Long Range Transport and Wet Deposition Fluxes of Major Chemical Species in Snow at Gulmarg in North Western Himalayas (India)

The study reports snow chemistry and long range transport of pollutants at Gulmarg in north-western Himalayan region of India during winters of 2012–2013. The pH of snowmelt varied between 5.16 and 7.68 with an average of 5.90. The frequency distribution of pH of snowmelt showed that the maximum number of samples (31%) had pH between 6.81 and 7.20. However, 12% samples were observed to be acidic (below 5.6). Scavenging ratios (SR) values suggested that crustal components (Ca, Mg) are efficiently removed by snow. The study site has significant influence of non-marine sources. Wet deposition contributed 34, 27, 45, 71, 8 and 13 meq m fluxes of nssSO4, NO3, NH4, nssCa, nssMg and nssK respectively. Both local emissions as well as long range transport (LRT) of pollutants were found to be the sources of these ionic species. Backward airmass trajectory calculations showed that this site received airmasses from six major sectors i.e., i) North Atlantic Ocean origin (NAO), ii) African origin (Af), iii) Middle East origin (ME), iv) European origin (Eu), v) Western India origin (InW), vi) Pakistan origin (Pk). The highest average pH (7.58) of the snowfall was noticed during InW airmasses which had the lowest ratios of nssSO4/nssCa and NO3/nssCa. Very high pH has been observed in precipitation samples at Indian sites due to buffering of acidic components by atmospheric dust rich in CaCO3. The lowest pH (4.94) was noticed for ME airmasses which had the highest nssSO4/nssCa and NO3/nssCa ratios. Data of present study was compared with a study reported almost three decades ago. We noticed a drastic increase in the concentrations of anthropogenic components such as nssSO4 (114%), NO3 (109%) and NH4 (90%). This is probably due to increase in LRT of pollutants as well as local activities during past three decades.


INTRODUCTION
Rapid urbanization and industrialization processes during past few decades have led to global concern about various processes such as acid deposition, climate change, and monsoon modification etc. (Andreae and Crutzen, 1997;IPCC, 2014).If the present trend of growth rate are continued, Asian SO 2 and NOx emissions are expected to exceed that of European and North American emissions by 2020 (Galloway, 1995).Increasing emissions of aerosols are also going to affect air quality further affecting global and regional atmospheric phenomenon (IPCC, 2014).Deposition of such anthropogenic constituents via wet and dry removal processes has significant adverse impacts on terrestrial and aquatic ecosystems (Seinfeld and Pandis, 2006).Snowfall Generally, snow composition varied from site to site depending upon sources, type of sampling site, elevation from sea level, meteorological conditions, methods of sampling, regional and global scale transport of pollutants in relation to airmasses etc. (Marinoni et al., 2005).Airmass trajectories combined with Snow chemistry data provide valuable information about the origin of air pollutants (Fleming et al., 2012;Kulshrestha and Kumar, 2014) and their impact on various ecosystems through deposition processes.
Himalayan region which is considered as very sensitive ecosystem in terms of atmospheric deposition (Kuylenstierna et al., 2001) is affected by local and long range transport of pollution sources (Kulshrestha and Kumar, 2014).Local sources such as tourist activities, transport and other human activities have significant effect on snow chemistry further having adverse impacts on aquatic and terrestrial ecosystems.In spite of its sensitivity, annual and seasonal depositions of various chemical species are poorly understood.There are some, by far very few, papers on the aerosols, rain water and snow geochemistry in the Himalayas (Gajananda et al., 2005;Tiwari et al., 2012;Kuniyal et al., 2013).Also, the comprehensive studies on fresh snowfall chemistry are limited in western Himalayan region of India (Naik et al., 1995;Kulshrestha and Kumar, 2014).Hence, the present study was carried out at Gulmarg to study the chemical characteristics of snow and differentiation of local vs distance sources of pollution.In this study, relative contributions of marine and non-marine sources have also been calculated during different airmass trajectory using HYSPLIT model.Non-marine fraction is further differentiated into crustal associated and anthropogenic contributions.In addition, this study reports wet deposition fluxes (winter and spring) and scavenging ratio of various chemical constituents.In order to note changes in snow components which occurred during past three decades, an attempt has also been made to compare the present results with data of Gulmarg reported for the year 1986-87.

Sampling Site
Gulmarg is a hill station located in Baramula district in Jammu & Kashmir state of India (Fig. 1) at 34.06°N and 74.38°E in north-western Himalayan ranges at ~2690 m above sea level.It is surrounded by Afghanistan and Pakistan to the north-west and Tibet to the north-east.Gulmarg is located 52 km to the south-west from Srinagar having ~730 inhabitants in this hill station.Gulmarg is one of the most famous tourist spots which receive several thousand tourists every year.Snowfall occurs during winter and spring seasons (November-May).Gulmarg is very attractive in terms of the green vegetation and forest having trees of Birch, Christmas, Apple etc.There are no major industrial units around this hill station hence the site represents high altitude rural characteristics.The major sources of air pollution at this site are tourist activities and emissions from electricity used in generators in various hotels.Most of the population use biomass as a source of energy for domestic heating and cooking purposes.

Sample Collection
Fresh snowfall samples were collected on event basis using prewashed plastic trays (20 cm diameter) during November 2012-May 2013.During this period, a total of 35 snowfall samples were collected.The tray was washed properly with high quality deionized water and dried before use.Sampler was placed at ~2 m height above the ground level.We have followed similar method which was used by Naik et al. (1995).The tray was kept outside just before the start of snowfall and was removed immediately after snowfall to avoid contamination.In order to get representative samples, collection was done in duplicate to observe any difference in two nearby samples.Random chemical analysis of such samples suggested no significant difference in the duplicate samples.The frozen snow was transferred from tray into pre-cleaned polypropylene bottles using polyethylene gloves and stored at 4°C which were then transported to the laboratory for their chemical analysis.The precautions were taken to avoid any contamination (Mayewski et al., 1983;Kang et al., 2004).These samples were stored in the refrigerator at the site which was later transferred to the laboratory as soon as possible latest by one month from the collection time.Samples were later processed for analysis of pH, EC, HCO 3 -and major ions.Fine aerosol samples were collected during snowfall event for calculation of scavenging ratios.The aerosol samples were collected on Whatman 41 cellulose filters (Dia = 47 mm) using a low volume pump (40 L min -1 ).A rotameter was fit in the line to measure the flow rate.The sampling duration varied according to snowfall event.A total of 8 samples were collected during this period.Precautions were taken to avoid contamination both in the laboratory and in the field (Kulshrestha et al., 2009).A field blank was also collected in the same manner.The samples were stored in polypropylene bags and refrigerated.The method of extraction of filters and analysis of aerosol samples was used as reported by Singh et al. (2014).

Chemical Analysis of Snowfall Samples
The electrical conductivity and the pH of collected samples were measured immediately after their receipt in the laboratory.The electrical conductivity of samples was measured with Thermo Orion 5Star conductivity meter, calibrated with standard KCl solution.The pH of samples was measured with EUTECH pH meter, calibrated with standard buffer solutions of pH 4, 7 and 10.Prior to chemical analysis, the snowmelt samples were filtered through nylon syringe filter (pore size of 0.2 µm).The major cations (Na + , NH 4 + , K + , Ca 2+ and Mg 2+ ) and major anions (F -, Cl -, NO 3 -and SO 4 2-) were analyzed by ion chromatograph (Metrohm 883 Basic IC Plus).Details of the method are given elsewhere (Singh et al., 2014).Manual titration method was used for estimation of HCO 3 -using 0.0025 N H 2 SO 4 (APHA, 1998).

QA/QC of Data
Quality check of chemical analysis of snowfall was carried out by calculating ion balance and conductivity balance (Ayers, 1995;Kulshrestha et al., 2003Kulshrestha et al., , 2005)).A significant correlation (R 2 = 0.90) was found between sum of anions (F -, Cl -, NO 3 -, SO 4 2-and HCO 3 -) and sum of cations (Na + , NH 4 + , K + , Ca 2+ and Mg 2+ ) which indicated good ion balance for samples.Very good correlation between measured electrical conductivity (EC) and calculated conductivity (R 2 = 0.86) further confirmed good quality of dataset.

Frequency Distribution of pH of Snowmelt
In general, the pH of the snowmelt varied from 5.16 to 7.68 with an average value of 5.90.The pH value of 5.6 is considered as the natural pH of cloud water due to equilibration of atmospheric CO 2 (Charlson and Rodhe, 1982).However, pH of precipitation is affected by other anions especially sources of acidic species.Still in all investigations other strong acidic anions Cl -, NO 3 -, SO 4 2were found in the precipitations worldwide which are referred as marine or anthropogenic contributions.Besides, volcanic eruption, forest fire and huge alive forest biomass transpiration and microbial activity in the soil influence atmosphere chemistry as well.Precipitation samples having pH value more than 5.6 have been termed as alkaline precipitation (Kulshrestha et al., 2005).Similar range of pH values of precipitation has been reported at higher altitude in Indian region (Naik et al., 1995;Tiwari et al., 2012;Budhavant et al., 2014b).Fig. S1 shows the percent frequency distribution of pH of snowfall samples.Maximum number of samples had pH between 6.81 and 7.20 (31%).
Only 12% samples represented below 5.6 pH ranges.Acidic precipitation has been reported at few other sites in Indian region (Kumar et al., 1993;Kulshrestha et al., 2005).
According to Das et al. (2005), 43% of precipitation samples were observed to be acidic in nature at state botanical garden in Bhubaneswar, India while 18% and 7% samples of rain water were found to be acidic rain at Delhi and Hyderabad respectively (Kulshrestha et al., 1996(Kulshrestha et al., , 2003)).17% snowfall samples were found acidic at Kothi (Kullu district) in north western Himalayan region of India (Kulshrestha and Kumar, 2014).Total 16 out of 42 EANET sites showed pH < 5 with the maximum number from China, Japan, Malaysia and Thailand (EANET, 2011).

Clusterwise Chemical Composition of Snowmelt
Backward airmass trajectories for 120 h of 5 000 m above ground level were calculated using the HYSPLIT model from NOAA for all snowfall samples (Draxler and Rolph, 2003).Similar height has been applied by Kuniyal et al. (2013) to study the composition and transport of aerosols in north western Himalayan region of India.Total six clusters were identified viz.North Atlantic Ocean origin (NAO), African origin (Af), Middle East origin (ME), European origin (Eu), Western India origin (InW) and Pakistan origin (Pk).Typical example of each airmass trajectory has been shown in Figs.2(a)-2(f).Percent occurrence of snowfall during each cluster is shown in Fig. S2.Table 1 gives the chemical compositions of major ionic species.The description of pH with its chemical composition for all six airmasses is given below.
North Atlantic Ocean origin (NAO) -Airmasses coming from North Atlantic Ocean and passed over Europe to Afghanistan to Jammu & Kashmir have been referred as NAO (Fig. 2(a)).Among all air clusters, the highest numbers of events (31%) have been represented by this cluster.The average pH of the samples during NAO airmasses was noticed as 6.96 (Table 1) which was the third highest among all the clusters.Alkaline precipitation has been reported globally for airmasses originated from ocean (Sakihama et al., 2008;Satyanarayana et al., 2010).The average pH can be explained based on nssSO 4 2-/nssCa 2+ and NO 3 -/nssCa 2+ ratios given in Fig. S3.These ratios are very useful to explain acidity of precipitation (Jain et al., 2000;Satyanarayana et al., 2010).The highest concentration of Na + among all cations and Cl -among all anions clearly indicated the influence of   (Nakamae and Shiotani, 2013).High contribution of SO 4 2-in snow samples might be due to both marine as well as anthropogenic contributions.Airmasses originating from North Atlantic Ocean with high concentrations of SO 4 2in precipitation samples have been reported at Montseny in North East Spain (Avila and Alacron, 1999).
African origin (Af) -Airmasses coming from African continent and passed over Middle East to Pakistan before reaching the sampling site have been termed as Af (Fig. 2(b)).This class represented 20% of snowfall events.During these airmasses, the average pH was 6.54.Its pH can also be explained in the same manner like NAO by ratios of nssSO 4 2-/nssCa 2+ and NO 3 -/nssCa 2+ (Fig. S3).Very high concentrations of Ca 2+ among all the ions indicated crustal dominance possibly influence of Saharan dust.Abundance of Ca 2+ has been reported in global precipitation in airmasses coming from African continents (Avila and Alacron, 1999;Satyanarayana et al., 2010;Budhvant et al., 2014b).The concentrations of SO 4 2-were noticed to be the highest in this cluster in comparison to all airmasses which might be due to its sources in African region as well as further its addition from Middle East region during the transport.Airmasses originating from African region with high concentrations of SO 4 2-have been reported in global precipitation (Avila and Alacron, 1999;Reddy et al., 2008;Satyanaryana et al., 2010).Very high concentration of NO 3 -might be due to oxidation of NO x emitted from various sources such as combustion of fossil fuel, industrial activities, and biomass burning (Seinfeld and Pandis, 2006).Biomass burning and agricultural activities in this region might be responsible for the highest concentrations of NH 4 + .Further, enhanced concentrations of K + in this airmass confirmed the influence of biomass burning.In general, K + is considered as a tracer for biomass burning (Kulshrestha et al., 2004).
Middle East origin (ME) -Airmasses coming from Middle East and reached to the sampling site via Pakistan have been termed as ME (Fig. 2(c)).This group represented 17% of the total snowfall events.The average pH (5.44) was the lowest in this cluster which is explained with basis of the highest nssSO 4 2-/nssCa 2+ and NO 3 -/nssCa 2+ ratios (Fig. S3).The highest concentration of SO 4 2-among all anions might be due to fossil fuel combustion used for various purposes by Middle East countries.Similar to our study, Reddy et al. (2008) reported very high concentrations of SO 4 2-in air masses coming from Gulf over Bay of Bengal and Arabian Sea during ICARB.Besides SO 4 2-, this cluster also showed high concentrations of NO 3 -.However, the concentrations of Ca 2+ were the lowest in this cluster which resulted in the lowest pH.
European origin (Eu) -Airmasses originating from continental Europe reaching to the sampling site via Afghanistan and Jammu & Kashmir have been referred as Eu (Fig. 2(d)).This class represented the third lowest number of snowfall events (14%).The average pH of snowfall during these airmasses was observed to be slightly acidic (5.52).The second lowest pH value in these airmasses with respect to all other air clusters is justified from ratios of nssSO 4 2-/nssCa 2+ and NO 3 -/nssCa 2+ (Fig. S3).The highest contribution of Cl -and Na + among all ions suggested that the marine sources had very significant influence on these airmasses (Fig. 2(d)).Very high concentrations of SO 4 2and NO 3 -might be responsible for acidic pH during these airmasses.Similar to our observations, high concentrations of SO 4 2-and NO 3 -have been reported in airmasses originating from Europe in precipitation samples at Spain (Avila and Alacron, 1999).
Western India origin (InW) -Airmasses originated in Western India have been termed as InW (Fig. 2(e)).This group represented 12% of the total snowfall events.The average pH (7.58) of the snowfall was the highest in these airmasses with respect to all airmasses.Alkaline precipitation has been reported by many workers in Indian region (Kulshrestha et al., 2005;Satyanarayana et al., 2010;Kulshrestha, 2013).The lowest ratio of nssSO 4 2-/nssCa 2+ and NO 3 -/nssCa 2+ is justifying its highest pH value in comparison to all other air clusters.The concentration of Ca 2+ was the highest in these airmasses in comparison to all the air clusters providing the highest buffering of the acidity as reflected from the highest pH.Very high concentration of Ca 2+ might be due to atmospheric dust rich in calcium carbonate (Khemani, 1989;Kulshrestha, 2013).Significant amounts of SO 4 2-and NO 3 -might be due to adsorption of their precursor gases (SO 2 and NO 2 ) onto the dust components (Kulshrestha et al., 2003).
Pakistan origin (Pk) -Air masses originated from Pakistan reaching to the sampling site has been referred as Pk (Fig. 2(f)).This cluster represented the lowest number of events (6%).The pH of snowfall samples was alkaline (7.01).Similar range of pH values has been reported in precipitation samples at various sites in Pakistan (Khattak et al., 2012;Shahid et al., 2013).The moderate pH value of this cluster can also be explained by moderate nssSO 4 2-/nssCa 2+ and NO 3 -/nssCa 2+ ratios.Among all ions, Ca 2+ had the highest concentrations.Very similar observations showing the dominance of transported dust in precipitation and aerosol samples have been reported at various sites in Pakistan (Begum et al., 2011;Khattak et al., 2012;Shahid et al., 2013).Very high concentrations of SO 4 2-among all anions suggested a significant influence of anthropogenic sources.Tremendous growth of industries and diesel driven vehicles might be responsible for elevated concentrations of SO 2 which further affects SO 4 2-concentrations (Khattak et al., 2012).Similarly, high concentrations of NO 3 -might be due to NO 2 emissions from vehicles in Pakistan.High concentrations of NH 4 + in this cluster might be due to agricultural activities and biomass burning (Khattak et al., 2012).However, trajectory information has its limitations e.g., there is a possibility that materials originated from one site can be mixed with other.There is always a possibility that source regions identified based upon the airmass trajectories may contribute overlapping signatures as some of airmasses are similar and pass over the same region.Hence, the firm inferences about the composition for different cluster should be taken with caution.

Chemical Composition of Snowmelt and its Comparison with Previous Study
Table 2 gives descriptive statistics of major ions of snowfall along with pH and EC.On an average, the equivalent concentrations of ionic species followed the order-Ca 2+ > Na + > Cl -> NH 4 + > SO 4 2-> HCO 3 -> NO 3 -> Mg 2+ > K + > F -.The Samplewise concentration (µeq L -1 ) of different ionic species has been given in Table S1.Fig. 3 shows the comparison of ionic concentration of the present study with the snowfall chemistry data of 1986-87 at Gulmarg as reported by Naik et al. (1995).Fig. 4 shows that in a span of about 3 decades, there has been a remarkable percent increase in the concentrations of all the major ions.Relative percent increase has been calculated by the following formula-Relative% increase = (C present -C previous ) × 100/C previous (1) In order to understand the effect of changes due to increased human activities during past three decades, nssSO 4 2-, NO 3 -, and NH 4 + are considered as the major anthropogenic ions, their detailed discussion is given below.
As compared to 1986-87 values, NO 3 -showed a remarkable increase (114%).NO 3 -at this site is mostly contributed by anthropogenic activities such as vehicular traffic which is increased exponentially emitting significant amount of NO x .Gulmarg has witnessed a very fast growth in number of tourists during past three decades.The number of tourists visited was reached to more than 15 lakhs in 2012 (http://www.greaterkashmir.com)which is very high number as compared to previous years.In addition, increased consumption of diesel in electricity generator sets by various hotels and Gondola during power failures (http://ww2.gulmargalpine.com/).Several fold increase in NO 3 -concentration in precipitation due to increased vehicular emissions during past two decades has been noticed by Singh and co-workers (2015).
The concentration of NH 4 + in the present study has been noticed 87% higher than the value reported from 1986-87.Generally, NH 4 + is contributed by human and animal excretions, agriculture activities, livestocks, human population etc. (Galloway, 1995;Singh and Kulshrestha, 2012).Hence, significant increase in NH 4 + in snowfall may be attributed to direct input of ammonia from various biogenic and anthropogenic sources which have increased during past three decades.It is supported from the fact that the number of horses used for tourists activities have increased and reached to 3000 in 2013 (http://www.greaterkashmir.com).Piles of horse-dung are littered in every corner of Gulmarg creating sanitation problem which might be a significant source of ammonia.Apart from these, humans are also considered as a good source of NH 3 + (Singh and Kulshrestha,  Among anions, SO 4 2-which is contributed by the oxidation of SO 2 showed 2 fold increase in concentrations as compared to the values recorded in 1986-87.Diesel driven vehicular traffic is an important source of oxides of sulphur in Gulmarg area.Since, there is no major industry nearby, long range transport is an additional source of SO 4 2-at the site.The present study showed 5.9 as average pH at Gulmarg which is 0.8 unit lower the pH of snowmelt (6.7) reported during 1986-87.The decrease in pH is possibly due to the increase in acidic species such as nssSO 4 2-and NO 3 -.It can also be explained on the basis of elevated ratios of nssSO 4 2-/nssCa 2+ and NO 3 -/nssCa 2+ (Jain et al., 2000).However, precipitation chemistry has very high spatial and temporal variations.Hence, comparison of the present study has some uncertainties.Future studies would be able to confirm the trends of decreasing pH and increasing acidity due to increasing concentrations of oxides of sulphur or nitrogen at the site.

Source Contribution at Gulmarg
Marine contribution: Sea salt is made up of mainly Na + , Cl -and Mg 2+ with some fraction of Ca 2+ , SO 4 2-and K + .In order to estimate marine contribution, sodium ratios were calculated by assuming Na + as a reference element for marine source (Keene et al., 1986).Sodium ratios for Cl -, SO 4 2-, K + , Ca 2+ and Mg 2+ have been given in Table S2.All ratios except Cl -/Na + were higher than standard sea water ratios of different components.Average, Cl -/Na + ratio was very close to sea water value (1.16) indicating that Cl -was completely contributed by marine sources.Almost similar Cl -/Na + ratios have been reported in snow/ice core samples globally (Marinoni et al., 2005;Yalcin et al., 2006).Mg 2+ / Na + ratios were bit higher than the standard sea water ratio reflecting dominance of marine contribution with some contribution from other source, probably crustal sources as discussed in the next subsection.SO 4 2-/Na + , K + /Na + and Ca 2+ /Na + were very high in comparison to standard sea salt values.Elevated ratios of SO 4 2-/Na + , K + /Na + and Ca 2+ /Na + might be due to higher contribution by non-marine sources.Similarly, elevated ratios for SO 4 2-/Na + , K + /Na + and Ca 2+ / Na + have been reported at various other sites (Jain et al., 2000;Zhang et al., 2007).
Sea salt fraction (ssf) and non sea salt fraction (nssf) of each ionic species were calculated by the following formula-% ssf = 100 [X/Na + ] Sea Water /[X/Na + ] snowfall (2) where, [X] is the concentration of desired ionic species in µeq L -1 ; [X/Na + ] Sea Water is the standard ratio of sea water (Keene et al., 1986).
Table S2 presents the percent sea salt fraction and non sea salt fraction of Cl -, SO 4 2-, K + , Ca 2+ and Mg 2+ in snowfall samples.Almost complete fractions of Cl -and Mg 2+ are contributed by marine sources.Large fractions of nssf of SO 4 2-, K + and Ca 2+ indicated their origin from non marine sources as discussed in the next subsection.Similar ranges of nssSO 4 2-and nssCa 2+ have been reported at various sites in snow samples (Naik et al., 1995;Kang et al., 2004).High concentration of nssf of SO 4 2-has also been reported in precipitation samples over Indian Ocean during INDOEX (Kulshrestha et al., 1999;Granat et al., 2002).Similar range of nssK + has been reported in precipitation samples at higher altitude sites in India (Naik et al., 1995).
Non-marine contribution: Non-marine sources can be categorised into two major categories i.e., crustal and anthropogenic sources.Out of these two sources, anthropogenic sources mostly enhance the acidity of precipitation while crustal sources decrease the acidity by buffering of the acidifying species (Rodhe et al., 2002;Kulshrestha, 2013).Due to opposite characteristics in controlling acidity of precipitation, it is essential to quantify separately the non-marine fraction into crustal associated fractions and anthropogenic fractions.We have termed crustal associated fractions which has fractions of acidic components (SO 4 2-, NO 3 -) present as salt of calcium i.e., CaSO 4 or Ca(NO 3 ) 2 .As illustrated in Fig. S4, we have followed the approach of Kulshrestha et al. (1997) and Jain et al. (2000) to calculate the contribution of crustal associated fraction and anthropogenic fraction of ionic species.
Then, the percent Anthro fractions of each component were calculated as follows-% Anthro x = % nss x -% CF x (5) With the help of the above mentioned equation, the percent contribution of crustal fractions (CF) and anthropogenic fractions (Anthro) of each ionic species are given in Table 3. Very high crustal Ca 2+ at this site might be due to long range transport of dust from various airmasses.nssCa 2+ has been reported in snow samples at Himalaya and Tibetan Plateau due to transported dust (Mayewski et al., 1983).Among nssSO 4 2-, high value of Anthro SO 4 2-might be due to significant contribution from various airmasses approaching at Gulmarg.This might be due to fossil fuel combustion at the origin of airmasses as well as picking it during the transport of airmasses before reaching at the site.Apart from long range transport, contribution from local sources such as use of electric generators which are mostly operated on diesel can not be ruled out.Various hotels at Gulmarg are forced to use these generators due to frequent power failure.The presence of Anthro SO 4 2-in the form of (NH 4 ) 2 SO 4 and NH 4 HSO 4 has been reported in precipitation worldwide (Pitts and Pitts, 1986;Kulshrestha et al., 2003).CF SO 4 2-at this site might be due to adsorption of SO 2 onto CaCO 3 rich dust particles forming Calcium Sulphate (Kulshrestha, 2013).
NO 3 -is found to be dominated by anthropogenic source in comparison to crustal sources (Table 3).Apart from local sources, Anthro NO 3 -might be due to the emissions of NO x from fossil fuel combustion and biomass burning coming from various airmasses.NO 3 -has been reported in airmasses due to long range transport in global precipitation (Avila and Alacron, 1999;Satyanarayana et al., 2010).
The maximum fraction of nssK + is contributed by crustal sources.Apart from biomass burning, nssK + due to crustal sources has been reported in precipitation (Zhang et al., 2007).Sometimes local soils contain very high level of potassium (Jain et al., 2000).Besides marine origin, Mg 2+ is also contributed by crustal sources.Mg 2+ has been reported in snow samples due to significant contribution from crustal sources (Kang et al., 2004).NH 4 + are contributed mainly by anthropogenic sources which might be due to significant contribution from local sources like animal and human excreta, effluents from various hotels with huge biomass Average contribution of different source categories: Marine, crustal and anthropogenic fractions of different ionic components were calculated to find out contribution of each source category.Average% marine contribution in each airmass cluster was calculated as follows-Average marine% = ∑ssf × 100/∑x (6) here ∑ssf = Sum of concentration of all ssf values in each airmass cluster in µeq L -1 ; ∑x = Sum of concentration of all components in each airmass cluster in µeq L -1 .The average crustal% for each airmass cluster was calculated as follows-Average crustal% = ∑CF × 100/∑x (7) here ∑CF = Sum of concentration of all CF values in each airmass cluster in µeq L -1 .The average Anthro% for each air cluster airmass cluster was calculated as follows-Average Anthro% = 100 -Average marine% -Average custal% (8) Average percent contribution calculated from the above formula for different source categories i.e., marine, crustal and anthropogenic sources is given in Fig. S5.It is very clear from figure that the order of dominance has been Marine (38%) > Crustal (32%) > Anthropogenic (30%).Significant influence of the marine sources followed by custal and anthropogenic sources has also been reported in precipitation samples by other workers globally (Zhang et al., 2007).The dominance of crustal sources at Gulmarg is mainly due to transported dust.The dominance of crustal fraction has been reported in snow samples worldwide (Mayewski et al., 1983;Shrestha et al., 2002).Anthropogenic contribution (29.9%) at this site is mainly due to various airmasses such as African, Middle East and European origin.However, the impact of anthropogenic sources is nullified significantly due to the dominance of crustal contributions over anthropogenic contribution as reflected from the alkaline nature of snowmelt at Gulmarg (pH = 5.90).

Neutralization Potential
The neutralizing tendency of cationic species in samples can be calculated with the help of neutralization factor.The neutralization factor of nssCa 2+ , nssMg 2+ and NH 4 + was calculated by using the following formula- where [X] = concentration of nssCa 2+ , nssMg 2+ and NH 4 + in µeq L -1 .Neutralization factor of nssCa 2+ , nssMg 2+ and NH 4 + for Gulmarg are calculated.The order of neutralization factor followed the following order nssCa 2+ (1.17) > NH 4 + (0.73) > nssMg 2+ (0.13).The greatest neutralization of snowfall acidity occurs by nssCa 2+ .The maximum neutralization by nssCa 2+ and NH 4 + in precipitation acidity has been reported by other workers worldwide (Kulshrestha et al., 2003; Zhang  et al., 2007; Satyanarayana et al., 2010).In India, suspended dust rich in calcium carbonate neutralizes acidic components in rain/snow samples (Jain et al., 2000).The maximum neutralization by nssCa 2+ might be due to transported dust from InW, Pk and Af airmasses mainly.The role of transported dust has been reported in the neutralization of precipitation chemistry (Avila and Alacron, 1999; Zhang et  al., 2007).

Wet Deposition Fluxes through Snowfall Deposition
Fluxes of wet deposition flux (F) during winter season of 2012-13 were calculated for all ionic species by the following formula- here F = Deposition flux in meq m -2 ; C = Average concentration of ionic components in µeq L -1 ; V = Volume of snowmelt (34.1 litres for the sampling period); A = Area of tray (314 cm 2 ).Table 4 represents the average wet deposition fluxes for all the samples collected during winter and spring seasons.It is very clear from this table that the average wet deposition fluxes followed the order-Ca 2+ > Na + > Cl -> NH 4 + > SO 4 2-> HCO 3 -> NO 3 -> Mg 2+ > K + > F -.The highest value of wet deposition flux was recorded for Ca 2+ which may be due to crustal influence.Very high wet deposition fluxes for Ca 2+ have been reported in India and other regions of the world (Kulshrestha et al., 2003;Zhang et al., 2007).Elevated deposition fluxes for Na + and Cl - might be due to marine aerosols deposited at the site.Acidic species like SO 4 2-and NO 3 -are lesser in comparison

Scavenging Ratios
The concurrent measurements of the chemical components of snowfall and aerosol help to understand aerosol removal by precipitation (Granat et al., 2002).Scavenging coefficients, scavenging rate, rain-out efficiencies and scavenging ratios are some reported parameters to demonstrate the scavenging of air pollutants (Hicks, 2005).In the present study, we have been estimated scavenging ratios (SR) assuming that the concentration of a chemical species in precipitation is related to its concentration in surface air using the following calculations (Granat et al., 2002;Kulshrestha et al., 2009) where C snowfall = The concentration of a component in snowfall (nmol kg -1 ); C aerosol = The concentration of the same component in air (nmol m -3 ); Da = Density of air; This expresses SR in kg of air per kg of water.Table 5 gives SR for all ionic species.Scavenging ratio is the highest for Ca 2+ followed by Mg 2+ > Na . Similar results have been reported by other workers (Granat et al., 2002; Kulshrestha et al.,  2009; Budhavant et al., 2014a).Encinas and co-workers (2004) have suggested that particle size, and hygroscopicity, cloud type and rain intensity are the major factors affecting the scavenging ratios of aerosols.The differences in SR values also depend on the difference in origin of air masses at cloud forming level and the surface (Kulshrestha et al., 2009).Most of Ca 2+ is scavenged by below cloud scavenging as reported by Kulshrestha et al. (2009).Below cloud scavenging of crustal components in India is mainly responsible for alkaline precipitation (Kulshrestha et al., 2003).

CONCLUSION
The average pH of snowmelt was observed to be 5.90 ranging between 5.16 to 7.68.The range of pH observed in this study is very similar to the values reported at many sites of higher altitude in the Indian region.Among all ionic , NO 3 -and NH 4 + had significantly higher wet deposition fluxes during the study period.However, the highest flux was recorded for Ca 2+ .The value of scavenging ratio was the highest for Ca 2+ indicating very efficient removal of Ca 2+ causing alkaline nature of snowmelt.Samples having lower concentration of Ca 2+ showed higher acidity.Airmass trajectory calculations revealed that the site was receiving airmasses from six different sectors vizi) North Atlantic Ocean origin (NAO), ii) African origin (Af), iii) Middle East origin (ME), iv) European origin (Eu), v) Western India origin (InW), vi) Pakistan origin (Pk).Snowmelt had the lowest pH (4.94) during ME airmasses.These samples had the highest ratios of nssSO 4 2-/nssCa 2+ and NO 3 -/nssCa 2+ .Contrary to this, InW airmasses had the highest pH (7.58) and the lowest ratios of nssSO 4 2-/nssCa 2+ and NO 3 -/nssCa 2+ indicating significant influence of crustal sources over anthropogenic sources.A comparison of the present study with the study reported previously revealed that the present wet depositions of anthropogenic components are much higher than the values reported three decades ago.A remarkable increase in the concentrations of nssSO 4 2-(114%) and NO 3 -(109%) was noticed which might be due to increased tourist activities, vehicular traffic, biomass burning and diesel based generator during power failure.Open disposal of garbage from various hotels, animal excreta and various tourist activities might be responsible for 90% increase in NH 4 + .Decreasing pH of snow due to anthropogenic components at Gulmarg is probably the first stage alarm which suggests continuous monitoring of acid deposition scenario in the Himalayan system in order to prevent disaster in near future.

ACKNOWLEDGEMENT
Financial support received from JNU as CBF, LRE and DST-PURSE grants is gratefully acknowledged.Authors Bablu Kumar, Sudha Singh and Gyan Prakash Gupta acknowledge the award of fellowships from UGC.Our sincere thank to Mr Shahid and Mr. Shamsulhaq for assisting in collection of snowfall samples.

Fig. 2 .
Fig. 2. Examples of six different airmass trajectories arriving at the site using HYSPLIT model.NAO = North Atlantic Ocean origin, Af = African origin, ME = Middle East origin, Eu = European origin (Eu), InW = Western India origin, Pk = Pakistan origin.

Table 1 .
Average concentrations (µeq L -1 ) of major ions, pH and No. of samples during diffferent clusters.
previous = Concentration of the same chemical species for the year 1986-87).

Table 3 .
Percent contribution of Marine Fraction, Crustal Fraction (CF) and Anthropogenic Fraction (Anthro) of various ionic species.

Table 4 .
Average wet deposition fluxes during winter and spring seasons (meq m -2 ).

Table 5 .
Average concentrations of concurrent measurements of the chemical components of snowfall and aerosols and Scavenging ratios (SR) for major ions (n = 8).