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  1. Free, publicly-accessible full text available June 2, 2023
  2. Streams in the southeastern United States Coastal Plains serve as an essential source of energy and nutrients for important estuarine ecosystems, and dissolved organic matter (DOM) exported from these streams can have profound impacts on the biogeochemical and ecological functions of fluvial networks. Here, we examined hydrological and temperature controls of DOM during low-flow periods from a forested stream located within the Coastal Plain physiographic region of Alabama, USA. We analyzed DOM via combining dissolved organic carbon (DOC) analysis, fluorescence excitation–emission matrix combined with parallel factor analysis (EEM-PARAFAC), and microbial degradation experiments. Four fluorescence components were identified: terrestrial humic-like DOM, microbial humic-like DOM, tyrosine-like DOM, and tryptophan-like DOM. Humic-like DOM accounted for ~70% of total fluorescence, and biodegradation experiments showed that it was less bioreactive than protein-like DOM that accounted for ~30% of total fluorescence. This observation indicates fluorescent DOM (FDOM) was controlled primarily by soil inputs and not substantially influenced by instream production and processing, suggesting that the bulk of FDOM in these streams is transported to downstream environments with limited in situ modification. Linear regression and redundancy analysis models identified that the seasonal variations in DOM were dictated primarily by hydrology and temperature. Overall, high discharge and shallowmore »flow paths led to the enrichment of less-degraded DOM with higher percentages of microbial humic-like and tyrosine-like compounds, whereas high temperatures favored the accumulation of high-aromaticity, high-molecular-weight, terrestrial, humic-like compounds in stream water. The flux of DOC and four fluorescence components was driven primarily by water discharge. Thus, the instantaneous exports of both refractory humic-like DOM and reactive protein-like DOM were higher in wetter seasons (winter and spring). As high temperatures and severe precipitation are projected to become more prominent in the southeastern U.S. due to climate change, our findings have important implications for future changes in the amount, source, and composition of DOM in Coastal Plain streams and the associated impacts on downstream carbon and nutrient supplies and water quality.« less
  3. Penicillins and cephalosporins belong to the β-lactam antibiotic family, which accounts for more than half of the world market for antibiotics. Misuse of antibiotics harms human health and the environment. Here, we describe an easy, fast, and sensitive optical method for the sensing and discrimination of two penicillin and five cephalosporin antibiotics in buffered water at pH 7.4, using fifth-generation poly (amidoamine) (PAMAM) dendrimers and calcein, a commercially available macromolecular polyelectrolyte and a fluorescent dye, respectively. In aqueous solution at pH 7.4, the dendrimer and dye self-assemble to form a sensor that interacts with carboxylate-containing antibiotics through electrostatic interaction, monitored through changes in the dye’s spectroscopic properties. This response was captured through absorbance, fluorescence emission, and fluorescence anisotropy. The resulting data set was processed through linear discriminant analysis (LDA), a common pattern-base recognition method, for the differentiation of cephalosporins and penicillins. By pre-hydrolysis of the β-lactam rings under basic conditions, we were able to increase the charge density of the analytes, allowing us to discriminate the seven analytes at a concentration of 5 mM, with a limit of discrimination of 1 mM.
  4. Quantifying and characterizing groundwater flow and discharge from barrier islands to coastal waters is crucial for assessing freshwater resources and contaminant transport to the ocean. In this study, we examined the groundwater hydrological response, discharge, and associated nutrient fluxes in Dauphin Island, a barrier island located in the northeastern Gulf of Mexico. We employed radon ( 222 Rn) and radium (Ra) isotopes as tracers to evaluate the temporal and spatial variability of fresh and recirculated submarine groundwater discharge (SGD) in the nearshore waters. The results from a 40-day continuous 222 Rn time series conducted during a rainy season suggest that the coastal area surrounding Dauphin Island was river-dominated in the days after storm events. Groundwater response was detected about 1 week after the precipitation and peak river discharge. During the period when SGD was a factor in the nutrient budget of the coastal area, the total SGD rates were as high as 1.36 m day –1 , or almost three times higher than detected fluxes during the river-dominated period. We found from a three-endmember Ra mixing model that most of the SGD from the barrier island was composed of fresh groundwater. SGD was driven by marine and terrestrial forces, andmore »focused on the southeastern part of the island. We observed spatial variability of nutrients in the subterranean estuary across this part of the island. Reduced nitrogen (i.e., NH 4 + and dissolved organic nitrogen) fluxes dominated the eastern shore with average rates of 4.88 and 5.20 mmol m –2 day –1 , respectively. In contrast, NO 3 – was prevalent along the south-central shore, which has significant tourism developments. The contrasting nutrient dynamics resulted in N- and P-limited coastal water in the different parts of the island. This study emphasizes the importance of understanding groundwater flow and dynamics in barrier islands, particularly those urbanized, prone to storm events, or located near large estuaries.« less