Integrating Navajo Pottery Techniques To Improve Silver Nanoparticle-Enabled Ceramic Water Filters for Disinfection.

Point-of-use treatment technologies can increase access to safe drinking water in rural areas. Sustained use of these technologies is uncommon due to oversight of community needs, user-perceived risks, long-term maintenance, and conflict with traditional practices. Nanosilver-enabled ceramic water filters are unique due to the use of locally sourced materials available at or near the target community; however, technical limitations persist (e.g., nanosilver's uncontrolled release and passivation from sulfide or chloride). This work aims to overcome these limitations by impregnating nanosilver onto ceramics with a Navajo pottery rosin, collected from pinyon trees with a third-generation artisan. Here, we investigate this sustainable and novel material for drinking water treatment; the study ranges from a proof of concept to testing under realistic conditions. Results show that when embedded in a thin film, the biopolymer controlled ionic silver dissolution and prevented silver passivation from sulfide and chloride. When applied to ceramic filters, the biopolymer effectively immobilized nanosilver in a range of waters. Over a 25 day study to emulate household-use conditions, this coating method sustained disinfection of a coculture of Gram-positive and Gram-negative bacteria while controlling biofouling. Overall, the use of this Navajo pottery material can facilitate adoption while providing the needed technological advancement to these widely used treatment devices.

Protozoan-Priming and Magnesium Conditioning Enhance Legionella pneumophila Dissemination and Monochloramine Resistance.

Opportunistic pathogens (OPs) are of concern in drinking water distribution systems because they persist despite disinfectant residuals. While many OPs garner protection from disinfectants via a biofilm lifestyle, Legionella pneumophila (Lp) also gains disinfection resistance by being harbored within free-living amoebae (FLA). It has been long established, but poorly understood, that Lp grown within FLA show increased infectivity toward subsequent FLA or human cells (i.e., macrophage), via a process we previously coined "protozoan-priming". The objectives of this study are (i) to identify in Lp a key genetic determinant of how protozoan-priming increases its infectivity, (ii) to determine the chemical stimulus within FLA to which Lp responds during protozoan-priming, and (iii) to determine if more infectious forms of Lp also exhibit enhanced disinfectant resistance. Using Acanthamoeba castellanii as a FLA host, the priming effect was isolated to Lp's sidGV locus, which is activated upon sensing elevated magnesium concentrations. Supplementing growth medium with 8 mM magnesium is sufficient to produce Lp grown in vitro with an infectivity equivalent to that of Lp grown via the protozoan-primed route. Both Lp forms with increased infectivity (FLA-grown and Mg2+-supplemented) exhibit greater monochloramine resistance than Lp grown in standard media, indicating that passage through FLA not only increases Lp's infectivity but also enhances its monochloramine resistance. Therefore, laboratory-based testing of disinfection strategies should employ conditions that simulate or replicate intracellular growth to accurately assess disinfectant resistance.

A Structural Equation Model to Decipher Relationships among Water, Sanitation, and Health in Colonias-Type Unincorporated Communities.

The colonias along the United States-Mexico border are generally self-built neighborhoods of low-income families that lack basic infrastructure. While some government assistance has provided roads and electricity, water and wastewater services are still lacking in many colonias. This research is the first to collect a comprehensive dataset on water, sanitation, health, and living conditions in these unincorporated neighborhoods through collection of water samples and surveys; 114 households in 23 colonias across three geographically diverse Texas counties are studied. Water quality is assessed via traditional microbial indicators, chlorine, and arsenic. This complex dataset requires an advanced statistical tool to disentangle relationships among diverse factors. Structural equation modeling is utilized to identify relationships among surveyed and measured variables. The model reveals that colonias residents with well/hauled water accurately predict their water quality, while those with treated+piped water tend to think that their water is worse than it actually is. Dwelling quality and connection to sanitary sewers influence perceived health risks and household health, respectively. Furthermore, these communities have an overwhelming need and desire for point-of-use water treatment. This model can inform decision making and may be adapted to probe other questions and social dynamics for water and sanitation in unincorporated communities elsewhere.

Laccase removal of 2-chlorophenol and sulfamethoxazole in municipal wastewater.

Laccases were studied for their ability to remove two compounds, 2-chlorophenol and sulfamethoxazole, in batch studies, both in buffered solutions and in wastewater samples from different points in a municipal water resource recovery facility. Two enzymes with and without a mediator (acetosyringone) were investigated: a commercial product derived from Myceliphthora thermophile and a laboratory-generated enzyme mix derived from Tramates versicolor. The chlorophenol was removed rapidly by the commercial enzyme in the presence of acetosyringone, but the primary products were coupling complexes of the reactants. Excellent removal was achieved without acetosyringone by the natural enzyme mix. Sulfamethoxazole was poorly removed in all laboratory-generated chemically buffered solutions, but was very well removed, without the addition of mediators, in secondary effluent suspensions from a municipal water resource recovery facility. Mechanistic studies are still required, but the results suggest that treatment via direct addition of enzymes is feasible to remove recalcitrant compounds in municipal wastewater.

DLVO Approximation Methods for Predicting the Attachment of Silver Nanoparticles to Ceramic Membranes.

This article examines the influence of three common stabilizing agents (citrate, poly(vinylpyrrolidone) (PVP), and branched poly(ethylenimine) (BPEI)) on the attachment affinity of silver nanoparticles to ceramic water filters. Citrate-stabilized silver nanoparticles were found to have the highest attachment affinity (under conditions in which the surface potential was of opposite sign to the filter). This work demonstrates that the interaction between the electrical double layers plays a critical role in the attachment of nanoparticles to flat surfaces and, in particular, that predictions of double-layer interactions are sensitive to boundary condition assumptions (constant charge vs constant potential). The experimental deposition results can be explained when using different boundary condition assumptions for different stabilizing molecules but not when the same assumption was assumed for all three types of particles. The integration of steric interactions can also explain the experimental deposition results. Particle size was demonstrated to have an effect on the predicted deposition for BPEI-stabilized particles but not for PVP.

Incentivizing Decentralized Sanitation: The Role of Discount Rates.

In adoption decisions for decentralized sanitation technologies, two decision makers are involved: the public utility and the individual homeowner. Standard life cycle cost is calculated from the perspective of the utility, which uses a market-based discount rate in these calculations. However, both decision-makers must be considered, including their differing perceptions of the time trade-offs inherent in a stream of costs and benefits. This study uses the discount rate as a proxy for these perceptions and decision-maker preferences. The results in two case studies emphasize the dependence on location of such analyses. Falmouth, Massachusetts, appears to be a good candidate for incentivizing decentralized sanitation while the Allegheny County Sanitary Authority service area in Pennsylvania appears to have no need for similar incentives. This method can be applied to any two-party decision in which the parties are expected to have different discount rates.

Comprehensive understanding of nano-sized particle separation processes using nanoparticle tracking analysis.

The understanding of nano-sized particle separation processes has been limited by difficulties of nanoparticle characterization. In this study, nanoparticle tracking analysis (NTA) was deployed to evaluate the absolute particle size distributions in laboratory scale flocculation and filtration experiments with silver nanoparticles. The results from NTA were consistent with standard theories of particle destabilization and transport. Direct observations of changes in absolute particle size distributions from NTA enhance both qualitative and quantitative understanding of particle separation processes of nano-sized particles.

Designing Solute-Tailored Selectivity in Membranes: Perspectives for Water Reuse and Resource Recovery.

Treatment of nontraditional source waters (e.g., produced water, municipal and industrial wastewaters, agricultural runoff) offers exciting opportunities to expand water and energy resources via water reuse and resource recovery. While conventional polymer membranes perform water/ion separations well, they do not provide solute-specific separation, a key component for these treatment opportunities. Herein, we discuss the selectivity limitations plaguing all conventional membranes, which include poor removal of small, neutral solutes and insufficient discrimination between ions of the same valence. Moreover, we present synthetic approaches for solute-tailored selectivity including the incorporation of single-digit nanopores and solute-selective ligands into membranes. Recent progress in these areas highlights the need for fundamental studies to rationally design membranes with selective moieties achieving desired separations.

Seasonal contamination of well-water in flood-prone colonias and other unincorporated U.S. communities.

Many of the six million residents of unincorporated communities in the United States depend on well-water to meet their needs. One group of unincorporated communities is the colonias, located primarily in several southwestern U.S. states. Texas is home to the largest number of these self-built communities, of mostly low-income families, lacking basic infrastructure. While some states have regulations that mandate minimum infrastructure for these communities, water and sewage systems are still lacking for many of their residents. Unprotected wells and self-built septic/cesspool systems serve as the primary infrastructure for many such colonias. This research was designed to probe how wells and septic/cesspool systems are influenced by heavy rainfall events. Such events are hypothesized to impact water quality with regard to human health. Inorganic and microbiological water quality of the wells in nine colonias located in Nueces County, Texas, were evaluated during dry and wet periods. Nueces County was selected as an example based on its flooding history and the fact that many colonias there depend entirely on well-water and septic/cesspool systems. The results demonstrate that well-water quality in these communities varies seasonally with respect to arsenic (up to 35 µg/L) and bacterial contamination (Escherichia coli), dependent on the amount of rainfall, which leaves this population vulnerable to health risks during both wet and dry periods. Microbial community analyses were also conducted on selected samples. To explore similar seasonal contamination of well-water, an analysis of unincorporated communities, flooding frequency, and arsenic contamination in wells was conducted by county throughout the United States. This nationwide analysis indicates that unincorporated communities elsewhere in the United States are likely experiencing comparable challenges for potable water access because of a confluence of socioeconomic, infrastructural, and policy realities.

Water Treatment: Are Membranes the Panacea?

Alongside the rising global water demand, continued stress on current water supplies has sparked interest in using nontraditional source waters for energy, agriculture, industry, and domestic needs. Membrane technologies have emerged as one of the most promising approaches to achieve water security, but implementation of membrane processes for increasingly complex waters remains a challenge. The technical feasibility of membrane processes replacing conventional treatment of alternative water supplies (e.g., wastewater, seawater, and produced water) is considered in the context of typical and emerging water quality goals. This review considers the effectiveness of current technologies (both conventional and membrane based), as well as the potential for recent advancements in membrane research to achieve these water quality goals. We envision the future of water treatment to integrate advanced membranes (e.g., mixed-matrix membranes, block copolymers) into smart treatment trains that achieve several goals, including fit-for-purpose water generation, resource recovery, and energy conservation.

Particle size distribution dynamics during precipitative softening: declining solution composition.

Particle removal is a critical step in the treatment of surface water for potable use, and the majority of drinking water treatment plants employ precipitative coagulation processes such as alum and iron "sweep-floc" coagulation or lime softening for particle pre-treatment. Unfortunately, little is quantitatively known about how particle size distributions are shaped by simultaneous precipitation and flocculation. In an earlier paper, we demonstrated the effects of the saturation ratio, the mixing intensity and the seed concentration on the rates of homogeneous nucleation, precipitative growth and flocculation during precipitation of calcium carbonate at constant solution composition using electronic particle counting techniques. In this work, we extend those findings to systems more closely emulating the conditions in actual softening processes (i.e., declining solution composition). Key findings include the strong dependence of the rate of flocculation on the initial saturation ratio and demonstration of the benefits of seeding precipitative softening from the perspective of optimizing the effluent particle size distribution. The mixing intensity during precipitation was also shown to strongly influence the final particle size distribution. Implications of the findings with respect to softening practice are discussed.

Reverse osmosis desalination: water sources, technology, and today's challenges.

Reverse osmosis membrane technology has developed over the past 40 years to a 44% share in world desalting production capacity, and an 80% share in the total number of desalination plants installed worldwide. The use of membrane desalination has increased as materials have improved and costs have decreased. Today, reverse osmosis membranes are the leading technology for new desalination installations, and they are applied to a variety of salt water resources using tailored pretreatment and membrane system design. Two distinct branches of reverse osmosis desalination have emerged: seawater reverse osmosis and brackish water reverse osmosis. Differences between the two water sources, including foulants, salinity, waste brine (concentrate) disposal options, and plant location, have created significant differences in process development, implementation, and key technical problems. Pretreatment options are similar for both types of reverse osmosis and depend on the specific components of the water source. Both brackish water and seawater reverse osmosis (RO) will continue to be used worldwide; new technology in energy recovery and renewable energy, as well as innovative plant design, will allow greater use of desalination for inland and rural communities, while providing more affordable water for large coastal cities. A wide variety of research and general information on RO desalination is available; however, a direct comparison of seawater and brackish water RO systems is necessary to highlight similarities and differences in process development. This article brings to light key parameters of an RO process and process modifications due to feed water characteristics.

Transformation kinetics of cyclophosphamide and ifosfamide by ozone and hydroxyl radicals using continuous oxidant addition reactors.

The detection of pharmaceuticals in water and wastewater has triggered human and ecological health concerns. As highly toxic compounds, chemotherapy agents (CAs), such as the cyclophosphamide (CYP) and ifosfamide (IFO) structural isomers, represent a unique threat. This research elucidated the fate of CYP and IFO during ozonation and advanced oxidation by hydroxyl radicals (HO•). Novel semi-batch reactors were used to determine the second-order rate constants for CYP and IFO with O3 and HO•. These reactors provided independent control of the oxidant exposure through continuous and constant aqueous ozone and peroxone (O3-H2O2) addition. The rate constants for transformation of CYP and IFO by ozone were 2.58 ± 0.40 M-1s-1 and 6.95 ± 0.21 M-1s-1, respectively, indicating that ozone alone is not suitable for treating CAs. Transformation of CYP and IFO by hydroxyl radicals was fast, with rate constants of 2.69(±0.17)×109 M-1s-1 and 2.73(±0.16)×109 M-1s-1, respectively. The major transformation products formed by O3 and HO attack consisted of the 4-hydroxy-, 4-keto-, dechloroethyl-, and imino- derivatives of CYP and IFO. Low yields of the active metabolites of the CAs, namely phosphoramide mustard and isophosphoramide mustard, were detected. These findings suggest that treated water may retain the ability to alkylate DNA and confer toxicity.

Particle size distribution dynamics during precipitative softening: constant solution composition.

In the treatment of surface water for potable use, precipitative coagulation (e.g., lime softening, alum or iron sweep coagulation) is widely utilized prior to particle removal processes. The particle size distribution (PSD) formed during such processes is a prime determinant of the removal efficiency for suspended and dissolved contaminants, but little is known quantitatively about how PSDs change by simultaneous precipitation and flocculation. Using precipitative softening as an example, detailed measurements of the PSD (using electronic particle counting) were made during precipitation of CaCO(3) under conditions of constant solution composition. Examination of the time-varying PSDs revealed dramatic changes resulting from nucleation, crystal growth, and flocculation. The influence of the saturation ratio, seed concentration, and mixing intensity on those processes was quantified. Implications with respect to the design and operation of water treatment facilities are discussed.

Perceived versus actual water quality: Community studies in rural Oaxaca, Mexico.

Compromised water quality risks public health, which becomes particularly acute in economically marginalized communities. Although the majority of the clean-water-deprived population resides in Sub-Saharan Africa and Asia, a significant portion (32 million) lives in Meso- and Latin-America. Oaxaca is one of the marginalized southern states of Mexico, which has experienced high morbidity from infectious diseases and also has suffered from a high rate of infant mortality. However, there has been a paucity of reports on the status of water quality of culturally diverse rural Oaxaca. This study follows community-based participatory research methods to address the data gap by reporting on water quality (chemical and microbiological) and by exploring social realities and water use practices within and among communities. Surveys and water quality analyses were conducted on 73 households in three rural communities, which were selected based on the choice of water sources (i.e., river water, groundwater, and spring water). Statistically significant variations among communities were observed including the sanitation infrastructure (p-value 0.001), public perception on water quality (p-value 0.007), and actual microbiological quality of water (p-value 0.001). Results indicate a high prevalence of diarrheal diseases, a desire to improve water quality and reduce the cost of water, and a need for education on water quality and health in all the surveyed communities. The complexities among the three studied communities highlight the need for undertaking appropriate policies and water treatment solutions.

Multilevel modeling of retention and disinfection efficacy of silver nanoparticles on ceramic water filters.

This research examined how variations in synthesis methods of silver nanoparticles affect both the release of silver from ceramic water filters (CWFs) and disinfection efficacy. The silver nanoparticles used were stabilized by four different molecules: citrate, polyvinylpyrrolidone, branched polyethylenimine, and casein. A multilevel statistical model was built to quantify if there was a significant difference in: a) extent of silver lost, b) initial amount of silver lost, c) silver lost for water of different quality, and d) total coliform removal. Experiments were performed on location at Pure Home Water, a CWF factory in Tamale, Ghana using stored rainwater and dugout water (a local surface water). The results indicated that using dugout vs. rainwater significantly affects the initial (p-value 0.0015) and sustained (p-value 0.0124) loss of silver, but that silver type does not have a significant effect. On average, dugout water removed 37.5µg/L more initial silver and had 1.1µg/L more silver in the filtrate than rainwater. Initially, filters achieved 1.9 log reduction values (LRVs) on average, but among different silver and water types this varied by as much as 2.5 LRV units. Overall, bacterial removal effectiveness was more challenging to evaluate, but some data suggest that the branched polyethylenimine silver nanoparticles provided improved initial bacterial removal over filters which were not painted with silver nanoparticles (p-value 0.038).

Fouling mechanisms in the integrated system with softening and ultrafiltration.

Softening is designed to remove hardness ions, but it can also remove NOM and particles, yielding the possibility to use the process as a pretreatment for ultrafiltration. The objectives of this research were to understand the nature of the fouling mechanisms for ultrafiltration when used for waters that either require softening or have been softened, and to use that understanding to determine promising options for the use of softening as a pretreatment before ultrafiltration. To understand fouling mechanisms in the integrated system with softening and ultrafiltration, three different levels of softening performance in terms of removal of inorganics and organic matter were selected. Experiments were performed with both natural waters and synthetic waters with similar (but separable) inorganic, organic, and particulate characteristics. The synthetic waters were used to distinguish among inorganic fouling by precipitates, organic fouling, particulate fouling, and combined fouling by particles and organic matter. The results showed that organic matter played a major role in fouling, either by itself or by adsorption onto particles, and that softening pretreatment effectively reduced the foulants prior to ultrafiltration.

The influence of hydraulic loads on depth filtration.

The influence of hydraulic loads on the detachment of particles from the collector surface or from previously retained particles was observed in a packed glass beads column. A hydraulic shock load (i.e., 20% increase of flow rate) was applied after 4 h of particle attachment at a constant flow rate. A single type of particle suspension (Min-U-Sil 5, nearly pure SiO(2)) and three different chemical conditions (pH control, alum and polymer destabilization) were utilized. The magnitude of particle detachment increased with increasing particle size for non-Brownian particles because more shear force was applied to large particles due to their large surface area. More favorable particles (i.e., particles with small surface charge) were detached to a lesser extent than unfavorable particles during the hydraulic shock loads application. This phenomenon can be caused by floc strength. In some cases, when the zeta potential of influent particles was relatively high, the magnitude of detachment of bigger particles (e.g., 4.0-5.0 µm) was less than that of smaller particles (e.g., 3.0-4.0 µm). This can be attributable to the breakup of detached flocs as an individual particle. It was also found that the shape of the curve relating the magnitude of particle detachment and particle size can be concave, linear, or convex depending on physicochemical conditions such as floc strength.

Competitive separation of di- vs. mono-valent cations in electrodialysis: effects of the boundary layer properties.

In electrodialysis desalination, the boundary layer near ion-exchange membranes is the limiting region for the overall rate of ionic separation due to concentration polarization over tens of micrometers in that layer. Under high current conditions, this sharp concentration gradient, creating substantial ionic diffusion, can drive a preferential separation for certain ions depending on their concentration and diffusivity in the solution. Thus, this study tested a hypothesis that the boundary layer affects the competitive transport between di- and mono-valent cations, which is known to be governed primarily by the partitioning with cation-exchange membranes. A laboratory-scale electrodialyzer was operated at steady state with a mixture of 10mM KCl and 10mM CaCl(2) at various flow rates. Increased flows increased the relative calcium transport. A two-dimensional model was built with analytical solutions of the Nernst-Planck equation. In the model, the boundary layer thickness was considered as a random variable defined with three statistical parameters: mean, standard deviation, and correlation coefficient between the thicknesses of the two boundary layers facing across a spacer. Model simulations with the Monte Carlo method found that a greater calcium separation was achieved with a smaller mean, greater standard deviation, or more negative correlation coefficient. The model and experimental results were compared for the cationic transport number as well as the current and potential relationship. The mean boundary layer thickness was found to decrease from 40 to less than 10 µm as the superficial water velocity increased from 1.06 to 4.24 cm/s. The standard deviation was greater than the mean thickness at slower water velocities and smaller at faster water velocities.

Laccase-catalyzed oxidation of oxybenzone in municipal wastewater primary effluent.

Pharmaceuticals and personal care products (PPCPs) are now routinely detected in raw and treated municipal wastewater. Since conventional wastewater treatment processes are not particularly effective for PPCP removal, treated wastewater discharges are the main entry points for PPCPs into the environment, and eventually into our drinking water. This study investigates the use of laccase-catalyzed oxidation for removing low concentrations of PPCPs from municipal wastewater primary effluent. Oxybenzone was selected as a representative PPCP. Like many other PPCPs, it is not recognized directly by the laccase enzyme. Therefore, mediators were used to expand the oxidative range of laccase, and the efficacy of this laccase-mediator system in primary effluent was evaluated. Eight potential mediators were investigated, and 2,2'-Azino-bis(3-ethylbenzthiazoline-6sulphonic acid) diammonium salt (ABTS), a synthetic mediator, and acetosyringone (ACE), a natural mediator, provided the greatest oxybenzone removal efficiencies. An environmentally relevant concentration of oxybenzone (43.8 nM, 10 µg/L) in primary effluent was completely removed (below the detection limit) after two hours of treatment with ABTS, and 95% was removed after two hours of treatment with ACE. Several mediator/oxybenzone molar ratios were investigated at two different initial oxybenzone concentrations. Higher mediator/oxybenzone molar ratios were required at the lower (environmentally relevant) oxybenzone concentration, and ACE required higher molar ratios than ABTS to achieve comparable oxybenzone removal. Oxybenzone oxidation byproducts generated by the laccase-mediator system were characterized and compared to those generated during ozonation. Enzymatic treatment generated byproducts with higher mass to charge (m/z) ratios, likely due to oxidative coupling reactions. The results of this study suggest that, with further development, the laccase-mediator system has the potential to extend the treatment range of laccase to PPCPs not directly recognized by the enzyme, even in a primary effluent matrix.