Global distributions, source-type dependencies, and concentration ranges of per- and polyfluoroalkyl substances in groundwater.

A meta-analysis was conducted of published literature reporting concentrations of per- and polyfluoroalkyl substances (PFAS) in groundwater for sites distributed in 20 countries across the globe. Data for >35 PFAS were aggregated from 96 reports published from 1999 to 2021. The final data set comprises approximately 21,000 data points after removal of time-series and duplicate samples as well as non-detects. The reported concentrations range over many orders of magnitude, from ng/L to mg/L levels. Distinct differences in concentration ranges are observed between sites located within or near sources versus those that are not. Perfluorooctanoic acid (PFOA), ranging from <0.03 ng/L to ~7 mg/L, and perfluorooctanesulfonic acid (PFOS), ranging from 0.01 ng/L to ~5 mg/L, were the two most reported PFAS. The highest PFAS concentration in groundwater is ~15 mg/L reported for the replacement-PFAS 6:2 fluorotelomer sulfonate (6:2 FTS). Maximum reported groundwater concentrations for PFOA and PFOS were compared to concentrations reported for soils, surface waters, marine waters, and precipitation. Soil concentrations are generally significantly higher than those reported for the other media. This accrues to soil being the primary entry point for PFAS release into the environment for many sites, as well as the generally significantly greater retention capacity of soil compared to the other media. The presence of PFAS has been reported for all media in all regions tested, including areas that are far removed from specific PFAS sources. This gives rise to the existence of a "background" concentration of PFAS that must be accounted for in both regional and site-specific risk assessments. The presence of this background is a reflection of the large-scale use of PFAS, their general recalcitrance, and the action of long-range transport processes that distribute PFAS across regional and global scales. This ubiquitous distribution has the potential to significantly impact the quality and availability of water resources in many regions. In addition, the pervasive presence of PFAS in the environment engenders concerns for impacts to ecosystem and human health.

PFAS in soil and groundwater following historical land application of biosolids.

The land application of digested sewage sludge (biosolids) is widely employed across the globe. Studies show that biosolids contain significant amounts of inorganic and organic materials, as well as emerging pollutants, including per- and polyfluorinated alkyl substances (PFAS). With the wide range of pollutants commonly reported in biosolids, the potential risks associated with long-term land application operations are concerning. In this study, PFAS in surface soils, deeper soils into the vadose zone, and immediately-underlying groundwater was measured at an agricultural station with a long record of biosolids applications plus irrigation using treated wastewater. Twelve PFAS homologues were detected in every near surface soil sampled 0-30 cm depth below ground surface with multiple PFAS (especially short-chain) distributed through the soil profile. Average measured concentrations of PFAS in these soils suggest the soil burden PFOS>PFDA>PFOA for all substations sampled, independent of the historical loading rates and patterns of agricultural operations on those substations. Measured concentrations of PFOA and PFOS in the soil profile (0-90 cm) suggest these compounds have migrated to deeper soil depths (up to 9 m below the surface) with quantifiable concentrations in the soil and the immediate underlying groundwater located approximately 17 m below. Estimates of the total mass of PFAS in surface soils were effectively made using PFAS levels reported in sludges from the USEPA NSSS combined with long-term loading rates on record at the substations. With the land application of biosolids in the USA regulated by the USEPA, additional and updated risk assessments and surveys to include emerging pollutants such as PFAS are needed to protect public health and the environment.

In-situ activation of persulfate by iron filings and degradation of 1,4-dioxane.

Activation of persulfate by iron filings and subsequent degradation of 1,4-dioxane (dioxane) was studied in both batch-reactor and column systems to evaluate the potential of a persulfate-enhanced permeable reactive barrier (PRB) system for combined oxidative-reductive removal of organic contaminants from groundwater. In batch experiments, decomposition of persulfate to sulfate and degradation of dioxane both occurred rapidly in the presence of iron filings. Conversely, dioxane degradation by persulfate was considerably slower in the absence of iron filings. For the column experiments, decomposition and retardation of persulfate was observed for transport in the columns packed with iron filings, whereas no decomposition or retardation was observed for transport in columns packed with a reference quartz sand. Both sulfate production and dioxane degradation were observed for the iron-filings columns, but not for the sand column. The pH of the column effluent increased temporarily before persulfate breakthrough, and significant increases in both ferrous and ferric iron coincided with persulfate breakthrough. Multiple species of free radicals were produced from persulfate activation as determined by electron paramagnetic resonance (EPR) spectroscopy. The impact of the oxidation process on solution composition and iron-filings surface chemistry was examined using ICP-MS, SEM-EDS, and XRD analyses. A two-stage reaction mechanism is proposed to describe the oxidation process, consisting of a first stage of rapid, solution-based, radical-driven decomposition of dioxane and a second stage governed by rate-limited surface reaction. The results of this study show successful persulfate activation using iron filings, and the potential to apply an enhanced PRB method for improving in-situ removal of organic contaminants from groundwater.

Amending greenroof soil with biochar to affect runoff water quantity and quality.

Numbers of greenroofs in urban areas continue to grow internationally; so designing greenroof soil to reduce the amount of nutrients in the stormwater runoff from these roofs is becoming essential. This study evaluated changes in extensive greenroof water discharge quality and quantity after adding biochar, a soil amendment promoted for its ability to retain nutrients in soils and increase soil fertility. Prototype greenroof trays with and without biochar were planted with sedum or ryegrass, with barren soil trays used as controls. The greenroof trays were subjected to two sequential 7.4cm/h rainfall events using a rain simulator. Runoff from the rain events was collected and evaluated. Trays containing 7% biochar showed increased water retention and significant decreases in discharge of total nitrogen, total phosphorus, nitrate, phosphate, and organic carbon. The addition of biochar to greenroof soil improves both runoff water quality and retention.

Evaporative mass transfer behavior of a complex immiscible liquid.

A series of laboratory experiments was conducted with a multiple-component immiscible liquid, collected from the Picillo Farm Superfund Site in Rhode Island, to examine liquid-vapor mass-transfer behavior. The immiscible liquid, which comprises solvents, oils, pesticides, PCBs, paint sludges, explosives, and other compounds, was characterized using gas chromatography and gas chromatography/mass spectrometry to determine mole fractions of selected constituents. Batch experiments were conducted to evaluate equilibrium phase-partitioning behavior. Two sets of air-stripping column studies were conducted to examine the mass-transfer dynamics of five selected target compounds present in the immiscible-liquid mixture. One set of column experiments was designed to represent a system with free-phase immiscible liquid present; the other was designed to represent a system with a residual phase of immiscible liquid. Initial elution behavior of all target components generally appeared to be ideal for both systems, as the initial vapor-phase concentrations were similar to vapor-phase concentrations measured for the batch experiment and those estimated using Raoult's law (incorporating the immiscible-liquid composition data). Later-stage removal of 1,2-dichlorobenzene appeared to be rate limited for the columns containing free-phase immiscible liquid and no porous medium. Conversely, evaporative mass transfer appeared to be ideal throughout the experiment conducted with immiscible liquid distributed relatively uniformly as a residual phase within a sandy porous medium.