Chemosphere 251 (2020) 126374

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Characterization and role of derived dissolved organic matter on

arsenic mobilization in alluvial aquifers of Punjab, Pakistan
Aroosa Malik a, Ambreen Parvaiz a, Nisbah Mushtaq a, Ishtiaque Hussain a, Tariq Javed b,
Hafiz Ur Rehman c, Abida Farooqi a, *
a
Environmental Geochemistry Laboratory, Faculty of Biological Sciences, Department of Environmental Sciences, Quaid-i-Azam University, Islamabad,
Pakistan
b
Isotope Application Division, Pakistan Institute of Nuclear Science and Technology (PINSTECH), Nilore, Islamabad, Pakistan
c
Graduate School of Science and Engineering, Kagoshima University, Kagoshima, 890-0065, Japan

h i g h l i g h t s g r a p h i c a l a b s t r a c t

As concentartions were above the

WHO limit with an increasing trend
from northern to southern side of the
study area.

Reductive dissolution, competitive
desorption with dissolved organic
matter probabaly results in As
mobilization in groundwater.

Geochemical data show terrestrially-
derived dissolved organic matter in
northern part while exhibit mixed
source in the southern part.

a r t i c l e i n f o a b s t r a c t

Article history: Biogeochemical mobilization of arsenic in groundwater depends on the presence of dissolved organic
Received 4 August 2019 matter (DOM) that likely promotes the As release, i.e., reductive dissolution, complexation, competition,
Received in revised form and electron shuttling. We investigated the role of DOM in As release, along with its complete charac-
26 February 2020
terization, in the Indus plain of Pakistan, one of the worst arsenic impacted zones in the South Asian
Accepted 27 February 2020
region. In total, 60 groundwater and 15 soil samples, collected at six sites from north to south within the
Available online 3 March 2020
flood plain of the Ravi River, Lahore, Pakistan were investigated. Arsenic concentration ranged from
Handling Editor: Tsair-Fuh 9.61 mg/L to 386 mg/L in the groundwater samples (high As observed in areas close to the river). Dissolved
organic carbon (DOC) in 29 groundwater samples ranged between 0 and 10.1 mg-C/L. A moderately
Keywords: positive correlation of As with DOC and Fe in the northern part of the study area suggest the reductive
Arsenic (As) dissolution of FeOOH associated with dissolved organic matter (DOM). The reductive dissolution plays an

Dissolved organic matter (DOM) essential role for As enrichment in the area evidenced by the lower concentrations of SO2 4 , NO3 , and
Groundwater PO4 4
3 and a non-correlative pattern with As. In contrast, a positive correlation of As with PO3 , DOC, and
Indus plain
HCO 3 in the southern part indicate competitive desorption behind the As release. Fluorescence
excitation-emission matrix intensity data of DOM indicate the maximum presence of humic-like sub-
stances in the northern part that gradually shifts to aromatic, fulvic and protein type towards the
southern part. Specific ultraviolet absorbance and fluorescence index display aromatic and terrestrial
(allochthonous) sources of DOM near the riverbank and mixed (both allochthonous and autochthonous)
source away from the river. The positive correlations of As with DOC and fluorescence intensity also
attest that DOM played a vital role in the As mobilization in groundwater of the study area.
© 2020 Elsevier Ltd. All rights reserved.

* Corresponding author.
E-mail address: afarooqi@qau.edu.pk (A. Farooqi).

https://doi.org/10.1016/j.chemosphere.2020.126374
0045-6535/© 2020 Elsevier Ltd. All rights reserved.
2 A. Malik et al. / Chemosphere 251 (2020) 126374
1. Introduction
Globally, a high concentration of arsenic (As) in groundwater
has become an issue of serious concern in recent decades. High
levels of As in ground water are derived from the ubiquitous vol-
canic rocks and As-rich mineral deposits (McArthur et al., 2004;
Bauer and Blodau, 2006). It has long been found in drinking water
supplies, such as Vietnam (Hoang et al., 2010; Lawati et al., 2012),
Cambodia (Berg et al., 2007; Lawson et al., 2013), India (Chakraborti
et al., 2008; Kumar et al., 2010), Bangladesh (Halim et al., 2009;
Neumann et al., 2009; Jiang et al., 2013) China (Guo et al., 2014; Zhu
et al., 2015), Mongolia (Guo et al., 2011), Nepal (Gurung et al., 2005),
Taiwan (Nath et al., 2008), Pakistan (Farooqi et al., 2009; Rasool
et al., 2016;Fatima et al., 2018 Mushtaq et al., 2018; Van Geen
et al., 2019), Latin America (Bundschuh et al., 2008, 2009; Nicolli
et al., 2010) and USA (Kim et al., 2011; Inamdar et al., 2012).
Dissolved Organic Matter (DOM) in groundwater plays a vital
role in the biogeochemical mobilization of As from sedimentary
environments to groundwater (Mladenov et al., 2010). DOM
(0.45 mm) in-ground and surface waters is a blend of heterogeneous
compound consisting of humic acids (HA), fulvic acids (FA),
aliphatic compounds, carbohydrates and proteins (Her et al., 2003;
Baker and Spencer, 2004). DOM serves as a carbon source Her et al.,
2003for the stimulation of microbially assisted reductive dissolu-
tion, particularly As adsorbed on Fe/Mn oxide minerals ensuring
the release of As3þ in the aqueous phase (Guo et al., 2019). Other
DOM involving processes such as complexation, competition and
electron shuttling also promote the As release (Gorny et al., 2015).
Reactivity of DOM strongly influences As mobilization (Guo
et al., 2019) depending on the source material. DOM source can
be internal (sedimentary type) such as buried peat, animal burrows
and microbially treated substances, or external (surface materials)
such as recharge from ponds, wetlands and anthropogenic activ-
ities percolating into the aquifers that provide an easy source of
degradable or labile DOM for the As mobility (Neumann et al.,
2009; McArthur et al., 2004; Lawson et al., 2013). Primitive sour-
ces of DOM, existing in buried peats, likely encountered a long
history of inclusion and utilization in metabolic procedures since
their deposition. Such metabolic handling may offer a less receptive
leftover organic matter with sluggish rates of As mobilization in the
groundwater (Tareq et al., 2013; Anwar et al., 2013). Conversely, a
young surface-inferred organic matter brought into the subsurface
are rarely involved in metabolic procedures, suggesting a higher
reactivity source of organic matter that may boost the rate of As
discharge (Postma et al., 2012).
Studies have demonstrated that surface- (terrestrial) derived
DOM fortify the indigenous microbial group that utilizes DOM as an
electron donor for respiration and prompt more noteworthy rates
of As discharge into groundwater (Reza et al., 2010; Guo et al.,
2014). Due to the heterogeneous nature of DOM, it contributes in
several processes, for example, refractory organic matter triggers
the As release in water by creating the water-dissolvable complexes
or forming As and DOM complexes either by positively charged
amino groups (-NHþ) or by metal cation bridges, prompting the
blockage of As sorption on metal-rich mineral surfaces ( Li et al.,
2019). In addition, the competitive sorption of As mediated by
dissolved humic substances were negatively charged DOM acts as a
rival for As at sorption sites, thus enhance the As mobility from soil
to water (Sahoo and Mukherjee, 2015; Gorny et al., 2015). More-
over, the DOM, which functions as an electron shuttle, alters the
redox chemistry of site surfaces and As species potentially lead
towards the As discharge in water (Mladenov et al., 2015).
The role and source of DOM for As mobilization has been
assessed by different incubation experiments (Bauer and Blodau,
2006; Neumann et al., 2014), and spectroscopic characterization
(Huang et al., 2012; Mladenov et al., 2015; Li et al., 2019) in various
parts of the world, not a single research has been done in the Indus
plain of Pakistan, one of the worst arsenic impacted zones in the
south Asian region, particularly to examine the DOM origin and its
role in As mobilization.
Pakistan is confronted with a grim threat to public health due to
the intake of As polluted water. High As groundwater has widely
been reported in Sindh and Punjab provinces with concentrations
reaching up to 1900 mg/L (Nickson et al., 2000; Farooqi et al., 2007a;
Mushtaq et al., 2018; Ali et al., 2019; Van Geen et al., 2019). Nickson
et al., 2000 reported 906 mg/L of As in its groundwater from one of
the districts in north Punjab (Muzaffargarh) of Pakistan. The au-
thors declared that Indus alluvial plain is the hot spot of As
enrichment. Continuous intake of As polluted water causes sick-
nesses such as black foot disease, cancer (skin, stomach, bladder), as
well as coronal heart diseases (Tareq et al., 2010).
In Pakistan, numerous studies have been conducted on As
concentration in groundwater and soil. As mobility under both oxic
and anoxic conditions is observed. Authors (e.g., Farooqi et al.,
2007a, b; Fatima et al., 2018) proposed that As seeps to underly-
ing aquifers from the sediments through the oxidation of pyrite
minerals or the reduction of FeOOH adsorption that alters the redox
potential of the groundwater. Mushtaq et al. (2018) reported that a
major As release mechanism is the desorption of As from metal
surfaces under alkaline conditions. These studies suggest that the
release process might be mediated due to the presence of DOM,
which eased the mobility of As by complexation or competitive
sorption. Not only the amount of DOM but also the source
(aromaticity and reactivity) of DOM are vital factors that control the
As release in groundwater. Identification and characterization of
DOM to elucidate whether it is sedimentary, or terrestrial is of
greater significance. In Pakistan, such studies have not been con-
ducted in the past that investigate the source of DOM for the As
mobilization.
Aims of the study are (1) to determine the As and DOC con-
centrations at varying depths in groundwater, (2) characterize the
nature of DOM in groundwater to reveal its source, and (3)
comprehend the role of DOM on mobilization mechanism of As.
The study will enhance our understanding of the As release
mechanism, will help the government for future planning in the
installation of tube wells for drinking water, and for public health
workers for mitigation purposes.
2. Study area description
The study area is located on a flat alluvial plain along the east
bank of the Ravi River, Lahore (between 31150 -31450 N and 74 010 -
74 390 E), Pakistan (Fig. 1). Lahore is the second largest city of
Pakistan after Karachi with a population of more than 6 million.
Major sources of groundwater recharge for Lahore are rainfall and
River Ravi that contribute to the groundwater aquifers. The average
rainfall is at the order of 575 mm per year, but this can vary from
300 to 1200 mm, which annually accounts for more than 40% input
to the groundwater recharge. About 40 mm groundwater recharge
per annum is contributed from rainwater in monsoon season (June
to September). The remaining recharge supply is fulfilled by the
Ravi River (Mushtaq et al., 2018). River Ravi originates from the
Himalayas in Himachal Pradesh, India, flows through northwestern
India into northeastern Pakistan, streams through Lahore via
Jammu and Kashmir, and finally discharges into the Chenab River
(Fig. 1).
The Lahore aquifer is composed of unconsolidated alluvial soil of
quaternary age. Sediments deposited in this aquifer are mostly
sand, comprising a high proportion of fine sand and silt that has
 A. Malik et al. / Chemosphere 251 (2020) 126374
Fig. 1. Location and Geographical map of study Area in District Lahore, Pakistan.
been derived by the ancestral streams of the Holocene and
Pleistocene-Recent periods (Green and Blough, 1994; Farooqi et al.,
2007a,b). Chief constituent minerals of the sediments are quartz,
muscovite, biotite, clay, and chlorite in association with a small
ratio of heavy minerals. Clay and sand on the edges of the aquifer’s
depression can accelerate the seeping of saline water from sur-
rounding areas to the aquifer. The aquifer under and around Lahore
city is about 400 m deep with a high transmission rate of about
2100 m2/day and hydraulic conductivity varies from 25 m/day to
70 m/day (Ahmed et al., 2011).
3. Materials and methods
3.1. Sample collection
Total groundwater samples (n ¼ 60) from the hand pump and
bore wells at various depths (from 20 to 90 m) and soil (n ¼ 15)
samples (10 cm depth from the surface) were collected at six sites
(Fig. 1) along the flood plain of the Ravi River, Lahore, Pakistan.
Spatial distribution of collected samples (recorded via handheld
GPS: HC Garmin) is shown in Fig. 2. Before sample collection, each
water source was purged for >5 min. All water samples were
filtered through Whatman filter paper No. 0.42 mm and stored in
3
250 mL polyethylene bottles that were rinsed and soaked twice
with double deionized water before use. The duplicate sampling
strategy was adopted for groundwater samples. One set of samples
was used for cations and trace metals analysis (Fe, Mn, As), by
adding 2 to 3 drops of HNO3 to bring the pH of the samples less than
2. The second set of samples was preserved without acidification
and used for anionic analysis including NO 3 and PO4
3
(APHA,
2005). Samples used for dissolved organic carbon (DOC), Fluores-
cence excitation-emission matrix (F-EEM), and Fourier-transform
infrared spectroscopy (FTIR) were first filtered at the field with
0.45 mm filters in amber glass bottles (Reza et al., 2010). Amber glass
bottles were pre-combusted for 4 h at 300  C to eliminate organic
material contamination. After filtration, samples were capped
tightly and retained in dark to avoid the occurrence of unenviable
photochemical reactions (Tareq et al., 2013).
Soil samples were collected in polyethylene bags and were used
for minor element analysis (As, Fe, Mn, Ni, Co, Ca, Zn, Pb), total
organic carbon (TOC) and C13 isotope. Samples were kept in cold
and dry box and transported to Isotope Application Division Lab,
Pakistan Institute of Nuclear Science and Technology (PINSTECH),
Islamabad for chemical analysis. Soil samples were pre-processed
in the laboratory before final analysis. They were dried in an oven
at 110e120  C, crushed, and sieved with 200 mesh size in the
4 A. Malik et al. / Chemosphere 251 (2020) 126374
Fig. 2. Spatial Distribution of Arsenic in selected villages along River Ravi transect.
laboratory to remove materials >2 mm in size (Farooqi et al., 2009).
For trace metal analysis soil samples were digested according to the
protocol followed by Nicolli et al. (2010), using 1:1 HNO3 and H2O2.
3.2. Analysis
In groundwater, pH, electrical conductivity (EC) and total dis-
solved solids (TDS) were measured in-situ using a portable HANNA
instrument that was calibrated before use. The alkalinity was done
via the titrimetric method (APHA, 2005), after immediate trans-
portation of the samples to the hydro-geochemistry laboratory of
the Environmental Sciences Department, Quaid-i-Azam University,
Islamabad. Concentrations of major anions Cl, SO2 3
4 and PO4 were
analyzed by DIONEX-500 Ion Chromatography. While NO 3 was
analyzed by Potentiometric Ion selective electrode (ISE) (Oakton
Ion 5, Acron series). Analyses for major cations (Naþ, Kþ, Mg2þ,
Ca2þ) and heavy elements (Fe, Mn, Ni, Co, Zn, Cu, and Pb) were
performed on high-resolution Inductively Coupled Plasma Mass
Spectrometer (ICP-MS) (7500C, Agilent) at Isotope Application Di-
vision Lab, PINSTECH Islamabad. Instead of ORP, which was not
possible due to the non-availability of freshwater at some house-
holds, proxy parameters such as NO3, SO4, Fe and Mn were done.
Elemental concentrations (e.g., Ni, Co, Zn, Ca and Pb) were
determined from soil samples only. The concentration of NHþ 4 was
determined by UVeVisible Spectrophotometer (DR-5000, HACH).
Arsenic concentration in groundwater was detected by using
continuous flow hybrid generation atomic flame spectrophotom-
eter (AI-3200 series, Aurora), while As in soil samples was analyzed
by Inductively Coupled Plasma Optical Emission Spectrometer (ICP-
OES) (iCAP6000, Thermo) at Isotope Application Division Lab,
PINSTECH. Before analysis the instrument was calibrated and
detection limit, provided at as the footnote in tables was calculated
according to the levels prescribed by APHA (2005).
Dissolved organic carbon (DOC) in groundwater samples was
analyzed by high-temperature catalytic oxidation method with a
TOC 5000 Analyzer (Shimadzu, Japan). All essentials were acidified
to pH 2 with 6 M HCl and then passed from CO2-free carrier gas for
10 min at a flow rate of 100 mL/min to remove inorganic carbon
before injection. The sample injection frequency was 4e5 times
and the average standard error for all samples was within 5%.
 A. Malik et al. / Chemosphere 251 (2020) 126374 5

In soil samples, the TOC was calculated through the facile pro-
cedure of the Walkley-Black method that reduces the potassium
dichromate (K2Cr2O7) by organic (carbon) compounds, followed by
the measurement of unreduced dichromate titration with ferrous
sulfate (FeSO4) (Walkley, 1947).
TOC ð%Þ ¼ 3ð1  T = SÞ=W
3.3. Geo-statistical analysis
Geographical locations of the sampling sites, marked on Google
Earth, are shown in Fig. 2. Basic mathematical and descriptive
statistical analyses were performed on SPSS Statistics 20 and
XLSTAT-2017. Pearson correlation coefficient, graphical represen-
tations of groundwater and soil parameters, contour plots of F- EEM
and FTIR spectra were drawn using Origin Pro 8.5.

Where the terms T, S, and W are the volume of FeSO4 (ml) used in a
titration, the volume of FeSO4 in blank, and weight of the dried
sample, respectively.
To measure the aromaticity and SUVA254 at a wavelength of 254
of samples, a UVeVisible Spectrophotometer (DR-5000, HACH) was
used, following the procedures of Routh and Grossman (2001). The
Fluorescent character of samples was measured by Fluorescence
Spectro-photometer (F-4500-Hitachi, Japan) with excitation and
emission slit of bandwidths of 10 nm, scanning speed of 500 nm/
min, and excitation (Ex) was 250e400 nm with an emission scan-
ning range of 300e520 nm. Average fluorescence intensities were
obtained by scanning each sample three times following the
method of Tareq et al. (2013). Instrumental calibration, before
analysis, was done by checking the Raman peak of ultra-pure water
at 340 nm. Ultra-pure water was also used for the blank analysis. To
reduce the effect of Raman scattering, the EEM response to ultra-
pure water was subtracted from the fluorescence spectra (Singh
et al., 2013).
Fourier Transform Infra-Red (FTIR) analysis of the soil samples
was conducted after the method of Reyes and Crisoto (2016), using
the Nicolet 370 FTIR spectrometer which was equipped with DTGS
detector and KBr beam splitter. Samples were then sent to the
isotopic division of PINSTECH for d13C stable isotope measurement
by Isotope Ratio Mass Spectrometer (IRMS: Delta Plus-V, Thermo
Scientific) following the procedures of Cawley et al. (2012). d13C
stable isotope analysis was done for soil samples only to charac-
terize the TOC.
4. Results and discussions
4.1. DOM and groundwater chemical characteristics
Physiochemical data, As and DOC concentrations and their
depth profiles for all the groundwater samples are summarized in
Table 1 and Table 2, respectively. Groundwater samples from the
selected six sampling sites (Northern Villages: Bhadru, Gopi Rai,
Amarkot; Southern Villages: Khudpur, Samada and Ludhreutar) have
As concentration in the range between 9.61 mg/L and 386 mg/L with
98% of the samples are above WHO permissible limit (10 mg/L) and
24% samples exceeding national drinking water quality standard
(50 mg/L). The maximum concentration of As (386.09 mg/L) is
detected at Khudpur with its 95% samples exceeding WHO
permissible levels. High concentrations (usually >100 mg/L) of As
are potentially observed in all the villages except in Amarkot
(average observed value: 21 mg/L). Areas lying closer (Khudpur) to
the Ravi River showed higher As compared to those located away
(Amarkot) from the river (Fig. 2). Remoteness or nearness of the
area from the river causes the As concentrations to fluctuate. Areas
located away from river showed less As in groundwater than those
lie closer to the river (Farooqi et al., 2007a; Rasool et al., 2015;
Fatima et al., 2018). Mushtaq et al. (2018) detected even higher As
concentrations (548 mg/L) in groundwater of Kot Maiga as the area
under their research is more proximal to Ravi River and adjacent to
the present study area.

Table 1
Descriptive statistics of physio-chemical parameters of groundwater samples of current area.

Statistics Well pH EC (mS/ TDS Na⁺ K⁺ Ca⁺2 Mg⁺2 HCO₃⁻ Cl⁻ SO₄⁻2 PO₄⁻3 NO₃⁻2 As0 Fe Mn
Parameters (Units) Depth (m) cm) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (ug/L) (mg/L) (mg/L)

WHO e e 6.5 1500 600 200 12 100 50 e 250 250 0.1 50 10 0.3 0.05
e9.2 e1000
Villages Bhadru Min. 31 7.1 346 221 22 4.0 41 8 67 9 14 0.04 2.5 20.1 0.3 bdl
(N¼07) Max. 46 8.1 1025 656 50 13 136 28 590 71 114 0.06 3.3 121.1 1.2 0.5
Mean 38 7.7 583 373 35 7.6 69 16 272 30 54 0.05 2.8 50.4 0.3 0.2
SD 7.4 0.4 258 165 10 4.0 36 8 196 26 33 0.008 0.4 34.3 0.5 0.2
Gopi Rai (N¼ Min. 18 7.1 361 231 26 2.5 21 10.5 187 7.3 20 0.02 2.5 22.4 bdl bdl
15) Max 229 8.2 1606 1028 475 11 107 59 968 444 273 0.4 3.4 132 1.6 0.5
Mean 61 7.6 1038 665 210 6.1 70 31 537 181 99 0.06 2.9 60.9 0.4 0.2
SD 51 0.31 490 314 147 2.5 30 16 257 137 61 0.1 0.3 33.6 0.5 0.2
Amarkot Min 27 7.6 426 273 14 4.1 38 24 227 1.2 27 0.01 2.1 16.2 bdl bdl
(N¼06) Max 55 8.1 813 520 45 48 77 52 432 28 83 0.1 3.8 31.9 bdl 0.2
Mean 44 7.9 662 424 27 13 56 39 353 15 48 0.04 3.0 21.3 bdl 0.03
SD 12 0.2 154 98 12 17 15 10 90 10 19 0.04 0.7 6.0 bdl 0.1
Min 21 7.1 410 262 19 3.4 35 17 215 15 29 0.02 0.1 9.6 bdl bdl
Khudpur Max 61 8.0 1690 1082 220 32 166 62 732 251 209 0.2 3.6 386.1 1.2 0.7
(N¼16) Mean 30 7.5 1044 668 125 16.2 84 34 494 90 114 0.1 2.61 89.9 0.3 0.2
SD 10 0.3 364 233 61 11 32 11.5 159 64.5 54 0.04 1.02 131 0.4 0.2
Lodh-reutar Min 31 8.1 1298 831 236 3.8 8.2 7 733 67 172 0.1 2.5 18 bdl bdl
(N¼03) Max. 46 8.6 2400 1536 681 9.5 58 46 1254 123 314 1.7 3.1 237 0.2 0.06
Mean 36 8.3 1714 1097 433 6.8 30 26 930 934 239 0.7 2.9 160 0.1 0.03
SD 8.8 0.2 598 383 227 2.9 25 19 283 28 72 0.9 0.3 123 0.1 0.2
Samada Min 24 7.9 710 850 62 3.7 4.5 1 150 71 27 0.1 2.4 15 bdl bdl
(N¼10) Max. 76 8.7 2760 1470 616 9.3 26 24 660 248 358 0.7 4.4 136 bdl 0.04
Mean 46 8.2 1788 1219 338 6.2 13 10 367 153 210 0.3 3.4 71 bdl 0.01
SD 17 0.2 770 1072 200 2.3 7.8 8.5 180 64 153 0.25 0.8 423 bdl 0.1

Bdl ¼ below detection limit Detection limits for As ¼ 2 mg/L, NO3 ¼ 0.1 mg/L, PO3
4 ¼ 0.01 mg/L, Fe ¼ 0.01 mg/L, Mn ¼ 0.025 mg/L.
6 A. Malik et al. / Chemosphere 251 (2020) 126374

Table 2
Descriptive statistics of DOC, UVA, SUVA, Fluorescence Intensities and FI in groundwater samples and d13C in soil samples of current study.

Statistics DOC (mg- UV254 (1/ SUVA (L/ Fluorescence-Excitation Emission Matrix Intensity (R.U) TOC Soil-d13C
Parameters C/L) cm) mg.m) (%) (‰)
Protein-I Protein-II Humic-like Humic-like Humic-like Fulvic Acid FI
270nm/ 270nm/ 260nm/ (microbial) (terrestrial) (390nm/
306 nm 340 nm 450 nm 300nm/390 340nm/440 510 nm)
(Peak B) (Peak T) (Peak A) nm (Peak M) nm (Peak C) (Peak D)

Villages Min. 2 5.1 0.6 64 92 276 299 167 2.5 0.6 2.3 e
Bhadru Max. 4.1 17.5 6.1 79 124 334 316 206 3.6 1.2 2.6 e
(N¼05) Mean 3.4 11.2 3.5 72 98 305 307 186 0.5 0.9 2.5 26.28
SD 0.9 4.7 2.3 10.5 1.4 41 12 27 4.3 1 0.2 e
Min. 0.9 4.3 0.4 38 58 181 137 70 24 0.6 3.9 20.97
Gopi Rai (N¼ Max. 9.7 51 8.1 107 187 422 349 223 8.4 1.1 5.1 26.8
13) Mean 5.7 12.7 2.0 64 96 283 209 121 15.8 0.8 4.2 24.03
SD 2.8 15 2.5 30 56 97 86 59 7.1 0.9 0.6 2.92
Min. 4 4.1 0.4 e e e e e e 0.9 e e
Amarkot Max. 10 9.4 2.3 88.92 69.80 51.59 60.51 52.44 35.64 1.7 2.1 e
(N¼05) Mean 6.3 6.263 1.3 e e e e e e 1.4 e e
SD 2.7 2.147 0.82 e e e e e e 1.3 e e
Min. 0.0 0 0 30.4 94 489 330 311 33.6 0.8 3.9 e
Khudpur Max. 7.5 28 16 61 158 950 913 950 238 1.3 4.9 e
(N¼11) Mean 4.0 9.5 3.5 49.5 123 702.3 541 534 96 1 4.4 26.7
SD 2.5 8.0 4.7 13.1 24 166 236 244 81.4 0.9 0.5 e
Min. 0.3 0 0.2 39.3 76 197 144 120 6.7 1.2 2.3 24.68
Lodhre-utar Max. 5.9 6.1 1.4 67.1 119 377 443 254 19 1.9 2.6 25.09
(N¼03) Mean 1.9 3.8 1.1 53 104 267 253 173 2.5 1.5 2.4 24.89
SD 3.4 3.3 0.9 14 25 97 165 71 14.1 16 0.2 0.29
Min. 0.2 0 0 33.7 51 87 89 86 29.2 0.8 3.5 24.5
Samada Max. 10 15.4 2.6 112 181 242 508 241 0.8 1.5 3.8 26.74
(N¼08) Mean 4.4 6.9 1.5 83.4 135.5 190 254 156 12.13 1.3 3.6 25.63
SD 3.8 4.52 1.0 43.2 73.4 89 233 79 15.1 1.32 0.2 1.57

The variation in As levels in all the groundwater samples mostly
exhibited at depths between 20 and 90 m with an exception at
220 m (Fig. 3a). Deep aquifer (>100 m) shows the negligible
amount of As, excluding a sample from Gopi Rai. Water in the deep
aquifer is less affected with As as compared to the shallow alluvial
aquifer, also observed in past studies (Tareq et al., 2013; Fatima
et al., 2018). The overall behavior of As within villages observed to
be inconsistent as bore-wells having As concentrations greater than
50 mg/L was present in close proximity to wells that showed lower
values (<50 mg/L), as observed in Khudpur and Gopi Rai. Existence of
low As intervening zones between high As zones are typically
associated with aquifers present in alluvial flood plains (Kumar
et al., 2010; Guo et al., 2011) that are potentially safe wells for
drinking water in As-affected areas.
The DOC content in all the groundwater samples ranged from
0 to 10 mg-C/L (Table 2). The detected values are higher than
commonly found DOC values (<1.0e3.0 mg-C/L) in groundwater
(Anwar et al., 2013), but coherent with earlier studies (Kim et al.,
2011; Guo et al., 2014). No systematic pattern of DOC distribution
was witnessed in the entire study area. Deviations depending on
the depth and locations of the sampling site are also observed in the
concentrations of DOC (Fig. 3b). This may suggest the prevalence of
varying conditions, soil type and diversified source of DOC in the
study area (Mladenov et al., 2015; Yates et al., 2016). The DOC
concentrations are maximum at Gopi Rai and Amarkot showing a
range of 0.9e9.7 mg-C/L, 4-10 mg-C/L with 40% and 80% ground-
water samples above 5 mg-C/L, respectively. The overall same trend
for DOC concentrations was observed in all the villages, as of As,
exhibiting the active variation at the depths of 20e70 m. DOC
content was negligible in the deeper aquifer (>100 m), indicating

Fig. 3. Vertical depth profile of (a) As (b) DOC in study area.

 A. Malik et al. / Chemosphere 251 (2020) 126374
the recent recharge of DOM in the upper (shallow) aquifer
(<100 m) was possibly from terrestrial sources which are discussed
in detail in next sections. DOC distribution in groundwater usually
depends on various processes, i.e., DOC sorption on mineral phases
(Schwesig et al., 2003; Scott and Rothstein, 2014), competition
(Bolan et al., 2011), biotic uptake (Kaiser and Kalbitz, 2012; Zhu
et al., 2015), surface precipitation (Shen et al., 2015) and complex
formation ( Sahoo and Mukherjee, 2015). Soil with higher organic
matter contents generate competitive environment for the limited
available binding sites on soil colloids, ultimately inhibiting the
DOM sorption (Lilienfein et al., 2004), whereas increased levels of
Fe, Mn and Al oxide facilitate DOM sorption on mineral surfaces
(Scott and Rothstein, 2014). Previous studies indicated that DOM
reacts with mineral phases when it percolates, along with rain-
water, on its way to the groundwater, eventually form complexes
and mobilize other elements such as As (Shen et al., 2015) or seep
with minor interaction in case of rapid flow (Bolan et al., 2011;
Kaiser and Kalbitz, 2012). As the study area is situated on an alluvial
floodplain, where rainfall and River Ravi are the major sources of
groundwater recharge. So, the vertical variation of DOC content
may depend on river flow and rainfall period, as reported in other
studies (Cawley et al., 2013; Shen et al., 2015; Kulkarni et al., 2017).
Alluvial floodplains have high flow periods that result in increased
concentrations of DOC along with aromatically dominated down-
stream DOM pool observed (Schwesig et al., 2003; Bolan et al.,
2011; Chiu et al., 2019). The saturated inland water flow con-
strained the soil sorption, competition and biotic uptake (Asano
et al., 2006; Castellano and Kaye, 2009), eventually these DOC
retentive processes cause the chemical modification in DOM as it
percolates downward (Schwesig et al., 2003; Kaiser and Kalbitz,
2012). Soil column from which DOM is leached to the saturated
zone alters both the concentration and composition of DOM (Bolan
et al., 2011; Kaiser and Kalbitz, 2012).
Overall TOC ranged from 2.1 to 5.1% in the studied samples
(Table 2). The soil of Khudpur and Gopi Rai is TOC-rich among the
investigated samples at other sites, while samples at Amarkot were
TOC-poor. Our study shows low TOC contents in the studied sam-
ples than observed elsewhere (Reza et al., 2010), suggesting
rigorous agricultural practices that naturally lower the TOC content
of soil (Ahmed et al., 2011). Previous studies also directed that
cropland usually has the least TOC content than the forestland or
grassland, mainly due to the vegetation type and litter quantity
(Bolan et al., 2011; Li et al., 2019). Though, < 0.16 ppb of As content
found in all the soil samples, which is lower than the typically
observed values (Halim et al., 2009; Hoang et al., 2010). The reason
may be the depth (10 cm) from which the samples were collected.
Arsenic content in soil usually increases with depth, depending on
its source, soil type and mineralogy (Lawati et al., 2012; Guo et al.,
2014). TOC (%) does not correlate well with As (mg/L) in ground-
water samples (Fig. 4), except in Khudpur area where the TOC
content increases with the rise in As concentration. Gopi Rai
showed more TOC in soil with least As concentration in the same
well. Wells with As < 150 mg/L usually contained more TOC content
except in Ludhreutar. This indicates that TOC likely enhances the As
mobilization from sediments to the solution, thereby enabling As to
leach into the groundwater by desorption or due to a change in the
redox potential of As and mineral phases (Reza et al., 2010).
4.2. Arsenic mobilization and its relationship with other redox
parameters (Fe, Mn, SO4, NO3 and PO 4)
All the groundwater samples exhibit neutral to weakly alkaline
pH ranging from 7.1 to 8.7 (average ¼ 7.9) with maximum pH value
recorded in Samada and Ludhreutar. Variable pH in the study area
showed different redox conditions. High pH of groundwater plays
7
Fig. 4. TOC (soil) and As (groundwater) in study area.
an important role in As release as it controls the adsorption and
desorption of As from mineral oxide surfaces (Farooqi et al., 2009;
Fatima et al., 2018). Other parameters, such as EC (values between
346 and 2760 mS/cm) and TDS (values between 221 and 1770 mg/L),
of groundwater samples showed significant variation with the
highest observed value of EC in Samada followed by Ludhreutar.
High pH and EC of groundwater means an alkaline environment
that favors the As release from mineral bounds under oxidizing
conditions or may initiate the As desorption from FeOOH (Farooqi
et al., 2007a, b; Qurat-ul-Ain et al., 2017). Farooqi et al. (2009), in
another study, highlighted that extensive use of fertilizers increases
the pH and EC of soil in east Punjab, Pakistan which fastens the As
release from soil particles to the shallow groundwater. TDS and EC
are well-correlated and interconnected (r2 ¼ 1.00), an increase in
one causes a simultaneous increase of the other as a result of ion-
exchange (Bundschuh et al., 2008; Rasool et al., 2015). A gradual
increase in EC and TDS from the northern side of the study area to
the southern side possibly indicate the effect of evaporation (Ali
et al., 2019), since Naþ and Cl ions are found as major cation and
anion in the study area, also observed by Mushtaq et al. (2018).
The Naþ (13e681 mg/L) ion was the major cation while HCO 3
(67e1254 mg/L) and Cl (7e443.6 mg/L) were the major anions in
groundwater samples. Higher HCO 3 concentrations, found
throughout the study area, could be due to the organic matter
oxidation and carbonate dissolution (Kar et al., 2010). High HCO 3
ions in groundwater induce the alkaline pH (Rasool et al., 2015) as
well as the DOM as a dynamic source for HCO 3 in groundwater
under low redox conditions (Jiang et al., 2013). The presence of
HCO 3 in groundwater at high pH further enhances the desorption
process of As due to competitive sorption (Smedley and
Kinniburgh, 2002; Kim et al., 2011). Concentrations of SO2 4 var-
ied between 14 and 358 mg/L with maximum values measured at
Samada (average: 210 mg/L), followed by Ludhreutar. Most
groundwater samples from the northern part of the study area
contain SO24 within the WHO recommended limit. An increased
concentration of SO2 4 in southern part may indicate the fact that it
could be due to the poor drainage system of domestic waste or due
to the increased use of fertilizers for agricultural activities as re-
ported in other studies (Farooqi et al., 2007a, b; Fatima et al., 2018).
NO3 varies between 0.1 and 4.41 mg/L, with the highest values at
Samada, however, the NO 3 in the entire samples were within the
recommended value of WHO. Mostly groundwater samples of the
8 A. Malik et al. / Chemosphere 251 (2020) 126374

northern part contain PO3 4 within the WHO limit. Overall PO4
3
ranges from 0.01 to 1.7 mg/L. Samples from Samada and Ludhreutar
exhibit increased concentrations, which may be due to the exces-
sive use of phosphate fertilizers, and agricultural run-off (Anwar
et al., 2003). It is possible that agricultural activities, such as the
use of fertilizers and crop residuals potentially increase the phos-
phate concentrations in groundwater as observed elsewhere (Li
et al., 2019). PO3 3þ
4 behaves like that of As , it strongly competes
with As, ultimately takes its place and adsorb on metal oxide sur-
face under alkaline conditions (Halim et al., 2009; Sahoo and
Mukherjee, 2015). A moderately positive correlation of As
 2
(Table 3b) with PO3 4 and HCO3 (r ¼ 0.39 and 0.37), respectively, in
southern part of the study area, may suggest the occurrence of
competitive desorption behind the As release, as it is also observed
by other researchers in the nearby areas (Farooqi et al., 2007a;
Mushtaq et al., 2018) and other parts of the world (Kim et al., 2011;
Nicolli et al., 2010). Another promising feature observed in the
study area is the slight positive correlation of As with DOC
(r2 ¼ 0.33). The values of DOC in this southern side of the study area
are >3 mg-C/L. It may be suggested that high concentrations of

PO3
4 , HCO3 and DOM possibly enhance the desorption, wherein, As
desorbs due to the competition for adsorption sites on mineral
oxide surfaces (Halim et al., 2009; Bhattacharya et al., 2014). As in
the southern part of the study area does not exhibit a significant
correlation with Fe (r2 ¼ 0.30) and Mn (r2 ¼ 0.10).
Concentrations of Fe (bdl-1.6 mg/L) and Mn (bdl-0.7 mg/L)
varied and both exceed the WHO recommended limits. Fe and Mn
contents were negligible in Amarkot and Samada, and the values
exhibit a decreasing trend from northern to the southern side,
possibly controlled by geomorphological change within the study
area (Tareq et al., 2013; Mladenov et al., 2010). As content in
groundwater exhibits a moderately positive correlation with DOC
(r2 ¼ 0.49) and Fe (r2 ¼ 0.41) (Table 3a) in the northern side of
villages than on the other side which showed r2 ¼ 0.33 and
r2 ¼ 0.32, respectively. In contrast, Mn and As do indicate identical
correlation, i.e., r2 ¼ 0.31 in northern side. The positive correlation
of As with DOC and Fe, especially in northern part, denotes
adsorption of As on Fe(oxy)hydroxides and consequently,
microbially-assisted reductive dissolution of FeOOH in the presence
of DOM plays an essential role for As release in groundwater
(Mladenov et al., 2010; Ali et al., 2019). This mechanism of As
release is also proposed by numerous researchers in different parts
of the world (Lawati et al., 2012; Guo et al., 2014). The less signif-
icant positive correlation between As and Mn indicate that pro-
cesses which involve As, Fe and Mn mobilizations probably show
decoupling since Mn re-precipitates ensuing the reductive disso-
lution of iron/manganese hydroxides whereas the released As re-
mains in groundwater (Reza et al., 2010). The fact is further

supported by the detection of low levels of SO2 2
4 (r ¼ 0.028), NO3
2 3 2
(r ¼ 0.123) and PO4 (r ¼ 0.075). Furthermore, no correlation
was observed among the above oxides and As, particularly in the
northern side of villages. Based on these facts, we presume that
neutral to slightly alkaline pH, strong positive correlation of As with
DOC and Fe could be the main cause of arsenic release in Bhadru
and Gopi Rai as an outcome of reductive dissolution of Fe- and Mn-
(oxy) hydroxides (Mladenov et al., 2010; Anwar et al., 2013; Gorny
et al., 2015). Whereas, in Amarkot the dissolved Fe might have been
re-precipitated as FeCO3 (siderite) under low redox conditions,

Table 3(a)
Pearson correlation coefficient matrix of physio-chemical parameters of groundwater with Arsenic in villages Bhadru, Gopi Rai and Amarkot (N ¼ 28).
SO2 PO3 NO2
Variables Depth pH EC TDS Na HCO3 Cl 4 4 3 As Fe Mn DOC

Depth 1
pH ¡0.76 1
EC 0.337 ¡0.606 1
TDS 0.337 ¡0.606 1.000 1
Na 0.078 0.428 0.503 0.503 1
HCO3 0.130 0.404 0.463 0.463 0.879 1
Cl 0.020 0.436 0.470 0.470 0.941 0.81 1
SO4 0.169 0.319 0.323 0.323 0.833 0.69 0.827 1
PO4 0.137 0.213 0.169 0.169 0.26 0.066 0.026 0.063 1
NO3 0.035 0.043 0.173 0.173 0.066 0.008 0.011 0.067 0.037 1
As 0.020 0.171 0.209 0.209 0.227 0.212 0.301 0.028 0.075 0.123 1
Fe 0.056 0.147 0.096 0.096 0.182 0.169 0.142 0.018 0.168 0.106 0.41 1
Mn 0.060 0.230 0.212 0.198 0.117 0.169 0.031 0.161 0.021 0.024 0.31 0.552 1
DOC 0.340 0.192 0.043 0.043 0.223 0.218 0.217 0.290 0.180 0.101 049 0.03 0.063 1

Values in bold are showing a significance positive correlation with significant level 0.5.

Table 3 (b)
Pearson correlation coefficient matrix of physio-chemical parameters of groundwater with Arsenic in villages Khudpur, Ludhreutar and Samada (N ¼ 29).
SO2 PO3 NO2
Variables Depth pH EC TDS Na HCO3 Cl 4 4 3 As Fe Mn DOC

Depth 1
pH 0.485 1
EC 0.071 0.123 1
TDS 0.314 0.417 0.052 1
Na 0.032 0.336 0.786 ¡0.107 1
HCO3 0.353 0.066 0.319 0.633 0.558 1
Cl 0.105 0.008 0.615 0.221 0.708 0.297 1
SO4 0.159 0.311 0.707 0.158 0.901 0.438 0.724 1
PO4 0.083 0.371 0.014 0.269 0.147 0.247 0.106 0.102 1
NO3 0.330 0.427 0.033 0.402 0.243 0.032 0.241 0.216 0.140 1
As 0.007 0.074 0.036 0.228 0.102 0.37 0.057 0.056 0.39 0.133 1
Fe 0.218 0.208 0.244 0.136 0.162 0.169 0.035 0.098 0.065 0.026 0.30 1
Mn 0.071 0.098 0.124 0.056 0.069 0.044 0.101 0.159 0.002 0.012 0.10 0.07 1
DOC 0.118 0.221 0.175 0.116 0.204 0.064 0.341 0.267 0.135 0.201 0.33 0.15 0.07 1

Values in bold are showing a significance positive correlation with significant level 0.5.
 A. Malik et al. / Chemosphere 251 (2020) 126374
leading to the zero Fe in the groundwater (Acharyya and Shah,
2010; Guo et al., 2014; Kim et al., 2015). High pH (7.9), low SO2⁻
(48 mg/L) and NO 
3 (3 mg/L) along with moderate HCO3 (353 mg/L),
Mn (0.03 mg/L) and DOC (6.3 mg-C/L) values, particularly in
Amarkot, indicate incomplete reducing conditions that could
reductively dissolute As from Mn-oxide surfaces. This partial anoxic
condition in Amarkot might be the probable cause behind the ex-
istence of low levels of As (Bhattacharya et al., 2014; Ali et al., 2019).
4.3. DOM characteristics
Table 2 shows the SUVA254 of DOM of the investigated samples.
A large range of SUVA values are observed, i.e., from 0.0 to 16.2.
Khudpur and Gopi Rai exhibited the highest SUVA, i.e., 0e16.2 and
0.44e8.08, respectively, while Ludhreutar and Samada showed
lower ranges. Most groundwater samples from northern part of the
study area (including Khudpur) exhibited higher SUVA character
(>2), proposing higher aromaticity, consistent with other studies
(Lapworth et al., 2007; Zheng et al., 2014). Whereas, a few samples
from Amarkot behaved differently and exhibited SUVA value aver-
aging 1.3. While Ludhreutar and Samada displayed mixed source (of
DOM) with SUVA value < 2 but >1, similar to the study carried out
in Bangladesh (Tareq et al., 2013). SUVA holding the mixed source
of DOM usually suggests a contribution from both aromatic and
aliphatic DOM compounds (Cawley et al., 2013). The mixed source
represents both the allochthonous and autochthonous characters.
The fluorescence EEM Intensity (RU) data for six different fluo-
rescent components of DOM are presented in Table 2. However,
several peaks were observed for the whole study area (Fig. 5a, b, c,
d, e, f). Three major regions, i.e., Peak A, M and C which account
typically for different types of humic acid-like moieties (Palanti
et al., 2000), are found in abundance in almost all the villages
except Amarkot which showed minor peak. A broad peak M
assigned to marine humic acid-like moieties, possibly suggest mi-
crobial processing (Pan et al., 2017). They are usually characterized
as less hydrophobic compounds with low molecular weight (Bolan
et al., 2011; Shen et al., 2015). Both peaks A and C attributed to
humic acid-like and terrestrially derived humic-like substances,
indicating the presence of soil and terrestrial plant-derived DOC
compounds (Chiu et al., 2019). These compounds generally iden-
tified as hydrophobic in nature, having the high molecular weight
and aromatic structure. The right shift in Em wavelength signifies a
structural modification and increased aromaticity in the study area,
as supported by the previous literature (Pan et al., 2017; Chiu et al.,
2019) Khudpur and Bhadru showed maximum RU on these three
peak regions. Most samples from the entire study area exhibit
strong fluorescent intensity due to the humic acid-like substance
that might have formed from sediments by microbial oxidation of
sedimentary organic matter or from vertically infiltrated surface
plant-derived organic matter into the aquifer (Anwar et al., 2013;
Mladenov et al., 2015). Compared to other peaks, peak-D is minor in
the entire study area except in Khudpur. The fluorescence peak
around Ex/Em ¼ 390nm/510 nm (Peak-D) indicates a fulvic acid
character of the soil, commonly characterized as relatively low
molecular weight compounds, formed as a result of microbial
processing (Bolan et al., 2011). Weaker soil fulvic-like peak may
depict the reduced concentrations of phenolic and carboxylic
characters, i.e., aliphatic organic compounds (Tareq et al., 2013).
PARAFAC characterized DOM fluorescent properties into several
components, where Component C-1 represents microbial/terres-
trial fulvic-acid like fluorescent character (Pan et al., 2017).
Fulvicelike substances of DOM usually identified as more labile
components possibly being linked with microbial activity (Tye and
Lapworth, 2016; Chiu et al., 2019). Mladenov et al. (2015) reported
the decreased fulvic-like and protein-like fluorescence component
9
with lower FI in older groundwater samples, suggesting that aro-
4 matic and loganiaceous compounds are the source of DOM input in
the region, where microbial Fe reduction or mineral dissolution
causes the DOM and As mobilization from mineral phases (Bauer
and Blodau, 2006). Kaiser and Kalbitz (2012) stated that down-
ward cycling of DOM generally decreases the chances of low mo-
lecular weight compounds to seep at higher depths. Whereas Peak
B (Ex/Em ¼ 270nm/306 nm) and T (Ex/Em ¼ 270nm/340 nm)
typically belong to protein type, e.g., tyrosine (Anwar et al., 2013),
found in reasonable concentrations than that of a fulvic-like peak,
especially in the southern part of the study area, where it is
detected in medium concentrations. Typically, agricultural and
animal wastes are supposed as the main contributors of proteinous
character. Lapworth et al. (2007) investigated the source of DOM in
two groundwater aquifers, where they detected sheep waste as a
source of DOM in one aquifer while a terrestrial and microbial
mixed source in the other one. In the former case, agricultural
animal waste had high protein peak intensity (Chiu et al., 2019).
This is not unusual considering the hygiene situation of rural
Punjab, Pakistan, where animal waste is frequently dumped
directly into the water bodies (Farooqi et al., 2007b). Notably, the
lower observance of tyrosine-like moieties in the northern-side of
villages may be due to the small molecular size (hydrophilic in
nature) of protein-like substances that causes it to assimilate
instantly and release humic acid-like substances by micro-
organisms. Since the sanitation conditions are relatively better in
the northern part of the study area than in the southern part.
Amarkot showed the least As and fluorescence content intensity at
all recorded Ex/Em wavelengths among all the villages, suggesting
the area is less polluted and less impacted (Cawley et al., 2013).
The fluorescence intensity of humic-like peak for the northern
side villages and the southern side villages range from 51.59 to 422
RU (nm1) and from 87 to 950 RU (nm1), respectively. Northern
side villages show a stronger positive correlation (r2 ¼ 0.78,
p ¼ 0.0001) between fluorescence intensity and DOC (Fig. 6a).
Southern side of the study area also exhibit good correlation, i.e.,
r2 ¼ 0.57, p ¼ 0.004 (Fig. 6b), indicating that most of the DOC in
groundwater is mainly composed of humic substances, i.e., aro-
matic organic compounds, along with minute presence of soil fulvic
acid and with some proteinous character at some sites. It is sug-
gested that terrestrially (sedimentary) derived DOM may be the
dominant type with some sites exhibiting a mixed character (Tareq
et al., 2013; Mladenov et al., 2015). In general, variation in the
fluorescent character in the study area is consistent with the results
reported in previous studies (Kaiser and Kalbitz, 2012; Mladenov
et al., 2015). Earlier researches have reported humic acid-like
substances that were characterized as bulky molecules with com-
plex structures supposed to be more resilient for micro-organisms
to consume than the protein-like substances with simple structures
(Schwesig et al., 2003; Pan et al., 2017). These features lead to a
decrease in DOM biodegradability with increasing depth
(Castellano and Kaye, 2009; Kaiser and Kalbitz, 2012). However,
Scott and Rothstein (2014), having different perspective, stated that
soil retains more hydrophobic DOM moieties than hydrophilic ones
as DOM percolates to depth, leading authors (Tareq et al., 2013) to
state that DOM in groundwater, indicating fulvic and protein-like
character as the dominant relative to the surface water.
Fluorescence Index (FI) values (Table 2) range from 0.6 to 1.9 for
groundwater samples in the studies samples with Bhadru, Gopi Rai
and Khudpur exhibiting lower average values of 0.9, 0.8 and 1,
respectively, suggesting the presence of terrestrially derived
(vascular plants or allochthonous source) substances (DOM) in
groundwater samples (Johnson et al., 2011). Whereas, the
remaining villages displayed the FI values higher than 1.2 but less
than 1.8, indicating mixed source, involving both terrestrial and
10 A. Malik et al. / Chemosphere 251 (2020) 126374

Fig. 5. Fluorescence excitation emission matrix of DOC of a) Bhadru b) Gopi Rai c) Amarkot d) Khudpur e) Ludhreutar and f) Samada (the scale show Fluorescence Intensity (R.U).

Fig. 6. Correlations between DOC and Fluorescence Intensity in Groundwater samples of (a) Northern side of villages (b) South-western side of villages.

microbial influences on DOM (Inamdar et al., 2012), which would
allow both the allochthonous (from surrounding landscape or
plants) and autochthonous DOM inputs (from bacteria and algae)
(Mladenov et al., 2015). FI proposed that where a rise in FI occurs, it
is complemented by an increase in labile carbon in a system that
previously seems to be dominated by hardly decomposable
terrestrial carbon (Tye and Lapworth, 2016). FI findings also
correlate well with SUVA-254 results (Fig. 7). Khudpur, Bhadru and
Gopi Rai showed purely terrestrial sources while the remaining
three sites represent more labile DOM source. Our results are
consistent with other studies (Palanti et al., 2000; Sierra et al.,
2005; Inamdar et al., 2012; Zheng et al., 2014; Mladenov et al.,
 A. Malik et al. / Chemosphere 251 (2020) 126374
Fig. 7. Multi-variate plot between SUVA-254 and Fluorescence Index representing
selected villages of Lahore for DOM source.
2015) where the DOM sources in Bangladesh (Tareq et al., 2013)
Bengal delta basin (Zhu et al., 2015), United Kingdom (Lapworth
et al., 2007) had excess fulvic acid and tryptophan (protein) peak
signatures.
FTIR spectra of DOC for the investigated samples are shown in
Fig. 8. Pronounced spectral bands signify carboxylic (CeO), humics
and aromatic (C]C) rings at 1717 cm1, 1630 cm1, 1515 cm1 and
1240 cm1, respectively, in almost all villages. They were more
profoundly observed than the amides (C]O) and amines. High
carboxylic and aromatic groups usually attribute to terrestrial hu-
mic substances. It must be noted that different spectral bands found
in this study resemble the data reported from elsewhere (Abdulla
Fig. 8. FTIR Spectra of DOC of a) Gopi Rai b) Khudpur c) Ludhreutar and d) Samada.
11
et al., 2010; Reyes and Crisoto, 2016). Gopi Rai and Samada dis-
played several robust spectral peaks at 1384 cm1, 3422 cm1 and
3300 cm1 than other villages. These bands are assigned to phe-
nols, HeOH stretching of carboxyl, and phenol and amides,
respectively. Along with the sulphonic group at 1140 cm1 the
above organic fractions could be linked to carboxyl moieties of
aromatic rings (Zheng et al., 2014). Spectral bands around 1700 to
1500 cm1 indicate the presence of protein sources. Amide-II at
1555 cm1 represents protein and amino sugars, but in lower
quantities. Aliphatic groups (CeH) at 2800 cm1 and 2920 cm1
were observed in all the villages, except Khudpur. The results of FTIR
analysis of DOM in groundwater samples indicate the agreement
with the spectroscopic profile determined, suggesting that the
source and composition (in terms of function group and chemical
compounds) of DOM are similar. Aromatic character in all the vil-
lages is detected in profound concentrations, along with varying
content of protein-like compounds in some samples, directing that
the source of DOM is humic (terrestrial) or somehow mixed in
nature.
4.4. DOM and its role on As release
DOM supposed to have a significant positive effect on As
speciation and its mobility in groundwater. It is a major contributor
to the reducing environment (Reza et al., 2010; Kim et al., 2015. As
correlates well with DOM in the northern part of the study area, i.e.,
r2 ¼ 0.49 (Table 3a) in groundwater, suggesting the DOC played an
important role in As mobilization process. The moderately positive
correlation of As with DOC (r2 ¼ 0.49) and Fe (r2 ¼ 0.41) in the
northern part support the fact that reduction of Fe oxide minerals
possibly mobilized As from sediments to groundwater (Mladenov
et al., 2010; Ali et al., 2019). Different researches explored that
12 A. Malik et al. / Chemosphere 251 (2020) 126374
Fig. 9. Correlation between As and (a) Fluorescence Intensity of humic-like peak and b) SUVA of groundwater samples of northern side of villages.
surface-inferred DOC is the main source that promotes microbial
assisted Fe reduction due to its increased reactivity, and also
stimulated As mobilization in Bangladesh (Neumann et al., 2009),
Cambodia (Lawson et al., 2013) and southwest Songnen basin,
China (Guo et al., 2014). As concentrations showed significantly
positive correlation with humic-like fluorescence intensity
(r2 ¼ 0.79, p ¼ 0.0001) and SUVA (r2 ¼ 0.56, p ¼ 0.0001) of DOM in
the northern side of villages (Fig. 9a and b). These positive corre-
lations between As and DOM indicate that humic part (aromatic) of
DOM imparted a vital role in As release by microbially-assisted
reduction of As from Fe/Mn mineral oxide surfaces (Guo et al.,
2011; Anwar et al., 2013; Bhattacharya et al., 2014). Humic DOM
can also influence As mobility by forming organo-metallic com-
plexes or by competitive desorption of As (Huang et al., 2012;
Mladenov et al., 2015) from hematite and goethite (2006; Zhu et al.,
2015) to groundwater. Several authors (e.g. Mladenov et al., 2010; Li
et al., 2019) reported that groundwaters of flood plains in
Bangladesh contained complex humic-like substances and lower
redox conditions potentially directing towards the As release from
sediments to groundwater. Anwar et al. (2013) reported DOM as a
source of As along with the role of changing redox conditions; that
lead to the As mobility by self-degradation. Guo et al. (2014) found a
positive correlation of TOC with As in sediments of Songnen basin,
China which the authors interpreted as the combined activity of
DOM and microbes on As bounded iron oxyhydroxides minerals.
The use of fertilizers possibly accelerates the fertility of the soil that
enhances soil humification and increases the fraction of aromatic
Fig. 10. Correlation between As and Fluorescence Intensity of protein-like peak of groundwater samples of (a) northern side of villages and (b) south-western side of villages.
compounds (Fellman et al., 2008). The prevalence of humic acid-
like DOM in the study area and its variable sources may, there-
fore, contribute into the inconsistent spatial behavior of arsenic
concentrations over short distances (Mladenov et al., 2015). Con-
centrations of As do not exhibit significant correlation with fluo-
rescence intensities of protein-like DOM (r2 ¼ 0.26, p ¼ 0.06)
(Fig. 10a) in groundwater of northern villages indicating a slight
role of microbially derived surface DOM in As mobility (Mladenov
et al., 2015). Lower protein-like DOM substances suggest a
decrease in the aromatic character and insignificant influence of
microbial degradation (Cawley et al., 2012; Li et al., 2019).
On the other hand, SUVA values (Table 2) for the southern side of
villages indicate a mixed source for DOM (terrestrial and microbial).
Here, SUVA (r2 ¼ 0.57, p ¼ 0.0001) (Fig. 11a) of DOM correlates well
with As, indicating that the mixed or intermediary source of DOM
positively influenced the As release. Increased SUVA values (Fig. 11)
showed the samples of Khudpur display the terrestrial source of
DOM in the study area. The positive correlation of SUVA with As
further suggests the presence of both high and low aromatic DOM
compounds. Likewise, As concentrations displayed a strong posi-
tive linear correlation with humic-like fluorescence intensity
(r2 ¼ 0.64, p ¼ 0.002) (Fig. 11b) that additionally signifies the
increased contribution of hydrophobic DOM compounds in As
mobilization, consistent to the data reported in Li et al. (2019).
Compared to humic-like fluorescent intensity, protein-like fluo-
rescence intensity (r2 ¼ 0.43, p ¼ 0.02) (Fig. 10b) of DOM also
observed in the southern side of villages, suggest the presence of
 A. Malik et al. / Chemosphere 251 (2020) 126374 13

Fig. 11. Correlation between As and (a) SUVA b) Fluorescence Intensity of humic-like peak of groundwater samples of south-western side of villages.

the humic as well as protein-like DOM compounds. The positive two medium of different depths, as this is also observed in studies
correlation of protein-like compounds with As indicates the conducted elsewhere (Anwar et al., 2003; Gandhi et al., 2004; Reza
reasonable contribution of aliphatic DOM that are likely derived et al., 2010; Tareq et al., 2013). In the study area, detailed soil
from microbial or chemical degradation, in the mobilization pro- characterization for the source of groundwater DOC at relevant
cess (Mladenov et al., 2015; Chiu et al., 2019). Increased protein depths is an open question that needs to be investigated further.
content in DOM may also regard the process of photo-irradiation of
DOM, which transforms more aromatic compounds into less aro-
5. Conclusions
matic moieties, i.e., into aliphatic compounds (Pullin et al., 2004).
This can amend the complexation potential of DOM with mineral
Higher As concentrations were found in Khudpur that is located
phases, by changing their chemical speciation, thereby enhancing
close to the Ravi River as compared with the lower As concentra-
the DOM and As mobility (Bolan et al., 2011; Guo et al., 2019). This
tions observed in Amarkot that is located away from the river. These
may reflect the influence of both autochthonous (microbial) and
observations suggest that Ravi River plays a vital role in contami-
allochthonous (terrestrial) mixed sources to the DOM pool in the
nation of the local aquifer. Remoteness or nearness of the area from
area’s groundwater, ultimately enhancing the As release mecha-
the river causes the As concentrations to fluctuate. Irregular pattern
nism from sediments to groundwater (Cawley et al., 2012). This
of DOC distribution in the entire study area suggest prevalence of
provides strong evidence for the mixed DOM source, as shown by
varying conditions and diversified source of DOC. DOC levels in all
the SUVA values in this area. The plausible release mechanism of As
the groundwater samples mostly lie at the depths of 20e70 m, as
could be the competitive desorption, complex formation or by
observed for As too. Negligible DOC content in the deeper aquifer
altering the redox potential of mineral surfaces and As redox state
(>100 m) indicate that the recent recharge contributed the
(Gorny et al., 2015; Mushtaq et al., 2018; Li et al., 2019). Mladenov
terrestrial sources derived DOM in the upper (shallow) aquifer
et al. (2015) encountered a similar situation in Bangladesh, where
(<100 m). Variant positive correlations between fluorescence in-
they found both humic as well as mixed DOM (both humic-like and
tensities at different peaks and DOC in the study area indicate that
amino acid-like) character in surface and groundwater samples.
most of the DOC in groundwater is mainly composed of humic
They proposed that the role of DOM in As mobility is not confined
substances, i.e., aromatic organic compounds, along with minute
to drive the microbially-assisted reductive dissolution of mineral
soil fulvic acid and some proteinous character at few sites. Based on
phases but it also enhances As release by competitive adsorption or
these facts, we presume that terrestrially (sedimentary) derived
by electron shutting reactions facilitated by humics, as evidenced in
DOM was the dominant type with some sites exhibiting a mixed
several studies (Huang et al., 2012; Li et al., 2019).
character. Results of other characterization tools are in accord with
these results. Moreover, a significantly positive correlation of As
4.5. Stable isotopic composition of TOC with fluorescence intensities at different Ex/Em and SUVA indicate
that DOM played a vital role in As mobility in the groundwater.
The composition of d13C isotopes in TOC of soil samples are given Based on this study, we conclude that northern part of study area (also
Khudpur) are rich in terrestrially derived DOM while southern part exhibited mixed
in Table 2. The number of soil samples analyzed is limited but the
source of DOM that ultimately caused mobilization on the alluvial flood plain.
results are relevant and conclusive to complement the situation. As
Furthermore, sediment cores will help to understand the release mechanism.
The d13C values for the analyzed soil samples ranged from 20.97
to 26.79‰. Khudpur, Samada and Bhadru exhibit that the TOC is
derived from terrestrial source (C3 plants) while Amarkot and
Declaration of competing interest
Lodhreutar showed phytoplankton being the source of carbon
(Cawley et al., 2012; Oestreich et al., 2016; Guo et al., 2014), and
The authors declare no conflict of interest with anyone.
samples from Gopi Rai displayed more variations than all other
villages (20.97 to 26.79). The d13C values of TOC do not
completely resonate with the findings of other characterization Declaration of competing interest
tools because TOC detected was of surface soil samples and
remaining techniques analyzed the groundwater at different I on behalf of all authors declare that there is no conflict of
depths, so it’s natural that the hydro-geochemistry varies between interst.
14 A. Malik et al. / Chemosphere 251 (2020) 126374
CRediT authorship contribution statement
Aroosa Malik: Data curation, Writing - original draft. Ambreen
Parvaiz: Conceptualization, Methodology, Software. Nisbah
Mushtaq: Software, Validation. Ishtiaque Hussain: Visualization,
Investigation. Tariq Javed: Visualization, Investigation. Hafiz Ur
Rehman: Writing - review & editing. Abida Farooqi: Writing -
review & editing.
Acknowledgments
The Authors are indebted to Higher Education Commission for
providing the funds through PAK-US grant Program.
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