Raymond Peter A.

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Dual isotope analyses indicate efficient processing of atmospheric nitrate by forested watersheds in the northeastern U.S.

( 2008-07-15) Barnes, Rebecca T. ; Raymond, Peter A. ; Casciotti, Karen L.

Nitrogen from atmospheric deposition serves as the dominant source of new nitrogen to forested ecosystems in the northeastern U.S.. By combining isotopic data obtained using the denitrifier method, with chemistry and hydrology measurements we determined the relative importance of sources and control mechanisms on nitrate (NO3-) export from five forested watersheds in the Connecticut River watershed. Microbially produced NO3- was the dominant source (82-100%) of NO3- to the sampled streams as indicated by the δ15N and δ18O of NO3-. Seasonal variations in the δ18O-NO3- in streamwater are controlled by shifting hydrology and temperature affects on biotic processing, resulting in a relative increase in unprocessed NO3- export during winter months. Mass balance estimates find that the unprocessed atmospherically derived NO3- stream flux represents less than 3% of the atmospherically delivered wet NO3- flux to the region. This suggests that despite chronically elevated nitrogen deposition these forests are not nitrogen saturated and are retaining, removing, and reprocessing the vast majority of NO3- delivered to them throughout the year. These results confirm previous work within Northeastern U.S. forests and extend observations to watersheds not dominated by a snow-melt driven hydrology. In contrast to previous work, unprocessed atmospherically derived NO3- export is associated with the period of high recharge and low biotic activity as opposed to spring snowmelt and other large runoff events.
Lability of DOC transported by Alaskan rivers to the Arctic Ocean

(American Geophysical Union, 2008-02-09) Holmes, Robert M. ; McClelland, James W. ; Raymond, Peter A. ; Frazer, Breton B. ; Peterson, Bruce J. ; Stieglitz, Marc

Arctic rivers transport huge quantities of dissolved organic carbon (DOC) to the Arctic Ocean. The prevailing paradigm is that DOC in arctic rivers is refractory and therefore of little significance for the biogeochemistry of the Arctic Ocean. We show that there is substantial seasonal variability in the lability of DOC transported by Alaskan rivers to the Arctic Ocean: little DOC is lost during incubations of samples collected during summer, but substantial losses (20–40%) occur during incubations of samples collected during the spring freshet when the majority of the annual DOC flux occurs. We speculate that restricting sampling to summer may have biased past studies. If so, then fluvial inputs of DOC to the Arctic Ocean may have a much larger influence on coastal ocean biogeochemistry than previously realized, and reconsideration of the role of terrigenous DOC on carbon, microbial, and food-web dynamics on the arctic shelf will be warranted.
Riverine coupling of biogeochemical cycles between land, oceans, and atmosphere

(Ecological Society of America, 2011-02) Aufdenkampe, Anthony K. ; Mayorga, Emilio ; Raymond, Peter A. ; Melack, John M. ; Doney, Scott C. ; Alin, Simone R. ; Aalto, Rolf E. ; Yoo, Kyungsoo

Streams, rivers, lakes, and other inland waters are important agents in the coupling of biogeochemical cycles between continents, atmosphere, and oceans. The depiction of these roles in global-scale assessments of carbon (C) and other bioactive elements remains limited, yet recent findings suggest that C discharged to the oceans is only a fraction of that entering rivers from terrestrial ecosystems via soil respiration, leaching, chemical weathering, and physical erosion. Most of this C influx is returned to the atmosphere from inland waters as carbon dioxide (CO2) or buried in sedimentary deposits within impoundments, lakes, floodplains, and other wetlands. Carbon and mineral cycles are coupled by both erosion–deposition processes and chemical weathering, with the latter producing dissolved inorganic C and carbonate buffering capacity that strongly modulate downstream pH, biological production of calcium-carbonate shells, and CO2 outgassing in rivers, estuaries, and coastal zones. Human activities substantially affect all of these processes.
Animating the carbon cycle

( 2013-08) Schmitz, Oswald J. ; Raymond, Peter A. ; Estes, James A. ; Kurz, Werner A. ; Holtgrieve, Gordon W. ; Ritchie, Mark E. ; Schindler, Daniel E. ; Spivak, Amanda C. ; Wilson, Rod W. ; Bradford, Mark A. ; Christensen, Villy ; Deegan, Linda A. ; Smetacek, Victor ; Vanni, Michael J. ; Wilmers, Christopher C.

Understanding the biogeochemical processes regulating carbon cycling is central to mitigating atmospheric CO2 emissions. The role of living organisms has been accounted for, but the focus has traditionally been on contributions of plants and microbes. We develop the case that fully “animating” the carbon cycle requires broader consideration of the functional role of animals in mediating biogeochemical processes and quantification of their effects on carbon storage and exchange among terrestrial and aquatic reservoirs and the atmosphere. To encourage more hypothesis-driven experimental research that quantifies animal effects we discuss the mechanisms by which animals may affect carbon exchanges and storage within and among ecosystems and the atmosphere. We illustrate how those mechanisms lead to multiplier effects whose magnitudes may rival those of more traditional carbon storage and exchange rate estimates currently used in the carbon budget. Many animal species are already directly managed. Thus improved quantitative understanding of their influence on carbon budgets may create opportunity for management and policy to identify and implement new options for mitigating CO2 release at regional scales.
Seasonal and annual fluxes of nutrients and organic matter from large rivers to the Arctic Ocean and surrounding seas

( 2011-03) Holmes, Robert M. ; McClelland, James W. ; Peterson, Bruce J. ; Tank, Suzanne E. ; Bulygina, Ekaterina ; Eglinton, Timothy I. ; Gordeev, Viacheslav V. ; Gurtovaya, Tatiana Y. ; Raymond, Peter A. ; Repeta, Daniel J. ; Staples, Robin ; Striegl, Robert G. ; Zhulidov, Alexander V. ; Zimov, Sergey A.

River inputs of nutrients and organic matter impact the biogeochemistry of arctic estuaries and the Arctic Ocean as a whole, yet there is considerable uncertainty about the magnitude of fluvial fluxes at the pan-arctic scale. Samples from the six largest arctic rivers, with a combined watershed area of 11.3 x 106 km2, have revealed strong seasonal variations in constituent concentrations and fluxes within rivers as well as large differences among the rivers. Specifically, we investigate fluxes of dissolved organic carbon, dissolved organic nitrogen, total dissolved phosphorus, dissolved inorganic nitrogen, nitrate, and silica. This is the first time that seasonal and annual constituent fluxes have been determined using consistent sampling and analytical methods at the pan arctic scale, and consequently provide the best available estimates for constituent flux from land to the Arctic Ocean and surrounding seas. Given the large inputs of river water to the relatively small Arctic Ocean, and the dramatic impacts that climate change is having in the Arctic, it is particularly urgent that we establish the contemporary river fluxes so that we will be able to detect future changes and evaluate the impact of the changes on the biogeochemistry of the receiving coastal and ocean systems.
Biomass offsets little or none of permafrost carbon release from soils, streams, and wildfire : an expert assessment

(IOPScience, 2016-03-07) Abbott, Benjamin W. ; Jones, Jeremy B. ; Schuur, Edward A. G. ; Chapin, F. Stuart ; Bowden, William B. ; Bret-Harte, M. Syndonia ; Epstein, Howard E. ; Flannigan, Michael ; Harms, Tamara K. ; Hollingsworth, Teresa N. ; Mack, Michelle C. ; McGuire, A. David ; Natali, Susan M. ; Rocha, Adrian V. ; Tank, Suzanne E. ; Turetsky, Merritt R. ; Vonk, Jorien E. ; Wickland, Kimberly ; Aiken, George R. ; Alexander, Heather D. ; Amon, Rainer M. W. ; Benscoter, Brian ; Bergeron, Yves ; Bishop, Kevin ; Blarquez, Olivier ; Bond-Lamberty, Benjamin ; Breen, Amy L. ; Buffam, Ishi ; Cai, Yihua ; Carcaillet, Christopher ; Carey, Sean K. ; Chen, Jing M. ; Chen, Han Y. H. ; Christensen, Torben R. ; Cooper, Lee W. ; Cornelissen, Johannes H. C. ; de Groot, William J. ; DeLuca, Thomas Henry ; Dorrepaal, Ellen ; Fetcher, Ned ; Finlay, Jacques C. ; Forbes, Bruce C. ; French, Nancy H. F. ; Gauthier, Sylvie ; Girardin, Martin ; Goetz, Scott J. ; Goldammer, Johann G. ; Gough, Laura ; Grogan, Paul ; Guo, Laodong ; Higuera, Philip E. ; Hinzman, Larry ; Hu, Feng Sheng ; Hugelius, Gustaf ; JAFAROV, ELCHIN ; Jandt, Randi ; Johnstone, Jill F. ; Karlsson, Jan ; Kasischke, Eric S. ; Kattner, Gerhard ; Kelly, Ryan ; Keuper, Frida ; Kling, George W. ; Kortelainen, Pirkko ; Kouki, Jari ; Kuhry, Peter ; Laudon, Hjalmar ; Laurion, Isabelle ; Macdonald, Robie W. ; Mann, Paul J. ; Martikainen, Pertti ; McClelland, James W. ; Molau, Ulf ; Oberbauer, Steven F. ; Olefeldt, David ; Paré, David ; Parisien, Marc-André ; Payette, Serge ; Peng, Changhui ; Pokrovsky, Oleg ; Rastetter, Edward B. ; Raymond, Peter A. ; Raynolds, Martha K. ; Rein, Guillermo ; Reynolds, James F. ; Robards, Martin ; Rogers, Brendan ; Schädel, Christina ; Schaefer, Kevin ; Schmidt, Inger K. ; Shvidenko, Anatoly ; Sky, Jasper ; Spencer, Robert G. M. ; Starr, Gregory ; Striegl, Robert ; Teisserenc, Roman ; Tranvik, Lars J. ; Virtanen, Tarmo ; Welker, Jeffrey M. ; Zimov, Sergey A.

As the permafrost region warms, its large organic carbon pool will be increasingly vulnerable to decomposition, combustion, and hydrologic export. Models predict that some portion of this release will be offset by increased production of Arctic and boreal biomass; however, the lack of robust estimates of net carbon balance increases the risk of further overshooting international emissions targets. Precise empirical or model-based assessments of the critical factors driving carbon balance are unlikely in the near future, so to address this gap, we present estimates from 98 permafrost-region experts of the response of biomass, wildfire, and hydrologic carbon flux to climate change. Results suggest that contrary to model projections, total permafrost-region biomass could decrease due to water stress and disturbance, factors that are not adequately incorporated in current models. Assessments indicate that end-of-the-century organic carbon release from Arctic rivers and collapsing coastlines could increase by 75% while carbon loss via burning could increase four-fold. Experts identified water balance, shifts in vegetation community, and permafrost degradation as the key sources of uncertainty in predicting future system response. In combination with previous findings, results suggest the permafrost region will become a carbon source to the atmosphere by 2100 regardless of warming scenario but that 65%–85% of permafrost carbon release can still be avoided if human emissions are actively reduced.
Multiple-source heterotrophy fueled by aged organic carbon in an urbanized estuary

( 2010-08-02) Griffith, David R. ; Raymond, Peter A.

The lower Hudson River is a highly urbanized estuary that receives large inputs of treated wastewater. To determine how organic matter from wastewater influences carbon cycling in this type of system, we measured chlorophyll a, pCO2, dissolved organic carbon (DOC), δ13C-DOC, and Δ14C-DOC along the salinity gradient and at wastewater treatment plants. Isotopic mixing curves indicate a net removal of DOC that is 13C enriched and 14C depleted. The amount of DOC removed was consistent with CO2 evasion from the estuary. During two transects at average to low flow, the lower Hudson River Estuary was a heterotrophic system with CO2 evasion balanced by the utilization of aged DOC derived from wastewater and marine phytoplankton that enter the estuary at the seaward end-member. DOC removals were largest during a period of high river flow, when isotopic mixing curves also suggest large contributions from labile terrestrial OC sources. Overall, our results suggest that net heterotrophy in the lower Hudson River Estuary is fueled by aged labile DOC derived from a combination of sources, which are influenced by seasonal phytoplankton blooms, hydrological conditions, and the nature of wastewater inputs.
Environmental turbulent mixing controls on air-water gas exchange in marine and aquatic systems

(American Geophysical Union, 2007-05-17) Zappa, Christopher J. ; McGillis, Wade R. ; Raymond, Peter A. ; Edson, James B. ; Hintsa, Eric J. ; Zemmelink, Hendrik J. ; Dacey, John W. H. ; Ho, David T.

Air-water gas transfer influences CO2 and other climatically important trace gas fluxes on regional and global scales, yet the magnitude of the transfer is not well known. Widely used models of gas exchange rates are based on empirical relationships linked to wind speed, even though physical processes other than wind are known to play important roles. Here the first field investigations are described supporting a new mechanistic model based on surface water turbulence that predicts gas exchange for a range of aquatic and marine processes. Findings indicate that the gas transfer rate varies linearly with the turbulent dissipation rate to the inline equation power in a range of systems with different types of forcing - in the coastal ocean, in a macro-tidal river estuary, in a large tidal freshwater river, and in a model (i.e., artificial) ocean. These results have important implications for understanding carbon cycling.
A land-to-ocean perspective on the magnitude, source and implication of DIC flux from major Arctic rivers to the Arctic Ocean

(American Geophysical Union, 2012-12-14) Tank, Suzanne E. ; Raymond, Peter A. ; Striegl, Robert G. ; McClelland, James W. ; Holmes, Robert M. ; Fiske, Gregory J. ; Peterson, Bruce J.

A series of seasonally distributed measurements from the six largest Arctic rivers (the Ob', Yenisey, Lena, Kolyma, Yukon and Mackenzie) was used to examine the magnitude and significance of Arctic riverine DIC flux to larger scale C dynamics within the Arctic system. DIC concentration showed considerable, and synchronous, seasonal variation across these six large Arctic rivers, which have an estimated combined annual DIC flux of 30 Tg C yr−1. By examining the relationship between DIC flux and landscape variables known to regulate riverine DIC, we extrapolate to a DIC flux of 57 ± 9.9 Tg C yr−1for the full pan-arctic basin, and show that DIC export increases with runoff, the extent of carbonate rocks and glacial coverage, but decreases with permafrost extent. This pan-arctic riverine DIC estimate represents 13–15% of the total global DIC flux. The annual flux of selected ions (HCO3−, Na+, Ca2+, Mg2+, Sr2+, and Cl−) from the six largest Arctic rivers confirms that chemical weathering is dominated by inputs from carbonate rocks in the North American watersheds, but points to a more important role for silicate rocks in Siberian watersheds. In the coastal ocean, river water-induced decreases in aragonite saturation (i.e., an ocean acidification effect) appears to be much more pronounced in Siberia than in the North American Arctic, and stronger in the winter and spring than in the late summer. Accounting for seasonal variation in the flux of DIC and other major ions gives a much clearer understanding of the importance of riverine DIC within the broader pan-arctic C cycle.
Estimates of new and total productivity in central Long Island Sound from in situ measurements of nitrate and dissolved oxygen

( 2013-01) Collins, James R. ; Raymond, Peter A. ; Bohlen, Walter Franklin ; Howard-Strobel, Mary M.

Biogeochemical cycles in estuaries are regulated by a diverse set of physical and biological variables that operate over a variety of time scales. Using in situ optical sensors, we conducted a high-frequency time-series study of several biogeochemical parameters at a mooring in central Long Island Sound from May to August 2010. During this period, we documented well-defined diel cycles in nitrate concentration that were correlated to dissolved oxygen, wind stress, tidal mixing, and irradiance. By filtering the data to separate the nitrate time series into various signal components, we estimated the amount of variation that could be ascribed to each process. Primary production and surface wind stress explained 59% and 19%, respectively, of the variation in nitrate concentrations. Less frequent physical forcings, including large-magnitude wind events and spring tides, served to decouple the relationship between oxygen, nitrate, and sunlight on about one-quarter of study days. Daytime nitrate minima and dissolved oxygen maxima occurred nearly simultaneously on the majority (> 80%) of days during the study period; both were strongly correlated with the daily peak in irradiance. Nighttime nitrate maxima reflected a pattern in which surface-layer stocks were depleted each afternoon and recharged the following night. Changes in nitrate concentrations were used to generate daily estimates of new primary production (182 ± 37 mg C m-2 d-1) and the f-ratio (0.25), i.e., the ratio of production based on nitrate to total production. These estimates, the first of their kind in Long Island Sound, were compared to values of community respiration, primary productivity, and net ecosystem metabolism, which were derived from in situ measurements of oxygen concentration. Daily averages of the three metabolic parameters were 1660 ± 431, 2080 ± 419, and 429 ± 203 mg C m-2 d-1, respectively. While the system remained weakly autotrophic over the duration of the study period, we observed very large day-to-day differences in the f-ratio and in the various metabolic parameters.
Particulate organic carbon and nitrogen export from major Arctic rivers

(John Wiley & Sons, 2016-05-11) McClelland, James W. ; Holmes, Robert M. ; Peterson, Bruce J. ; Raymond, Peter A. ; Striegl, Robert ; Zhulidov, Alexander V. ; Zimov, Sergey A. ; Zimov, Nikita ; Tank, Suzanne E. ; Spencer, Robert G. M. ; Staples, Robin ; Gurtovaya, Tatiana Y. ; Griffin, Claire G.

Northern rivers connect a land area of approximately 20.5 million km2 to the Arctic Ocean and surrounding seas. These rivers account for ~10% of global river discharge and transport massive quantities of dissolved and particulate materials that reflect watershed sources and impact biogeochemical cycling in the ocean. In this paper, multiyear data sets from a coordinated sampling program are used to characterize particulate organic carbon (POC) and particulate nitrogen (PN) export from the six largest rivers within the pan-Arctic watershed (Yenisey, Lena, Ob', Mackenzie, Yukon, Kolyma). Together, these rivers export an average of 3055 × 109 g of POC and 368 × 109 g of PN each year. Scaled up to the pan-Arctic watershed as a whole, fluvial export estimates increase to 5767 × 109 g and 695 × 109 g of POC and PN per year, respectively. POC export is substantially lower than dissolved organic carbon export by these rivers, whereas PN export is roughly equal to dissolved nitrogen export. Seasonal patterns in concentrations and source/composition indicators (C:N, δ13C, Δ14C, δ15N) are broadly similar among rivers, but distinct regional differences are also evident. For example, average radiocarbon ages of POC range from ~2000 (Ob') to ~5500 (Mackenzie) years before present. Rapid changes within the Arctic system as a consequence of global warming make it challenging to establish a contemporary baseline of fluvial export, but the results presented in this paper capture variability and quantify average conditions for nearly a decade at the beginning of the 21st century.
Flow-weighted values of runoff tracers (δ18O, DOC, Ba, alkalinity) from the six largest Arctic rivers

(American Geophysical Union, 2008-09-20) Cooper, Lee W. ; McClelland, James W. ; Holmes, Robert M. ; Raymond, Peter A. ; Gibson, J. J. ; Guay, Christopher K. ; Peterson, Bruce J.

We present new flow-weighted data for δ 18OH2O, dissolved organic carbon (DOC), dissolved barium and total alkalinity from the six largest Arctic rivers: the Ob', Yenisey, Lena, Kolyma, Yukon and Mackenzie. These data, which can be used to trace runoff, are based upon coordinated collections between 2003 and 2006 that were temporally distributed to capture linked seasonal dynamics of river flow and tracer values. Individual samples indicate significant variation in the contributions each river makes to the Arctic Ocean. Use of these new flow-weighted estimates should reduce uncertainties in the analysis of freshwater transport and fate in the upper Arctic Ocean, including the links to North Atlantic thermohaline circulation, as well as regional water mass analysis. Additional improvements should also be possible for assessing the mineralization rate of the globally significant flux of terrigenous DOC contributed to the Arctic Ocean by these major rivers.
Landscape-level controls on dissolved carbon flux from diverse catchments of the circumboreal

(American Geophysical Union, 2012-08-21) Tank, Suzanne E. ; Frey, Karen E. ; Striegl, Robert G. ; Raymond, Peter A. ; Holmes, Robert M. ; McClelland, James W. ; Peterson, Bruce J.

While much of the dissolved organic carbon (DOC) within rivers is destined for mineralization to CO2, a substantial fraction of riverine bicarbonate (HCO3−) flux represents a CO2 sink, as a result of weathering processes that sequester CO2 as HCO3−. We explored landscape-level controls on DOC and HCO3− flux in subcatchments of the boreal, with a specific focus on the effect of permafrost on riverine dissolved C flux. To do this, we undertook a multivariate analysis that partitioned the variance attributable to known, key regulators of dissolved C flux (runoff, lithology, and vegetation) prior to examining the effect of permafrost, using riverine biogeochemistry data from a suite of subcatchments drawn from the Mackenzie, Yukon, East, and West Siberian regions of the circumboreal. Across the diverse catchments that we study, controls on HCO3− flux were near-universal: runoff and an increased carbonate rock contribution to weathering (assessed as riverwater Ca:Na) increased HCO3− yields, while increasing permafrost extent was associated with decreases in HCO3−. In contrast, permafrost had contrasting and region-specific effects on DOC yield, even after the variation caused by other key drivers of its flux had been accounted for. We used ionic ratios and SO4 yields to calculate the potential range of CO2 sequestered via weathering across these boreal subcatchments, and show that decreasing permafrost extent is associated with increases in weathering-mediated CO2 fixation across broad spatial scales, an effect that could counterbalance some of the organic C mineralization that is predicted with declining permafrost.
Linkages among runoff, dissolved organic carbon, and the stable oxygen isotope composition of seawater and other water mass indicators in the Arctic Ocean

(American Geophysical Union, 2005-12-07) Cooper, Lee W. ; Benner, Ronald ; McClelland, James W. ; Peterson, Bruce J. ; Holmes, Robert M. ; Raymond, Peter A. ; Hansell, Dennis A. ; Grebmeier, Jacqueline M. ; Codispoti, Louis A.

Concentrations of dissolved organic carbon (DOC) and δ18O values have been determined following sampling of runoff from a number of major arctic rivers, including the Ob, Yenisey, Lena, Kolyma, Mackenzie and Yukon in 2003-2004. These data are considered in conjunction with marine data for DOC, δ18O values, nutrients, salinity, and fluorometric indicators of DOC that were obtained as part of the Shelf-Basin Interactions program at the continental shelf-basin boundary of the Chukchi and Beaufort Seas. These marine data indicate that the freshwater component is most likely derived from regional sources, such as the Mackenzie, the Bering Strait inflow and possibly eastern Siberian rivers, including the Kolyma, or the Lena but not rivers further west in the Eurasian arctic. Contributions of freshwater from melted sea ice to marine surface waters appeared to be insignificant over annual cycles compared to runoff, although on a seasonal basis, freshwater from melted sea ice was locally dominant following a major sea-ice retreat into the Canada Basin in 2002. DOC concentrations were correlated with the runoff fraction, with an apparent meteoric water DOC concentration of 174 ± 1 μM (standard error). This concentration is lower than the flow-weighted concentrations measured at river mouths of the five largest Arctic rivers (358 to 917 μM), indicating that removal of terrigenous DOC during transport through estuaries, shelves and in the deep basin. DOC data indicate that flow-weighted concentrations in the two largest North American arctic rivers, the Yukon (625μM) and the Mackenzie (382 μM), are lower than in the three largest Eurasian arctic rivers, the Ob (825 μM), the Yenesey (858 μM) and the Lena (917 μM). A fluorometric indicator of chromophoric dissolved organic matter (CDOM) that has provided estimates of terrigenous DOC concentrations in the Eurasian Arctic was not correlated with DOC concentrations in the Amerasian marine waters studied, except below the upper Arctic Ocean halocline. Nutrient distributions and concentrations as well as derived nutrient ratios suggest the CDOM fluorometer may be responding to the release of chromophoric materials from continental shelf sediments. Shipboard incubation experiments with undisturbed sediment cores indicate that continental shelf sediments on the Bering and Chukchi Sea shelves are likely to be a net source of DOC to the Arctic Ocean.
Auxiliary material for "Estimates of new and total productivity in central Long Island Sound from in situ measurements of nitrate and dissolved oxygen"

( 2013) Collins, James R. ; Raymond, Peter A. ; Bohlen, Walter Franklin ; Howard-Strobel, Mary M.

Biogeochemical cycles in estuaries are regulated by a diverse set of physical and biological variables that operate over a variety of time scales. Using in situ optical sensors, we conducted a high-frequency time-series study of several biogeochemical parameters at a mooring in central Long Island Sound from May to August 2010. During this period, we documented well-defined diel cycles in nitrate concentration that were correlated to dissolved oxygen, wind stress, tidal mixing, and irradiance. By filtering the data to separate the nitrate time series into various signal components, we estimated the amount of variation that could be ascribed to each process. Primary production and surface wind stress explained 59% and 19%, respectively, of the variation in nitrate concentrations. Less frequent physical forcings, including large-magnitude wind events and spring tides, served to decouple the relationship between oxygen, nitrate, and sunlight on about one-quarter of study days. Daytime nitrate minima and dissolved oxygen maxima occurred nearly simultaneously on the majority (> 80%) of days during the study period; both were strongly correlated with the daily peak in irradiance. Nighttime nitrate maxima reflected a pattern in which surface-layer stocks were depleted each afternoon and recharged the following night. Changes in nitrate concentrations were used to generate daily estimates of new primary production (182 ± 37 mg C m-2 d-1) and the f-ratio (0.25), i.e., the ratio of production based on nitrate to total production. These estimates, the first of their kind in Long Island Sound, were compared to values of community respiration, primary productivity, and net ecosystem metabolism, which were derived from in situ measurements of oxygen concentration. Daily averages of the three metabolic parameters were 1660 ± 431, 2080 ± 419, and 429 ± 203 mg C m-2 d-1, respectively. While the system remained weakly autotrophic over the duration of the study period, we observed very large day-to-day differences in the f-ratio and in the various metabolic parameters.

Raymond Peter A.

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