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Docu 198
Docu 198
Mujtaba Baqar a,b,⁎, Yumna Sadef b, Sajid Rashid Ahmad b, Adeel Mahmood c,d,⁎⁎,
Jun Li d, Gan Zhang d
H I G H L I G H T S
• Pioneer OCPs study from northern tribu- taries of the River Ravi, Lahore,
Pakistan.
• Ongoing OCPs usage was identified.
• Ecological risks were exceeding RQ value
1 at all studied streams.
• Higher carcinogenic risks associated to al- drin, dieldrin, p,p'-DDT and β-
endosulfan.
G R A P H I C A L A B S T R A C T
a r t i c l e i n f o
Article history:
Received 18 July 2017
Received in revised form 27 September 2017
Accepted 22 October 2017
Available online xxxx
This study monitored the human health risks through dermal exposure, hazardous
risks to ecological integrity, contamination levels, spatio-temporal distribution,
and congener specific analysis of organochlorine pesticides (OCPs) across River
Ravi and its three northern tributaries (Nullah Bein, Nullah Basanter and Nullah
Deg). The residual levels of OCPs isomers were screened for water (n = 54) and
surface sediment (n = 54) samples from twenty seven sampling sites in two
alternate seasons (pre-monsoon and post-monsoon). The ∑OCPs con- centrations ranged
from 13.61 to 1992.18 ng/g dry weight and 12.89 to 128.16 ng/L with predominance
of β- endosulfan and p,p′-DDT in sediment and water matrixes, respectively.
Distribution pattern revealed significant- ly higher concentrations in upstream and
midstream, suggesting considerable transboundary OCPs pollution. Calculated ratios
of α-HCH/γ-HCH, o,p′-DDT/p,p′-DDT, (DDE + DDD) / ∑DDTs and cis/trans-chlordane for
water and sediments identified the fresh addition of lindane, technical DDTs and
chlordane in the study area. Risk quotient (RQ) based ecological risk was found
to be N1 at all studied streams during both seasons and elu- cidates higher risks
for endosulfan (α-endosulfan) and endrin. Human health risk assessment indicated
absence of hazardous (non-carcinogenic) risk through bathing in studied streams; as
the hazard index values ranged from
1.09E − 05 to 2.48E − 02 (acceptable limit; b1). However, the calculated
carcinogenic risk possessed by OCPs
through dermal exposure ranged from 1.39E − 10 to 1.98E − 05 that highlighted the
considerable carcinogenic
https://doi.org/10.1016/j.scitotenv.2017.10.234
0048-9697/© 2017 Elsevier B.V. All rights reserved.
292 M.
Baqar et al. / Science of the Total Environment 618 (2018) 291–305
1. Introduction
The organochlorine pesticides (OCPs) are synthetic chemicals that are of great
global concern due to their persistence, toxicity, bioaccumu- lation, and adverse
ecological effects (Dan et al., 2012; Parween et al.,
2014). They have been extensively used all around the world, predom- inantly
during 1950–1980s in agricultural countries to intensify the ag- ricultural
productivity (Maurya and Kumar, 2013). However, often b0.1% of the applied
pesticides target their pests, while N 99.9% fraction escapes into environment
through surface runoff, spray carry-over, in- filtration or residue retention on
food crops (Pimentel, 1995; Miller,
2004; Zhang et al., 2011) and have a tendency of long distance travel in the
environment (El-Shahawi et al., 2010).
Pakistan is an agro-based country; where 70% of its population is ag- riculture
dependent that makes it self-sufficient in terms of the food production (Hussain
and Routary, 2012). The consumption of pesticides in this agricultural country has
been increased significantly from 1954 through 2003 from 254 metric tons/year to
78,132 metric tons/year, re- spectively (Tariq et al., 2004; Syed and Malik, 2011;
Sultana et al., 2014). Currently, the pesticides consumption rate is increasing
with an annual rate of 6% (WWF, 2007) that would further increase manifold as
several vector-borne epidemics hit the country (Jahan, 2011; Nieto et al., 2012).
Another principal source of OCPs in environmental matrixes of Pakistan is
uncontrolled disposal of thousands of kilograms of obsolete or/and banned OCPs,
within or in the neighborhood of abandoned OCPs facto- ries in various parts of
the country (Eqani et al., 2012a; Tariq et al.,
2007). The prohibition in the production or usage of DDTs and other OCPs after
Stockholm Convention on the Persistent Organic Pollutant in 2001, to which
Pakistan is also a party, left behind the largest stock of obsolete pesticides,
demolished factories, chemical storages and dump grounds in/around the populated
cities of the country (Jan et al., 2009; Syed and Malik, 2011; Eqani et al.,
2012a). Moreover, the in- land use of banned OCPs is still reported in many
parts of Pakistan owing to their low cost, effectiveness and inappropriate national
regula- tory mechanism (Syed and Malik, 2011; Eqani et al., 2011; Tariq et al.,
2007). Consequently, a substantial fraction of the applied OCPs contam- inates
various environmental compartments of the country (Ahad et al.,
2010; Syed and Malik, 2011; Malik et al., 2011; Alamdar et al., 2014; Sul- tana et
al., 2014; Mahmood et al., 2014a; Syed et al., 2014a; Zehra et al.,
2015; Ali et al., 2016a). However, to date no policy has been developed to prevent
the illegal practice and unsafe storage of the banned POPs (Ahad et al., 2010).
The environmental contamination of OCPs is of serious concern par- ticularly for
aquatic ecosystems as they receive uncontrolled wastewa- ter and agricultural
runoffs in Pakistan (Jamil et al., 2015). Moreover, the water is a primary medium
for the transportation of OCPs from an application area to elsewhere (Yadav et
al., 2015). In aquatic environ- ment, hydrophobic nature of OCPs leads to their
subsequent accumula- tion in surface sediments with in the water bodies; this
makes them bioavailable even decades after their prohibition (Oliveira et al.,
2016). They accumulate in upper trophic level in the food chain and possess high
risk of pesticides poisoning, particularly in developing countries where it is
reported to be 13 folds higher than developed countries (Yadav et al., 2015).
Among the surface water bodies of Pakistan, the River Ravi, a transboundary
river has a strategic importance for being surrounded by most-intensive
agricultural region of the country, i.e. Rachna Doab and Bari Doab, and
simultaneously being the most polluted river of Pakistan (Syed et al., 2013,
2014a). Among the five tributaries of the
River (four exists in Pakistan), the Nullah Deg, Nullah Basanter and Nul- lah Bein
were focused in present study. All of these tributaries are transboundary streams
and are part of Rechna Doab, receiving the sur- face runoff and sub-surface
flow from the surrounding agricultural areas. The water of the Nullahs is used
for domestic, livestock and irriga- tion purposes through unregulated irrigation
pumps, and based upon the temperature and rainfall patterns, the cultivation in
the catchment area is of cereal crops, i.e. rice grown during the summer monsoon
(kharif) season whereas wheat is cultivated during the drier winter (rabi) season.
Likewise, the ongoing inland use of banned OCPs is re- ported from Rachna Doab
(Syed and Malik, 2011; Eqani et al., 2011,
2012b). Consequently, a substantial fraction of the applied OCPs con- taminates
environment of the region.
Therefore, the present study was aimed to reveal the occurrence, human health
risk through dermal exposure, ecological risks, source fin- gerprints and spatial-
temporal variation of OCPs in water and surface sediments across the northern
tributaries of River Ravi in Pakistan. To the best of our knowledge, present
study provides the baseline data for the level of OCPs from the study area that
could be significantly valu- able in global freshwater ecological and human health
risk studies.
The study was conducted along the Nullah Deg, Nullah Bein and Nul- lah Basantar,
located in Upper Rachna Doab in Narowal, Sialkot and Sheikhupura districts of
Pakistan. The sampling was also conducted along the River Ravi, upstream and
downstream to the confluence points of these three tributaries up to the Balloki
headworks on the River. A preliminary survey was conducted in June 2015, prior
to re- search sampling design to obtain background knowledge about the sources of
pollutants, nature of the tributaries and to finalize the sam- pling points based
on their accessibility. In order to record the sampling sites, they were marked on
field using GARMIN eTrax 20 GPS device. The water and sediments samples were
collected from twenty seven sam- pling sites (Fig. 1) in two distinct phases
(i.e. post-monsoon and pre- monsoon period) during September 2015 to May 2016.
The details of the sampling sites along with their spatial and selection criteria
descrip- tion are provided as Table S.1.
Fig. 1. Representation of sampling sites along River Ravi and its northern
tributaries.
Quality assurance and control procedures were strictly ensured for all the
samples. For instrumental calibration, standards were used on daily basis. To
ensure prevention of any sample contamination, all the glassware was thrice rinsed
with double distilled water followed by baking at 450 °C in muffle furnace for 4 h
each time before usage. The field, procedural and solvent blanks were analyzed
with each batch of
15 samples to check any cross-contamination and repeatability in the analysis.
All the reagents/chemicals used were analytical grade, and purchased from Sigma-
Aldrich now Merck KGaA (Germany). Surrogate and internal standards were purchased
from CPAchem Ltd. (Bulgaria) and Dr. Ehrenstorpher GmbH (Germany), respectively.
Agilent Mass Hunter Workstation Software - Quantitative Analysis was used for
peaks analysis and data acquisition. The instrumental and method de- tection
limits were calculated and corrected in accordance with the pro- cedure previously
described by Syed et al. (2014a). Concisely, instrumental detection limits were
detected from the lowest standards and extrapolation to the resultant analyte
values which generated a signal-to-noise ratio (3:1). Any isomer/congener
determined below in- strumental detection limits was considered as not detected
(ND). Meth- od detection limits were estimated to be thrice of standard deviation
of the blank (Mahmood et al., 2014a). Mean recovery value of TCmX (sur- rogate
standard) in sediments and water samples were 83.4% and 88.6%,
respectively. All the analytical results were corrected to the recovery ra- tios
and blanks analyzed. For quantification of calibration curves, the calibration
standards of 2, 10, 20, 50, 100, and 200 μg/L were used.
Table 1
Descriptive statistical of OCPs in water and sediments during pre-monsoon and post-
monsoon.
OCPs Water (ng/L)
Sediments (ng/g)
Post-monsoon Pre-monsoon
Post-monsoon Pre-monsoon
The ∑DDTs levels were found higher than ∑HCHs in water during both sampling
seasons. This trend was in consistent to the findings of previous studies (Covaci
et al., 2001; Sandra et al., 2006; Syed and Malik, 2011; Sultana et al., 2014;
Chakraborty et al., 2016). The higher levels of DDTs than HCHs might be associated
to their lower degradabil- ity than HCHs (Ulusoy et al., 2016; Syed and Malik,
2011). Moreover, the HCHs have relative higher vapor pressure that lowers its
accumulation in the sediments (Guo et al., 2007). However, the correlation was
inversed in sediments matrix during pre-monsoon season; where the relative higher
HCHs concentrations were recorded. This unusual OCPs pattern was attributed to
abrupt increase in γ-HCH concentration that has been associated with ongoing usage
of lindane in the study area (discussed later). The lower heptachlor levels in the
environment are at- tributed to its higher hydrolysis and evaporation rate in the
environ- ment (Milun et al., 2016). The aldrin transforms to dieldrin, which is
relatively more persistent and possesses higher affinity for sediments (Villeneuve
et al., 1999). This complex transformation is also evident from the accumulation
pattern in sediments from the current study area.
The compositional profile of DDTs and HCHs are summarized in Table S.2. The
compositional profile of DDTs revealed the predominance of p,p′-DDT (pre-monsoon:
69%; post-monsoon: 53%) in water and o,p′- DDT (pre-monsoon: 52%; post-monsoon:
32%) in sediments. Among the HCHs, the γ-HCH (47%) and ε-HCH (54%) were most
dominant iso- mers in the sediments matrix during pre-monsoon and post-monsoon
seasons, respectively. In the context of the water compartment, the β- HCH (25%)
and ε-HCH (29%) have shown the highest contribution of the total HCHs. Such high
levels of the o,p′-DDT and p,p′-DDT are indica- tors of ongoing DDTs usage in the
study area. Among the metabolites of the DDTs, the dominance of p,p′-DDE in water
is attributed to its hydro- phobic nature and persistence (long half-life and
chemical stability) in aquatic environment (Naso et al., 2005).
A comparative analysis of OCPs concentrations in water and sedi- ments from River
Ravi and its northern tributaries (Nullah Deg, Nullah Bein and Nullah
Basantar) with previously published data from Pakistan and worldwide is
summarized in Tables 2 and 3, respectively.
3.2.1. Nationwide comparison
The ∑DDTs concentrations in sediment compartment from present study area were much
higher than those reported from Chenab River, Ravi River and Rawal Lake
Reservoir (Malik et al., 2011), Mehmood Booti Drain (Ali et al., 2016a), Indus
River (Ali et al., 2016b), Korang River, Ling Stream and Lai Nullah (Malik et
al., 2014). However, the
∑DDTs levels were comparable or slightly higher to those from River Chenab (Eqani
et al., 2011), River Ravi (Syed et al., 2014a), Soan River (Malik et al., 2014),
Nullah Aik and Nullah Palkhu (Mahmood et al.,
2014a), and slightly lower than Lila stream (Syed et al., 2014b). In the water
compartment, multiple conclusions were drawn as ∑DDTs levels were found to be
lower than those from Indus River (Ali et al.,
2016b) and Chenab River (Eqani et al., 2012b), and simultaneously higher than
the findings from Rawal Lake and Simly Lake (Iram et al.,
2009) and Nullah Aik and Palkhu (Mahmood et al., 2014a).
The ∑HCHs levels in sediments were higher than all previous stud- ies consulted,
except the two studies from River Ravi and Lila Stream, a tributary to Nullah Deg
(Malik et al., 2011; Syed et al., 2014b). However, the ∑HCHs contents in water were
comparable to data from Nullah Aik and Palkhu (Mahmood et al., 2014a) but lower
than those in Indus River and Chenab River (Ali et al., 2016b; Eqani et al.,
2012b). For the HCB, the concentrations in sediments were found relatively higher
than all previ- ously studies from Pakistan (Ali et al., 2016a, 2016b; Mahmood
et al.,
2014a; Malik et al., 2014; Syed et al., 2014a, 2014b), while the levels in water
samples were comparable to the data from Indus River (Ali et al., 2016b) and
lower than two previous studies from Chenab River (Eqani et al., 2012b), and its
two tributaries, i.e. Nullah Aik and Palkhu (Mahmood et al., 2014a).
Table 2
Comparison of OCPs levels in water and sediments with other studies from Pakistan.
Location Environmental compartment
∑DDTs HCB ∑
Chlordane
∑
Endosulfan
Table 3
Comparison of OCPs levels in water and sediments from other developing countries.
Location Environmental
compartment
∑DDTs HCB ∑
Chlordane
∑
Endosulfan
(Parween et al., 2014; Malik et al., 2009; Hellar-Kihampa et al., 2013; Da et al.,
2017; Lu & Liu, 2016; Wang et al., 2016; Lugo-Ibarra et al., 2011; Harman et al.,
2013; Oliveira et al., 2016; Kafilzadeh, 2015; Barakat et al., 2012, 2013;
Verhaert et al., 2013; Yun et al., 2014). However, the ∑DDTs levels were similar to
the findings from River Tamiraparani (India), Mocu and Xnoha (Mexico), and River
Mae Klong and its tribu- taries (Thailand) (Kumarasamy et al., 2012; Poolpak et
al., 2008; Hinojosa-Garro et al., 2016). In water segment, the ∑DDTs concentra-
tions were analogous to water bodies from India, China and Iran viz. Brahmaputra
River and Hooghly River (Chakraborty et al., 2016), Weihe River and Jiulong
River Estuary (Wang et al., 2016; Wu et al.,
2017), and River Karun and Tashk Lake (Behfar et al., 2013;
Kafilzadeh, 2015), respectively.
The ∑HCHs levels in sediments and water were comparable to those in River
Tamiraparani, Brahmaputra River and Hooghly River from India (Kumarasamy et al.,
2012; Chakraborty et al., 2016), Qarun Lake from Egypt (Barakat et al., 2013), and
East Lake from China (Yun et al., 2014). Nevertheless, the current ∑DDTs and
∑HCHs levels in water were found to be much lower than the findings from River
Ganga, River Ghaggar and River Yamuna, India (Singh et al., 2007; Kaushik et
al., 2010; Kaushik et al., 2008), and higher than the levels from River
Pangani, Tanzania (Hellar-Kihampa et al., 2013), and Weihe River and River
Chao, China (Wang et al., 2016; Yu et al., 2014). Concerning ∑endosulfan, the
concentrations in sediments from
present study were only comparable to the levels from Mocu and Xnoha, Mexico
(Hinojosa-Garro et al., 2016), while higher than all the other referred studies.
The ∑endosulfan contents in water matrix were similar to those in Brahmaputra
River and Hooghly River (Chakraborty et al., 2016); but were lower to the
other water bodies. On the other hand, the HCB and ∑chlordane concentrations in
sedi- ments were in excess of all the previous international studies consulted
(Table 3).
The spatial distribution patterns of ∑OCPs and isomers concentra- tions in water
and sediments of the River Ravi and its northern tribu- taries are illustrated
in Figs. 2 and 3, respectively. The stream-wise OCPs distribution evaluation has
revealed higher levels of OCPs contam- ination in sediments from downstream sites
of the River Ravi, with highest concentrations being observed at the site R6
(Head Balloki). The River Ravi up to this point receive industrial wastewater
from major industrial zones of Lahore, Sheikhupura city and Kala Shah Kaku
together with the untreated urban wastewater discharged from Lahore city (Akhtar et
al., 2014; Syed et al., 2014b; Khanum et al., 2017). Among the tributaries, the
Nullah Deg is the longest transboundary tributary of the River Ravi in Pakistan
that have shown highest OCPs levels in sedi- ments from the sampling sites D8,
D11 and D12 during post-monsoon
M. Baqar et al. / Science of the Total Environment 618 (2018) 291–305
297
period, while the sites D-3 and D-4 were found to be the most contam- inated sites
in pre-monsoon season. The highest levels of OCPs contam- ination in midstream
sampling sites (D-3 and D-4) of Nullah Deg during pre-monsoon season could be
attributed to the ongoing OCPs usage in the study area (Syed and Malik, 2011;
Eqani et al., 2011; Mahmood et al., 2014a), and simultaneously these sites exist
in the most intensive- ly cultivated zone. In monsoon season, the surface
sediments are washed away with strong water currents and often deposited in
down- stream areas. This is also reflected by higher OCPs concentrations in
downstream sites (D8, D11 and D12) during post-monsoon season. Moreover, the
sampling site D8 is located immediately downstream to the Kala Shah Kaku industrial
area and in literature, obsolete pesticides dumping site and storage stores were
reported on the bank of Nullah Deg in this industrial area (Syed et al., 2014b;
Ahad et al., 2010). During the monsoon season, the runoff from adjacent flood
plain brings sedi- ments to the Nullah Deg (Jamil et al., 2015) that increases the
OCPs con- tamination at downstream sites to the Kala Shah Kaku during post-
monsoon season. Along the Nullah Bein and Nullah Basanter, no distinc- tive spatial
variation trend was observed that might be particularly at- tributed to the
similar agricultural activities; without any major
industrial wastewater source located along these streams. Nevertheless,
considerable OCPs levels in upstream-most sites along River Ravi, Nul- lah Deg,
Nullah Bein and Nullah Basanter reveals the transboundary OCPs pollution,
originating from India and Indian held Jammu and Kash- mir as all of these
streams are of transboundary nature (National Disaster Management Authority-United
Nations Development Pro- gramme, 2010; Mojaz Foundation, 2013).
The OCPs distribution analysis in sediments from studied streams re- vealed the
highest levels of OCPs contamination in Nullah Deg and Nul- lah Basanter with mean
∑OCPs levels appeared in the order: Nullah Deg N Nullah Basantar N River Ravi N
Nullah Bein and Nullah Basantar N Nullah Deg N Nullah Bein N River Ravi
during pre-monsoon and post-monsoon seasons, respectively. In water compartment of
the stud- ied streams, order of OCPs contamination was same as in sediment dur- ing
pre-monsoon season, while the OCPs distribution pattern in post- monsoon sampling
season was Nullah Bein N Nullah Deg N Nullah Basantar N River Ravi. The
highest levels of OCPs in Nullah Deg and Nul- lah Basanter are possible associated
with obsolete pesticides storage and industrial activities in the catchment of
these two streams; besides that ongoing usage of banned pesticides have also been
reported in
Fig. 2. Spatial distribution of ∑OCPs levels in water and sediments samples during
post-monsoon and pre-monsoon seasons.
298 M.
Baqar et al. / Science of the Total Environment 618 (2018) 291–305
Fig. 3. Relative spatial distribution of OCPs in water and sediments samples during
post-monsoon and pre-monsoon seasons.
3.4.1. HCHs
The isomer ratios among OCPs have been widely used in the past to identify the
possible sources of OCPs (Syed et al., 2014a; Yu et al., 2014;
Sultana et al., 2014; Mahmood et al., 2014a). The HCHs technical mixture contains
60–70% α-HCH, 5–12% β-HCH, 10–15% γ-HCH, 6–10% δ-HCH and 3–4% ε-HCH (Mahmood et
al., 2014a). While, the lindane products contain N99% of γ-HCH (Yu et al., 2014).
Among the HCH isomers, the β-HCH is the most persistent due to its lowest vapor
pressure, and α- HCH and γ-HCH have relative higher volatility (Syed et al.,
2013). In the present study, β-HCH in sediments constitute 27% of all HCHs isomers
during both sampling seasons which is higher than its fraction in HCHs technical
mixture, indicating historic use of HCH products in the study area. Moreover, a
ratio of α-HCH/γ-HCH was used to identify the source of HCHs. The ratio b3
indicates the fresh use of lindane (Sultana et al.,
2014). The α-HCH/γ-HCH ratios calculated for water and sediment ma- trixes from
current study area were found to be lower than 3 at all the sampling sites (Table
4), indicating the fresh addition of lindane in studied streams due to its possible
ongoing usage in the region. The current find- ings were in consistent to the
findings from adjacent study areas from Pakistan (Syed et al., 2014a; Sultana et
al., 2014; Mahmood et al., 2014a).
3.4.2. DDTs
The DDTs technical mixture is generally comprised of 75% p,p′-DDT,
15% o,p′-DDT, 5% p,p′-DDE, and remaining 5% is a blend of o,p′-DDE, o,p′-
M. Baqar et al. / Science of the Total Environment 618 (2018) 291–305
299
DDD and p,p′-DDD (Yu et al., 2014). In Pakistan, the ban of DDTs (tech- nical
mixture) has led to a shift towards dicofol usage that contains ~5% DDTs (Mahmood
et al., 2014a). In riverine environment, the parent DDTs are degraded into DDE via
oxidation-dehydrochlorination process under aerobic conditions, and DDD via
reductive-dechlorination pro- cess under anaerobic conditions (Syed et al., 2014a;
Mahmood et al.,
2014a). Therefore, the ratio of parent DDTs compound to its metabolites is widely
used to identify the pollution source/s and ongoing usage of DDTs.
The ratio o,p′-DDT/p,p′-DDT was used to indicate the source pesti-
cide, technical DDTs or dicofol for DDTs contamination in the environ- ment. The
ratio N1.3 indicates dicofol as a source of DDTs for the reason that o,p′-DDT
concentration in commercial dicofol products is higher than the p,p′-DDT (Qiu et
al., 2004; Syed et al., 2014a). In our study, the o,p′-DDT/p,p′-DDT ratios have
indicated the application of technical DDTs products in most of the catchment
area (post-mon- soon:61% and pre-monsoon:85% of the sampling sites). However,
the results have also identified the commercial dicofol products as source of DDTs
at certain sampling sites in the study area. Moreover, the ratio (DDE + DDD) /
∑DDTs was also used to identify the age of DDTs con- tamination. In the current
study, the calculated range for (DDE + DDD)
/ ∑DDTs ratio was ranged from 0.05 to 0.68 (Table 4), indicating fresh input of
technical DDTs in the study area.
At the same time, the level of environmental degradation of DDTs was scrutinized
by using the DDE to DDD ratio, with value N1 indicating aerobic decomposition of
parent DDTs (Syed et al., 2014a). The DDE/ DDD ratios were found to be ranged from
0.15 to 2.73 (mean: 1.1) and 0.49 to 2.2 (mean: 1.01) in sediments and
water, respectively. Thus, the DDTs metabolites in the River Ravi and its
tributaries are resul- tant from both aerobic and anaerobic decomposition as the
water flow in the studied streams is mainly attributed to monsoon flow. Besides, the
streams also receive highly polluted sewage and industrial waste-
2014; Jiang et al., 2009). So, the ratio of α-endosulfan to β-endosulfan is
expedient to evaluate the age of contaminant and its pollution source; the value
N1 indicates the ongoing usage and newer environmental contamination of technical
endosulfan product (Yu et al., 2014). In pres- ent study, the ratio of α-
endosulfan to β-endosulfan in sediments at majority of the sampling sites (57% in
post-monsoon and 52% in pre- monsoon seasons) were found below 1, while remaining
sites exceed the unity (RQ N 1). Thus, indicating the older usage as well as
fresh usage of endosulfan technical mixture in the catchment basin of the study
area.
MEC
water with high oxygen demand (Baqar et al., 2014) from adjacent in-
dustrial estates and highly populated cities, contributing towards anaerobic
conditions in the water channels.
RQ i ¼
PNEC
EC50or LC50
ð1Þ
3.4.3. Chlordane
The chlordane isomers, cis-chlordane and trans-chlordane, consti-
PNEC ¼
n
f
ð2Þ
tutes up to 75% of the technical chlordane mixture, with trans- chlordane
being relatively more degradable in the environment (Yamada et al., 2008). The
ratio of cis-chlordane to trans-chlordane N1 indicates the historical usage of
chlordane technical mixture in any area (Yu et al., 2014; Bidleman et al., 2002).
In our study, the ratios of cis/trans chlordane at most of the sampling sites
(89% during pre- monsoon and 67% during post-monsoon) were b1; indicating the ongo-
ing usage of chlordane in the study area. The chlordane usage is proba- bly higher
during rabi crops cultivation (drier season), as shown by the pre-monsoon season
results.
3.4.4. Endosulfan
The technical endosulfan mixture is composed of 70% α-endosulfan and 30% β-
endosulfan isomers, while α-isomer in the environment is relatively easier to
decompose than its β counterpart (Sultana et al.,
RQ ¼ X RQi
ð3Þ
i¼1
The calculated ecological risk of OCPs to the fish in the studied streams is
shown in Fig. 4 that is significantly valuable for screening eco- logical risk in
the region and would be beneficial for future ecological studies. According to the
literature, 0.01 ≤ RQi b 0.1 indicates low risk;
0.1 b RQi b 1 represents medium ecological risk and RQi N 1 expresses
high risk (Palma et al., 2014; Zheng et al., 2016). Among the studied OCPs, the
∑endosulfan, α-endosulfan and endrin possesses high eco- logical risk (RQ N 1)
during both studied seasons, and β-endosulfan holds high and medium ecological
risks during pre-monsoon and post-monsoon seasons, respectively. Whereas, o,p′-DDT
and isodrin possesses medium ecological risk; and low ecological risk was
deter- mined for all other OCPs in the study area (Fig. 4b). Among the OCPs,
Table 4
Ratios of different OCPs for source apportionment.
Ratio Water
Sediments
Pre-monsoon Post-monsoon
Pre-monsoon Post-monsoon
the ∑endosulfan (LC50: 1.25 μg/L) implies highest RQi.m and RQi.ex values during
both pre-monsoon and post-monsoon seasons, followed by α-endosulfan (LC50: 1 μg/L)
and Endrin (LC50: 3 μg/L).
The stream-wise risk quotients evaluated, both RQ.m and RQ.ex,
were exceeding the RQ value 1 at all the studied streams during both seasons,
representing the occurrence of high ecological risk associated with OCPs
contamination in the study area (Fig. 5). The Nullah Deg dur- ing pre-monsoon
season exhibited highest risk with RQ.m and RQ.ex values of 4.77 and 12.71,
respectively. Similar findings were evaluated for the Nullah Bein; where RQ.m
(3.45) represented highest level eco- logical risk. Whereas, the spatial
distribution of ecological risk along the sampling point reveals that the RQ values
for all the sampling points were representing high risk (range: 1.13–11.68 during
pre-monsoon and 1.11–6.56 during post-monsoon). The highest risk (RQ = 11.68
during pre-monsoon and 6.56 during post-monsoon) was evaluated at site D8,
downstream point to obsolete pesticides dumping site along the Nullah Deg. The α-
endosulfan and endrin contributed significantly with 93% and 88% of the total
risk estimated during pre-monsoon and post-monsoon seasons, respectively. Thus,
highlighting the necessity of an immediate elimination of ongoing OCPs usage in
the study area to avoid ecological stress on the freshwater fish.
Moreover, to assess the OCPs toxicological effects to ecological integ- rities of
the River Ravi and its tributaries, concentrations from the cur- rent study were
compared with the recommended or/and permissible limits for water and sediment
matrixes. However, as no environmental quality guidelines or standards are
available for OCPs levels in Pakistan. So in order to assess the ecological risk
possessed by OCPs, the limits from European Council, US Environmental Protection
Agency (USEPA) and Canadian Council of Ministers of the Environment (CCME) were
used. For sediments fraction (Table 5), the results from present study were
compared with probable effect level (PEL) and interim freshwater sediment quality
guidelines (ISQG); equivalent to threshold effect level (TEL) from Sediment
Quality Guidelines for the Protection of Aquatic
Life (CCME, 1998). Moreover, the findings were also compared with threshold effect
concentration (TEC) and probable effect concentration (PEC) values proposed by
MacDonald et al. (2000) and accepted by US EPA in 2003 (Florida Department of
Enviroment Protection, 2003). The concentrations of ∑DDTs (95%; 70%),
heptachlor (93%; 20%),
∑DDD (86%; 23%), γ-HCH/lindane (66%; 50%), endrin (50%; 4%),
∑DDE (39%; 20%), dieldrin (40%; 14%) and chlordane (13%; 11%) were found to be
exceeding threshold limits (ISQG) and PEL values. In total 88% of the sampling
sites were measured with higher TEC values for total DDTs (∑DDT + ∑DDE +
∑DDD), whereas ∑DDTs (75%), endrin (61%), dieldrin (57%), ∑DDD (48%), ∑DDE (32%),
γ- HCH/lindane (32%), heptachlor (14%) and chlordane (13%) were also exceeding the
TEC limits. However, on comparison with PEC values, it was revealed that only γ-
HCH/lindane with 25% of the sampling sites was prominently exceeding PEC limit
(i.e. 4.99 ng/g), while in case of other OCPs, b10% of the sampling sites were in
violation to PEC limits (Table 5). The sites with significant toxic levels (in
excess to PEC or PEL) indicated the pollution hotspots in terms of the uppermost
proba- ble aquatic ecological impacts.
In context to water samples, the results were compared with European Council
directives (Directive 2013/39/EU of the European Par- liament and of the Council)
and National Recommended Aquatic Life Criteria Table established by USEPA (2004)
(Table 6). The comparison exhibited that the OCPs levels in all the samples were
within criterion maximum concentration (CMC) and criterion continuous concentration
(CCC) values; except for p,p′-DDT, where 86% of the sampling sites were exceeding
the CCC value (0.001 μg/L). The limits set by European Coun- cil (2013), i.e.
maximum allowable concentration (MAC) and annual av- erage (AA) were violated for
heptachlor at all the sampling sites. Whereas, the endosulfan, p,p′-DDT and
∑DDTs were exceeding the AA limits by 20%, 24% and 12%, respectively. The presence
of aforemen- tioned OCPs at higher toxic levels in the sediments may cause
serious adverse toxicological and ecological effects, particularly to benthic
Fig. 4. RQi.m and RQi.ex values associated to OCPs isomers during post-monsoon and
pre-monsoon seasons.
M. Baqar et al. / Science of the Total Environment 618 (2018) 291–305
301
Fig. 5. Total RQ.m and RQ.ex values from studied streams during post-monsoon and
pre-monsoon seasons.
organisms. Nevertheless, most of the OCPs concentrations in water were within the
criteria/limits for aquatic life; except for heptachlor, en- dosulfan, p,p′-DDT and
∑DDTs that exhibit serious concerns for eco- logical integrity in the region.
Table 5
Comparison of OCPs concentration in sediments with Sediment Quality Guidelines from
a) Canada and b) USA; all values are expressed in ng/g.
The humans are directly exposed to contaminants in the water sys- tem through
drinking and/or bathing activities (Yang et al., 2014). In the study area, though
groundwater is the principal source for drinking pur- poses. However, the
frequent bathing and fishing practices were ob- served in all the studied
streams, particularly in upstream and midstream areas to overcome heat stress
condition in the region. More- over, the water from the Nullahs was also drawn to
adjacent agricultural farmlands through illegal water-suction pumps, and children
from the surrounding areas were observed taking bath under the pumped water.
Therefore, the human health risk to OCPs through dermal expo- sure was evaluated
by integrating toxicity and exposure data. The human health risk model
established by USEPA (1989) was employed to assess non-carcinogenic human health
risk (Eq. (4)) and carcinogenic human health risk (Eq. (5)).
∑DDD
0.95–896.47 3.54 8.51 4.88 28
HI ¼ E=RfD
ð4Þ
∑DDEf 0.95–164.38 1.42
6.75 3.16 31.3
∑DDTg 1.02–971 1.19
4.77 4.16 62.9
Total DDT h 3.37 –1607.73 –
– 5.28 572
R ¼ E SF:
ð5Þ
where, RfD represents reference dose (mg/kg·day), SF is the cancer slope factor
(mg/kg·day)−1 and E is the exposure level to particular OCP (mg/kg·day). The
RfD and SF values (Table 7) calculated by USEPA- Integrated Risk Information
System (IRIS) (https://www.epa. gov/iris) for various OCPs were used for the
evaluation of non- carcinogenic and carcinogenic risk. The dermal exposure to
OCPs from
302 M.
Baqar et al. / Science of the Total Environment 618 (2018) 291–305
Table 6
Comparison of OCPs concentration in water with standards values by a) USEPA and b)
European Council; all values are expressed in μg/L.
surface water through bathing (i.e. dermal) in the contaminated streams was
calculated by using Eq. (6) (Yang et al., 2014).
TE 0:5
Edermal ¼ 6τ π
ðC k Asb EF FE EDÞ=500=BW=AT=f ð6Þ
where, τ is lag time for each pollutant in the body (here assumed 1 h); TE is
bath time (0.4 h); C is concentration of a particular OCP in water (in mg/L); k is
dermal permeability parameter (0.001 cm/h); Asb is body surface area (16,600
cm2); EF is frequency of exposure (365 days/
year); FE is bathing frequency (0.5 times/day); ED is exposure duration (67 years
for Pakistan) (Waqas et al., 2017); BW is average body weight (72 kg for
Pakistan) (Sultana et al., 2014); AT is average time (25,550 days); and f is
absorption ratio (1) (Yang et al., 2014).
The calculated non-carcinogenic and carcinogenic risk of OCPs for the study area
is summarized in Table 7. The results elaborated that the HI (non-carcinogenic
risk) values were ranged from 1.1E − 05 to
2.33E − 02 and 1.09E − 05 to 2.48E − 02 during post-monsoon and pre-monsoon
seasons, respectively. However, the acceptable limit for HI in literature is 1
(USEPA, 1989; Yang et al., 2014; Sultana et al.,
2014). Therefore, at all the sampling sites the non-carcinogenic human
health risk associated to OCPs were found within the acceptable limit and hence
considered to be safe in terms of non-carcinogenic risk through bathing in the
studied streams.
In case of carcinogenic risk, the USEPA suggested that the acceptable carcinogenic
risk limit should be 10−6 (one in million) (Siriwong et al.,
2009; Waqas et al., 2017). The calculated carcinogenic risk to OCPs through
dermal exposure ranged from 1.39E − 10 to 1.98E − 05 and
6.59E − 10 to 1.19E − 05 during post-monsoon and pre-monsoon sea- sons,
respectively; with highest risk exhibited by aldrin during both sampling seasons.
The risk characterization indicated that the carcino- genic risk associated to
aldrin and dieldrin in post-monsoon season and p,p′-DDT, aldrin, dieldrin and α-
HCH in pre-monsoon season were exceeding the threshold limit (10−6). The
current findings were strengthened by previously published data from the
neighboring areas, reporting carcinogenic risk associated with OCPs environmental
contamination (Sultana et al., 2014; Mahmood et al., 2014b; Mumtaz et al., 2015).
The current results were also in consistent with those from Ebro River, Spain
(Ferré-Huguet et al., 2009), Central Thailand (Siriwong et al., 2009), and
Kazakhastan (Sailaukhanuly et al., 2016).
M. Baqar et al. / Science of the Total Environment 618 (2018) 291–305
303
Therefore, the carcinogenic risk assessment indicates that the water of River Ravi
and its three northern tributaries, i.e. Nullah Bein, Nullah Basanter and Nullah
Deg is possessing carcinogenic risk to local popula- tion and is unsafe for human
bathing purposes. However, the current calculations are optimal for only screening
of human health risk. So, fur- ther studies are recommended to more precisely
assess the human risks to OCPs exposure that would complement the current
investigation. Moreover, the water of these streams is being used for irrigation
pur- poses. So, the human health risk associated with OCPs contamination in the
studied streams might be much more and this such level cannot be ignored.
4. Conclusions
The occurrence, distribution, source finger printing and risk to eco- logical and
human health associated to OCPs contamination in River Ravi and its three northern
tributaries were assessed. Among the 23 iso- mers analyzed, the p,p′-DDT and β-
endosulfan were most dominant OCPs in water and sediment matrixes, respectively.
The calculated ratios among OCPs isomers and metabolites indicated the ongoing
usage of OCPs, particularly lindane, technical DDTs and chlordane in the study
area. The OCPs distribution at relative higher levels was observed at midstream
and downstream sampling sites. The RQ values associated to ∑endosulfan, α-
endosulfan and endrin depicted high levels of eco- logical risk to fish (RQ N 1).
Moreover, the levels of certain OCPs were also found exceeding the threshold
limits and maximum limits set by EC, USEPA and CCME. The human health risk
assessment clearly highlighted the carcinogenic risk (through dermal exposure)
associated to occurrence of aldrin, dieldrin, p,p′-DDT and β-endosulfan at certain
sampling sites and higher risk was observed in pre-monsoon season. The present
study in the absence of any OCPs data from the study area provides baseline data
for future freshwater ecological and human health risk studies. Nevertheless, more
OCPs risk assessment studies are needed to be conducted to assess the carcinogenic
health risk with consumption of contaminated food. So, the actual risk to human
health associated to River Ravi and its three northern tributaries might be much
more and such levels cannot be ignored.
Acknowledgement
We are thankful to Mr. Muhammad Akhtar and Mr. Abdul Qadir for their help during
extensive sampling in the study area. Furthermore, we like to extend our thanks to
Ms. Iqra Aslam and Ms. Uzma Ashraf for helping in analytical and guidance for
GIS mapping.
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