 16.51±23.67 19.08±34.53 30.19±54.02

Ca2+ 143.71±113.19 125.38±74.02 121.05±91.18 139.74±117.74

Mg2+ 35.17±4.08 34.59±5.97 70.80±48.43 38.04±7

Silica 28.80±6.86 30.89±6.35 28.74±6.53 20.57±6.39

H2O2 0.14 ± 0.30 0.15± 0.12 0.17 ± 0.34 0.21± 0.04

Table. 1. Statistical summary of different physico-chemical parameters for the pre and

postmonsoon hard rock and alluvial aquifer samples (all concentration in ppm except

for EC (μS/cm) and pH); ND- not detected

4.2 Hydrochemical processes influencing major ion groundwater chemistry

Based on the plots of major cations (Ca2+, Mg2+, Na+ and K+) and anions (HCO3-, Cl-, SO42-),

the hydrochemical facies of the groundwater was derived from piper trilinear diagrams for

both alluvial and hard rock aquifer samples (Fig. 9 a,b). In the premonsoon alluvial aquifer

samples, the groundwater type is of Ca-Mg-Cl and Ca-HCO3-Cl. In the postmonsoon alluvial

aquifer samples, the majority of the water type is of Ca-Na-HCO3-Cl type. For the

premonsoon and postmonsoon hard rock aquifer samples the water type is of Ca-Mg-Cl

whereas for the postmonsoon samples the major water type is Ca-Cl.

18
 a Hard Rock b Hard Rock
Alluvium Alluvium

Fig. 9. a. Piper trilinear plot for pre-monsoon samples; b: piper trilinear plot for post-

monsoon samples

4.3 Inference of the provenance of spring water through geochemical data

The thermal spring water is Ca-Cl water type with neutral in pH (~7) and a relatively high

salinity (~1300 μS.cm-1) which suggests a long circulation time. Among the alkali metals,

sodium is found to be the most abundant whereas calcium is dominant among the alkaline

earth metals. From the anions, bicarbonate and chloride are abundant. Although, the spring

water sample has no iron but the groundwater sample collected from the borewell just north

of the spring has high iron content (~5.4 mg/l) (Table 2). A comparative summary of the

hydrochemical constituents of the spring water sample and the borewell sample collected

~100 m north of the spring lying within the same geothermal field has been tabulated in

Table 2 along with the water constituents from the sample collected from the western and

eastern alluvial aquifers. The average concentration of hydrogen peroxide from the Sohna

thermal spring water falling along the active Sohna fault and geothermal field was measured

to be ~0.535 ± 0.014 mg/l. Lower concentration of hydrogen peroxide was recorded within

samples collected from hard rock aquifers outside the geothermal field (~0.138 ± 0.095 mg/l).

19
 Sohna Tube-well water Tube well water Tube well water

Constituent Thermal (Just North of (Alluvium - West (Alluvium - East

Spring Sohna Spring) of Sohna Spring) of Sohna Spring)

EC 1340 ± 21.2 1370 ± 38.7 1780 ± 28.5 2241 ± 41.2

Temperature 40 ± 0.9 42 ± 0.8 27.6 ± 1.2 26 ± 0.5

pH 6.9 7 7 7.4

Na+ 111.3 ± 28.7 112.2 ± 19.8 156.7 ± 14.1 173 ± 6.9

K+ 9.9 ± 0.9 10.1 ± 1.2 5.9 ± 1.6 2.2 ± 0.5

Ca2+ 131 ± 15.6 97.5 ± 2.8 110 ± 5.8 279.7 ± 9.6

Mg2+ 32.85 ± 2.8 33.08 ± 5.1 35.02 ± 1.9 45.03 ± 5.2

Cl¯ 244.68 ± 12.1 236.24 ± 15.8 290.61 ± 29.6 656.21 ± 14.8

HCO3¯ 325.80 ± 15.1 359.21 ± 20.8 342.76 ± 40.5 412.76 ± 28.6

SO42¯ 42.83 ± 1.5 35.10 ± 2.5 74.57 ± 28.4 85.13 ± 15.2

Total Fe ND 5.44 ± 0.8 0.0182 ± 0.01 ND

H2O2 0.51 ± 0.012 0.56 ± 0.017 0.28 ± 0.0098 0.26 ± 0.0015

Silica 37.24 ± 0.22 40.86 ± 0.25 32.87 ± 0.16 27.73 ± 0.51

Water type Ca-Cl Na-Cl Na-Cl Ca-Cl

Table 2. Physicochemical parameters analysed for the Sohna thermal spring water,

tube well sample north of the spring and alluvium tube well water sample west and

east of the spring (Concentrations in mg/l except water type, EC (μS.cm-1), pH and

Temperature (°C), ND – not detected (below the detection level of instrument)).

20
 Fig. 10. Piper plot for the samples described in Table 2.

High Ca (131 mg/l) content was recorded within the spring water samples. The samples from

the alluvium west of the spring also had comparable calcium ion concentration as the spring

water (110 mg/l) whereas the eastern alluvium had a relatively higher calcium ion

concentration (~279 mg/l) as compared to the spring water. The Mg and Cl ion

concentrations also show comparable values as the western alluvial aquifer sample (Table 2).

Piper plot in fig. 10 shows that the western alluvial sample has similar water facies as

compared to the eastern alluvium sample further validating that the spring water sample is

derived from the western alluvium as previously observed (Thussu, 2001). Therefore, the

spring water is inferred to be derived from the western alluvial aquifers. Mixing of shallow

water with hot water during discharge has not been suggested as there are no shallow aquifers

reported within the region. High noble gas concentration such as Helium (4He) was reported

at the Sohna spring produced from α-decay of natural Uranium and Thorium by Cinti et al.,

2009. The high helium and high salinity indicates a very long residence time as well as fault

activity within the crust. The hydrochemical parameters suggest that the water from the

21
alluvium west of the spring seeps into the ground and enters the hard rock fractures and

joints. At a depth of ~ 915 m, the water starts moving upward through the joints and fractures

finally issuing out from the hinge region of the synformal fold (Fig. 8). This suggests that the

changes in the hydrochemical properties are largely dependent on the circulation pattern of

the water through the interconnected fractures within the bedrock lying along the active

Sohna fault.

4.4 Evidence of hydrogen peroxide and hydrogen gas production at rock water interface

The interaction of water with the stressed rock volume at the rock-water interface is

considered key to the production of hydrogen peroxide. Laboratory simulations have shown

that at the rock water boundary, the p-hole (O¯) turns into a highly reactive oxygen species

(ROS) in the form of •O radical which converts H2O into H2O2 (Balk et al., 2009). According

to the reaction, for every two positive holes, one H2O2 molecule is formed. The closure of the

battery circuit in the lab simulation was achieved by joining the stressed rock end to the

unstressed rock end through a copper wire. In the field, the closure of the circuit can be

achieved by the electrolytical conductivity of water across the rockbed which is represented

here by the hard rock aquifer such as the Sohna geothermal aquifer. The concentration of

hydrogen peroxide in the water samples collected from the spring and from the borewell

north of the spring was the highest as compared to the groundwater samples collected from

the western and eastern alluvium as well as from the surrounding hard rock aquifers (Table

1,2).

Apart from the stress activation of peroxy links and migration of positive holes within

crystalline oxides and silicates, evidence also suggests that redox reactions involving the

splitting off of H2 to form peroxy anions occur within fused silica wherein O3SiOH pairs are

converted into H2 and peroxy links (O3Si – OO –SiO3) (Kita et al., 1982). Molecular

22
hydrogen (H2) production also takes place due to charge transfer conversion of Si-OH pairs

into Si-O/ \O-Si and H2 (equation 7) (Freund, 1985).

Si-OH HO-Si  Si-O/ \O-Si + H2 (7)

This hydrogen production has been evidenced to be frictionally driven during rock fracturing

associated with cataclastic rock (McMahon et al., 2016). Preseismic increases in H2 gas

associated with nucleation process of stress-corrosion mechanism have been reported within

a deep Nagashima well along the active Yoro-Ise Bay fault zone (Ito et al., 1999). It has been

reported that hydrogen gas generation increases with high frictional work associated with

even small magnitude earthquakes (M<3) (Hirose et al., 2011; Ito et al., 1999; King, 1986;

Sato, 1986). Laboratory experiments have shown that hydrogen gas is generated when freshly

pulverized rocks react with water suggesting that exposed mineral surfaces formed by

tectonic crustal deformation react with groundwater releasing H2 (Sugisaki et al., 1983).

Detailed studies validate that the anomalous increase in hydrogen content associated with

seismic events is the result of the reaction between groundwater and Si and Si-O radicals post

rock rupture along the active fault plane (Kravtsov and Fridman, 1974; Mazor, 1991).

Further, the same mechanism is reported to form hydrogen peroxide along active faults when

freshly exposed bedrock reacts with groundwater (Freund, 1985).

High concentration of dissolved hydrogen (0.188 cm3 STP/l) was reported in the Sohna

spring water samples by Cinti et al., 2009. Therefore a longer circulation time of geothermal

water through the interconnected fractures within the stressed quartzite bedrock and the

simultaneous occurrence of small magnitude earthquakes could possibly lead to the observed

increase in the dissolved hydrogen content. Thermal camera images of the exposed hard rock

from the region show that the fractures/joints have higher internal radiative temperatures as

compared to the rest of the rock volume (Fig. 11 a & b) which suggests internal heat

production possibly from frictional work acting along the fracture planes.

23
 Fig. 11. (a) Camera image of the exposed quartzite hard rock near the geothermal spring at

28.244°N, 77.065 °E; (b) Thermal camera image of the region in (a) showing higher

radiative internal temperatures at the fractures planes (black arrows); white circle (lower

left corner) depicts freshly exposed rock having highest temperatures in the field of view of

the region as compared to the other rock surfaces.

Alternatively, study discussing the dark production of hydrogen peroxide in the alluvial

aquifer of Rifle, CO suggests that the production of hydrogen peroxide is highly spatially

variable governed by several processes such as dark biological production, metal-mediated

oxidation of organic matter and cycling of metal species (e.g. Iron) through a series of redox

reactions (Yuan et al., 2017). The absence of Iron species in the thermal spring water sample

suggests that the interconversion of Fe2+ to Fe3+ is not responsible for the generation of

hydrogen peroxide in the spring water samples. The production of hydrogen peroxide in the

Sohna spring water sample therefore seems to be dependent on the conversion of ROS

species (O-) produced through the transfer of stress activated p-holes within the subsurface

rock.

A study by Borda et al. 2003 describes the production of hydrogen peroxide upon addition of

pyrite (FeS2) to deoxygenated water. The production of hydrogen peroxide is initiated by the

conversion of Fe (III) to Fe (II) at sulfur-deficient (defect) sites on pyrite surfaces resulting in

24
the generation of a hydroxyl radical with a correspondingly high concentration of sulfate

(SO42-). In order to assess whether this process is active in the Sohna spring site, the mineral

phases of the rock and soil sediments was done.

Fig. 12 a and b shows the XRD diffractogram of the rock sample analysis and nearby soil

sediment analysis respectively of Aravalli hard rock outcrop at Sohna.

25
 Fig. 12 a. Hard rock sediment XRD and b. XRD diffractogram of nearby soil sediments of

Sohna hard rock outcrop

The peaks seen in this XRD diffractogram show that the prominent minerals consist of

Quartz and Calcite with traces of chromium in the rock sample analysis (Supplementary

Table 6).

According to the d-spacing value, other minor minerals were also identified by soil sediment

analysis of the region. The minerals were identified based on the d-spacing values at °2theta

(Supplementary Table 7). In both the XRD data for rock and soil sample analysis shown

above, Pyrite (FeS2) has not been detected in the mineral composition. Therefore the role of

pyrite and the reduction of Fe(III) to Fe(II) leading to the production of hydroxyl ion might

not be a significant contributor of hydrogen peroxide in the groundwater in this study. Also,

if Iron reduction was playing a role in the production of hydroxyl radical then Iron would

have been detected in the total iron concentration in the spring water samples.

Further, if the process of the formation of hydroxyl radical on pyrite surfaces is the dominant

process leading to the formation of hydrogen peroxide, then sulphate concentration would be

higher in the geothermal samples as compared to the western alluvial aquifer. To discount the

26
role of pyrite and redox conversion of Iron as the source of hydrogen peroxide production, we

analysed the sulfate ion concentrations (based on chloride to sulphate ratio (Cl/SO4 ratio)).

The obtained ratios showed that the western alluvial aquifer sample showed sulphate

enrichment relative to seawater (Cl/SO4 ~ 4). The ratio for the Sohna thermal spring samples

showed slight enrichment (Cl/SO4 ~ 6) whereas the eastern alluvial aquifer showed a ratio

similar to that of seawater (Cl/SO4 ~ 7). This indicates that the sulphate concentration in the

groundwater samples from the western alluvial aquifer is higher than the spring and the

borewell samples north of the geothermal aquifer. Therefore, the hydrogen peroxide

concentration having being higher in the spring water samples indicates that the process of

hydroxyl ion formation on pyrite surfaces is highly unlikely.

All the physico-chemical analysis and seismic data point at two important deductions, one

that the region experiences continuous minor crustal deformation and therefore seismic stress

is active as seen from the frequent microtremor activity. Secondly, comparatively higher

concentration of hydrogen peroxide measured in the geothermal water samples is associated

with this crustal deformation and stress build-up activating the peroxy defects within the

bedrock along the fault zone. The hydrogen gas and hydrogen peroxide production both are

inferred to be the result of rock water interaction taking place due to constant availability of

freshly exposed rock surface for aqueous chemical interaction along the active fault zone.

The physico-chemical properties and the long circulation time through the interconnected

fractures, both suggest that the presence of hydrogen peroxide within the geothermal waters

can be attributed to the stress activation of positive holes taking place upon rock deformation

from microtremor events along lineaments and faults.

Hydrogen peroxide distribution linked to microtremor activity in the study region

The spatial distribution map of hydrogen peroxide concentration was prepared for the study

region in the premonsoon season (April, 2015) in order to observe correlation with the

27
distribution of hydrogen peroxide and microtremor activity. The spatial interpolation map for

the alluvial region showed that the region with high peroxide concentration falls adjacent to

the intersection zones of MDSSF, DSR and a lineament running NE-SW (Fig. 13a).

According to the laboratory simulations, it was inferred that the stress activated charge

carriers can travel distances of kilometres in the field therefore any major seismic event in the

far field Himalayan tectonic convergent boundary can activate the faults such as the MDSSF

leading to observed changes within the seismic zones of the study region. The distribution of

hydrogen peroxide concentration ranges from 0-1 ppm in the premonsoon season. Further a

region falling adjacent to the Delhi mega fold having a distinct lineament along which the

epicentre of a microtremor event was recorded on 13th April, 2015 with a magnitude of 2.1

also shows high concentration of hydrogen peroxide within the samples collected on April

26th, 2015 from the aquifers adjacent to the epicentre (Fig. 13b).

28
Fig. 13. Premonsoon spatial distribution of hydrogen peroxide concentration; a, magnified

image of the region with high peroxide ion concentrations; b. Part of Delhi mega fold hard

rock region showing high hydrogen peroxide concentration within the aquifers adjacent to the

microtremor epicentre falling along a distinct linear fracture (13.4.2015).

The region close to the thermal spring water along the active Sohna fault also shows

comparatively higher concentration of hydrogen peroxide. It is inferred that seismic stress

build up and the seismic swarms in these zones correlate positively with the high hydrogen

peroxide concentration. The frequent microtremor activity leads to crustal deformation post

29
stress build up intermittently when movement occurs along one or more faults and fractures

resulting in fluctuations in the hydrogen peroxide concentration.

5.0 Conclusion

The findings of this study support that reactive oxygen species potentially result from

deformation of mineral defects from seismic stress and can be potential indicators of seismic

activity. However, further research is required to validate these results. Continuous

monitoring of hydrogen peroxide concentration within the geothermal field over extended

periods of time should therefore be undertaken to monitor rock stress and the associated

seismicity experienced in the form of microtremors or moderate to large magnitude

earthquakes.

Geothermal zones lying along active faults or deep hard rock aquifers can be explored in

detail to infer premonitory earthquake signals by quantifying the relationship of seismicity

derived from rock stress, dependent on groundwater interactions. By measuring the

concentration of hydrogen peroxide within geothermal waters especially springs falling along

active fault boundaries, the estimation of seismic stress can possibly be achieved. Accurate

and timely estimation of this indirect measure of seismic stress would require continuous

monitoring of groundwater chemical properties. This can further be employed for devising

models for early warning system for disaster preparedness and reduction.

Author Contributions

P.S. has prepared the final manuscript and conducted the field work and data analysis. S.M.

provided inputs for data analysis and interpretation.

Competing Interests

The authors declare that they have no competing interests.

30
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Author Contribution

P.S. has prepared the final manuscript and conducted the field work and data analysis. S.M.

provided inputs for data analysis and interpretation.

38