Engineering topics

Roebuck, Jr., J. Alan

Publications and source records attributed to Roebuck, Jr., J. Alan.

2 records

DOE OSTI2023

Riverine organic matter functional diversity increases with catchment size

A large amount of dissolved organic matter (DOM) is transported to the ocean from terrestrial inputs each year (~0.95 Pg C per year) and undergoes a series of abiotic and biotic reactions, causing a significant release of CO 2 . Combined, these reactions result in variable DOM characteristics (e.g., nominal oxidation state of carbon, double-bond equivalents, chemodiversity) which have demonstrated impacts on biogeochemistry and ecosystem function. Despite this importance, however, comparatively few studies focus on the drivers for DOM chemodiversity along a riverine continuum. Here, we characterized DOM within samples collected from a stream network in the Yakima River Basin using ultrahigh-resolution mass spectrometry (i.e., FTICR-MS). To link DOM chemistry to potential function, we identified putative biochemical transformations within each sample. We also used various molecular characteristics (e.g., thermodynamic favorability, degradability) to calculate a series of functional diversity metrics. We observed that the diversity of biochemical transformations increased with increasing upstream catchment area and landcover. This increase was also connected to expanding functional diversity of the molecular formula. This pattern suggests that as molecular formulas become more diverse in thermodynamics or degradability, there is increased opportunity for biochemical transformations, potentially creating a self-reinforcing cycle where transformations in turn increase diversity and diversity increase transformations. We also observed that these patterns are, in part, connected to landcover whereby the occurrence of many landcover types (e.g., agriculture, urban, forest, shrub) could expand DOM functional diversity. For example, we observed that a novel functional diversity metric measuring similarity to common freshwater molecular formulas (i.e., carboxyl-rich alicyclic molecules) was significantly related to urban coverage. These results show that DOM diversity does not decrease along stream networks, as predicted by a common conceptual model known as the River Continuum Concept, but rather are influenced by the thermodynamic and degradation potential of molecular formula within the DOM, as well as landcover patterns.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2023

Self-diagnosis of model suitability for continuous measurements of stream-dissolved organic carbon derived from in situ UV–visible spectroscopy

Application of high-frequency monitoring of dissolved organic carbon (DOC) is difficult in instances where training datasets are challenging to develop (e.g., remote locations) and the relationship between optical features and DOC concentration changes due to environmental or landscape shifts (e.g., climate or land-use change). We developed and compared three partial least squares (PLS) models using in situ water level measurements, conductivity, and UV–Vis spectral attenuation to predict DOC. Two site-specific models were developed using data from a hillslope-dominated forest or a low-relief wetland-pond-dominated stream catchment. The third model, using data from both sites, exhibited the best performance (DOC range = 4–15.5 mg C L −1 , mean = 8.38 mg C L −1 , training RMSE = 0.34 mg C L −1 , internal validation RMSE = 0.50 mg C L −1 , external validation RMSE = 2.43 mg C L −1 ). We further demonstrate using PLS model statistics to monitor performance and elucidate when and how models should be updated. These statistics, Hotelling's T 2 and squared prediction errors, are useful consistency checks for the predictions made and detect underlying inconsistencies that, if undetected, can reduce the robustness of DOC prediction. For example, via the T 2 statistic, we identified the summer–autumn transition as a period when DOC composition differed from what was represented in the training dataset. We also determined that elevated SUVA 254 values contributed to the overall bias observed in predictions made during the subsequent year as part of the external validation. This enabled the application of a bias correction that reduced the RMSE from 2.43 to 0.89 mg C L −1 . The method presented here could be applied to future monitoring programs enabling model updates to monitor DOC fluxes accurately from optical datasets (e.g., attenuance or fluorescence) in the face of developing datasets in remote locations or environmental change. In conclusion, implementation of this approach may also identify possible regime shifts or landscape and hydrologic change associated with climate and other environmental changes relevant to terrestrial to aquatic fluxes.

UV-VIS spectroscopy↗