Purified Chlorine Dioxide as an Alternative to Chlorine Disinfection to Minimize Chlorate Formation During Postharvest Produce Washing.

The washwater used to wash produce within postharvest washing facilities frequently contains high chlorine concentrations to prevent pathogen cross-contamination. To address concerns regarding the formation and uptake of chlorate (ClO3-) into produce, this study evaluated whether switching to chlorine dioxide (ClO2) could reduce chlorate concentrations within the produce. Because ClO2 exhibits lower disinfectant demand than chlorine, substantially lower concentrations can be applied. However, ClO3- can form through several pathways, particularly by reactions between ClO2 and the chlorine used to generate ClO2 via reaction with chlorite (ClO2-) or chlorine that forms when ClO2 reacts with produce. This study demonstrates that purging ClO2 from the chlorine and ClO2- mixture used for its generation through a trap containing ClO2- can scavenge chlorine, substantially reducing ClO3- concentrations in ClO2 stock solutions. Addition of low concentrations of ammonia to the produce washwater further reduced ClO3- formation by binding the chlorine produced by ClO2 reactions with produce as inactive chloramines without scavenging ClO2. While chlorate concentrations in lettuce, kale, and broccoli exceeded regulatory guidelines during treatment with chlorine, ClO3- concentrations were below regulatory guidelines for each of these vegetables when treated with ClO2 together with these two purification measures. Switching to purified ClO2 also reduced the concentrations of lipid-bound oleic acid chlorohydrins and protein-bound chlorotyrosines, which are exemplars of halogenated byproducts formed from disinfectant reactions with biomolecules within produce.

Imparting Multifunctionality in Zr-MOFs Using the One-Pot Mixed-Linker Strategy: The Effect of Linker Environment and Enhanced Pollutant Removal.

The development of mixed-linker metal-organic frameworks (MOFs) is an efficient strategy to improve the performance of MOFs. Herein, we successfully integrate tetrakis(4-carboxyphenyl)porphyrin (TCPP) into different Zr-MOFs via a facile one-pot solvothermal synthesis while preserving the integrity of their frameworks. The functional groups, length of primary linkers, and the inner pore structure significantly affected the properties of the synthesized TCPP@MOFs, such as surface area, average pore size, and 1O2 productivity. Among them, TCPP@PCN-777 demonstrated the largest surface area (2386 cm2/g, as measured by N2 uptake) and the highest 1O2 generation rate (1.15 h-1, [1O2]ss = 2.66 × 10-12 M) under irradiation. The TCPP loading was also shown to affect the crystal phase, morphology, surface area, and photochemical properties of the synthesized MOFs. Therefore, TCPP@PCN-777s with various TCPP loadings were synthesized to investigate the optimum loading. The optimized TCPP@MOF, TCPP@PCN-777-30, was evaluated for its removal of model contaminant ranitidine (RND) through both adsorption and photodegradation. TCPP@PCN-777-30 showed a higher adsorption capacity toward RND than both the parent MOF (PCN-777) and commercially available activated carbon, and effectively degraded RND in aqueous solution (>99% photodegradation in 1 h). With irradiation, TCPP@PCN-777-30 showed a minimal loss in adsorption efficiency over four consecutive treatment cycles, confirming the reusability of the material enabled through the incorporation of TCPP into the MOF structure. This work not only developed an efficient multifunctional material for environmental remediation but also forwarded knowledge on the effect of linker environment (i.e., functional groups, framework structure, and linker ratio) on the properties of TCPP@MOFs to guide future research on mixed-linker MOFs.

Formation of Oleic Acid Chlorohydrins in Vegetables during Postharvest Chlorine Disinfection.

High chlorine doses (50-200 mg/L) are used in postharvest washing facilities to control foodborne pathogen outbreaks. However, chlorine can react with biopolymers (e.g., lipids) within the produce to form chlorinated byproducts that remain in the food. During chlorination of micelles of oleic acid, an 18-carbon alkene fatty acid, chlorine added rapidly across the double bond to form the two 9,10-chlorohydrin isomers at a 100% yield. The molar conversion of lipid-bound oleic acid to 9,10-chlorohydrins in chlorine-treated glyceryl trioleate and produce was much lower, reflecting the restricted access of chlorine to lipids. Yields from spinach treated with 100 mg/L chlorine at 7.5 °C for 2 min increased from 0.05% (0.9 nmol/g-spinach) for whole leaf spinach to 0.11% (2 nmol/g) when shredding increased chlorine access. Increasing temperature (21 °C) and chlorine contact time (15 min) increased yields from shredded spinach to 0.83% (22 nmol/g) at 100 mg/L chlorine and to 1.8% (53 nmol/g) for 200 mg/L chlorine. Oleic acid 9,10-chlorohydrin concentrations were 2.4-2.7 nmol/g for chlorine-treated (100 mg/L chlorine at 7.5 °C for 2 min) broccoli, carrots, and butterhead lettuce, but 0.5-1 nmol/g for cabbage, kale, and red leaf lettuce. Protein-bound chlorotyrosine formation was higher in the same vegetables (5-32 nmol/g). The Chinese hamster ovary cell chronic cytotoxicity LC50 value for oleic acid 9,10-chlorohydrins was 0.106 mM. The cytotoxicity associated with the chlorohydrins and chlorotyrosines in low masses (9-52 g) of chlorine-washed vegetables would be comparable to that associated with trihalomethanes and haloacetic acids at levels of regulatory concern in drinking water.

Sunlight-Driven Chlorate Formation during Produce Irrigation with Chlorine- or Chloramine-Disinfected Water.

The increasing use of chlorine- or chloramine-containing irrigation waters to minimize foodborne pathogens is raising concerns about the formation and uptake of disinfection byproducts into irrigated produce. Chlorate has received particular attention in the European Union. While previous research demonstrated the formation of chlorate from dark disproportionation reactions of free chlorine and uptake of chlorate into produce from roots, this study evaluated chlorate formation from solar irradiation of chlorine- and chloramine-containing irrigation droplets and uptake through produce surfaces. Sunlight photolysis of 50 µM (3.6 mg/L as Cl2) chlorine significantly enhanced the formation of chlorate, with a 7.2% molar yield relative to chlorine. Chlorate formation was much less significant in sunlit chloramine solutions. In chlorinated solutions containing 270 µg/L bromide, sunlight also induced the conversion of bromide to 280 µg/L bromate. Droplet evaporation and the resulting increase in chlorine concentrations approximately doubled sunlight-induced chlorate formation relative to that in the bulk solutions in which evaporation is negligible. When vegetables (broccoli, cabbage, chicory, lettuce, and spinach) were sprayed with chlorine-containing irrigation water in a sunlit field, sunlight promoted chlorate formation and uptake through vegetable surfaces to concentrations above maximum residue levels in the European Union. Spraying with chloramine-containing waters in the dark minimized chlorate formation and uptake into the vegetables.

Enhanced Pollutant Adsorption and Regeneration of Layered Double Hydroxide-Based Photoregenerable Adsorbent.

Efforts to combine photocatalysts with organic and inorganic adsorbents in engineered composite materials have been pursued extensively to harness sunlight for a green, sustainable regeneration of exhausted adsorbent. Recent advances combining benchmark photocatalyst, titanium dioxide (TiO2), with an inorganic adsorbent, layered double hydroxides (LDHs), have shown potential for an inorganic adsorbent-photocatalyst system but faced critical limitations in realizing practical applications: low adsorption capacity and slow, inefficient photocatalytic regeneration. This study presents an enhanced TiO2/LDH based material that demonstrates a dramatically increased efficiency for both decontamination through adsorption and subsequent solar, photocatalytic regeneration. The combination of delamination and high temperature treatment of LDH is utilized to drastically enhance the adsorption capacity toward model contaminant Methyl Orange to 1450-1459 mg/g, which is even higher than most commercial and lab-synthesized carbon-based adsorbents. Light-active plasmonic nanoparticles are employed to increase the photocatalytic regeneration performance, and experimental results show that the synthesized composite material regains above 97% of its adsorption capacity for 5 cycles of regeneration and readsorption. Overall, the results of this study demonstrate potential for the development of inorganic multifunctional adsorbents that can harness a variety of chemical reactions without the loss of adsorptivity over long-term use.

Titanium Dioxide-Layered Double Hydroxide Composite Material for Adsorption-Photocatalysis of Water Pollutants.

Although adsorption has gained favor among numerous water treatment technologies as an effective pollutant removal method, its application is often hindered by challenges with its resource- and energy-intensive regeneration procedure once the available adsorption sites are exhausted. Herein, we present adsorption-photocatalysis composite materials combining layered double hydroxides (LDHs) and titanium dioxide (TiO2) for water treatment. Incorporation of the photocatalyst into the material opens opportunities to harness light from the sun or lamps for oxidative degradation of the adsorbed contaminants on the material surface, to free adsorption sites for material reuse. In addition to allowing photocatalytic regeneration, the addition of TiO2 to colloidal suspensions of delaminated LDH enabled the formation of TiO2-LDH composites with far superior adsorptive performances compared to their parent LDH compounds. During the material synthesis, positively charged LDH layers and negatively charged TiO2 particles combine through electrostatic attraction to yield composites with dramatically enhanced adsorption capacities toward model contaminants, methyl orange and 2,4-dichlorophenoxyacetic acid, by 16.0 and 76.7 times, respectively. Combining delaminated LDH with TiO2 allowed us to maximize the exposure of positively charged surfaces to the contaminants, in a form that can be used as a solid adsorbent. After regeneration, the material regained up to 92% of its adsorption efficiency toward model contaminants. In light of our findings showing significantly different kinetics of adsorption and photocatalytic regeneration, we propose a new scheme to utilize adsorption-photocatalysis systems, in which the two processes are separated to better utilize their unique strengths.

Water Disinfection in Rural Areas Demands Unconventional Solar Technologies.

Providing access to safe drinking water is a prerequisite for protecting public health. Vast improvements in drinking water quality have been witnessed during the last century, particularly in urban areas, thanks to the successful implementation of large, centralized water treatment plants and the distribution of treated water via underground networks of pipes. Nevertheless, infection by waterborne pathogens through the consumption of biologically unsafe drinking water remains one of the most significant causes of morbidity and mortality in developing rural areas. In these areas, the construction of centralized water treatment and distribution systems is impractical due to high capital costs and lack of existing infrastructure. Improving drinking water quality in developing rural areas demands a paradigm shift to unconventional, innovative water disinfection strategies that are low cost and simple to implement and maintain, while also requiring minimal infrastructure. The implementation of point-of-use (POU) disinfection techniques at the household- or community-scale is the most promising intervention strategy for producing immediate health benefits in the most vulnerable rural populations. Among POU techniques, solar-driven processes are considered particularly instrumental to this strategy, as developing rural areas that lack safe drinking water typically receive higher than average surface sunlight irradiation. Materials that can efficiently harvest sunlight to produce disinfecting agents are pivotal for surpassing the disinfection performance of conventional POU techniques. In this account, we highlight recent advances in materials and processes that can harness sunlight to disinfect water. We describe the physicochemical properties and molecular disinfection mechanisms for four categories of disinfectants that can be generated by harvesting sunlight: heat, germicidal UV radiation, strong oxidants, and mild oxidants. Our recent work in developing materials-based solar disinfection technologies is discussed in detail, with particular focus on the materials' mechanistic functions and their modes of action for inactivation of three common types of waterborne pathogens (i.e., bacteria, virus, and protozoa). We conclude that different solar disinfection technologies should be applied depending on the source water quality and target pathogen due to significant variations on susceptibility of microbial components to disparate disinfectants. In addition, we expect that ample research opportunities exist on reactor design and process engineering for scale-up and improved performance of these solar materials, while accounting for the infrastructure demand and capital input. Although the practical implementation of new treatment techniques will face social and economic challenges that cannot be overlooked, novel technologies such as these can play a pivotal role in reducing water borne disease burden in rural communities in the developing world.