JOURNAL OF ENVIRONMENTAL ENGINEERING

Modeling Nicotine-Induced Chlorine Loss in Drinking Water Using Updated EPANET-MSX
Burkhardt JB, Burkhart B and Shang F
Multispecies water quality modeling is critical for simulating complex chemical reactions in drinking water distribution systems. An updated EPANET 2.2-compatible version of EPANET multi-species eXtension (EPANET-MSX) was used, which included dispersion and improved mass balance reporting, to simulate an experimental study. The use of EPANET-MSX was supplemented by an automated Python script to process experimental data, handle model execution, and analyze results. Nicotine-associated chlorine loss in drinking water-initially investigated from a drinking water security perspective-modeled with EPANET-MSX was compared with bottle test and test injection data. Two reaction models were tested (with and without a reactive intermediate), and the model that included a reactive intermediate nicotine species using dispersion was found to produce the best model agreement with experimental data. These results provide a demonstration of the new features within EPANETMSX in the context of the nicotine-chlorine reaction.
Assessment of Municipal Solid-Waste Landfill Liner Performance
Jain P, Winslow KM, Townsend TG, Krause M and Tolaymat TM
The leachate collection system (LCS) and leak detection system (LDS) flow rate data from 240 cells (or a combination of cells) at 54 municipal solid-waste landfills (located in seven US states) with double-liner systems were analyzed to assess the performance of the primary liner system. The average LCS leachate collection rates for the study sites ranged from 380 L ha day (40.7 gal. acre day) to 22,400 L ha day (2,390 gal. acre day) on a sitewide basis, and the average LDS leachate collection rates ranged from 1.8 L ha day (0.2 gal. acre day) to 577 L ha day (61.7 gal. acre day) on a sitewide basis. Assuming all leachate generated is collected either by the LCS or LDS, the data suggest that the primary liner systems' aggregated efficiency is over 98%. The collection efficiency at sites that used a composite liner (geomembrane underlain by a geosynthetic clay liner or a compacted clay liner) system was not statistically different from the sites that used only a geomembrane as the primary liner (geomembrane underlain by a permeable layer) (median of 99% for both types). Leakage rates were compared with those estimated from the equations used by the hydrologic evaluation of landfill performance (HELP) model. The comparison suggests that the equations used by the HELP model to estimate leakage through the liner overestimate the leakage rate through geomembrane primary liners but underestimate the leakage rate through composite primary liners based on the HELP-model-default defect size and suggested defect frequency. It is also possible that groundwater intrusion could contribute to a portion of the leachate collected from the LDS because leachate quality data collected from a few sites indicated the LCS leachate had a higher concentration of most constituents than the leachate collected from LDS.
Flushing Home Plumbing Pipes Contaminated with Aqueous Film-Forming Foam Containing Per- and Polyfluoroalkyl Substances
Szabo J, Witt S, Sojda N, Schupp D and Magnuson M
Per- and polyfluoroalkyl substances (PFAS) from aqueous film forming foam (AFFF) can be accidentally backflushed into drinking water systems during firefighting operations or at industrial facilities. If this contaminated water enters household plumbing systems, homeowners may need to decontaminate their plumbing. This study examines the persistence of PFAS from AFFF on home plumbing, along with the effects of flushing and stagnation. Two sources of AFFF were investigated, representing older formulations (that contain longer chain PFAS) and newer formulations (that contain shorter chain PFAS). Experiments were conducted in copper, polyvinyl chloride (PVC), and cross-linked polyethylene (PEX) pipes with flushing after contamination followed by intermittent flow and periods of stagnation meant to mimic typical household use. Flushing immediately reduced the PFAS concentration in water leaving the pipe by 99.95% to 99.99%. However, PFAS concentration increased after periods of stagnation, corresponding to slow release of adhered PFAS. Flushing may be a valuable part of the decontamination process, but flushing parameters and duration need to be optimized for local conditions.
Investigation of Chloramines, Disinfection Byproducts, and Nitrification in Chloraminated Drinking Water Distribution Systems
Abulikemu G, Mistry JH, Wahman DG, Alexander MT, Kennicutt AR, Bollman JD and Pressman JG
Four chloraminated drinking water distribution systems (CDWDSs) required to maintain numeric versus "detectable" residuals were spatially and temporally sampled for water quality and associated trihalomethane (THM) and haloacetic acid (HAA) formation. Monochloramine decreased from entry point (EP) to maximum residence time (MRT) samples while THMs and HAAs initially increased and then stabilized or slightly decreased. Subsequently, EP and MRT samples were used in laboratory-held studies to further evaluate disinfectant residual stability, chloramine speciation, and nitrification occurrence. MRT water exhibited a faster monochloramine concentration decline compared to EP water, indicating a decreasing disinfectant residual stability from increasing water age through distribution. Using a simple technique based on published inorganic chloramine chemistry, samples were also investigated for nondisinfectant positive interference (NDPI) on total chlorine measurements. NDPI concentrations represented up to 100% of the total chlorine concentration when total chlorine concentrations decreased to 0.05 mg-Cl/L, indicating little to no effective disinfectant residual remained.
Apparent Reactivity of Bromine in Bromochloramine Depends on Synthesis Method: Implicating Bromine Chloride and Molecular Bromine as Important Bromine Species
Brodfuehrer SH, Goodman JB, Wahman DG, Speitel GE and Katz LE
The chloramination of bromide containing waters results in the formation of bromine containing haloamines: monobromamine (NHBr), dibromamine (NHBr), and bromochloramine (NHBrCl). Many studies have directly shown that bromamines are more reactive than chloramines in oxidation and substitution reactions with organic water constituents because the bromine atom in oxidants is more labile than the chlorine atom. However, similar studies have not been performed with NHBrCl. It has been assumed that NHBrCl has similar reactivity as bromamines with organic constituents in both oxidation and substitution reactions because NHBrCl, like bromamines, rapidly oxidizes N,N-diethyl-p-phenylenediamine. In this study, we examined the reactivity of NHBrCl with phenol red to determine if NHBrCl reacts as readily as bromamines in an isolated substitution reaction. NHBrCl was synthesized two ways to assess whether NHBrCl or the highly reactive intermediates, bromine chloride (BrCl) and molecular bromine (Br), were responsible for bromine substitution of phenol red. NHBrCl was found to be much less reactive than bromamines with phenol red and that BrCl and Br appeared to be the true brominating agents in solutions where NHBrCl is formed. This work highlights the need to reexamine what the true brominating agents are in chloraminated waters containing bromide.
Evaluation of the Immobilization of Coexisting Heavy Metal Ions of Pb, Cd , and Zn from Water by Dairy Manure-Derived Biochar: Performance and Reusability
Wallace AR, Su C, Sexton M and Sun W
Heavy metals including Cd, Pb, and Zn are prevalent stormwater and groundwater contaminants derived from natural and human activities, and there is a lack of cost-effective treatment for their removal. Recently, biochar has been increasingly recognized as a promising low-cost sorbent that can be used to remediate heavy metal contaminated water. This study evaluates the immobilization/release performance of dairy manure-derived biochar (DM-BC) as a sustainable material for competitive removal of coexisting heavy metal ions from water and explains the underlying mechanism for regeneration/reusability of biochar. Results showed that the metal ions exhibited competitive removal in the order of Pb ≫ Zn > Cd. The pH played a decisive role in influencing metal ion speciation affecting the electrostatic attraction/repulsion and surface complexation. Higher pH led to greater removal for Pb and Cd, whereas Zn showed maximum removal at pH ≈ 7.5. Diffuse reflectance infrared spectroscopy, scanning electron microscopy, and X-ray diffraction confirmed the interactions and precipitation reactions of oxygen-containing functional groups (e.g., ─OH, , and Si─O) as key participants in metal immobilization. Langmuir, Freundlich, and Redlich-Peterson isotherm modeling data showed varied and unique results depending on the metal ion and concentration. The removal kinetics and model fitting showed that the three steps of intraparticle diffusion might be more representative for describing the immobilization processes of metal ions on the external surface and internal pores. In the flow-through columns, DM-BC effectively retained the mixed metal ions of Cd, Pb, and Zn showing 100% removal for the duration of the column run over three cycles of regeneration and reuse.
Supercritical Water Oxidation as an Innovative Technology for PFAS Destruction
Krause MJ, Thoma E, Sahle-Damesessie E, Crone B, Whitehill A, Shields E and Gullett B
Water above 374 °C and 22.1 MPa, becomes supercritical, a special state where organic solubility increases and oxidation processes are accelerated. Supercritical water oxidation (SCWO) has been previously shown to destroy hazardous substances such as halogenated compounds. Three separate providers of SCWO technology were contracted to test the efficacy of SCWO systems to reduce per- and poly-fluoroalkyl substances (PFAS) concentrations from solutions of dilute aqueous film-forming foam (AFFF). The findings of all three demonstration studies, showed greater than 99% reduction of the total PFAS identified in a targeted-compound analysis, including perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). PFOS was reduced from 26.2 mg/L to 240 μg/L, 30.4 mg/L to 0.310 μg/L, and 190 mg/L to 8.57 μg/L, from the Aquarden, Battelle, and 374Water demonstrations, respectively. Similarly, PFOA was reduced from 930 to 0.14 μg/L, 883 to 0.102 μg/L, and 3,100 μg/L to non-detect in the three evaluations. Additionally, chemical oxygen demand of the dilute AFFF was shown to reduce from 4,750 to 5.17 mg/L after treatment, indicating significant organic compound destruction. In one demonstration, a mass balance of the influent and effluent found that the targeted compounds accounted for only 27% of the generated fluoride, suggesting that more PFAS were destroyed than measured and emphasizing the limitations of targeted analysis alone. As a destructive technology, SCWO may be an alternative to incineration and could be a permanent solution for PFAS-laden wastewaters rather than disposal by injection into a deep-well or landfilling. Additional investigation of reaction by-products remains to be conducted for a complete assessment of SCWO's potential as a safe and effective PFAS treatment technology.
Removal of Fluoride from Water Using a Calcium-Modified Dairy Manure-Derived Biochar
Wallace AR, Su C, Choi YK, Kan E and Sun W
This study investigated the removal of fluoride from water using a calcium-modified dairy manure-derived biochar (Ca-DM500). The Ca-DM500 showed a 3.82 - 8.86 times higher removal of fluoride from water than the original (uncoated) manure-derived biochar (DM500). This is primarily attributed to strong precipitation/complexation between fluoride and calcium. The Freundlich and Redlich-Peterson sorption isotherm models better described the experimental data than the Langmuir model. Additionally, the removal kinetics were well described by the intraparticle diffusion model. The Ca-DM500 showed high reactivity per unit surface area [0.0001, 0.03, 0.16 mg F per m for Douglas fir-derived biochar (DF-BC), DM500. and Ca-DM500, respectively] for retention of fluoride reflecting the importance of surface complexation. The copresence of anions reduced removal by Ca-DM500 in the order . The sorption behavior of fluoride in a continuous fixed-bed column was consistent with the Thomas model. Column studies demonstrated that the Ca-DM500 shows a strong affinity for fluoride, a low release potential, and a stable (unreduced) removal capacity through regeneration and reuse cycles.
Numerical Model for Decontamination of Organic Contaminants in Polyethylene Drinking Water Pipes in Premise Plumbing by Flushing
Haupert LM and Magnuson ML
Polymeric materials such as polyethylene are used extensively for indoor drinking water applications. These materials are subject to permeation by organic compounds such as those found in petroleum products and industrial chemicals, which can result in water quality issues with potential health effects. Although flushing is a common decontamination technique, disagreements and knowledge gaps in the scientific literature complicate prediction of how much flushing may be required to address organic contamination incidents. This paper utilizes a numerical solution to the diffusion equation to predict flushing decontamination times for toluene in cross-linked polyethylene tubing. Results suggest that for premise plumbing materials typically used for indoor drinking water applications, contaminated polyethylene tubing can be resistant to decontamination by flushing, possibly requiring days of continuous flushing to achieve contaminant removal to below regulatory levels.
Signal Decomposition of Conductivity Sensor Measurements on the Allegheny River, Pennsylvania
Brown KJ, Norris GA, Kovalcik KD, Kamal AS, Patnode K and Landis MS
Surface water conductivity measurements were used to evaluate the combined contribution of anions in western Pennsylvania from brines discharged by sources such as oil and gas wastewater treatment, coal-fired power plants, and coal mining activities. Conductivity sensor data were collected in the Allegheny River during a US Environmental Protection Agency and US Fish and Wildlife study that included seven sites covering 256 river km during the fall of 2012. Intermittent discharges, such as oil and gas wastewater, and continuous sources contributing to the conductivity were quantified using constrained and adaptive decomposition of time-series (CADETS) frequency analysis. CADETS was able to quantify the intermittent or short-term component of conductivity at sites where the intermittent fraction was 1 to 22% of the total conductivity. The demonstrated efficacy of the CADETS method for surface water quality analysis suggests it could be widely used to evaluate other water sensor data in rivers with both continuous and intermittent source impacts.
Reflection on Molecular Approaches Influencing State-of-the-Art Bioremediation Design: Culturing to Microbial Community Fingerprinting to Omics
Czaplicki LM and Gunsch CK
Bioremediation is generally viewed as a cost effective and sustainable technology because it relies on microbes to transform pollutants into benign compounds. Advances in molecular biological analyses allow unprecedented microbial detection and are increasingly incorporated into bioremediation. Throughout history, state-of-the-art techniques have informed bioremediation strategies. However, the insights those techniques provided were not as in depth as those provided by recently developed omics tools. Advances in next generation sequencing (NGS) have now placed metagenomics and metatranscriptomics within reach of environmental engineers. As NGS costs decrease, metagenomics and metatranscriptomics have become increasingly feasible options to rapidly scan sites for specific degradative functions and identify microorganisms important in pollutant degradation. These omic techniques are capable of revolutionizing biological treatment in environmental engineering by allowing highly sensitive characterization of previously uncultured microorganisms. Omics enables the discovery of novel microorganisms for use in bioaugmentation and supports systematic optimization of biostimulation strategies. This review describes the omics journey from roots in biology and medicine to its current status in environmental engineering including potential future directions in commercial application.
Characterization of Turbulent Properties in the EPA Baffled Flask for Dispersion Effectiveness Testing
Zhao L, Wang B, Armenante PM, Conmy R and Boufadel MC
The baffled flask test (BFT) has been proposed by United States Environmental Protection Agency to be adopted as the official standard protocol for testing dispersant effectiveness. The mixing energy in the baffled flask is investigated in this paper. Particle image velocimetry (PIV) was used to measure the water velocity in the flask placed at an orbital shaker that was rotated at seven rotation speeds: 100, 125, 150, 160, 170, 200, and 250 rpm. Two dimensional velocity fields in large and small vertical cross sections of the flask for each rotation speed were obtained. The one-dimensional (1D) energy spectra indicates the existence of inertial subrange. The estimated average energy dissipation rates were in the range 7.65×10 to 4 W/kg for rotation speeds of Ω=100-250 rpm, of which it is larger than the one estimated by prior studies using single-point velocity measurement techniques for Ω=100 and 200 rpm. Factors such as instruments used, velocity components measured, and different analysis methods could contribute to the discrepancies in the results. The Kolmogorov scale estimated in this study for all seven rotation speeds approached the size of oil droplets observed at sea, which is 50-400 μm. The average energy dissipation rate, ε and Kolmogorov microscale, η, in the flasks were correlated to the rotation speed, and it was found that Exp (0.043Ω) with = 0.97 and Exp (-0.015Ω) with = 0.98.
Coliform Sources and Mechanisms for Regrowth in Household Drinking Water in Limpopo, South Africa
Mellor JE, Smith JA, Samie A and Dillingham RA
Resource-limited communities throughout the developing world face significant environmental health problems related to the myriad of coliform sources within those communities. This study comprehensively investigated contamination sources and the biological and chemical mechanisms sustaining them in two adjacent communities in rural Limpopo, South Africa. An 8-month study was conducted of household ( = 14) and source water quality, measurements of biofilm layers on the inside of household water storage containers and water transfer devices, and also hand-based coliforms and hand-washing effectiveness. A 7-day water container incubation experiment was also performed to determine the biological and chemical changes that occur in a household water storage container independent of human interference. Results indicate that household drinking water frequently becomes contaminated after collection but before consumption (197 versus 1,046 colony-forming units/100 mL; = 266; < 0.001). The most important contamination sources include biofilm layers on the inside of storage containers (1.85 ± 1.59 colony-forming units/cm; = 44), hands (5,097 ± 2,125 colony-forming units/hand; = 48), and coliform regrowth resulting from high assimilable organic carbon (AOC) levels during storage. A maximum specific growth rate, , of 0.072 ± 0.003 h was determined for total coliform bacteria on AOC, and a high correlation between AOC concentrations and the growth potential of total coliform bacteria was observed. These results support the implementation of point-of-use water treatment and other interventions aimed at maintaining the safe water chain and preventing biological regrowth.
Comparison of Hollow-Fiber Ultrafilters with Pleated Capsule Filters for Surface and Tap Water Samples Using U.S. EPA Method 1623
Kimble GH, Amburgey JE and Hill VR
The EPA method 1623 is designed specifically for the detection of and , but the method has some issues with low and variable recoveries. Ultrafiltration has been used effectively for microorganism recovery from water samples but is not approved by the EPA. To determine the efficacy of using ultrafiltration, 10-L tap water and surface water samples were seeded with and and concentrated with either a pleated capsule filter or a hollow-fiber ultrafilter. For , oocyst recovery in tap water was significantly higher for ultrafiltration (68%) versus the capsule filter (37%); ultrafiltration recovered 65% of oocysts in surface water versus 61% for the capsule filter. However, cyst recovery was mixed. In tap water, the capsule filter produced a significantly better recovery (85%) of compared with ultrafiltration (63%), but the surface water ultrafiltration recovery (81%) was significantly better than the capsule filter recovery (40%). Overall, ultrafiltration recoveries were equal to or better for , but recoveries of were varied depending on the filter used and the type of water analyzed.
Evaluating the Mobility of Arsenic in Synthetic Iron-containing Solids Using a Modified Sequential Extraction Method
Shan J, Sáez AE and Ela WP
Many water treatment technologies for arsenic removal that are used today produce arsenic-bearing residuals which are disposed in non-hazardous landfills. Previous works have established that many of these residuals will release arsenic to a much greater extent than predicted by standard regulatory leaching tests (e.g. the toxicity characteristic leaching procedure, TCLP) and, consequently, require stabilization to ensure benign behavior after disposal. In this work, a four-step sequential extraction method was developed in an effort to determine the proportion of arsenic in various phases in untreated as well as stabilized iron-based solid matrices. The solids synthesized using various potential stabilization techniques included: amorphous arsenic-iron sludge (ASL), reduced ASL via reaction with zero valent iron (RASL), amorphous ferrous arsenate (PFA), a mixture of PFA and SL (M1), crystalline ferrous arsenate (HPFA), and a mixture of HPFA and SL (M2). The overall arsenic mobility of the tested samples increased in the following order: ASL > RASL > PFA > M1 > HPFA > M2.
Synthetic Musk Fragrances in a Conventional Drinking Water Treatment Plant with Lime Softening
Wombacher WD and Hornbuckle KC
Synthetic musk fragrances are common personal care product additives and wastewater contaminants that are routinely detected in the environment. This study examines the presence eight synthetic musk fragrances (AHTN, HHCB, ATII, ADBI, AHMI, musk xylene, and musk ketone) in source water and the removal of these compounds as they flow through a Midwestern conventional drinking water plant with lime softening. The compounds were measured in water, waste sludge, and air throughout the plant. HHCB and AHTN were detected in 100% of the samples and at the highest concentrations. A mass balance on HHCB and AHTN was performed under warm and cold weather conditions. The total removal efficiency for HHCB and AHTN, which averaged between 67% to 89%, is dominated by adsorption to water softener sludge and its consequent removal by sludge wasting and media filtration. Volatilization, chlorine disinfection, and the disposal of backwash water play a minor role in the removal of both compounds. As a result of inefficient overall removal, HHCB and AHTN are a constant presence at low levels in finished drinking water.
Reconstructing Contaminant Deposition in a San Francisco Bay Marina, California
Love AH, Esser BK and Hunt JR
Two sediment cores were collected from a marina in the San Francisco Bay to characterize historical sediment contamination resulting from the direct discharge of industrial wastewater from Naval Air Station Alameda. Depth profiles of trace metals, petroleum hydrocarbons, and radionuclides were determined with a 12-cm spacing down to a depth of 120 cm. The chronology of sediment accumulation is established by depth profiles of sedimentary time markers in conjunction with information on site history. The traditional approach of determining sediment accumulation rates by measuring atmospheric (210)Pb deposition was obscured by a larger source of (210)Pb in the sediments from the decay of anthropogenic (226)Ra, likely from luminescent paints used at this facility and released to the marina. The sedimentation rates inferred from the data indicate that the greatest amount of contamination by trace metals and petroleum hydrocarbons took place between 1940 and 1960. In addition, anthropogenic (226)Ra activities are positively correlated with some of the contaminants in the sediments, allowing the wastewater discharged from the facility to be distinguished from baywide contamination. In locations such as this, where there is a complex history of contaminant deposition, a source-specific tracer may be the only feasible method of attributing historical contamination to a point source.
Experimental Validation and Applications of a Fluid Infiltration Model
Kao CS and Hunt JR
Horizontal infiltration experiments were performed to validate a plug flow model that minimizes the number of parameters that must be measured. Water and silicone oil at three different viscosities were infiltrated into glass beads, desert alluvium, and silica powder. Experiments were also performed with negative inlet heads on air-dried silica powder, and with water and oil infiltrating into initially water moist silica powder. Comparisons between the data and model were favorable in most cases, with predictions usually within 40% of the measured data. The model is extended to a line source and small areal source at the ground surface to analytically predict the shape of two-dimensional wetting fronts. Furthermore, a plug flow model for constant flux infiltration agrees well with field data and suggests that the proposed model for a constant-head boundary condition can be effectively used to predict wetting front movement at heterogeneous field sites if averaged parameter values are used.
BUOYANT ADVECTION OF GASES IN UNSATURATED SOIL
Seely GE, Falta RW and Hunt JR
In unsaturated soil, methane and volatile organic compounds can significantly alter the density of soil gas and induce buoyant gas flow. A series of laboratory experiments was conducted in a two-dimensional, homogeneous sand pack with gas permeabilities ranging from 110 to 3,000 darcy. Pure methane gas was injected horizontally into the sand and steady-state methane profiles were measured. Experimental results are in close agreement with a numerical model that represents the advective and diffusive components of methane transport. Comparison of simulations with and without gravitational acceleration permits identification of conditions where buoyancy dominates methane transport. Significant buoyant flow requires a Rayleigh number greater than 10 and an injected gas velocity sufficient to overcome dilution by molecular diffusion near the source. These criteria allow the extension of laboratory results to idealized field conditions for methane as well as denser-than-air vapors produced by volatilizing nonaqueous phase liquids trapped in unsaturated soil.
Modeling PFAS Removal Using Granular Activated Carbon for Full-Scale System Design
Burkhardt JB, Burns N, Mobley D, Pressman JG, Magnuson ML and Speth TF
Per- and polyfluoroalkyl substances (PFAS) are increasingly of interest to drinking water utilities due to state regulations, the release of federal and state health advisories, and public concern. Pilot-scale data were fitted for 16 PFAS species and five commercial-activated carbons using an open-source pore and surface diffusion model that includes an automated parameter-fitting tool. The estimated model parameters are presented, and an uncertainty analysis was evaluated considering the expected temporal variability of influent concentrations. Expected treatment performance differed between two seasons in the pilot phase for the same carbon, which was not captured by modeled uncertainty. However, modeling results can support a utility's decision to choose activated carbon, and make design and operational decisions that can address changing water production rates and treatment goals. For the utility that undertook this pilot study and their desired treatment goals, granular activated carbon (GAC) was found to be an effective treatment technology for PFAS removal.