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0 (N ) Using preformed nitrate to infer recent changes in DOM remineralization in the upper thermocline of the subtropical North Pacific OS41B - 17 Jeffrey Abell & Steve Emerson, University of Washington, School of Oceanography, Box 355351 [email protected] 3. N0 Mass Balance Ni POCf DOCi 40°N Marathon N0 Ni DOCf T, S O2 < O2sat AOU = O2sat - O2 N0 = Nm + AOU / R intensity of the anomaly is proportional to the magnitude of DOC remineralization and the DOC:DON remineralization ratio. From N 0 Nm Ni R NO3 :POCPOC and/or the C:N ratio of DOM degradation has increased in the past h R NO3 :DOCDOC R O 2 :POCPOC R O 2 :NO3 h b R O 2:DOCDOC R O 2:NO3 30°N O cean Dat a View 35°N STUD97 NO3 100 0.1 5 1 10 Depth 0.1 1 200 300 15°N 20°N 25°N O cean Dat a View 30°N 35°N 0 0 0 100 0 0 25 100 80 60 40 20 0 0 0 c 200 DOC = 25 M RNO3:DOC = 0.03 25.4 - 25.8 T -34 -3.5 DOC = 15 M RNO3:DOC = 0.10 -24 -4.0 DOC = 10 M RNO3:DOC = 0.17 2 3 4 5 6 7 DON (M) 50 0 25 15°N 0 20°N 25°N 30°N Ocean Data View O cean Dat a View 100 0 20 10°N 35°N Figure 2. a) N , b) NO3, and c) AOU distributions in the eastern subtropical North Pacific along 152W during November 1997. Cruistrack is depicted in Figure 5 (STUD97). 0 Negative N values are shaded white to green. The solid and dotted white lines represent the 25.4 and 26.1 t isopycnals respectively. Table 4. For the STUD97 and GS2000 cruises, we compared the observed preformed nitrate values with those calculated from the 0 AOU, DOC, and DON data. Observed N , as determined from the equation in Fig 3a, was averaged over each isopycnal range 0 between 10N and 30N. Calculated N is the average preformed nitrate as determined from the equation in Fig 3b. We assume RO2:DOC = -1.3, RO2:NO3 = -10 and Ni is equivalent to the average surface nitrate concentration in winter at the site of the outcrops 0 (Anderson and Sarmiento, 1994; Levitus and Boyer, 1994). N was then calculated after substituting respective values for DOC and RNO3:DOC. Standard deviation in parentheses is based on the error in the DOC and RNO3:DOC terms. Observed and calculated 0 N agree well suggesting that DOM degradation at high C:N ratios 0 is primarily responsible for the negative N anomaly. 5 10 Depth O cean Dat a View Ocean Data View 5 1 Depth Figure 6. Contours represent the deviation in N that would result from a change in the magnitude of DOM remineralization given a specific C:N ratio. Currently, 25 umol/kg of DOC is remineralized at a C:N ratio of 30 along the isopycnals above 25.4 t. If the C:N remained constant between 1980 and 1997, the magnitude of DOM remineralization would have had to increase by 10umol/kg 0 to explain the –0.99 umol/kg deviation in N (solid arrow). This is equivalent to a 60% increase in DOM remineralization during this time period. If, instead the magnitude remained constant, the C:N ratio would have had to increase from near Redfield values to 30. 5 7. Conclusion 400 25°N 30°N Ocean Data View O cean Dat a View 10 DOC = 15 M RNO3:DOC = 0.07 the C:N remineralization ratio could explain the temporal 0 trends observed in N . At this point, it is difficult to separate 35°N the relative importance of each of these factors. Evidence 25.4 - 26.1 T WOCE-P16N Sep 1991 d -22 -4.6 DOC = 10 M RNO3:DOC = 0.20 2 3 4 5 6 DON (M) station ALOHA have been used 1 -0.71 7 from shifts in the phytoplankton community structure at 0 to suggest that DOM production and utilization has increased over the past few 100 DEPTH [M] AOU (moles/kg) 100 80 60 40 20 0 Both an increase in the magnitude of DOM degradation or -29 -2.0 decades (Karl, 1999; Karl et al., 2001). Our results would 200 support this conclusion. However, we cannot unequivocally 5 1 show that there was an increase in the utilization rate of Figure 4. AOU, DOC and DON data from a) STUD97 and b) GS2000 were used to determine the magnitude and remineralization ratio of DOM along shallow isopycnal layers. GS2000 data is from a longitudinal section conducted along 24N between 110 and 158W in January 2000. Plots of AOU vs. DOC and DON were used to determine the magnitude of DOC degradation (DOC) and the remineralization ratio (RNO3:DOC) along each isopycnal. To determine RNO3:DOC, the regression slope of AOU vs. DOC was divided by AOU vs. DON for each pair of graphs. On the upper isopycnals, in the region of the negative preformed nitrate anomaly, RNO3:DOC is low and DOM degradation increases AOU without returning a significant amount of nitrate to the water column. On deeper isopycnals, where preformed nitrate is positive, both DOC and DON contribute to AOU and RNO3:DOC approaches the Redfield ratio (0.15). 25.8 - 26.1 T DOC (M) 250 100 80 60 40 20 0 DOM along the isopycnal in response to an increase in 300 10 400 20°N e 25°N 30°N 35°N 40°N calculated from AOU, DOC, and DON data agrees well with observed values N0 Negative anomaly primarily results from DOM remineralization at high C:N ratio Isopycnal (t) Stud97 24 .4 - 24.9 24.9 - 25.4 25.4 -25.8 25.8 - 26.1 GS2000 ML – 25.4 25.4 – 26.1 0 0 Ni (mol/kg) Calculated N (mol/kg) Observed N (mol/kg) 0 0 1.80 4.60 -1.20 (0.21) -1.20 (0.27) 1.56 (0.26) 5.00 (0.26) -1.72 -0.83 1.69 5.56 0 3.2 -0.46 (0.20) 3.69 (0.38) -0.41 3.83 supply at the outcrop regions. A reduction in the quality of the DOM (as expressed in the C:N ratio) could have also resulted from the community shift. Alternatively, a decrease STUD97 Nov 1997 0 in the circulation rate could also lead to an increase in DOM 0 -0.94 0 0 remineralization without requiring any increase in supply or 0 100 1 0 -2 degradation rate or C:N ratio. 5 -1 -1 200 5 300 50 150 400 -60 -2.0 30 40 50 60 70 80 25 Depth 100 300 100 80 60 40 20 0 24.9 - 25.4 T 200 0 10 STUD97 AOU 100 80 60 40 20 0 DOC = 25 M RN03:DOC = 0.03 30 10 10°N 100 1 400 Ocean Data View 10 15 0 -1 5 15 Marathon May 1984 0 AOU (moles/kg) b 0 -50 -1.6 35°N O cean Dat a View 25°N c 30°N Ocean Data View 20°N 25°N 10 400 10°N 15°N 20°N 0 25°N 60°N 50° N 40°N 30° N 20°N 10°N EQ 120°E 150°E 180°E150°W120°W 30°N Ocean Data View 15°N 400 300 DOC (M) b 24.4 - 24.9 T 25 1 10°N 100 80 60 40 20 0 Ocean Data View 400 60° N 50°N 40°N 30° N 20° N 10° N EQ 120°E150° E 180°E 150° W120°W 10 Depth 1 10 10 300 ML - 25.4 T 30 40 50 60 70 80 Stud 97 5 300 20 200 0 1 10 a 15 C:N -1 -1 200 10 0 0 Depth -1 5 1 5 1 0 0 0 0 -1 -0.5 GS2000 Remineralization approaches Redfield values on isopycnals where N0 is positive 0 -2 4. DOM Remineralization Data Little nitrate is remineralized from DOM on isopycnals where N0 is negative. 1 1 0 0 0 10 5 -0.21 0 -1 5 0.05 Figure 3b. Integrating DOM remineralization into the N mass balance. Both POC flux across the isopycnal (POC) and DOC degradation along the isopycnal (DOC) contribute to AOU and m N . These values are dependent upon POC, DOC, the 0 residence time of water () and the isopycnal height (h). When N is solved using these mass balance equations, the POC terms cancel and only DOC, RO2:DOC, RO2:NO3, and RNO3:DOC remain. In the case where no DOM is remineralized (i.e. DOC = 0), the 0 calculated N would equal the initial nitrate at the outcrop (Ni). However, if DOC > 0 and RNO3:DOC is less than the Redfield ratio, 0 N will be less than Ni. In this way, DOC degradation may allow for negative anomalies in the preformed nitrate distribution. 0 0 100 0 -1 a 0 -1 15 FIONA AUG 1980 0 Figure 3a. N mass balance in a “particulate-only” ocean. For a water parcel advecting along an isopycnal, O2 is depleted as NO3 increases due to the biological degradation of sinking particulate m organic matter. The measured NO3 (N ) in the parcel at depth is a combination of biological degradation and the NO3 originally present at the surface (Ni). This latter contribution is the true 0 preformed nitrate value. We estimate the preformed nitrate as N m = N + AOU / R, where AOU is apparent oxygen utilization and R is the stoichiometric relationship between oxygen depletion and nitrate regeneration. Assuming R does not vary significantly 0 along the path of the isopycnal, N should be constant along isopycnals. STUD97 PreNO3 90°W 100 may have increased since the late 1970’s due to changes in the Within anomaly, AOU varies from 0-50 umol/kg and NO3 varies from 0.1-5 umol/kg 120°W AOU R O 2 :NO3 two decades. This supports recent findings that DOM production Negative anomaly of 0-2.5 umol/kg between mixed layer and 25.4 t 150°W -0.5 N0 eastern subtropical North Pacific, we infer that the magnitude 180°E DOCi 0 temporal trends in the N distribution along similar transects in the 150°E -1.5 -0.5 results agree with the observed N distribution and show that the EQ 120°E 20 0 N0 0 2. N0 Distribution -2 WOCE-P16N 20°N 1 R NO 3 :DOCDOC Stud97 Calculated phytoplankton community structure (Karl et al., 2001). 25 Fiona 0.5 h a 2 R NO 3 :POCPOC 60°N 1.5 N Ni m POCi O cean Dat a View to calculate N using AOU, DOC and DON data. Nm DOCf preformed nitrate. We develop a simple isopycnal mass balance 0 C:N may have increased from 7 to 30 1 with a high C:N ratio is primarily responsible for negative R O 2 :DOCDOC 80°N Nm O2 h DOC (umol/kg) in the eastern subtropical North Pacific that degradation of DOM R O 2 :POCPOC Ocean Data View 1995). Here we present quantitative evidence from two transects Nm T, S O2 = O2sat AOU = 0 N0 = Nm a DOCi 0 nitrogen-poor dissolved organic matter (Emerson & Hayward, POCf AOU O i Of feature is created during nitrate uptake by vertically migrating diatom mats, nitrate uptake by respiring bacteria or degradation of DOCf 1 It has been suggested that this Integrating DOM into the mass balance allows for negative anomalies in N0 Oi 1 from Redfield stoichiometry. b N0 POCi 0 remineralization in the upper thermocline deviates significantly Of DOM remineralization may have increased by 60% in response to an increase in DOM export or a slowing of circulation 1 Its presence indicates that nitrogen N0 decreases by about 1umol/kg between 1980 and 1997 10 mixed layer and 25.4 t. O2 5 Pacific is characterized by a negative anomaly between the Ideally N0 is constant along isopycnals and reflects the initial N03 at the outcrop 6. Reasons for N0 Decrease 10 0 The preformed nitrate (N ) distribution in the subtropical North 5. Temporal Trends in N0 -1 1 1. Introduction 8. References 35°N Figure 5. A comparison of N distributions along similar cruise transects. Cruises in (a) were conducted along 152-158W between 1980 and 1997. Contours, shading, and isopycnals are similar to Fig. 2a for b) Fiona, c) Marathon, d) Woce-P16N, and e) 0 Stud97. To compare the N distribution between cruises, we calculate the weighted average between 100m and 25.4 t along 20N to 30N. These averages are listed to the left of each section. No effort is made to correct for calibration differences among cruises for nitrate, oxygen, and oxygen saturation determinations. 0 A trend to more negative N is evident between 1980 and 1997. This suggests that the magnitude and/or C:N ratio of DOM remineralization increased during this time. Abell, et al. 2000. Distributions of TOP, TON, and TOC in the North Pacific subtropical gyre: implications for nutrient supply in the surface ocean and remineralization in the upper thermocline. Journal of Marine Research, 58(N): 1-21. Anderson, L.A. and Sarmiento, J.L., 1994. Redfield ratios of remineralization determined by nutrient data analysis. Global Biogeochemical Cycles, 8: 65-80. Emerson, S. and Hayward, T.L., 1995. Chemical tracers of biological processes in shallow waters of the North Pacific: Preformed nitrate distributions. Journal of Marine Research, 53: 499-513. Garcia, H., and L. Gordon. Oxygen solubility in seawater: Better fitting equations. Limnology and Oceanography, 37, 1307-1312, 1992. Levitus, S., and T.P. Boyer. World Ocean Atlas 1994. US Dept of Commerce, Washington, D.C. 1994 Karl, D.M., et al., 2001. Long-term changes in plankton community structure and productivity in the North Pacific Subtropical Gyre: The domain shift hypothesis, DeepSea Research II, 48, 1449-1470. Karl, D.M., 1999. A sea of change: Biogeochemical variability in the North Pacific Subtropical Gyre. Ecosystems, 2: 181-214. Schlitzer, R. Ocean Data View. http://www.awi-bremerhaven.de/GEO/ODV, 2001 WOCE P16N. http://whpo.ucsd.edu/data/tables/onetime/1tim_pac.htm