Representing a large region with few sites: The Quality Index approach for field studies.

Many environmental studies require the characterization of a large geographical region using a range of representative sites amenable to intensive study. A systematic approach to selecting study areas can help ensure that an adequate range of the variables of interest is captured. We present a novel method of selecting study sites representing a larger region, in which the region is divided into subregions, which are characterized with relevant independent variables, and displayed in mathematical variable space. Potential study sites are also displayed this way, and selected to cover the range in variables present in the region. The coverage of sites is assessed with the Quality Index, which compares the range and standard deviation of variables among the sites to that of the larger region, and prioritizes sites that are well-distributed (i.e. not clumped) in variable space. We illustrate the method with a case study examining relationships between agricultural land use, physiography and stream phosphorus (P) export, in which we selected several variables representing agricultural P inputs and landscape susceptibility to P loss. A geographic area of 110,000km2 was represented with 11 study sites with good coverage of four variables representing agricultural P inputs and transport mechanisms taken from commonly-available geospatial datasets. We use a genetic algorithm to select 11 sites with the highest possible QI and compare these, post-hoc, to our sites. This approach reduces subjectivity in site selection, considers practical constraints and easily allows for site reselection if necessary. This site selection approach can easily be adapted to different landscapes and study goals, as we provide an algorithm and computer code to reproduce our approach elsewhere.

Nonlinear response of riverine N2O fluxes to oxygen and temperature.

One-quarter of anthropogenically produced nitrous oxide (N2O) comes from rivers and estuaries. Countries reporting N2O fluxes from aquatic surfaces under the United Nations Framework Convention on Climate Change typically estimate anthropogenic inorganic nitrogen loading and assume a fraction becomes N2O. However, several studies have not confirmed a linear relationship between dissolved nitrate (NO3-) and river N2O fluxes. We apply recursive partitioning analysis to examine the relationships between N2O flux and NO3-, dissolved oxygen (DO), temperature, land use and surficial geology in the Grand River, Canada, a seventh-order river in an agricultural catchment with substantial urban population. Results suggest that N2O flux is high when hypoxia exists. Temperature, not NO3-, was the primary correlate of N2O flux when hypoxia does not occur suggesting NO3- is not limiting N2O production and further increases in NO3- may not lead to comparable increases in N2O flux. This work indicates that a linear relationship between NO3- and N2O is unlikely to exist in most agricultural and urban impacted river systems. Most N2O is produced during hypoxia so quantifying the extent of hypoxia is a necessary first step to quantifying N2O fluxes in lotic systems. Predicted increases in riverine hypoxia via eutrophication and increased temperature due to climate change may drive nonlinear increases in N2O production.

Coupled cycles of dissolved oxygen and nitrous oxide in rivers along a trophic gradient in southern Ontario, Canada.

Diel (24-h) cycling of dissolved O2 (DO) in rivers is well documented, but evidence for coupled diel changes in DO and nitrogen cycling has only been demonstrated in hypereutrophic systems where DO approaches zero at night. Here, we show diel changes in N2O and DO concentration at several sites across a trophic gradient. Nitrous oxide concentration increased at night at all but one site in spring and summer, even when gas exchange was rapid and minimum water column DO was well above hypoxic conditions. Diel N2O curves were not mirror images of DO curves and were not symmetrical about the mean. Although inter- and intrasite variation was high, N2O peaked around the time of lowest DO at most of the sites. These results suggest that N2O must be measured several times per diel period to characterize curve shape and timing. Nitrous oxide concentration was not significantly correlated with NO3- concentration, contrary to studies in agricultural streams and to the current United Nations Intergovernmental Panel for Climate Change protocols for N2O emission estimation. The strong negative correlation between N2O concentration and daily minimum DO concentration suggested that N2O production was limited by DO. This is consistent with N2O produced by nitrite reduction. The ubiquity of diel N2O cycling suggests that most DO and N2O sampling strategies used in rivers are insufficient to capture natural variability. Ecosystem-level effects of microbial processes, such as denitrification, are sensitive to small changes in redox conditions in the water column even in low-nutrient oxic rivers, suggesting diel cycling of redox-sensitive compounds may exist in many aquatic systems.