United States Environmental Protection Agency Municipal Environmental Research Laboratory Cincinnati OH 45268 Research and Development EPA-600/S2-82-018 August 1982 Project Summary Seattle Distribution System Corrosion Control Study: Volume III. Potential for Drinking Water Contamination from Tin/Antimony Solder Carlos E. Herrera, Gregory J. Kirmeyer, and Brian P. Hoyt This study was conducted to evalu- ate the potential leaching of metals into drinking water from tin/antimony solder. The study consisted of five research steps: (1) An investigation of the theory of corrosion products that formed from the solder was con- ducted using pe-pH diagrams and gal- vanic coupling relationships, (2) static laboratory metal leaching tests were performed to determine the extent of antimony leaching from the solder, (3) field water samples were taken from buildings that contained tin/antimony soldered plumbing, (4) continuous- flow metal leaching tests were used to compare metal leaching from tin/an- timony solder with lead/tin solder under three water treatments (lime plus sodium carbonate, lime plus sodium bicarbonate, and lime plus sodium bicarbonate plus silicate), and (5) corrosion films that formed on both tin/antimony and lead/tin solder were analyzed by scanning electron microscopy and X-ray diffraction. The results indicate that increases in metal concentrations resulting from the corrosion of tin/antimony solder are minimal. Metal leaching from the solder is inhibited by the sacrificial corrosion of tin and the formation of a stable, double-layer tin passivation film (SnO and SnO2). Side-by-side tests comparing metal leaching from tin/antimony with that from lead/tin solders show substantial reductions in standing water lead concentrations when tin/antimony solder is used. The use of tin/antimony solder in place of lead-based solders should result in reduced human exposure to lead from drinking water with only minimal increases in antimony exposure. This Project Summary was devel- oped by EPA's Municipal Environ- mental Research Laboratory, Cincinnati, OH, to announce key find- ings of the research project that is fully documented in a separate report of the same title (see Project Report ordering information at back). Introduction The Seattle Water Department (SWD) serves an average of 161 mgd of high quality water to a population of more than 1 million in the Greater Seattle area. The water originates in the Cas- cades from two mountain sources— the ------- Cedar and Toll Rivers. The watersheds are well protected and the water requires only disinfection with gaseous chlorine to meet state requirements These mountain waters, which are pre- dominantly rainfall and snowmelt runoff, are very soft and tend to be highly corrosive to the unlined, metallic pipes in home plumbing systems. The corrosiveness of Cedar and Tolt water results from several related fac- tors, including: • Acidity, as indicated by low pH (after chlorination andfluoridation, pH is reduced to a range of 6.8 to 7.2 for the Cedar supply and 5.8 to 6.2 for the Tolt supply); • Dissolved oxygen concentration at saturated conditions; • Insufficient calcium and bicarbo- nate alkalinity in the water to form protective calcium carbonate films on pipe surfaces; and • A relatively high [halogen + suit a - te]/'alkalinity ratio that indicates conditions favorable to pitting corrosion. In 1970, three factors combined to intensify the corrosiveness of the water supplies. First, the chlorine dosage at the open distribution reservoir outlets was increased to decrease the occur- rence of positive bacteriological sam- ples within the distribution system. Second, ammoniation of the water supply was stopped at the request of the U.S. Public Health Service to enable a free chlorine residual to be maintained throughout the distribution system. This change from combined chlorination to free chlorination was implemented to provide quicker, more effective disinfec- tion of the unfiltered water supply. The third factor that increased corrosive- ness was the initiation of flouridation with hydrofluorosilicic acid in 1970. Corrosion of the plumbing systems and the associated water quality degra- dation has been a major concern of the SWD for many years. Studies performed from 1972 to 1976 demonstrate that the levels of lead, copper, and iron in over- night standing tap water often exceed the maximum contaminant levels defined by the National Interim Primary and Secondary Drinking Water Regula- tions. Cadmium and zinc were also found to increase after overnight stand- ing in home plumbing, but they rarely exceeded their maximum levels. These metals originate from the copper and galvanized pipes and the solders used in home plumbing systems. Although the health impact of metal levels from over- night standing water is not an accute problem, it is certainly desirable to re- duce exposure where possible. The use of lead-based solders to join copper pipe can create a problem with regard to lead leaching. To reduce the potential for lead contributions from this source, the maximum allowable lead in solder was limited to 0.20% by amend- ment of the Seattle plumbing code. The effect of this amendment was to require contractors to use 95/5 tin/antimony solder Purpose and Scope of Work This study was undertaken to evalu- ate the potential leaching of metals into drinking water from the tin/antimony solder now being used in Seattle plumb- ing. The study consisted of five research steps: (1) An investigation of the theory of corrosion products that formed from the solder was conducted using pe-pH diagrams and galvanic coupling rela- tionships, (2) static laboratory metal leaching tests were performed to deter- mine the extent of antimony leaching from the solder, (3) field water samples were taken from the buildings that con- tained tin/antimony soldered plumbing, (4) continuous flow metal leaching tests were used to compare metal leaching from tin/antimony solder with that from lead/tin solder under three water treat- ments (lime plus sodium carbonate, lime plus sodium bicarbonate, and lime plus sodium bicarbonate plus silicate), and (5) corrosion films that formed on both tin/antimony and lead/tin solder were analyzed by scanning electron microscopy and X-ray diffraction. Procedures, Results and Discussion Theoretical Analysis An investigation of the theory of cor- rosion products formed from the solder was conducted using pe-pH diagrams and galvanic coupling relationships. Results indicated that the leaching of antimony from the solder may be inhi- bited by two mechanisms: 1. Sacrificial Corrosion. Though antimony alone is quite soluble, the galvanic coupling relationships among the three metals that make up a soldered joint (tin, antimony, and copper) indicate that the corro- sion of tin is theoretically more favorable than the corrosion of antimony. Tin, therefore, mayactas a sacrificial anode. 2. Passivation. Since tin can be passi vated by tin oxide, a passivation filrr may cover the entire surface of tht solder and therby inhibit meta leaching from the solder. Laboratory Experiments Laboratory experiments were con- ducted to verify the theoretical phase of the study Twenty test specimens con- structed from tin/antimony solder and copper sheet were immersed in Cedar water in a sealed 50-ml glass container. The samples were held under static conditions at 20°C for periods of 0.5 to 98 hr. In addition, two samples of anti- mony metal equalling the weight of antimony in the solder specimens were tested as described above for a 70-hr period. The laboratory static coupon tests demonstrated that antimony dissolution from tin/antimony solder is substan- tially less than the theoretical or observed dissolution from pure anti- mony metal. The highest antimony con- centration observed in the tin/antimony solder coupon test was 3.7 fjg/L, whereas 18,000/ug/L and 22,000//g/L of dissolved antimony were observed in the pure antimony metal corrosion tests. These results support the theoretical conclusions already put forward. In the short term, the inhibition of antimony leaching from tin/antimony solder is a result of the galvanic coupling relation- ship, namely the sacrificial corrosion of tin. Field Sampling The University of Washington has been using 95/5 tin/antimony solder on building plumbing systems™Since about 1968. The field study consisted of taking 0.95-L samples of overnight tap water that had stood overnight in eight buildings on the University campus. The plumbing systems of the buildings tested ranged from 1 to 10 years in age and supposedly consisted of copper pip- ing bonded with 95/5 tin/antimony solder. Samples of running water (0.95 L) were taken at the mechanical room (where the building plumbing connects with the distribution system) of each building to obtain the characteristics of the inflowwater The 0.95-L water sam- ple that had stood overnight was then taken from the potable water tap fur- thest from the mechanical room of the building. ------- The samples were then analyzed for temperature, conductivity, alkalinity, total and dissolved antimony, and total lead, copper, and zinc. The field sampling showed that, in the long term, antimony corrosion is inhi- bited by the passivation of tin in the solder. Of all the samples tested, a detectable antimony concentration was found in only one building water sam- ple. In addition, scanning electron microscopy showed that two distinct passivation films were present on the tin/antimony-soldered joints removed from the buildings at the University of Washington. Metal Leaching Tests Short pipe sections of copper, copper plus 50/50 lead/tin solder, and copper plus 95/5 tin/antimony solder were attached to continuous flow test units for comparison of copper, lead, tin, and antimony leaching under three alterna- tive treatments. Two velocities were used in establishing corrosion films in the metal leaching sections. The pipe sections were periodically removed from the continuous flow test unit and dissolved metals were determined after periodic 22- to 24-hr contact with test water in the laboratory. The side-by-side metal leaching tests indicated that lead leaching is substan- tially less from tin/antimony solder than from lead/tin solder. Some lead initially leaches from the tin/antimony solder; but after approximately 6 weeks of testing, lead leaching was reduced to below the detection limit. Antimony leaching from the 95/5 tin/antimony solder was also consistently below the detection limit of 1.4^g/L. Conclusions Lead leaching is substantially reduced and the subsequent increase in the antimony concentration of the drinking water is minimal if tin/antimo- ny solder is used in plumbing systems in place of lead-based solder. The low metal leaching levels from 95/5 tin/an- timony solder are mainly because of the sacrificial corrosion of tin and the for- mation of a tin oxide passivation film that protects the surface of the solder from corrosion. The theoretical and experimental results obtained in this study therefore indicate that 95/5 tin/antimony solder would be an excellent replacement for lead-based solders in private and com- mercial plumbing systems where lead leaching is a problem. The full report was submitted in ful- fillment of Grant No. R-806686-010 by the Seattle Water Department under the sponsorship of the U.S. Environ- mental Protection Agency. Carlos E. Herrera, Gregory J. Kirmeyer, and Brian P. Hoyt are with the Seattle Water Department, Seattle, WA 98144. Marvin C. Gardels is the EPA Project Officer (see below). The complete report, entitled "Seattle Distribution System Corrosion Control Study: Volume III. Potential for Drinking Water Contamination from Tin/ Antimony Solder," (Order No. PB 82-231 242; Cost: $10.50, subject to change) will be available only from: National Technical Information Service 5285 Port Royal Road Springfield, VA22161 Telephone: 703-487-4650 The EPA Project Officer can be contacted at: Municipal Environmental Research Laboratory U.S. Environmental Protection Agency Cincinnati, OH 45268 t US. GOVERNMENT PRINTING OFFICE 1982-559-017/0768 ------- United States Center for Environmental Research Fees^aid" Environmental Protection Information Agency Cincinnati OH 45268 pVotectn Agency _ EPA 335 Official Business Penalty for Private Use $300 RETURN POSTAGE GUARANTEED T. . „. Third-Class Bulk Rate MfcRL00632«0 LOU w T1LLEY REGION V EPA LIBRARIAN 230 S DEARBORN ST CHICAGO IL 60604 ------- |