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.

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.

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.

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.

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.

Sequential drinking water sampling as a tool for evaluating lead in flint, Michigan.

Eliminating the sources of human lead exposure is an ongoing public health goal. Identifying the make-up of household plumbing and service line material type is important for many reasons including understanding lead release sources and mechanisms, targeting locations for lead service line (LSL) removal, and assessing the effectiveness of lead remediation strategies. As part of the response to Flint, Michigan's drinking water lead public health crisis, a return to their original drinking water source (Lake Huron) and an increase in orthophosphate dose was implemented in late 2015. In 2016, EPA performed multiple rounds of sequential or "profiling" water sampling to evaluate corrosion control effectiveness and identify lead sources in homes and service lines, as well as to evaluate the effectiveness of corrosion control treatment with time on the different plumbing components. The results showed that lead levels, including high lead levels likely associated with particles, decreased with time in homes sampled during the 11-month evaluation period. Although sequential sampling indicated that brass fittings, brass fixtures, and galvanized pipes were lead sources, LSLs were the greatest source of lead when present. Following the removal of LSLs, the total mass of lead contributed to the drinking water decreased by 86% on average.

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.

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.

The inhibition of Pb(IV) oxide formation in chlorinated water by orthophosphate.

Historically, understanding lead solubility and its control in drinking water has been based on Pb(II) chemistry. Unfortunately, there is very little information available regarding the nature of Pb(IV) oxides in finished drinking water and water distribution systems, and the conditions under which they persist. The objective of this research was to explore the impact of orthophosphate on the realistic pathways that lead to the formation of Pb(IV) oxides in chlorinated water. The results of XRD and XANES analysis showed that, in the absence of orthophosphate (DIC = 10 mg C/L, 24 degrees C, pH 7.75-8.1, 3 mg Cl2/L goal), Pb(IV) oxides formed with time following a transformation from the Pb(II) mineral hydrocerussite. Under the same experimental conditions, orthophosphate dosing inhibited the formation of Pb(IV) oxides. The Pb(II) mineral hydroxypyromorphite, Pb5(PO4)3OH, was the only mineral phase identified during the entire study of over 600 days, although the presence of some chloropyromorphite, Pb5(PO4)3Cl, could not be ruled out The conclusions were further supported by SEM, TEM, and XANES analysis of lead colloids, and lead precipitation experiments conducted in the absence of free chlorine. The findings provide an important explanation for the absence of Pb(IV) oxides in some water systems that have used, or currently use, orthophosphate for corrosion control when otherwise, based on disinfection practices and water quality, its presence would be anticipated, as well as why the conversion from free chlorine to chloramines was not observed to increase lead release.

Identification and distribution of vanadinite (Pb5(V5+O4)3Cl) in lead pipe corrosion by-products.

This study presents the first detailed look at vanadium (V) speciation in drinking water pipe corrosion scales. A pool of 34 scale layers from 15 lead or lead-lined pipes representing eight different municipal drinking water distribution systems in the Northeastern and Midwestern portions of the United States were examined. Diverse synchrotron-based techniques, including bulk XANES (X-ray absorption near edge spectroscopy), micro-XANES, micro-XRD (X-ray diffraction), and micro-XRF (X-ray fluorescence) mapping were employed along with traditional powder XRD, SEM-EDXA (scanning electron microscopy-energy dispersive X-ray analysis), and ICP-OES (inductively coupled plasma-optical emission spectrometry) to evaluate vanadium speciation and distribution in these deposits. Vanadinite (Pb5(VO4)3Cl) was positively identified, and occurred most frequently in the surface layers. Low V(tot) in these waters is likely the limiting factor in the abundance of vanadinite in the pipe scales, along with the existence of divalent lead. The occurrence of V in these samples as a discrete mineral is important because it is formed in the presence of very low concentrations of V in the finished water, it provides a mechanism to concentrate microg x L(-1) amounts of V from the water to near-percent levels in the pipe scales, and the robustness of V accumulation and release in response to water chemistry changes is likely different than it would be with a sorption accumulation mechanism. Extrapolation from limited existing water chemistry data in this study provides an estimate of deltaG(f)degrees for vanadinite as approximately -3443 kJ x mol(-1), or less, leading to a log K(s)0 value of approximately -86 for the reaction Pb5(VO4)3CI(s) equilibrium {Pb2+}5 + {VO4(3-) + {Cl-}, in which {} denotes activity.

Lead exposures in U.S. Children, 2008: implications for prevention.

OBJECTIVE: We reviewed the sources of lead in the environments of U.S. children, contributions to children's blood lead levels, source elimination and control efforts, and existing federal authorities. Our context is the U.S. public health goal to eliminate pediatric elevated blood lead levels (EBLs) by 2010. DATA SOURCES: National, state, and local exposure assessments over the past half century have identified risk factors for EBLs among U.S. children, including age, race, income, age and location of housing, parental occupation, and season. DATA EXTRACTION AND SYNTHESIS: Recent national policies have greatly reduced lead exposure among U.S. children, but even very low exposure levels compromise children's later intellectual development and lifetime achievement. No threshold for these effects has been demonstrated. Although lead paint and dust may still account for up to 70% of EBLs in U.S. children, the U.S. Centers for Disease Control and Prevention estimates that >or=30% of current EBLs do not have an immediate lead paint source, and numerous studies indicate that lead exposures result from multiple sources. EBLs and even deaths have been associated with inadequately controlled sources including ethnic remedies and goods, consumer products, and food-related items such as ceramics. Lead in public drinking water and in older urban centers remain exposure sources in many areas. CONCLUSIONS: Achieving the 2010 goal requires maintaining current efforts, especially programs addressing lead paint, while developing interventions that prevent exposure before children are poisoned. It also requires active collaboration across all levels of government to identify and control all potential sources of lead exposure, as well as primary prevention.