1 2 Journal of Geophysical Research: Biogeosciences 3 Supporting Information for 4 5 Chesapeake Bay nitrogen fluxes derived from a land-estuarine ocean biogeochemical modeling system: Model description, evaluation and nitrogen budgets 6 7 Yang Feng1, Marjorie A. M. Friedrichs1, John Wilkin2, Hanqin Tian3, Qichun Yang3, Eileen E. Hofmann4, Jerry D. Wiggert5 and Raleigh R. Hood6 8 1Virginia 9 10 11 2Institute 3International 12 13 14 Institute of Marine Science, College of William and Mary, Gloucester Point, Virginia of Marine and Coastal Sciences, Rutgers University, New Brunswick, New Jersey Center for Climate and Global Change Research and School of Forestry and Wildlife Sciences, Auburn University, Auburn, Alabama 4Center 5Department 6Horn for Coastal Physical Oceanography, Old Dominion University, Norfolk, Virginia of Marine Science, University of Southern Mississippi, Stennis Space Center, Mississippi Point Laboratory, University of Maryland Center for Environmental Science, Cambridge, Maryland 15 16 17 18 19 20 21 22 23 24 Contents of this file Model Equations for Biogeochemistry Additional Supporting Information (Files uploaded separately) 25 Model Equations for Biogeochemistry 26 The biogeochemical source/sink equations for the estuarine biogeochemical model state 27 variables that specifically pertain to the nitrogen cycle are described in the below text as well as 28 summarized in Tables A1 and A2. Model function symbols are defined in Table A3, and 29 parameter definitions and values are provided in Table A4 (see appendix in the text). 30 31 Phytoplankton 32 Phytoplankton are increased by primary production and decreased by grazing, mortality, 33 aggregation and sinking. Two additional processes, exudation to semi-labile DON and 34 ammonium were added. The exudation to ammonium pool was limited by coupled water column 35 nitrification/denitrification through the low oxygen condition. Changes in phytoplankton due to 36 those biological processes are finally determined as: 37 ¶P ¶P = [1- g - ( fNTR + fDNF )w ] m0 LI (LNO3 + LNH 4 )P - gZ - mP P - t (DS + P)P - wP ¶t ¶t (1) 38 39 Chlorophyll 40 The sources and sinks of chlorophyll are consistent with those for phytoplankton: 41 ¶[Chl] = r[Chl ] [1- g - ( f NTR + fDNF )w ] m 0 LI (LNO3 + LNH 4 )[Chl] ¶t Z ¶[Chl] -g [Chl]- mP [Chl]- t (DS + P)[Chl]- wP P ¶z (2) 42 43 Zooplankton, Small and large detritus 44 The zooplankton source term is the assimilation of phytoplankton. The loss terms represent 45 excretion and mortality. The efficiency of the assimilation is β, and the remainder (1- β)Z is lost 46 to semi-labile DON and ammonium through sloppy feeding and to large detritus by fecal pellet 47 production. 48 æ ¶Z P2 ö = b gZ - ç lBM + lE b Z - mZ Z 2 2÷ ¶t KP + P ø è (3) 49 50 Small and large detritus 51 Phytoplankton and zooplankton mortality is transferred into the small and large detritus pools, 52 respectively. Phytoplankton and small detritus aggregate to large detritus. Following Druon et al. 53 [2010], part of the small and large detritus pools are transferred to semi-labile DON by bacterial 54 solubilization with an efficiency of δN. The remaining detrital material is remineralized. The 55 remineralization rate is limited by water column nitrification and denitrification processes. 56 ¶DS ¶D = mP P - t (DS + P)DS - éëdN + (1- dN ) ( fNTR + fDNF )ùû rDS DS - wS S ¶t ¶z (4) 57 ¶DL ¶D = (1- b )(1- l )gZ + mZ Z 2 + t (DS + P)2 - éëdN + (1- dN ) ( fNTR + fDNF )ùû rDL DL - wL L ¶t ¶z (5) 58 59 Semi-labile and refractory DON 60 Semilabile DON may be gained through phytoplankton exudation, sloppy feeding, bacterial 61 solubilization, and lost through remineralization. The rate of remineralization is limited by 62 temperature as well as nitrification/denitrification. ¶[DON ]SL = gm0 LI (LNO3 + LNH 4 )P + (1- b )le gZ + d N (rDS DS + rDL DL ) ¶t k[ DON ]SL T 63 -r[ DON ]SL e 64 The refractory DON does not participate directly in the biogeochemical cycling, however it does 65 affect light attenuation. 66 67 Nitrate ( fNTR + fDNF )[DON ]SL (6) 68 Nitrate is taken up by phytoplankton during photosynthesis and produced through nitrification. In 69 addition, nitrate is lost to the atmosphere as nitrogen gas through water column denitrification, 70 the rate of which is limited by the availability of oxygen. The time rate of change due to 71 biological process for nitrate is: ¶[NO3 ] k T = -m0 LI LNO3 P - hDNF éë fDNF, fWC ùûmin (1- dN ) ( rDS DS + rDL DL ) + r[ DON ]SL e [ DON ]SL [DON ]SL ¶t { 72 + nf NTR [NH 4 ] } (7) 73 74 Ammonium 75 The sources of ammonium include phytoplankton exudation and sloppy feeding, zooplankton 76 excretion, and remineralization of small detritus, large detritus and semi-labile organic nitrogen. 77 The sinks of ammonium include nitrification and uptake by phytoplankton. The time rate of 78 change due to biological processes for ammonium is: é æ ¶[NH 4 ] P 2 öù = m0 éë-LNH 4 + ( f NTR + fDNF )(LNO3 + LNH 4 )w ùû LI P + ê(1- b )l (1- e )g + ç lBM + lE b ÷ú Z ¶t K P + P 2 øû è ë 79 { +( f NTR + fDNF ) (1- dN ) ( rDS DS + rDL DL ) + r[ DON ]SL e k[ DON ]SL T } [DON ]SL - nf NTR [NH 4 ] (8) 80 81 Inorganic Suspended Solids 82 Inorganic suspended solids do not participate in the water column biogeochemical cycle, 83 however they do affect light attenuation. Concentrations of ISS are reduced by sinking and 84 increased by seabed resuspension. 85 ¶[ISS] ¶[ISS] = -wISS ¶t ¶z 86 87 Dissolved Oxygen (9) 88 The oxygen increased or decreased due to the above biological processes with the 89 stoichiometry 90 ammonium. The phytoplankton exudated semi-labile DOC during photosynthesis. The semi- 91 labile DOC exudation process does not follow the Redfield ratio. Druon et al. [2010] describe a 92 carbon excess-based semi-labile DOC exudation process, which is the carbohydrate production 93 over the nutrient-based part. The oxygen produced by the synthesis of carbohydrates (carbon 94 excess uptake) has a one to one molar ratio following the equation: CO2 +H20 + energy -> 95 (CH2O) + O2. The oxygen uptake from oxidation of DON with a C to N ratio of 96 therefore, the oxygen production by this part is 97 hO :NO =138 :16 and hO2 :NH4 =106 :16 when consuming 1 mole of nitrate or 2 3 hC:N = 6.6, g ChC:N m0 LI (1- LNH - LNO )P . 4 3 In addition to the biochemical sources and sinks of oxygen, there is gas exchange 98 across the air-sea interface, which modified the oxygen concentration in the top layer. The air- 99 sea oxygen exchange was calculated as vkO2 vkO2 Dz ([O2 ]sat -[O2 ]) 100 where 101 calculated from Garcia and Gordon [1992]. is the gas exchange coefficient for oxygen, and as in Fennel et al. [2013], [O2 ]sat is the oxygen saturation ¶[O2 ] = +m0 éëhO2 :NO3 LNO3 + hO2 :NH 4 LNH 4 - hO2 :NH 4 f NTRw (LNO3 + LNH 4 )ùû LI P ¶t é æ P 2 öù -hO2 :NH 4 ê(1- b ) l (1- e ) g + ç lBM + lE b ÷ú Z K P + P 2 øû è ë { -hO2 :NH 4 f NTR (1- dN ) ( rDS DS + rDL DL ) + r[ DON ]SL e k[ DON ]SL T [DON ]SL } -2 f NTR n[NH 4 ] +g ChC:N m 0 LI (1- LNH 4 - LNO3 )P +v 102 KO2 Dz ([O2 ]sat -[O2 ]) 103 104 Bottom boundary conditions (10) 105 The fate of organic matter reaching the benthos includes: (1) resuspension; (2) remineralization; 106 (3) burial. The resuspension of the organic matter is back to the water column as DS. The 107 fraction of resuspension is ϕ1, which is a function of the bottom stress [Druon et al. 2010]: 108 2 2 f1 = G Gc , where G = t b + t b is the bottom shear stress, Gc = 0.05Pa is the critical shear 109 stress [Xu and Hood, 2006]. Therefore, the time rate of change of small detritus in the model’s 110 bottom layer is: 111 x ¶DS ¶t = z=H f1 Dz y FTON (11) FTON = wP P z=H + wDS DS z=H + wDL DL z=H 112 where 113 0.5797 f2 = 0.092FBC , where a maximum of 75% of carbon burial efficiency is applied [Druon et al. 114 2010] and 115 hC:N wP P z=H + hC :N (wD DS z=H + wD DL z=H ) h =106 /16 C:N 116 phytoplankton. 117 The rest (1- ϕ1)(1- ϕ2) is remineralized through coupled nitrification and denitrification processes 118 in the benthos. The regeneration of the organic matter includes the ammonium form and semi- 119 labile DON form, and follows the implementation for sediments below normal oxic waters 120 described in Fennel et al. [2006, see their eq. 15]. To account for the observed shift in benthic 121 influx and efflux rates that occurs below hypoxic to anoxic overlying waters [Rysgaard et al., 122 1994], an additional term is included to regulate these benthic regeneration rates in response to 123 the seasonal transition to hypoxic in the overlying waters. i.e., as hypoxia in the overlying water 124 column intensifies, the benthic nitrification-denitrification balance will shift toward the latter. FBC is the flux of total organic carbon in the sediment, which is B B S L . is the carbon to nitrogen ratio in hC :N = 9.3 is the carbon to nitrogen ratio in bottom small and large detritus. B B 125 126 . The fraction of the buried organic matter is The amount of NH4 regenerated is: 127 ¶[NH 4 ] (1- f1 )(1- f2 ) = hNF/DNF FTON (1+ 3LBO2 ) ¶t z=H Dz LBO2 = (12) K BO2 fB (O2 ) - fB (O2max ) f (O ) = B 2 O2 z=H + K BO2 K BO 1- fB (O2max ) , 2 is the half-saturation coefficient , 128 Where 129 for sediment denitrification, and equals 26.5 mmole-O m-3. 130 131 132 The amount of semi-labile DON regenerated is: ¶[DON]SL ¶t = g [ BDON ]SL z=H (1- f1 )(1- f2 ) FTON (1+ 3LBO2 ) Dz (13) g[ BDON ] = 0.01 is the fraction of bottom semilabile DON produced through coupled 133 Where, 134 nitrification and denitrification. SL 135 136 137 The oxygen consumption during this process is: ¶[O]2 ¶t = -hO2 :NF/DNF z=H (1- f1 )(1- f2 ) FTON (1- LBO2 ) Dz (14) hNF/DNF and hO :NF/DNF are stoichiometric relations drawn from Fennel et al. [2006]. 138 The terms 139 The term 140 and denitrification. 2 h[ BDON ] is the fraction of bottom semilabile DON produced through coupled nitrification 141 142 At the bottom, particles that hit the bottom are resuspended when bottom stress exceeds critical 143 shear stress, which is calculated by [Xu and Hood, 2006] 144 1 145 is the resuspension rate. x ( G - Gc ) , where x = 4320 gm-2d-1Pa-