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.

Pre-pyrolysis metal and base addition catalyzes pore development and improves organic micropollutant adsorption to pine biochar.

Biochars were produced from pine feedstock pretreated with aqueous base, NaOH, at pH 9 and 11, and alkali and alkaline earth metals (AAEMs) Na, K, Ca, and Mg at 10-3 and 1 M. The effects of base and AAEM feedstock pretreatment on biochar surface area, pore size distribution, and adsorption capacity of two organic micropollutants (OMPs), 2,4-dichlorophenoxyacetic acid and sulfamethoxazole, from surface water with background dissolved organic matter (DOM) were evaluated. Base pretreatment significantly increased surface area within micropores (<2 nm diameter). AAEM pretreatment caused pore widening, increasing surface area within pores >2 nm in diameter. The catalytic activity of AAEMs, assessed by generation of non-micropore surface area, decreased in the following order: Ca > K > Na > Mg. All pretreated biochars outperformed untreated biochar for OMP adsorption. Biochar pretreated by aqueous base at pH 11 showed over an order of magnitude increase in OMP adsorption, nearly matching the performance of commercial activated carbon. OMP adsorption from surface water was positively correlated with biochar micropore surface area and negatively correlated with non-micropore surface area, which was linked to higher levels of DOM competition. Base and AAEM pretreatment of biochar feedstocks can increase OMP adsorption for water treatment applications by tuning pore structure and surface area.

Modeling and experimental approaches for determining fluoride diffusion kinetics in bone char sorbent and prediction of packed-bed groundwater defluoridator performance.

Fluoride (F) in groundwater (GW) in excess of 1.5 mg/L is a globally distributed problem impacting the health of hundreds of millions of people, many of whom cannot access centralized treatment infrastructure. Animal (e.g., cow) bone char has received emerging interest as a low-cost F sorbent for use in decentralized household and community water treatment. Pilot column tests using full-sized granular bone char particles can be used to assess treatment performance of fixed-bed contactors, but are costly, time consuming, and require large amounts of test water. Rapid small-scale column tests (RSSCTs) can be used to simulate F uptake in bone char contactors if the relationship between F intraparticle diffusion kinetics and bone char particle size is known. Two common approaches to the RSSCT assume either constant (CD) or linear proportional (PD) sorbate diffusivity as a function of sorbent particle size. This study used experimentally determined pseudo-equilibrium and kinetic F sorption data in model groundwater as inputs to the homogeneous surface diffusion model (HSDM) to determine F intraparticle diffusion coefficients for different-sized bone char particles, and to fit RSSCT and pilot column breakthrough data to evaluate CD and PD approaches. Results of this study, corroborated by incorporation of additional literature data, indicate approximately linearly proportional diffusivity of F as a function of bone char particle size. Congruently, the PD-RSSCT approach provided a superior simulation of pilot column F breakthrough compared to the CD-RSSCT. PD-RSSCT breakthrough data closely matched pilot breakthrough on a scaled service time basis up to around 500 bed volumes, corresponding to a relative F breakthrough of about 40%, and provided a slightly conservative indicator of F removal thereafter. The PD-RSSCT was compared with a hybrid modeling and empirical workflow using the HSDM with experimentally determined pseudo-equilibrium and kinetic parameter inputs as time-and-cost-saving approaches to evaluating full-sized groundwater treatment system performance. This comparison and a sensitivity analysis of HSDM input parameters used in the hybrid workflow indicated that greater precision can be obtained using the PD-RSSCT.

Environmental Comparison of Biochar and Activated Carbon for Tertiary Wastewater Treatment.

Micropollutants in wastewater present environmental and human health challenges. Powdered activated carbon (PAC) can effectively remove organic micropollutants, but PAC production is energy intensive and expensive. Biochar adsorbents can cost less and sequester carbon; however, net benefits depend on biochar production conditions and treatment capabilities. Here, life cycle assessment was used to compare 10 environmental impacts from the production and use of wood biochar, biosolids biochar, and coal-derived PAC to remove sulfamethoxazole from wastewater. Moderate capacity wood biochar had environmental benefits in four categories (smog, global warming, respiratory effects, noncarcinogenics) linked to energy recovery and carbon sequestration, and environmental impacts worse than PAC in two categories (eutrophication, carcinogenics). Low capacity wood biochar had even larger benefits for global warming, respiratory effects, and noncarcinogenics, but exhibited worse impacts than PAC in five categories due to larger biochar dose requirements to reach the treatment objective. Biosolids biochar had the worst relative environmental performance due to energy use for biosolids drying and the need for supplemental adsorbent. Overall, moderate capacity wood biochar is an environmentally superior alternative to coal-based PAC for micropollutant removal from wastewater, and its use can offset a wastewater facility's carbon footprint.

Biochar sorbents for sulfamethoxazole removal from surface water, stormwater, and wastewater effluent.

This study examined sorption of the human and veterinary antibiotic sulfamethoxazole (SMX) at environmentally relevant concentrations from laboratory clean water, surface water, stormwater, and wastewater effluent to wood and wastewater-sludge derived biochars produced under a wide range of conditions. SMX sorption by commercial powdered activated carbon (PAC) was also quantified as a benchmark. Wood-based biochar produced around 850 °C performed similarly to PAC. Biochar sorption capacity increased with surface area up to ∼400 m(2)/g. However, a further increase in surface area did not correspond to an increase in sorption capacity. Sorbent H:C ratios correlated with SMX uptake by PAC and wood-based biochars, but not for the sludge-based biochars. This is possibly due to an indirect influence of the high ash content in sludge-based biochars, as the isolated ash fraction exhibited negligible SMX sorption capacity. The presence of dissolved organic matter (DOM) in the natural and anthropogenic waters fouled most of the sorbents (i.e., decreased SMX uptake). The sludge-based biochars experienced less DOM fouling relative to wood-based biochar, particularly in the wastewater effluent. Biochar and PAC sorption kinetics were similar when examined over a contact time of four-hours, suggesting their performance ranking would be consistent at contact times typically utilized in water treatment systems. In the presence of DOM, SMX relative removal (C/C0) was independent of SMX initial concentration when the initial concentration was below 10 µg/L, thus permitting the relative removal results to be applied for different SMX initial concentrations typical of environmental and anthropogenically impacted waters.