Fluoride removal in batch and column systems using bonechar produced in a top-lit updraft drum gasifier and furnace.

Hundreds of millions of people are exposed to excessive levels of fluoride in drinking water, predominately in low-resource communities. Activated alumina is recognized as the best available technology for fluoride removal from drinking water by the United States Environmental Protection Agency, but it has substantial economic and environmental costs. Bonechar is a more environmentally friendly and potentially lower cost alternative adsorbent. Here, fluoride adsorption from groundwater (pH 8.1 ± 0.2) by activated alumina was compared with bonechar primarily produced from bovine bones at peak heating temperatures between 400 and 1100 °C in a modular top-lit updraft drum (TLUD) stove (using a bone-wood mixture) and furnace. TLUD and furnace bonechar produced at peak heating temperatures 650-1000 °C and 400-800 °C, respectively, outperformed activated alumina in batch tests (i.e., required smaller doses to achieve 90% fluoride removal). The impact of using bovine versus swine bones to produce bonechar had a negligible impact on fluoride adsorption. A wide range of peak heating temperatures in the TLUD achieved by varying primary air flow rates and fuel selection (e.g., bone-to-wood mass ratios) produced efficient fluoride adsorbents. This finding demonstrates that a TLUD can be a robust, operationally flexible production system. Fluoride removal by TLUD and furnace bonechars showed strong, negative correlations (R2 ≥0.88) with organic matter content. Bonechar pilot column tests indicated that the mass transfer zone was captured (i.e., immediate fluoride breakthrough was not observed) at an empty bed contact time (EBCT) of 5 min, increasing EBCT to 30 min had a minimal impact on adsorption efficiency, and intermittent operation (3-10 d shut-off periods) decreased effluent fluoride concentrations. Furnace bonechars produced at peak heating temperatures 400-700 °C outperformed activated alumina in pilot columns. Differences in adsorption efficiencies in batch and column tests were associated with the linearity of fluoride adsorption. A theoretical model quantifying adsorption linearity with Freundlich 1/n values was able to predict adsorber performance solely based on batch test data.

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.

Degradation and Deactivation of Bacterial Antibiotic Resistance Genes during Exposure to Free Chlorine, Monochloramine, Chlorine Dioxide, Ozone, Ultraviolet Light, and Hydroxyl Radical.

This work investigated degradation (measured by qPCR) and biological deactivation (measured by culture-based natural transformation) of extra- and intracellular antibiotic resistance genes (eARGs and iARGs) by free available chlorine (FAC), NH2Cl, O3, ClO2, and UV light (254 nm), and of eARGs by •OH, using a chromosomal ARG ( blt) of multidrug-resistant Bacillus subtilis 1A189. Rate constants for degradation of four 266-1017 bp amplicons adjacent to or encompassing the acfA mutation enabling blt overexpression increased in proportion to #AT+GC bps/amplicon, or in proportion to #5'-GG-3' or 5'-TT-3' doublets/amplicon, with respective values ranging from 0.59 to 2.3 (×1011 M-1 s-1) for •OH, 1.8-6.9 (×104 M-1 s-1) for O3, 3.9-9.2 (×103 M-1 s-1) for FAC, 0.35-1.2(×101 M-1 s-1) for ClO2, and 2.0-8.8 (×10-2 cm2/mJ) for UV at pH 7, and from 1.7-4.4 M-1 s-1 for NH2Cl at pH 8. For FAC, NH2Cl, O3, ClO2, and UV, ARG deactivation paralleled degradation of amplicons approximating a ∼800-1000 bp acfA-flanking sequence required for natural transformation in B. subtilis, whereas deactivation outpaced degradation for •OH. At practical disinfectant exposures, eARGs and iARGs were ≥90% degraded/deactivated by FAC, O3, and UV, but recalcitrant to NH2Cl and ClO2. iARG degradation/ deactivation always lagged cell inactivation. These findings provide a quantitative framework for evaluating ARG fate during disinfection/oxidation, and support using qPCR as a proxy for tracking ARG deactivation under carefully selected circumstances.

Simplified Modeling of Organic Contaminant Adsorption by Activated Carbon and Biochar in the Presence of Dissolved Organic Matter and Other Competing Adsorbates.

Cyclohexanol, phenol, benzoic acid, and phenanthrene fractional removal (italicized words are defined within the main text) by pulverized granular activated carbon and biochar adsorption in deionized water and stormwater was independent of target-adsorbate initial concentrations (C0) when C0s were below concentration thresholds. This permits a simple-modeling approach. C0-independent removal in deionized water at low-target-adsorbate concentrations potentially suggests that DOM in the deionized water induce a competitive effect that causes deviations from the Freundlich model. The Ideal Adsorbed Solution Theory-Equivalent Background Compound model was used to determine the magnitude of concentration thresholds and the competitive effect of stormwater DOM and possibly deionized water DOM. These competing substances' competitive effects were influenced by target-compound adsorbability and structure. Concentration thresholds positively correlate with competing substances' competitive effect and negatively correlate with target-adsorbate-Freundlich 1/n values. In deionized water, concentration thresholds increase as target-compound adsorbability decreases. In stormwater, concentration thresholds do not correlate with adsorbability, potentially because stormwater DOM is better suited to compete for aromatic-compound-adsorption sites. The extent known-competitor adsorbates decrease target-adsorbate removal in the presence of DOM is investigated, which depends on the competing adsorbates' relative adsorbabilities and if they adsorb to a different subpopulation of adsorption sites.

Evaluating Activated Carbon Adsorption of Dissolved Organic Matter and Micropollutants Using Fluorescence Spectroscopy.

Dissolved organic matter (DOM) negatively impacts granular activated carbon (GAC) adsorption of micropollutants and is a disinfection byproduct precursor. DOM from surface waters, wastewater effluent, and 1 kDa size fractions were adsorbed by GAC and characterized using fluorescence spectroscopy, UV-absorption, and size exclusion chromatography (SEC). Fluorescing DOM was preferentially adsorbed relative to UV-absorbing DOM. Humic-like fluorescence (peaks A and C) was selectively adsorbed relative to polyphenol-like fluorescence (peaks T and B) potentially due to size exclusion effects. In the surface waters and size fractions, peak C was preferentially removed relative to peak A, whereas the reverse was found in wastewater effluent, indicating that humic-like fluorescence is associated with different compounds depending on DOM source. Based on specific UV-absorption (SUVA), aromatic DOM was preferentially adsorbed. The fluorescence index (FI), if interpreted as an indicator of aromaticity, indicated the opposite but exhibited a strong relationship with average molecular weight, suggesting that FI might be a better indicator of DOM size than aromaticity. The influence of DOM intermolecular interactions on adsorption were minimal based on SEC analysis. Fluorescence parameters captured the impact of DOM size on the fouling of 2-methylisoborneol and warfarin adsorption and correlated with direct competition and pore blockage indicators.

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.

Modeling nonequilibrium adsorption of MIB and sulfamethoxazole by powdered activated carbon and the role of dissolved organic matter competition.

This study demonstrates that the ideal adsorbed solution theory-equivalent background compound (IAST-EBC) as a stand-alone model can simulate and predict the powdered activated carbon (PAC) adsorption of organic micropollutants found in drinking water sources in the presence of background dissolved organic matter (DOM) under nonequilibrium conditions. The IAST-EBC represents the DOM competitive effect as an equivalent background compound (EBC). When adsorbing 2-methylisoborneol (MIB) with PAC, the EBC initial concentration was a similar percentage, on average 0.51%, of the dissolved organic carbon in eight nonwastewater impacted surface waters. Using this average percentage in the IAST-EBC model yielded good predictions for MIB removal in two nonwastewater impacted waters. The percentage of competitive DOM was significantly greater in wastewater impacted surface waters, and varied markedly in DOM size fractions. Fluorescence parameters exhibited a strong correlation with the percentage of competitive DOM in these waters. Utilizing such correlations in the IAST-EBC successfully modeled MIB and sulfamethoxazole adsorption by three different PACs in the presence of DOM that varied in competitive effect. The influence of simultaneous coagulant addition on PAC adsorption of micropollutants was also investigated. Coagulation caused the DOM competitive effect to increase and decrease with MIB and sulfamethoxazole, respectively.

Sunlight-driven photochemical halogenation of dissolved organic matter in seawater: a natural abiotic source of organobromine and organoiodine.

Reactions of dissolved organic matter (DOM) with photochemically generated reactive halogen species (RHS) may represent an important natural source of organohalogens within surface seawaters. However, investigation of such processes has been limited by difficulties in quantifying low dissolved organohalogen concentrations in the presence of background inorganic halides. In this work, sequential solid phase extraction (SPE) and silver-form cation exchange filtration were utilized to desalt and preconcentrate seawater DOM prior to nonspecific organohalogen analysis by ICP-MS. Using this approach, native organobromine and organoiodine contents were found to range from 3.2-6.4 × 10(-4) mol Br/mol C and 1.1-3.8 × 10(-4) mol I/mol C (or 19-160 nmol Br L(-1) and 6-36 nmol I L(-1)) within a wide variety of natural seawater samples, compared with 0.6-1.2 × 10(-4) mol Br/mol C and 0.6-1.1 × 10(-5) mol I/mol C in terrestrial natural organic matter (NOM) isolates. Together with a chemical probe method specific for RHS, the SPE+ICP-MS approach was also employed to demonstrate formation of nanomolar levels of organobromine and organoiodine during simulated and natural solar irradiation of DOM in artificial and natural seawaters. In a typical experiment, the organobromine content of 2.1 × 10(-4) mol C L(-1) (2.5 mg C L(-1)) of Suwannee River NOM in artificial seawater increased by 69% (from 5.9 × 10(-5) to 1.0 × 10(-4) mol Br/mol C) during exposure to 24 h of simulated sunlight. Increasing I(-) concentrations (up to 2.0 × 10(-7) mol L(-1)) promoted increases of up to 460% in organoiodine content (from 8.5 × 10(-6) to 4.8 × 10(-5) mol I/mol C) at the expense of organobromine formation under the same conditions. The results reported herein suggest that sunlight-driven reactions of RHS with DOM may play a significant role in marine bromine and iodine cycling.