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THE EFFECTS OF PHOSPHATE AND SILICATE INHIBITORS ON SURFACE ROUGHNESS AND COPPER RELEASE IN WATER DISTRIBUTION SYSTEMS
Title
THE EFFECTS OF PHOSPHATE AND SILICATE INHIBITORS ON SURFACE ROUGHNESS AND COPPER RELEASE IN WATER DISTRIBUTION SYSTEMS.
Creator
MacNevin, David, Taylor, James, University of Central Florida
Abstract / Description
The effects of corrosion inhibitors on water quality and the distribution system were studied. This dissertation investigates the effect of inhibitors on iron surface roughness, copper surface roughness, and copper release. Corrosion inhibitors included blended poly/ortho phosphate, sodium orthophosphate, zinc orthophosphate, and sodium silicate. These inhibitors were added to a blend of surface water, groundwater, and desalinated brackish water. Surface roughness of galvanized iron, unlined...
Show moreThe effects of corrosion inhibitors on water quality and the distribution system were studied. This dissertation investigates the effect of inhibitors on iron surface roughness, copper surface roughness, and copper release. Corrosion inhibitors included blended poly/ortho phosphate, sodium orthophosphate, zinc orthophosphate, and sodium silicate. These inhibitors were added to a blend of surface water, groundwater, and desalinated brackish water. Surface roughness of galvanized iron, unlined cast iron, lined cast iron, and polyvinyl chloride was measured using pipe coupons exposed for three months. Roughness of each pipe coupon was measured with an optical surface profiler before and after exposure to inhibitors. For most materials, inhibitor did not have a significant effect on surface roughness; instead, the most significant factor determining the final surface roughness was the initial surface roughness. Coupons with low initial surface roughness tended to have an increase in surface roughness during exposure, and vice versa, implying that surface roughness tended to regress towards an average or equilibrium value. For unlined cast iron, increased alkalinity and increased temperature tended to correspond with increases in surface roughness. Unlined cast iron coupons receiving phosphate inhibitors were more likely to have a significant change in surface roughness, suggesting that phosphate inhibitors affect stability of iron pipe scales. Similar roughness data collected with new copper coupons showed that elevated orthophosphate, alkalinity, and temperature were all factors associated with increased copper surface roughness. The greatest increases in surface roughness were observed with copper coupons receiving phosphate inhibitors. Smaller increases were observed with copper coupons receiving silicate inhibitor or no inhibitor. With phosphate inhibitors, elevated temperature and alkalinity were associated with larger increases in surface roughness and blue-green copper (II) scales.. Otherwise a compact, dull red copper (I) scale was observed. These data suggest that phosphate inhibitor addition corresponds with changes in surface morphology, and surface composition, including the oxidation state of copper solids. The effects of corrosion inhibitors on copper surface chemistry and cuprosolvency were investigated. Most copper scales had X-ray photoelectron spectroscopy binding energies consistent with a mixture of Cu2O, CuO, Cu(OH)2, and other copper (II) salts. Orthophosphate and silica were detected on copper surfaces exposed to each inhibitor. All phosphate and silicate inhibitors reduced copper release relative to the no inhibitor treatments, keeping total copper below the 1.3 mg/L MCLG for all water quality blends. All three kinds of phosphate inhibitors, when added at 1 mg/L as P, corresponded with a 60% reduction in copper release relative to the no inhibitor control. On average, this percent reduction was consistent across varying water quality conditions in all four phases. Similarly when silicate inhibitor was added at 6 mg/L as SiO2, this corresponded with a 25-40% reduction in copper release relative to the no inhibitor control. Hence, on average, for the given inhibitors and doses, phosphate inhibitors provided more predictable control of copper release across changing water quality conditions. A plot of cupric ion concentration versus orthophosphate concentration showed a decrease in copper release consistent with mechanistic control by either cupric phosphate solubility or a diffusion limiting phosphate film. Thermodynamic models were developed to identify feasible controlling solids. For the no inhibitor treatment, Cu(OH)2 provided the closest prediction of copper release. With phosphate inhibitors both Cu(OH)2 and Cu(PO4)·2H2O models provided plausible predictions. Similarly, with silicate inhibitor, the Cu(OH)2 and CuSiO3·H2O models provided plausible predictions.
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Date Issued
2008
Identifier
CFE0002001, ucf:47621
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0002001
USING ELECTROCHEMICAL MONITORING TO PREDICT METAL RELEASE IN DRINKING WATER DISTRIBUTION SYSTEMS
Title
USING ELECTROCHEMICAL MONITORING TO PREDICT METAL RELEASE IN DRINKING WATER DISTRIBUTION SYSTEMS.
Creator
Vaidya, Rajendra, Taylor, James, University of Central Florida
Abstract / Description
ABSTRACT Corrosion of distribution system piping and home plumbing materials is a major concern in the water community. Iron release adverse affects aesthetic water quality and the release of copper and lead is regulated by the Lead and Copper rule (LCR) and can adversely affect consumer health. Corrosion control is typically done by pH regulation and/or addition of corrosion inhibitors. Monitoring of corrosion control is typically done after the fact by monitoring metal release, functional...
Show moreABSTRACT Corrosion of distribution system piping and home plumbing materials is a major concern in the water community. Iron release adverse affects aesthetic water quality and the release of copper and lead is regulated by the Lead and Copper rule (LCR) and can adversely affect consumer health. Corrosion control is typically done by pH regulation and/or addition of corrosion inhibitors. Monitoring of corrosion control is typically done after the fact by monitoring metal release, functional group concentration of the selected chemical species or water quality. Hence, the associated laboratory analyses create a significant delay prior to the assessment of corrosion in drinking water systems. As corrosion in drinking water systems is fundamentally an electrochemical process, measurement of the electrical phenomena associated with corrosion can be use for real-time corrosion monitoring. This dissertation focuses on using parameters associated with electrochemical corrosion monitoring (EN) measurements in a field facility to predict and control the release of Iron, Copper and Lead in finished waters produced from ground, surface and saline sources with and without usage of corrosion inhibitors. EN data has not been used previously to correlate water quality and metal release; hence the use of EN data for corrosion control in drinking water systems has not been developed or demonstrated. Data was collected over a one year period from a large field facility using finished waters that are distributed to each of the fourteen pilot distribution systems (PDSs), corrosion loops and Nadles each. The PDSs have been built from aged pipes taken from existing distribution systems and contain links of PVC, lined cast Iron, unlined cast Iron and galvanized Steel pipe. The effluent for each PDS was split in two parts. One was delivered to the corrosion loops which are made from coiled copper pipe with lead-tin coupon inserted inside each loop and the other was delivered to the Nadles which housed the EN probes with electrodes for Fe or Cu or Pb-Sn. Finished water quality was monitored in and out of each PDS and total and dissolved Copper and Lead were monitored out of each corrosion loop. Photographs, scanning electron microscope (SEM) micrographs and energy disruptive x-ray spectroscopy (EDAX) conducted on all EN electrodes. EN electrodes showed dark brown to blackish voluminous scales for Fe, and EDAX revealed occurrence of two scales in distinct areas for all Fe electrodes; one comprised of porous, spongy looking structures and scales with more Fe content where the other had denser and more compact scales richer in Ca and P or Si. Cu electrodes had an orange to dark brown thin scale with blue green spots. Small pits were consistently observed mostly in the centre of such blue green spots which were identified as copper carbonates. The Pb electrodes visually showed a thin shiny transparent film with a surface very similar to the unexposed electrodes. Numerous pits were visually for pH controls and not seen for inhibitors; but SEM revealed that all electrodes had pits but the inhibitors reduced number and size of pits compared with pH controls. Thin hexagonal hydrocerussite plates were observed to occur in distinct growth areas and the presence of P or Si inhibitor seemed to increase the occurrence of hydrocerussite. Both Fe & Pb release were mostly in the particulate form while Cu release was mostly in the dissolved form. Total and dissolved Fe, Cu and Pb release models using EN parameters were developed by nonlinear regression. Fe release increased with localized corrosion (PF) and the EN model predicts that Fe release can be effectively controlled to the same degree by pH elevation or inhibitors. Cu release increased with general corrosion (LPRCR) and was also influenced by localized corrosion (ECNCR). However general corrosion was more significant for copper release which was mostly in the dissolved form. Pb release was depended on both general corrosion (LPRCR & HMCR) and localized corrosion (PF). The EN models predict that both Cu and Pb release is highest for pH control and all inhibitors reduced Cu and Pb release, which is consistent with the data. Inhibitors ranked by increasing effectiveness for reducing both Cu and Pb release are pH elevation, Si, ZOP, OP and BOP. EN monitoring is faster and less labor intensive than water quality monitoring and represents a significant advance for controlling metal release in drinking water distribution systems. The EN models were found to be comparable to water quality models developed from this study for metal release, and since EN is a real-time technique it offers a tremendous advantage over traditional water quality sampling techniques. Remote access of EN monitoring equipment is possible and the system requires little to no maintenance with the exception of a power supply or battery. The rapid turn around of corrosion rates from EN can be used to estimate metal release in drinking water proactively and mitigating measures can be implemented before the full adverse impacts are realized.
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Date Issued
2007
Identifier
CFE0001953, ucf:47430
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0001953
EFFECTS OF SOURCE WATER BLENDING FOLLOWING TREATMENT WITH SODIUM SILICATE AS A CORROSION INHIBITOR ON METAL RELEASE WITHIN A WATER DISTRIBUTION SYSTEM
Title
EFFECTS OF SOURCE WATER BLENDING FOLLOWING TREATMENT WITH SODIUM SILICATE AS A CORROSION INHIBITOR ON METAL RELEASE WITHIN A WATER DISTRIBUTION SYSTEM.
Creator
Lintereur, Phillip, Duranceau, Steven, University of Central Florida
Abstract / Description
A study was conducted to investigate and quantify the effects of corrosion inhibitors on metal release within a pilot distribution system while varying the source water. The pilot distribution system consisted of pre-existing facilities from Taylor et al (2005). Iron, copper, and lead release data were collected during four separate phases of operation. Each phase was characterized by the particular blend ratios used during the study. A blended source water represented a water that had been...
Show moreA study was conducted to investigate and quantify the effects of corrosion inhibitors on metal release within a pilot distribution system while varying the source water. The pilot distribution system consisted of pre-existing facilities from Taylor et al (2005). Iron, copper, and lead release data were collected during four separate phases of operation. Each phase was characterized by the particular blend ratios used during the study. A blended source water represented a water that had been derived from a consistent proportion of three different source waters. These source waters included (1) surface water treated through enhanced coagulation/sedimentation/filtration, (2) conventionally treated groundwater, and (3) finished surface water treated using reverse osmosis membranes. The corrosion inhibitors used during the study were blended orthophosphate (BOP), orthophosphate (OP), zinc orthophosphate (ZOP), and sodium silicate (Si). This document was intended to cite the findings from the study associated with corrosion treatment using various doses of sodium silicate. The doses were maintained to 3, 6, and 12 mg/L as SiO2 above the blend-dependent background silica concentration. Sources of iron release within the pilot distribution system consisted of, in the following order of entry, (1) lined cast iron, (2) un-lined cast iron, and (3) galvanized steel. Iron release data from these materials was not collected for each individual iron source. Instead, iron release data represented the measurement of iron upon exposure to the pilot distribution system in general. There was little evidence to suggest that iron release was affected by sodium silicate. Statistical modeling of iron release suggested that iron release could be described by the water quality parameters of alkalinity, chlorides, and pH. The R2 statistic implied that the model could account for only 36% of the total variation within the iron release data set (i.e. R2 = 0.36). The model implies that increases in alkalinity and pH would be expected to decrease iron release on average, while an increase in chlorides would increase iron release. The surface composition of cast iron and galvanized steel coupons were analyzed using X-ray photoelectron spectroscopy (XPS). The surface analysis located binding energies consistent with Fe2O3, Fe3O4, and FeOOH for both cast iron and galvanized steel. Elemental scans detected the presence of silicon as amorphous silica; however, there was no significant difference between scans of coupons treated with sodium silicate and coupons simply exposed to the blended source water. The predominant form of zinc found on the galvanized steel coupons was ZnO. Thermodynamic modeling of the galvanized steel system suggested that zinc release was more appropriately described by Zn5(CO3)2(OH)6. The analysis of the copper release data set suggested that treatment with sodium silicate decreased copper release during the study. On average the low, medium, and high doses decreased copper release, when compared to the original blend source water prior to sodium silicate addition, by approximately 20%, 30%, and 50%, respectively. Statistical modeling found that alkalinity, chlorides, pH, and sodium silicate dose were significant variables (R2 = 0.68). The coefficients of the model implied that increases in pH and sodium silicate dose decreased copper release, while increases in alkalinity and chlorides increased copper release. XPS for copper coupons suggested that the scale composition consisted of Cu2O, CuO, and Cu(OH)2 for both the coupons treated with sodium silicate and those exposed to the blended source water. Analysis of the silicon elemental scan detected amorphous silica on 3/5 copper coupons exposed to sodium silicate. Silicon was not detected on any of the 8 control coupons. This suggested that sodium silicate inhibitor varied the surface composition of the copper scale. The XPS results seemed to be validated by the visual differences of the copper coupons exposed to sodium silicate. Copper coupons treated with sodium silicate developed a blue-green scale, while control coupons were reddish-brown. Thermodynamic modeling was unsuccessful in identifying a controlling solid that consisted of a silicate-based cupric solid. Lead release was generally decreased when treated with sodium silicate. Many of the observations were recorded below the detection limit (1 ppb as Pb) of the instrument used to measure the lead concentration of the samples during the study. The frequency of observations below the detection limit tended to increase as the dose of sodium silicate increased. An accurate quantification of the effect of sodium silicate was complicated by the observations recorded below detection limit. If the lead concentration of a sample was below detection limit, then the observation was recorded as 1 ppb. Statistical modeling suggested that temperature, alkalinity, chlorides, pH, and sodium silicate dose were important variables associated with lead release (R2 = 0.60). The exponents of the non-linear model implied that an increase in temperature, alkalinity, and chlorides increased lead release, while an increase in pH and sodium silicate dose were associated with a decrease in lead release. XPS surface characterization of lead coupons indicated the presence of PbO, PbO2, PbCO3, and Pb3(OH)2(CO3)2. XPS also found evidence of silicate scale formation. Thermodynamic modeling did not support the possibility of a silicate-based lead controlling solid. A solubility model assuming Pb3(OH)2(CO3)2 as the controlling solid was used to evaluate lead release data from samples in which lead coupons were incubated for long stagnation times. This thermodynamic model seemed to similarly describe the lead release of samples treated with sodium silicate and samples exposed to the blended source water. The pH of each sample was similar, thus sodium silicate, rather than the corresponding increase in pH, would appear to be responsible if a difference had been observed. During the overall study, the effects of BOP, OP, ZOP, and Si corrosion inhibitors were described by empirical models. Statistically, the model represented the expected value, or mean average, function. If these models are to be used to predict a dose for copper release, then the relationship between the expected value function and the 90th percentile must be approximated. The USEPA Lead and Copper Rule (LCR) regulates total copper release at an action level of 1.3 mg/L. This action level represents a 90th percentile rather than a mean average. Evaluation of the complete copper release data set suggested that the standard deviation was proportional to the mean average of a particular treatment. This relationship was estimated using a linear model. It was found that most of the copper data sub-sets (represented by a given phase, inhibitor, and dose) could be described by a normal distribution. The information obtained from the standard deviation analysis and the normality assumption validated the use of a z-score to relate the empirical models to the estimated 90th percentile observations. Since an analysis of the normality and variance (essentially contains the same information as the standard deviation) are required to assess the assumptions associated with an ANOVA, an ANOVA was performed to directly compare the effects of the inhibitors and corresponding doses. The findings suggested that phosphate-based inhibitors were consistently more effective than sodium silicate when comparing the same treatment levels (i.e. doses). Among the phosphate-based inhibitors, the effectiveness of each respective treatment level was inconsistent (i.e. there was no clear indication that any one phosphate-based inhibitor was more effective than the other). As the doses increased for each inhibitor, the results generally suggested that there was a corresponding tendency for copper release to decrease.
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Date Issued
2008
Identifier
CFE0002383, ucf:47737
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0002383
EFFECTS OF ORTHOPHOSPHATE CORROSION INHIBITOR IN BLENDED WATER QUALITY ENVIRONMENTS
Title
EFFECTS OF ORTHOPHOSPHATE CORROSION INHIBITOR IN BLENDED WATER QUALITY ENVIRONMENTS.
Creator
Stone, Erica, Duranceau, Steven, University of Central Florida
Abstract / Description
This study evaluated the effects of orthophosphate (OP) inhibitor addition on iron, copper, and lead corrosion on coupons exposed to different blends of groundwater, surface water, and desalinated seawater. The effectiveness of OP inhibitor addition on iron, copper, and lead release was analyzed by statistical comparison between OP treated and untreated pilot distribution systems (PDS). Four different doses of OP inhibitor, ranging from zero (control) to 2 mg/L as P, were investigated and non...
Show moreThis study evaluated the effects of orthophosphate (OP) inhibitor addition on iron, copper, and lead corrosion on coupons exposed to different blends of groundwater, surface water, and desalinated seawater. The effectiveness of OP inhibitor addition on iron, copper, and lead release was analyzed by statistical comparison between OP treated and untreated pilot distribution systems (PDS). Four different doses of OP inhibitor, ranging from zero (control) to 2 mg/L as P, were investigated and non-linear empirical models were developed to predict iron, copper, and lead release from the water quality and OP doses. Surface characterization evaluations were conducted using X-ray Photoelectron Spectroscopy (XPS) analyses for each iron, galvanized steel, copper, and lead/tin coupon tested. Also, a theoretical thermodynamic model was developed and used to validate the controlling solid phases determined by XPS. A comparison of the effects of phosphate-based corrosion inhibitor addition on iron, copper, and lead release from the PDSs exposed to the different blends was also conducted. Three phosphate-based corrosion inhibitors were employed; blended orthophosphate (BOP), orthophosphate (OP), and zinc orthophosphate (ZOP). Non-linear empirical models were developed to predict iron, copper, and lead release from each PDS treated with different doses of inhibitor ranging from zero (control) to 2 mg/L as P. The predictive models were developed using water quality parameters as well as the inhibitor dose. Using these empirical models, simulation of the water quality of different blends with varying alkalinity and pH were used to compare the inhibitors performance for remaining in compliance for iron, copper and lead release. OP inhibitor addition was found to offer limited improvement of iron release for the OP dosages evaluated for the water blends evaluated compared to pH adjustment alone. Empirical models showed increased total phosphorus, pH, and alkalinity reduced iron release while increased silica, chloride, sulfate, and temperature contributed to iron release. Thermodynamic modeling suggested that FePO4 is the controlling solid that forms on iron and galvanized steel surfaces, regardless of blend, when OP inhibitor is added for corrosion control. While FePO4 does not offer much control of the iron release from the cast iron surfaces, it does offer protection of the galvanized steel surfaces reducing zinc release. OP inhibitor addition was found to reduce copper release for the OP dosages evaluated for the water blends evaluated compared to pH adjustment alone. Empirical models showed increases in total phosphorus, silica, and pH reduced copper release while increased alkalinity and chloride contributed to copper release. Thermodynamic modeling suggested that Cu3(PO4)2•2H2O is the controlling solid that forms on copper surfaces, regardless of blend, when OP inhibitor is added for corrosion control. OP inhibitor addition was found to reduce lead release for the OP dosages evaluated for the water blends evaluated compared to pH adjustment alone. Empirical models showed increased total phosphorus and pH reduced lead release while increased alkalinity, chloride, and temperature contributed to lead release. Thermodynamic modeling suggested that hydroxypyromorphite is the controlling solid that forms on lead surfaces, regardless of blend, when OP inhibitor is added for corrosion control. The comparison of phosphate-based inhibitors found increasing pH to reduce iron, copper, and lead metal release, while increasing alkalinity was shown to reduce iron release but increase copper and lead release. The ZOP inhibitor was not predicted by the empirical models to perform as well as BOP and OP at the low dose of 0.5 mg/L as P for iron control, and the OP inhibitor was not predicted to perform as well as BOP and ZOP at the low dose of 0.5 mg/L as P for lead control. The three inhibitors evaluated performed similarly for copper control. Therefore, BOP inhibitor showed the lowest metal release at the low dose of 0.5 mg/L as P for control of iron, copper, and lead corrosion.
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Date Issued
2008
Identifier
CFE0002382, ucf:47760
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0002382
Assessment of a Surface Water Supply for Source and Treated Distribution System Quality
Title
Assessment of a Surface Water Supply for Source and Treated Distribution System Quality.
Creator
Rodriguez, Angela, Duranceau, Steven, Lee, Woo Hyoung, Sadmani, A H M Anwar, University of Central Florida
Abstract / Description
This study focused on providing a source to tap assessment of surface water systems with respect to (i) the use of alternative biomonitoring tools, (ii) disinfection byproduct (DBP) formation and control, and (iii) corrosion control. In the first study component, two water systems were microbiologically evaluated using adenosine triphosphate (ATP) bioluminescence technology. It was determined that microbial ATP was useful as a surrogate for biomonitoring within a surface water system when...
Show moreThis study focused on providing a source to tap assessment of surface water systems with respect to (i) the use of alternative biomonitoring tools, (ii) disinfection byproduct (DBP) formation and control, and (iii) corrosion control. In the first study component, two water systems were microbiologically evaluated using adenosine triphosphate (ATP) bioluminescence technology. It was determined that microbial ATP was useful as a surrogate for biomonitoring within a surface water system when paired with traditional methods. Although microbial activity differed between distribution systems that used either chloramine or chlorine disinfectant, in both cases flowrate and season affected microbial ATP values. In the second study component, total trihalomethanes (TTHM) and haloacetic acids (HAA5) DBP formation and disinfectant stability was investigated using a novel DBP control process. The method relied on a combination of sulfate, ultraviolet light irradiation, pH, and aeration unit operations. Results indicate respective decreases in 7-day TTHM and HAA5 formation potentials of 36% - 57% and 20% - 47% for the surface waters investigated. In the third component of this work, a corrosion study assessed the effect of disinfectant chemical transitions on the corrosion rates of common distribution system metals. When a chlorine based disinfection system transitioned between chlorine and chloramine, mild steel corrosion increased by 0.45 mils per year (mpy) under chloramine and returned to baseline corrosion rates under chlorine. However, when a chloramine based disinfection system transitioned between chloramine and chlorine, mild steel corrosion increased in tandem with total chlorine levels. Unlike the chlorine system, the mild steel corrosion rates did not return to baseline under chloramine after exposure to 5 mg/L of total chlorine. Surface water systems should consider the use of ATP as a surrogate for biomonitoring, consider the novel treatment process for DBP formation control, and consider corrosion control in disinfectant decision-making activities.
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Date Issued
2019
Identifier
CFE0007901, ucf:52751
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0007901