An evaluation of properly operated NSF/ANSI-53 Pb certified drinking water filters in Benton Harbor, MI.

Communities across the United States and particularly in the Midwest continue to grapple with the complications associated with aging infrastructure. This includes the presence of lead (Pb)-bearing plumbing components such as lead service lines, downstream galvanized iron pipes, and Pb/tin solder. The community of Benton Harbor, MI, experienced six Pb action level exceedances between 2018 and 2021, leading to increasing community concern and a request from the state of Michigan for the US Environmental Protection Agency involvement. Between 9 November and 17 December 2021, US EPA Region 5 and Office of Research and Development, along with the state of Michigan, conducted a water filter efficacy and Pb-nanoparticulate (<100 nm) study to evaluate the performance of NSF/ANSI-53 Pb-certified drinking water filters and the presence of nanoparticulate. In this study, a total of 199 properly installed and operated drinking water filters (combination of faucet mounted and pitcher) were tested in their residential locations. One hundred percent of the water filters were found to perform to the standard to which they were certified, with filtered drinking water Pb concentrations below 5 ppb (maximum observed was 2.5 ppb). In addition, Pb particulate was identified; however, discrete Pb-containing nanoparticles were not widely found or identified.

Quartz Crystal Microbalance with Dissipation: A New Approach of Examining Corrosion of New Copper Surfaces in Drinking Water.

Corrosion of copper material in drinking water systems causes public health concerns and plumbing failures. This study investigated the early corrosion of new copper surfaces in situ using a novel technique: quartz crystal microbalance with dissipation (QCMD). The QCMD results showed that increasing the water pH from 6.5 to 9.0 and the addition of 6 mg/L orthophosphate at pH 6.5 and 9.0 slowed down the copper surface mass changes as indicated by the reduced changes in frequency (Δf5) at 51-89% and total copper release at 29-72%. The water pH 9.0 without orthophosphate was the most likely to induce localized corrosion relative to other conditions at pH 6.5 and pH 9.0 with orthophosphate. Based on the changes in dissipation values (ΔD5) from QCMD and the morphology, microstructure, and composition of the deposited copper corrosion byproducts, digital microscopy, field-emission scanning electron microscopy with energy dispersive spectroscopy, and X-ray photoelectron spectrometry analyses confirmed that the pH and orthophosphate inhibited copper corrosion with different mechanisms. QCMD provided sensitive, rapid, and continuous responses to mass and surface changes and can be useful for evaluating early water corrosivity to new copper.

Lead Particle Size Fractionation and Identification in Newark, New Jersey's Drinking Water.

Following a pH reduction in their drinking water over a span of more than 20 years, the City of Newark, New Jersey, has struggled with elevated lead (Pb) release from Pb service lines and domestic plumbing in the zone fed by the Pequannock Water Treatment Plant. In response, Newark initiated orthophosphate addition and provided faucet-mounted point-of-use (POU) filters and pitcher filters certified for Pb and particulate reduction under NSF/ANSI Standards 53 and 42 to residential homes in that zone. Water chemistry analysis and size fractionation sampling were performed at four of these houses. Analysis of the particulate material retained by the fractionation filters revealed that Pb was dominantly present in the water as fine Pb(II) orthophosphate particles. A considerable amount of the particulates occurred as a nanoscale fraction that sometimes passed through the POU faucet or pitcher filtration units. Scanning electron microscopy, transmission electron microscopy, and energy-dispersive spectroscopy analyses showed that the nanoparticles (<100 nm) and their aggregates were composed of Pb, phosphorus, and chlorine, which are consistent with pyromorphite, Pb5(PO4)3Cl. Electron diffraction and X-ray analyses supported the presence of hydroxypyromorphite and chloropyromorphite nanoparticles and the size range estimates from the imaging. This research confirmed that nonadherent Pb(II)-orthophosphate nanoparticles were an important form of Pb in drinking water in the Pequannock water quality zone of Newark.

Synthesis and characterization of stable lead (II) orthophosphate nanoparticle suspensions.

There is great interest in producing nanoparticles for various applications. The objective of this work was to develop a procedure for reproducibly creating stable lead (Pb) phosphate nanoparticle aqueous suspensions. A stable 5 mg/L Pb-phosphate nanoparticle "stock" suspension was synthesized via chemical precipitation of Pb and orthophosphate in water at pH 7.5 with 4.4 mg soluble PO4/L and 7 mg C/L dissolved inorganic carbon. The stock suspension was subsequently diluted to produce stable 0.10 mg/L Pb "challenge" water suspensions without compromising the nanoparticle size, structure, mineralogy and solubility. Specifically, the hexagonal hydroxypyromorphite nanoparticles had an average diameter of 38 nm based on transmission electron microscopy analysis and an associated Pb solubility of 0.001 mg/L. The properties of the stock suspensions were not impacted by further dilutions, and the challenge water suspensions remained stable for 24 hours. In the context of drinking water, a protocol to produce such a stable Pb nanoparticle challenge water suspension would be very useful in evaluating Pb bioavailability, identifying Pb remediation strategies, and testing filter effectiveness to remove Pb from water.

Georgeite: A Rare Copper Mineral with Important Drinking Water Implications.

Significant research has been conducted on copper corrosion and solubility in drinking water, including the establishment of the "cupric hydroxide model". The model describes the temporal aging and associated solubility changes of copper minerals beginning with the most soluble solid, cupric hydroxide. Although the model explains copper levels in field observations well, there are aspects of the model that are not well understood, including a lack of evidence of the presence of cupric hydroxide in drinking water distribution systems. This study aimed to understand the effect of water chemistry on the solubility and properties of newly precipitated cupric solids, including mineral identification. Bench-scale copper precipitation tests were performed in water under a matrix of pH and dissolved inorganic carbon conditions. Copper solids were analyzed using a combination of materials analysis tools including XRD, FT-IR, TGA, and inorganic carbon analyses. Copper solids were X-ray amorphous, isotropic, and were light blue to blue. Based on repeated analysis, georgeite (Cu2(CO3)(OH)2·6H2O) was conclusively identified as the solid at all test conditions. Georgeite is an extremely rare, amorphous malachite analog, and because of its rarity, very little has been reported on its presence in any environment.

Impact of orthophosphate on the solubility and properties of lead orthophosphate nanoparticles.

Orthophosphate (PO4) is a commonly used corrosion control treatment to reduce lead (Pb) concentrations in drinking water. PO4 reduces Pb concentrations by forming relatively insoluble lead phosphate (Pb-PO4) minerals. In some cases, however, Pb-PO4 minerals have been observed to form nanoparticles, and if suspended in water, these nanoparticles can be mobile and reach consumer taps. Although recent research on Pb-PO4 particles has been performed, there remains a need to improve our understanding of the nature of Pb-PO4 nanoparticles. For that reason, Pb precipitation experiments were conducted to generate Pb-PO4 nanoparticles in bench scale studies for analysis. The study objective was to observe how pH, dissolved inorganic carbon (DIC), and PO4 impacted the properties of Pb-PO4 particles. Specifically, particle size, surface charge, mineralogy, and solubility were analysed. Hydrocerussite was precipitated when no PO4 was present, hydroxypyromorphite (Pb5(PO4)3OH) nanoparticles (<100 nm diameter) were precipitated when excess PO4 relative to Pb necessary to completely precipitate the mineral was present, and a mixture of the two minerals was precipitated when an insufficient amount of PO4 was present. Hydroxypyromorphite particles were less soluble than hydrocerussite by up to two orders of magnitude. The estimated K sp,OH of 10-66.87 in this work closely aligned with previous K sp,OH estimates that ranged from 10-66.77 to 10-62.79. Hydroxypyromorphite particles would not settle in water which was likely due to their small size and high negative charge. The mobility and size of these particles indicates that there are potential implications for such particulate Pb to remain suspended in water and thus be present in the tap water.

Microelectrode investigation of iron and copper surfaces aged in presence of monochloramine.

Ductile iron and copper coupons were aged 137-189 days and 2 days, respectively, with 2 mg Cl2 L-1 monochloramine under four water chemistries (pH 7 or 9 and 0 or 3 mg L-1 orthophosphate). Subsequently, microelectrode profiles of monochloramine concentration, oxygen concentration, and pH were measured from the bulk water to near the coupon reactive surface, allowing estimation of flux and apparent surface reaction rate constants for monochloramine and oxygen. Both metals showed similar trends with orthophosphate where orthophosphate decreased metal reactivity with monochloramine (pH 9) and oxygen (pH 7). Comparing iron and copper coupons, apparent surface reaction rate constants for monochloramine and oxygen were one and two orders of magnitude greater, respectively, for iron coupons under all conditions. Overall, this research provides the first insights into monochloramine concentration, oxygen concentration, and pH by direct measurement near ductile iron and copper reactive surfaces aged in the presence of monochloramine.

Applying microelectrodes to investigate aged ductile iron and copper coupon reactivity during free chlorine application.

In drinking water distribution systems, including premise plumbing, dissolved oxygen (DO) and free chlorine (FC) are common oxidants and ductile iron (DI) and copper (Cu) are commonly used pipe materials. Microelectrodes as a tool have been applied in previous corrosion research and were used in this study to collect quantifiable data and understand DO and FC reactivity and pH changes at the water-metal interface. Using microelectrodes, pH, DO, and FC profiles from the bulk water to near and at the surface of aged DI (154-190 d) and Cu (2 d and 86-156 d) coupons were investigated during periods of flow and stagnation (30 min). Using the measured microelectrode profiles, oxidant fluxes and apparent surface reaction rate constants were calculated to elucidate differences between DO and FC reactivity with the coupons. Microelectrodes were successfully applied to measure pH, DO, and FC profiles from the bulk water to near aged DI and Cu coupon surfaces; Cu coupons aged quickly and exhibited less reactivity at 2 d with DO and FC than aged DI coupons did after 154-190 d; and for the aged DI coupon experiments, orthophosphate presence stabilized pH profiles where without orthophosphate pH fluctuations of greater than 2 pH units occurred from the bulk water to the DI coupon surface.

Comprehensive characterization of aerobic groundwater biotreatment media.

Aerobic biotreatment systems can treat multiple reduced inorganic contaminants in groundwater, including ammonia (NH3), arsenic (As), iron (Fe), and manganese (Mn). While individual systems treating multiple contaminants simultaneously have been characterized and several systems treating one contaminant have been compared, a comparison of systems treating co-occurring contaminants is lacking. This study assessed the treatment performance and microbial communities within 7 pilot- and full-scale groundwater biotreatment systems in the United States that treated waters with pH 5.6-7.8, 0.1-2.0 mg/L dissolved oxygen, 75-376 mg CaCO3/L alkalinity, < 0.03-3.79 mg NH3-N/L, < 4-31 µg As/L, < 0.01-9.37 mg Fe/L, 2-1220 µg Mn/L, and 0.1-5.6 mg/L total organic carbon (TOC). Different reactor configurations and media types were represented, allowing for a broad assessment of linkages between water quality and microbial communities via microscopy, biofilm quantification, and molecular methods. Influent NH3, TOC, and pH contributed to differences in the microbial communities. Mn oxidase gene copy numbers were slightly negatively correlated with the influent Mn concentration, but no significant relationships between gene copy number and influent concentration were observed for the other contaminants. Extracellular enzyme activities, community composition, and carbon transformation pathways suggested heterotrophic bacteria may be important in nitrifying biofilters. Aerobic groundwater biofilters are complex, and improved understanding could lead to engineering enhancements.

Biodesalination using halophytic cyanobacterium Phormidium keutzingianum from brackish to the hypersaline water.

The biodesalination potential at different levels of salinity of Phormidium keutzingianum (P. keutzingianum) was investigated. A wide range of salinity from brackish to hypersaline water was explored in this study to ensure the adaptability of P. keutzingianum in extreme stress conditions. Brackish to hypersaline salt solutions were tested at selected NaCl concentrations 10, 30, 50, and 70 g.L-1. Chloride, pH, nitrate, and phosphate were the main parameters measured throughout the duration of the experiment. Biomass growth estimation revealed that the studied strain is adaptable to all the salinities inoculated. During the first growth phase (till day 20), chloride ion was removed up to 43.52% and 45.69% in 10 and 30 g.L-1 of salinity, respectively. Fourier transform infrared spectrometry analysis performed on P. keutzingianum showed the presence of active functional groups at all salinity levels, which resulted in biosorption leading to the bioaccumulation process. Samples for scanning electron microscopy (SEM) analysis supported with electron dispersive X-ray spectroscopy analysis (EDS) showed NaCl on samples already on day 0. This ensures the occurrence of the biosorption process. SEM-EDS results on 10th d showed evidence of additional ions deposited on the outer surface of P. keutzingianum. Calcium, magnesium, potassium, sodium, chloride, phosphorus, and iron were indicated in SEM-EDS analysis proving the occurrence of the biomineralization process. These findings confirmed that P. keutzingianum showed biomass production, biosorption, bioaccumulation, and biomineralization in all salinities; hence, the strain affirms the biodesalination process.

A holistic approach to lead pipe scale analysis: Importance, methodology, and limitations.

With lead service lines (LSLs) remaining for decades to come, scale analyses are critical to helping limit lead exposure from drinking water. This laboratory has used an integrated suite of analytical techniques to characterize the elemental composition, mineral identification, and physical features of scales, helping the water industry to evaluate, predict, and reduce lead corrosion. The methods used in this laboratory to prepare and analyze the LSL scale, and guidance to achieving reliable and meaningful results, are described. Primary methods include the following: optical microscopy, powder X-ray diffraction, inductively coupled plasma spectroscopy, X-ray fluorescence, scanning electron microscopy with energy dispersive spectroscopy, combustion and coulometric analyses of C and S, and X-ray absorption spectroscopy. Examples of associated pitfalls and ways to avoid them are provided, including pipe excavation/transport, sample preparation, analysis, and data interpretation. Illustrative examples are presented of practical scale analysis questions that could be answered by combinations of pipe scale analyses.

Material recovery from electronic waste using pyrolysis: Emissions measurements and risk assessment.

Electronic waste (e-waste) generation has been growing in volume worldwide, and the diversity of its material composition is increasing. Sustainable management of this material is critical to achieving a circular-economy and minimizing environmental and public health risks. This study's objective was to investigate the use of pyrolysis as a possible technique to recover valuable materials and energy from different components of e-waste as an alternative approach for limiting their disposal to landfills. The study includes investigating the potential environmental impact of thermal processing of e-waste. The mass loss and change in e-waste chemicals during pyrolysis were also considered. The energy recovery from pyrolysis was made in a horizontal tube furnace under anoxic and isothermal conditions of selected temperatures of 300 °C, 400 °C, and 500 °C. Critical metals that include the rare earth elements and other metals (such as In, Co, Li) and valuable metals (Au, Ag, Pt group) were recovered from electronic components. Pyrolysis produced liquid and gas mixtures of organic compounds that can be used as fuels. Still, the process also emitted particulate matter and semi-volatile organic products, and the remaining ash contained leachable pollutants. Furthermore, toxicity characteristics leaching procedure (TCLP) of e-waste and partly oxidized products were conducted to measure the levels of pollutants leached before and after pyrolysis at selected temperatures. TCLP result revealed the presence of heavy metals like As, Cr, Cd, and Pd. Lead was found at 160 mg/L in PCBs leachate, which exceeded the toxicity characteristics (TC) limit of 5 mg/L. Liquid sample analysis from TCLP also showed the presence of C10-C19 components, including benzene. This study's results contribute to the development of practical recycling alternative approaches that could help reduce health risks and environmental problems and recover materials from e-waste. These results will also help assess the hazard risks that workers are exposed to semi-formal recycling centers.

Effectiveness of point-of-use and pitcher filters at removing lead phosphate nanoparticles from drinking water.

Orthophosphate (PO4) addition is a common corrosion control treatment used to lower lead (Pb) concentrations at the consumer's tap by forming relatively insoluble Pb-phosphate (Pb-PO4) minerals. However, some Pb-PO4 particles that can form in drinking water are mobile nanoparticles (i.e., 0.001-0.1 µm) that have the potential to reach the tap. Point-of-use (POU) or pitcher filters are often used to manage risks during distribution system upsets, when corrosion control treatment is not optimized, or following Pb service line replacements. To abide by industry convention, POU and pitcher filters must be NSF/ANSI-certified for Pb reduction (NSF/ANSI-53) using a test water containing dissolved Pb and large Pb particles. Certification for particulates reduction (NSF/ANSI-42) is done using a test water that contains particles, but not leaded particles. To address the lack of testing for Pb nanoparticles, this study challenged six certified commercially available faucet-mounted POU (3) and pitcher (3) filters with aqueous suspensions of Pb-PO4 nanoparticle. For the water quality investigated, the Pb particles formed ranged between 0.016 and 0.098 µm, based on scanning electron microscopy, transmission electron microscopy, and dynamic light scattering analysis. These particles represented 98.5% of total Pb in suspension. The total Pb removals were between 44.6 and 65.1% for the POU filters, and between 10.9 and 92.9% for the pitcher filters. The electron microscopy results confirm that Pb-PO4 nanoparticles passed through the filters. The findings can inform future efforts to re-examine the test waters used in the certification challenge tests.

Removal of strontium from drinking water by conventional treatment and lime softening in bench-scale studies.

The United States Environmental Protection Agency Contaminant Candidate List 3 lists strontium as a contaminant for potential regulatory consideration in drinking water. Very limited data is available on strontium removal from drinking water and as a result, there is an immediate need for treatment information. The objective of this work is to evaluate the effectiveness of coagulation/filtration and lime-soda ash softening treatment methods to remove strontium from surface and ground waters. Coagulation/filtration jar test results on natural waters showed that conventional treatment with aluminum and iron coagulants were able to achieve only 12% and 5.9% strontium removal, while lime softening removed as high as 78% from natural strontium-containing ground water. Controlled batch experiments on synthetic water showed that strontium removal during the lime-soda ash softening was affected by pH, calcium concentration and dissolved inorganic carbon concentration. In all softening jar tests, the final strontium concentration was directly related to the initial strontium concentration and the removal of strontium was directly associated with calcium removal. Precipitated solids showed well-formed crystals or agglomerates of mixed solids, two polymorphs of calcium carbonate (vaterite and calcite), and strontianite, depending on initial water quality conditions. X-ray diffraction analysis suggested that strontium was likely incorporated in the calcium carbonate crystal lattice and was likely responsible for removal during lime softening.

Transformation of silver nanoparticles in fresh, aged, and incinerated biosolids.

The purpose of this research was to assess the chemical transformation of silver nanoparticles (AgNPs) in aged, fresh, and incinerated biosolids in order to provide information for AgNP life cycle analyses. Silver nanoparticles were introduced to the influent of a pilot-scale wastewater (WW) treatment system consisting of a primary clarifier (PC), aeration basin, and secondary clarifier. The partitioning of the AgNPs between the aqueous and solid phases in the system was monitored. Less than 3% of the total AgNPs introduced into the PC were measured at the overflow of the PC. Biosolids were collected from the pilot-scale system for silver analyses, including Ag concentration and speciation. Additionally, biosolids were collected from a publically owned treatment works (POTW). The POTW biosolids were spiked with AgNPs, AgNO3, and Ag2S. One set of the spiked POTW biosolids was aged for one month, and another set was analyzed within 24 h via X-ray absorption spectroscopy (XAS) and scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM-EDX) in order to determine Ag chemical speciation and elemental associations. Replicates of the aged and 24-h samples were also incinerated at 850 °C for 4 h. The residual ash was analyzed by XAS and SEM-EDX. The results show that AgNPs are converted to Ag-sulfur (as sulfide and sulfhydryl) species in fresh and aged biosolids, which is in agreement with other studies on AgNPs in biosolids. Results from linear combination fitting of the XAS data for incinerated biosolids show that a significant proportion of the spiked silver (30-50%) is converted to elemental Ag in the incineration process. In addition to elemental Ag, the results suggest the presence of additional Ag-S complexes such as Ag2SO4 (up to 25%), and silver associated with sulfhydryl groups (26-50%) in the incinerated biosolids. Incinerated biosolids spiked with AgNO3 and Ag2S exhibited similar transformations. These transformations of AgNPs should be accounted for in life-cycle analyses of AgNPs and in management decisions regarding the disposal of incinerated biosolids.

Inhibition of sulfate-reducing bacteria by metal sulfide formation in bioremediation of acid mine drainage.

Acid mine drainage (AMD) containing high concentrations of sulfate and heavy metal ions can be treated by biological sulfate reduction. It has been reported that the effect of heavy metals on sulfate-reducing bacteria (SRB) can be stimulatory at lower concentrations and toxic/inhibitory at higher concentrations. The quantification of the toxic/inhibitory effect of dissolved heavy metals is critical for the design and operation of an effective AMD bioremediation process. Serum bottle and batch reactor studies on metal toxicity to SRB indicate that insoluble metal sulfides can inhibit the SRB activity as well. The mechanism of inhibition is postulated to be external to the bacterial cell. The experimental data indicate that the metal sulfides formed due to the reaction between the dissolved metal and biogenic sulfide act as barriers preventing the access of the reactants (sulfate, organic matter) to the necessary enzymes. Scanning electron micrographs of the SRB cultures exposed to copper and zinc provide supporting evidence for this hypothesis. The SRB cultures retained their ability to effect sulfate reduction indicating that the metal sulfides were not lethally toxic to the SRB. This phenomenon of metal sulfide inhibition of the SRB has to be taken into account while designing a sulfate-reducing bioreator, and subsequently an efficient biotreatment strategy for AMD. Any metal sulfide formed in the bioreactor needs to be removed immediately from the system to maintain the efficiency of the process of sulfate reduction.