Mechanistic Study of Arsenate Adsorption onto Different Amorphous Grades of Titanium (Hydr)Oxides Impregnated into a Point-of-Use Activated Carbon Block.

Millions of households still rely on drinking water from private wells or municipal systems with arsenic levels approaching or exceeding regulatory limits. Arsenic is a potent carcinogen, and there is no safe level of it in drinking water. Point-of-use (POU) treatment systems are a promising option to mitigate arsenic exposure. However, the most commonly used POU technology, an activated carbon block filter, is ineffective at removing arsenic. Our study aimed to explore the potential of impregnating carbon blocks with amorphous titanium (hydr)oxide (THO) to improve arsenic removal without introducing titanium (Ti) into the treated water. Four synthesis methods achieved 8-16 wt.% Ti loading within the carbon block with 58-97% amorphous THO content. The THO-modified carbon block could adsorb both oxidation states of arsenic (arsenate and arsenite) in batch or column tests. Modified carbon block with higher Ti and amorphous content always led to better arsenate removal, achieving arsenic loadings up to 31 mg As/mg Ti after 70,000 bed volumes in continuous flow tests. Impregnating carbon block with amorphous THO consistently outperformed impregnation using crystalline TiO2. The best-performing system (TTIP-EtOH carbon block) was an amorphous THO derived using titanium isopropoxide, ethanol, and acetic acid via sol-gel technique, aged at 80° for 18 hours and dried overnight at 60°. Comparable pore size distribution and surface area of the impregnated carbon blocks suggested that chemical properties play a more crucial role than physical and textural properties in removing arsenate via amorphous Ti-impregnated carbon block. Freundlich isotherms indicated energetically favorable adsorption for amorphous chemically synthesized adsorbents. The mass transport coefficients for the amorphous TTIP-EtOH carbon block were fitted using a pore surface diffusion model, resulting in Dsurface = 3.1×10-12 cm2/s and Dpore = 3.2×10-6 cm2/s. Impregnating the carbon block with THO enabled effective arsenic removal from water without adversely affecting the pressure drop across the unit or the carbon block's ability to remove polar organic chemical pollutants efficiently.

Real-time monitoring and prediction of water quality parameters and algae concentrations using microbial potentiometric sensor signals and machine learning tools.

The overarching hypothesis of this study was that temporal microbial potentiometric sensor (MPS) signal patterns could be used to predict changes in commonly monitored water quality parameters by using artificial intelligence/machine learning tools. To test this hypothesis, the study first examines a proof of concept by correlating between MPS's signals and high algae concentrations in an algal cultivation pond. Then, the study expanded upon these findings and examined if multiple water quality parameters could be predicted in real surface waters, like irrigation canals. Signals generated between the MPS sensors and other water quality sensors maintained by an Arizona utility company, including algae and chlorophyll, were collected in real time at time intervals of 30 min over a period of 9 months. Data from the MPS system and data collected by the utility company were used to train the ML/AI algorithms and compare the predicted with actual water quality parameters and algae concentrations. Based on the composite signal obtained from the MPS, the ML/AI was used to predict the canal surface water's turbidity, conductivity, chlorophyll, and blue-green algae (BGA), dissolved oxygen (DO), and pH, and predicted values were compared to the measured values. Initial testing in the algal cultivation pond revealed a strong linear correlation (R2 = 0.87) between mixed liquor suspended solids (MLSS) and the MPSs' composite signals. The Normalized Root Mean Square Error (NRMSE) between the predicted values and measured values were <6.5%, except for the DO, which was 10.45%. The results demonstrate the usefulness of MPSs to predict key surface water quality parameters through a single composite signal, when the ML/AI tools are used conjunctively to disaggregate these signal components. The maintenance-free MPS offers a novel and cost-effective approach to monitor numerous water quality parameters at once with relatively high accuracy.

Critical Review of Advances in Engineering Nanomaterial Adsorbents for Metal Removal and Recovery from Water: Mechanism Identification and Engineering Design.

Nanomaterial adsorbents (NAs) have shown promise to efficiently remove toxic metals from water, yet their practical use remains challenging. Limited understanding of adsorption mechanisms and scaling up evaluation are the two main obstacles. To fully realize the practical use of NAs for metal removal, we review the advanced tools and chemical principles to identify mechanisms, highlight the importance of adsorption capacity and kinetics on engineering design, and propose a systematic engineering scenario for full-scale NA implementation. Specifically, we provide in-depth insight for using density functional theory (DFT) and/or X-ray absorption fine structure (XAFS) to elucidate adsorption mechanisms in terms of active site verification and molecular interaction configuration. Furthermore, we discuss engineering issues for designing, scaling, and operating NA systems, including adsorption modeling, reactor selection, and NA regeneration, recovery, and disposal. This review also prioritizes research needs for (i) determining NA microstructure properties using DFT, XAFS, and machine learning and (ii) recovering NAs from treated water. Our critical review is expected to guide and advance the development of highly efficient NAs for engineering applications.

Measurement of free chlorine levels in water using potentiometric responses of biofilms and applications for monitoring and managing the quality of potable water.

Residual free chlorine is not monitored continuously at scale in drinking water distribution systems because existing real-time sensor technologies require frequent maintenance, cleaning, and calibration, which makes these products too costly to be used throughout a distribution system. As a result, current measurement approaches require manual sampling, which is not feasible for the consistent monitoring of free chlorine because chlorine concentrations vary significantly throughout pipeline distribution and over time and space. This research presents an alternative and cost-effective method of predicting free chlorine levels in drinking water using graphite electrodes coated with naturally grown microbial biofilms. This Microbial Potentiometric Sensor (MPS) array was installed in a Continuously Mixed Batch Reactor (CMBR), and drinking water containing variable free chlorine concentrations. The chlorine concentrations were introduced in a controlled manner, and the MPS signals were monitored over time. MPS signals were measured from the change in Open Circuit Potential (OCP) across the MPS array in real-time. An empirically derived relationship between the normalized change in OCP and free chlorine was established by fitting individual and average MPS data to a decaying exponential growth function in order to predict free chlorine levels. The results show that free chlorine can be predicted with reasonable accuracy, with model validation showing an average absolute error of ±0.09 ppm below 1.1 ppm and ±0.30 ppm between 1.1 and 2.7 ppm. However, the accuracy of predictions was reduced at higher free chlorine levels. The researchers conclude that MPS systems may benefit drinking water distribution systems by measuring free chlorine. These advantages of the MPS are especially pronounced in the developing world because this system is inexpensive and does not require routine maintenance or cleaning. The system relies on a naturally forming and regenerating biofilm and an inexpensive potentiometric meter to produce stable measurements.

Microbial potentiometric sensor array measurements in unsaturated soils.

The overarching goal of this study is to demonstrate a novel technology for monitoring changes in electrical potential of unsaturated soils using biofilm-populated electrodes. The novelty of the study stems from the fact that it demonstrates a method for measuring open-circuit potentials (OCP) in environments without the presence of an electrolyte solution. This study also reveals that using a biofilm-populated electrode as a reference in stable environments could successfully be employed to assess and monitor the electrochemical potential generated by plants and microorganisms. The findings imply that long-term (months to years) and real-time measurements of the open-circuit potential in unsaturated soils are possible. Because MPS arrays can directly measure open-circuit potential from the biofilm, the challenges related to locally induced electrochemical changes caused by microorganisms in the soil to achieve optimum physiological levels are eliminated. The simplicity of the technology, which allows for multiple indicator electrodes to be referenced against an "internal" reference electrode, enables spatial-temporal monitoring of the changes in the soil and the generation of 2D- or 3D-signal patterns. Once a signal pattern, generated by an array of sensors, develops (usually after 30 to 90 days), it does not significantly change unless the soil is exposed to external stimuli. The observed OCP phenomena, however, suggests that the change in OCP signal is independent of changes in soil conductivity resulting from the addition of water. In brief, findings suggest that the proposed technology can enable multidimensional profiling and long-term monitoring of changes occurring in unsaturated soils without direct implications of presence of water. The changes in the 2D or 3-D signal patterns, however, can be correlated to other important parameters that characterize soil health.

Microbial potentiometric sensor: A new approach to longstanding challenges.

The underlying hypothesis of this study is that simple potentiometric measurements between sensing electrodes and a shared reference electrode - Microbial Potentiometric Sesnor (MPS) system - can be employed in a long-term, continuous mode of operation to resolve the spatial and temporal changes in environmental systems. To address the hypothesis, (1) a conceptual description of the MPS system and its postulated principle of operation are provided; (2) the MPS system performance is documented under controlled laboratory conditions; and (3) the capabilities of the MPS system are documented under quiescent and dynamic field condition. In a laboratory setting, the variability among different MPS signals was insignificant confirming the postulated high accuracy and reproducibility of the sensor performance. It also demonstrated statistically significant correlations with dissolved oxygen (DO) and oxidation-reduction potential (ORP) sensors, while showing capabilities of operating under anoxic and anaerobic conditions. Regardless of their locations in the model wetland system, three MPS sensors functioned without interruption and cleaning for a period >2 years, and thus demonstrating long-term durability of the MPS technology. In real batch-wastewater treatment facility, the deployed MPS system signals were able to describe the organic carbon trends and correlate with each treatment phase in a cycle. Data reproducibility and reliability exceeded the expectations better describing the carbon treatment levels than the DO and ORP sensors (p < 4.4 × 10-162 vs phase adjusted p < 3.0 × 10-58). While MPS signals correlate with specific parameters that describe the local process or environments, it is more prudent to employ both the magnitude and pattern of a composite signal like the MPS signal describe the change to reflect any shift in the local environment. When compared to a baseline pattern, this change in signal magnitude and pattern reveals important information that can be employed to tailor and optimize any condition or process which involves microorganisms.

An experimental approach for determining thermodynamic surface complexation descriptors of weak-acid oxyanions onto metal (hydr)oxides: Case study of arsenic and titanium dioxide.

The extensive literature review suggests that there are two main reasons for contradictory thermodynamic parameter values obtained via sorption experiments: (1) many of the studies are conducted under unrealistic conditions where the sorbate/sorbent ratios are so high that physisorption is artificially induced; or (2) many of the studies incorrectly calculate the equilibrium constants. The goal of this study is to demonstrate a methodology that describes how to properly determine and verify theoretically predicted thermodynamic descriptors. The study employs arsenate and titanium dioxide as a model sorbate-sorbent pair, which is equilibrated under realistic conditions for a period of 3 days at two different pH conditions (~6.5 and ~8.5) and three different temperatures (7 °C, 25 °C and 35 °C) in 10 mM NaHCO3. At pH ≈ 8.55, ΔGo values were -83.38 ±â€¯1.62 kJ/mol, -88.13 ±â€¯0.66 kJ/mol, and -90.78 ±â€¯0.61 kJ/mol for sorption performed at 7 °C, 25 °C and 35 °C, respectively. Decreasing the pH to about 6.65 resulted in slightly less negative values of ΔGo to -73.38 ±â€¯1.58 kJ/mol, -77.14 ±â€¯1.52 kJ/mol, and -78.75 ±â€¯1.53 kJ/mol for sorption conducted at the same respective temperature conditions. These values overlap with the ΔGo ranges reported for sorption of arsenate on metal oxides. Change in enthalpy values of ΔHo = -19.04 kJ/mol at pH ≈ 6.65 and ΔHo =-9.35 kJ/mol at pH ≈ 8.55 were observed. Based on reports, which suggest that at lower pH more bidentate ligands are being formed, these values are expected. The change in entropy values ranged from ΔSo = 0.19 kJ/mol K at pH ≈ 6.55 to ΔSo = 0.26 kJ/mol K at pH ≈ 8.55, which suggests lower level of disorder among the created complexes at lower pH and it is in line with the rationale that bidentate complexes are better organized on the surface of the sorbent and less susceptible with desorption. These findings clearly demonstrate that experimentally obtained ΔG0 and other thermodynamic values and trends could be obtained to reflect and confirm model predictions when the existing sorption theory is properly translated into experimental practice. The sorbate-sorbent bond in chemisorption has covalent character, characterized with short bond length and higher bond energy, which makes it less reversible when compared to physisorption, and therefore highly significant from a sorbent remediation-performance practical point of view and long-term waste sorbents disposal. While thermodynamic parameter modeling represents a good first step in determining the suitability of an initial design, experimental techniques potentially have the ability to provide far more superior description of the thermodynamic sorbent/sorbate interactions under realistic conditions.

Copper release and transformation following natural weathering of nano-enabled pressure-treated lumber.

Commercially available lumber, pressure-treated with micronized copper azole (MCA), has largely replaced other inorganic biocides for residential wood treatment in the USA, yet little is known about how different outdoor environmental conditions impact the release of ionic, nano-scale, or larger (micron-scale) copper from this product. Therefore, we weathered pressure treated lumber for 18 months in five different climates across the continental United States. Copper release was quantified every month and local weather conditions were recorded continuously to determine the extent to which local climate regulated the release of copper from this nano-enabled product during its use phase. Two distinct release trends were observed: In cooler, wetter climates release occurred primarily during the first few months of weathering, as the result of copper leaching from surface/near-surface areas. In warmer, drier climates, less copper was initially released due to limited precipitation. However, as the wood dried and cracked, the exposed copper-bearing surface area increased, leading to increased copper release later in the product lifetime. Single-particle-ICP-MS results from laboratory prepared MCA-wood leachate solutions indicated that a) the predominant form of released copper passed through a filter smaller than 0.45 micrometers and b) released particles were largely resistant to dissolution over the course of 6 wks. Toxicity Characteristic Leaching Procedure (TCLP) testing was conducted on nonweathered and weathered MCA-wood samples to simulate landfill conditions during their end-of-life (EoL) phase and revealed that MCA wood released <10% of initially embedded copper. Findings from this study provide data necessary to complete a more comprehensive evaluation of the environmental and human health impacts introduced through release of copper from pressure treated lumber utilizing life cycle assessment (LCA).

Physisorption and chemisorption of T4 bacteriophages on amino functionalized silica particles.

Bacteriophages, or phages, are receiving increasing interest as recognition tools for the design of bioactive surfaces. However, to maintain the activity of surface-bound phages, the immobilization strategy must provide the right orientation and not compromise the phages' integrity. The objectives of this study were to characterize the phage sorption capacity and the immobilized phage activity for aminated silica particles functionalized with T4 phages. Two functionalization strategies were compared; physisorption, based on electrostatic adhesion, and chemisorption, where the phage and the particle are coupled using a carbodiimide cross-linker. We report that chemisorption, at maximum adsorption conditions on 1 µm particles, yielded 16 functional phages per particle, which is 2.5 times more than by the physisorption method. Particle diameter is shown to have an important impact on phage attachment and 1.8 µm particles were found to have ∼4 times more phages per surface area than 0.5 µm particles. Higher surface coverage is attributed to the lower steric hindrance on bigger particles. These findings provide important guidelines for the design of phage-functionalized particles for environmental, biomedical, or sensing applications.

Developing and interpreting aqueous functional assays for comparative property-activity relationships of different nanoparticles.

It is difficult to relate intrinsic nanomaterial properties to their functional behavior in the environment. Unlike frameworks for dissolved organic chemicals, there are few frameworks comparing multiple and inter-related properties of engineered nanomaterials (ENMs) to their fate, exposure, and hazard in environmental systems. We developed and evaluated reproducibility and inter-correlation of 12 physical, chemical, and biological functional assays in water for eight different engineered nanomaterials (ENMs) and interpreted results using activity-profiling radar plots. The functional assays were highly reproducible when run in triplicate (average coefficient of variation [CV]=6.6%). Radar plots showed that each nanomaterial exhibited unique activity profiles. Reactivity assays showed dissolution or aggregation potential for some ENMs. Surprisingly, multi-walled carbon nanotubes (MWCNTs) exhibited movement in a magnetic field. We found high inter-correlations between cloud point extraction (CPE) and distribution to sewage sludge (R2=0.99), dissolution at pH8 and pH4.9 (R2=0.98), and dissolution at pH8 and zebrafish mortality at 24hpf (R2=0.94). Additionally, most ENMs tend to distribute out of water and into other phases (i.e., soil surfaces, surfactant micelles, and sewage sludge). The activity-profiling radar plots provide a framework and estimations of likely ENM disposition in the environment.

Compact light-emitting diode optical fiber immobilized TiO2 reactor for photocatalytic water treatment.

A key barrier to implementing photocatalysis is delivering light to photocatalysts that are in contact with aqueous pollutants. Slurry photocatalyst systems suffer from poor light penetration and require post-treatment to separate the catalyst. The alternative is to deposit photocatalysts on fixed films and deliver light onto the surface or the backside of the attached catalysts. In this study, TiO2-coated quartz optical fibers were coupled to light emitting diodes (OF/LED) to improve in situ light delivery. Design factors and mechanisms studied for OF/LEDs in a flow-through reactor included: (i) the influence of number of LED sources coupled to fibers and (ii) the use of multiple optical fibers bundled to a single LED. The light delivery mechanism from the optical fibers into the TiO2 coatings is thoroughly discussed. To demonstrate influence of design variables, experiments were conducted in the reactor using the chlorinated pollutant para-chlorobenzoic acid (pCBA). From the degradation kinetics of pCBA, the quantum efficiencies (Φ) of oxidation and electrical energies per order (EEO) were determined. The use of TiO2 coated optical fiber bundles reduced the energy requirements to deliver photons and increased available surface area, which improved Φ and enhanced oxidative pollutant removal performance (EEO).

Human health tradeoffs in wellhead drinking water treatment: Comparing exposure reduction to embedded life cycle risks.

Treatment of drinking water decreases human health risks by reducing pollutants, but the required materials, chemicals, and energy emit pollutants and increase health risks. We explored human carcinogenic and non-carcinogenic disease tradeoffs of water treatment by comparing pollutant dose-response curves against life cycle burden using USEtox methodology. An illustrative wellhead sorbent groundwater treatment system removing hexavalent chromium or pentavalent arsenic serving 3200 people was studied. Reducing pollutant concentrations in drinking water from 20 µg L-1 to 10 µg L-1 avoided 37 potential cancer cases and 64 potential non-cancer disease cases. Human carcinogenicity embedded in treatment was 0.2-5.3 cases, and non-carcinogenic toxicity was 0.2-14.3 cases, depending on technology and degree of treatment. Embedded toxicity impacts from treating Cr(VI) using strong-base anion exchange were <10% of those from using weak base anion exchange. Acidification and neutralization contributed >90% of the toxicity impacts for treatment options requiring pH control. In scenarios where benefits exceeded burdens, tradeoffs still existed. Benefits are experienced by a local population but burdens are born externally where the materials and energy are produced, thus exporting the health risks. Even when burdens clearly exceeded benefits, cost considerations may still drive selecting a detrimental treatment level or technology.

Coupling Light Emitting Diodes with Photocatalyst-Coated Optical Fibers Improves Quantum Yield of Pollutant Oxidation.

A photocatalyst-coated optical fiber was coupled with a 318 nm ultraviolet-A light emitting diode, which activated the photocatalysts by interfacial photon-electron excitation while minimizing photonic energy losses due to conventional photocatalytic barriers. The light delivery mechanism was explored via modeling of evanescent wave energy produced upon total internal reflection and photon refraction into the TiO2 surface coating. This work explores aqueous phase LED-irradiated optical fibers for treating organic pollutants and for the first time proposes a dual-mechanistic approach to light delivery and photocatalytic performance. Degradation of a probe organic pollutant was evaluated as a function of optical fiber coating thickness, fiber length, and photocatalyst attachment method and compared against the performance of an equivalent catalyst mass in a completely mixed slurry reactor. Measured and simulated photon fluence through the optical fibers decreased as a function of fiber length, coating thickness, or TiO2 mass externally coated on the fiber. Thinner TiO2 coatings achieved faster pollutant removal rates from solution, and dip coating performed better than sol-gel attachment methods. TiO2 attached to optical fibers achieved a 5-fold higher quantum yield compared against an equivalent mass of TiO2 suspended in a slurry solution.

Electrical energy per order and current efficiency for electrochemical oxidation of p-chlorobenzoic acid with boron-doped diamond anode.

Electrochemical oxidation (EO) is an advanced oxidation process for water treatment to mineralize organic contaminants. While proven to degrade a range of emerging pollutants in water, less attention has been given to quantify the effect of operational variables such applied current density and pollutant concentration on efficiency and energy requirements. Particular figures of merit were mineralization current efficiency (MCE) and electrical energy per order (EEO). Linear increases of applied current exponentially decreased the MCE due to the enhancement of undesired parasitic reactions that consumed generated hydroxyl radical. EEO values ranged from 39.3 to 331.8 kW h m-3 order-1. Increasing the applied current also enhanced the EEO due to the transition from kinetics limited by current to kinetics limited by mass transfer. Further increases in current did not influence the removal rate, but it raised the EEO requirement. The EEO requirement diminished when decreasing initial pollutant loading with the increase of the apparent kinetic rate because of the relative availability of oxidant per pollutant molecule in solution at a defined current. Oxidation by-products released were identified, and a plausible degradative pathway has been suggested.

Ranking nano-enabled hybrid media for simultaneous removal of contaminants with different chemistries: Pseudo-equilibrium sorption tests versus column tests.

The underlying hypothesis of this study was that pseudo-equilibrium and column testing conditions would provide the same sorbent ranking trends although the values of sorbents' performance descriptors (e.g. sorption capacity) may vary because of different kinetics and competition effects induced by the two testing approaches. To address this hypothesis, nano-enabled hybrid media were fabricated and its removal performances were assessed for two model contaminants under multi-point batch pseudo-equilibrium and continuous-flow conditions. Calculation of simultaneous removal capacity indices (SRC) demonstrated that the more resource demanding continuous-flow tests are able to generate the same performance rankings as the ones obtained by conducing the simpler pseudo-equilibrium tests. Furthermore, continuous overlap between the 98% confidence boundaries for each SRC index trend, not only validated the hypothesis that both testing conditions provide the same ranking trends, but also pointed that SRC indices are statistically the same for each media, regardless of employed method. In scenarios where rapid screening of new media is required to obtain the best performing synthesis formulation, use of pseudo-equilibrium tests proved to be reliable. Considering that kinetics induced effects on sorption capacity must not be neglected, more resource demanding column test could be conducted only with the top performing media that exhibit the highest sorption capacity.

Ranking traditional and nano-enabled sorbents for simultaneous removal of arsenic and chromium from simulated groundwater.

Water from many municipal and private wells are treated to meet arsenic (As(V)) regulations, and new regulations for hexavalent chromium (Cr(VI)) are soon possible. Rather than adding costly capital infrastructure, we explored many types of sorbents' ability to remove both oxygenated anions simultaneously. In laboratory pseudo-equilibrium tests, metal (hydr)oxide sorbents demonstrated high affinity for As(V) but exhibited 30 to 100-fold lower capacities to remove Cr(VI). WBAX resins had some ability to sorb both Cr(VI) and As(V), but competing anions lowered their sorption capacity for As(V) by >90% compared to in a deionized water matrix. Nano-enabled sorbents with iron or titanium nanoparticles embedded inside the porous structure of an anion exchange resin demonstrated high ability to remove both pollutants simultaneously despite competition, with the tested sorbents showing 11µmol/g capacity for Cr(VI) and 19µmol/g for As(V) in simulated groundwater on average. To quantitatively rank sorbents' ability to remove multiple pollutants, a Simultaneous Removal Capacity scoring tool is proposed. This index uses both absolute removal capacity for each contaminant and relative capacity for multiple contaminants, and may be applied to simultaneous removal of any set of aqueous or atmospheric contaminants. Here, the five nano-enabled sorbents ranked in the top seven out of twelve sorbents tested for simultaneous Cr(VI) and As(V) removal. This work demonstrated traditional and novel nano-enabled sorbents can reduce multiple contaminants of health concern, resulting in groundwater treated to drinking water standards.

Nano-enabling of strong-base ion-exchange media via a room-temperature aluminum (hydr)oxide synthesis method to simultaneously remove nitrate and fluoride.

This study demonstrated a new room-temperature method for synthesizing aluminum (hydr)oxide material inside the pores of strong-base ion-exchange resin to fabricate a novel class of hybrid media capable of simultaneously removing nitrate and fluoride as model groundwater contaminants. The aluminum (hydr)oxide hybrid media was fabricated by reducing aluminum ion precursors with borohydride within ion-exchange resin at room temperature, followed by exposure to environmental oxygen. The hybrid media was characterized, and its performance to simultaneously remove nitrate and fluoride was determined in simple and complex water matrices using short-bed column tests operated under conditions realistic for point-of-use systems. Results revealed that, although not optimized, aluminum (hydr)oxide hybrid media was able to simultaneously remove nitrate and fluoride, which was not possible with neither unmodified strong-base ion-exchange resin nor conventional granular activated alumina alone. Future modifications and optimizations of this relatively simple and inexpensive fabrication process have the potential to yield an entire class of hybrid media suitable for point-of-use/point-of-entry water treatment systems.

Challenges in photocatalytic reduction of nitrate as a water treatment technology.

Management of ubiquitous nitrate contamination in drinking water sources is a major engineering challenge due to its negative impacts from eutrophication to immediate risk to human health. Several water treatment technologies exist to manage nitrate pollution in water sources. However, the most widely used technologies are phase separation treatments. In this context, nanoscale photocatalysis emerges as a highly promising transformative technology capable of reducing nitrate to innocuous nitrogen with noticeable selectivity. This critical review describes the photocatalytic reduction mechanisms of nitrate towards undesirable products (nitrite, ammonium) and the more desirable product (dinitrogen). The mechanisms are based on the standard reduction potential of each individual species and highlight the contribution of reducing species (e.g. CO2-) radicals formed from different hole scavengers. The strategic use of different pure, doped, and composite nanoscale photocatalysts is discussed on the basis of reduction mechanisms' overall conversion, kinetic rates, and selectivity towards N2. The choice of light source affects pathways and influences by-product selectivity because direct photolysis of N-intermediates, which has been overlooked in the literature. In addition, the re-oxidation of nitrite and ammonia as drawback process is explained. Finally, an exhaustive analysis presents the photocatalytic reduction applications for treating real water matrices and the competing effect of other species. Overall, this critical review aims to contribute to the understanding of the potential application/constraints of photocatalysis in inorganic nitrogen management, and guide researchers towards future efforts required for widespread implementation.