Gas exchange can be a key component of the dissolved oxygen (DO) mass balance in aquatic ecosystems. Quantification of gas transfer rates is essential for the estimation of DO production and consumption rates, and determination of assimilation capacities of systems receiving organic inputs. Currently, the accurate determination of gas transfer rate is a topic of debate in DO modeling, and there are a wide variety of approaches that have been proposed in the literature. The current study investigates the use of repeated measures of stable isotopes of O₂ and DO and a dynamic dual mass-balance model to quantify gas transfer coefficients (k) in the Grand River, Ontario, Canada. Measurements were conducted over a longitudinal gradient that reflected watershed changes from agricultural to urban. Values of k in the Grand River ranged from 3.6 to 8.6 day⁻¹, over discharges ranging from 5.6 to 22.4 m³ s⁻¹, with one high-flow event of 73.1 m³ s⁻¹. The k values were relatively constant over the range of discharge conditions studied. The range in discharge observed in this study is generally representative of non-storm and summer low-flow events; a greater range in k might be observed under a wider range of hydrologic conditions. Overall, k values obtained with the dual model for the Grand River were found to be lower than predicted by the traditional approaches evaluated, highlighting the importance of determining site-specific values of k. The dual mass balance approach provides a more constrained estimate of k than using DO only, and is applicable to large rivers where other approaches would be difficult to use. The addition of an isotopic mass balance provides for a corroboration of the input parameter estimates between the two balances. Constraining the range of potential input values allows for a direct estimate of k in large, productive systems where other k-estimation approaches may be uncertain or logistically infeasible.
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