STOTEN-24295; No of Pages 13

Science of the Total Environment xxx (2017) xxx–xxx

Contents lists available at ScienceDirect

Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

Sedimentary black carbon and organochlorines in Lesser Himalayan

Region of Pakistan: Relationship along the altitude
Usman Ali a, Andrew James Sweetman b, Rahat Riaz a, Jun Li c, Gan Zhang c,
Kevin C. Jones b, Riffat Naseem Malik a,⁎
a
Department of Environmental Sciences, Quaid-i-Azam University, Islamabad 45320, Pakistan
b
Centre for Chemicals Management, Lancaster Environment Centre, Lancaster University, Bailrigg, Lancaster LA1 4YQ, UK
c
State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China

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

• First investigation of sedimentary black

carbon and organochlorines in Lesser
Himalayan Region of Pakistan
• Implication for upslope, short/long-
range transport and local emission
sources contribute to the contamination
of Lesser Himalayan Region
• Black carbon showed influential rela-
tionship in sedimentary distribution of
OCs along altitudinal zones

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

Article history: Black carbon (BC) and total organic carbon (TOC) along with their relationship with organochlorine pesticides
Received 10 July 2017 (OCPs) and polychlorinated biphenyls (PCBs) were assessed in Lesser Himalayan Region (LHR) in different alti-
Received in revised form 30 September 2017 tudinal zones based on anthropogenic influence/source proximity under the scope of this study. Results revealed
Accepted 9 October 2017
the concentrations of BC, TOC, OCPs and PCBs varied between 0.3 and 43.5 mg g−1, 1.7–65.4 mg g−1, 0.59–
Available online xxxx
3.64 ng g−1 and 0.01–1.31 ng g−1, respectively. Spatial distribution trends have shown higher levels of OCPs
Editor: Kevin V. Thomas and PCBs contamination near populated and urban areas along the altitude. It is implicated that upslope, short
and long-range transport and local emission sources contribute to the contamination of different altitudinal
Keywords: zones of LHR. The relationship of BC and TOC with OCPs and PCBs was evaluated using principal component anal-
Lesser Himalayan Region ysis (PCA) and Pearson correlation analysis that indicated higher sorptive influence of BC over TOC in distribution
OCPs status of organochlorines in LHR. Further research is required to find relationship of BC and TOC in surface river-
PCBs ine sediments, particularly in aquatic systems along the altitude in mountain regions of the world.
Black carbon © 2017 Elsevier B.V. All rights reserved.
Altitude
Local source emissions

1. Introduction

Organochlorine pesticides (OCPs) and polychlorinated biphenyls

⁎ Corresponding author at: Department of Environmental Sciences, Faculty of Biological
(PCBs) are anthropogenic groups of persistent organic pollutants
Sciences, Quaid-i-Azam University, Islamabad, PO 45320, Pakistan. (POPs) that are ubiquitous in the environment (Dai et al., 2011; Meng
E-mail address: r_n_malik@qau.edu.pk (R.N. Malik). et al., 2017; Nouira et al., 2013). Owing to their stability, ecotoxicity,

http://dx.doi.org/10.1016/j.scitotenv.2017.10.071
0048-9697/© 2017 Elsevier B.V. All rights reserved.

Please cite this article as: Ali, U., et al., Sedimentary black carbon and organochlorines in Lesser Himalayan Region of Pakistan: Relationship along
the altitude, Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.10.071
2 U. Ali et al. / Science of the Total Environment xxx (2017) xxx–xxx

carcinogenicity, bio-accumulative effects and long range atmospheric
transport potential, these compounds have become a global concern
(Li et al., 2015; Montuori et al., 2016). Although, these chemical com-
pounds are banned/restricted in many countries, these are still being
observed in environmental media, even in remote regions such as
polar which is considered as the most clean environment in the past
(Meire et al., 2012). These chemicals generally transported from
warmer regions towards the colder regions and have shown mountain
cold trapping at high altitude areas (Blais et al., 1998; Yang et al.,
2013). Though mountain regions are also considered as relatively
clean environments, they may experience different behavior of organic
chemicals as compared to other remote regions such as arctic in terms
of industrialization, dense population, short distance ecological gradient
changes, local meteorological changes and most important the

Fig. 1. Study area map and sampling sites.

Please cite this article as: Ali, U., et al., Sedimentary black carbon and organochlorines in Lesser Himalayan Region of Pakistan: Relationship along
the altitude, Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.10.071
 U. Ali et al. / Science of the Total Environment xxx (2017) xxx–xxx
proximity to emission sources (Kallenborn, 2006; Liu et al., 2014;
Tremolada et al., 2008).
Sediments play an important role in the global fate and distribution
of hydrophobic organic compounds (Salem et al., 2013) because of larg-
er retention capacity, hydrophobicity, low water solubility and sorption
to particulate matter (Kucuksezgin and Tolga Gonul, 2012). Usually,
sediments are considered as principal or ultimate sink for organochlo-
rines but they could also re-emit them into the environment as a sec-
ondary source (Salem et al., 2013). According to Guzzella et al. (2008),
sediments are among those environmental matrices that could be con-
sidered as the best media for mapping possible pollution sources of
POPs. It is well known that POPs fate and distribution is mainly inclined
by sedimentary organic matter (Parween et al., 2014) but this tradition-
al paradigm has now changed with the better understanding of the po-
tential role of black carbon (BC) present in the sediments (Sánchez-
García et al., 2012). BC is a type of carbonaceous geosorbents mainly in-
cluding carbon rich residues from fire or heat, dominated by aromatic
structures and chemically heterogeneous in nature (Aller, 2016). It is
also ubiquitous in the environment and influence broad range of bio-
geochemical processes (Schmidt and Noack, 2000; Watson et al.,
2005). N 80% of BC is suggested to ends up in soils and sediments
where it could reside for a longer period of time (Forbes et al., 2006;
Hammes et al., 2007). Owing to its porous nature and condensed struc-
ture, BC is believed to affect the overall behavior of POPs in the sedi-
ments via occlusion thereby limiting the bioavailability of POPs and
conditioning of their transport (Ahrens and Depree, 2004; Huang
et al., 2003; Jonker and Koelmans, 2002; Koelmans et al., 2006). There-
fore, understanding the role of carbon moieties (TOC and BC) in distri-
bution of organic contaminants in sediments particularly along the
altitude is essential to determine.
Himalaya is a massive mountain range that is part of the Third Pole
Environment (Yao et al., 2012) and separates the Indian subcontinent
from Tibetan Plateau (Mughal et al., 2016). The lower stretch of this
mountain range that lies in Pakistan is comprised of Azad Jammu &
Kashmir (AJK), Rawalpindi-Islamabad districts and the entire Hazara di-
vision with an estimated area of 23,295 km2 (Hussain and Ilahi, 1991).
This mountainous region may receive local, regional and continental
emissions because of exposure to monsoon winds in summer and west-
erlies in winter season. The region exhibits the altitude range that is fa-
vorable mixing layer for persistent organic pollutants. Further, the
geography of the region indicates that it could receive semivolatile or-
ganic compounds from nearby industrial regions of Punjab. Therefore,
the study of OCs and carbon moieties (TOC and BC) in lower stretch of
greater Himalaya is important. In current study, we investigate sedi-
mentary levels of TOC, BC, OCPs and PCBs along Neelum-Jhelum River
system in Lesser Himalayan Region (LHR). Although, regional studies
(Guzzella et al., 2011; Guzzella et al., 2016; Wang et al., 2006; Wang
et al., 2008; Yang et al., 2013; Zheng et al., 2012) have been carried
out in the Himalayan and Tibetan Plateau in order to assess the levels
Table 1
BC, TOC and their comparison with other studies conducted around the globe.
Location Altitude Sample type
masl
Lesser Himalaya Region 357–2324 Surface
Yamuna River ~216 Surface
Seven Pan Arctic Rivers Surface
Swedish Continental Shelf Surface
Nam Co Lake, Tibetan Plateau 4722 Core
Slovenian alpine lacustrine sediments 1383–2150 Core
Alps, Switzerland 1850 Core
Lake Ledvica (Alps, Slovenia) 1830 Core
Lake Planina (Alps, Slovenia) 1430 Core
Lake Oberaar, Switzerland 2303 Core
Lake Stein, Switzerland 1930 Core
Please cite this article as: Ali, U., et al., Sedimentary black carbon and organochlorines in Lesser Himalayan Region of Pakistan: Relationship along
the altitude, Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.10.071
3
of POPs, no study has focused the LHR, Pakistan to explore the levels
of organochlorines in context of relationship with BC along the altitude.
Our specific objectives for this study were to: (i) assess the levels of OCs
and carbon moieties (BC and TOC) in sediments from LHR; (ii) study the
spatial and altitudinal relationship with implication of local sources; and
(iii) investigate the relationship of OCs with BC and TOC in LHR.
2. Materials and methods
2.1. Study area and sediment sampling
Four sampling zones from LHR were identified for sediment sam-
pling along Neelum-Jhelum River System based on anthropogenic influ-
ence/source proximity at different altitudinal ranges i-e., Zone A, B, C
and D at 357–383, 397–733, 737–975 and 1351–2324 masl, respectively
(Fig. 1). Zone C is most likely influenced by anthropogenic activities as
the sampling sites in this zone are close to dense population of
Muzaffarabad city and Neelum-Jhelum Hydropower Project. Sampling
sites in Zone A and more particularly in B are relatively less affected
by anthropogenic sources. Sampling sites from Zone D are considered
as remote owing to very low anthropogenic influence. The Neelum
River originates from Krishansar Lake (Indian occupied Jammu & Kash-
mir), enters into Pakistan from Gurez sector of the Line of Control. On
both sides of the river, Neelum valley is situated that has mountainous
rugged topography and steep slopes (Akram et al., 2011). The valley is
situated northeast of the Muzaffarabad city and parallel to the Kaghan
valley (Mughal et al., 2016). The Neelum River joins the Jhelum River
at Domail, near Muzaffarabad (Nawaz and Shafique, 2003). The Jhelum
River rises on the north western side of Pir Panjal, drains alluvial lands in
Kashmir valley and flows through the Wular Lake (Archer and Fowler,
2008). It is the second biggest tributary of Indus River system and the
whole upper Jhelum River basin drains into the Mangla Dam, the second
biggest reservoir of Pakistan (Mahmood et al., 2015). It was constructed
in 1967 on Jhelum River in Pir Panjal range of upper Siwaliks, to im-
pound the water for the purpose of irrigation, hydroelectric power gen-
eration and control of floods (Mirza et al., 2012). It covers an area of
26,500 ha (Ali et al., 2011), mainly fed by two perennial (Poonch and
Jhelum) and two non-perennial rivers (Khad and Kanshi), divided into
five sub-basins namely Main Mangla, Jhelum, Poonch, Khad and Jari
(Saleem et al., 2015). The storage capacity of the reservoir is being con-
tinuously reduced owing to high sedimentation rate as a result of ero-
sion prone catchment area (Saleem et al., 2013; Saleem et al., 2015).
Detail of each sampling site is given in SI Table 1. Sediment samples
were collected in composite of three from each sampling site. Hand
trowel was used for collection of all sediment samples and kept in poly-
ethylene bags. They were then transported to the Department of Envi-
ronmental Sciences, Quaid-i-Azam University where stored frozen at
−4 °C until further analysis.
TOC BC Reference
−1 −1
mg g mg g
1.7–65.4 0.3–43.5 This study
13.7 ± 5.1 0.46 ± 0.23 Parween et al. (2014)
5.7 ± 0.3–20.2 ± 0.3 0.17 ± 0.07–1.5 ± 0.1 Elmquist et al. (2008)
4.8–168 0.58–17.66 Sánchez-García et al. (2012)
0.49–1.09 Cong et al. (2013)
3.6–9.2 Muri et al. (2002)
10–30 1.5–3.3 Bogdal et al. (2011)
66–157 3.6–9.2 Bogdal et al. (2011); Muri et al. (2002)
68–168 3.3–10.5 Bogdal et al. (2011); Muri et al. (2003)
0.8–1.5 0.2–0.3 Bogdal et al. (2011)
1.7–4.4 1.2–3 Bogdal et al. (2011)
4 U. Ali et al. / Science of the Total Environment xxx (2017) xxx–xxx

2.2. Analysis of organochlorines and QA/QC
Sedimentary OCs were measured according to the procedure de-
scribed elsewhere (Ali et al., 2015b; Bajwa et al., 2016) and is presented
in detail in the supporting information. Briefly, 20 g of sediment sample
was taken for each site and Soxhlet extracted with DCM. Surrogates
(TCmX, PCB-30, −198 and −209) were added prior to the extraction.
Column chromatography was used for clean-up of the samples. Analysis
was done by using GC–MS/MS Agilent 7890/7000 system having
VARIAN, CP-Sil 8 CB, 50 m, 0.25 mm, 0.25 μm capillary column, operated
in multiple reaction monitoring mode with an EI source (−70 eV). All
the reported values were corrected by the blank values and surrogate
recoveries. Following were the targeted analytes for sedimentary analy-
sis: α-HCH, β-HCH, γ-HCH, o,p′-DDD, p,p′-DDD, o,p′-DDE, p,p′-DDE, o,p′-
DDT, p,p′-DDT, cis-chlordane (CC), trans-chlordane (TC), β-endosulfan,
heptachlor, HCB, tri-PCBs (− 28, − 37), tetra-PCBs (− 44, − 49, − 52,
− 60, − 66, − 70, − 74, − 77), penta-PCBs (− 82, − 87, − 99, − 101,
−105, −114, −118, −126), hexa-PCBs (−128, −138, −153, −156,

Fig. 2. Spatial distribution of BC and TOC in LHR.

Please cite this article as: Ali, U., et al., Sedimentary black carbon and organochlorines in Lesser Himalayan Region of Pakistan: Relationship along
the altitude, Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.10.071
 U. Ali et al. / Science of the Total Environment xxx (2017) xxx–xxx
− 158, − 166, − 169) and hepta-PCBs (− 170, − 179, − 180, − 183,
−187, −189).
2.3. TOC and BC analysis
Total organic carbon was determined by treating sediment samples
with 1 M HCL in order to remove inorganic carbon (Sun et al., 2008)
and then analyzed at Vario EL III Elemental Analyser (Germany). Black
carbon was detected using chemo-thermal oxidation (CTO-375) meth-
od, previously used by (Ali et al., 2015a; Elmquist et al., 2008; Elmquist
et al., 2007; Gustafsson et al., 2001). Several methods are being used for
BC determination such as thermal/optical reflectance (TOR) (Fang et al.,
2015; Han et al., 2007), Benzene Polycarboxylic Acids (BPCA) and Cr2O7
methods (Hammes et al., 2007) because BC is a complex combustion
continuum and difficult to quantify, but the CTO-375 method we used
in this study is most thoroughly evaluated in inter laboratory compari-
sons along with provision of favorable results with different BC standard
materials (Nam et al., 2008). Keeping in view CTO-375 method, 2–3 g of
dried sediment samples were taken, first exposed to thermal oxidation
at 375 °C for 18 h in a muffle furnace under constraint air flow, then
digested with 1 N HCL and residual organic carbon was analyzed as
black carbon using Vario EL III Elemental Analyser (Germany). See
supporting information for QA/QC.
3. Results and discussion
3.1. BC and TOC fractions
The sedimentary carbon content (TOC and BC) from Lesser Himala-
yan Region and its comparison with other global studies has shown in
Table 1. Overall, the TOC varied between 1.7 and 65.4 mg g−1 with av-
erage concentration of 28.7 ± 13.9 mg g−1. This concentration is higher
than reported for surface sediments of Yamuna River (13.7 ±
5.1 mg g−1) by Parween et al. (2014) but far lower than surface sedi-
ment samples of Swedish Continental Shelf (4.8–168 mg g−1;
Sánchez-García et al., 2012). Our reported values were also lower than
sediment core samples taken from Slovenian alpine lacustrine sedi-
ments (70–200 mg g− 1; Muri et al., 2002) while comparable with
those of Mexican margin sediments (17.6–79.9 mg g−1; Gélinas et al.,
2001). The levels of BC varied between 0.3 and 43.5 mg g−1 with aver-
age concentration of 16.1 ± 13.9 mg g−1 which was higher than surface
sediments of seven Pan-Arctic Rivers (0.17 ± 0.07–1.5 ± 0.1 mg g−1
Elmquist et al., 2008) and Yamuna River (0.46 ± 0.23 mg g−1;
Parween et al., 2014). Though, BC is omnipresent in the environment,
marine sediments are considered as their ultimate sink where N90% of
the BC burial occurs in the continental shelf on global scale (Fang
et al., 2015). Owing to this reason, we compared our values with those
of marine sediments data as well. It was noted that our reported values
of BC for LHR were higher than continental shelf sediments of Sweden
(0.58–17.66 (2.41 ± 2.18) mg g−1; Sánchez-García et al., 2012), Gulf
of Maine, USA (0.11–1.73 (0.65 ± 0.46) mg g− 1; Gustafsson and
Gschwend, 1998) and Gulf of Cádiz, SW Spain (0.10–1.10 (0.40 ±
0.30) mg g−1; Sánchez-García et al., 2013). This higher concentration
might be attributed to the fresh and direct input of BC in the riverine
sediments of LHR as a result of anthropogenic activities. When com-
pared with core sediment samples around the globe, we observed that
our reported values were higher than BC sedimentary concentrations
from eastern basin of Nam Co Lake (0.49–1.09 mg g− 1; Cong et al.,
2013), Alps, Switzerland (1.5–3.3 mg g− 1; Bogdal et al., 2011) and
Lake West Pine Pond, New York (0.6–8 mg g−1; Husain et al., 2008).
The spatial distribution of BC and TOC is depicted in Fig. 2. Spatially,
highest concentration of TOC (mg g−1) was observed in Zone C (33.7
± 12.1) and with slight difference, Zone A also exhibited the same con-
centration (33.4 ± 16.8) which might attributed to sedimentary load,
adjacent runoff and urban/rural waste water discharge (Saleem et al.,
2013). Zone B (24.8 ± 11.6) and D (23 ± 13.7) contained comparatively
Please cite this article as: Ali, U., et al., Sedimentary black carbon and organochlorines in Lesser Himalayan Region of Pakistan: Relationship along
the altitude, Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.10.071
5
lower TOC levels owing probably to quick runoff and lower input from
adjacent anthropogenic activities. BC results showed interesting infor-
mation when observing altitudinal concentrations. Higher concentra-
tions of BC were observed at some highest studied altitudes i-e., Parla
in Zone C (43.5 mg g− 1 at altitude of 915 masl) and Kel in Zone D
(36.9 mg g−1 at altitude of 2050 masl), apart from the fact that higher
altitude sites are comparatively less affected by anthropogenic and
urban activities. There is a strong possibility of transportation of BC
from other regions via long range atmospheric transport because BC
form we measured could be resistant to CTO-375 method thereby pri-
marily determined in the form of small and light BC particles
(Hammes et al., 2007) that can easily be transported in remote regions
(Bogdal et al., 2011). So, we implicate that owing to the higher concen-
trations at higher altitudes clearly indicates long range transport of
these pollutants in the region. We could also implicate that BC exhibits
the upslope enrichment like that of persistent organic pollutants. Apart
from long range atmospheric transport, several other activities in the re-
gion might also contribute to the BC pollution such as fossil fuel and bio-
mass burning, vehicle emissions and development of mega projects
such as Neelum Jhelum Hydropower Project particularly in Zone C.
BC/TOC is a widely accepted marker of BC sources such as industrial ac-
tivity, household coal combustion, traffic pollution, biomass burning, in-
cineration and condensation of aromatic and acetylenic molecules in
gas phase (Muri et al., 2002). BC/TOC b 0.11 has been the indication of
incomplete biomass burning as source of BC while a value of 0.5 indi-
cates the industrial activities, fossil fuels burning and traffic emissions
as BC source (Liu et al., 2011). Our study area indicated mix sources of
BC as BC/TOC ranged between 0.008 and 2.58 except one site which
showed outlier value of 12.9.
3.2. Organochlorines
To summarize the results, descriptive statistics of measured com-
pound concentrations are provided in Table 2. The OCPs studied here
were widely distributed in the surface sediments of LHR with total con-
centration of ∑OCPs were in the range between 0.59 and 3.64 ng g−1.
Among the analyzed residues of OCPs, ∑DDTs were the predominant
with average concentration of 1.13 ± 0.86 ng g−1 followed by β–
endosulfan (0.054 ± 0.015 ng g−1), ∑ HCHs (0.033 ± 0.03 ng g−1),
∑chlordane (0.026 ± 0.02 ng g−1), HCB (0.01 ± 0.02 ng g−1) and hep-
tachlor (0.008 ± 0.01 ng g−1). For ∑DDTs, the concentration ranged
between 0.57 and 3.51 ng g−1, comparable with Nam Co, Tibetan Pla-
teau (0.4–4.1 ng g−1; Cheng et al., 2014) and European high altitude
mountain Andean Lakes (0.019–4.1 ng g− 1; Borghini et al., 2005).
The concentration range reported here is much lower as compared to
riverine sediments of Edo State, Nigeria (n.d.–970 ng g− 1; Ogbeide
et al., 2016) and Eastern Cape, South Africa (n.d.–110 ng g−1; Awofolu
and Fatoki, 2003). Among DDTs, p,p′ − DDT was the dominant
congener (51.3%) followed by p,p′–DDE N o,p′–DDT N p,p′–DDD N o,p′–
DDD N o,p′–DDE. ∑ HCH ranged between 0.002 and 0.11 ng g−1,
Table 2
Descriptive statistics showing mean levels of OCPs (ng g−1) and PCB (ng g−1) in LHR.
Compound Mean ± SD Range
∑HCH 0.03 ± 0.03 0.00–0.11
∑DDT 1.13 ± 0.86 0.57–3.51
∑Chl 0.03 ± 0.02 0.00–0.07
β-Endosulfan 0.05 ± 0.02 0.03–0.09
Heptachlor 0.01 ± 0.01 0.00–0.04
HCB 0.01 ± 0.02 0.00–0.12
∑OCPs 1.24 ± 0.89 0.59–3.64
Tri-PCBs 0.06 ± 0.08 0.00–0.35
Tetra-PCBs 0.08 ± 0.12 0.00–0.59
Penta-PCBs 0.02 ± 0.04 0.00–0.20
Hexa-PCBs 0.09 ± 0.04 0.01–0.18
Hepta-PCBs 0.01 ± 0.01 0.00–0.05
∑PCBs 0.27 ± 0.27 0.01–1.31
6 U. Ali et al. / Science of the Total Environment xxx (2017) xxx–xxx

much lower than Nam Co, Tibetan Plateau (0.7–2.8 ng g−1; Cheng et al.,
2014) and Eastern Cape, South Africa (n.d. − 177 ng g−1; Awofolu and
Fatoki, 2003). Among HCH isomers, β–HCH was the dominant metabo-
lite (40.5%) followed by γ–HCH and α–HCH. Concentration of other
OCPs were ranged as follows: β–endosulfan (0.03–0.09 ng g− 1), ∑
chlordane (0.003–0.07 ng g−1), HCB (0–0.12 ng g−1) and heptachlor
(0.001–0.04 ng g−1). The sediments contamination with OCPs indicates
its long term application in the region. It has been reported in the Na-
tional Implementation Plan for phasing out and elimination of POPs
from Pakistan that Azad Jammu & Kashmir holds 31.5 MT of obsolete
pesticides which might be the major input for sedimentary
contamination (GoP, 2009). Further, pesticides production in Pakistan
was observed to be increased from 1982 to 1997 from 1.4 to
13.8 million kg along with imports of pesticides from 3.5 to
31 million kg (Younas et al., 2013). The total concentration of PCBs
(31 congeners) ranged from 0.01 to 1.31 ng g−1 with a mean value of
0.27 ng g−1, lower than sedimentary PCB concentrations of Canadian
Arctic Lake (∑68PCBs: 2.4–39 ng g− 1; Muir et al., 1996) and North-
West Scotland Lake (∑7PCBs: 1–12 ng g−1; Rose and Rippey, 2002)
while comparable with Lake Chungará (∑37PCBs: 0.16–2.45 ng g−1;
Pozo et al., 2007). Overall, PCB-169, −28 and −52 showed the highest
contribution in total of studied PCBs with 25.9, 20.3 and 6.1%. Further,

Fig. 3. Spatial distribution of OCPs and PCBs in LHR.

Please cite this article as: Ali, U., et al., Sedimentary black carbon and organochlorines in Lesser Himalayan Region of Pakistan: Relationship along
the altitude, Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.10.071
 U. Ali et al. / Science of the Total Environment xxx (2017) xxx–xxx 7

with in compound groups, PCB-28 in tri-, PCB-52 in tetra-, PCB-101 in
penta-, PCB-169 in hexa- and PCB-170 in hepta-PCBs showed higher
contributions.
3.3. Spatial/altitudinal distribution and source implications
All the studied contaminants are essentially of anthropogenic origin
so regional or local emissions and short or long-range transport process-
es may affect the spatial distribution patterns. Moreover, mountain en-
vironments have been shown to cause cold trapping effect which means
contaminants could accumulate at higher altitudes via cold condensa-
tion process (Daly and Wania, 2005; Westgate, 2013; Westgate and
Wania, 2013). The results of spatial/altitudinal distribution are depicted
in Fig. 3, 4a–c. Further, the simple graphical representation of distribu-
tion of OCPs and PCBs in different altitudinal zones is presented in SI
Figs. 1, 2 and 3. Lower altitude zones generally showed lower levels of
both OCPs and PCBs particularly Zone A apart from the fact that it is sit-
uated near anthropogenic sources. This zone is also close to the industri-
al cities of Gujrat and Gujranwala. Whereas, Zone B which is relatively
clean than Zone A exhibits higher levels that shows the upslope trans-
port of contaminants in the LHR. Moreover, lower chlorinated groups
have shown increasing trend along the altitude. Blais et al. (1998)
found lower chlorinated PCBs in snow samples collected from Rocky
Mountains, Canada and they supported the cold condensation theory
according to which more volatile less chlorinated di- and tri-PCBs
were preferentially enriched with increasing altitude owing to their
higher liquid vapor pressures. Local source emissions are also highlight-
ed in case of Zone C where highest levels of contamination were ob-
served which is close to the densely populated urban area of the
Muzaffarabad and influenced by the mega developmental activities of

Fig. 4. a–c: Spatial distribution of DDTs (a), OCPs (b) and PCBs (c) in different sampling zones of LHR.

Please cite this article as: Ali, U., et al., Sedimentary black carbon and organochlorines in Lesser Himalayan Region of Pakistan: Relationship along
the altitude, Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.10.071
8 U. Ali et al. / Science of the Total Environment xxx (2017) xxx–xxx

Fig. 4 (continued).

the Neelum-Jhelum Hydropower project. Higher POPs levels in vicinity
of industrialized and densely populated regions are reported in the liter-
ature which indicated the influence of regional and local sources
(Aichner et al., 2013; Kallenborn, 2006; Schuster et al., 2010; von
Waldow et al., 2010). Other studies including Gasic et al. (2009) also
highlighted the cities as ongoing source of organic contaminants. If we
exclude Zone C from our altitudinal pattern, it is shown that Zone D
also exhibits comparatively higher levels of OCPs and PCBs as compared
to Zone A and B despite the fact that it is relatively cleanest zone in
terms of anthropogenic source emissions. There are several possibilities
for such comparatively higher concentrations at this altitude range of
1351–2324 masl. First, this zone is next to Zone C and there is strong
possibility of transport of contaminants from Zone C (737–975 masl)
to Zone D according to the upslope enrichment phenomena of volatile
organic chemicals. Second, long range atmospheric transport could
also be the source of contamination in this high-altitude region. Back-
ward trajectory analysis (brief methodology presented in supporting in-
formation) suggested that air mass over this high-altitude region could
be the source of long range atmospheric transport of organic pollutants
(SI Figs. 4, 5, 6 and 7). Third, it might be the possibility of re-release of
contaminants from high altitude glacier regions to this zone. Recently,
Sharma et al. (2015) reported that melting Himalayan glaciers could
be the major contributor of POPs in Gangetic Plain. Guzzella et al.
(2016) revealed that melting glaciers could contribute as secondary
source of POPs in lake sediments in southern slopes of Mount Everest.
Overall, we could implicate that upslope, short and long-range transport
and local emission sources contribute to the contamination of different
altitudinal zones of Lesser Himalayan Region. Here, it should be

Please cite this article as: Ali, U., et al., Sedimentary black carbon and organochlorines in Lesser Himalayan Region of Pakistan: Relationship along
the altitude, Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.10.071
 U. Ali et al. / Science of the Total Environment xxx (2017) xxx–xxx 9

Fig. 4 (continued).

considered that our sampling sites along mountains of Lesser Himala-
yan Region exhibits diverse range rather than sampling from the slope
of a single mountain (Daly and Wania, 2005) which could ultimately af-
fects the transport mechanisms of organic pollutants in a region.
3.4. Role of BC-versus-TOC in explaining the OCs distribution
Due to higher sorption capacity of BC over TOC (Accardi-Dey and
Gschwend, 2002), the role of carbon moieties (TOC and BC) in sedimen-
tary distribution of OCs was evaluated for LHR. Previously, it has been
shown that OCPs and PCBs can extensively adsorb with BC which is
sometimes two orders of magnitude higher than absorption of TOC
(Bucheli and Gustafsson, 2000; Bucheli and Gustafsson, 2003; Hung
et al., 2010; Jonker and Koelmans, 2002; Jonker and Smedes, 2000).
Principal component analysis using XlStat was performed on overall
data set in order to evaluate the potential role of carbon moieties. The
results are depicted in Fig. 5. Component 1 explained 45.2% of variance
while component 2 explained 14.8% of the overall variance. BC clearly
influences ∑ HCHs, HCB and all PCB congener groups (Tri-, Tetra-,
Penta-, Hexa- and Hepta-) in first component of the PCA. TOC did not
show any relationship with OCPs and PCBs. Further, Pearson correlation
analysis was performed for each zone having different altitudinal ranges
and the results are presented in Table 3. No significant relationships
were observed in case of TOC neither in case of BC with OCPs and
PCBs in Zone A (357–383 masl) except hepta-PCBs that was under influ-
ence of BC. Results of Zone B (397–733 masl) are interesting that most
of the OCs showed stronger relationship with both TOC (r = 0.50–
0.90) and BC (r = 0.54–0.86). Zone C showed higher influence of BC
upon several OCPs and PCBs over TOC primarily owing to the source
similarity. For example, BC showed stronger correlation with ∑HCHs,

Please cite this article as: Ali, U., et al., Sedimentary black carbon and organochlorines in Lesser Himalayan Region of Pakistan: Relationship along
the altitude, Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.10.071
10 U. Ali et al. / Science of the Total Environment xxx (2017) xxx–xxx

PC1 (45.22 %)

Fig. 5. Principal component analysis depicting BC vs TOC relationship with other OCPs and PCBs.

∑DDT, ∑Chl, β-endosulfan, HCB and with overall OCPs with r values
of 0.73, 0.67, 0.73, 0.59, 0.72 and 0.69, respectively. Further, all PCBs ex-
cept penta-group showed significant relationship with BC with r values
of 0.88 (tri-PCBs), 0.57 (tetra-PCBs), 0.67 (hexa-PCBs), 0.54 (hepta-
PCBs) and 0.73 (∑PCBs). Penta-PCBs express weak correlation with
BC (r = 0.45) that indicates distinguish sources of penta-PCBs and BC.
At highest altitude Zone D (1351–2324 masl), no significant relation-
ship was observed in case of both BC and TOC with OCPs except HCB
vs BC (r = 0.72). Whereas, in case of PCBs, lower to medium chlorinated
groups (tri- to penta-PCBs) showed correlation with both BC and TOC.
The preferential relationship of certain OCPs with BC relative to TOC be-
tween different altitudinal zones might owed to the co-emission of
OCPs and BC, dominance of BC to adsorb OCPs, more stable discharge
of BC than TOC and larger sorption of OCPs to BC after deposition in sed-
iments (Hung et al., 2010; Sánchez-García et al., 2010). Moreover, BC
structure develops spherules/aciniform agglomerates owing to which
onion like structure of sub μm size with surface area of ~ 63 m2 g− 1
has evolved which contributes in greater sorption of OCPs (Ali et al.,
2014; Semple et al., 2013). The higher sorptive relationship of BC with
PCBs has also been documented in the literature (Ali et al., 2015b;
Jonker et al., 2004; Zimmerman et al., 2004). These compounds can pen-
etrate into the narrow pores of BC, where they interact with aromatic
pore walls of BC via π–π forces (Pehkonen et al., 2010), particularly
the planar congeners of PCBs. Further, this stronger relationship of BC
vs PCBs than TOC could also be explained by different degradability of
both carbon fractions (Ali et al., 2014). BC is considered as the most
inert form of carbon which is difficult to degrade biologically and chem-
ically over time. Whereas, TOC is relatively easy to degrade in the envi-
ronment, hence facilitating the desorption of OCs more quickly than
from BC owing to which BC showed stronger affinity with OCs as com-
pared to TOC in the sediments of LHR (Accardi-Dey and Gschwend,
2002).
3.5. Composition of OCs
The technical mixture of HCH contains 60–70% α-, 5–12% β-, 10–12%
γ-, 6–10% δ-HCH and minor amounts of other isomers (Barakat et al.,
2013) while lindane consists of almost 99% γ-HCH (Dai et al., 2011).
Therefore, the high ratio of α-HCH to γ-HCH (between 3 and 7) provides
an indication of technical HCH while high γ-HCH percentage showed

Table 3
Pearson correlation (r) of BC vs TOC with OCPs and PCBs at different altitudinal zones of LHR.

OCs compounds Zone A Zone B Zone C Zone D

BC TOC BC TOC BC TOC BC TOC

∑HCH 0.189 (0.654) 0.096 (0.821) 0.840 (0.009) 0.902 (0.002) 0.733 (0.038) 0.439 (0.276) 0.429 (0.289) 0.018 (0.966)
∑DDT −0.185 (0.661) −0.011 (0.978) 0.744 (0.034) 0.712 (0.047) 0.671 (0.069) 0.191 (0.651) −0.245 (0.559) 0.294 (0.479)
∑Chlordane 0.360 (0.381) 0.566 (0.143) 0.260 (0.535) 0.506 (0.201) 0.732 (0.039) −0.197 (0.640) 0.176 (0.677) −0.316 (0.445)
β-Endo −0.016 (0.970) 0.083 (0.845) 0.697 (0.055) 0.442 (0.273) 0.593 (0.121) 0.053 (0.901) 0.048 (0.910) 0.080 (0.850)
Heptachlor 0.468 (0.242) 0.090 (0.832) −0.108 (0.799) −0.008 (0.985) 0.042 (0.921) 0.356 (0.387) −0.108 (0.800) 0.142 (0.738)
HCB 0.436 (0.280) 0.716 (0.046) 0.670 (0.069) 0.633 (0.092) 0.718 (0.045) −0.049 (0.908) 0.717 (0.045) 0.379 (0.354)
∑OCPs −0.170 (0.687) −0.061 (0.885) 0.818 (0.013) 0.805 (0.016) 0.688 (0.059) 0.202 (0.631) −0.148 (0.727) 0.283 (0.496)
Tri-PCBs −0.393 (0.336) −0.428 (0.290) 0.730 (0.040) 0.739 (0.036) 0.885 (0.004) 0.296 (0.477) 0.594 (0.120) 0.537 (0.170)
Tetra-PCBs −0.250 (0.551) −0.435 (0.281) 0.736 (0.037) 0.756 (0.030) 0.576 (0.135) −0.177 (0.674) 0.595 (0.120) 0.525 (0.181)
Penta-PCBs −0.280 (0.502) 0.086 (0.839) 0.746 (0.034) 0.717 (0.045) 0.446 (0.268) −0.097 (0.819) 0.589 (0.124) 0.513 (0.193)
Hexa-PCBs 0.382 (0.350) 0.365 (0.374) 0.870 (0.005) 0.719 (0.044) 0.670 (0.069) 0.510 (0.196) 0.663 (0.073) 0.101 (0.812)
Hepta-PCBs 0.706 (0.050) 0.465 (0.246) 0.540 (0.167) 0.720 (0.044) 0.536 (0.171) 0.333 (0.420) 0.024 (0.955) −0.118 (0.781)
∑PCBs 0.154 (0.716) 0.071 (0.868) 0.798 (0.018) 0.793 (0.019) 0.733 (0.038) 0.149 (0.726) 0.616 (0.104) 0.499 (0.208)

Brackets contain p-values at α = 0.05.

Please cite this article as: Ali, U., et al., Sedimentary black carbon and organochlorines in Lesser Himalayan Region of Pakistan: Relationship along
the altitude, Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.10.071
 U. Ali et al. / Science of the Total Environment xxx (2017) xxx–xxx
the dominant lindane contamination in the environment (Li et al.,
2012a). The overall α-HCH/γ-HCH ratio ranged between 0.02 and 7.74
with average of 1.04 (SI Table 2) indicating mix sources of both lindane
and technical HCH. Further, higher percentage of β-HCH (40.5%) was
observed over α- and γ-HCH (SI Fig. 8). β-HCH is reported to be resis-
tant to microbial degradation and most stable isomer (Salvadó et al.,
2013) with lower water solubility and vapor pressure (Xiao et al.,
2004). Moreover, α- and γ-HCH could also be transformed to β-HCH
after prolonged aging (Salvadó et al., 2013). γ-HCH was also observed
in significant percentage (36.8%), showed clear indication of recent lin-
dane use in the region, a similar pattern previously reported for Lake
Qarun of Egypt (Barakat et al., 2013).
The ratio of DDE + DDD/DDT b 0.5 indicated direct input of DDT and
ratios N0.5 indicated the past or historical usage of DDT (Li et al., 2012b).
In LHR, these ratios were found between 0.03 and 2.01. Zone A, B and D
showed average DDE + DDD/DDT ratios of 0.07, 0.25 and 0.26, respec-
tively (SI Table 2), indicating direct inputs of DDTs while this ratio is
higher (1.16) in Zone C that indicates historical application of DDTs.
The ratios of DDE/DDD was b 1 in Zone A (0.93), indicating aerobic bio-
transformation process (Pazi et al., 2012) and N1 in Zone B, C and D
(1.20, 1.71 and 1.35 respectively), indicating anaerobic type of degrada-
tion processes in these areas. Moreover, the ratios of o,p′-DDT/p,p′-DDT
provides the information about the use of technical DDT or dicofol.
Technical DDTs comprised mainly of 15% o,p′-DDT and 85% p,p′-DDT
while dicofol shows the reverse pattern (Qiu et al., 2005). In our study
area, technical DDT was mainly used as the ratios of o,p′-DDT/p,p′-
DDT were found b1, ranging between 0.01 and 0.86.
Technical chlordane was reported to be used as an agricultural pes-
ticide for citrus, corn, home lawns, gardens and as termiticide in house
foundation (Li et al., 2006). Chlordane, technically composed of 8–13%
cis- and 8–15% trans-chlordane, the ratio (CC/TC) of which generally
lies between 1.2 and 1.3 (Lin et al., 2012). This ratio would generally
be decreased in the environment owing to faster degradation of cis-
chlordane over trans-chlordane (Ali et al., 2014). The values of CC/TC
in Zone A, C and D were 0.34, 0.67 and 0.40, respectively (SI Table 2), in-
dicated old chlordane sources in the region while Zone B exhibits value
of 1.12 that indicates technical grade application of chlordane.
The PCB profile was mainly composed of hexa- and tetra-PCBs with
31.9 and 31.6%, respectively followed by lower chlorinated tri-PCBs
(22.9%). Penta-PCBs (9.1%) and hepta-PCBs (4.4%) exhibited compara-
tively lower concentrations. In comparison with Aroclor technical mix-
tures, apparently no significant resemblance was shown with any
Aroclor mixture, however, higher presence of hexa-PCBs may be attrib-
uted towards Aroclor mixture of 1260 (SI Fig. 9).
4. Conclusions
This study provides the levels of carbon fractions (BC and TOC) and
OCs in surface sediments along the altitude in the Neelum-Jhelum
River system of Lesser Himalayan Region of Pakistan. Comparable levels
of TOC and higher levels of BC in comparison with other reported data
indicated anthropogenic influence in the region whereas the ratios of
BC/TOC specified the mix sources of biomass and fossil fuel burning.
DDTs among OCPs while hexa- and tetra-homologue groups among
PCBs were the predominant organic contaminants in the studied region.
It is implicated that upslope, short and long-range transport and local
emission sources contribute to the contamination of different altitudinal
zones of Lesser Himalayan Region. Zone C that is close to the densely
populated region of the Muzaffarabad, have shown higher levels of con-
tamination owing to source proximity. PCA and correlation analysis re-
vealed that BC potentially have influential effect on most of the OCPs
and PCBs distribution because of its higher sorption capacity. It is sug-
gested to further investigate the relationships of organic contaminants
with carbon fractions including both BC and TOC particularly in surface
sediments along the higher altitudes.
Please cite this article as: Ali, U., et al., Sedimentary black carbon and organochlorines in Lesser Himalayan Region of Pakistan: Relationship along
the altitude, Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.10.071
11
Acknowledgements
This research was supported by the Higher Education Commission,
Pakistan under National Research Program for Universities (Project #
20-4730/R&D/HEC/14/1188). Usman Ali is highly thankful to Higher Ed-
ucation Commission of Pakistan for awarding fellowship to Lancaster
Environment Centre, Lancaster University, United Kingdom under In-
ternational Research Support Initiative Program (IRSIP).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.scitotenv.2017.10.071.
References
Accardi-Dey, A., Gschwend, P.M., 2002. Assessing the combined roles of natural organic
matter and black carbon as sorbents in sediments. Environ. Sci. Technol. 36, 21–29.
Ahrens, M.J., Depree, C.V., 2004. Inhomogeneous distribution of polycyclic aromatic hy-
drocarbons in different size and density fractions of contaminated sediment from
Auckland Harbour, New Zealand: an opportunity for mitigation. Mar. Pollut. Bull.
48, 341–350.
Aichner, B., Bussian, B., Lehnik-Habrink, P., Hein, S., 2013. Levels and spatial distribution of
persistent organic pollutants in the environment: a case study of German forest soils.
Environ. Sci. Technol. 47, 12703–12714.
Akram, M., Iqbal, A., Husaini, S., Malik, F., 2011. Determination of boron contents in water
samples collected from the Neelum valley, Azad Kashmir, Pakistan. Biol. Trace Elem.
Res. 139, 287–295.
Ali, Z., Shelly, S., Bibi, F., Joshua, G., Khan, A., Khan, B., Akhtar, M., 2011. Peculiarities of
Mangla reservoir: biodiversity with sustainable use options. J. Anim. Plant Sci. 21,
372–380.
Ali, U., Syed, J.H., Junwen, L., Sánchez-García, L., Malik, R.N., Chaudhry, M.J.I., Arshad, M., Li,
J., Zhang, G., Jones, K.C., 2014. Assessing the relationship and influence of black carbon
on distribution status of organochlorines in the coastal sediments from Pakistan. En-
viron. Pollut. 190, 82–90.
Ali, U., Mahmood, A., Syed, J.H., Li, J., Zhang, G., Katsoyiannis, A., Jones, K.C., Malik, R.N.,
2015a. Assessing the combined influence of TOC and black carbon in soil–air
partitioning of PBDEs and DPs from the Indus River Basin, Pakistan. Environ. Pollut.
201, 131–140.
Ali, U., Syed, J.H., Mahmood, A., Li, J., Zhang, G., Jones, K.C., Malik, R.N., 2015b. Influential
role of black carbon in the soil–air partitioning of polychlorinated biphenyls (PCBs)
in the Indus River Basin, Pakistan. Chemosphere 134, 172–180.
Aller, M.F., 2016. Biochar properties: transport, fate, and impact. Crit. Rev. Environ. Sci.
Technol. 46, 1183–1296.
Archer, D., Fowler, H., 2008. Using meteorological data to forecast seasonal runoff on the
river Jhelum, Pakistan. J. Hydrol. 361, 10–23.
Awofolu, R., Fatoki, O., 2003. Persistent organochlorine pesticide residues in freshwater
systems and sediments from the Eastern Cape, South Africa. Water SA 29, 323–330.
Bajwa, A., Ali, U., Mahmood, A., Chaudhry, M.J.I., Syed, J.H., Li, J., Zhang, G., Jones, K.C.,
Malik, R.N., 2016. Organochlorine pesticides (OCPs) in the Indus River catchment
area, Pakistan: status, soil–air exchange and black carbon mediated distribution.
Chemosphere 152, 292–300.
Barakat, A.O., Khairy, M., Aukaily, I., 2013. Persistent organochlorine pesticide and PCB
residues in surface sediments of Lake Qarun, a protected area of Egypt. Chemosphere
90, 2467–2476.
Blais, J.M., Schindler, D.W., Muir, D.C., Kimpe, L.E., Donald, D.B., Rosenberg, B., 1998. Accu-
mulation of persistent organochlorine compounds in mountains of western Canada.
Nature 395, 585–588.
Bogdal, C., Bucheli, T.D., Agarwal, T., Anselmetti, F.S., Blum, F., Hungerbühler, K., Kohler,
M., Schmid, P., Scheringer, M., Sobek, A., 2011. Contrasting temporal trends and rela-
tionships of total organic carbon, black carbon, and polycyclic aromatic hydrocarbons
in rural low-altitude and remote high-altitude lakes. J. Environ. Monit. 13,
1316–1326.
Borghini, F., Grimalt, J.O., Sanchez-Hernandez, J.C., Barra, R., García, C.J.T., Focardi, S., 2005.
Organochlorine compounds in soils and sediments of the mountain Andean lakes.
Environ. Pollut. 136, 253–266.
Bucheli, T.D., Gustafsson, Ö., 2000. Quantification of the soot-water distribution coefficient
of PAHs provides mechanistic basis for enhanced sorption observations. Environ. Sci.
Technol. 34, 5144–5151.
Bucheli, T.D., Gustafsson, Ö., 2003. Soot sorption of non-ortho and ortho substituted PCBs.
Chemosphere 53, 515–522.
Cheng, H., Lin, T., Zhang, G., Liu, G., Zhang, W., Qi, S., Jones, K.C., Zhang, X., 2014.
DDTs and HCHs in sediment cores from the Tibetan Plateau. Chemosphere 94,
183–189.
Cong, Z., Kang, S., Gao, S., Zhang, Y., Li, Q., Kawamura, K., 2013. Historical trends of atmo-
spheric black carbon on Tibetan Plateau as reconstructed from a 150-year lake sedi-
ment record. Environ. Sci. Technol. 47, 2579–2586.
Dai, G., Liu, X., Liang, G., Han, X., Shi, L., Cheng, D., Gong, W., 2011. Distribution of organ-
ochlorine pesticides (OCPs) and poly chlorinated biphenyls (PCBs) in surface water
and sediments from Baiyangdian Lake in North China. J. Environ. Sci. 23, 1640–1649.
Daly, G.L., Wania, F., 2005. Organic contaminants in mountains. Environ. Sci. Technol. 39,
385–398.
Elmquist, M., Zencak, Z., Gustafsson, Ö., 2007. A 700 year sediment record of black carbon
and polycyclic aromatic hydrocarbons near the EMEP air monitoring station in
Aspvreten, Sweden. Environ. Sci. Technol. 41, 6926–6932.
12 U. Ali et al. / Science of the Total Environment xxx (2017) xxx–xxx
Elmquist, M., Semiletov, I., Guo, L., Gustafsson, Ö., 2008. Pan-Arctic patterns in black car-
bon sources and fluvial discharges deduced from radiocarbon and PAH source appor-
tionment markers in estuarine surface sediments. Glob. Biogeochem. Cycles 22.
http://onlinelibrary.wiley.com/doi/10.1029/2007GB002994/epdf.
Fang, Y., Chen, Y., Tian, C., Lin, T., Hu, L., Huang, G., Tang, J., Li, J., Zhang, G., 2015. Flux and
budget of BC in the continental shelf seas adjacent to Chinese high BC emission
source regions. Glob. Biogeochem. Cycles 29, 957–972.
Forbes, M., Raison, R., Skjemstad, J., 2006. Formation, transformation and transport of
black carbon (charcoal) in terrestrial and aquatic ecosystems. Sci. Total Environ.
370, 190–206.
Gasic, B., Moeckel, C., MacLeod, M., Brunner, J.r., Scheringer, M., Jones, K.C., Hungerbühler,
K., 2009. Measuring and modeling short-term variability of PCBs in air and character-
ization of urban source strength in Zurich, Switzerland. Environ. Sci. Technol. 43,
769–776.
Gélinas, Y., Prentice, K.M., Baldock, J.A., Hedges, J.I., 2001. An improved thermal oxidation
method for the quantification of soot/graphitic black carbon in sediments and soils.
Environ. Sci. Technol. 35, 3519–3525.
GoP, 2009. National Implementation Plan (NIP) for Phasing out and Elimination of
POPs from Pakistan under Stockholm Convention Article 7(a). Government of
Pakistan. http://chm.pops.int/Implementation/NIPs/NIPSubmissions/tabid/253/
Default.aspx.
Gustafsson, Ö., Gschwend, P.M., 1998. The flux of black carbon to surface sediments on
the New England continental shelf. Geochim. Cosmochim. Acta 62, 465–472.
Gustafsson, Ö., Bucheli, T.D., Kukulska, Z., Andersson, M., Largeau, C., Rouzaud, J.-N.,
Reddy, C.M., Eglinton, T.I., 2001. Evaluation of a protocol for the quantification of
black carbon in sediments. Glob. Biogeochem. Cycles 15, 881–890.
Guzzella, L., Roscioli, C., Binelli, A., 2008. Contamination by polybrominated diphenyl
ethers of sediments from the Lake Maggiore basin (Italy and Switzerland).
Chemosphere 73, 1684–1691.
Guzzella, L., Poma, G., De Paolis, A., Roscioli, C., Viviano, G., 2011. Organic persistent toxic
substances in soils, waters and sediments along an altitudinal gradient at Mt.
Sagarmatha, Himalayas, Nepal. Environ. Pollut. 159, 2552–2564.
Guzzella, L., Salerno, F., Freppaz, M., Roscioli, C., Pisanello, F., Poma, G., 2016. POP and PAH
contamination in the southern slopes of Mt. Everest (Himalaya, Nepal): long-range
atmospheric transport, glacier shrinkage, or local impact of tourism? Sci. Total Envi-
ron. 544, 382–390.
Hammes, K., Schmidt, M.W.I., Smernik, R.J., Currie, L.A., Ball, W.P., Nguyen, T.H.,
Louchouarn, P., Houel, S., Gustafsson, Ö., Elmquist, M., Cornelissen, G., Skjemstad,
J.O., Masiello, C.A., Song, J., Peng, P.a., Mitra, S., Dunn, J.C., Hatcher, P.G., Hockaday,
W.C., Smith, D.M., Hartkopf-Fröder, C., Böhmer, A., Lüer, B., Huebert, B.J., Amelung,
W., Brodowski, S., Huang, L., Zhang, W., Gschwend, P.M., Flores-Cervantes, D.X.,
Largeau, C., Rouzaud, J.-N., Rumpel, C., Guggenberger, G., Kaiser, K., Rodionov, A.,
Gonzalez-Vila, F.J., Gonzalez-Perez, J.A., de la Rosa, J.M., Manning, D.A.C., López-
Capél, E., Ding, L., 2007. Comparison of quantification methods to measure fire-
derived (black/elemental) carbon in soils and sediments using reference materials
from soil, water, sediment and the atmosphere. Glob. Biogeochem. Cycles 21.
http://onlinelibrary.wiley.com/doi/10.1029/2006GB002914/epdf.
Han, Y., Cao, J., An, Z., Chow, J.C., Watson, J.G., Jin, Z., Fung, K., Liu, S., 2007. Evaluation of
the thermal/optical reflectance method for quantification of elemental carbon in sed-
iments. Chemosphere 69, 526–533.
Huang, W., Peng, P.a., Yu, Z., Fu, J., 2003. Effects of organic matter heterogeneity on sorp-
tion and desorption of organic contaminants by soils and sediments. Appl. Geochem.
18, 955–972.
Hung, C.-C., Gong, G.-C., Ko, F.-C., Chen, H.-Y., Hsu, M.-L., Wu, J.-M., Peng, S.-C., Nan, F.-H.,
Yeager, K.M., Santschi, P.H., 2010. Relationships between persistent organic pollut-
ants and carbonaceous materials in aquatic sediments of Taiwan. Mar. Pollut. Bull.
60, 1010–1017.
Husain, L., Khan, A., Ahmed, T., Swami, K., Bari, A., Webber, J.S., Li, J., 2008. Trends in atmo-
spheric elemental carbon concentrations from 1835 to 2005. J. Geophys. Res. Atmos.
113.
Hussain, F., Ilahi, I., 1991. Ecology and Vegetation of Lesser Himalayas Pakistan. 187. De-
partment of Botany, University of Peshawar.
Jonker, M.T., Koelmans, A.A., 2002. Sorption of polycyclic aromatic hydrocarbons and
polychlorinated biphenyls to soot and soot-like materials in the aqueous environ-
ment: mechanistic considerations. Environ. Sci. Technol. 36, 3725–3734.
Jonker, M.T., Smedes, F., 2000. Preferential sorption of planar contaminants in
sediments from Lake Ketelmeer, The Netherlands. Environ. Sci. Technol. 34,
1620–1626.
Jonker, M.T., Hoenderboom, A.M., Koelmans, A.A., 2004. Effects of sedimentary sootlike
materials on bioaccumulation and sorption of polychlorinated biphenyls. Environ.
Toxicol. Chem. 23, 2563–2570.
Kallenborn, R., 2006. Persistent organic pollutants (POPs) as environmental risk factors in
remote high-altitude ecosystems. Ecotoxicol. Environ. Saf. 63, 100–107.
Koelmans, A.A., Jonker, M.T., Cornelissen, G., Bucheli, T.D., Van Noort, P.C., Gustafsson, O.,
2006. Black carbon: the reverse of its dark side. Chemosphere 63, 365–377.
Kucuksezgin, F., Tolga Gonul, L., 2012. Distribution and ecological risk of organochlorine
pesticides and polychlorinated biphenyls in surficial sediments from the Eastern Ae-
gean. Mar. Pollut. Bull. 64, 2549–2555.
Li, J., Zhang, G., Qi, S., Li, X., Peng, X., 2006. Concentrations, enantiomeric compositions,
and sources of HCH, DDT and chlordane in soils from the Pearl River Delta, South
China. Sci. Total Environ. 372, 215–224.
Li, W., Yang, H., Gao, Q., Pan, H., 2012a. Residues of organochlorine pesticides in water and
suspended particulate matter from Xiangshan Bay, East China Sea. Bull. Environ.
Contam. Toxicol. 89, 811–815.
Li, W., Yang, H., Gao, Q., Pan, H., Yang, H., 2012b. Residues of organochlorine pesticides in
water and suspended particulate matter from Xiangshan Bay, East China Sea. Bull. En-
viron. Contam. Toxicol. 89, 811–815.
Li, C.-c., Huo, S.-l., Xi, B.-d., Yu, Z.-q., Zeng, X.-y., Zhang, J.-t., Wu, F.-c., Liu, H.-l., 2015. His-
torical deposition behaviors of organochlorine pesticides (OCPs) in the sediments of a
shallow eutrophic lake in Eastern China: roles of the sources and sedimentological
conditions. Ecol. Indic. 53, 1–10.
Please cite this article as: Ali, U., et al., Sedimentary black carbon and organochlorines in Lesser Himalayan Region of Pakistan: Relationship along
the altitude, Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.10.071
Lin, T., Hu, L., Shi, X., Li, Y., Guo, Z., Zhang, G., 2012. Distribution and sources of organochlo-
rine pesticides in sediments of the coastal East China Sea. Mar. Pollut. Bull. 64,
1549–1555.
Liu, S., Xia, X., Zhai, Y., Wang, R., Liu, T., Zhang, S., 2011. Black carbon (BC) in urban and
surrounding rural soils of Beijing, China: spatial distribution and relationship with
polycyclic aromatic hydrocarbons (PAHs). Chemosphere 82, 223–228.
Liu, X., Li, J., Zheng, Q., Bing, H., Zhang, R., Wang, Y., Luo, C., Liu, X., Wu, Y., Pan, S., 2014.
Forest filter effect versus cold trapping effect on the altitudinal distribution of PCBs:
a case study of Mt. Gongga, eastern Tibetan Plateau. Environ. Sci. Technol. 48,
14377–14385.
Mahmood, R., Babel, M.S., Shaofeng, J., 2015. Assessment of temporal and spatial changes
of future climate in the Jhelum river basin, Pakistan and India. Weath. Clim. Extremes
10, 40–55.
Meire, R.O., Lee, S.C., Targino, A.C., Torres, J.P.M., Harner, T., 2012. Air concentrations and
transport of persistent organic pollutants (POPs) in mountains of southeast and
southern Brazil. Atmos. Pollut. Res. 3, 417–425.
Meng, J., Hong, S., Wang, T., Li, Q., Yoon, S.J., Lu, Y., Giesy, J.P., Khim, J.S., 2017. Traditional
and new POPs in environments along the Bohai and yellow seas: an overview of
China and South Korea. Chemosphere 169, 503–515.
Mirza, Z.S., Nadeem, M.S., Beg, M., Sulehria, A., Shah, S.I., 2012. Current status of fisheries
in the Mangla reservoir, Pakistan. Biologia 58, 31–39.
Montuori, P., Aurino, S., Garzonio, F., Triassi, M., 2016. Polychlorinated biphenyls and or-
ganochlorine pesticides in Tiber River and estuary: occurrence, distribution and eco-
logical risk. Sci. Total Environ. 571, 1001–1016.
Mughal, M.S., Khan, M.S., Khan, M.R., Mustafa, S., Hameed, F., Basharat, M., Niaz, A., 2016.
Petrology and geochemistry of Jura granite and granite gneiss in the Neelum Valley,
Lesser Himalayas (Kashmir, Pakistan). Arab. J. Geosci. 9, 1–12.
Muir, D.C., Omelchenko, A., Grift, N.P., Savoie, D.A., Lockhart, W.L., Wilkinson, P., Brunskill,
G.J., 1996. Spatial trends and historical deposition of polychlorinated biphenyls in Ca-
nadian midlatitude and Arctic lake sediments. Environ. Sci. Technol. 30, 3609–3617.
Muri, G., Cermelj, B., Faganeli, J., Brancelj, A., 2002. Black carbon in Slovenian alpine lacus-
trine sediments. Chemosphere 46, 1225–1234.
Muri, G., Wakeham, S.G., Faganeli, J., 2003. Polycyclic aromatic hydrocarbons and black
carbon in sediments of a remote alpine lake (Lake Planina, northwest Slovenia). En-
viron. Toxicol. Chem. 22, 1009–1016.
Nam, J.J., Gustafsson, O., Kurt-Karakus, P., Breivik, K., Steinnes, E., Jones, K.C., 2008. Rela-
tionships between organic matter, black carbon and persistent organic pollutants in
European background soils: implications for sources and environmental fate. Envi-
ron. Pollut. 156, 809–817.
Nawaz, M.F., Shafique, M.M., 2003. Data Integration for Flood Risk Analysis by Using GIS/
RS as Tools.
Nouira, T., Risso, C., Chouba, L., Budzinski, H., Boussetta, H., 2013. Polychlorinated biphe-
nyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in surface sediments
from Monastir Bay (Tunisia, Central Mediterranean): occurrence, distribution and
seasonal variations. Chemosphere 93, 487–493.
Ogbeide, O., Tongo, I., Ezemonye, L., 2016. Assessing the distribution and human health
risk of organochlorine pesticide residues in sediments from selected rivers.
Chemosphere 144, 1319–1326.
Parween, M., Ramanathan, A., Khillare, P., Raju, N., 2014. Persistence, variance and toxic
levels of organochlorine pesticides in fluvial sediments and the role of black carbon
in their retention. Environ. Sci. Pollut. Res. 21, 6525–6546.
Pazi, I., Kucuksezgin, F., Gonul, L.T., 2012. Occurrence and distribution of organochlorine
residues in surface sediments of the Candarli Gulf (Eastern Aegean). Mar. Pollut.
Bull. 64, 2839–2843.
Pehkonen, S., You, J., Akkanen, J., Kukkonen, J.V., Lydy, M.J., 2010. Influence of black carbon
and chemical planarity on bioavailability of sediment-associated contaminants. Envi-
ron. Toxicol. Chem. 29, 1976–1983.
Pozo, K., Urrutia, R., Barra, R., Mariottini, M., Treutler, H.-C., Araneda, A., Focardi, S., 2007.
Records of polychlorinated biphenyls (PCBs) in sediments of four remote Chilean An-
dean lakes. Chemosphere 66, 1911–1921.
Qiu, X., Zhu, T., Yao, B., Hu, J., Hu, S., 2005. Contribution of dicofol to the current DDT pol-
lution in China. Environ. Sci. Technol. 39, 4385–4390.
Rose, N.L., Rippey, B., 2002. The historical record of PAH, PCB, trace metal and fly-ash par-
ticle deposition at a remote lake in north-west Scotland. Environ. Pollut. 117, 121–132.
Saleem, M., Iqbal, J., Shah, M.H., 2013. Study of seasonal variations and risk assessment of
selected metals in sediments from Mangla Lake, Pakistan. J. Geochem. Explor. 125,
144–152.
Saleem, M., Iqbal, J., Shah, M.H., 2015. Geochemical speciation, anthropogenic contamina-
tion, risk assessment and source identification of selected metals in freshwater
sediments—a case study from Mangla Lake, Pakistan. Environ. Nanotech. Monit.
Manag. 4, 27–36.
Salem, D.M.A., Khaled, A., El Nemr, A., 2013. Assessment of pesticides and polychlorinated
biphenyls (PCBs) in sediments of the Egyptian Mediterranean coast. Egypt. J. Aquat.
Res. 39, 141–152.
Salvadó, J.A., Grimalt, J.O., López, J.F., de Madron, X.D., Pasqual, C., Canals, M., 2013. Distri-
bution of organochlorine compounds in superficial sediments from the Gulf of Lion,
northwestern Mediterranean Sea. Prog. Oceanogr. 118, 235–248.
Sánchez-García, L., Cato, I., Gustafsson, Ö., 2010. Evaluation of the influence of black car-
bon on the distribution of PAHs in sediments from along the entire Swedish conti-
nental shelf. Mar. Chem. 119, 44–51.
Sánchez-García, L., Cato, I., Gustafsson, Ö., 2012. The sequestration sink of soot black car-
bon in the northern European shelf sediments. Glob. Biogeochem. Cycles 26. http://
onlinelibrary.wiley.com/doi/10.1029/2010GB003956/epdf.
Sánchez-García, L., de Andrés, J.R., Gélinas, Y., Schmidt, M.W., Louchouarn, P., 2013. Differ-
ent pools of black carbon in sediments from the Gulf of Cádiz (SW Spain): method
comparison and spatial distribution. Mar. Chem. 151, 13–22.
Schmidt, M.W., Noack, A.G., 2000. Black carbon in soils and sediments: analysis, distribu-
tion, implications, and current challenges. Glob. Biogeochem. Cycles 14, 777–793.
Schuster, J.K., Gioia, R., Sweetman, A.J., Jones, K.C., 2010. Temporal trends and controlling
factors for polychlorinated biphenyls in the UK atmosphere (1991−2008). Environ.
Sci. Technol. 44, 8068–8074.
 U. Ali et al. / Science of the Total Environment xxx (2017) xxx–xxx
Semple, K.T., Riding, M.J., McAllister, L.E., Sopena-Vazquez, F., Bending, G.D., 2013. Impact
of black carbon on the bioaccessibility of organic contaminants in soil. J. Hazard.
Mater. 261, 808–816.
Sharma, B.M., Nizzetto, L., Bharat, G.K., Tayal, S., Melymuk, L., Sáňka, O., Přibylová, P., Audy,
O., Larssen, T., 2015. Melting Himalayan glaciers contaminated by legacy atmospheric
depositions are important sources of PCBs and high-molecular-weight PAHs for the
Ganges floodplain during dry periods. Environ. Pollut. 206, 588–596.
Sun, X., Peng, P.a., Song, J., Zhang, G., Hu, J., 2008. Sedimentary record of black carbon in
the Pearl River estuary and adjacent northern South China Sea. Appl. Geochem. 23,
3464–3472.
Tremolada, P., Villa, S., Bazzarin, P., Bizzotto, E., Comolli, R., Vighi, M., 2008. POPs in moun-
tain soils from the Alps and Andes: suggestions for a ‘precipitation effect’ on altitudi-
nal gradients. Water Air Soil Pollut. 188, 93–109.
von Waldow, H., MacLeod, M., Jones, K., Scheringer, M., Hungerbühler, K., 2010. Remote-
ness from emission sources explains the fractionation pattern of polychlorinated bi-
phenyls in the northern hemisphere. Environ. Sci. Technol. 44, 6183–6188.
Wang, X.-p., Yao, T.-d., Cong, Z.-y., Yan, X.-l., Kang, S.-c., Zhang, Y., 2006. Gradient distribu-
tion of persistent organic contaminants along northern slope of central-Himalayas,
China. Sci. Total Environ. 372, 193–202.
Wang, X.-p., Yao, T.-d., Wang, P.-l., 2008. The recent deposition of persistent organic pol-
lutants and mercury to the Dasuopu glacier, Mt. Xixiabangma, central Himalayas. Sci.
Total Environ. 394, 134–143.
Watson, J.G., Chow, J.C., Chen, L.-W.A., 2005. Summary of organic and elemental carbon/
black carbon analysis methods and intercomparisons. Aerosol Air Qual. Res. 5,
65–102.
Please cite this article as: Ali, U., et al., Sedimentary black carbon and organochlorines in Lesser Himalayan Region of Pakistan: Relationship along
the altitude, Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.10.071
13
Westgate, J.N., 2013. Proximity to Potential Source Regions and Mountain Cold-trapping
of Semi-volatile Organic Contaminants. University of Toronto.
Westgate, J.N., Wania, F., 2013. Model-based exploration of the drivers of mountain cold-
trapping in soil. Environ. Sci.: Processes Impacts 15, 2220–2232.
Xiao, H., Li, N., Wania, F., 2004. Compilation, evaluation, and selection of physical-
chemical property data for α-, β-, and γ-hexachlorocyclohexane. J. Chem. Eng. Data
49, 173–185.
Yang, R., Zhang, S., Li, A., Jiang, G., Jing, C., 2013. Altitudinal and spatial signature of persis-
tent organic pollutants in soil, lichen, conifer needles, and bark of the southeast Tibet-
an Plateau: implications for sources and environmental cycling. Environ. Sci. Technol.
47, 12736–12743.
Yao, T., Thompson, L.G., Mosbrugger, V., Zhang, F., Ma, Y., Luo, T., Xu, B., Yang, X., Joswiak,
D.R., Wang, W., 2012. Third pole environment (TPE). Environ. Dev. 3, 52–64.
Younas, A., Hilber, I., ur Rehman, S., Khwaja, M., Bucheli, T.D., 2013. Former DDT factory in
Pakistan revisited for remediation: severe DDT concentrations in soils and plants
from within the area. Environ. Sci. Pollut. Res. 20, 1966–1976.
Zheng, X., Liu, X., Jiang, G., Wang, Y., Zhang, Q., Cai, Y., Cong, Z., 2012. Distribution of PCBs
and PBDEs in soils along the altitudinal gradients of Balang Mountain, the east edge of
the Tibetan Plateau. Environ. Pollut. 161, 101–106.
Zimmerman, J.R., Ghosh, U., Millward, R.N., Bridges, T.S., Luthy, R.G., 2004. Addition of car-
bon sorbents to reduce PCB and PAH bioavailability in marine sediments: physico-
chemical tests. Environ. Sci. Technol. 38, 5458–5464.