Colloid Mobilization in a Fractured Soil during Dry–Wet Cycles: Role of Drying Duration and Flow Path Permeability

In subsurface soils, colloids are mobilized by infiltrating rainwater, but the source of colloids and the process by which colloids are generated between rainfalls are not clear. We examined the effect of drying duration and the spatial variation of soil permeability on the mobilization of <i>in situ</i> colloids in intact soil cores (fractured and heavily weathered saprolite) during dry–wet cycles. Measuring water flux at multiple sampling ports at the core base, we found that water drained through flow paths of different permeability. The duration of antecedent drying cycles affected the amount of mobilized colloids, particularly in high-flux ports that received water from soil regions with a large number of macro- and mesopores. In these ports, the amount of mobilized colloids increased with increased drying duration up to 2.5 days. For drying durations greater than 2.5 days, the amount of mobilized colloids decreased. In contrast, increasing drying duration had a limited effect on colloid mobilization in low-flux ports, which presumably received water from soil regions with fewer macro- and mesopores. On the basis of these results, we attribute this dependence of colloid mobilization upon drying duration to colloid generation from dry pore walls and distribution of colloids in flow paths, which appear to be sensitive to the moisture content of soil after drying and flow path permeability. The results are useful for improving the understanding of colloid mobilization during fluctuating weather conditions

Effects of Iron on Optical Properties of Dissolved Organic Matter

Iron is a source of interference in the spectroscopic analysis of dissolved organic matter (DOM); however, its effects on commonly employed ultraviolet and visible (UV–vis) light adsorption and fluorescence measurements are poorly defined. Here, we describe the effects of iron­(II) and iron­(III) on the UV–vis absorption and fluorescence of solutions containing two DOM fractions and two surface water samples. In each case, regardless of DOM composition, UV–vis absorption increased linearly with increasing iron­(III). Correction factors were derived using iron­(III) absorption coefficients determined at wavelengths commonly used to characterize DOM. Iron­(III) addition increased specific UV absorbances (SUVA) and decreased the absorption ratios (<i>E</i>₂:<i>E</i>₃) and spectral slope ratios (<i>S</i>_R) of DOM samples. Both iron­(II) and iron­(III) quenched DOM fluorescence at pH 6.7. The degree and region of fluorescence quenching varied with the iron:DOC concentration ratio, DOM composition, and pH. Regions of the fluorescence spectra associated with greater DOM conjugation were more susceptible to iron quenching, and DOM fluorescence indices were sensitive to the presence of both forms of iron. Analyses of the excitation–emission matrices using a 7- and 13-component parallel factor analysis (PARAFAC) model showed low PARAFAC sensitivity to iron addition

A Framework for Identifying Organic Compounds of Concern in Hydraulic Fracturing Fluids Based on Their Mobility and Persistence in Groundwater

We developed a screening framework for identifying organic components of hydraulic fracturing fluid with increased probability of exposure via groundwater based on mobility, persistence, toxicity, and frequency of use. Of 996 organic fracturing fluid compounds identified by the U.S. Environmental Protection Agency and FracFocus for four states, data were available to perform an initial screening of 659 compounds for sufficient mobility and persistence to reach a water well under fast and slow groundwater transport scenarios. For the fast transport scenario, 15 compounds identified on at least 50 FracFocus reports were predicted to have an elevated exposure potential, which was defined as ≥10% of the initial concentration remaining at a transport distance of 94 m, the average setback distance in the United States. Of these 15 compounds, two were identified on >20% of FracFocus reports (naphthalene and 2-butoxyethanol), four were compounds identified on >5% of reports, and three had health-based standards

Fate of 4-Nonylphenol and 17β-Estradiol in the Redwood River of Minnesota

The majority of previous research investigating the fate of endocrine-disrupting compounds has focused on single processes generally in controlled laboratory experiments, and limited studies have directly evaluated their fate and transport in rivers. This study evaluated the fate and transport of 4-nonylphenol, 17β-estradiol, and estrone in a 10-km reach of the Redwood River in southwestern Minnesota. The same parcel of water was sampled as it moved downstream, integrating chemical transformation and hydrologic processes. The conservative tracer bromide was used to track the parcel of water being sampled, and the change in mass of the target compounds relative to bromide was determined at two locations downstream from a wastewater treatment plant effluent outfall. In-stream attenuation coefficients (<i>k</i>_stream) were calculated by assuming first-order kinetics (negative values correspond to attenuation, whereas positive values indicate production). Attenuation of 17β-estradiol (<i>k</i>_stream = −3.2 ± 1.0 day^–1) was attributed primarily due to sorption and biodegradation by the stream biofilm and bed sediments. Estrone (<i>k</i>_stream = 0.6 ± 0.8 day^–1) and 4-nonylphenol (<i>k</i>_stream = 1.4 ± 1.9 day^–1) were produced in the evaluated 10-km reach, likely due to biochemical transformation from parent compounds (17β-estradiol, 4-nonylphenolpolyethoxylates, and 4-nonyphenolpolyethoxycarboxylates). Despite attenuation, these compounds were transported kilometers downstream, and thus additive concentrations from multiple sources and transformation of parent compounds into degradates having estrogenic activity can explain their environmental persistence and widespread observations of biological disruption in surface waters

Inhibition of Biodegradation of Hydraulic Fracturing Compounds by Glutaraldehyde: Groundwater Column and Microcosm Experiments

The rapid expansion of unconventional oil and gas development has raised concerns about the potential contamination of aquifers; however, the groundwater fate and transport of hydraulic fracturing fluid compounds and mixtures remains a significant data gap. Degradation kinetics of five hydraulic fracturing compounds (2-propanol, ethylene glycol, propargyl alcohol, 2-butoxyethanol, and 2-ethylhexanol) in the absence and presence of the biocide glutaraldehyde were investigated under a range of redox conditions using sediment-groundwater microcosms and flow-through columns. Microcosms were used to elucidate biodegradation inhibition at varying glutaraldehyde concentrations. In the absence of glutaraldehyde, half-lives ranged from 13 d to >93 d. Accurate mass spectrometry indicated that a trimer was the dominant aqueous-phase glutaraldehyde species. Microbial inhibition was observed at glutaraldehyde trimer concentrations as low as 5 mg L^–1, which demonstrated that the trimer retained some biocidal activity. For most of the compounds, biodegradation rates slowed with increasing glutaraldehyde concentrations. For many of the compounds, degradation was faster in the columns than the microcosms. Four compounds (2-propanol, ethylene glycol, propargyl alcohol, and 2-butoxyethanol) were found to be both mobile and persistent in groundwater under a range of redox conditions. The glutaraldehyde trimer and 2-ethylhexanol were more rapidly degraded, particularly under oxic conditions

In-Stream Attenuation of Neuro-Active Pharmaceuticals and Their Metabolites

In-stream attenuation was determined for 14 neuro-active pharmaceuticals and associated metabolites. Lagrangian sampling, which follows a parcel of water as it moves downstream, was used to link hydrological and chemical transformation processes. Wastewater loading of neuro-active compounds varied considerably over a span of several hours, and thus a sampling regime was used to verify that the Lagrangian parcel was being sampled and a mechanism was developed to correct measured concentrations if it was not. In-stream attenuation over the 5.4-km evaluated reach could be modeled as pseudo-first-order decay for 11 of the 14 evaluated neuro-active pharmaceutical compounds, illustrating the capacity of streams to reduce conveyance of neuro-active compounds downstream. Fluoxetine and <i>N</i>-desmethyl citalopram were the most rapidly attenuated compounds (<i>t</i>_1/2 = 3.6 ± 0.3 h, 4.0 ± 0.2 h, respectively). Lamotrigine, 10,11,-dihydro-10,11,-dihydroxy-carbamazepine, and carbamazepine were the most persistent (<i>t</i>_1/2 = 12 ± 2.0 h, 12 ± 2.6 h, 21 ± 4.5 h, respectively). Parent compounds (e.g., buproprion, carbamazepine, lamotrigine) generally were more persistent relative to their metabolites. Several compounds (citalopram, venlafaxine, <i>O</i>-desmethyl-venlafaxine) were not attenuated. It was postulated that the primary mechanism of removal for these compounds was interaction with bed sediments and stream biofilms, based on measured concentrations in stream biofilms and a column experiment using stream sediments

Spatial Dependence of Reduced Sulfur in Everglades Dissolved Organic Matter Controlled by Sulfate Enrichment

Sulfate inputs to the Florida Everglades stimulate sulfidic conditions in freshwater wetland sediments that affect ecological and biogeochemical processes. An unexplored implication of sulfate enrichment is alteration of the content and speciation of sulfur in dissolved organic matter (DOM), which influences the reactivity of DOM with trace metals. Here, we describe the vertical and lateral spatial dependence of sulfur chemistry in the hydrophobic organic acid fraction of DOM from unimpacted and sulfate-impacted Everglades wetlands using X-ray absorption spectroscopy and ultrahigh-resolution mass spectrometry. Spatial variation in DOM sulfur content and speciation reflects the degree of sulfate enrichment and resulting sulfide concentrations in sediment pore waters. Sulfur is incorporated into DOM predominantly as highly reduced species in sulfidic pore waters. Sulfur-enriched DOM in sediment pore waters exchanges with overlying surface waters and the sulfur likely undergoes oxidative transformations in the water column. Across all wetland sites and depths, the total sulfur content of DOM correlated with the relative abundance of highly reduced sulfur functionality. The results identify sulfate input as a primary determinant on DOM sulfur chemistry to be considered in the context of wetland restoration and sulfur and trace metal cycling