Implications of sample treatment on characterization of riverine dissolved organic matter.

High-resolution mass spectrometry techniques are widely used in the environmental sciences to characterize natural organic matter and, when utilizing these instruments, researchers must make multiple decisions regarding sample pre-treatment and the instrument ionization mode. To identify how these choices alter organic matter characterization and resulting conclusions, we analyzed a collection of 17 riverine samples from East River, CO (USA) under four PPL-based Solid Phase Extraction (SPE) treatment and electrospray ionization polarity (e.g., positive and negative) combinations: SPE (+), SPE (-), non-SPE (-), and non-SPE (+). The greatest number of formula assignments were achieved with SPE-treated samples due to the removal of compounds that could interfere with ionization. Furthermore, the SPE (-) treatment captured the most formulas across the widest chemical compound diversity. In addition to a reduced number of assigned formulas, the non-SPE datasets resulted in altered thermodynamic interpretations that could cascade into incomplete assumptions about the availability of organic matter pools for heterotrophic microbial respiration. Thus, we infer that the SPE (-) treatment is the best single method for characterizing environmental organic matter pools unless the focus is on lipid-like compounds, in which case we recommend a combination of SPE (-) and SPE (+) to adequately characterize these molecules.

Effects of Fe/S ratio on the kinetics and microbial ecology of an Fe(III)-dosed anaerobic wastewater treatment system.

Effects of Fe(III)/sulfate (Fe/S) ratio on organic carbon oxidation kinetics and microbial ecology of a novel Fe(III)-dosed anaerobic wastewater treatment system were investigated in this study. Fixed-film batch bioreactors under three Fe/S molar ratios (1, 2, and 3) yielded COD oxidation rates that increased with the Fe/S ratio, and estimated Michaelis-Menten model parameters Vmax ranging in 0.47-1.09 mg/L⋅min and Km in 2503-3267 mg/L. Both iron and sulfate reducing bacteria contributed to the organics oxidation, and the produced sludge materials contained both biomass (32-45 wt.%) and inorganic precipitates from biogenic ferrous iron and sulfide (68-55 wt.%). Spectroscopic and chemical elemental analyses indicated that the inorganic fraction of the sludge materials contained both FeS and FeS2, and had Fe/S stoichiometric ratios close to 1. Microbiological analyses of the biofilm samples revealed that the major putative iron- and sulfate reducers were Geobacter sp. and Desulfovibrio sp. along with noticeable N-fixing and fermentative bacteria. The COD oxidation rate had a positive correlation with the relative abundance of iron reducers, and both increased with the Fe/S ratio. A conceptual framework was proposed to illustrate the effects of Fe/S ratio on organics oxidation rate, microbial ecology and their interplays.

Anoxia stimulates microbially catalyzed metal release from Animas River sediments.

The Gold King Mine spill in August 2015 released 11 million liters of metal-rich mine waste to the Animas River watershed, an area that has been previously exposed to historical mining activity spanning more than a century. Although adsorption onto fluvial sediments was responsible for rapid immobilization of a significant fraction of the spill-associated metals, patterns of longer-term mobility are poorly constrained. Metals associated with river sediments collected downstream of the Gold King Mine in August 2015 exhibited distinct presence and abundance patterns linked to location and mineralogy. Simulating riverbed burial and development of anoxic conditions, sediment microcosm experiments amended with Animas River dissolved organic carbon revealed the release of specific metal pools coupled to microbial Fe- and SO42--reduction. Results suggest that future sedimentation and burial of riverbed materials may drive longer-term changes in patterns of metal remobilization linked to anaerobic microbial metabolism, potentially driving decreases in downstream water quality. Such patterns emphasize the need for long-term water monitoring efforts in metal-impacted watersheds.