Impacts of orthophosphate-polyphosphate blends on the dissolution and transformation of lead (II) carbonate.

Orthophosphate-polyphosphate blends are commonly used to control lead release into drinking water, but little is known about how they interact with lead corrosion scale. Conventional corrosion control practice assumes that orthophosphate controls lead release by forming insoluble Pb-phosphate minerals, but this does not always occur, and under certain conditions, phosphate blends may increase lead release. Here, we used continuously-stirred tank reactors to compare orthophosphate-polyphosphate blends with orthophosphate on the basis of lead (II) carbonate dissolution and transformation at environmentally relevant phosphate concentrations. Three model polyphosphates-tripoly-, trimeta- and hexametaphosphate-were used. Hexametaphosphate was the strongest complexing agent (1.60-2.10 molPb/molPolyphosphate), followed by tripolyphosphate and trimetaphosphate (1.00 and 0.07 molPb/molPolyphosphate, respectively. At equivalent orthophosphate and polyphosphate concentrations (as P), orthophosphate-trimetaphosphate had minimal impact on lead release, while orthophosphate-tripolyphosphate increased dissolved lead. Orthophosphate-hexametaphosphate also increased dissolved lead, but only over a 24-h stagnation. Both orthophosphate-tripolyphosphate and orthophosphate-hexametaphosphate increased colloidal lead after 24-h. Increasing the concentrations of hexameta- and tripoly-phosphate increased dissolved lead release, while all three polyphosphates inhibited the formation of hydroxypyromorphite and reduced the phosphorus content of the resulting lead solids. We attributed the impacts of orthophosphate-polyphosphates to a combination of complexation, adsorption, colloidal dispersion, polyphosphate hydrolysis, and lead mineral precipitation.

Early phase effects of silicate and orthophosphate on lead (Pb) corrosion scale development and Pb release.

Orthophosphate is widely used to control lead (Pb) release in drinking water distribution systems, but phosphorus addition is not sustainable. Alternative corrosion control treatments are needed, and sodium silicate is one possibility. Here, pre-corroded Pb coupons-with and without free chlorine-were used to examine early-phase corrosion scale development after silicate addition, with orthophosphate as a reference corrosion inhibitor. Scale development was evaluated in terms of total Pb release, phase transformation, electrochemical impedance, morphological changes, Pb dissolution kinetics, and short-term Pb-Cu galvanic corrosion. Elevated Pb release occurred for approximately one month after silicate addition, and total Pb release peaked at 1968.1 µg/L and 1176.9 µg/L from systems with and without free chlorine, respectively. In contrast, orthophosphate-treated coupons exhibited fewer, less pronounced spikes in Pb release. By day 354, the median total Pb release from orthophosphate-treated coupons with and without free chlorine had decreased to 3.7 and 5.0 µg/L, respectively, while the median total Pb release from corresponding silicate-treated coupons was much higher, at 44.9 µg/L and 34.3 µg/L. Calcium lead apatite (Ca0.56Pb3.77(PO4)3OH0.67) was identified in orthophosphate-treated scales, with hydroxylpyromorphite (Pb5(PO4)3OH) present in the absence of free chlorine. Plattnerite occurred on coupons in all chlorinated systems. Pb silicate compounds were not detected, but Ca2SiO4 and Na2Ca2(SiO3)3 were identified by X-ray powder diffraction. The charge transfer: film resistance ratio characterizing the orthophosphate-treated coupons decreased slowly while that of the silicate-treated coupons increased after silicate was added. These variations suggest orthophosphate provided better corrosion control than silicate did. Silicate treatment generally caused degradation of the top Pb scale layer, resulting in elevated Pb release, while orthophosphate encouraged the growth of more structured, generally thicker, corrosion scales that were effective in limiting Pb release.

Seasonal Lead Release into Drinking Water and the Effect of Aluminum.

Monitoring lead in drinking water is important for public health, but seasonality in lead concentrations can bias monitoring programs if it is not understood and accounted for. Here, we describe an apparent seasonal pattern in lead release into orthophosphate-treated drinking water, identified through point-of-use sampling at sites in Halifax, Canada, with various sources of lead. Using a generalized additive model, we extracted the seasonally varying components of time series representing a suite of water quality parameters and we identified aluminum as a correlate of lead. To investigate aluminum's role in lead release, we modeled the effect of variscite (AlPO4·2H2O) precipitation on lead solubility, and we evaluated the effects of aluminum, temperature, and orthophosphate concentration on lead release from new lead coupons. At environmentally relevant aluminum and orthophosphate concentrations, variscite precipitation increased predicted lead solubility by decreasing available orthophosphate. Increasing the aluminum concentration from 20 to 500 µg L-1 increased lead release from coupons by 41% and modified the effect of orthophosphate, rendering it less effective. We attributed this to a decrease in the concentration of soluble (<0.45 µm) phosphorus with increasing aluminum and an accompanying increase in particulate lead and phosphorus (>0.45 µm).

Pilot-scale comparison of sodium silicates, orthophosphate and pH adjustment to reduce lead release from lead service lines.

Sodium silicate is thought to mitigate lead release via two mechanisms: by increasing pH and by forming a protective silica film. A pilot-scale study using an excavated lead service line (LSL) fed with water from a Great Lakes source was undertaken to: (1) clearly distinguish the pH effect and the silica effect; (2) compare sodium silicate to orthophosphate and pH adjustment; (3) determine the nature of silica accumulation in the pipe scale. The LSL was cut into segments and acclimated with water at pH 7.1. Median dissolved lead was 197 µg/L in the last 8 weeks of acclimation and dropped to 16 µg/L, 54 µg/L, and 85 µg/L following treatment with orthophosphate (dose: 2.6 mg-PO4/L, pH: 7.9), pH adjustment (pH: 7.9) and sodium silicate (dose: 20 mg-SiO2/L, pH: 7.9), respectively. When silica dose was increased from 20 mg-SiO2/L to 25 mg-SiO2/L (pH: 8.1), lead release destabilized and increased (median dissolved lead: 141 µg/L) due to formation of colloidal dispersions composed mainly of lead- and aluminum-rich phases as detected by field flow fractionation used with inductively coupled plasma mass spectrometry. Si was present in the scale at a maximum of 2.2 atomic % after 17 weeks of silica dosing at 20 mg- SiO2/L. Under the conditions tested, sodium silicate did not offer any benefits for reducing lead release from this LSL other than increasing pH. However, sodium silicate resulted in lower levels of biofilm accumulation on pipe walls, as measured by heterotrophic plate counts, when compared to orthophosphate.

Controlling lead release due to uniform and galvanic corrosion - An evaluation of silicate-based inhibitors.

Silicates have been added to drinking water for decades, both to sequester iron/manganese and as a corrosion control treatment for lead. But the mechanisms by which they might act to limit lead release are not well understood. We evaluated the effects of two silicate formulations on lead release due to uniform and galvanic corrosion over a wide range of pH and dissolved inorganic carbon concentrations. We compared these results to better-characterized systems, with added ortho- or polyphosphate and in an inhibitor-free control. Independent of pH, silicates did not consistently mitigate lead release due to either uniform or galvanic corrosion. Furthermore, lead carbonates appeared to determine lead solubility in the presence of sodium silicate. While silicate treatment did promote the formation of a nanometer-thick silicon layer on lead and a decrease in crystallite size at the scale surface, these changes did not inhibit lead release. But unlike polyphosphate-which is known to form soluble complexes with lead and disperse particulate metals-high ratio silicate did not exacerbate lead release. Metasilicate did exacerbate lead release, especially at pH 7 and 5 mg DIC/L; this suggests that silicate formulation may have an important effect on the dispersion of lead-rich particles.

Impact of sodium silicate on lead release and colloid size distributions in drinking water.

Sodium silicates have been used in drinking water treatment for decades as sequestrants and corrosion inhibitors. For the latter purpose they are poorly understood, which presents a potential public health risk. We investigated a common sodium silicate formulation as a treatment for lead release and compared it to orthophosphate, a well-established lead corrosion control treatment. We also compared the size distributions of colloids generated in silicate and orthophosphate-treated systems using field flow fractionation with multielement detection. At a moderate dose of 24 mg SiO2/L, sodium silicate yielded a median lead release of 398 µg/L, while orthophosphate yielded 67 µg Pb/L. At an elevated dose of 48 mg SiO2/L, sodium silicate dispersed corrosion scale in cast iron pipe sections and lead service lines, resulting in a substantial release of colloidal iron and lead. In the silicate-treated system, a silicon-rich coating occurred at the lead-water interface, but lead carbonate remained the major corrosion product and appeared to control lead levels. These data suggest that, as a corrosion control treatment for lead, sodium silicate is inferior to orthophosphate in circumneutral pH water with low alkalinity. And, as with polyphosphate, excess silicate can be highly detrimental to controlling lead release.

Inorganic contaminants in Canadian First Nation community water systems.

While previous Canadian studies have examined microbiological water quality in First Nations, there is little published information on inorganic contaminants. In Atlantic Canada, the lead, manganese, and arsenic content of First Nations' drinking water has been measured for more than a decade, but the data have not been analyzed comprehensively. These contaminants are linked with health problems, and high levels in drinking water are a cause for concern. We examined 12 years of data from 47 First Nation community water systems to identify systems experiencing difficulties meeting sampling frequency or regulatory guidelines. While most contaminant concentrations were below guideline values, we identified elevated concentrations and issues with sampling frequency. No system met both sampling frequency requirements - a minimum of one sample per year per analyte - and regulatory guidelines. Exceedance rates for lead, manganese, and arsenic were high in some systems. Moreover, current sampling procedures for lead specify that taps be flushed prior to sampling, which is known to underestimate lead exposure. We find that a switch to random daytime sampling would at least sometimes yield higher estimates of lead at the tap. Our analysis demonstrates the need for increased monitoring and updated sampling procedures to better characterize inorganic contaminant occurrence in First Nations.

Source Water Characteristics and Building-specific Factors Influence Corrosion and Point of Use Water Quality in a Decentralized Arctic Drinking Water System.

Access to clean and safe drinking water is a perpetual concern in Arctic communities because of challenging climatic conditions, limited options for the transportation of equipment and process chemicals, and the ongoing effects of colonialism. Water samples were gathered from multiple locations in a decentralized trucked drinking water system in Nunavut, Canada, over the course of one year. The results indicate that point of use drinking water quality was impacted by conditions in the source water and in individual buildings and strongly suggest that lead and copper measured at the tap were related to corrosion of onsite premise plumbing components. Humic-like substances were the dominant organic fraction in all samples, as determined by regional integration of fluorescence data. Iron and manganese levels in the source water and throughout the water system were higher in the winter and lower in the summer months. Elevated concentrations of copper (>2000 µg L-1) and lead (>5 µg L-1) were detected in tap water from some buildings. Field flow fractionation coupled with inductively coupled plasma mass spectrometry and ultraviolet-visible spectrometry was used to demonstrate the link between source water characteristics (high organics, iron and manganese) and lead and copper in point of use drinking water.

Manganese Increases Lead Release to Drinking Water.

Lead and manganese are regulated in drinking water due to their neurotoxicity. These elements have been reported to co-occur in drinking water systems, in accordance with the metal-scavenging properties of MnO2. To the extent that manganese is a driver of lead release, controlling it during water treatment may reduce lead levels. We investigated transport of lead and manganese at the tap in a full-scale distribution system: consistent with a cotransport phenomenon, the two metals were detected in the same colloidal size fraction by size-exclusion chromatography with multielement detection. We also studied the effect of manganese on lead release using a model distribution system: increasing manganese from 4 to 215 µg L-1 nearly doubled lead release. This effect was attributed primarily to deposition corrosion of lead by oxidized phases of manganese, and we used 16S rRNA sequencing to identify bacteria that may be relevant to this process. We explored the deposition corrosion mechanism by coupling pure lead with either MnO2-coated lead or pure lead exposed to MnO2 in suspension; we observed galvanic currents in both cases. We attributed these to reduction of Mn(IV) under anaerobic conditions, and we attributed the additional current under aerobic conditions to oxygen reduction catalyzed by MnO2.

Fluorescence Spectra Predict Microcystin-LR and Disinfection Byproduct Formation Potential in Lake Water.

Disinfection byproducts (DBPs) and algal toxins can be expensive to monitor and represent significant potential risks to human health. DBPs, including haloacetic acids and trihalomethanes, are possible or probable human carcinogens. Microcystin-LR-produced by cyanobacteria-is linked with various adverse health effects. Here we show that fluorescence spectra predict both microcystin-LR occurrence and DBP formation potential (DBPfp) in lake water. We compared models with either fluorescence spectra or a suite of water quality predictors as inputs. A regularized logistic regression model with fluorescence spectral inputs correctly classified 94% of test data with respect to microcystin-LR occurrence, with a 96% probability of correctly ranking a detect/nondetect pair. Regularized linear regression predicted DBPfp based on fluorescence inputs with a combined R2 of 0.83 on test data. A gradient-boosted classifier with seven water quality inputs was comparable in detecting microcystin-LR (91% correct), as was UV254 in predicting DBPfp (combined test R2 = 0.84), but no single parameter matched fluorescence spectra over both predictive tasks. Results highlight the potential for multiparameter monitoring via fluorescence spectroscopy, extending previous work on predicting DBPs alone. As a high-frequency monitoring tool, this approach could supplement mass spectrometric methods that may only be applicable at low frequency due to resource limitations.

Understanding the Impact of Extracellular Polymeric Substances on Lead Release in Drinking Water Systems.

Lead release in a lead (Pb, anode)-iron oxide (α-Fe2O3, cathode) galvanic system was studied under the influence of synthetic extracellular polymeric substances (sEPS). Sodium alginate, bovine serum albumin (BSA), and cytochrome c represented extracellular polysaccharides, proteins, and electrochemically active components, respectively. Microbiologically influenced corrosion was investigated using sEPS and pelleted and resuspended Pseudomonas aeruginosa cells. Relative to the anaerobic inorganic control, Pb release increased by 156, 202, and 198 µg/L when sEPS was present on the cathode side at 200 mg/L (100 mg/L alginate + 100 mg/L BSA), 400 mg/L (200 mg/L alginate + 200 mg/L BSA), and 200 mg/L with 123.84 mg/L cytochrome c, respectively, under anaerobic conditions. When the cathode was aerated, Pb release increased by 75, 260, and -71 µg/L under the aforementioned conditions, all relative to the aerated inorganic control. When sEPS was instead present on the anode side, sEPS caused localized corrosion on Pb and resulted in higher Pb release than predicted by electric current. P. aeruginosa generally enhanced corrosion; when cells were dosed in the anode side, part of the oxidized Pb was immobilized by cells or organic compounds adhered to the electrodes.

Galvanic Corrosion of Lead by Iron (Oxyhydr)Oxides: Potential Impacts on Drinking Water Quality.

Lead exposure via drinking water remains a significant public health risk; this study explored the potential effects of upstream iron corrosion on lead mobility in water distribution systems. Specifically, galvanic corrosion of lead by iron (oxyhydr)oxides was investigated. Coupling an iron mineral cathode with metallic lead in a galvanic cell increased lead release by 531 µg L-1 on average-a 9-fold increase over uniform corrosion in the absence of iron. Cathodes were composed of spark plasma sintered Fe3O4 or α-Fe2O3 or field-extracted Fe3O4 and α-FeOOH. Orthophosphate immobilized oxidized lead as insoluble hydroxypyromorphite, while humic acid enhanced lead mobility. Addition of a humic isolate increased lead release due to uniform corrosion by 81 µg L-1 and-upon coupling lead to a mineral cathode-release due to galvanic corrosion by 990 µg L-1. Elevated lead in the presence of humic acid appeared to be driven by complexation, with 208Pb and UV254 size-exclusion chromatograms exhibiting strong correlation under these conditions (R2average = 0.87). A significant iron corrosion effect was consistent with field data: lead levels after lead service line replacement were greater by factors of 2.3-4.7 at sites supplied by unlined cast iron distribution mains compared with the alternative, lined ductile iron.

Lake Recovery Through Reduced Sulfate Deposition: A New Paradigm for Drinking Water Treatment.

This study examined sulfate deposition in Nova Scotia from 1999 to 2015, and its association with increased pH and organic matter in two protected surface water supplies (Pockwock Lake and Lake Major) located in Halifax, Nova Scotia. The study also examined the effect of lake water chemistry on drinking water treatment processes. Sulfate deposition in the region decreased by 68%, whereas pH increased by 0.1-0.4 units over the 16-year period. Average monthly color concentrations in Pockwock Lake and Lake Major increased by 1.7 and 3.8×, respectively. Accordingly, the coagulant demand increased by 1.5 and 3.8× for the water treatment plants supplied by Pockwock Lake and Lake Major. Not only was this coagulant increase costly for the utility, it also resulted in compromised filter performance, particularly for the direct-biofiltration plant supplied by Pockwock Lake that was found to already be operating at the upper limit of the recommended direct filtration thresholds for color, total organic carbon and coagulant dose. Additionally, in 2012-2013 geosmin occurred in Pockwock Lake, which could have been attributed to reduced sulfate deposition as increases in pH favor more diverse cyanobacteria populations. Overall, this study demonstrated the impact that ambient air quality can have on drinking water supplies.

Understanding the Role of Particulate Iron in Lead Release to Drinking Water.

Lead service lines (LSLs) are a major source of drinking water lead, and high iron levels are frequently observed along with elevated lead release. A model distribution system, dosed with orthophosphate, was used to evaluate the effect of corroded iron distribution mains on lead release from recovered LSLs. Lead release was higher by 96 µg L(-1), on average, from LSLs supplied by corroded iron compared to the inert reference material (PVC). This effect may be explained by deposition of semiconducting iron oxide particles within LSLs. When galvanic cells with lead and magnetite (Fe3O4) electrodes were short-circuited, lead release increased 8-fold and a current averaging 26 µA was observed. In effluent from LSLs with an upstream iron main, colloidal lead and iron occurred in the same size fraction-possibly due to release of colloidal particles from LSL corrosion scale enriched with iron. Under these circumstances, high molecular weight (>669 kDa) (208)Pb and (56)Fe elution profiles, observed via size-exclusion chromatography, were highly correlated (average R(2) = 0.97). Increasing orthophosphate from 0.5 to 1.0 mg L(-1) (as PO4(3-)) accompanied an average reduction in lead release of 6 µg L(-1) month(-1) but did not significantly reduce the effect of an upstream iron main.

Evaluating the Effects of Full and Partial Lead Service Line Replacement on Lead Levels in Drinking Water.

Lead service line replacement (LSLR) is an important strategy for reducing lead exposure via drinking water, but jurisdictional issues can sometimes interfere with full replacement of the lead line. The effects of full and partial LSLR on lead levels were assessed using 5 × 1-L sample profiles collected at more than 100 single-unit residences. Profiles comprised four sequential standing samples (L1-L4) and a free-flowing sample (L5) drawn after a 5 min flush of the outlet. At 45 sites with full lead service lines, 90th percentile lead levels in standing samples ranged from 16.4 to 44.5 µg L(-1) (L1 and L4, respectively). In the free-flowing sample (L5), 90th percentile lead was 9.8 µg L(-1). Within 3 days, full LSLR had reduced L3-L5 lead levels by more than 50%, and within 1 month, lead levels were significantly lower in every liter of the sample profile. Conversely, partial LSLR more than doubled premises plumbing (L1, L2) lead release in the short term and did not reduce L1, L2 lead release in the long term. Even 6 months after partial LSLR, 27% of first-draw lead levels were greater than 15 µg L(-1) (the U.S. EPA action level), compared with 13% pre-replacement.

A new analytical approach to understanding nanoscale lead-iron interactions in drinking water distribution systems.

High levels of iron in distributed drinking water often accompany elevated lead release from lead service lines and other plumbing. Lead-iron interactions in drinking water distribution systems are hypothesized to be the result of adsorption and transport of lead by iron oxide particles. This mechanism was explored using point-of-use drinking water samples characterized by size exclusion chromatography with UV and multi-element (ICP-MS) detection. In separations on two different stationary phases, high apparent molecular weight (>669 kDa) elution profiles for (56)Fe and (208)Pb were strongly correlated (average R(2)=0.96, N=73 samples representing 23 single-unit residences). Moreover, (56)Fe and (208)Pb peak areas exhibited an apparent linear dependence (R(2)=0.82), consistent with mobilization of lead via adsorption to colloidal particles rich in iron. A UV254 absorbance peak, coincident with high molecular weight (56)Fe and (208)Pb, implied that natural organic matter was interacting with the hypothesized colloidal species. High molecular weight UV254 peak areas were correlated with both (56)Fe and (208)Pb peak areas (R(2)=0.87 and 0.58, respectively). On average, 45% (std. dev. 10%) of total lead occurred in the size range 0.05-0.45 µm.