Precipitation chemistry over urban, rural and high altitude Himalayan stations
in eastern India

Arindam Roy, Abhijit Chatterjee, Suresh Tiwari, Chirantan Sarkar, Sanat
Kumar Das, Sanjay Kumar Ghosh, Sibaji Raha

PII: S0169-8095(16)30148-X
DOI: doi: 10.1016/j.atmosres.2016.06.005
Reference: ATMOS 3710

To appear in: Atmospheric Research

Received date: 8 April 2016
Revised date: 25 May 2016
Accepted date: 7 June 2016

Please cite this article as: Roy, Arindam, Chatterjee, Abhijit, Tiwari, Suresh, Sarkar,
Chirantan, Das, Sanat Kumar, Ghosh, Sanjay Kumar, Raha, Sibaji, Precipitation chem-
istry over urban, rural and high altitude Himalayan stations in eastern India, Atmospheric
Research (2016), doi: 10.1016/j.atmosres.2016.06.005

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Precipitation chemistry over urban, rural and high altitude
Himalayan stations in eastern India

Arindam Roya, Abhijit Chatterjeea,b,c*, Suresh Tiwarid, Chirantan Sarkara, Sanat
Kumar Dasa,b, Sanjay Kumar Ghoshb,c and Sibaji Rahaa,b,c

Environmental Sciences Section, Bose Institute, Kolkata-700054, India

CAPSS, Bose Institute, Salt Lake, Kolkata-700091, India
NFAPSS, Bose Institute, Darjeeling-734101, India

Indian Institute of Tropical Meteorology, New Delhi-110060, India


A study of precipitation (rainwater) chemistry during the two consecutive summer
monsoon seasons of 2013 and 2014 at a high altitude station (2200 m asl) at eastern Himalaya
region (Darjeeling); a typical metropolitan urban location (Kolkata), and a rural environment
near the Bay of Bengal (Falta) was conducted. The volume-weighted mean (VWM)
concentration shows that total ionic composition was maximum over Kolkata (391 µeq l -1)
followed by Falta (204 µeq l-1) and Darjeeling (64 µeq l-1). 85 % rain samples were alkaline
over Kolkata, whereas, 55 and 65 % samples were acidic over Falta and Darjeeling

respectively. Ca2+ was the most potential species to completely neutralize the acidity over
Kolkata, whereas, NH4+ was the potential species to partially neutralize the acidity over Falta

and Darjeeling. The deposition fluxes of anthropogenic and dust species over Kolkata was
remarkably higher than Falta and Darjeeling. Anthropogenic and dust chemical species in

rainwater were found to be dominant over Kolkata and Falta when the air masses passes from
the polluted continental region. Rainwater acidity over Darjeeling was highest when air

masses arrived from the Arabian Sea compared to air masses from the Bay of Bengal.
Positive matrix factorization model was used for the source apportionment of the ionic
species scavenged by rain. Comparable contributions of marine, dust, and anthropogenic

sources were identified a major source over Kolkata. The major contributions were identified
from marine and fossil fuel burning over Falta, whereas, marine, biomass/coal burning,
ammonia from agricultural activities and domestic wastes were identified as the major
sources over Darjeeling.

Keywords: Rainwater Chemistry, Rainwater Acidity, Source Apportionment, Ionic Species,
Eastern Himalaya

Corresponding author,
Dr. Abhijit Chatterjee
Environmental Sciences Section, Bose Institute, Kolkata-700054, India
Tel.: +91-9051585800; Fax: +91-33-2355-3886
E-mail address:

The acidification of rainwater is primarily related to the emissions of acidic species such as SO2 and NOx in the atmosphere. 1995. as these gases are the precursors of major acids H2SO4 and HNO3. 2002). 2006. 2008). Usually. Mg2+.. the alkaline rainfalls show very low concentrations of secondary species SO42. Glavas and Moschonas.and high concentrations of primary species like Ca2+. 2009) and micro-meteorological factors (Seto and Hara. Soil-derived alkaline species and gaseous ammonia have their potential to neutralize a fraction of the acidic constituents and influence the atmospheric acidity (Al- Momani et al.. Strayer et SC al. CE biogeochemical cycle as well as the climate change (Tiwari et al. 2005. 2015). K+ and secondary species like NH4+. André et al. gases IP for both the local and long-range transport...and NO3.. Pelicho et al. The first process refers to the MA washout of the aerosols and gases present below the cloud and scavenged by raindrops along their fall. Cape et al. Tiwari et al. However. (2015) studied long- . 2007). process of scavenging of chemical species by rain R (Celle-Jeanton et al. 2007).. The chemical composition of precipitation or rainwater gives an idea about the impact of AC local and long-range transport from upwind sources on the chemistry of local precipitation (Sakihama et al.. the most efficient pathway to remove the P atmospheric pollutants is below cloud scavenging which is a major pointer of the ecosystem. Introduction The chemical composition of rainwater strongly depends on the atmospheric chemical composition and several factors are responsible to govern the concentrations of chemical T species in precipitation as types and distributions of sources of atmospheric aerosols. 2006.. There are two main processes through which aerosols and gases get scavenged by NU rain called below-cloud scavenging or “washout” and in-cloud scavenging or “rainout” (Mouli et al. ACCEPTED MANUSCRIPT 1. 2012. The second process corresponds to the condensation of water vapour on aerosol D particles during the formation of cloud droplets and incorporation of gases surrounding the TE droplets by aqueous-phase reactions..

2013 and 2014. While precipitation chemistry was studied over several Indian cities. NU Tiwari et al. Kolkata in eastern India remained an unexplored territory for such studies. Ravichandran et al. a high altitude hill station at eastern Himalaya. references therein). Earlier. 2005 .. 2000) and T future emissions of these pollutants in Asia will be equal to or even greater than the combined IP emissions of Europe and North America by 2020 as estimated by Galloway (1995). Chate et al.... Kulshrestha et al. 2003 . The present study on precipitation or rainwater chemistry has been performed at three AC different stations with absolutely different atmospheric environments in eastern India during monsoon (June-September) for two consecutive years. Safai et al. 2011) TE and various stations along Indo-Gangetic Plain or IGP (Tiwari et al. 2007 .. Das et al. Budhavant et al. Saxena et al... Rastogi and Sarin. 2002 . 2009. R Rainwater chemistry has been largely studied at different urban and rural locations at SC northern parts (Kulshrestha et al.. D Rastogi and Sarin. a few precipitation studies were made at the north- . such studies on precipitation chemistry at the eastern part of India are rare. 2003. 2007. 2005. 2007) in eastern India. Kumar et al.. a mega city with typical urban atmosphere at IGP and over Darjeeling. Chate et al. western and P CE south-western India. 1996 . a rural station at IGP and near the north-east coast of Bay of Bengal (BoB).. 1996 . The emissions of SO2 and NOx in east Asia are increasing significantly due to the fast-growing economy (Lee et al. 2006 . Budhavant et al.. 1994. 1994 ... The study has been made over Falta. 2004. Balachandran et al. As far as Himalaya is concerned. Kumar et al. Rao et al. 1996 . 2010) and urban atmosphere (Singh et al.. 2016).. 2009. Naik et al. a few studies were performed over rural atmosphere near the east coast of BoB (Das et al. Tiwari et al. ACCEPTED MANUSCRIPT term trends in various acidic and alkaline components both in cloud and rainwater over a complex topography in the northern Pennines of England.. 2005 .. 2003 .... western and south-western parts MA of India (Khemani et al.. 2001 . In comparison to the studies made over several stations in northern. 2002. 1995 .. Kolkata. Momin et al. Kulshrestha et al..

The city is bounded to the west and northwest by the river Hooghly spread along 80 km.33 °N and 88.. formerly known as Calcutta. medium and heavy) are quite high during the daytime. census2011. The sampling site is a residential-cum-commercial site at northern Kolkata and within 100 meters. (3) the possible source region of chemical species in rainwater. Methodology D 2. Sundarban mangroves forest.20 °E).5 million according to the 2011 census report: http://www. the world’s largest mangrove eco-region at the land-ocean boundary of the Ganges delta is situated at about 90 km from Kolkata. (2) the major factors regulating the rainwater acidity. urban and the Himalayan locations T simultaneously in order to investigate the effect of different atmospheric environments on the IP chemical composition of rainwater. and Darjeeling inside the campus of Bose Institute (Fig.html). R The objectives of the study are to investigate (1) the spatial variation in rainwater SC chemistry over a typical urban and a rural atmosphere at IGP and a high altitude Himalayan NU region over eastern part of India. and (4) to find out the possible role MA of long-range transport of chemical species in rainwater in receptor sites over study regions. Description of sampling site TE Rainwater samples were collected from three different locations in the eastern part of P India at Kolkata. 1).in / census/city/215-kolkata. Falta. is the second most populous city of India (~ 4.1. Thus. this study is an effort made for the first time in India where precipitation chemistry has been studied over rural coastal. . 2. The detail CE descriptions of the sites are given below: AC (i) Kolkata ( several busy roads are passing where the densities of all types of vehicles (light. 2012) but eastern Himalaya in India has yet been unexplored. ACCEPTED MANUSCRIPT western part of Himalaya (Tiwari et al.

The National Highway (NH55). agricultural AC activities etc. reaching up to 70 m tall and 4 m trunk diameter. office buildings. schools and colleges buildings. biomass burning. 77 and 138 over Kolkata. There is a huge vegetation cover in and around of the Darjeeling by a Japanese cedar (Cryptomaria japonica) tree which a very large evergreen tree. 88º15’E) is situated in the eastern Himalaya elevated 2200 NU m from the mean sea level.2 Collection of rainwater and chemical analysis The total number of rainwater samples collected during the study period were 130. (iii) Darjeeling (27º 01’N. The major R local source of anthropogenic aerosols is Diesel-driven small boats which run for the SC villagers to cross the river for 5-6 times a day. The nearest sea coast is the Bay of Bengal which is at around 40 km from this station. and Darjeeling respectively during the monsoon (June – September) period. The sampling site is located at an elevation of 200 m from the MA main town center which is covered by several hotels and resorts. D having high vehicular traffic density connects Darjeeling to Siliguri which is located on the TE foothill of Himalaya. Sarkar et al. 2014. 2014. This P CE mountain railway is a world heritage site. is a narrow gauge railway which runs by coal and diesel for the tourists. ACCEPTED MANUSCRIPT (ii) Falta (22.06 °E) which is situated at ~50 km south of Kolkata. (Adak et al. 2. Darjeeling represents a typical urban atmosphere with major anthropogenic sources of vehicular emissions. The sampling site represents a typical rural station with less vehicular strength. Darjeeling Himalayan Railway (also known as “Toy Train”). with red-brown bark which peels in vertical strips. 2013 and 2014. 2015). bus and car stands. Rainwater samples were collected daily basis from around 09:00 AM every day (24 hours sample) by a bulk collector consisting of a . The site is situated on the bank of the river Hooghly at the west.. There are several T agricultural fields in and around the sampling site where farmers use to farm rice during the IP monsoon period. shopping malls. Falta. is situated.18 °N and 88..

pH and conductivity meter were standardized using standard pH solution (pH 4.0 mM) were used as eluent for anion analysis with the flow rate of 0. SC Samples were filtered using 0.3. Samples with bird droppings. K+.01. leaves. Tiwari et al. 0.. 0. Prior to use.9 ml min-1 with separate columns.45 µm Millipore filter paper and transferred to 100 ml polypropylene bottles pre-cleaned in Milli-Q water. Thymol (< 5 mg) was added to the NU samples as a preservative to prevent the decomposition of volatile components like NH4+ MA (Gillett and Ayers. The samplers were installed on the rooftop at a height of ~10 m (Falta) and ~15 m (Darjeeling and Kolkata) from T the ground and ~2 m from the rooftop of each campus of Bose Institute at all three stations. IP pH and specific conductivity of rainwater samples were measured using a digital pH and R conductivity meter (Sartorious Professional Meter. D TE Metrohm.7 ml min-1.0 and 9. The samples were then refrigerated at 4 ºC for further chemical analysis. ACCEPTED MANUSCRIPT polypropylene funnel of 8-inch diameter and a polyethylene bottle of 2 L capacity. Switzerland). NO3- and SO42-) were determined by using Ion Chromatography (861 Advanced Compact IC.08 . The detection limits of the measured water soluble ionic species were 0.7 mM) and pyridine 2.2) and KCl solution for pH and conductivity measurement respectively. The concentrations of water soluble ionic species in field blanks were found to be negligible in most of the blanks. the samplers were cleaned and soaked in Milli-Q water and dried. Na2CO3 (3. Several field blank samples were also analyzed AC for the correction of the sample data. 1991.05. Mg2+.06. Water-soluble ionic species (Na+.05. whereas. Cl-.6- P dicarboxylic acid (PDCA) (0. 0. Quality control Field blanks were prepared using de-ionized water during cleaning/washing of rain collecting funnel and were analyzed for chemical species as rain sample. dust fall or any other visible contaminants were discarded. HNO3 (1. PP20) immediately after the collection. 2. 0. 2015). Ca2+. 0. 0. NH4+.08.2 mM) and NaHCO3 (1.7 mM) were used as eluent for cation analysis with the flow CE rate of 0.06.

. The higher significant correlation coefficients (R2 > 0. The ratio was found to be 0. whereas. After adding bicarbonate anions. however. the ratio is expected to be closed to unity. The association of CO32-/HCO3.etc. however.8. and 1 % for SO42–. If all the major anions and cations are analyzed. ACCEPTED MANUSCRIPT and 0. The analytical precision was calculated from repeated measurements running standard samples of ionic species.with Ca2+ has been studied by Herut et al. Mg2+.. K+ and NH4+ was ~2%. IP Ion balance technique was used to check the quality of analytical data of water soluble R ionic species for three stations. Bicarbonate (HCO3-) anions could not be measured directly because of analytical limitations in the present study but calculated from measured pH of rainwater samples (Granat 1972).. (2000) and Kulshreshtha et al.08±0. PO43. The concentration of Ca2+ in rainwater over Kolkata was found to be much AC higher than Falta and Darjeeling (discussed later). The precision was found to be 3.16. and Darjeeling respectively for this study period.and ∑+ were observed over all the stations. for Cl– .. K+. 5. Mg2+ T respectively. the ratio over Kolkata shows significant deviation from unity indicates the possible P missing of anions like bicarbonate (HCO3-). bicarbonate concentrations over Falta and Darjeeling were found to be negligible. NH4+.14 for Kolkata. The ratio values close to unity TE over Falta and Darjeeling show completeness and correctness of the analytical measurements. Over an Indian urban metropolis like Kolkata with massive industrial.13 and 1. 1.06±0. the ratio of the sum of anions (∑-) to SC the sum of cations (∑+) helps us to understand the completeness and correctness of the NU chemical analysis. Kulshreshtha et al.Na+. NO3– and SO42– respectively.07 ppm for Na+. The mean ionic ratio i. . 6. C2O42-). Cl–. 2005). 1996.9) between ∑. (2003) over areas with high enrichment of Ca2+. CH3COO-.7±0. CE F-. the ratio value over Kolkata varying 0.e. vehicular and other anthropogenic activities. Ca2+. Weak organic acids and fluoride play important roles in rainwater chemical composition in India (Kumar et al. NO3–. weak organic acids (HCOO-. Any sample D deviating far from this ratio has been discarded after analysis. Ca2+. MA Falta.7 to 0.

the pH value is of less than 5. 55 and 65 % were acidic in Falta and Darjeeling respectively.2 to 6.6. Spatial variability of pH and conductivity in rainwater over eastern part of India IP The fundamental test to judge the acidity in rainwater is to check the pH and R SC conductivity which were done for all three stations. It shows that maximum frequency contribution of the samples occurred in the range of 6.1 (acidic) and 4. commonly classified as acid rain CE because of anthropogenic input of SOx. rainwater acidity might be neutralized by alkaline species whereas. whereas. ACCEPTED MANUSCRIPT one could expect significant contributions of those weak organic acid anions in rainwater composition which remained unanalyzed in our study. Thus. 3. According to earlier studies. 2012). Piñeiro et al. 4. Thus.4 (alkaline). average pH values and frequency distribution indicates that over Kolkata. over Falta and Darjeeling.0 D (28%) and 4. 1982.0 – 6. The pH values in rainwater over Kolkata AC were alkaline (85 %).6 with an average of NU 5.0 ± 0. Oliveira et al.3 ± 1. however. at Falta and Darjeeling was in the range of 5. Wu and Han (2015) observed ~ 60 % acidic rain events over Three Gorges Reservoir (TGR) at southern China due to un-neutralized NO3– and SO42–. the result will be commented in detail in the following section through the support of the acidic and neutralizing potentials and neutralizing factors of the respective alkaline . the pH values varied from 4. During the study period. Falta and Darjeeling respectively. TE the value of pH in rainwater is usually ~ 5. However. Fig 2 shows the frequency distribution of pH of rainwater over three MA stations. and other acid precursors into the atmosphere (Charlson and Rodhe.5 – 5.3 to 6.. in a clean atmosphere.0 (33%) respectively.1.5 (43%) in Kolkata.4 to 6.8 (acidic) over Kolkata.9 with an average of 6. NOx. rainwater remained un-neutralized or partially neutralized.1 with an average of 5.0-6.1 ± 1. (2014) also suggested that the higher pH values are due to higher concentrations of alkaline species and its consequence more basic nature of rainwater.6 (pH) due to the dissolution of atmospheric CO2 P in rain droplets. Results and Discussion T 3.

28 μS cm−1). . Sinhagad (Budhavant et al. ACCEPTED MANUSCRIPT cationic species.2. The very limited study was conducted in high altitude in India and the pH values were varying from 5.44 to 6.1 μS cm−1). Meerut (30 μS cm−1) MA or Ballia (23. SC The mean specific conductivity over Kolkata.17 and varied from 5. 2009) and 5. 20±15 and 11±9 μS cm−1 respectively.. Kullu (Tiwari et al. 11 μS cm−1). Falta (204 µeq l-1. The total ionic species concentrations were found to directly related to the specific conductivity over Kolkata AC (391 µeq l-1. The mean specific conductivity over Kolkata was NU similar to other Indo-Gangetic Plain stations like Kanpur (26. 2012). The specific conductivity of Darjeeling fell in the range of average specific conductivity of rainwater reported for 10 D background stations in India and ranged from 7 to 57 μS cm−1 (IMD. It was also TE observed that alkaline rain events showed 40-45 % higher specific conductivity than acidic P rain events at all three stations. 2015). Falta and Darjeeling were 28±17. which is a highly polluted IP region in the world. 1982).... Anatolaki and Tsitouridou (2009) showed higher specific CE conductivity in rainwater with higher pH over an urban station in Greece. (2015). Falta and Darjeeling indicating serious atmospheric pollution. Spatial variation of natural and anthropogenic chemical species over the study region Rainwater is a function of the proportions of chemicals constituents in it and was calculated by the summation of measured volume-weighted mean (VWM) concentrations of ionic species over Kolkata.36 for the north western Himalayan region.73 to 7. the average pH value was found 5.16 to 6.21 for western Indian site. In T a recent study at eight different locations in Indo-Gangetic Plains. 20 μS cm−1) and Darjeeling (64 µeq l-1.73 ± 0. 3.7 μS cm−1) as reported by Tiwari et al.03 R (Tiwari et al.

Ci is the ionic concentration of individual component (μeq l-1).> Na+ > NH4+ > Cl-> NO3. The important observation is that the concentration of Ca2+ over Kolkata was ~70 times higher than Darjeeling.> NH4+ > NO3. 2015). 1380 and 1597 mm rainfall corresponding to the total number of rain samples collected over Kolkata. ACCEPTED MANUSCRIPT The VWM (over the entire monsoons in 2013 and 2014) of ionic constituents in rainwater was calculated as: N   eq  C P T i i  i 1 VWM  (1) IP  l  N P i 1 i R SC Where. The volume-weighted MA mean (VWM) concentrations and the statistical information of the chemical constituents of rainwater over three stations have been shown in Table 1.with the contribution of 55-60 % to the total ionic species. The VWM concentrations of the D total ionic species were found to be the highest over Kolkata (391 µeq l-1) followed by Falta TE (204 µeq l-1) and Darjeeling (64 µeq l-1). The secondary aerosols (NH4+.> NH4+ >Mg2+ >NO3. Falta and Darjeeling respectively.~Na+ > SO42.> Ca2+ > K+ Darjeeling: Cl.and SO42-) contributions were 35-40 % during the study period. The abundances of the chemical constituents in P rainwater samples for three stations are as follows: CE Kolkata: Ca2+ > SO42-. NO3.> Mg2+ > K+ AC Falta: Cl ~Na+ > SO42. It is noteworthy . NU We recorded 2249. Ca2+ was found to be the most abundant species in Kolkata contributing ~ 30 % to the total ionic species whereas its abundances were much lower (~3%) over Falta and Darjeeling..> Ca2+ > Mg2+ > K+ Thus. Pi and N are the rain amount for each rain event (in mm) and the total number of rainfall event (Akpo et al. The most abundant species over Falta and Darjeeling were Na+ and Cl.

Contributions of sea salt were highest over Falta (60%) and Darjeeling (66%) whereas..was originated as sea-salt species during monsoon. Here we have assumed that AC Cl. In order to categorize chemical constituents of rainwater into natural and T anthropogenic sources. it was around 32%. . ACCEPTED MANUSCRIPT that SO42. whereas. The VWM concentrations of natural and anthropogenic species over three stations have also been given in Table 1. we calculated sea and non-sea salt contributions of the species like IP Ca2+.was the second most abundant species and K+ was the least abundant species over all the stations. Mg2+ and K+ by the following equation assuming Na+ as the reference element R for sea water (Keene et al. at Falta and Darjeeling. the wet deposition flux (WDF) of natural (sea-salt and dust species) and anthropogenic species over all three locations were also calculated by the following equation to see their deposition. However. Kolkata showed the lowest contribution (27%). 1986) : SC    X  ss  X  Na      (2)  Na  sea nss-X = Xtot – ss-X NU (3) MA where ss-X and nss-X are the sea-salt and non-sea salt fractions of the desired component X.  X  +  Na   is the standard ratio of the component X to Na in sea water and Xtot is the total D   sea TE concentration of X in rainwater. SO42-. soil-dust species were computed as [(nss-Ca2+) + (nss-Mg2+)] and anthropogenic species were computed as [(NH4+) + (NO3-) + (nss-SO42-) + (K+)]. in the case of dust. the contribution of anthropogenic aerosols in rainwater was highest at Kolkata (40%). In addition to this. P Thus. During the study period. sea-salt species were computed as [(Na+) + (Cl-) + (ss-SO42-) + (ss-Ca2+) + (ss- CE Mg2+)]. it was dominant over Kolkata (33%) and very low contribution over Falta (8%) and Darjeeling (3%).

. One of our earlier studies (Chatterjee et al. This is quite expected SC as Falta is closed to Bay of Bengal (BoB) with the higher influence of fresh marine air masses than other stations. The source characterization of ionic species at all three stations will be discussed in detail in later section.. 2010) observed the minimum concentration of Ca2+ in PM10 (respirable particulate matter with aerodynamic diameter less than 10 µm) at Darjeeling during the monsoon season. Here. The concentration and deposition fluxes of anthropogenic species over Kolkata were higher than Falta and Darjeeling. But the deposition flux of sea-salt species over Kolkata was higher than D TE Falta which was due to higher rainfall amount over Kolkata compared to Falta. The calculated total wet deposition T fluxes of natural and anthropogenic species for the entire study period for both two monsoon IP seasons (2013 and 2014) are depicted in Fig 3. we observed that as MA the southerly marine air masses traveled more towards the north. Fujita et al. We observed that almost 90 % soil-dust species over Kolkata was constituted by nss-Ca2+ and thus mostly calcareous soil. The concentrations and deposition fluxes of soil-dust species at Kolkata were much higher than P Falta and negligible at Darjeeling. (2000) reported that the concentration of sea-salt NU species exponentially decreases with the distance from the coast. 3.3 Estimation of Neutralization Factor. Acid Neutralization Potential in Rainwater . This high soil-dust concentration at Kolkata could mainly CE be associated with the wind/vehicle driven roadside dust whereas dust species over Falta AC were mainly from open agricultural fields. the sea-salt species got diluted by 16 % reaching over Kolkata and ~66 % reaching over high altitude Himalayan station (Darjeeling). ACCEPTED MANUSCRIPT VWM (mgm 3 )  R(m) WDF (kgha1 )  (4) 100 Where R is total rainfall expressed in the meter. It was observed that the concentration of sea- R salt species was highest in Falta followed by Kolkata and Darjeeling.

2 – not play major roles in the neutralization of the acidity and are mostly originate from marine sources. (1996). the ratio in NU Falta was much higher than 1.3 and 5. 5. Darjeeling showed higher ratio values (Av: 1. range: 1. On the other hand.54) for 85 % samples and slightly higher than 1. The acidic potential is the sum of the concentrations of NO3.9) for 55 % samples and less than 1.4. K+ and SO42− which generate from sea spray and they have no or minimum role in governing acidity/alkalinity of rainwater. nss-Mg2+ and nss-K+ (Kumar et al.34 – 0. range: 1. Thus.1. Mg2+.1) for 65 % samples and lower values (Av: 0. Ca2+ and Mg2+ using the formulae suggested by Parashar et al. The ratio was found to be much R less than 1. 1.and SO42− are the major acidic species which increase AC acidity. 2002).3) reflected in the mean pH values of 6. The neutralization factors were calculated for NH4+.08) for 15 % samples in Kolkata which indicates the neutralization of rainwater acidity for most of the samples over Kolkata. The neutralization factors (NF) of the respective alkaline species are calculated as follows: . range: 1. ACCEPTED MANUSCRIPT The ratio of Acidic Potential (AP) to Neutralization Potential (NP) is the useful indicator of chemical nature of the precipitation. Mg2+. CE It is well known that NO3.0 over Kolkata. Thus.42.0 MA (Av: 0. nss-Ca2+. Na+ and Cl. range: 0.04.01 – 1.0 SC (Av: 1. The mean ratio values (0.14 and 1.65. and K+ are the major alkaline species which neutralize the acidity.9. range: 0. non-sea fractions of those species are usually taken for the estimation of neutralizing factors. Similarly.0 (Av: 0..95) for 45 % samples. whereas.and nss-SO42− and neutralization potential is the sum of the T concentrations of NH4+.. range: 0. Ca2+. We did not find the non-sea contribution of K+ and Mg2+ in rainwater samples over Darjeeling as stated earlier. the ratios indicate partial or incomplete neutralization of acidity for 55 and 65 TE % samples over Falta and Darjeeling respectively. Falta. The AP/NP IP ratio was estimated for all the stations and shown in Table 3.83 – 0.9.4 – 2.8 – 0. There are some neutral salts of Ca2+.0 (Av: 1.6.96) for 35 % D samples. and Darjeeling P respectively (Table 2). NH4+.

It was observed that NF was higher for Ca2+ followed by NH4+ and K+ over Kolkata. They observed that more than 80 % acidity was neutralized by NH4+.. NF of NH4+ over Darjeeling was much higher than Kothi (0. all the alkaline species together could not completely neutralize the acidity of rainwater and made it acidic over Falta and Darjeeling.. a high altitude station at western India (Budhavant et al..33). Ca2+ alone had the potential to completely neutralize the acidity of rainwater over Kolkata metropolis and made it alkaline in nature. But over Falta and Darjeeling. India (Kulshrestha et al. 2010). On the other hand.4 Long-range transport of atmospheric aerosols/gases and its effect on rainwater .. 2009). 2005) and Singapore (Hu et al. Tiwari et al. NH4+ showed higher NF over Darjeeling (although less than 1. 2003). the feature was opposite with higher NF of NH4+ than Ca2+. D The higher NF of NH4+ than Ca2+ was also observed over a rural station near Bhubaneswar TE on the east coast of Bay of Bengal (Das et al. ACCEPTED MANUSCRIPT nss  Ca 2  NF Ca 2   2 (5) NO3   nss  SO4     NH 4 NF NH 4 2 (6) NO3   nss  SO4 T IP nss  Mg 2  NF Mg 2  (7) R 2 NO3   nss  SO4 SC nss  K  NF K  2 (8) NO3   nss  SO4 NU The neutralization factors for the cationic species for all the stations are shown in MA Table 2. The potential of NH4+ to neutralize the P CE acidity of rainwater was also observed over Delhi. Das et al. a rural location at western Himalaya (Tiwari et al. 3.06). 2005. Thus.. 2012) and Sinhagad (0...0) AC compared to Kolkata and Falta. (2012) observed that Ca2+ and NH4+ played a crucial role in acidity neutralization of rainwater in the form of CaSO4 and (NH4)2SO4 over Kothi at western Himalaya.

1 Air masses over Kolkata P CE We observed higher sea-salt concentrations for mixed air masses. The D VWM concentrations of chemical species were estimated for different types of air masses for TE all the stations and shown in Table 3. originating from Bay of Bengal (BoB) and MA originating from Arabian Sea (AS).4) in nature indicating more transport of acidic species which left partially neutralized by local and transported alkaline species. As marine air . 3. we have computed 7 day air-mass back trajectories.2 Air masses over Falta It was observed that the marine air masses carried much higher sea-salt particles and continental air masses carried much higher anthropogenic and dust species over Falta as expected as the site is the nearest station and closed to the Bay of Bengal. Continental air masses increased the ratio values (> 1. using T Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) model IP (http://www. 3. 4 shows the representative figures for different types of air masses for all three stations. Only mixed type air masses were found to arrive at NU Darjeeling and have been divided into two groups.noaa.html).3). higher anthropogenic and dust concentrations for continental air masses.0) and rainwater was observed acidic (pH=5. Fig. Air masses were divided into three groups as R marine (marine overpass only). mixed (both marine and land overpasses) and continental SC (land overpasses only).0 indicating complete neutralization of rainwater acidity (pH = 6. whereas. arriving at an altitude of 500 m above ground level over all three stations for all the days on which rain samples were collected. We observed all three types of air masses over Falta. ACCEPTED MANUSCRIPT In order to investigate the transport of aerosols from long distances.4. The AP/NP ratio for mixed AC air masses was much less than 1. It is important to mention here that pure marine air masses are not applicable for Kolkata and

The pH values for respective air masses strongly support the same. D Thus. we may assume that the anthropogenic and dust species associated with marine air masses were of local origin over Falta. anthropogenic and dust species associated to mixed or continental air masses is T the sum of local and transported species.8 µeq l-1 respectively. Xnon-marine and Xmarine are the concentrations MA (µeq l-1) of anthropogenic or dust species associated to non-marine (mixed or continental) and pure marine source respectively. The AP/NP ratio CE over Falta was less than unity for marine air masses indicating complete neutralization of AC locally generated acidic species by locally generated alkaline species.7 µeq l-1 and 20. Similarly. These acidic species transported by non-marine air masses were partially neutralized by local and transported alkaline species and hence rainwater became acidic. The ratio was higher than unity for mixed and continental air masses indicating more transport of acidic species than alkaline species. The air masses originating from AS passed over Indian peninsula followed by BoB and West Bengal/Bangladesh before reaching Darjeeling. We .3 Air masses over Darjeeling The mixed air masses originating from BoB reached Darjeeling after passing over West Bengal. we observed that mixed air masses enhanced anthropogenic and dust species by TE 24 µeq l-1 and 2. 3. Hence.4.5 µeq l-1 respectively. ACCEPTED MANUSCRIPT masses do not carry anthropogenic and dust components. India or Bangladesh. We have thus calculated the enhanced IP concentrations of anthropogenic and dust species driven by mixed and continental air masses R by the following equations: SC X E  X nonmarine  X marine (9) NU Where XE (µeq l-1) is the enhanced concentration of anthropogenic or dust species with respect to the local species concentration. continental air masses enhanced P anthropogenic and dust species by 59.

The anthropogenic species for AS air masses were higher and double of T BoB air masses whereas the dust species concentrations were almost equal for both of them. This could be due to the longer marine overpasses of the air masses originating from BoB than from AS. the normalized residual distribution and the factor scores of the individual ionic species (Anderson. India or Bangladesh) was common for both BoB and AS.. m.1).2. A minimum of object function Q is extracted from the PMF method (equation 2).. Rainwater acidity associated with AS was also higher (pH = 4. k  1. It uses directly measured data whereas TE Principal Component Analysis (PCA) uses normalized data. NU MA 3.. PMF solves a constrained and P weighted least-squares optimization equation to convert data to a set of profile and score CE matrices: p X ik   g ij f jk  eik (i  1...2. gij represents the profile matrice of compound i at jth sources... 2002).2)... p.2.8) than BoB air masses (pH=5.5 Source apportionment of chemical species in rainwater by Positive Matrix Factorization (PMF) model D PMF is a mathematical receptor model. based on the calculation of uncertainties (u): .... The user needs to select several number of factors which depend on the normalized sum of error squares (Q-value). j  1. IP The AP/NP ratio for AS air masses was much higher (1.5) than that for BoB (1. fjk represents the score matrice at jth source and kth sampling. ACCEPTED MANUSCRIPT observed that the sea-salt species from BoB (45 µeq l-1) was higher than that from AS (27.. 2001.. This R indicates that more acidic species were transported by AS air masses mainly from southern SC Indian peninsular regions as the last part of air mass pathways (West Bengal. and eik is the residual factor for compound i at kth sampling...1 µeq l-1).. n) AC j 1 (10) where xik represents the concentration of ionic species compound i at kth sampling. Anderson et al.

SO42.1 Sources of chemical species over Kolkata Three factors were extracted for Kolkata where the first factor (factor 1) is found to be highly loaded with Na+ and Cl. Table 4 CE shows the loading of ionic species in each factor along with their percentage contribution as AC estimated from the PMF model. Kolkata. Factor 3 is highly loaded with NO3-.. k  1. . 2007). The uncertainty (U) is T calculated using the following equation (Polissar et al.and NH4+ with 35 % contribution... Paatero. 3.. This factor could be related to the anthropogenic sources like fossil fuel combustion (vehicular and industrial emissions). 2004. and Darjeeling.. Reff et al. ACCEPTED MANUSCRIPT m n 2 Q i 1  e k 1 ik / u ik  i  1. PMF model was used to apportioning the sources of various chemical species (ionic species) P scavenged by rainwater over three different stations.. the calculation is: NU MA 5 U  MDL 6 (11) D More details about the PMF method were described by several studies (Paatero and TE Tapper. 1998): IP U (EF  conc) 2  (MDL) 2  R (10) SC where EF represents an error fraction (EF = the percent uncertainty × 100). Factor 2 has a high loading of Ca2+ and Mg2+ and could be due to the scavenging of soil-dust particles. m.. and MDL represents the method detection limit.. This factor contributes 34 %. 1994.with the contribution of 31 %. Falta. n  (11) where uik represents the uncertainty of compound i at kth sampling.. 1997. This could be associated with sea-salt particles or marine source.2.5.2. Jorquera and Rappenglück.. If the concentration is less than or equal to the MDL.

Factor 2 is loaded with Na+ and Cl- which clearly indicates the contribution of marine source i. Factor 2 is highly loaded with Na+ and Cl. Marine source over Darjeeling contributes 37 % during monsoon.3 Sources of chemical species over Darjeeling CE Four factors were extracted for this high altitude Himalayan station. P 3. High loading of NO3. This factor contributes 22 %.e. the association of Ca2+ and Mg2+ with NO3- indicates the soil-derived nitrates. NH4+ is found to D be loaded on factor 4 with 15 % contribution. (2005) reported that one of the sources of nitrate in rainwater in Indian regions is soil where nitrate is emitted into the atmosphere in the form of Ca (NO3)2.5.and NO3.2 Sources of chemical species over Falta T Four distinct factors were extracted for the rural station Falta using PMF model. coal burning and human and animal wastes that are quite expected in a metropolitan urban atmosphere like Kolkata. Use of fertilizers in agricultural activities and microbial processes also . tractors in paddy fields during rice farming in monsoon.5. Also. SC Villagers use diesel driven pumps.with the contribution of 35 % associated MA with sea-salt particles. Factor 1 shows high loading of SO42. IP Factor 1 is highly loaded with SO42. NU Diesel is also used to run generators for power supply. This could be associated with the human and TE animal wastes along with fertilizers used in agricultural activities.representing biomass burning and/or coal burning (for domestic use and AC running “Toy Train”). Kulshrestha et al. motor-boat for the passengers crossing rivers etc.could be associated with vehicular emissions. 3.and moderately with Ca2+ and Mg2+ with 18 % contribution.with the contribution of 34 %. Factor 3 is loaded with Ca2+ and Mg2+ with 16 % contribution representing soil-dust particles mostly from open fields in this rural station. ACCEPTED MANUSCRIPT biomass burning. Factor 3 is highly loaded with NO3. sea-salt species. This could be R associated with the fossil fuel burning for agricultural activities by the local villagers.

Factor 4 is associated with agricultural activities. dust. the contributions of sea-salt. 55 and 65 % events over Falta and Darjeeling were acidic (mean P pH of 5. 85 % rain events over Kolkata were alkaline with TE mean pH of 6. Ca2+ was found to be the most potential and abundant CE neutralizing species over Kolkata. Positive Matrix Factorization model was applied to apportion the sources of chemical species in rainwater.1. whereas.3 and 5. The study revealed that water soluble chemical species in rainwater over MA Kolkata were almost double of Falta and six times higher than Darjeeling. IP 4.0 respectively). Sea-salt species concentration was highest over Falta. 2000). Another reason for such significant contributions from NH4+ is the unscientific dumping T of domestic wastes and unplanned drainage systems in and around Darjeeling. ACCEPTED MANUSCRIPT emits nitrate from soil (Isherwood. fertilizers used in tea gardens and human and animal wastes with high loading of NH4+ (23 %). and anthropogenic sources were found to be comparable (30-35 %). Continental air masses increased anthropogenic and dust species by many folds than mixed or marine air masses over Kolkata and Falta. Rainwater acidity over Darjeeling was increased when air masses arrived from the Arabian Sea compared to the Bay of Bengal. Over Kolkata. Falta shows equal contributions from a marine source and fossil fuel burning . anthropogenic and dust species over Kolkata D were remarkably higher than other stations. whereas. Conclusion R SC A study on rainwater chemistry was carried out over three different atmospheric environments (Kolkata: an urban station. NH4+ was the potential neutralizing element over Falta and Darjeeling. It was observed that continental air masses transported more acidic species than alkaline species and thus rainwater acidity was significantly increased over Kolkata and Falta. whereas. Ca2+ alone neutralized the rainwater acidity over Kolkata but acidic AC species over Falta and Darjeeling were left un-neutralized for 55-65 % events. Falta: a rural station near Bay of Bengal and NU Darjeeling: a high altitude Himalayan station) in eastern India during the monsoon seasons of 2013 and 2014.

Thanks are due to Dr Anandamay Adak. The acidic rain events over the stations R situated near the BoB and at high altitude in eastern Himalaya as observed in this study are of SC paramount importance. Yasodhara Yadav. and domestic wastes. ACCEPTED MANUSCRIPT (~35%) and equal contributions from soil-derived dust species and agricultural activities (~15%). Mr Vivek Gurung for their consistent support and help in sampling and Ms Debolina Seal for chemical analysis. MA It could also damage the plant tissues of tall trees either through foliage or roots and reduce the canopy cover over Darjeeling with a high density of vegetation of the type Japanese cedar D (Cryptomaria japonica). The contribution of the marine source (37%) was higher than biomass/coal burning (22 %) and vehicular emissions (18%) over Darjeeling. Authors also like to thank Council of Scientific and Industrial Research (CSIR). K. Sabyasachi Majee. animal. . Roy. which in turn affects the growth NU of plants/crops at both these stations where agriculture is one of the major economic sources. Mr. Department of Science AC and Technology. Govt of India for providing fellowship to Mr A. Roy (first author). High acidity could alter the soil chemistry and lead to soil infertility by reducing the concentrations of major nutrients in the soil. D. Bose Institute for his overall logistic support. The high acidity of rainwater could also contaminate the ground TE water and surface water affecting drinking water quality at both the rural coastal and urban Himalayan stations. Mrs. Authors would also like to thank Mr. P CE Acknowledgement Authors would like to thank Science and Engineering Council. Government of India for supporting the study under IRHPA (Intensification of Research in High Priority Areas) scheme. A significant contribution (23 %) of T NH4+ was observed over Darjeeling because of agricultural activities and unscientific IP treatment of human.

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minimum and volume weighted mean (µeql-1) concentrations of major ions in rainwater over three stations Table 2: Neutralization factor of cationic species and AP/NP ratio for three stations T Table 3: Concentrations (Mean ± SD) of chemical species. P CE AC . Marine. mixed and continental air masses are represented by blue. pH and AP/NP ratio for different IP air masses over different stations R Table 4: Factors extracted from PMF model related to various sources for different stations SC Figure captions NU Figure 1: Geographical map showing sampling locations (sampling sites are indicated by yellow asterisks) MA Figure 2: Frequency distributions of pH of rainwater over different stations Figure 3: Spatial variations of the deposition fluxes of rainwater chemical species D Figure 4: Representative figures of different air mass trajectories arriving at different stations. ACCEPTED MANUSCRIPT Table captions Table 1: Maximum. Air masses from Bay of Bengal and Arabian Sea are represented by pink and white coloured lines respectively for Darjeeling. green and red coloured TE lines respectively for Kolkata and Falta.

6 87.8 16.3 BDL 0.5 5.2 57.9 BDL 17.0 15.4 0.3 2.4 19.7 Mg2+ 68.7 3.5 149.4 1.9 7.7 10.6 463.6 93.2 NU Anthropogenic 156.1 37.6 MA D P TE CE AC .4 8.8 60.4 BDL 1.4 19.0 123.4 SC Ca2+ 194. 128.5 BDL 3.3 414.1 11.8 302.9 39.2 112.3 40.3 BDL 12.2 Na+ 266.7 4.9 22 0.1 R NH4+ 219.5 T NO3.5 42.1 IP SO42.6 K+ 56 BDL 14.8 33.1 28.3 BDL 1.6 0.3 21. minimum and volume weighted mean concentrations (µeql-1) of chemical species in rainwater over three stations Sampling area Kolkata Falta Darjeeling Max Min VWM Max Min VWM Max Min VWM - Cl 180.9 1.5 6.7 65 19. 244.3 13.2 11.1 Sea-salt 104.3 36.3 6.8 2. ACCEPTED MANUSCRIPT Table 1: Maximum.4 9.7 BDL 7.7 55.8 24.4 8.9 Dust 130.9 1.5 55.9 3.7 8.3 54.9 116.1 275.

00 1.15 0. ACCEPTED MANUSCRIPT Table 2: Neutralization factor of cationic species and AP/NP ratio for three stations Sampling Neutralization Factor AP/NP 2+ area Ca NH4+ Mg2+ K + Kolkata 1.11 0.00 1.65 T Falta 0.04 0.65 0.14 IP Darjeeling 0.07 0.10 0.30 R SC NU MA D P TE CE AC .27 0.02 0.35 0.41 0.

2 28.5±0.9±0.0 13.5 1.4 MA D P TE CE AC .2 1.3±0.2±0.0±0.4±1.7 235.6 2.4 Bay of Bengal 45.4 6.8 9.4 SC Continental 69.5 1.2 88.4 0.3±0.5 5.0 52.1 T Kolkata Continental 45.8 6.3±0.8 5.1 17.4 240.7 0. pH and AP/NP ratio for different air masses over different stations Sea salt Anthropogenic Dust Air masses pH AP/NP (µeq l-1) (µeq l-1) (µeq l-1) Mixed 118.8±0.3 NU Darjeeling Arabian Sea 27.9 5.3 R Falta Mixed 88.8 1.4 1.2 1.0 4. ACCEPTED MANUSCRIPT Table 3: VWM concentrations (Mean ± SD) of chemical species.3 90.5 27.7±0.3 IP Marine 224.8±0.2 4.3±0.3 5.5±0.1±0.3 65.

2 78.5 16.2 Darjeeling NU Factor 3 (18%) 2.4 0 7.8 0 0 30.3 92.6 18.2 83.6 0.3 5.5 2.9 2.7 1. NO3.4 1.4 6.2 59.1 8.9 83.9 26.3 29.6 32.9 66.1 0 61.2 0.2 13.4 0 88 10.9 2.9 6.6 Factor 4 (15%) 3 31.8 88.6 7. Na+ NH4+ K+ Ca2+ Mg2+ Factor 1 (31%) 77.6 0 6.2 12 89.2 21.8 36.9 10.2 IP Factor 1 (34%) 18.7 35.3 Kolkata Factor 2 (34%) 15.4 84.1 21.5 T Factor 3 (35%) 7.2 86.7 12.6 1.9 MA D P TE CE AC .7 4.7 89.4 29.5 13.5 0 0 78.6 Factor 2 (35%) 67.4 Factor 4 (23%) 7. ACCEPTED MANUSCRIPT Table 4: Factors extracted from PMF model related to various sources for different stations Cl.1 11.1 24.6 11.1 27.2 15.6 0 0 4.7 87.4 2.8 0 86.4 4.8 9.7 SC Factor 1 (22%) 12 0 67.5 24. SO42.9 22.8 6.5 Factor 2 (37%) 78.3 87.9 6 Falta R Factor 3 (16%) 10.

1: Geographical map showing sampling locations (sampling sites are indicated by yellow asterisks) . ACCEPTED MANUSCRIPT T R IP SC NU MA D P TE CE AC Fig.

2: Frequency distributions of pH values in rainwater over different environment over eastern part of India P CE AC . ACCEPTED MANUSCRIPT T R IP SC NU MA D TE Fig.

ACCEPTED MANUSCRIPT T R IP SC NU MA D TE Fig.3: Spatial variations of the wet deposition fluxes of chemical species in rainwater P CE AC .

mixed and continental air masses are represented by blue. Marine. . ACCEPTED MANUSCRIPT T R IP SC NU MA D P TE CE AC Fig.4: 7 day air-mass back trajectories arriving at different monitoring stations during the study period an altitude of 500 m. green and red coloured lines respectively for Kolkata (a) and Falta (b). At Darjeeling (c). pink and white lines represent from BOB and AS respectively.

ACCEPTED MANUSCRIPT Highlights  First-time precipitation chemistry was conducted in eastern Himalayan region T  Precipitation events over eastern Himalayan region were mostly acidic IP  Major precipitation events were alkaline over metropolitan urban atmosphere at IGP R  The scavenging of anthropogenic species dominated over other species in urban SC metropolis whereas the scavenging of sea-salt species dominated over other species in NU rural and Himalayan environments MA D P TE CE AC .