Quantitative Microbial Risk Assessment Framework Incorporating Water Ages with Legionella pneumophila Growth Rates.

Water age in drinking water systems is often used as a proxy for water quality but is rarely used as a direct input in assessing microbial risk. This study directly linked water ages in a premise plumbing system to concentrations of Legionella pneumophila via a growth model. In turn, the L. pneumophila concentrations were used for a quantitative microbial risk assessment to calculate the associated probabilities of infection (Pinf) and clinically severe illness (Pcsi) due to showering. Risk reductions achieved by purging devices, which reduce water age, were also quantified. The median annual Pinf exceeded the commonly used 1 in 10,000 (10-4) risk benchmark in all scenarios, but the median annual Pcsi was always 1-3 orders of magnitude below 10-4. The median annual Pcsi was lower in homes with two occupants (4.7 × 10-7) than with one occupant (7.5 × 10-7) due to more frequent use of water fixtures, which reduced water ages. The median annual Pcsi for homes with one occupant was reduced by 39-43% with scheduled purging 1-2 times per day. Smart purging devices, which purge only after a certain period of nonuse, maintained these lower annual Pcsi values while reducing additional water consumption by 45-62%.

Design and operational considerations in response to Legionella occurrence in Las Vegas Valley groundwater.

Legionella occurrence monitoring is not required by United States Environmental Protection Agency (USEPA) drinking water regulations, and few occurrence studies exist for Legionella in source water or distribution systems. Legionella occurrence was monitored in Las Vegas Valley (Las Vegas, Nevada, USA) drinking water sources, including non-treated surface water, seasonal groundwater (61 wells, before and after chlorination), finished water (after treatment at water treatment facilities), and chlorinated distribution system water (at 9 reservoirs and 75 sample locations throughout the network). Legionella pneumophila was detected at least once at each of the wells sampled before chlorination, with an overall positivity rate of 38% (343/908). During well start-up (time<2 hours; turbidity>3 NTU), L. pneumophila concentrations averaged 2,792±353 MPN/100 mL, with a median of 105 MPN/100 mL, and range of <1 to 90,490 MPN/100 mL across 61 seasonally operated (typically April-October) groundwater wells. After initial flushing (turbidity<3 NTU), the average concentration decreased by more than two orders of magnitude to 24±3 MPN/100 mL but ranged from <1 to >2,273 MPN/100 mL. This trend indicates that stagnation (up to 391 days) contributed to greater initial concentrations, and flushing alone was incapable of complete L. pneumophila elimination. L. pneumophila concentration was significantly, positively correlated with total aqueous adenosine triphosphate (ATP) (p<0.00001, r=0.41-0.71), turbidity (p<0.00001, r=0.27-0.51), orthophosphate (p=0.35-0.076, r=0.51-0.59), and pump depth (p=0.032, r=0.40). During a full-scale assessment of chlorination (Ct=0.7 to 10.5 mg-min/L; T=26.6-28.1°C), substantial reduction of Legionella spp. (up to 2.5 logs) was observed; although, detectable concentrations were still measured. Extrapolating from a Chick-Watson model (log inactivation=0.28*(Ct); R2=0.87) constructed from the full-scale chlorination results, 3- and 4-log inactivation in Las Vegas Valley groundwater would require 10.8 and 14.3 mg-min/L, respectively; at least 3-log inactivation was required to bring Legionella spp. to below detection at the studied well. Chlorine exposure (Ct=0.1 to 10.9 mg-min/L) at most wells discharging directly to the distribution system was insufficient to fully inactivate Legionella spp. After discussing these findings with the state regulatory agency, direct-to-distribution wells (38 of 61 wells) remained out of operation; the distribution system, wells, and reservoirs were monitored for Legionella and chlorine residual, and additional treatment scenarios were identified for further evaluation. Legionella was either not detected or was well controlled in surface water, finished effluent from the drinking water treatment plant, chlorinated reservoirs, and the chlorinated distribution system. This study emphasizes the importance of utility-driven, non-regulatory research in order to protect public health and also identifies the need for greater occurrence monitoring and guidance for Legionella in groundwater supplies.

2-Aminoimidazole Reduces Fouling and Improves Membrane Performance.

Biofouling is difficult to control and hinders the performance of membranes in all applications but is of particular concern when natural waters are purified. Fouling, via multiple mechanisms (organic-only, biofouling-only, cell-deposition-only, and organic+biofouling), of a commercially available membrane (control) and a corresponding membrane coated with an anti-biofouling 2-aminoimidazole (2-AI membrane) was monitored and characterized during the purification of a natural water. Results show that the amount of bacterial cell deposition and organic fouling was not significantly different between control and 2-AI membranes; however, biofilm formation, concurrent or not with other fouling mechanisms, was significantly inhibited (95-98%, p<0.001) by the 2-AI membrane. The limited biofilm that formed on the 2-AI membrane was weaker (as indicated by the polysaccharide to protein ratio) and thus presumably easier to remove. The conductivity rejection by the 2-AI and control membranes was not significantly different throughout the 75-hour experiments, but the rejection of dissolved organic carbon by biofouled (biofouling-only, cell-deposition-only, and organic+biofouling) 2-AI membranes was statistically higher (10-12%, p=0.003-0.07). When biofouled, the water permeance of the 2-AI membranes decreased significantly less (p<0.05) over 75 hours than that of the control membranes, whether or not other additional types of fouling occurred concurrently. Despite the initially lower water permeances of 2-AI membranes (11% lower on average than controls), the 2-AI membranes outperformed the controls (10-11% higher average water permeance) after biofilm formation occurred. Overall, 2-AI membranes fouled less than controls without detriment to water productivity and solute rejection.

Fit-for-purpose treatment goals for produced waters in shale oil and gas fields.

Hydraulic fracturing (HF), or "fracking," is the driving force behind the "shale gas revolution," completely transforming the United States energy industry over the last two decades. HF requires that 4-6 million gallons per well (15,000-23,000 m3/well) of water be pumped underground to stimulate the release of entrapped hydrocarbons from unconventional (i.e., shale or carbonate) formations. Estimated U.S. produced water volumes exceed 150 billion gallons/year across the industry from unconventional wells alone and are projected to grow for at least another two decades. Concerns over the environmental impact from accidental or incidental release of produced water from HF wells ("U-PW"), along with evolving regulatory and economic drivers, has spurred great interest in technological innovation to enhance U-PW recycling and reuse. In this review, we analyze U-PW quantity and composition based on the latest U.S. Geographical Survey data, identify key contamination metrics useful in tracking water quality improvement in the context of HF operations, and suggest "fit-for-purpose treatment" to enhance cost-effective regulatory compliance, water recovery/reuse, and resource valorization. Drawing on industrial practice and technoeconomic constraints, we further assess the challenges associated with U-PW treatment for onshore U.S. operations. Presented are opportunities for targeted end-uses of treated U-PW. We highlight emerging technologies that may enhance cost-effective U-PW management as HF activities grow and evolve in the coming decades.

Nanobubble Technologies Offer Opportunities To Improve Water Treatment.

Since first hypothesizing the existence of nanobubbles (NBs) in 1994, the empirical study of NB properties and commercialization of NB generators have rapidly evolved. NBs are stable spherical packages of gas within liquid and are operationally defined as having diameters less than 1000 nm, though they are typically in the range of 100 nm in one dimension. While theories still lack the ability to explain empirical evidence for formation of stable NBs in water, numerous NB applications have emerged in different fields, including water and wastewater purification where NBs offer the potential to replace or improve efficiency of current treatment processes. The United Nations identifies access to safe drinking water as a human right, and municipal and industrial wastewaters require purification before they enter water bodies. These protections require treatment technologies to remove naturally occurring (e.g., arsenic, chromium, fluoride, manganese, radionuclides, salts, selenium, natural organic matter, algal toxins), or anthropogenic (e.g., nitrate, phosphate, solvents, fuel additives, pharmaceuticals) chemicals and particles (e.g., virus, bacteria, oocysts, clays) that cause toxicity or aesthetic problems to make rivers, lakes, seawater, groundwater, or wastewater suitable for beneficial use or reuse in complex and evolving urban and rural water systems. NBs raise opportunities to improve current or enable new technologies for producing fewer byproducts and achieving safer water. This account explores the potential to exploit the unique properties of NBs for improving water treatment by answering key questions and proposing research opportunities regarding (1) observational versus theoretical existence of NBs, (2) ability of NBs to improve gas transfer into water or influence gas trapped on particle surfaces, (3) ability to produce quasi-stable reactive oxygen species (ROS) on the surface of NBs to oxidize pollutants and pathogens in water, (4) ability to improve particle aggregation through intraparticle NB bridging, and (5) ability to mitigate fouling on surfaces. We conclude with key insights and knowledge gaps requiring research to advance the use of NBs for water purification. Among the highest priorities is to develop techniques that measure NB size and surface properties in complex drinking and wastewater chemistries, which contain salts, organics, and a wide variety of inorganic and organic colloids. In the authors' opinion, ROS production by NB may hold the greatest promise for usage in water treatment because it allows movement away from chemical-based oxidants (chlorine, ozone) that are costly, dangerous to handle, and produce harmful byproducts while helping achieve important treatment goals (e.g., destruction of organic pollutants, pathogens, biofilms). Because of the low chemical requirements to form NBs, NB technologies could be distributed throughout rapidly changing and increasingly decentralized water treatment systems in both developed and developing countries.

Lower molecular weight fractions of PolyDADMAC coagulants disproportionately contribute to N-nitrosodimethylamine formation during water treatment.

N-nitrosodimethylamine (NDMA) is a chloramine disinfection by-product, and its formation in drinking waters can increase due to the addition of cationic polydiallyldimethylammonium chloride (polyDADMAC). PolyDADMAC is a cationic polymer added as a coagulant or coagulant aid to enhance turbidity removal during sedimentation and filtration. This paper answers two central questions to understanding the nature of the NDMA precursors in polyDADMAC. First, what is the reactivity of different molecular weight (MW) fractions of polyDADMAC with chloramines? NDMA formation potential (NDMAFP) and kinetic experiments with chloramines were conducted for non-fractionated (raw) and size-excluded fractions (<3K, 3-10K, and >10K Da.) of polyDADMAC. The lower MW fraction (<3K Da.) of polyDADMAC solutions was responsible for forming 64 ±â€¯6% of the NDMA, despite containing only 8.7 and 9.8% of the carbon or nitrogen present in the bulk polymer. The chloramine demand kinetics of the lowest MW fraction were also >2× faster than the higher MW fractions. Therefore, in a water treatment application the lower MW polyDADMAC likely contributes to most of the NDMA attributed to the use of polyDADMAC. The second question was: can 1H and 13C nuclear magnetic resonance spectroscopy (NMR) be used to characterize the molecular structures in polyDADMAC that react with chloramines? A peak for 1H NMR dimethylamine (DMA), a known low MW NDMA precursor, was found in a commercial polyDADMAC solution and decreased upon chloramination. The estimated DMA alone could not account for the observed NDMAFP, indicating the presence of other low MW precursors. Diffusion order spectroscopy (DOSY) NMR also showed multiple lower MW organics in polyDADMAC that change upon chloramination, including a 1.5× decrease in MW, suggesting chloramines cleave CC or CN bonds. These reactions may produce intermediates responsible for NDMA formation. Polymer manufacturers could use NMR to synthesize polyDADMAC with less DMA and other low MW compounds that produce NDMA upon chloramination.

Low risk posed by engineered and incidental nanoparticles in drinking water.

Natural nanoparticles (NNPs) in rivers, lakes, oceans and ground water predate humans, but engineered nanoparticles (ENPs) are emerging as potential pollutants due to increasing regulatory and public perception concerns. This Review contrasts the sources, composition and potential occurrence of NNPs (for example, two-dimensional clays, multifunctional viruses and metal oxides) and ENPs in surface water, after centralized drinking water treatment, and in tap water. While analytical detection challenges exist, ENPs are currently orders of magnitude less common than NNPs in waters that flow into drinking water treatment plants. Because such plants are designed to remove small-sized NNPs, they are also very good at removing ENPs. Consequently, ENP concentrations in tap water are extremely low and pose low risk during ingestion. However, after leaving drinking water treatment plants, corrosion by-products released from distribution pipes or in-home premise plumbing can release incidental nanoparticles into tap water. The occurrence and toxicity of incidental nanoparticles, rather than ENPs, should therefore be the focus of future research.

Polyacrylonitrile-based carbonized fibers and metal-carbonized fiber nanocomposites for thermal transport.

This work examines the fabrication and thermal analysis of metal-carbon composite fibers prepared via an electrospinning process. The metal-carbon composite fibers of silver, copper, gold, and nickel were prepared by electrospinning of a composite solution of polyacrylonitrile (PAN) and metal precursor followed by heat treatment in air, nitrogen to 1000 degrees C and in 6% H2, respectively. Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Fourier Transform Infrared Spectroscopy (FTIR), Energy dispersive spectroscopy (EDS) and Scanning thermal microscopy (SThM) were applied to characterize the metal-carbon fibers. TEM analysis showed a relatively uniform, contact-free distribution of the nanoparticles on the surface of the carbon fibers with size range of 3 nm-10 nm. Thermal analysis data showed an enhancement in the thermal conductivity of the nanomaterials when compared with the model PAN-based carbonized fibers. This was attributed to the incorporation of metal nanoparticles in the fiber matrix and on the surface.

Methods for describing the electromagnetic properties of silver and gold nanoparticles.

This Account provides an overview of the methods that are currently being used to study the electromagnetics of silver and gold nanoparticles, with an emphasis on the determination of extinction and surface-enhanced Raman scattering (SERS) spectra. These methods have proven to be immensely useful in recent years for interpreting a wide range of nanoscience experiments and providing the capability to describe optical properties of particles up to several hundred nanometers in dimension, including arbitrary particle structures and complex dielectric environments (adsorbed layers of molecules, nearby metal films, and other particles). While some of the methods date back to Mie's celebrated work a century ago, others are still at the forefront of algorithm development in computational electromagnetics. This Account gives a qualitative description of the physical and mathematical basis behind the most commonly used methods, including both analytical and numerical methods, as well as representative results of applications that are relevant to current experiments. The analytical methods that we discuss are either derived from Mie theory for spheres or from the quasistatic (Gans) model as applied to spheres and spheroids. In this discussion, we describe the use of Mie theory to determine electromagnetic contributions to SERS enhancements that include for retarded dipole emission effects, and the use of the quasistatic approximation for spheroidal particles interacting with dye adsorbate layers. The numerical methods include the discrete dipole approximation (DDA), the finite difference time domain (FDTD) method, and the finite element method (FEM) based on Whitney forms. We discuss applications such as using DDA to describe the interaction of two gold disks to define electromagnetic hot spots, FDTD for light interacting with metal wires that go from particle-like plasmonic response to the film-like transmission as wire dimension is varied, and FEM studies of electromagnetic fields near cubic particles.

Designing, fabricating, and imaging Raman hot spots.

We have developed a probe of the electromagnetic mechanism of surface-enhanced Raman scattering via Au nanodisk arrays generated by using on-wire lithography. In this approach, disk thickness and interparticle gap are precisely controlled from 5 nm to many micrometers. Confocal Raman microscopy demonstrates that disk thickness and gap play a crucial role in determining surface-enhanced Raman scattering intensities. Theoretical calculations also demonstrate that these results are consistent with the electromagnetic mechanism, including the surprising result that the largest enhancement does not occur for the smallest gaps.