Leveraging DOM UV absorbance and fluorescence to accurately predict and monitor short-chain PFAS removal by fixed-bed carbon adsorbers.

Carbon adsorbent fouling by dissolved organic matter (DOM) inhibits the ability of the widely-used rapid small-scale column test (RSSCT) to accurately predict the removal of organic micropollutants (OMP) from water by full-scale carbon adsorbers. Here, the adsorption of 11 short-chain per-/poly-fluoroalkyl substances (PFAS) from groundwater, surface water, and wastewater was examined in pilot columns as well as RSSCTs using constant diffusivity (CD) and proportional diffusivity (PD) designs. Neither the CD- or PD-RSSCT accurately predicted pilot adsorber breakthrough of PFAS using standard diffusional mass transfer models. However, PFAS breakthrough relative to optical property (e.g., peak C, UV absorbance at 254 nm) breakthrough remained constant between pilot column, CD-RSSCT, and PD-RSSCT designs. This finding permitted accurate breakthrough predictions for the sum of PFAS and for 9 of the 11 PFAS on an individual basis in pilot columns using RSSCTs. Multiple linear regressions incorporating influent and treated water optical parameters enabled the modeling approach to be applied to water sources with heterogeneous DOM characteristics. It is hypothesized that this methodology was successful because (i) optical parameters adequately quantified the competitive nature of DOM and their adsorption behaved similar to OMP and (ii) competitive adsorption by low-molecular weight DOM was the predominant fouling mechanism. An OMP monitoring approach was developed for waters containing DOM with heterogenous characteristics that also relied on raw and treated water optical properties. UVA254 and fluorescence monitoring could therefore enable water treatment to remove PFAS in a variety of scenarios that face inhibitory cost and analytical limitations, such as decentralized and low-resource settings.

Biochar Water Treatment for Control of Organic Micropollutants with UVA Surrogate Monitoring.

Biochar adsorbent can be produced in low-resource settings using local materials and simple pyrolysis technology, and it has shown promise for uptake of micropollutants (MPs) such as pesticides, pharmaceuticals, industrial compounds, and chemicals released from consumer goods present in water at ng/L to µg/L levels. Accordingly, the use of biochar in water treatment applications where granular activated carbon (GAC) is economically or logistically infeasible is gaining interest. Monitoring treatment systems for individual MPs require laboratory analytical techniques that are typically cost-prohibitive and impractical for low-resource settings. Therefore, identification of surrogate parameters(s) for adsorbent bed life that can be measured inexpensively and in the field is a high priority. Background dissolved organic matter (DOM) is ubiquitous in natural and anthropogenic waters at concentrations typically 1,000 to 100,000 that of MPs. Some constituents of DOM foul the adsorbent and reduce bed life for removal of target contaminants. Aromatic DOM foulants absorb ultraviolet light at a wavelength of 254 nm (UVA254). Because DOM fouling directly affects MP adsorption capacity and DOM is a bulk water parameter that can be quantified using relatively inexpensive and portable instruments, it could be exploited as a surrogate for monitoring biochar adsorber bed life under field conditions. The objective of this study was to quantify removal of MPs from waters containing different types and concentrations of background DOM (surface water, wastewater, dump leachate) and thus exhibiting different UVA254 breakthrough profiles in bench-scale column experiments. Breakthrough profiles of weakly to moderately adsorbing MPs, including herbicides, pharmaceuticals and personal care products, and perfluoroalkyl acids, were collected using biochars generated under different pyrolysis conditions and a commercial GAC as a performance benchmark. Optimal conditions for biochar water treatment include using biochar produced from wood at ≥850°C under slightly aerobic conditions, empty bed contact times of ≥30 min, and upstream treatment processes to reduce DOM. Relative UVA254 breakthrough (C/C 0) up to 0.6-0.9 corresponded to ≥90% MP removal for most MP-water combinations studied.