Considering a Utility-Centric Framework Based on "Minimum Orthophosphate" Criteria for Mitigation of Elevated Cuprosolvency in Drinking Water.

Gaps in the United States Environmental Protection Agency (US EPA) Lead and Copper Rule (LCR) leave some consumers and their pets vulnerable to high cuprosolvency in drinking water. This study seeks to help proactive utilities who wish to mitigate cuprosolvency problems through the addition of orthophosphate corrosion inhibitors. The minimum doses of orthophosphate necessary to achieve acceptable cuprosolvency in relatively new copper pipe were estimated as a function of alkalinity via linear regressions for the 90th, 95th, and 100th percentile copper tube segments (R2 > 0.98, n = 4). Orthophosphate was very effective at reducing cuprosolvency in the short term but, in some cases, resulted in higher long-term copper concentrations than the corresponding condition without orthophosphate. Alternatives to predicting "long-term" results for copper tubes using simpler bench tests starting with fresh Cu(OH)2 solids showed promise but would require further vetting to overcome limitations such as maintaining water chemistry and orthophosphate residuals and to ensure comparability to results using copper tube.

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.

Orthophosphate Interactions with Destabilized PbO2 Scales.

This research presents two case studies in which a change in the disinfectant from free chlorine to chloramine caused an increase in lead corrosion. In both systems, the predominantly tetravalent lead (PbO2) scales destabilized as a result of disinfectant change. Orthophosphate corrosion control was used in both systems, and the effect of this treatment chemical on the destabilized PbO2 scales was examined. The absence of chemical reactivity between PbO2 and phosphorus is well known, and this research confirms that phosphorus does not interact with the legacy PbO2 scales. Instead, phosphorus and calcium were found to permeate through the destabilized PbO2 material and react with divalent lead [Pb(II)] at the surface of a basal litharge (PbO) layer. This reaction precipitated a crystalline lead phosphate in both systems, which could not be specifically identified by any known powder diffraction files. Further analysis suggested that the compound formed was not the typically modeled hydroxypyromorphite but rather a calcium-substituted hydroxypyromorphite. During scale formation, calcium is frequently bound to the Pb(II) phosphate crystal lattice structure, causing measurable crystal lattice distortion in powder X-ray diffraction patterns. The results of this study illustrate the longevity of legacy scales and how disequilibrium compounds persist long after treatment changes have been made.

Modeled Impacts of Drinking Water Pb Reduction Scenarios on Children's Exposures and Blood Lead Levels.

In recent years, environmental lead (Pb) exposure through drinking water has resulted in community public health concerns. To understand potential impacts on blood Pb levels (BLLs) from drinking water Pb reduction actions (i.e., combinations of lead service lines [LSL] and corrosion control treatment [CCT] scenarios), EPA's Stochastic Human Exposure and Dose Simulation (SHEDS)-Multimedia/Integrated Exposure Uptake and Biokinetic (IEUBK) model was applied for U.S. children aged 0 to <6 years. The results utilizing a large drinking water sequential sampling data set from 15 cities to estimate model input concentration distributions demonstrated lowest predicted BLLs for the "no LSLs" with "combined CCT" scenario and highest predicted BLLs for the "yes LSLs" and "no CCT" scenario. Modeled contribution to BLLs from ingestion of residential drinking water ranged from ∼10 to 80%, with the highest estimated for formula-fed infants (age 0 to <1 year). Further analysis using a "bounding" data set spanning a range of realistic water Pb concentrations and variabilities showed BLL predictions consistent with the sequential sampling-derived inputs. Our study illustrates (1) effectiveness of LSL replacement coupled with CCT for reducing Pb in drinking water and children's BLLs, and (2) in some age groups, under realistic local and residential water use conditions, drinking water can be the dominant exposure pathway.

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.

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.

POU water filters effectively reduce lead in drinking water: a demonstration field study in flint, Michigan.

A field study was conducted to test the effectiveness of faucet-mounted point of use (POU) water filters for removing high concentrations of lead in drinking water from premise plumbing sources and lead service lines (LSL). These filters were concurrently certified for total lead removal under NSF/ANSI Standard 53 (NSF/ANSI-53) and for fine particulate (Class I) reduction under NSF/ANSI Standard 42 (NSF/ANSI-42). In 2016, filtered and unfiltered drinking water samples were collected at over 345 locations in Flint, Michigan. Over 97% of filtered water samples contained lead below 0.5 µg/L. The maximum lead concentration in filtered water was 2.9 µg/L, well below the bottled water standard. The effectiveness of the POU activated carbon block filters in reducing lead concentrations, even above the 150 µg/L NSF/ANSI-53 challenge standard, is likely related to trapping particles due to the small effective pore size of the filters, in addition to ion-exchange or sorption removal of soluble lead. Properly installed and maintained POU filters, certified under both NSF/ANSI-53 (for total lead) and NSF/ANSI-42 (for fine particulate), can protect all populations, including pregnant women and children, by reducing lead in drinking water to levels that would not result in a significant increase in overall lead exposure.

Mineralogical Evidence of Galvanic Corrosion in Drinking Water Lead Pipe Joints.

Galvanic corrosion as a mechanism of toxic lead release into drinking water has been under scientific debate in the U.S. for over 30 years. Visual and mineralogical analysis of 28 lead pipe joints, excavated after 60+ years from eight U.S. water utilities, provided the first direct view of three distinct galvanic corrosion patterns in practice: (1) no evidence of galvanic corrosion; (2) galvanic corrosion with lead cathode; (3) galvanic corrosion with lead anode. Pattern 3 is consistent with empirical galvanic series (lead → brass → copper in order of increasing nobility) and poses the greatest risk of Pb exposure. Pattern 2 is consistent with galvanic battery reversion. The identification of copper-sulfate minerals (Pattern 2), and lead-sulfate and lead-chloride minerals (Pattern 3) in galvanic zones illustrated the migration of chloride and sulfate toward the anode. Geochemical modeling confirmed the required pH drop from the bulk water level to at least pH 3.0-4.0 (Pattern 2) and pH < 5.5 (Pattern 3) in order to form these minerals. Despite joints being over 60 years old, galvanic zones in Pattern 3 were active and possibly posed an important source of lead to drinking water. Importantly, Pattern 3 was not observed in samples from systems representing water qualities favoring PbO2 formation.

A Model for Estimating the Impact of Orthophosphate on Copper in Water.

The nature of copper phosphate minerals in drinking water distribution systems has remained largely unsolved despite being an important link to reducing cuprosolvency. Chemical equilibrium modeling has also largely failed to accurately predict soluble copper in the presence of orthophosphate. The objective of this work was to develop and validate an empirical copper solubility model that considered pH, dissolved inorganic carbon (DIC), and orthophosphate from a series of bench-scale copper precipitation experiments. An empirical model was constructed that allows for the determination of copper levels in a system given pH, DIC, and orthophosphate data. The predictive reliability of this model was assessed by evaluating a collection of cuprosolvency data from two decades of research and field observations and water treatment reports. The tests yielded a firm correlation between predicted and observed copper levels attested by a regression coefficient of 0.86 for a total of 851 observations.

Design and Testing of USEPA'S Flint Pipe Rig for Corrosion Control Evaluation.

The US Environmental Protection Agency's Office of Research and Development designed, fabricated, and installed four pipe rigs in Flint, Mich., to help the city optimize corrosion control. The lead service line (LSL) pipe loops were constructed of polyvinyl chloride pipe and fittings and welded steel channel frames. Each pipe rig consisted of four approximately 4 ft-long sections of 0.75 in. inside diameter lead pipe that were excavated from homes fed by the Flint distribution system. The rigs were operated on a set daily on/off schedule such that a specified amount of water passed through each pipe using a solenoid valve-operated timer system. Solenoid problems resulted in sporadic and enhanced daily flow volume (but no flow rate changes) that prevented restabilization of pipe scales. Lead levels were relatively sporadic and statistically different during this period. After the solenoids were replaced, the lead pipe rigs were successfully conditioned, and lead release with consistent influent water chemistry became relatively stable. Average lead levels across all 16 loops ranged between approximately 2 and 5 µg/L after the solenoid replacement. The lead results were consistent with levels measured from LSLs from homes in the city during sequential sampling efforts.

Scale Formation Under Blended Phosphate Treatment for a Utility With Lead Pipes.

US corrosion control practice often assumes that the orthophosphate component of blended phosphate corrosion inhibitors causes the formation of low-solubility lead-orthophosphate solids that control lead release into drinking water. This study identified the solids that formed on the interior surface of a lead service line and a galvanized steel pipe excavated from a system using a proprietary blended phosphate chemical. The scale was analyzed by X-ray diffraction, X-ray fluorescence, and scanning electron microscopy/energy dispersive spectroscopy. Instead of crystalline lead-orthophosphate solids, a porous amorphous layer rich in aluminum, calcium, phosphorus, and lead was observed at the lead pipe scale-water interface. Thus, the mechanism inhibiting lead release into the water was not a thermodynamically predictable passivating lead-orthophosphate scale, but rather an amorphous barrier deposit that was possibly vulnerable to disturbances. Galvanized pipe scales showed relatively crystalline iron and zinc compounds, with additional surface deposition of aluminum, phosphorus, calcium, and lead.

Low contribution of PbO2-coated lead service lines to water lead contamination at the tap.

To determine if residential water sampling corroborates the expectation that formation of stable PbO2 coatings on lead service lines (LSLs) provides an effective lead release control strategy, lead profile sampling was evaluated for eight home kitchen taps in three U.S. cities with observed PbO2-coated LSLs (Newport, Rhode Island; Cincinnati and Oakwood, Ohio). After various water standing times, these LSLs typically released similar or lower peak lead levels (1 to 18 µg/L) than the lead levels from the respective kitchen faucets (1 to 130 µg/L), and frequently 50-80% lower than the lead levels typically reported from Pb(II)-coated LSLs in comparable published sampling studies. Prolonged stagnation (10-101 h) at the Cincinnati sites produced varying results. One site showed minimal (0-4 µg/L) increase in lead release from the PbO2-coated LSL, and persistence of free chlorine residual. However, the other site showed up to a 3-fold increase proportional to standing time, with essentially full depletion of the chlorine residual. Overall, lead release was consistently much lower than that reported in studies of Pb(II)-coated LSL scales, suggesting that natural formation of PbO2 in LSLs is an effective lead "corrosion" control strategy.

Detection and evaluation of elevated lead release from service lines: a field study.

Comparative stagnation sampling conducted in 32 homes in Chicago, Illinois with lead service lines demonstrated that the existing regulatory sampling protocol under the U.S. Lead and Copper Rule systematically misses the high lead levels and potential human exposure. Lead levels measured with sequential sampling were highest within the lead service lines, with maximum values more than four times higher than Chicago's regulatory compliance results using a first-draw sampling protocol. There was significant variability in lead values from different points within individual lead service lines and among different lead service line sites across the city. Although other factors could also influence lead levels, the highest lead results most often were associated with sites having known disturbances to the lead service lines. This study underscores the importance and interdependence of sample site selection, sampling protocol, and other factors in assessing lead levels in a public water system.

A national survey of lead and other metal(loids) in residential drinking water in the United States.

BACKGROUND: Exposure to lead (Pb), arsenic (As) and copper (Cu) may cause significant health issues including harmful neurological effects, cancer or organ damage. Determination of human exposure-relevant concentrations of these metal(loids) in drinking water, therefore, is critical. OBJECTIVE: We sought to characterize exposure-relevant Pb, As, and Cu concentrations in drinking water collected from homes participating in the American Healthy Homes Survey II, a national survey that monitors the prevalence of Pb and related hazards in United States homes. METHODS: Drinking water samples were collected from a national survey of 678 U.S. homes where children may live using an exposure-based composite sampling protocol. Relationships between metal(loid) concentration, water source and house age were evaluated. RESULTS: 18 of 678 (2.6%) of samples analyzed exceeded 5 µg Pb L-1 (Mean = 1.0 µg L-1). 1.5% of samples exceeded 10 µg As L-1 (Mean = 1.7 µg L-1) and 1,300 µg Cu L-1 (Mean = 125 µg L-1). Private well samples were more likely to exceed metal(loid) concentration thresholds than public water samples. Pb concentrations were correlated with Cu and Zn, indicative of brass as a common Pb source is samples analyzed. SIGNIFICANCE: Results represent the largest national-scale effort to date to inform exposure risks to Pb, As, and Cu in drinking water in U.S. homes using an exposure-based composite sampling approach. IMPACT STATEMENT: To date, there are no national-level estimates of Pb, As and Cu in US drinking water collected from household taps using an exposure-based sampling protocol. Therefore, assessing public health impacts from metal(loids) in drinking water remains challenging. Results presented in this study represent the largest effort to date to test for exposure-relevant concentrations of Pb, As and Cu in US household drinking water, providing a critical step toward improved understanding of metal(loid) exposure risk.

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.

Theoretical equilibrium lead(II) solubility revisited: Open source code and practical relationships.

A theoretical equilibrium lead(II) (Pb(II)) solubility model coded in Fortran (LEADSOL) was updated and implemented in open source R code, verified against LEADSOL output, and used to simulate theoretical equilibrium total soluble Pb(II) (TOTSOLPb) concentrations under a variety of practical scenarios. The developed R code file (app.R) is publicly available for download at GitHub (https://github.com/USEPA/TELSS) along with instructions to run the R code locally, allowing the user to explore Pb(II) solubility by selecting desired simulation conditions (e.g., water quality, equilibrium constants, and Pb(II) solids to consider). In addition, the R code serves as a reproducible baseline for alternative model development and future model improvements, allowing users to update, modify, and share the R code to meet their needs. Using the R code, several solubility diagrams were generated to highlight practical relationships related to TOTSOLPb concentrations, including the impact of pH and dissolved inorganic carbon, orthophosphate, sulfate, and chloride concentrations.

Rapid and simple lead service line detection screening protocol using water sampling.

Many water systems are challenged with uncertainty regarding service line material type. This work investigated using a simple drinking water flushed sampling approach and a more complicated and invasive sequential profile sampling approach to predict whether homes had an existing lead service line (LSL). Homes that never had an LSL (control groups) and homes with LSLs (study groups) in two communities having different degrees of corrosion control were sampled. Using control groups' results, community-specific "threshold" lead levels were determined and compared to results from study groups. The flushed sampling maximum lead concentration (FMC) of lead accurately predicted 100% and 60% of LSL sites for the community with poor and good corrosion control, respectively. The weighted average sequential profile lead concentration (WASLC) increased the 40% not identified as LSL sites by fully flushed samples to 100%. The WASLC closely followed by the maximum sequential profile lead concentration were most reliable in identifying LSLs.

Variability and sampling of lead (Pb) in drinking water: Assessing potential human exposure depends on the sampling protocol.

Lead (Pb) in drinking water has re-emerged as a modern public health threat which can vary widely in space and in time (i.e., between homes, within homes and even at the same tap over time). Spatial and temporal water Pb variability in buildings is the combined result of water chemistry, hydraulics, Pb plumbing materials and water use patterns. This makes it challenging to obtain meaningful water Pb data with which to estimate potential exposure to residents. The objectives of this review paper are to describe the root causes of intrinsic Pb variability in drinking water, which in turn impacts the numerous existing water sampling protocols for Pb. Such knowledge can assist the public health community, the drinking water industry, and other interested groups to interpret/compare existing drinking water Pb data, develop appropriate sampling protocols to answer specific questions relating to Pb in water, and understand potential exposure to Pb-contaminated water. Overall, review of the literature indicated that drinking water sampling for Pb assessment can serve many purposes. Regulatory compliance sampling protocols are useful in assessing community-wide compliance with a water Pb regulatory standard by typically employing practical single samples. More complex multi-sample protocols are useful for comprehensive Pb plumbing source determination (e.g., Pb service line, Pb brass faucet, Pb solder joint) or Pb form identification (i.e., particulate Pb release) in buildings. Exposure assessment sampling can employ cumulative water samples that directly capture an approximate average water Pb concentration over a prolonged period of normal household water use. Exposure assessment may conceivably also employ frequent random single samples, but this approach warrants further investigation. Each protocol has a specific use answering one or more questions relevant to Pb in water. In order to establish statistical correlations to blood Pb measurements or to predict blood Pb levels from existing datasets, the suitability of available drinking water Pb datasets in representing water Pb exposure needs to be understood and the uncertainties need to be characterized.

Framework for Modeling Lead in Premise Plumbing Systems Using EPANET.

The lead contamination of drinking water in homes and buildings remains an important public health concern. In order to assess strategies to measure and reduce exposure to lead from drinking water, models are needed that incorporate the multiple factors affecting lead concentrations in premise plumbing systems (PPS). In this study, the use of EPANET, a commonly used hydraulic and water quality model for water distribution systems, was assessed for its ability to predict lead concentrations in PPS. The model was calibrated and validated against data collected from multiple experiments in the EPA's Home Plumbing Simulator that contained a lead service line and other lead sources. The EPANET's first-order saturation kinetics model was used to simulate the dissolution of lead in the lead service line. A version of EPANET was developed to include one-dimensional mass dispersion. Modeling results were compared to experimental data, and recommendations were made to improve the EPANET-based modeling framework for predicting lead concentrations in PPS.

Water quality-pipe deposit relationships in Midwestern lead pipes.

The conventional wisdom of lead-scale solubility has been built over the years by geochemical solubility models, experimental studies, and field sampling utilizing multiple protocols. Rarely, have the mineral phases from scales formed in real-world drinking water lead service lines (LSLs) been compared to theoretical predictions. In this study, model predictions are compared to LSL scales from 22 drinking water distribution systems. The results show that only nine of the 22 systems had LSL scales that followed model predictions. The remaining systems had unpredictable scales some with unknown lead release characteristics demonstrating that predicting scale formation and lead release solely by models cannot be relied on in all cases to protect human health. Therefore, for many systems with LSLs, pilot studies with existing LSL scales will be necessary to evaluate and optimize corrosion control, and correspondingly, appropriate residential water sampling will be needed to demonstrate consistent and optimal system corrosion control.