Phosphate treatment to reduce plumbosolvency of drinking water also reduces discharges of copper into environmental surface waters

The majority of drinking water supply zones in the United Kingdom are currently dosed with phosphate in order to meet the drinking water quality standards for lead. Consequent reductions in other metals released from domestic plumbing might be expected. Lead, copper, zinc and nickel concentrations in the tap water of supply zones and in effluents from related sewage works were examined to assess reductions in the concentrations of these metals associated with the dosing of orthophosphate. This paper provides an analysis of the impact of phosphate dosing of drinking water on the metal concentrations in drinking water and sewage work effluents and the potential impacts in relation to the Water Framework Directive. Phosphate treatment the reduced average copper concentrations in drinking water by around 40% from 65 to 35 μg/L; the reduction is proportional to the phosphate dose. A corresponding 30% decrease in wastewater treatment work effluent concentrations is observed. No significant changes are evident in the zinc and nickel concentrations.     

Effects of flow and water chemistry on lead release rates from pipe scales

Lead release from pipe scales was investigated under different water compositions, stagnation times, and flow regimes. Pipe scales containing PbO₂ and hydrocerussite (Pb₃(OH)₂(CO₃)₂) were developed on lead pipes by conditioning the pipes with water containing free chlorine for eight months. Water chemistry and the composition of the pipe scales are two key factors affecting lead release from pipe scales. The water rarely reached equilibrium with pipe scales within one day, which makes solid-water contact time and corrosion product dissolution rates the controlling factors of lead concentrations for the conditions tested. Among five water compositions studied, a solution with orthophosphate had the lowest dissolved lead release rate and highest particulate lead release rate. Free chlorine also decreased the dissolved lead release rate at stagnant conditions. Water flow increased rates of release of both dissolved and particulate lead by accelerating the mass transfer of lead out of the porous pipe scales and by physically destabilizing pipe scales. Dissolved lead comprised the majority of the lead released at both stagnant and laminar flow conditions.     

Impact of water treatment on the contribution of faucets to dissolved and particulate lead release at the tap

A field study was performed in a building complex to investigate the extent and sources of lead (Pb) release in tap water and brass material was found to be the main contributor in the very first draw (250 mL). Based on these results, a pilot installation was built to study Pb leaching from old and new faucets in the presence and absence of a connection to Cu piping. Four water quality conditions were tested: i) no treatment; ii) addition of 0.8 mg P/L of orthophosphate; iii) pH adjustment to 8.4; and iv) adjustment to a higher chloride to sulfate mass ratio (CSMR; ratio from 0.3 to 2.9). Pb concentrations in samples taken from the faucets without treatment ranged from 1 to 52 μg/L, with a mean of 11 μg/L. The addition of orthophosphate @ 0.8 mg P/L (OrthoP) was the most effective treatment for all types of faucets tested. On average, OrthoP reduced mean Pb leaching by 41%, and was especially effective for new double faucets (70%). In the presence of orthophosphates, the relative proportion of particulate Pb (Pbpart) (>0.45 μm) increased from 31% to 54%. However, OrthoP was not efficient to reduce Zn release. The higher CSMR condition was associated with greater dezincification of yellow brass but not of red brass. Corrosion control treatment influenced Pb concentration equilibrium, directly impacting maximal exposure. Significantly higher Pb release (3 fold) was observed for 1 of the 8 faucets connected to Cu exposed to high CSMR water, suggesting the presence of galvanic corrosion.     

Effects of chloride,sulfate and natural organic matter (NOM) on the accumulation and release of trace-level inorganic contaminants from corroding iron

This study examined effects of varying levels of anions (chloride and sulfate) and natural organic matter (NOM) on iron release from and accumulation of inorganic contaminants in corrosion scales formed on iron coupons exposed to drinking water. Changes of concentrations of sulfate and chloride were observed to affect iron release and, in lesser extent, the retention of representative inorganic contaminants (vanadium, chromium, nickel, copper, zinc, arsenic, cadmium, lead and uranium); but, effects of NOM were more pronounced. DOC concentration of 1 mg/L caused iron release to increase, with average soluble and total iron concentrations being four and two times, respectively, higher than those in the absence of NOM. In the presence of NOM, the retention of inorganic contaminants by corrosion scales was reduced. This was especially prominent for lead, vanadium, chromium and copper whose retention by the scales decreased from >80% in the absence of NOM to <30% in its presence. Some of the contaminants, notably copper, chromium, zinc and nickel retained on the surface of iron coupons in the presence of DOC largely retained their mobility and were released readily when ambient water chemistry changed. Vanadium, arsenic, cadmium, lead and uranium retained by the scales were largely unsusceptible to changes of NOM and chloride levels. Modeling indicated that the observed effects were associated with the formation of metal–NOM complexes and effects of NOM on the sorption of the inorganic contaminants on solid phases that are typical for iron corrosion in drinking water.     

Impact of galvanic corrosion on lead release from aged lead service lines

Partial lead service line replacement (PLSLR) may be performed when tap water lead concentrations exceed the action level and in association with water main replacement or other maintenance. Partially replacing lead pipes with copper tubing can create a galvanic couple if the lead and copper are connected by a metal coupling, which can potentially enhance lead release by galvanic corrosion. The effect of two types of couplings, brass and plastic, on lead release after a simulated PLSLR was investigated in a set of laboratory-scale experiments. Experiments were conducted in a recirculation flow mode with intermittent stagnation periods using aged lead pipes harvested from Providence, RI. Release of both dissolved and particulate lead was higher for the brass-coupled systems than for the plastic-coupled systems, and galvanic corrosion was the primary cause of significant particulate lead release from the brass-coupled systems. For brass-coupled systems, longer stagnation times resulted in dramatically more release of particulate lead. Sampling of different volumes following stagnation showed that lead release for the brass-coupled systems was locally much higher in the region closest to the coupling. The impact of galvanic corrosion persisted for the six weeks of the experiment.     

Designing water supplies: Optimizing drinking water composition for maximum economic benefit

It is possible to optimize drinking water composition based on a valuation of the impacts of changed water quality. This paper introduces a method for assessing the potential for designing an optimum drinking water composition by the use of membrane desalination and remineralization. The method includes modeling of possible water quality blends and an evaluation of corrosion indices. Based on concentration-response relationships a range of impacts on public health, material lifetimes and consumption of soap have been valued for Perth, Western Australia and Copenhagen, Denmark. In addition to water quality aspects, costs of water production, fresh water abstraction and CO₂-emissions are integrated into a holistic economic assessment of the optimum share of desalinated water in water supplies. Results show that carefully designed desalination post-treatment can have net benefits up to €0.3 ± 0.2 per delivered m³ for Perth and €0.4(±0.2) for Copenhagen. Costs of remineralization and green house gas emission mitigation are minor when compared to the potential benefits of an optimum water composition. Finally, a set of optimum water quality criteria is proposed for the guidance of water supply planning and management.     

Impacts of blending ground, surface, and saline waters on lead release in drinking water distribution systems

The impacts of distribution water quality changes caused by blending different source waters on lead release from corrosion loops containing small lead coupons were investigated in a pilot distribution study. The 1-year pilot study demonstrated that lead release to drinking water increased as chlorides increased and sulfates decreased. Silica and calcium inhibited lead release to a lesser degree than sulfates. An additional 3-month field study isolated and verified the effects of chlorides and sulfates on lead release. Lead release decreased with increasing pH and increasing alkalinity during the 1-year pilot study; however, the effects of pH and alkalinity on lead release, were not clearly elucidated due to confounding effects. A statistical model was developed using nonlinear regression, which showed that lead release increased with increasing chlorides, alkalinity and temperature, and decreased with increasing pH and sulfates. The model indicated that primary treatment processes such as enhanced coagulation and RO (reverse osmosis membrane) were related to lead release by water quality. Chlorides are high in RO-finished water and increase lead release, while sulfates are high following enhanced coagulation and decrease lead release.     

Chemical partitioning and remobilization of heavy metals from sewage sludge dumped in Dublin Bay

During the disposal of sewage sludge to the marine environment, chemical changes may alter the mobility of trace elements, thus affecting their potential toxicity and availability to marine organisms. Primary sludge from the Ringsend treatment plant in Dublin receives both domestic waste and trade wastes which contain heavy metals, and approx. 250,000 tons per annum is periodically dumped in Dublin Bay. The purpose of this study was to determine changes which may occur in the chemical partitioning of heavy metals in the sludge during disposal. Samples of sludge were collected from the treatment plant in July 1987. Sequential chemical extraction of heavy metals (Cu, Pb, Cd, Zn, Fe, Mn) was carried out in a nitrogen-filled glove box using 1 M ammonium acetate, 1 M sodium acetate, 0.1 M hydroxylamine HCl (pH 2), 0.2 M ammonium oxalate (pH 3), 30% hydrogen peroxide and concentrated HNO₃. Seawater-extractable metal was determined by mixing subsamples of sludge with filtered seawater from Dublin Bay for 2 h. Chemical partitioning of heavy metals among solid phases in the sludge residue was redetermined by sequential chemical extraction. Both sludge and dumpsite sediments were analysed for total heavy metal content and organic content. The sludge was found to be only slightly anaerobic with a water content of 88% and significant concentrations of some metals, notably copper and zinc. Most of the non-residual copper, lead and cadmium was found in the organic/sulphidic fraction of the sludge (hydrogen peroxide extract), while the dominant phase for zinc was the moderately reducible fraction (ammonium oxalate extract) and only iron and manganese had substantial proportions of metal in more labile phases. Agitation with seawater mobilized cadmium and manganese to a significant extent (56 and 43%, respectively) but negligible amounts of copper or lead (0 and 2%, respectively). However, significant changes in solid-phase partitioning of lead and zinc occurred resulting in mobilization from stronglybound to more labile fractions. No deleterious effects were found at the dumpsite but localized effects are possibly due to the increased mobility of zinc, lead and particularly cadmium.     

Role of temperature, chlorine, and organic matter in copper corrosion by-product release in soft water

Soft, low alkalinity drinking waters tend to cause relatively high copper corrosion by-product release in plumbing systems. Long-term tests (6-8 months) in a synthetic, microbially stable soft tap water confirmed that lower pHs and higher temperatures increased copper release to water. Soluble copper release increased at lower temperature and lower pH. Low levels of free chlorine (0.7 mg/L) slightly increased copper release at pH 9.5, in marked contrast to the dramatic reductions in copper release that have been observed in soft waters in which Type III pitting corrosion is occurring. Gum xanthan and sodium alginate produced a microbially unstable water that reduced the pH and DO during stagnation in pipes--these indirect effects far outweighed their possible role in chelation or other modes of direct attack on copper surfaces.     

Secondary effects of anion exchange on chloride, sulfate, and lead release: systems approach to corrosion control

Water treatment processes can cause secondary changes in water chemistry that alter finished water quality including chloride, sulfate, natural organic matter (NOM), and metal release. Hence, the goal of this research was to provide an improved understanding of the chloride-to-sulfate mass ratio (CSMR) with regards to chloride and sulfate variations at full-scale water treatment plants and corrosion potential under simulated premise plumbing conditions. Laboratory corrosion studies were conducted using Pb-Sn solder/Cu tubing galvanic cells exposed to model waters with low (approx. 5 mg/L Cl⁻ and 10 mg/L SO₄^2-) and high (approx. 50 mg/L Cl⁻ and 100 mg/L SO₄^2-) concentrations of chloride and sulfate at a constant CSMR of ∼0.5. The role of NOM during corrosion was also evaluated by changing the type of organic material. In addition, full-scale sampling was conducted to quantify the raw water variability of chloride, sulfate, and NOM concentrations and the changes to these parameters from magnetic ion exchange treatment. Test conditions with higher concentrations of chloride and sulfate released significantly more lead than the lower chloride and sulfate test waters. In addition, the source of NOM was a key factor in the amount of lead released with the model organic compounds yielding significantly less lead release than aquatic NOM.     

Addressing corrosion control and valve tuberculation in a water distribution system supplied by a silica-laden groundwater

Metal corrosion and valve tuberculation within a water distribution system supplied by groundwater containing 52 mg/L silica were studied using a corrosion test rack installed within a residence to determine the effectiveness of phosphate-based (PB) and silica-based (SB) corrosion inhibitor (CI). Results indicated that internal corrosion control based on the use of phosphate-based or silica-based CIs did not significantly decrease iron, lead, or copper corrosion rates, and in one case, caused a negative impact on copper corrosion rate. Evaluations of metal coupons using scanning electron microscopy, electron dispersive X-ray analysis, and X-ray photoelectron spectrophotometry confirmed these findings. Since CI failed to reduce corrosion rates, valve tuberculation within the water system could not be controlled. Consequently, a valve replacement plan was developed in place of an internal corrosion control method using CIs. An opinion of probable replacement cost for 200 tuberculated valves approximated $3.3 million expended over 20 years.     

Effect of flow rate and lead/copper pipe sequence on lead release from service lines

A pilot experiment examined lead leaching from four representative configurations of service lines including: (1) 100% lead (Pb), (2) 100% copper (Cu), (3) 50% Pb upstream of 50% Cu, and (4) 50% Pb-downstream of 50% Cu using a range of flow rates. The cumulative mass of lead release indicated that a typical partial replacement configuration (50% lead downstream of copper) did not provide a net reduction in lead when compared to 100% lead pipe (85 mg for 50% Pb-downstream versus 83 mg for 100%-Pb) due to galvanic and deposition corrosion. The partially replaced service line configuration also had a much greater likelihood of producing water with "spikes" of lead particulates at higher flow rates, while tending to produce lower levels of lead at very low flow rates. After the first 214 days the galvanic current between copper and lead was only reduced by 34%, proving that galvanic impacts can be highly persistent even in water with optimized corrosion control by dosing of zinc orthophosphate. Finally, this experiment raises concern about the low flow rates used during some prior home sampling events, which may underestimate exposure to lead during normal water use, especially when galvanic Pb:Cu connections are present.     

Galvanic Corrosion of Lead Solder in Copper Pipework

The galvanic corrosion potentials of thirty-eight different waters were measured on site, using 'Oliphant' corrosion cells, for lead-tin solder coupled to copper. A wide range in corrosion potential was found, and the chloride-sulphate ratio had the most significant effect on corrosion potential. Tests to reduce corrosion potentials by dosing sulphate, silicate, zinc and orthophosphate were carried out. Zinc dosing, especially in combination with ortho-phosphate, was the most effective treatment for all waters, but posed problems.
Contamination of tapwater by galvanic corrosion of lead solder occurs early in the life of new plumbing, and risk of exposure to contamination can be reduced by flushing before drawing dietetic water. Best-of-all, lead-tin solder should not be used.     

管网内淡化水的化学稳定性及控制方法研究

为研究海水反渗透淡化水在管网中的化学稳定性及控制方法,实现减缓管网腐蚀和改善管网水质的目的,分别建立由PE、塑钢和旧铸铁管组成的3套管网,并模拟淡化水在管网中的输配。研究了淡化水在3套管网中的水质变化规律,并考察了投加CaCO3、将淡化水和水库水混合等措施提高淡化水在管网中化学稳定性的效果。综合化学稳定性判别指数LSI(-3.8～-2.2)、RSI(12.3～14.1)、CCPP(-12.5～-10.5 mg/L)可知,反渗透淡化水具有极严重的腐蚀性;PE管网在减缓管网腐蚀和改善管网水质方面优于塑钢管网;投加CaCO3、将淡化水和水库水混合等措施能显著改善淡化水水质。     

Seasonal variations in natural organic matter and its impact on coagulation in water treatment

In the past decade, a number of UK and US water utilities have been experiencing operational difficulties connected with the increased dissolved organic carbon (DOC) levels during the autumn and winter periods. This has been observed as an increase in the production of disinfection-by-products (DBP), and a greater coagulant demand. Resin adsorption techniques were used to fractionate raw water and investigate the variation in surface charge and coagulant-humic interactions over a 36-month period. A change in the natural organic matter (NOM) composition throughout the year was observed, with the fulvic acid fraction (FAF) increasing from 36% in September to 61% in November. However, a reduction in treatment performance is not simply due to an increase in DOC concentrations (from 4.3 to 14.5 mg L-1), but also a change in the charge density of the NOM. It was found that hydrophilic NOM fractions possess negligible charge density (<0.06 meq g-1DOC), and it is the hydrophobic NOM fractions, FAF in particular, that exert the greater dominance on coagulation control. The hydrophilic NOM fractions are less amenable to removal through conventional coagulation with metal salts, and are therefore likely to indicate the DOC residual remaining after treatment. Understanding the seasonal changes in NOM composition and character and their reactivity with coagulants should lead to a better optimisation of the coagulation process and a more consistent water quality.     

Catalysis of copper corrosion products on chlorine decay and HAA formation in simulated distribution systems

This study investigated the effect of copper corrosion products, including Cu(II), Cu₂O, CuO and Cu₂(OH)₂CO₃, on chlorine degradation, HAA formation, and HAA speciation under controlled experimental conditions. Chlorine decay and HAA formation were significantly enhanced in the presence of copper with the extent of copper catalysis being affected by the solution pH and the concentration of copper corrosion products. Accelerated chlorine decay and increased HAA formation were observed at pH 8.6 in the presence of 1.0 mg/L Cu(II) compared with that observed at pH 6.6 and pH 7.6. Further investigation of chlorine decay in the presence of both Suwannee River NOM and Cu(II) indicated that an increased reactivity of NOM with dissolved and/or solid surface-associated Cu(II), rather than chlorine auto-decomposition, was a primary reason for the observed rapid chlorine decay. Copper corrosion solids [Cu₂O, CuO, Cu₂(OH)₂CO₃] exhibited catalytic effects on both chlorine decay and HAA formation. Contrary to the results observed when in the absence of copper corrosion products, DCAA formation was consistently predominant over other HAA species in the presence of copper corrosion products, especially at neutral and high pH. This study improves the understanding for water utilities and households regarding chlorine residuals and HAA concentrations in distribution systems, in particular once the water reaches domestic plumbing where copper is widely used.     

Speciation of trace inorganic contaminants in corrosion scales and deposits formed in drinking water distribution systems

Sequential extractions utilizing the modified Tessier scheme (Krishnamurti et al., 1995) and measurements of soluble and particulate metal released from suspended solids were used in this study to determine the speciation and mobility of inorganic contaminants (As, Cr, V, U, Cd, Ni, and Mn) found in corrosion scales and particles mobilized during hydraulic flushing events. Arsenic, chromium and vanadium are primarily associated with the mobilization-resistant fraction that is resistant to all eluents used in this study and also bound in highly stable crystalline iron oxides. Very low concentrations of these elements were released in resuspension experiments. X-ray absorbance measurements demonstrated that arsenic in the sample with the highest As concentration was dominated by As(V) bound by iron oxides. Significant fractions of uranium and cadmium were associated with carbonate solids. Nickel and manganese were determined to be more mobile and significantly associated with organic fractions. This may indicate that biofilms and natural organic matter in the drinking water distributions systems play an important role in the accumulation and release of these inorganic contaminants.     

Potential effects of desalinated water quality on the operation stability of wastewater treatment plants

Desalinated water is expected to become the major source of drinking water in many places in the near future, and thus the major source of wastewater to arrive at wastewater treatment plants. The paper examines the effect of the alkalinity value with which the water is released from the desalination plant on the alkalinity value that would develop within the wastewater treatment process under various nitrification-denitrification operational scenarios. The main hypothesis was that the difference in the alkalinity value between tap water and domestic wastewater is almost exclusively a result of the hydrolysis of urea (NH₂CONH₂, excreted in the human urine) to ammonia (NH₃), regardless of the question what fraction of NH_3(aq) is transformed to NH₄⁺. Results from a field study show that the ratio between the alkalinity added to tap water when raw wastewater is formed (in meq/l units) and the TAN (total ammonia nitrogen, mole/l) concentration in the raw wastewater is almost 1:1 in purely domestic sewage and close to 1:1 in domestic wastewater streams mixed with light industry wastewaters. Having established the relationship between TAN and total alkalinity in raw wastewater the paper examines three theoretical nitrification-denitrification treatment scenarios in the wastewater treatment plant (WWTP). The conclusion is that if low-alkalinity desalinated water constitutes the major water source arriving at the WWTP, external alkalinity will have to be added in order to avoid pH drop and maintain process stability. The results lead to the conclusion that supplying desalinated water with a high alkalinity value (e.g. ≥ 100 mg/l as CaCO₃) would likely prevent the need to add costly basic chemicals in the WWTP, while, in addition, it would improve the chemical and biological stability of the drinking water in the distribution system.     

Effects of NOM properties on copper release from model solid phases

This study examined impacts of concentrations and properties of natural organic matter (NOM) on copper release from characteristic copper solid model phases such as tenorite CuO and malachite Cu₂(OH)₂CO₃. Unaltered Aldrich humic acid (AHA) and standard Suwannee River fulvic acid (SRFA) strongly increased copper release from the model phases but NOM alteration by chlorination or ozonation gradually suppressed or, at higher oxidant doses, eliminated these effects. The nature of NOM changes induced by chlorination and ozonation was examined using differential absorbance spectroscopy (DAS) and high-performance size-exclusion chromatography (HPSEC). The data of these methods show that NOM molecules with higher apparent molecular weight (AMW), higher aromaticities and contributions of protonation-active phenolic and carboxylic groups play a key role in adsorption and colloidal dispersion of the model solids. The data also show that metal release from model phases was well correlated with a number of spectroscopic parameters characterizing NOM properties, notably SUVA₂₅₄, spectral slopes of NOM absorbance, and differential absorbance at wavelength of 280 nm and 350 nm that is indicative of the contributions of carboxylic and phenolic functional groups. Changes of ζ-potential of the model solid phases were the strongest predictor of the enhancement of copper release especially in the system controlled by malachite. While effects of NOM on the ζ-potential of tenorite and malachite were prominent for unaltered NOM, its oxidation by chlorine and ozone was accompanied by a gradual decrease and ultimately disappearance of its surface activity.     

Impact of UV disinfection on microbially available phosphorus,organic carbon,and microbial growth in drinking water

UV irradiation at a wavelength of 253.7 nm (UV(254)) is commonly used for drinking water disinfection. UV radiation is known to convert organically combined phosphorus to orthophosphate and to degrade natural organic matter. We studied if UV disinfection increases the amount of microbially available forms of organic carbon and phosphorus in drinking waters with different characteristics, and if these changes in water chemical quality could enhance the microbial growth in drinking water. The UV(254) dose (15-50 mWs/cm(2)) used in waterworks reduced the concentration of assimilable organic carbon and the sum of the molecular size fractions. The release of microbially available phosphorus needed higher doses (204 mWs/cm(2)) of UV(254) radiation. Of bacteria in drinking water, 90% were inactivated with UV(254)-irradiation doses below 50 mWs/cm(2). A high dose (501 mWs/cm(2)) of UV(254) radiation inhibited the microbial growth in water.