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Anthropogenic sulphate aerosols and

large Cl-deficit in marine atmospheric


boundary layer of tropical Bay of Bengal

Manmohan Sarin, Ashwini Kumar,


Bikkina Srinivas, A. K. Sudheer & Neeraj
Rastogi

Journal of Atmospheric Chemistry

ISSN 0167-7764
Volume 66
Combined 1-2

J Atmos Chem (2010) 66:1-10


DOI 10.1007/s10874-011-9188-z

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Author's personal copy
J Atmos Chem (2010) 66:110
DOI 10.1007/s10874-011-9188-z

Anthropogenic sulphate aerosols and large Cl-deficit


in marine atmospheric boundary layer of tropical
Bay of Bengal

Manmohan Sarin & Ashwini Kumar & Bikkina Srinivas &


A. K. Sudheer & Neeraj Rastogi

Received: 24 December 2010 / Accepted: 2 May 2011 /


Published online: 10 June 2011
# Springer Science+Business Media B.V. 2011

Abstract Our long-term study provides an unequivocal evidence for near-quantitative (80
100%) depletion of chloride from sea-salts in the marine atmospheric boundary layer (MABL)
of tropical Bay of Bengal. During the late NE-monsoon (Jan-Mar), continental outflow from
south and south-east Asia dominate the wide-spread dispersal of pollutants over the Bay of
Bengal. Among anthropogenic constituents, SO42 (range: 0.635 g m3) is the most
dominant. The non-sea-salt SO42 (nss-SO42) constitutes a major fraction (5565%) of the
aerosol water-soluble ionic composition (WSIC), whereas contribution of NO3 is relatively
minor. The magnitude of Cl-deficit (with respect to its sea-salt proportion) exhibits linear
increase with the excess-nss-SO42 (excess over NH4+). We propose that displacement of HCl
from sea-salt aerosols by H2SO4 is a dominant reaction mechanism for the chloride-depletion.
These results also suggest that sea-salts could serve as a potential sink for anthropogenic SO2
in the downwind polluted marine environment. Furthermore, loss of hydrogen chloride,
representing a large source of reactive chlorine, has implications to the oxidant chemistry in
the MABL (oxidation of hydrocarbons and dimethyl sulphide).

Keywords Marine Aerosols . Sulphate . Cl-depletion . Bay of Bengal

1 Introduction

The production rate of sea-salts is estimated around 100010000 Tg year1 (Winter and Chylek
1997), and on mass basis they account for 3075% of the global budget of the natural
aerosols (Blanchard and Wookcock 1980). Sea-salt provides conducive substrate for host of
chemical reactions in the marine atmospheric boundary layer (MABL). They are involved in
heterogeneous phase reaction with acidic components (e.g. HNO3 and H2SO4) leading to the

M. Sarin (*) : A. Kumar : B. Srinivas : A. K. Sudheer


Physical Research Laboratory, Ahmedabad 380 009, India
e-mail: sarin@prl.res.in

N. Rastogi
Southern Ontario Centre for Atmospheric Aerosol Research, University of Toronto,
Toronto, ON, Canada
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2 J Atmos Chem (2010) 66:110

removal of nascent chlorine (referred as Cl-depletion) via super-saturation of HCl and its
subsequent volatilization as chloride radical (and other halogens). The process of Cl-depletion
from sea-salt aerosols is significantly pronounced over marine region affected by the polluted
air masses (Struges and Shaw 1993; Johansen et al. 1999; Kumar et al. 2008a, b). The release
of reactive chloride (as a free radical) is considered to be an important intermediate in the
oxidation reactions associated with the removal of light hydrocarbons and ozone in the
marine atmosphere (Singh and Kasting 1988; Vogt et al. 1996).
A number of studies have reported large variation in the magnitude of Cl-depletion
(ranging from few percent to 100%) over different oceanic regions (Graedel and Keene
1995; Song and Carmichael 1999; Maxwell-Meier et al. 2004; Quinn and Bates 2005; Hsu
et al. 2007). This variability has been attributed to complex interplay of several factors,
including variable wind-field, turbulence in the vicinity of sampling site and influence of
anthropogenic components. In general, aerosol chloride concentration decreases as the
particle size decreases, i.e. large amount of Cl is associated with coarse fraction (>1 m
diameter). However, chloride-deficit, relative to the sea-salt composition, increases with
decreasing particle size (Martens et al. 1973; Mouri and Okada 1993; Kerminen et al. 1998;
Yao et al. 2003; Hsu et al. 2007).
Based on a number of cruises conducted from 2001 to 2009 in the tropical Bay of
Bengal, this manuscript reports the first results on near-quantitative Cl-depletion from sea-
salt aerosols. During the late northeast monsoon (JanMar), advective transport of
pollutants from south/southeast Asia is dominant over the Bay.

2 Sampling and analytical technique

Aerosol samples were collected from the MABL of Bay of Bengal (BoB) during four research
cruises (Fig. 1), onboard ORV Sagar Kanya, in FebMar 2001, Feb 2003, Mar 2006, and Jan
2009. Bulk aerosols were sampled during all campaigns, whereas PM10 (particles having
aerodynamic diameter less than 10 m) samples were collected in Jan 2009. The time-period
of the cruises represent characteristic north-west and north-easterly winds from the Indian
Subcontinent and southeast Asia. A cruise was also undertaken in Sept 2002, during the
Asian summer monsoon when winds are confined within the MABL. The air-mass back-
trajectories (Fig. 2) and meteorological conditions are not favourable for the continental
transport during September. The complete reversal of winds during JanMarch is a
conspicuous feature over Bay of Bengal. For aerosol sampling, a high-volume sampler
(flow rate ~1 m3/min) was set up on the upper deck, 15 m asl, in front of the ships navigation
room. For each sample ambient air was filtered through PALLFLEX tissuquartz filters
(200250 mm2) for 1520 h cruising at a speed of more than 10 knots/h, thus, conforming to
the protocol that the relative wind is forward of the ships stack.
The aerosol samples collected during each cruise (summarized in Table 1) were returned to
the laboratory in sealed polythene bags. Subsequently, samples were subjected to chemical
analysis, involving anions (Cl, NO3 and SO42) and cations (Na+, NH4+, K+, Mg2+, and
Ca2+), by DIONEX Ion-Chromatograph (Rastogi and Sarin 2005; Rengarajan et al. 2007;
Kumar et al. 2008a, b). The concentrations of ionic species were corrected for procedural
blanks. Based on blank concentrations and average volume of air filtered (~2000 m3), the
detection limits for the water-soluble ionic species in aerosols were ascertained (18, 18, 20,
18, 25, 10, 30 and 30 ng m3 for Na+, NH4+, K+, Mg2+, Ca2+,Cl, NO3 and SO42
respectively). The reproducibility in the analytical data for the measured concentrations is
within 5% based on the repeat analysis of a number of samples and standards.
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J Atmos Chem (2010) 66:110 3

Fig. 1 Cruises undertaken on-


board ORV Sagar Kanya in the
Bay of Bengal during the late
NE-monsoon (JanMarch). One
cruise was also taken in September
when the winds are from
sea to land

3 Results and discussion

3.1 Chemical composition of aerosols over Bay of Bengal

The average water-soluble ionic composition (WSIC), expressed as the sum of mass
concentration of all cations and anions (in g m3), along with their minimum and
maximum concentrations during the different campaigns are summarized in Table 1. Also,
shown are the average abundances of individual constituent (cation and anion) of WSIC.
The Na+ concentrations are comparable during all campaign (except those during Sept
2002). However, significantly lower concentrations of chloride (Cl) compared to those
expected from Na+/Cl ratio in the sea-salts is conspicuous throughout our data set. The
deficiency of Cl in aerosols is interpreted as removal from sea-salt particles by acidic
constituents (SO42 and NO3) associated with the continental outflow. The contribution of
water-soluble constituents from dust, assessed through nss-Ca2+ and nss-Mg2+, is relatively
low (Ca2+ =5% and Mg2+ =2%; Fig. 3). The concentration levels of anthropogenic
components (nss-SO42 and NH4+) dominate the aerosol composition over BoB (Table 1).
The nss-SO42 constitutes major fraction of WSIC (averaging more than 55% of the total
WSIC, Fig. 3), during the period of late northeast monsoon (JanMar).

3.2 Chloride-depletion in the MABL of Bay of Bengal

The scatter-plot between mass concentrations of Na+ and Cl-, for the data collected during
the five cruises, is shown in Fig. 4a. It is noteworthy that deficiency of chloride, with
respect to Na+ and Cl ratio defined by the sea-water line, is significantly high in samples
collected during FebMar 2001, Mar 2003, Mar 2006 and Jan 2009. It may be argued that
contribution of Na+ from dust, if any, could lead to overestimation of Na+ (Fig. 4a), and
hence reflecting higher deficiency of chloride. In order to ascertain that such large Cl-deficit
is caused by its removal from sea-salt and not due to the enrichment of Na+ from dust, we
have examined the scatter-plot between Mg2+ and Na+ (Fig. 4b). The data points exhibit a
significant linear correlation (r2 =0.90; Fig. 4b) with a slope of 0.11 (similar to sea-water
line; weight ratio of Mg2+/Na+ =0.12), suggesting that bulk of Na+ is derived from sea-salts.
However, small enrichment of Mg2+ is observed at the low concentration which can be
attributed to its source from carbonate dust (also evident from significant contribution of
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4 J Atmos Chem (2010) 66:110

Fig. 2 Air-mass back-trajectories


computed for the cruise tracks in
the Bay of Bengal: (a)
September-2002 and (b) January-
2009, indicating dominance of
continental outflow during
JanMarch

nss-Ca2+ in the ion-balance). A recent study by Kumar et al. (2008a), from the Arabian Sea
has reported chloride deficiency of ~60% during the period of inter-monsoon (March
April). The large buffering capacity of mineral dust is a likely cause for the neutralization of
the acidic constituents (NO3 and nss-SO42) and hence lower magnitude of Cl-depletion
over the Arabian Sea than that over Bay of Bengal.
The Cl-depletion [also referred as Cl-deficit (%)] is defined by the following relation:
h i
Cl  depletion% 100 1:80Na  Cl m =1:80Na ;

where (1.80 * Na+) is the Cl concentration (in g m-3) expected from sea-salts; and Cl-m is
measured chloride (in g m3) in the sample. The Cl-deficit (%) measured over Bay of
Bengal for different sampling years are presented in Table 1. Several studies in the past
(Savoie and Prospero 1982; Kerminen et al. 1998; Johansen et al. 1999) have addressed to
the concept of chloride deficiency, ranging from 20 to 30%, resulting from chemical uptake
of nss-SO42 derived from DMS sources. We propose that relatively lower magnitude of
Table 1 Water-soluble ionic composition (WSIC) in of ambient aerosols during different campaigns over Bay of Bengal. All concentrations are expressed in units of g m3. N is the
number of samples collected in each cruise is shown in brackets

FebMar-01 (N=26) Sep-02 (N=11) Feb-03 (N=24) Mar-06 (N=23) Jan-09 (N=33)
J Atmos Chem (2010) 66:110

Min. Max. AvSd Min. Max. AvSd Min. Max. AvSd Min. Max. AvSd Min. Max. AvSd

WSIC 3.1 18.0 8.63.6 3.1 20.8 9.65.6 6.4 22.5 9.23.3 3.8 15.7 8.93.7 4.6 50.3 18.910.8
NH4+ bda 1.0 0.370.35 0.0 0.0 bd 2.3 0.70.7 0.2 1.9 0.90.6 0.1 4.8 1.71.2
Na+ 0.2 3.8 1.21.1 0.3 5.9 2.51.8 0.1 2.0 0.90.5 0.01 2.3 0.90.6 0.1 12.2 3.13.3
K+ 0.1 0.5 0.40.1 0.0 0.3 0.10.1 0.2 0.7 0.30.1 0.1 0.4 0.20.1 0.1 1.3 0.70.3
Mg2+ 0.1 0.6 0.20.14 0.1 0.8 0.30.2 0.1 0.4 0.20.1 0.1 0.3 0.20.1 0.0 0.5 0.20.1
Ca2+ 0.1 1.0 0.40.3 0.1 1.1 0.40.3 0.3 2.0 0.80.4 0.2 1.4 0.70.3 0.0 0.5 0.20.1
Cl 0.01 4.7 0.71.4 0.1 8.0 3.53.1 0.0 1.0 2.22.9 bd bd bd 1.5 0.30.4
NO3 bd 0.8 0.10.2 bd 0.5 0.20.2 0.1 3.0 0.70.8 bd 0.3 0.070.08 0.1 2.6 0.80.6
SO42 2.4 7.7 4.91.7 0.6 5.5 2.41.5 2.7 15.6 5.52.8 2.6 10.6 5.92.5 2.3 35.1 11.87.6
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nss-SO42 2.3 7.4 4.61.7 (94%)b 0.3 5.2 1.81.5 (75%) 2.2 15.3 5.32.8 (96%) 2.5 10.3 5.82.4 (98%) 2.0 35.0 11.37.7 (95%)
nss-SO42 (%)c 18.8 76.5 58.116.6 3.5 64.2 26.525.1 31.0 72.1 56.115.4 57.0 72.3 64.93.9 27.5 69.6 57.19.7
Cl-Deficit (%) 26.0 98.5 82.319.7 6.2 87.5 39.434.7 65.3 98.2 90.97.8 85.5 99.8 98.23.0 13.0 100.0 88.816.3
a
below detection limit
b
Contribution of nss-SO42 to total SO42
c
Fractional contribution of nss-SO42 to WSIC
5
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6 J Atmos Chem (2010) 66:110

Fig. 3 Long-term average frac-


tional contribution of water-
soluble ionic composition (WSIC)
of ambient aerosols in the MABL
of tropical Bay of Bengal during
JanMar, suggesting dominance of
anthropogenic NH4+ and SO42.
On average, nss-SO42 accounts
for more than 95% of total
sulphate

chloride depletion during Sept-2002 is attributed to background source of DMS (Table 1).
The dominance of continental sources during JanMar, compared to September month, is evident
from air-mass back-trajectories over BoB (Fig. 2). This further strengthens our argument that Cl-
deficit, during September-2002 cruise, is attributed to sulphate derived from DMS oxidation.

3.3 Processes controlling Cl-depletion: Role of acidic species

The scatter plot between equivalent concentrations of (Cl +NO3-) and Na+ (Fig. 5a)
indicates that the data points fall far away from the equiline and that the contribution of
NO3 (HNO3) to the chloride deficit is not significant in the chemical uptake by sea-salt
particles. On a spatio-temporal scale, aerosol NO3 concentration is 810 times lower than

Fig. 4 Scatter plot among Na+ and Cl and Na+ and Mg2+ for the ambient aerosols collected over Bay of
Bengal. The data points in (a) falling below the sea-water line imply large scale Cl-deficit
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J Atmos Chem (2010) 66:110 7

Fig. 5 Relationship between acidic constituents (NO3 and SO42) and Na+ suggesting that displacement of
HCl from sea-salts by H2SO4 is a dominant chemical reaction

that of nss-SO42 (Table 1). The chemical reaction involving sea-salt particles and HNO3
has been well documented for the chloride loss (Wu and Okada 1994; Zhuang et al. 1999;
Quinn and Bates 2005; Hsu et al. 2007). However, owing to lower concentration of NO3
in the MABL of BoB, we have argued in favour of acid-displacement reaction among
H2SO4 and NaCl to form Na2SO4 and HCl. Subsequent vapourization of HCl under super-
saturation leads to Cl-deficit from sea-salt aerosols. The uptake of fine mode sulphate
aerosols onto sea-salt is dictated by near-saturated (98%) relative humidity conditions.
Hsu et al. (2007) have observed a significantly lower ratio of [Cl +NO3] to Na+ (mean
value=0.17) with large scatter for fine mode aerosols over the subtropical South China Sea.
In this study, [Cl +NO3-]/Na+ ratio over BoB centres around 0.37, indicating the
dominance of SO42 aerosols in the chloride removal process over BoB region.
It is thus essential to invoke that the removal of chloride from sea-salt is attributed to
chemical reaction involving uptake of nss-SO42 (H2SO4) by sea-salts. We have also
examined the relationship between NH4+ and nss-SO42 (equivalent units; Fig. 6), the

Fig. 6 Scatter plot between the


nss-SO42 and NH4+ (in equiva-
lent units) in the aerosols collected
over Bay of Bengal
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8 J Atmos Chem (2010) 66:110

NH4+/nss-SO42 ratio of less than 1 (Av=0.57, except during Sept 2002), suggests the
dominance of NH4HSO4 rather than (NH4)2SO4. The lower ratio further emphasizes that acidic
nature of aerosols is mainly caused by higher abundance of sulphate. The excess nss-SO42 ,
over and above that neutralized by NH4+, plays an important role in the Cl-depletion via
volatilization of HCl. A significant linear correlation (r2 =0.88) between [(Cl +SO42-)(NH4+ +
nss-Ca2+)] versus Na+ (in equivalence units), and a slope of 0.90 (Fig. 5b) suggest the acid
displacement of chloride from sea-salts defined by the following chemical reaction
H2 SO4 g 2NaClaq ! Na2 SO4 2HClg:
The most notable feature of the data relates to the plot (Fig. 7) between Cl-deficit (neq m3)
and excess nss-SO42 (corrected for neutralization by NH4+ in equivalence units). The
deficiency of chloride (calculated based on Na+ concentration) exhibit a linear relationship
with excess-nss-SO42. Such an observation suggests the near-quantitative Cl-deficit is
caused by the high abundance of anthropogenic sulphate over tropical Bay of Bengal.

4 Conclusions and implications

A 10-year record of the chemical composition of ambient aerosols, studied from the MABL
of Bay of Bengal, has led us to make following important conclusions:
(a) The water-soluble ionic composition of aerosols is dominated by the anthropogenic
species (nss-SO42 and NH4+) associated with the continental outflow from south and
south-east Asia. Our results also document that the contribution of nss-SO42 to water-
soluble ionic composition of ambient aerosols has not substantially increased over the
past one decade.
(b) A near-quantitative Cl-depletion is attributed to the displacement of HCl from sea-salt
particles, suggesting their potential as a net sink for anthropogenic SO2 in the MABL;
and change in the size-distribution of sulphate aerosols from fine to coarse mode.
These results have important implications in assessing the role of chlorine as a free radical in
the lower troposphere (Finlayson-Pitts et al. 1989). Similar to its reactivity in the stratosphere

Fig. 7 A linear increase in


Cl-deficit (neq m3) with increase
in excess-nss-SO42 (neq m3) for
the chemical data of aerosols over
Bay of Bengal
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J Atmos Chem (2010) 66:110 9

(via photochemical production), chlorine atom is responsible for the destruction of ozone, an
important tropospheric oxidant (Solomon 1999). Keene et al. (1990), had suggested that
chloride atoms formed via chemical reactions with sea-salts would have major consequence
for the oxidation of dimethyl sulphide (DMS). A recent study (Raff et al. 2009) had
suggested the possibility of an enhancement in ozone levels in the troposphere due to
chemical reaction of chloride radical with volatile organic compounds (including methane),
thus favouring removal of reactive chlorine from the atmosphere. The suggested pathway will
extend the lifetime of nitrogen oxides, the main precursors of ozone production in the
atmosphere. In addition, there is a state of equilibrium between the reactive chlorine atom and
stable HCl (end product), which is finally removed via rainout or dry deposition.
As discussed in the earlier section, release of chlorine is governed by the acid displacement
reaction, wherein sea-salt particles exchange hydrochloric acid with another acid (H2SO4 and
HNO3). However, there is an ongoing debate on the reaction mechanism by which chloride is
released from sea-salt particles, either involving acid-base desorption or their reaction with
non-acidic N gases. In the latter case, rapid photolysis of Cl2 and ClNO2 has been proposed
for the production of Cl atom and ultimately HCl through subsequent reactions (Oum et al.
1998). Keene et al. (1990), had hypothesized a mechanism for the Cl loss initiated by reaction
of O3 at sea-salt aerosol surfaces, generating Cl2, followed by rapid photochemical
conversion of Cl2 to HCl via Cl atoms and recapture of HCl by the aerosols. A recent
study (Osthoff et al. 2008), has reported enhancement in the production of nitryl chloride
(ClNO2) during night-time reaction of N2O5 with chlorine-containing aerosol particles. The
photolysis of ClNO2 after sunrise can, thus, lead to a source of chlorine atom, when other
oxidants and radicals (e.g. OH and NO3) are less abundant. The production of ClNO2 is
expected to be relatively more favoured in the polluted continental outflow, near-coastal
locations where NOx, O3, sea-salt and aerosol sources co-exist. Our data set on chemical
composition of ambient aerosols over tropical Bay of Bengal provides a case study for the
chemistry of sea-salts in the rapidly changing scenario of growing anthropogenic activities.
The results presented here on near quantitative Cl-depletion provide clear evidence
supporting the acid (HCl) displacement reaction involving the sea-salt particles and
anthropogenic SO42-. We propose that relatively high concentration levels of nss-SO42
(range: 235 g m3), persistent over the Bay under favourable wind regimes during Jan
March, have overwhelming impact on Cl-depletion. A linear increase in the Cl-deficit with
increase in the mass fraction of nss-SO42- further provides credence to the displacement
reaction of HCl. The downwind polluted tropical marine regions, similar to Bay of Bengal,
demand further studies related to the night-time variability of reactive chlorine atom in order
to improve model simulations on the atmospheric chemistry of NOx and ozone.

Acknowledgement We thank the crew members of ORV SagarKanya for their help during different cruises
conducted in the Bay of Bengal. The funding support received from office of the ISRO-GBP (Bangalore,
India) is greatly acknowledged.

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