JOURNAL OF GEOPHYSICAL RESEARCH, VOL. 117, C06004, doi:10.1029/2011JC007737, 2012 Contribution of atmospheric nitrogen deposition to new production in the nitrogen limited photic zone of the northern Indian Ocean Arvind Singh,1,2 Naveen Gandhi,1,3 and R. Ramesh1 Received 4 November 2011; revised 10 April 2012; accepted 25 April 2012; published 6 June 2012. [1] Primary productivity in the sunlit surface layers of tropical oceans is mostly limited by the supply of reactive nitrogen (Nr) through upwelling, N2 fixation by diazotrophs, riverine flux and atmospheric deposition. The relative importance of these processes varies from region to region. Using recent data on the nitrogen content of aerosols over the ocean and marine new production in parts of the northern Indian Ocean for the period 1994–2006 CE, a quantitative assessment of the contribution of atmospheric deposition to new production in the two biogeochemically different basins of the northern Indian Ocean, viz., the Arabian Sea and the Bay of Bengal, is presented. By suitably converting the measured concentrations of aerosol nitrogen into fluxes and comparing them with 15N tracer-based direct new and primary production measurements, it is inferred that the contribution of atmospheric deposition to new production in the northern Indian Ocean could at best be 3%. Our estimate of 1.39 Tg N year1 of Nr flux into the northern Indian Ocean through aerosols is a step toward significantly reducing the uncertainty in the global nitrogen budget. Citation: Singh, A., N. Gandhi, and R. Ramesh (2012), Contribution of atmospheric nitrogen deposition to new production in the nitrogen limited photic zone of the northern Indian Ocean, J. Geophys. Res., 117, C06004, doi:10.1029/2011JC007737. 1. Introduction [2] Marine primary production (rate of carbon fixation, measured in mg C m2 day1) is one of the major sinks of atmospheric carbon dioxide, thus an important regulator of the Earth’s climate [Sabine et al., 2004]. The rate of transfer of fixed carbon from the sunlit layers of the ocean (i.e., the top 100 m) to the deeper layers is termed export production. This is believed to be approximately equal to the ‘new production’, i.e., the fraction of primary production sustained by the input of new nutrients into the photic zone, over annual time scales [Eppley and Peterson, 1979]. The availability of nutrients, especially reactive nitrogen (Nr), is known to limit the biological productivity in the surface ocean in many regions [Broecker, 1974]. As nitrogen is an essential nutrient for the growth of marine biota, we focus here on understanding the role of atmospheric deposition of nitrogen in affecting marine productivity. Regionally atmospheric deposition may have significant impacts on marine biogeochemistry and could support up to 30% of 1 Physical Research Laboratory, Ahmedabad, India. Now at Bermuda Institute of Ocean Sciences, St. Georges, Bermuda. Now at Indian Institute of Tropical Meteorology, Pune, India. 2 3 Corresponding author: A. Singh, Bermuda Institute of Ocean Sciences, 17 Biological Station, St. Georges GE01, Bermuda. ([email protected]) Copyright 2012 by the American Geophysical Union. 0148-0227/12/2011JC007737 the new production [Spokes et al., 2000]: on the other hand, atmospheric Si and P inputs may have only minimal impacts on regional new production as these inputs are usually smaller than the upward flux from below the sunlit layer [Krishnamurthy et al., 2010]. [3] Nitrogen enters the surface ocean through a number of processes; e.g., N2 fixation, upwelling/eddy diffusion, fertilizer use on land and waste discharge, and atmospheric deposition by aerosols [Galloway et al., 2004]. Molecular nitrogen (N2) is most abundant in the Earth’s atmosphere, but it can only be utilized by a specific group of marine microorganisms (diazotrophs such as Trichodesmium). Most other organisms assimilate oxidized and reduced forms of + nitrogen, i.e., reactive nitrogen (e.g., NO 3 , NH4 ) [e.g., Gandhi et al., 2011a]. Upwelling is an important process through which new nitrogen is introduced to the surface, but this occurs seasonally in specific regions of the ocean, e.g., in the western Arabian Sea during summer [Ryther et al., 1966]. Nitrogen inputs from fertilizer use on land and waste discharge are mostly limited to the coastal region [Seitzinger et al., 2006]. [4] Nitrogen is lost from the ocean through denitrification and anaerobic ammonium oxidation (anammox) to the atmosphere, and burial of organic matter in the sediments [e.g., Kuypers et al., 2003]. Recently, an imbalance between the nitrogen loss and gain rates has been observed that suggests nitrogen gain could have been underestimated; other less well–studied or currently unknown processes may exist and fix substantial amounts of N2 [Codispoti, 2007]. This C06004 1 of 11 C06004 SINGH ET AL.: ROLE OF N DEPOSITION IN NEW PRODUCTION prompted us to study one such input processes, i.e., atmospheric deposition to the ocean. [5] As a consequence of increasing anthropogenic activity such as deforestation, fossil fuel burning and industrialization, the global nitrogen emissions have increased since the preindustrial era [Galloway et al., 2004; Duce et al., 2008]. Wet and dry deposition of Nr (mainly nitrate and ammonia) can stimulate phytoplankton production and change phytoplankton community structure and composition, when not limited by other nutrients such as iron [Mills et al., 2004; Baker et al., 2007]. The western Arabian Sea, however, appears to be at least seasonally iron limited region [Naqvi et al., 2010] despite the supply of iron to this region through Arabian dust deposition [e.g., Krishnamurti et al., 1998]. The present study primarily focuses on the aerosol nitrogen influx and its contribution to new production in the northern Indian Ocean. [6] The Arabian Sea and the Bay of Bengal, the two northern Indian Ocean basins, located in similar latitudes, are significantly different in many aspects: strong winds during summer monsoon produce intense upwelling in the northwestern Arabian Sea. Nutrients brought up through upwelling enhance surface productivity. Cooler winds during the winter monsoon, lead to convective mixing in the northeastern Arabian Sea, which brings up nutrients from the deep, thus increasing surface productivity [e.g., Prakash and Ramesh, 2007]. In addition, the Arabian Sea receives nutrients through atmospheric transport from Arabia in the west and the Thar in the east [Krishnamurti et al., 1998]. These processes make the Arabian Sea one of the most productive regions in the world [Madhupratap et al., 1996; Smith, 2001; Kumar et al., 2004, 2010; Prakash and Ramesh, 2007; Prakash et al., 2008; Gandhi et al., 2010a]. On the other hand, a large influx of fresh water stratifies the Bay of Bengal surface, limiting surface productivity [Kumar et al., 2004; Singh et al., 2010; Singh and Ramesh, 2011]. The sources of atmospheric nitrogen deposition at these two sites may be different, but are believed to be mainly from the developing nations, India and China [Galloway et al., 2004]. Hence, these two basins of the northern Indian Ocean provide an ideal marine environment to study the impact of atmospheric deposition on the surface ocean biogeochemistry. [7] The contribution of atmospheric nitrogen deposition to new production is poorly constrained. Patra et al. [2007] discussed the relative significance of atmospheric deposition over vertical mixing in maintaining chlorophyll abundances in the northern Indian Ocean. Since atmospheric input is comparable to or less than new production because most of the production is otherwise fuelled by recycled nutrients [Eppley and Peterson, 1979]; a comparison of total primary production with atmospheric deposition might lead to erroneously large values [e.g., Srinivas et al., 2011]. Spokes et al. [2000] reported that up to 30% of the new production in the oligotrophic waters of the northeast Atlantic could be supported by atmospheric nitrogen inputs in spring. The northern Indian Ocean lacks any such an estimate. For example, systematic surface productivity measurements in the Bay of Bengal became available only during the last decade. In the open Bay of Bengal [Wiggert et al., 2006], where the supply of nutrients through riverine influx and upwelling is not significant, atmospheric deposition could be an important source of nitrogen. Kumar et al. C06004 [2004], based on limited data, suggested that a significant part of new production in the Bay of Bengal could be due to atmospheric deposition. Since then, more data have become available both on new production and atmospheric deposition in various parts of the northern Indian Ocean [Rastogi, 2005; Prakash, 2008; Gandhi, 2010]. Here we assess the role of atmospheric nitrogen deposition in contributing to new production in the northern Indian Ocean. 2. Methods [8] The measured concentrations of nitrate, nitrite and ammonium in aerosols are converted into dry and wet deposition fluxes. Dry deposition occurs when particles settle under gravity whereas during wet deposition particles are scavenged by precipitation. Productivity is estimated on the basis of uptake rates of nitrate, ammonium and urea during photosynthesis. 2.1. Calculation of Dry and Wet Deposition Fluxes [9] Nitrate, nitrite, and ammonia concentrations in aerosols collected over the Arabian Sea and the Bay of Bengal were obtained from the literature [Rhoads et al., 1997; Krishnamurti et al., 1998; Johansen et al., 1999; Gibb et al., 1999; Sarin et al., 1999; Bange et al., 2000; Rengarajan and Sarin, 2004; Rastogi, 2005; Kumar et al., 2008]. Aerosol measurements cover almost the entire Arabian Sea, whereas a lesser area is covered in the Bay of Bengal (Figure 1). We have estimated deposition fluxes from the nitrogen compounds’ concentration in the aerosol. Deposition of nitrogen occurs through gravitational settling (dry deposition) and precipitation (wet deposition). The dry deposition flux is given by Fd ¼ Vd Cd ; ð1Þ where Cd is the measured concentration of the compound of interest in aerosols, and Vd the particle settling velocity, which depends on complex interactions of various parameters such as wind speed, particle size, relative humidity, and sea surface roughness [Duce et al., 1991]; as a result Vd has large uncertainties. Thus, to simplify estimates of deposition fluxes, a mean value of Vd accounting for the aerosol size distribution, is frequently used. Vd of 1.5 cm s1 for nitrate and 0.05 cm s1 for ammonium were used (because Vd varies with particle size as does the mean size of particles removing nitrate and ammonium) in these calculations [Schafer et al., 1993], as was done earlier by Bange et al. [2000]. [10] The wet deposition flux, is given by Fw ¼ P S Cd ra 1 rw ; ð2Þ where P represents the rain rate, S the scavenging ratio and ra (1.2 kg m3), and rw (103 kg m3), the densities of air and water, respectively. S = Cr /Cd, where Cr is the concentration of the compound of interest in rain. S is 330 and 200 for nitrate and ammonium, respectively [Duce et al., 1991], calculated based on mass mixing ratios (i.e., both Cr and Cd are in kg/kg units) [Barrie, 1985]. Equation (2) was updated by Bange et al. [2000] after Duce et al. [1991]. For the estimation of the seasonal wet deposition flux, Bange et al. [2000] used a constant P, (780 mm year1 for the Arabian Sea, 2550 mm year1 for the Bay of Bengal) as estimated by 2 of 11 C06004 SINGH ET AL.: ROLE OF N DEPOSITION IN NEW PRODUCTION C06004 Figure 1. Aerosol sampling locations in the northern Indian Ocean. Legend: solid triangle, Gibb et al. [1999]; open triangle, Johansen et al. [1999]; diamond, Rhoads et al. [1997]; cross, Krishnamurti et al. [1998]; solid circle, Sarin et al. [1999]; solid square, Bange et al. [2000]; open square, Rengarajan and Sarin [2004]; open circle, Rastogi [2005]; asterisk, Kumar et al. [2008]. See auxiliary material for more details. Kumar and Prasad [1997]. High interannual and spatial variability of rainfall results in large uncertainties in wet deposition fluxes. To minimize these uncertainties, we estimated the wet deposition flux using rainfall data from the Global Precipitation Climatology Project (GPCP) (available at http://disc2.nascom.nasa.gov/Giovanni/tovas/rain.GPCP.2. shtml, latest accessed on September 5, 2011) for each location at the corresponding time (Tables 1–3; see also auxiliary material).1 GPCP data have an uncertainty of 7.4% [Xie et al., 2003]. For calculating the total deposition flux, the areas of the Arabian Sea and the Bay of Bengal are taken as 4.93 1012 m2 and 2.93 1012 m2, respectively [Bange et al., 2000]. We have estimated weighted averages of dry and wet deposition fluxes as there was a large variation in the data density and the resulting fluxes (Tables 1 and 2). GPCP data for the corresponding years are presented in Table 3, wet and dry deposition fluxes can be reproduced using this data and nitrogen concentrations from the papers cited in Table 1. 2.2. Calculation of New and Primary Production [11] The 15N tracer technique [Dugdale and Goering, 1967], besides providing an estimate of primary production, yields an estimate of new production as well (i.e., nitrate uptake/total nitrogen uptake). Primary production is estimated by summing the photic zone integrated uptake rates of nitrate, ammonia and urea and multiplied by the Redfield ratio (C:N:P :: 106:16:1). Because of simultaneous microbial processes occurring in the sunlit layer of ocean, variation 1 Auxiliary materials are available in the HTML. doi:10.1029/ 2011JC007737. in Redfield ratio (C:N:P varies from 70:10:1 to 200:27:1) introduces some error in the total production (carbon uptake rates) estimates [Arrigo, 2005, and references therein]. Since we compare only nitrogen uptake rates (based on the 15N tracer technique) with deposition fluxes, such errors are avoided here. More details of this technique are discussed by Kumar and Ramesh [2005]. 15N tracer technique-based new and primary production data in the northern Indian Ocean have been obtained from published studies [McCarthy et al., 1999; Watts et al., 1999; Watts and Owens, 1999; Sambrotto, 2001; Kumar et al., 2004, 2010; Prakash et al., 2008; Gandhi et al., 2010a; N. Gandhi et al., Primary and new production in the thermocline ridge region of the southern Indian Ocean:, submitted to Deep Sea Research, Part I, 2012] (Tables 1 and 2 and Figure 2); as in the case of aerosols, measurements cover most of the Arabian Sea, but are spatially limited in the Bay of Bengal. As for the aerosol deposition fluxes, we have estimated the weighted averages of new and primary production, and the contributions (in %) of aerosol deposition to new production are calculated as the ratios of the sum of dry and wet deposition fluxes to the new production (Tables 1 and 2). [12] The error in the productivity measurements is less than 10% [Gandhi et al., 2011a], overall error would be larger due to patchiness of the plankton and seasonal and interannual variations. 2.3. Errors in the Estimates [13] Estimates of deposition fluxes are more uncertain than the new production estimates as the former depends on several variables, e.g., wind speed, relative humidity and 3 of 11 4 of 11 CAS weighted average WAS WAS weighted average BOB EAS EAS weighted average CAS CAS weighted average WAS WAS weighted average BOB BOB weighted average EAS weighted average CAS EAS BOB weighted average CAS weighted average WAS WAS weighted average BOB EAS weighted average CAS EAS Region Jul–Aug 1995 Aug–Oct 1994 Jul–Aug 1995 Jul–Aug 2008 Jul–Aug 1995 Apr–May 2003 Mar–Apr 1995 Mar–Apr 1995 Mar–Apr 1995 Apr 2006 Jan 1995 Nov–Dec 1994 Jan 2003 Feb–Mar 2003 Feb–Mar 2004 Year 16 22 22 ND 42 42 6.1 44 15 5.0c (6) 5.0 3.7 (11) 4.9 (4) 11 (3) 5.2 4.8 (5) 4.8 30 18 18 7.2 7.2 17 (4) 1 6.3 30 8 26 26 ND ND 8.7 26b 10 14 8 PP 3.3 3.1 (5) 3.1 5.4 (9) 5.4 3.6c (6) 0.7 (8) 1.9 3.3 (3) 2.4 3.2 (17) 3.2 2.3 (6) 12.7 (6) 7.1 (11) 7.3 2.4 (13) NP Year Feb 1997 Feb 1999 Jan 1996 Nov–Dec 1994 Jan 1996 Feb 1997 Sambrotto [2001] Feb–Mar 2001 Apr–May 1994 Feb–Mar 1995 Apr 1995 May 1995 May 1995 Mar 1997 Mar–Apr 1998 Apr–May 2006 Jul–Aug 1995 Jul–Aug 1995–96 Jul–Aug 1995 Aug–Oct 1994 Summer Monsoon Watts et al. [1999] Sambrotto [2001] Gandhi et al. (submitted manuscript, 2012) Sambrotto [2001] Kumar et al. [2004] Sambrotto [2001] Sambrotto [2001] Spring Intermonsoon Sambrotto [2001] Mar 2001 Gandhi et al. [2010a] Apr–May 2006 McCarthy et al. [1999] Watts and Owens [1999] Winter Monsoon Kumar et al. [2010] Jan 1996 Kumar et al. [2010] Prakash et al. [2008] References 0.002 0.002 104 0.002 0.02 0.02 ND 0.01 0.01 (17) 0.01 0.01 0.01 0.01 (15) 0.01 (20) 104 (10) 0.01 (21) 0.01 104 0.01 0.01 0.001 0.002 0.03 0.01 0.01 0.001 0.002 0.003 0.01 0.11 0.003 0.05 0.00 0.02 0.03 0.03 0.01 0.02 0.01 0.11 0.00 (10) 0.03 (10) 0.04 (9) 0.02 0.02 (10) 0.02 0.03 (6) 0.04 (6) 0.04 0.01 (6) 0.01 (8) 0.01 0.02 (10) 0.05 (8) 0.04 (9) 0.03 (22) 0.03 (28) 0.02 (27) 0.03 (8) 0.01 (11) 0.03 0.11 WN 0.11 (4) DN 0.01 0.03 0.03 0.01 0.01 104 ND 0.02 0.02 0.01 0.02 0.02 0.02 0.05 0.07 0.04 0.04 0.02 0.03 0.01 0.04 ND 0.22 0.003 0.08 0.04 0.04 0.05 0.05 0.04 0.06 0.05 0.22 TAD Table 1. New Production, Primary Production, Total Atmospheric Nitrogen Deposition After Dividing the Northern Indian Ocean Into Four Zonesa Bange et al. [2000] Sarin et al. [1999] Johansen et al. [1999] Gibb et al. [1999] Rastogi [2005] Sarin et al. [1999] Sarin et al. [1999] Rhoads et al. [1997] Bange et al. [2000] Johansen et al. [1999] Bange et al. [2000] Rengarajan and Sarin [2004] Kumar et al. [2008] Rastogi [2005] Kumar et al. [2008] Rengarajan and Sarin [2004] Rengarajan and Sarin [2004] Krishnamurti et al. [1998] Gibb et al. [1999] Krishnamurti et al. [1998] Sarin et al. [1999] Krishnamurti et al. [1998] References 0.6 0.2 0.4 1.2 1.1 1.6 1.7 3.0 %C C06004 SINGH ET AL.: ROLE OF N DEPOSITION IN NEW PRODUCTION C06004 %C References ND ND ND ND TAD WN DN Kumar et al. [2004] Sep–Oct 2002 EAS CAS WAS WAS weighted average BOB BOB weighted average Nov 1995 1.5 (15) 1.5 2.6 (9) 2.6 ND ND 11 11 4 4 McCarthy et al. [1999] Year Fall Intermonsoon References PP NP Year Region Table 1. (continued) a NP, new production (mmol N m2 day1); PP, primary production (mmol N m2 day1); TAD, total (dry + wet, i.e., DN + WN) atmospheric nitrogen deposition (mmol N m2 day1); %C, percentage contribution of aerosol to NP, i.e., (TAD/NP) 100%; EAS, Eastern Arabian Sea; CAS, Central Arabian Sea; WAS, Western Arabian Sea; BOB, Bay of Bengal; ND, no data available. Data of new production and atmospheric deposition are obtained from the cited references; see auxiliary material for more details. Values given in parentheses are number of stations/samples. b PP is obtained from Kumar [2004]. Same number of samples is used for primary production to the new production unless otherwise specified. Above fluxes are calculated as described in section 2.1. c Weighted average of 6 samples from north and southeastern Arabian Sea. SINGH ET AL.: ROLE OF N DEPOSITION IN NEW PRODUCTION C06004 C06004 Table 2. New Production, Primary Production, Total Atmospheric Nitrogen Deposition, in the Northern Indian Oceana Season Region NP PP TAD %C WM SIM SM FIM WM SIM SM FIM Arabian Sea Arabian Sea Arabian Sea Arabian Sea Bay of Bengal Bay of Bengal Bay of Bengal Bay of Bengal 4.8 (53) 2.4 (22) 5.1 (29) 1.5 (15) ND 5.4 (9) ND 2.6 (9) 16.4 (53) 12.8 (20) 22.4 (29) 11 (15) ND 7.2 (9) ND 4.0 (9) 0.06 (43) 0.04 (137) 0.02 (52) ND 0.05 (12) 0.02 (21) ND ND 1.2 1.7 0.4 – – 0.4 – – NP, new production (mmol N m2 day1); PP, primary production (mmol N m2 day1); TAD, total (dry + wet) atmospheric nitrogen deposition (mmol N m2 day1); %C, percentage contribution of aerosol to NP, i.e., (TAD/NP) 100%; WM, winter monsoon; SIM, spring intermonsoon; SM, summer monsoon; FIM, fall intermonsoon; ND, no data available. Units and other details are the same as those in Table 1. Values in parentheses are number of stations/samples. NP, PP and TAD can be reproduced taking the weighted average of the data presented in Table 1. a rainfall, each with associated error. New production estimates are based on the 15N measurements using a mass spectrometer that is quite precise, however, uncertainties may arise from scaling up the estimates to large ocean areas. [14] If Vd has uncertainty sVd and Cd has sCd then error in Fd through Fd = Vd Cd is given by s Fd ¼ Fd sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi sV d 2 sC d 2 þ : Vd Cd ð3Þ Estimates of Vd, based on various long-term data sets and models, have an error 50% [Schafer et al., 1993]. Cd measurements are relatively well constrained and error is 15% (as reported by Kumar et al. [2008]; however uncertainly could be larger due to high variability in the atmosphere). Hence the overall uncertainty in dry deposition flux is 52%, dominated by sVd/Vd. Uncertainly in wet deposition fluxes are estimated by propagating respective Table 3. Rainfall Data Used for Wet Deposition Flux Estimates Over the Different Regions in the Northern Indian Ocean Date Region Rainfall (mm year1) Aug–Oct 1994 Apr–May 1994 Nov–Dec 1994 Feb–Mar 1995 Apr 1995 May 1995 Jul–Aug 1995 Jan 1996 Jan 1996 Feb 1997 Feb 1997 Mar 1997 Mar–Apr 1998 Feb 1999 Feb–Mar 2001 Mar 2001 Apr–May 2006 CAS EAS CAS CAS EAS CAS CAS/WASa EAS CAS/WASa CAS BOB CAS CAS BOB BOB EAS EAS 207 50 857 53 718 729 318 767 981 7 299 91 128 919 430 37 1249 a Sampling locations during Jul–Aug 1995 and Jan 1996 were close by and hence same rainfall is used for wet deposition flux estimates in CAS and WAS. 5 of 11 SINGH ET AL.: ROLE OF N DEPOSITION IN NEW PRODUCTION C06004 C06004 Figure 2. New and primary productivity sample locations in the northern Indian Ocean. Legend: asterisk, Watts et al. [1999]; open circle, McCarthy et al. [1999]; solid circle, Watts and Owens [1999]; cross, Sambrotto [2001]; diamond, Kumar et al. [2004]; open triangle, Prakash et al. [2008]; open square, Kumar et al. [2010]; solid triangle, Gandhi et al. [2010a]; solid square, Gandhi et al. (submitted manuscript, 2012). See auxiliary material for more details. uncertainties in Fw = P S Cd r1 a rw s Fw ¼ Fw sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi s 2 s 2 s 2 P S Cd þ þ ; P S Cd ð4Þ where sP and sS are uncertainties involved in rainfall and scavenging ratio, respectively. The above expression is based on the assumption that there is no error in ra and rw. Rainfall measurement has an analytical error of 7.4% [Xie et al., 2003]. S is most uncertain here and varies from 280–480 (excluding an outlier value of 870 reported by Wolf et al. [1986] from a short-term measurement on Bermuda) for nitrate and 160–340 for ammonium [Duce et al., 1991]. We adopted the average values reported by Duce et al. [1991], i.e., 330 and 200 for nitrate and ammonium, respectively. Hence the maximum uncertainty in sS could be (480–330) 100/330 = 45%. Thus, the uncertainly in wet deposition flux is 48%. Note that Duce et al. [1991] estimated S from the ratio of concentrations in rain and simultaneously measured air concentrations at ground level at various ocean provinces (but not in the Indian Ocean). Here it is assumed that S has the same range in northern Indian Oceanffi as in the other oceans. pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi The overall uncertainty ( sF2w þ sF2d ) in the estimated total nitrogen deposition flux is 71%, mainly caused by the large uncertainties in poorly constrained dry depositional velocities of nitrate and ammonium. 2.4. Zone Classification [15] We analyze the data into two ways. First (case A), the northern Indian Ocean is divided into four different zones (1) Western Arabian Sea, 50 –60 E; (2) Central Arabian Sea, 60 –70 E; (3) Eastern Arabian Sea, 70 –78 E; and (4) Bay of Bengal, 78 –95 E, and the results are presented in Table 1. These boundaries are not well constrained and are subjected to change (likely to vary by 2 depending on the sampling area). This division is based on the differences in biogeochemistry among these basins; e.g., the western Arabian Sea gets nutrients through upwelling during the summer monsoon, whereas the eastern Arabian Sea, by convective vertical mixing in the winter [Madhupratap et al., 1996; Prakash and Ramesh, 2007]. Second (case B), we consider the Arabian Sea and the Bay of Bengal as two different basins and list the results in Table 2. 3. Results and Discussion [16] Data from some simultaneous and nearly co-located measurements for new production and aerosol concentrations are available in both basins (Figures 1 and 2), but these were sampled during different cruises. Exactly simultaneous and co-located measurements of aerosol and ocean productivity are not possible since the standard protocols for measurements of the two are quite different: aerosol samples are mostly collected while ship is moving (by pumping air over a large area to increase the collected mass) and productivity measurements need the ship to be stationary, and are done over a limited spot. Even if done simultaneously, the aerosols collected may not represent any immediate effect on the ambient ocean because (1) they may be transported from elsewhere and (2) their timescales of interaction are different. As far as possible, we match the data of corresponding locations for deposition flux, primary and new production. 6 of 11 C06004 SINGH ET AL.: ROLE OF N DEPOSITION IN NEW PRODUCTION 3.1. Seasonal Variations in New Production and Atmospheric Deposition Flux [17] For the first case A, the aerosol deposition flux, new and total primary production (in mmol N m2 day1) of the Bay of Bengal and three zones of the Arabian Sea are listed in Table 1. Seasons are classified as winter (December– February), spring (March–May), summer (June–August), and fall (September–November). Aerosol data are not available for the fall intermonsoon in the Arabian Sea while in the Bay of Bengal, data for only the winter and spring intermonsoons are available. Also, there is no aerosol data for spring in the western Arabian Sea and summer in the eastern Arabian Sea. New and total primary production estimations are available for all the seasons in the Arabian Sea, while they are unavailable for the winter and summer monsoons in the Bay of Bengal. [18] In the eastern Arabian Sea, new production was maximum (7.3 mmol N m2 day1) during the winter monsoon and minimum (1.9 mmol N m2 day1) during the spring intermonsoon (Table 1). New production was somewhat moderate (5.0 mmol N m2 day1) during summer in the eastern Arabian Sea (Table 1). On the other hand, atmospheric nitrogen deposition was also maximum (0.22 mmol N m2 day1) during the winter in the eastern Arabian Sea. The observed higher new production could be result of higher atmospheric deposition in the eastern Arabian Sea besides prominent winter mixing in the region. Such higher deposition during the winter monsoon could be possible due to episodic events which were reported in some places in the ocean as well [Owens et al., 1992]. However, we note that reports on episodic events were overemphasized [Michaels et al., 1993]. Limited data suggest that there was 0.02 mmol N m2 day1 deposition during the spring intermonsoon, however, there is no such data for summer and fall intermonsoon over the eastern Arabian Sea. [19] In the central Arabian Sea, new production was significantly higher during the summer (5.2 mmol N m2 day1) than during the spring intermonsoon (3.3 mmol N m2 day1) and the winter monsoon (2.4 mmol N m2 day1). Atmospheric nitrogen deposition was minimum (0.01 mmol N m2 day1) in the summer monsoon over the central Arabian Sea. This is attributable to the winds blowing from the ocean to the Indian subcontinent during summer [Prakash and Ramesh, 2007]. Higher primary production in the summer monsoon suggests the importance of intense upwelling in the Arabian Sea. During the winter and spring intermonsoon, the central Arabian Sea witnessed equal amounts (0.04 mmol N m2 day1) of nitrogen deposition by aerosols (Table 1). [20] A significant seasonal variation in the new and primary production is observed during 1995 in the western Arabian Sea with maximum during the summer while minimum during the winter. Paucity of the data did not allow us to infer seasonal variation in the deposition flux in the western Arabian Sea (Table 1). Likewise, it is also difficult to infer the seasonal variability in the productivity and deposition fluxes in the Bay of Bengal (Table 1). [21] In the second case B, when the Arabian Sea is considered as a single basin, we observed seasonal variability in the new production and deposition flux. New and primary productions were higher during the summer monsoon than C06004 in other seasons in the Arabian Sea. This could be because of upwelling, which is induced by the summer Findlater jet [Findlater, 1969]. In addition, convective mixing could be responsible for new and primary production to be significantly higher during winter than in spring and fall intermonsoons. Nitrogen atmospheric deposition was higher during winter than during spring and summer monsoon (Table 2). 3.2. Spatial Variations in the Productivity and the Atmospheric Deposition Flux [22] In the first case A, new production was significantly higher in the eastern Arabian Sea during the winter monsoon than in the other three zones (Table 1), attributable to winter mixing, a well known process that occurs in the western coast of India [Madhupratap et al., 1996; Gandhi et al., 2011b]. All the three zones of the Arabian Sea depict comparable new production during the spring intermonsoon in 1995, suggesting no significant spatial variations in new production, possibly because of a common process (could be N2 fixation in the presence of diazotrophs) acting all over the Arabian Sea during this season [Gandhi et al., 2011a]. It was difficult to decipher any significant trend (increasing or decreasing) from the data set (Table 1). [23] In the second case B, we observed significant higher primary production in the Arabian Sea than the Bay of Bengal; however, new production was comparable. There was no such significant difference between the deposition fluxes in the two basins. Deposition flux was higher during the winter monsoon than in any other season in the Arabian Sea (Table 2). This might be attributable to the atmospheric inputs from the Thar desert [Krishnamurti et al., 1998]. [24] Flux estimations mostly pertained to the central Arabian Sea (Figure 1). When the Arabian Sea is considered as a whole (in the section 3.1) we note that deposition flux is higher during the winter monsoon (Table 2), and after dividing the Arabian Sea into three zones we observed that deposition flux was higher mainly in the eastern Arabian Sea (Table 1). Winds blowing from the Indian subcontinent during the winter monsoon, might have contributed to this flux. 3.3. Contribution of Atmospheric Nitrogen Deposition to New Production in the Northern Indian Ocean [25] In the case A, higher productivity was observed during the summer monsoon as expected, but the contribution from deposition flux was less (Table 1). This suggests that atmospheric deposition was not an important source of nitrogen to the Arabian Sea, and nitrogen through upwelling of deeper waters could be the most important source of new nitrogen to the surface waters during this season. These observations belong mainly to the central Arabian Sea and the western Arabian Sea, where intense winds cause upwelling during this season [Findlater, 1969]. [26] All the three components (atmospheric deposition, new production, and contribution of the former to the latter, i.e., 3%) were higher during the winter than during other seasons in the eastern Arabian Sea (Table 1). On the scale of global oceans and considering the residence time of nitrogen (i.e., 1000 years), 3% contribution from atmospheric nitrogen (being an additional input to the ocean unlike nitrogen inputs to the photic zone through upwelling) to new 7 of 11 C06004 SINGH ET AL.: ROLE OF N DEPOSITION IN NEW PRODUCTION production could be significant [Duce et al., 2008]. However, in regions such as the Arabian Sea, where seasonal upwelling prevails, atmospheric nitrogen deposition is masked by local upwelling of nitrate (Table 1). [27] In the case B, aerosol contributions are 1.2, 1.7 and 0.4% to the new production in the Arabian Sea during the winter monsoon, the spring intermonsoon and the summer monsoon, respectively. Although atmospheric deposition is the highest during winter monsoon its contribution to new production is maximum during the spring intermonsoon because of low new production during the spring, which could be attributed to the stratification resulting in the low supply of nutrients from below. Both the atmospheric deposition and its contribution to new production were higher during the winter monsoon than in the summer monsoon, as winds blowing from the land to the ocean during the winter increase the atmospheric contribution. On the other hand, both atmospheric deposition and its contribution to new production are low during summer (Table 2) as most of the nutrients are either upwelled or regenerated during the summer monsoon [Sambrotto, 2001]. [28] In the Bay of Bengal, simultaneous data for new production and atmospheric nitrogen deposition are only available for the spring intermonsoon (Table 2). New production during the spring intermonsoon in the Bay of Bengal is comparable to those during winter and summer monsoons in the Arabian Sea, while the aerosol contribution is less (0.4%). Also, upwelling is not a contributor to new production in the Bay of Bengal [Gauns et al., 2005]. The Bay of Bengal receives a large volume of river run-off (1.6 1012 m3 year1) [Subramanian, 1993]. It is likely that nitrogen flux from river run-off could play a significant role for new production in the coastal areas of the Bay of Bengal [Singh and Ramesh, 2011]. Higher new production could be triggered by cold core eddy formation during the spring intermonsoon in open ocean area of the Bay of Bengal [Prasanna Kumar et al., 2007; Gandhi et al., 2010b]. [29] The contribution of atmospheric deposition to new production was maximum (1.7%) in the Arabian Sea and minimum (0.4%) in the Bay of Bengal during the same season, i.e., the spring intermonsoon; however, the difference between the contributions during the summer monsoon in the Arabian Sea and during the spring intermonsoon in the Bay of Bengal is insignificant. [30] Using NOAA-AVHRR data of duration 1996–2003, Parameswaran et al. [2008] reported the significant impact of continental aerosols in the Arabian Sea: during March– April from the Indian subcontinent and during June– September from Arabian deserts, while in the Bay of Bengal, influence of the subcontinent was more during November– May and minimal during June–September. These observations are consistent with the results presented here. [31] Due to the limited seasonal and spatial matching of aerosol and new production observations (Tables 1 and 2), it is difficult to infer the role of deposition flux in the new and primary production in the Bay of Bengal. However, it is likely that there is a minor contribution of atmospheric deposition to new production in the Bay of Bengal. 3.4. Changes in the Redfield Ratio and Biodiversity [32] The Redfield ratio quantitatively links the marine carbon, nitrogen and phosphorus cycles in numerous biogeochemical C06004 applications. The sum of all biological processes in the ocean (including nitrogen fixation and denitrification) is believed to maintain the deep ocean C:N:P ratio at 106:16:1, but it is well known that N:P ratios vary strongly even within the nondiazotrophic autotrophs [Arrigo, 2005]. Reactive nitrogen flux in the South Asian region has increased significantly in the last few decades, and consequently the atmospheric deposition of reactive anthropogenic nitrogen over the northern Indian Ocean is among the highest in the world [Duce et al., 2008]. Such deposition fluxes are expected to alter the relative concentrations of marine macronutrients (N:P:Si) available for phytoplankton uptake, in turn resulting in a change in the phytoplankton community structure. As discussed by Duce et al. [2008], phosphorous concentration in the surface ocean is not significantly affected by anthropogenic activity and hence nitrogen deposition alone is likely to enhance N:P in the surface layers. Although the impact of atmospheric nitrogen deposition to marine new production is small, seasonal occurrences of potential dinitrogen fixers (Trichodesmium) in the Arabian Sea may be greatly affected. Unlike other plankton, the diazotrophs grow under very different environmental conditions (e.g., in the absence of nitrate and in warmer, stratified waters) [Karl et al., 2002]. Iron deposition by mineral aerosols, provided photic zone is not limited in phosphate, may promote the occurrence of diazotrophs [Mills et al., 2004]. [33] The present study suggests that atmospheric fluxes have minor contribution to the new production in the northern Indian Ocean as the nitrogen supply through upwelling and rivers dominate. However, the potential impacts of atmospheric fluxes in future would be determined by the changes in anthropogenic activity. The regions, where Nr deposition shows an increasing trend as estimated by Galloway et al. [2004], may face larger impacts (positive/ negative). At present, our knowledge is too limited to fix the time scale of impact of atmospheric nitrogen on oceanic production [Duce et al., 2008]. 3.5. Synthesis of the Available Estimates [34] We compared the nitrogen deposition flux estimations obtained from earlier work and the present study in the northern Indian Ocean. Duce et al. [1991] estimated a nitrogen deposition flux of 2 Tg year1 (FdNO3 = 0.14, FdNH4 = 0.17, FwNO3 = 0.49, FwNH4 = 1.17 Tg N year1) over the northern Indian Ocean using data obtained prior to 1984. This flux was dominated by wet ammonium flux. Duce et al. [1991] concluded that this large ammonium flux could be due to the source of ammonium from the ocean itself. Bange et al. [2000] estimated the total nitrogen deposition (both dry and wet) as 0.84 + 0.74 ≈ 1.58 Tg N year1 in the Arabian Sea. [35] Taking into account more data from the recent past, we have calculated 0.92 Tg N year1 flux into the Arabian Sea. NO 2 data (wherever available) was also included in this analysis. These fluxes were dominated by dry deposition of nitrogen (FdNO3+dNO2+dNH4 = 0.60, FwNO3+wNO2+wNH4 = 0.32 Tg N year1). The nitrogen deposition flux over the Bay of Bengal is significantly less than that in the Arabian Sea, i.e., 0.46 Tg N year1 (FdNO3+dNH4 = 0.31, FwNO3+wNH4 = 0.15 Tg N year1). Hence the total Nr deposition over the northern Indian Ocean is 1.39 Tg N year1. The fluxes presented here agree well with earlier estimates within the uncertainties. 8 of 11 C06004 SINGH ET AL.: ROLE OF N DEPOSITION IN NEW PRODUCTION [36] Duce et al. [2008] estimated a global average Nr deposition flux of 14.3 mmol N m2 year1 (reported value 200 mg N m2 year1). Our estimate of the deposition flux over the Arabian Sea is 13.4 mmol N m2 year1 (no data from fall intermonsoon) and 11.3 mmol N m2 year1 (no data from winter and fall) over the Bay of Bengal. Previous estimates by Duce et al. [2008] are not significantly different from our estimates, considering the associated uncertainties. New productivity in the Arabian Sea is 1.46 mol N m2 year1 hence the contribution of Nr deposition flux to the new productivity is 0.9%. The contribution of Nr deposition flux to the new productivity (1.46 mol N m2 year1) in the Bay of Bengal (no data from summer and fall) resembles that of the Arabian Sea. Large uncertainties in the deposition flux and paucity of data preclude the detection of any temporal trends in the deposition fluxes. Direct sampling of rain over the northern Indian Ocean could be important to better constrain the present estimates, as suggested by Baker et al. [2010] for the Atlantic region. [37] Organic nitrogen in aerosols could be an important component of Nr in the marine atmosphere [Cape et al., 2011, and references therein] that can contribute up to 24% of total soluble nitrogen in the aerosol [Lesworth et al., 2010]. Unfortunately, no data on the organic nitrogen content of aerosols are currently available for the Arabian Sea. However, a recent study in the Bay of Bengal reported that organic and inorganic aerosols combined can support 13% of the primary production [Srinivas et al., 2011]. This study indicates that there is a need of measurement of organic aerosols for better understanding biogeochemical cycle of nitrogen in the ocean. 3.6. Other Nitrogen Sources to the Arabian Sea [38] The Arabian Sea loses 60 Tg N year1 (i.e., 40% of global N loss) through pelagic denitrification and thus has global importance [Codispoti, 2007, and references therein]. Nitrogen gain into the Arabian Sea through N2 fixation is 15.4 Tg N year1 [Gandhi et al., 2011a] and a minor contribution (0.06 Tg N year1) from the rivers [Singh and Ramesh, 2011]. Major source of nitrogen in the Arabian Sea is via advection of waters from the south, i.e., 38 Tg N year1 [Bange et al., 2000]. In addition, the present estimates suggest that atmospheric deposition contributes 0.92 Tg N year1. Thus, nitrogen sources are somewhat comparable to the sinks in the Arabian Sea. However, this upward revision of nitrogen sources in the Arabian Sea does not solve the mystery of missing nitrogen in the world ocean [Codispoti, 2007]. To refer internal nutrient cycling, we have noted that high new production in the Arabian Sea could be sustained by an upward flux of nitrate (i.e., 22 Tg N year1 an average value of the nitrate flux reported by Gandhi et al. [2011b] in their Table 4, and integrated over the Arabian Sea). 3.7. Other Nitrogen Sources to the Bay of Bengal [39] Riverine fluxes and vertical mixing by eddies are the other and main sources of nitrogen to the Bay of Bengal [Prasanna Kumar et al., 2007]. Cyclonic eddies, that occur in the Bay during October–December, can increase the biological productivity of the Bay by injecting nutrients into the otherwise oligotrophic waters [Prasanna Kumar et al., 2007; Gandhi et al., 2010b]. However, the effect is not seen in the upper surface, restricting the eddy effect to below 20 m C06004 during the fall and the spring intermonsoons of 2002–2003 [Prasanna Kumar et al., 2007]. Productivity measurements during the same expedition, however, show higher new productivity in the Bay of Bengal [Kumar et al., 2004]. Observations during 2003 also did not show high Chlorophyll a or productivity associated with a cyclonic eddy [Muraleedharan et al., 2007]. Nitrogen inputs through rivers are most likely utilized in the estuarine and primary productivity in the coastal Bay of Bengal [Singh and Ramesh, 2011]; riverine impact on open ocean biological productivity is negligible [Duce et al., 2008]. Rivers of the Indian subcontinent contribute 0.38 Tg N year1 to the Bay of Bengal [Singh and Ramesh, 2011], comparable to the present estimate of the atmospheric deposition flux (0.46 Tg N year1) to the region. All these phenomena together suggest that the atmospheric inputs could be significantly higher during the above two seasons. However, our analysis based on the available data on aerosols does not confirm this (Tables 1 and 2). This also seems to indicate that N2 fixation and advective flux of nitrogen could be significant in the Bay of Bengal, where no such measurements have been reported so far. Unlike the Arabian Sea, nitrogen is not lost from the oxygen minimum zones of the Bay of Bengal via pelagic denitrification. Nevertheless, there is 4.1 Tg N year1 loss, mainly via sedimentary denitrification [Naqvi, 2008]. The Bay of Bengal still remains under-sampled, hence we cannot infer whether or not nitrogen fluxes are in balance in this region. 4. Conclusion [40] There is no significant spatial variation in new productivity in the three zones of the Arabian Sea (i.e., eastern, central and western) during the spring intermonsoon 1995. However, a significant seasonal variation in the western Arabian Sea is observed during 1995. Nitrogen deposition flux was higher in the winter monsoon in the eastern Arabian Sea than that in the other parts of the northern Indian Ocean. New production and deposition flux in the Arabian Sea were comparable to those in the Bay of Bengal. Aerosols deposit 1.39 Tg nitrogen per year in the northern Indian Ocean, with a major fraction (67%) in the Arabian Sea. Atmospheric fluxes make a minor contribution to the marine new productivity (maximum up to 3% in the eastern Arabian Sea during the winter monsoon). However, this minor contribution is likely to become important in the near future and play a crucial role in the removal of excess atmospheric CO2 through marine productivity. Nitrogen sources are comparable to sinks in the Arabian Sea, however, no such inference could be drawn for the Bay of Bengal due to paucity of data. 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