Stream solute monitoring has produced many insights into ecosystem and Earth system functions. Although new sensors have provided novel information about the fine‐scale temporal variation of some stream water solutes, we lack adequate sensor technology to gain the same insights for many other solutes. We used two machine learning algorithms – Support Vector Machine and Random Forest – to predict concentrations at 15‐min resolution for 10 solutes, of which eight lack specific sensors. The algorithms were trained with data from intensive stream sensing and manual stream sampling (weekly) for four full years in a hydrologic reference stream within the Hubbard Brook Experimental Forest in New Hampshire, USA. The Random Forest algorithm was slightly better at predicting solute concentrations than the Support Vector Machine algorithm (Nash‐Sutcliffe efficiencies ranged from 0.35 to 0.78 for Random Forest compared to 0.29 to 0.79 for Support Vector Machine). Solute predictions were most sensitive to the removal of fluorescent dissolved organic matter, pH and specific conductance as independent variables for both algorithms, and least sensitive to dissolved oxygen and turbidity. The predicted concentrations of calcium and monomeric aluminium were used to estimate catchment solute yield, which changed most dramatically for aluminium because it concentrates with stream discharge. These results show great promise for using a combined approach of stream sensing and intensive stream discrete sampling to build information about the high‐frequency variation of solutes for which an appropriate sensor or proxy is not available.
Uncertainty in the estimation of hydrologic export of solutes has never been fully evaluated at the scale of a small‐watershed ecosystem. We used data from the Gomadansan Experimental Forest, Japan, Hubbard Brook Experimental Forest, USA, and Coweeta Hydrologic Laboratory, USA, to evaluate many sources of uncertainty, including the precision and accuracy of measurements, selection of models, and spatial and temporal variation. Uncertainty in the analysis of stream chemistry samples was generally small but could be large in relative terms for solutes near detection limits, as is common for ammonium and phosphate in forested catchments. Instantaneous flow deviated from the theoretical curve relating height to discharge by up to 10% at Hubbard Brook, but the resulting corrections to the theoretical curve generally amounted to <0.5% of annual flows. Calibrations were limited to low flows; uncertainties at high flows were not evaluated because of the difficulties in performing calibrations during events. However, high flows likely contribute more uncertainty to annual flows because of the greater volume of water that is exported during these events. Uncertainty in catchment area was as much as 5%, based on a comparison of digital elevation maps with ground surveys. Three different interpolation methods are used at the three sites to combine periodic chemistry samples with streamflow to calculate fluxes. The three methods differed by <5% in annual export calculations for calcium, but up to 12% for nitrate exports, when applied to a stream at Hubbard Brook for 1997–2008; nitrate has higher weekly variation at this site. Natural variation was larger than most other sources of uncertainty. Specifically, coefficients of variation across streams or across years, within site, for runoff and weighted annual concentrations of calcium, magnesium, potassium, sodium, sulphate, chloride, and silicate ranged from 5 to 50% and were even higher for nitrate. Uncertainty analysis can be used to guide efforts to improve confidence in estimated stream fluxes and also to optimize design of monitoring programmes. © 2014 The Authors.
- PAR ID:
- 10196878
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Hydrological Processes
- Volume:
- 29
- Issue:
- 7
- ISSN:
- 0885-6087
- Page Range / eLocation ID:
- p. 1793-1805
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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