1000

100

Lead, pg/L

10

n

yu \
60 80 100 120 140 160

0 20 40
7 Elapsed Time, days

—o— C36000 —®— C84500
—o— C36000 —"— C85200
—¥— C83600 —*— C85400

—v¥*— C84400 —@— Pure lead

Figure 6. Lead leached from brass and pure
lead coupons during test run #2, pH =7.0.

51



Table A-15. Run 5: Cincinnati tap water, pH=7.5, 24 hour stand time

Study=Coupon
Analyte=Zn

Date __Time, days C36000 Pb free C83600_C84400 C84500 C85200 C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

08/03/93 0.49 0.02 004 004 008 015 009 001 0.01 0.01 0.30 860.01
08/11/93 1 217 196 017 013 O57 239 214 0.03 001 023 257 0.01
08/12/93 2 2.03 117° 0.23 (0.52 124 210 2.23 0.02 0.01 0.03 2.43 0.01
08/13/93 3 211 112 017 0.50 129° 2.25 2.33 0.02 0.01 0.02 3.55 0.01
08/17/93 7 2.28 100 0.22 0.47 175 242 255 002 001 006 139 0.01
08/18/93 8 0.70 077 0.23 0.40 145 241 248 001 001 0.02 1.20 © © 0.01
08/19/93 9 221 0.69 ~ 0.39 137° 235 221 002 001 0.01 130 60.01
08/20/93 10 226 061 0.26 0.39 129 225 2.01 001 0.01 0.02 154 0.02
08/24/93 14 183 046 0.22 O41 106 1.65 147 001 0.01 0.01 108 0.01
08/25/93 15 184 040 0.19 037 0.93 151 151 0.01 0.01 0.01 130 60.01
08/26/93 16 190 039 019 0.39 0.89 1.55 136 60.01 0.01 0.01 139 0.01
08/27/93 17 185 034 018 037 0.80 137 136 0.01 0.01 0.01 138 0.01
08/31/93 21 174 0.29 0.19 038 0.68 1.05 116 002 001 0.01 110 0.01
09/01/93 22 «158 = 0.24 ~ 033 057 088 0.98 0.01 0.02 0.01 121 0.01
09/02/93 23 160 0.21 -- 0.29 0.50 0.74 084 0.01 0.01 0.01 127 0.01
09/07/93 28 4067 4041 0.29 058 0.76 1.24 1.72 0.01 0.01 0.01 046 0.01
09/08/93 29 156 023 0.20 039 O51 0.66 0.97 001 O01 0.01 0.98 0.01
09/09/93 30 163 019 O15 032 043 O57 082 0.01 001 0.01 1.16 0.01
09/10/93 31 152 016 012 026 036 046 067 001 001 0.01 1.19 0.01
09/14/93 35 106 036 025 059 068 0.99 199 001 001 001 0.78 0.01
09/15/93 36 «155 «(018 = 0.14 0.31 038 040 O88 001 002 0.01 1.12 --

09/16/93 37 153 0415 012 025 032 036 0.76 0.01 0.01 0.01 1.17 0.01
09/20/93 41 104 030 020 049 054 0.80 L71i 0.01 001 O01 072 0.01
09/21/93 42 171 019 O14 032 037 0.42 0.93 0.01 0.01 0.03 128 0.01
09/23/93 44 171 014 O11 0.25 029 O35 0.74 0.01 0.00 0.01 132 0.01
09/24/93 45 165 012 0.09 023 0.25 032 066 0.00 0.01 0.01 1.25 0.00
09/29/93 50 171 016 012 035 030 O41 087 0.01 0.01 0.01 132 0.01
09/30/93 St 170 O14 O11 032 026 038 078 0.01 0.01 0.01 134 0.01
10/04/93 55 155 030 018 065 047 0.91 167 001 0.01 0.01 134 0.01
10/05/93 560 «164 «60170 OL 0360 0.260 0.38) 0.80 0.01 0.01 0.01 136 60.02
10/07/93 58 232 013 O11 037 0.26 042 0.84 0.02 0.01 0.01 164 0.01
10/12/93 63 125 030 0.17 0.66 0.44 1.02 164 0.01 0.01 0.01 153 0.01
10/14/93 65 184 014 009 030 020 042 062 002 001 0.01 146 0.01
10/18/93 69 #178 0.29 017 061 0.39 106 1.62 0.02 001 0.01 162 0.01
10/19/93 70 115 010 007 O21 O13 031 051 0.01 0.02 0.01 106 0.01
10/21/93 72 181 O17 O11 036 022 059 088 002 001 002 1.33 0.01
10/22/93 73 149 010 007 0.22 0.13 033 050 0.01 0.02 0.02 1,19 --

10/25/93 76 #175 019 0.12 O40 023 075 0.99 002 004 002 125 0.01
10/26/93 77 135 0.09 007 O21 012 033 046 0.02 002 002 115 0.02
10/28/93 79 135 0.08 007 019 010 030 032 002 002 002 1.11 0.02
11/01/93 83 190 022 014 047 0.24 0.93 114 002 002 002 147 0,02
11/02/93 84 147 010 008 022 012 037 O50 0.02 002 002 133 0,02
11/04/93 86 140 010 006 018 O10 030 036 002 0.02 002 119 0.02
11/05/93 87 136 0.008 006 017 009 0.27 031 0.02 002 0.02 ~ 0.02
11/08/93 90 173° 016 010 033 016 063 077 0.02 001 002 127 0.02
11/09/93 91 1.76 009 007 0.22 O11 0.35 042 0.02 001 0.01 153 0.01
11/15/93 97 2.11 ~ 0.15 O51 0.23 1.01 123 002 0.01 0.01 171 (0.01
11/16/93 98 136 0.10 007 019 009 032 038 001 0.02 0.01 132 0.01
11/18/93 100 1.20 007 006 016 0.07 0.26 0.25 0.02 002 0,02 1.12 0.02
11/19/93 101 117 007 005 014 007 0.24 0.22 0.02 002 0.01 106 0.01
11/22/93 104 150 0.13 008 027 O11 O50 048 0.01 001 0.01 129 0.01

115



however, have not been established and clearly greater research efforts are required to understand
the role of sulfate. Free chlorine, a strong oxidizing agent and an influential parameter on metal
dissolution rates, averaged 2.0 mg/L which was more than 0.5 mg/L greater than values observed
in any other test run. Free chlorine has not been conclusively demonstrated to alter metal
equilibrium conditions. Perceived increases in metal levels associated with free chlorine increases
are often misinterpretations of increased oxidation rates. The increased sulfate and free chlorine
levels observed during this test run were likely related to seasonal water quality variations in the
Ohio River (main source of Cincinnati tap water). Dissolved oxygen and TIC were not directly
measured during this test run. TIC was calculated using WATEQX®, a computer FORTRAN 77
program, and source water quality values. The calculated value was 14.3 mg C/L with a standard
deviation of 1.2 mg C/L.

Lead leached from brass coupons

Figure 3 shows lead leaching trends from the brass coupons (C36000 was tested in
duplicate) and duplicate pure lead coupons during test run 1. The greatest amount of lead leached
from the brass coupons occurred during the first 7 days of the test run. During this time lead
levels dropped off sharply with time and trends were difficult to differentiate. Initial high values
were thought to be related to new, clean coupon surfaces and thinly dispersed lead globules
present on the coupon surfaces at the start-up. The concentration of lead leached during this period
varied amongst brasses by no more than approximately 80 g/L and was generally a function of
the lead content of the brass; brasses with higher lead contents tended to leach higher amounts of
lead.

From approximately 7 to 15 days into the test run, lead concentrations gradually leveled
off and the variance between the magnitude in lead levels leached from the brasses narrowed.
During this time period, the relationship between the lead content of a brass and the amount of
lead leached from the brass became less apparent. Statistical comparisons between the lead
leaching trends during this time period showed that there was no significant difference between
most trends at 95% confidence.

After 15 days, the lead leaching trends appeared to split into two distinct groups. For
future reference, the groups will be labeled as the "low" group and the "high" group, in reference
to the relative magnitude of lead leached from the coupons. During the period between 15 to 60
days, the general trend of both groups continued to be a gradual downward one. The trends
visually appeared to level-off or stabilize after 60 to 70 days.

The "low" group consisted of the duplicate free-cutting brass (C36000) coupons and one
yellow brass (C85400) coupon. The amount of lead leached from these brasses was nearly
indistinguishable for the remainder of the run (after 60 days) as confirmed statistically in
Appendix Table 36. The similarity in lead leaching patterns was reflective of the similarity in
compositions of the two brasses (see Table 2). The quantity of lead in the two brasses overlapped
while free-cutting brass contained slightly more zinc and slightly less copper than the C85400

17



ov

Table A-49. Quality control table showing spike recovery analysis over the entire study period.

Spike recovery, % Spike recovery, %
Analyte Method* N Min. Max. — Mcan_ Std. Dev. Range, mg/L Analyte Method N Min. Max. Mean Std. Dev. Range, mg/L
Al ICAP 26 958 1050 99.4 24 0.100-1.000 NO; ALPKEMAA 2 1001 110.8 = 105.4 15 0.001-0.010
NO; ALPKEMAA = 32 84.7 127.8 =6103.6 = 10.3 0,100-1.000
Ca AAS 4 90.2 104.7 99.3 42 10,00-100.0 NO; ALPKEMAA 2 11.0 (116.3 93.7 32.1 1,000-10.00
Cu AAS 5 96.6 1038 100.1 33 0.001-0.010 Pb AAS 7 94.0 109.1 100.8 49 0.001-0.010
-Cu AAS 1 99.4 99.4 99.4 0.010-0.100 Pb " AAS 265 «87.2 = (116.6 :101.6. 63 0.010-0.100
Cu AAS 140 «858 «©1073 100.9 34 0.100-1.000 Pb AAS 111 86.0 = 116.3 100.1 69 0.100-1.000
Cu AAS 127) 73.8 108.3 99.9 44 1.000-10.00 Pb AAS 5 91.0 113.5 100.0 94 1,000-10.00
Cu AAS 1 100.5 100.5 100.5 10.00-100.0 Pb AAS 6 OA 106.2 98.4 63 10.00-100.0
Cu ICAP 25 89.8 105.7 98.8 3.0 0.100-1.000 Pb AAS 6 87.8 104.5 94.5 58 >100
Pb ICAP 22 93.6 102.8 99.3 22 0.100-1.000
Fe AAS 134 89.4 109.5 101.6 38 0.100-1.000 Pb ICAP 4 94.6 109.8 100.6 65 1,000-10.00
Fe AAS 105 86.0 1223 102.4 5.5 1,000-10.00
Fe AAS 1 1230 11230 1123 10.00-100.0 PO, ALPKEM AA 4 104.0 112.0 107.3 34 0.001-0.010
Fe ICAP 26 93.8 103.7 99.2 24 0.100-1.000 PO, ALPKEM AA 3 70.0 86.0 78.7 81 0.010-0.100
PO, ALPKEM AA 1 128.0 128.0 128.0 1.000-10.00
K AAS 26 86.3 119.4 103.5 72 1,000-10,00 PO, TECHNICONAA 20 92.0 106.1 96.4 3.6 0.100-1.000
K ICAP 14 93.8 49 102.1 ral 10.00-100.0 PO, TECHNICONAA 6 98.2 102.0 100.1 17 1,000-10.00
Mg AAS 15 88.6 103.9 95.8 5.2 10.00-100.0 s ICAP 22 94.3 107.1 100.7 37 10,00-100.0
Mg ICAP 26 94.9 103.2 98.5 21 10.00-100.0 SO, AUTOANALYZE 2 96.5 100.0 98.3 25 10.00-100.0
Mn AAS 35 89.3 108.5 102.2 48 0,100-1.000 Si ICAP 9 96.6 119.5 106.6 72 1,000-10.00
Mn AAS 61 98.0 108.4 = 103.5 26 1,000-10.00 SiO,  ALPKEM AA 16 79.9 131.7 96.2 13.4 1,000-10.00
Mn ICAP 26 90.7 102.2 98.4 24 0.010-0.100
Za AAS 103 94.6 1084 = 102.4 26 0.100-1.000
Na AAS 14 90.3 108.7 979 5.5 10.00-100.0 Zn AAS 135 89.0 110.9 100.1 43 1,000-10.00
Na ICAP 26 89.9 108.2 98.8 34 10.00-100.0 Zn AAS 4 97.0 100.5 98.4 17 10.00-100.0
Za ICAP 20 919 102.3 98.5 27 0.100-1.000
* Methodologies detailed in Table 3

‘AAS- atomic absorption spectrophotometer

AA- autoanalyzer



Table A-35. ‘Test Run 5, Extraction Water Quality, pH=7.5

Study=Coupon

Date ___Time, days _CL_CL2 E NH3__NO3__PH___TEMP__PO4 __SIO2__$O4_.TIC__TALK__DO CU FE PB ZN CAL K MG NA___MN. AL.

11/18/93 100 32.78 09 0.02 7.563 20.1 38 1081 135. 8.65 0.001 0.009 -0.00 0.015 39.73 4215 10.93 28.77 0.000
11/19/93 101 32.75 (0.78 0.02 7.593 22.5 . 1053 13.5 54.19 0.001 0.008 0,00 0.010 3895 ° 4195 10.92 2848 0.00
11/22/93 104 32.91 0.74 0.02 7564 = 22.7 . 106.7 13.61 54.09 9.44 0.000 0.007 -0.00 0.009 35.44 3.984 9.675 22.20 0.00
11/23/93 105 27.56 = 1.16 0.02 7552 14.4 . 89.27 14.23 56.28 9.19 0.001 0.007 -0.00 0.009 33.74 4.154 9,866 2638 0.000
11/30/93 112 23.98 1.01 0.02 T5111 19.8 . 76.14 14.03 54.88 -0.00 0.009 0,000 0.009 36.84 1.002 9.123 16.01 -0.00
12/02/93 i. 11 0.02 TAB 19 . 7535 14.00 54.32 9.12 -0.00 0.010 -0.00 0.011 3750 3863 8974 15.89 -0.00
12/03/93 11s. 0.92 0.02 744 223 5.17 75.35 13.9 54.36 0.000 0.010 -0.00 0.011 36.70 3,906 8951 15.50 -0.00
12/06/93 us . 0.83 0.02 74 227 5.17 66.35 12.02 48.76 10.29 0.001 0.012 -0.00 0.012 31.95 3.135 7.464 11.31 0.000
12/07/93 119. 1.08 0.02 7.624 = 123 5.17 66.35 12.04 48.39 0.001 0.009 0.000 0.010 33.24 . 7941 13.16 0.000
12/09/93 121. 0.92 0.02 7SIS 19.7 5.44 66.35 1216 46.36 9.355 0.002 0.009 0.000 0.008 32.67 . 7.864 12.23 0.000
12/13/93 25. 0.7 0.02 TAL 22.6 544 6635 1153 46.19 10.64 0.004 0.009 0.00 0.012 3213 . 8.141 1339 0.000
12/14/93 126. 121 0.02 7.583 10.9 544 59.34 10.59 42.55 10.2 0.002 0.009 -0.00 0.008 28.99 . 6814 8.957 0.000
12/16/93 128. 1 -0.02 755 18.7 . 59.34 10.57 42.08 0.003 0.009 0.00 6.009 2889 . 7.146 9.379  -0.00
12/20/93 132. 0.78 . 7514 22.4 . . 10.55 41.81 1043 0.004 0.008 0.001 0.012 30.26 . 7.285 9.574 0.000
12/21/93 133. 119 . 7409 10.5 . . 10.12 38.47 0.001 0.014 0.001 0.006 30.33 . 7.252 9.681 0.000
12/29/93 m1. 0.93 . 71377 18,2 . . 10.80 . 0.002 0.019 -0.00 0.017 29.62 . 7617 10.69 0.001
12/30/93 142 0.87 7.56 18 0.001 0.017 0.000 0,012 29.32 . 7484 10.63 0.000
O1/11/94 154 31.92 0.78 0.94 7.521 21 0.02 5.575 66.96 11.20 30.04 0.003 0.009 -0.00 0.011 32.73 2137 8440 14.45 0.000 0.094
O1/13/94 156 31.96 0.86 0.93 6564 161 . . 67.56 11.07 30.15 0.003 0.035 -0.00 0.011 31.93 2325 8147 14.22 0.000 0.086
OL/19/94 162 27.13 0.67 O85 6561 203 . . 6288. 17.91 0.001 0.017 -0.00 0.010 2841 1905 7.063 11.42 0.000 0.087
= 01/20/94 163 26.53 0.79 087 6493 193 002 . . . 19.04 0.00 0.045 0.00 0.008 2830 . 7.104 11.80 0.001 0.084
= 01/25/94 168 33.26 0.71 08 6538 229 002 . . . 25.25 0.000 0.023 -0.00 0.007 29.90 . 7.329 12.95 0.000 0.085
01/27/94 170 (31.02. 082. . . . . 25.33 0.00 0.015 0.000 0.011 3074 . 7741 14.03 0.000 0.075
01/28/94 171 31.18. 082. . . . . 24.84 0.00 0.015 0.000 0.012 3071 . 7664 13.71 0.000 0.060
01/31/94 174 (31.21. 082. . . . . 24.66 0.000 0.010 0.000 0.013 29.58 . 7592 13.79 -0.00 0.081
02/01/94 175 33.16 0s. . . . . 26.91 0.002 0.010 0.000 0.014 31.03 . 7824 1481 0.000 0.054
02/03/94 1733.11 Os . . . . 26.99 0.000 0.014 0.000 0.018 30.99 . 7.992 16.18 0.000 0.058
02/07/94 ASL 33.12 . . 26.99 .
02/08/94 182 30.11 27.38 0,003 0.007. 0.011 3139. 6.991 14.44 0.000 0.077
02/11/94 185-304 27.50 0.00 0.005 . 0.008 3143, 6.919 14.50 -0.00 0.053
02/14/94 188 3037. . . . . . . 27.33 0.001 0.007 . 0.009 3337 . 7.225 14.99 0.000 0.023
02/15/94 189 30.24. . . . . . . . 23.90 0.002 0.011. . 0.021 3259 . 7247 13.10 0.000 0.049
02/17/94 191 308. . . . + . . . WAAL . . 0.003. . . + . . .
02/22/94 196 31.02 . . . . . 5.650 4880 8.908 23.53 0.003 0.006. 0.019 3259 . 7.501 13.45 0.000 0.046
02/24/94 198 24.12. . . . . SATL 43.67 7.767 22.63 0.002 0.013. 0.012 2769 . 6.708 11.51 0.000 0.096

02/25/94 199 24.22. . . + . + . 5800 46.52 7.683 22.36 0.001 0.014 -0.00 0.013 2899 . 7.151 12,50 0.000 0.071



DISCLAIMER

The information in this document has been funded wholly or in part by the United
States Environmental Protection Agency. It has been subject to the Agency's peer and
administration review, and it has been approved for publication as an EPA document.
Mention of trade names or commercial products are for explanatory purposes only, and does
not constitute endorsement or recommendation for use.



Run 2: Cincinnati tap water, pH=7.0, 24 hour stand time

Date _ Time, days C36000 C36000 C83600 C84400 C84500 C85200 C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

02/20/92, 0.22 013 O01 0.02 002 0.01 0.002 000 008 0.00 0.65 0.00
02/21/92 0.06 016 O17 -0.03 -0.01 0.03 0.01 -0.01 0.00 -0.01 0.09 -0.00
02/25/92 456 4.70 038 060 020 984 321 006 0.05 0.05 8.66 0.05
02/26/92 3.89 480 0.79 118 099 823 2.90 0.01 0.00 0.00 7.37 0.00
02/27/92 436 0.70 126 089 834 2.60 0.01 0.01 001 644 0.03
02/28/92 243 3.74 0.60 106 073 7.56 209 0.08 0.04 0.04 7.00 0.05
03/03/92 5.98 353 051 092 065 620 2.92 002 001 001 512 0.01
03/04/92 533 3.21 O45 083 0.72 S17 2.76 0.04 003 0.03 5.46 0.03
03/05/92 5.76 3.67 050 089 0.95 5.08 2.93 0.03 003 003 485 0.04
03/06/92 5.90 332 051 086 0.76 5.79 3.15 0.02 002 002 5.83 0.04
03/10/92 531 354 044 0.75 O81 5.02 3.61 0.02 002 0.02 368 0.02
03/11/92 4.98 3.34 040 0.72 0.75 438 3.34 003 002 0.03 3.83 0.03
03/12/92 5.06 3.42 039 0.76 0.78 445 341 003 002 0.02 -0.03 0.02
03/13/92 4.93 342 040 0.75 0.76 430 3.64 0.02 0.01 003 367 0.02
03/17/92 495 356 032 0.72 O80 421 4.71 0.01 -0.01 -0.01 4.45 -0.01
03/18/92 442 339 035 073 0.78 3.50 419 0.00 000 -0.00 414 -0.01
03/19/92 454 3.70 036 0.79 086 3.29 444 0.02 002 001 416 0.02
03/20/92 443 3.69 035 080 080 3.25 459 -0.03 0.02 002 447 -0.02
03/25/92 447 3.89 0.29 0.68 0.78 2.65 4.60 001 -0.03 0.00 449 0.01
03/26/92 452 3.99 0.28 074 083 2.71 457 -0.02 -0.03 -0.05 432 -0.03
03/27/92 5.87 493 031 0.91 113° 3.52 653 0.03 0.01 O01 642 0.03
03/31/92 5.26 449 027 0.70 083 2.24 534 002 0.01 -0.00 534 0.01
04/01/92 428 3.99 0.25 0.65 0.68 202 4.79 -0.00 -0.03 -0.03 498 -0.01
04/02/92 556 518 0.31 084 102 260 602 001 001 -0.02 625 -0.00
04/03/92 497 465 029 0.79 091 231 492 002 0.02 002 506 0.01
04/07/92 481 465 0.22. 0.61 0.73 187 469 0.02 001 O01 4.77 0.01
04/08/92 479 436 0.24 067 0.78 1.93 414 0.00 -0.00 -0.00 4.76 0.01
04/09/92 415 3.67 0.22 062 072 178 383 -0.01 -0.01 -0.01 413 -0.00
04/14/92 4.75 455 017 053 0.61 178 232 0.00 -001 -0.01 458 -0.00
04/15/92 434 438 0.20 O56 0.71 162 3.79 -0.00 -0.01 005 461 0.00
04/16/92 436 460 0.21 060 0.73 171 3.88 -0.00 -0.01 -0.01 4.63 -0.00
04/17/92 4.56 0.15 053 0.68 168 3.90 -005 -0.04 -0.07 492 -0.06
04/23/92 856 615 037 1.26 147 3.64 5.96 -0.04 -0.05 -0.05 5.04 -0.06
04/24/92 467 482 013 050 058 1.76 3.80 -0.01 -0.05 -0.05 467 -0.04
04/28/92 421 445 O11 041 048 148 3.20 -0.04 -0.04 -0.04 449 -0.04
04/29/92 455 S15 015 0.50 0.58 156 3.29 -0.04 -0.04 -0.03 5.02 -0.04
04/30/92 410 471 014 046 058 143 2.97 -0.04 -0.04 -0.04 462 -0.03
05/01/92 443 512 013 O51 0.63 1.61 345 -0.07 -0.06 -0.05 4.99 -0.06
05/05/92 488 5.07 016 055 063 2.01 3.68 -0.03 -0.03 -0.03 4.68  -0.03
05/06/92 3.69 422 0.09 0.33 0.42 124 2.68 -0.03 -0.02 -0.04 4.88 -0.04
05/07/92 403 451 010 041 0.53 151 2.93 -0.06 -0.06 -0.05 4.67 -0.05
05/12/92 496 5.02 0.13 046 0.57 196 357 -0.04 -0.05 -0.07 5.17 -0.06
05/14/92 404 443 010 O41 051 145 268 -005 -0.03 -0.03 468 0.03
111



140

Elapsed Time, days

Figure 15. Effect of phosphate on lead leached from
pure lead at pH 7.5.



Table A-38. Statistical comparisons of zinc leaching trends using the Kruskal-Wallis one-way analysis of variance (ANOVA) on Ranks during test runs 1 to 3. All
of the data sets showed that the trends were statistically different (P<0.0001). The table shows the proceeding pairwise multiple comparisons of zinc leached from

individual alloys.
Test run #1 Test run #2 Test run #3
Pairwise multiple Pairwise multiple Pairwise multiple Pairwise multiple Pairwise multiple Pairwise multiple
comparison (p <0.05) comparison (p <0.05) comparison (p <0.05) comparison (p <0.05) comparison (p <0.05) comparison (p <0.05)
Statistical comparison over entire run after 60 days" over entire run**# after 60 days"® over entire run*** after 60 days"
36000 (1) .vs. C36000 (2) no difference no difference no difference no difference no difference no difference
36000 (1) .vs. C83600 different different different different different different
36000 (1) .vs. C84400 different different different different different different
€36000 (1) .vs. C84500 different different different different different different
36000 (1) .vs. C85200 different different different different different different
36000 (1)..vs. C85400 different different different no difference different different
€36000 (2) .vs. C83600 different different different different different different
an €36000 (2) .vs. C84400 different different different different different different
£ 36000 (2) .vs. C84500 different different different different different different
€36000 (2) .vs. C85200 different different different different different different
36000 (2) .vs. C85400 different different no difference different different different
C83600 .vs. C84400 different different different no difference different different
83600 .vs. C84500 different different different different different different
C83600 .vs. C85200 different different different different different different
C83600 .vs. C85400 different different different different different different
84400 .vs. C84500 different different no difference no difference no difference no difference
84400 .vs. C85200 different different different different different different
C84400 .vs. C85400 different different different different different different
C84500 .vs. C85200 different different different no difference different different
C84500 .vs. C85400 different different different different different different
85200 .vs. C85400 no difference different no difference no difference different different

F Failed Kolmorogov-Smimov test for normality (P<0.0001)
4 Student-Newman-Keuls Method for multiple comparisons
® Dunn's Method for multiple comparisons



1.6 T_T rs

i
© 3.0 mg PO,/L

1.4 - © 0.5 mg PO,/L 7
r 2 0.0 mg PO,/L

1.26 4

1.07 q

Zinc, mg/L
°
CO
T
1

“0 20 40 60 80 100 120 140
Elapsed Time, days

Figure 26. Effect of phosphate on zinc leached from
C84400 (red brass) coupon at pH 7.5.

71



Dissolution controls

The contribution of brass to lead and other metal concentrations in drinking water has been
well established as discussed. However, the factors influencing the degree of preferential metal,
particularly lead, dissolution from brass and other alloys have not been well defined. Metal
solubility relationships will probably be poor predictors of the amount of lead, copper, and zinc
leached from brasses under the normally non-equilibrium conditions found in drinking water.
Other mechanisms will likely control the amount of metal leached from an alloy. Physical and
structural characteristics of the alloy and alloy's surface (e. g. microstructure, chemical
composition, finish, etc..), for example, are important factors to consider. Landolt®® points out
that the surface composition of alloys usually differs from the bulk material due to factors such
as spontaneous corrosion reaction with the atmosphere and surface treatment processes.

The role of lead in the alloy's structure may influence metal dissolution rates. Lead is
insoluble in brass alloy systems. The melting point of lead with respect to the alloy system is low
and therefore is last to freeze. The result is that during the cooling period, lead tends to be
Squeezed toward the grain boundaries of the alloy in the form of globules. The pattern these
globules take at the alloy surface, which contacts water, likely influences the degree and speed of
lead leaching by increasing the available lead surface area. Further, cutting tools can smear the
lead globules over the surface. These effects may enhance the lead leaching characteristics of
alloys of seemingly low lead content.

Alloy surface area is an important driving force for the rate of metal dissolution. For
example, surface finishing techniques can increase surface area by creating grooves or etchings
in the surface. Polishing may increase lead surface area by spreading the soft lead globules over
the alloy's surface. Characteristics of brass production techniques will result in different surface
properties. The surface of cast brass, for example, is rough and presents greater surface area than
wrought brass, thus driving or increasing metal dissolution rates.

Interactions amongst the metals that comprise alloys may also control metal dissolution
Tates. Some researchers theorize that dezincification of copper-zinc alloys can result in additional
lead surface sites below removed zinc and thus leach as much if not more than a brass containing
more lead and less zinc. On the other hand, under certain water quality conditions, zinc may
contribute to a protective passivating film over the alloy surface.

Alloy composition would seem to be a logical control on metal leaching levels. Paige and
Covino” investigated selective metal leaching from 11 different copper based alloys in high purity
water of near neutral pH. The study specifically examined the effect of lead concentration in the
alloy, contact time, and water temperature on lead leaching from the alloy. Three sets of leaching
test runs were conducted. The first run evaluated leaching at three different temperatures: 25°C,
50°C, and 75°C in deionized water for two weeks. The second study used samples which were
pre-treated by an acetic acid process prior to being run for two weeks in deionized water at 25°C.
The third test run was conducted at 25°C in deionized water for 15 days. Their results indicated

7



Table A-19, Run 4: Cincinnati tap water, pH=7.5, 0.5 mg PO4/L, 72 hour stand time

Study=Coupon
Analyte=Pb

Date ___Time, days C36000_C36000_C83600_C84400 C84500_C85200 C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

02/22/93 5 405 46.1 2683 418.9 2262 1500 40.9 - 7A 234.2 0.5 597.7
03/08/93 19 180 202 46.7 828 448 20.0 9.3 0.2 1.0 213.9 -- 288.1
03/15/93 26 «19.6 «869182 86385 682.2 8636.30 = :18.9 = 10.0 0.0 0.7 234.9 0.1 345.4
03/22/93 33 12.8 11.4 24.3 38.7 22.8 10.3 5.6 0.4 04 206.1 03 234.6
03/29/93 40 16.0 13.0 21.1 31.4 20.3 10.4 5.3 -0.1 -0.1 246.7 70.3 224.6
04/05/93 47 163 106 13.7 214 11.7 5.5 3.7 0.1 -0.1 258.7 -~- 212.4
04/12/93 54.105 = 10.1 ~ 13.6 V7 5.2 22 0.2 0.5 225.3 0.6 177.4
04/19/93 61 129 14.7 111 5 . 3.3 -- 0.1 269.5 05 189.2
04/26/93 68 -- - - - - - ~ ~ -

05/03/93 1s 115 14.5 6.2 - x 2.2 -0.3 -- 251.8 0.2 176.1
05/10/93 82 108 132 5.8 z 5. z 2.0 0.6 0.4 242.2 0.6 187.4
05/18/93 90 117 13.8 5.9 5. a | 2.6 0.6 0.8 258.7 0.3 196.3
05/24/93 96 118 168 6.1 z 24 — 0.4 239.0 04 172.6
06/07/93 110 38.9 30.9 9.1 . 3.9 0.4 0.1 300.4 0.2 198.9
06/21/93 1240 32300 (23.3 . x 22 0.4 0.4 282.9 0.6 204.3



Table A-25. Run 5: Cincinnati tap water, pH=7.5, 72 hour stand time

Study=Coupon
Analyte=Cu

08/16/93 6 0.028 0.843 0.594 0.281 0.379 0.074 0.068 1.606 0.006 0.001 0.000 -0.00
08/23/93 13 0.022 1.206 0.709 0.822 0.795 0.198 0.112 1.603 0.009 0,003 0,004 0.002
08/30/93 20 0.011 1.086 0.783 1.081 0.899 0.359 0.129 1.286 0.009 0.005 0.001 0.001
09/07/93 28 0.007 0.806 0.584 0.813 0.756 0.234 0.155 0,934 0.009 0.006 0.001 0.001
09/14/93 35 0.007 0.724 0.591 0.837 0.779 0.199 0.175 0.788 0.014 0.007 0.002 0.003
09/20/93 41 0.004 0.557. 0.500 0.720 0.617 0.158 0.161 0.659 0.008 0.005 0.001 0.001
10/04/93 55 0.004 0.476 0.544 0.637 0.572 0.141 0.148 0.643 0.006 0.006 0.001 0.001
10/18/93 69 0.003 0.417 0.598 0.779 0.495 0.125 0.129 0.604 0.004 0.004 0,000 0,001
10/25/93 76 0.007 0.279 0.452 0.608 0.324 0.086 0.107 0.400 0.228 0.028 0.002 0.001
11/01/93 83 0.008 0.290 0.493 0.657 0.330 0.100 0.110 0.418 0.007 0.002 0 0.000
11/08/93 90 0.005 0.208 0.402 0.553 0.237 0.078 0.097 0.349 0.006 0.004 0.001 0.001
11/15/93 97 0.005 0.292 0.538 0.709 0.307 0.109 0.129 0.489 0.003 0,004 0,001 0,001
11/22/93 104 0.007 0.181 0.369 0.464 0.182 0.064 0.068 0.296 0.004 0.003 0.002 0,005
11/30/93 112 0.008 0.156 0.406 0511 0.199 0.063 0.075 0.326 0.004 0,003 0.001 0,003
12/06/93 118 0.004 0.204 0.466 0.625 0.205 0.085 0.104 0.389 0.003 0.001 -0.00 0,001
12/13/93 125 0.006 0.251 0.545 0.690 0.243 0.110 0.133 0.463 0.004 0.003 0.001 0.002
12/20/93 132 «0.004 0.209 NA 0.589 0.202 0.097 0.113 0.392 0,015 0.006 0.002 ??
LOWER pH to 6.5
01/31/94 174 0.034 0.971 1.991 1.982 0.870 0611 0.421 1.884 0.004 0.003 0.000 0.001
ADD PHOSPHATE=3.0 mg/L
02/14/94 188 0.014 0.369 0.650 0.714 0.379 0.216 0.176 0.634 0.001 0.001 0.000 -0.00
02/22/94 196 0.011 0.486 0.681 0.718 0.333 0.271 0.180 0.670 0.004 0,002 0.001 0.004

126



20 40 60 80 100 120 140 160

Time, days

Figure A-23. Pure zinc



Copper, mg/L

1.00
0.90
0.80
0.70
0.60
0.50

0.40

0.30

0.20
0.10 ke

0.00

rs a | T T TT

3.0 mg PO,/L
0.5 mg PO,/L
L 0.0 mg PO,/L 4

°

oe

0 20 40 60 980 100 120 140
Elapsed Time, days

Figure 21. Effect of phosphate on copper leached from
85200 (yellow brass) coupon at pH 7.5.

66



Lead coupons

The pH 7.0 test water was more corrosive towards lead than at pH 8.5 (Appendix Figure
F21). At pH 7.0, lead levels were highest at the start of the study and gradually dropped with
time. The lead levels never appeared to stabilize, even by the completion of the test run at 160
days. At pH 8.5, lead levels appeared to stabilize after only approximately 25 days. At the end
of the test runs, lead levels were more than 200 g/L higher than observed at pH 8.5. The results
show that pH clearly impacts lead solubility of pure lead. .

Copper coupon

The pH 7.0 test water was also more corrosive toward copper (Appendix Figure F22).
The leaching pattern over time was unlike lead in that copper levels started low (approximately
1 mg Cu/L) but increased rapidly to a peak at approximately 4 mg/L by 40 days. This pattern was
similar to that observed with copper leached from the brass for the same reasons. The copper
leaching trend proceeded to drop gradually for the remainder of the study, falling back to the
original level of about 1 mg/L in 160 days. It appeared that at the termination of the test run, the
copper levels were still decreasing and further time would be required for copper levels to
stabilize. This showed that it took a greater amount of time for copper concentrations leached
from new copper surfaces to stabilize under exposure to corrosive conditions.

Increasing the pH from 7.0 to 8.5 had a much different effect on the copper leached from
pure copper. The copper levels were significantly lower under these conditions and the trends
followed a different pattern. Copper levels started out at about 0.5 mg/L and gradually dropped
to approximately 0.25 mg/L by 120 days. It appeared that by 80 days into the test run leaching
trend had leveled off. The leaching trend was also smooth in comparison to the lower pH trend.

Zinc coupons

The lowest pH (7.0) test water was also the most corrosive towards pure zinc (Appendix
Figure F23). At pH 7.0, zinc levels started high (approximately 9 mg/L) then dropped rapidly
to about 4 mg/L by 20 days. The levels increased slightly to about 4.5 mg/L after about 60 days,
then leveled off for the remainder of the test run at about 4.5 mg/L. Zinc values, however, were
not smooth, fluctuating randomly about 4.5 mg/L.

Lower zinc levels were observed at pH 8.5. The zinc levels started out quite high, but
decreased rapidly over the first 30 days, falling to a more gradual decreasing slope. The trend
appeared to level off at about 60 days, to a concentration of about 0.25 mg/L. The curve was
relatively smooth.



able Ac2. Run 2: Cincinnati tap water, pH=7.0, 24 hour stand time

‘tudy=Coupon
alyte=Pb

Date __ Time, days C36000_C36000_C83600_C84400 C84500 C85200 C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

02/20/92 15.9 11.3 15.3 10.2 15.7 11.1 16.9 10.6 241 25.6 76 43.4
02/21/92 17.2 2.6 5.9 5.9 5.2 45 4.0 21 69 40 23 39.7
02/25/92 1 1090.9 762.1 3647.2 4075.1 4927.6 985.8 1901.4 20.4 1217.5 1630.4 18.5 4023.5
02/26/92 2 333.6 238.0 2682.1 2052.4 2345.5 338.4 577.6 4.6 999.2 915.5 2.7 1500.6
3- 188.9 2003.8 1408.0 1487.7. 311.5 319.9 3.4 985.0 1083.7 2.3 1116.7
175.9 1284 1168.7 803.3 973.6 222.4 207.7 23 894.5 918.1 36.5 857.3
109.4 129.9 566.9 470.4 536.9 129.8 112.5 3.2 991.8 943.8 25 632.6
106.1 83.9 387.4 343.4 384.1 1040 73.6 3.0 829.7 792.8 2.7 459.6
133.0 96.0 362.7 318.6 3564 96.9 76.2 35 911.3 813.6 2.7 471.4
179.7 1181 412.3 367.1 391.8 106.7 789 3.3 948.7 896.1 - 3.0 467.0
186.8 115.8 256.2 280.7 247.9 783 55.4 3.5 ~~ 859.1 3.5 563.4
179.6 100.5 209.0 2289 1806 75.5 50.5 40 711.4 727.2 3.5 362.1
175.6 91.9 195.5 199.5 184.7 73.3 50.6 3.6 806.0 762.8 21 419.0
179.3 995 202.0 209.3 183.0 85.9 54.6 2.9 888.0 829.3 1.9 447.9
241.8 161.4 1983 2362 162.1 99.4 52.3 0.1 1011.0 908.4 -0.8 410.5
200.3 121.5 162.8 1796 1506 905 418 0.5 814.3 763.6 0.9 370.4
197.1 129.5 183.4 190.7 142.0 964 43.7 0.5 752.1 746.4 397.7
192.5 133.6 181.3 193.3 138.0 96.0 481 1.0 873.9 843.1 0.5 358.4
231.7 183.6 176.6 192.9 128.6 113.5 39.1 0.2 824.6 817.4 - 321.1
185.3 149.6 159.1 191.1 107.3 94.2 35.9 759.0 773.6 03 321.7
258.4 245.1 259.7 275.1 1818 135.1 49.6 0.3 1372.1 1427.4 -0.1 412.0
225.9 232.3 170.3 185.7 1144 104.1 35.3 0.7 843.5 865.5 05 236.3
183.8 197.2 1465 159.2 982 910 35.1 0.6 759.5 781.6 0.5 205.9
197.5 230.1 176.6 194.6 125.2 107.8 40.7 15 975.5 989.4 14 236.2
195.3 222.9 163.2 188.7 122.8 982 41.6 0.6 863.3 875.5 0.4 = 220.7
191.6 219.2 1384 170.9 96.9 72.8 33.6 OS 632.6 663.8 197.7
159.2 204.0 131.7 159.3 90.4 72.4 30.0 0.2 661.9 682.7 0.3 192.4
151.5 205.9 117.2 142.2 85.6 64.2 34.0 0.8 586.3 605.6 10 161.9
120.4 1884 1148 1648 914 564 30.7 11 562.9 575.1 11 193.0
112.7 1776 1073 141.4 874 533 29.8 12 560.9 557.9 2.0 188.5
106.3 180.1 1175 135.7 83.6 49.7 32.0 0.7 587.4 594.1 187.5
109.5 195.2 123.0 141.9 89.3 50.1 34.0 11 597.2 611.9 1.0 193.8
107.0 2111 169.5 198.6 1288 49.8 33.7 10 930.9 926.5 0.5 410.5
103.5 2205 122.4 165.55 103.8 42.3 35.3 0.2 552.3 575.0 0.5 175.2
96.5 208.4 107.7 1536 944 374 36.6 0.3 470.7 473.9 0.8 176.9

85.2 203.1 122.2 1462 908 381 35.7 0.8 521.5 541.7 0.7 178.4

75.1 176.1 982 1173 77.0 33.0 33.2 0.6 482.3 485.6 0.4 145.4

92.8 200.1 1245 1305 89.2 340 384 0.5 585.5 561.9 0.1 169.2

85.5 207.7 124.9 155.7 112.3 345 41.3 0.5 587.4 602.6 0.1 196.8

72.5 183.1 113.8 1166 92.0 293 39.9 0.4 529.2 539.6 128.6

84.0 179.3 1085 125.9 91.3 29.0 39.3 0.4 543.7 541.8 0.2 127.4
101.8 200.0 135.7 179.7 158.9 33.7 49.3 0.8 616.1 623.8 0.9 205.8
92.9 173.3 115.3 135.7 106.9 27.9 44.3 -0.1 540.0 546.9 ~ 144.4

95



The amount of zinc leached from the brass coupons at pH 8.5 and 7.0 was dependent on
the amount of zinc in the alloy. The highest zinc levels were observed at the start of the study,
dropping slightly to approximately 60 days were leveled off. By the end of the test runs yellow
brasses leached more zinc than the pure zinc coupon. This suggested that critical zinc composition
exists when the brass takes on the leaching properties of pure zinc. Zinc levels were sensitive to
PH fluctuations.

The impact of pH on zinc levels increased with increasing pH. Largest differences in zinc
levels between pH 7.0 and 8.5 were observed with pure zinc and the yellow brasses. The
difference decreased as the zinc composition decreased. Lower zinc levels were observed at pH
8.5.

Orthophosphate did not appear to significantly impact zinc levels. In some cases, zinc
levels were slightly lower when orthophosphate was present. However the opposite observation
was made in other cases.

The impact of stagnation time based upon 24- and 72-hour standing sample comparisons
showed that there was little impact on lead leached from red brasses and no visual impact on the
yellow brasses. There was, however, significantly more lead leached from the pure lead coupon
after 72 hours than at 24-hours at pH 7.0 only. In the case of copper, higher levels leached from
the red brasses and pure copper after 72 hours at pH 7.0. Stand time did not impact copper
leached from the yellow brasses. Little difference between copper levels leached from all of the
coupons was observed at pH 8.5. Zinc leached from the brass coupons was most strongly
impacted by stagnation time. The largest differences were observed at pH 7.0. The pure zinc
coupon was not impacted by stand time. The impact of stagnation time decreased at pH 8.5. The
results clearly showed that the impact of stagnation time was dependent on the alloy composition
and "corrosiveness" of the water. Stagnation profiles conducted over 15 hours also suggested that
the alloy composition can also influence profiles.

How does data collected in this study apply to the "real world"? The data suggest that
when all other variables remain constant, the amount of lead leached from brass plumbing
products such as faucets can be reduced by reducing the amount of lead in the alloy. Highest lead
contributions will occur when the brass devices are newly installed. Appropriate precautions can
be taken to limit the lead exposure during this time such as flushing the device before consuming
the water. Although lower-lead containing brasses are a benefit in that they leach less lead, zinc
and copper dissolution must also be considered. Of particular concern is susceptibility of higher
zinc-containing yellow brass alloys to dezincification and associated plumbing failures. In
addition casting and machining considerations which were not specifically addressed in this report
must be considered. Truly low-lead containing brass alternatives to leaded brass such as the
bismuth brass evaluated in this study may serve to eliminate the lead contribution by brass. Other
issues such a production cost and practicality, and the dissolution of bismuth are still issues to
resolve. Orthophosphate appears to be effective at reducing lead levels when brass materials are
relatively new. The benefit appears to decrease with age and as other mechanism become more

31



80 100 120 140 160

Time, days

Figure A-9. Brass Alloy C85400, Yellow Brass



T T T
° 3.0 mg PO,/L |

© 0.5 mg PO,/L +
° 0.0 mg PO,/L

140
Elapsed Time, days

Figure 11. Effect of phosphate on lead leached from
84400 (red brass) coupon at pH 7.5.



6/91/11
£6/S1/TT
£6/60/1T
6/80/11
S6/SO/ET
S6/FO/TT
S6/TO/ET
£6/T0/1T
€6/82/01
€6/97/01
£6/SZ/01
€6/Zc/0T
£6/TZ/0T
6/61/01
6/81/01
£6/F1/0T
6/1/01
£6/L0/0T
€6/S0/0T
£6/+0/01
£6/0€/60
£6/67/60
£6/¥C/60
€6/€7/60
£6/17/60
£6/02/60
6/91/60
£6/S1/60
6/61/60
€6/01/60
£6/60/60
€6/80/60
£6/L0/60
€6/20/60
£6/T0/60
S6/TE/80
6/08/80
S6/L7/80
€6/92/80

RELLERBSRERAER

SAH *hypend so1eA\ voppency 's umy I9L, “Sev ore,



not conclusive, but certainly suggests that more exploration into the impact of orthophosphate on
copper corrosion is needed.

The impact of orthophosphate on zinc leached from the brasses was also difficult to
interpret (Figures 24 to 29). Zinc leaching trends from brass coupons C36000, C83600, and
C84400 showed small reductions in zinc levels when orthophosphate was present, and the
remaining brasses exhibited no benefit. Red brasses did not benefit more from orthophosphate
than the yellow brasses. Orthophosphate appeared to extend the time for zinc levels to stabilize,
but did not impact final zinc concentrations (Figure 30).

Impact of stagnation time on metals leached

The effect of stand time on metal levels leached from the coupons was investigated by
comparing 24- to 72-hour standing samples. As a point of clarification, the same coupon was
used for both test times; 24-hour samples were taken on weekdays and 72-hour samples were
taken over the weekend. Rather than discussing the influence of stand time on metals leached
from each brass, one representative red (C84500) and yellow (C85400) brass will be used to
demonstrate the general trends of each brass type group.

At pH 7.0 and 8.5, lead leached from red brass, coupon C84500 appeared to be slightly
higher (10 to 25 yg/L) after 72 hours while yellow brass was not affected by stand time (Figures
31 and 32). Lead leached from the pure lead coupons in pH 7.0 water were clearly impacted by
stand time, leaching as much as 100 ng/L more lead after 72 hours standing than 24 hours (Figure
33). At pH 8.5, however, no difference between 24- and 72-hour standing samples was observed
(not graphically represented), suggesting water quality plays an important role on the rate of lead
dissolution.

At pH 7.0, copper leached from red brass was generally higher (by as much as 0.5 to 1.0
mg/L) after 72 hours (Figure 34). This trend was also observed with the pure copper coupon
Figure 35). Yellow brass was affected by stand time in a completely unexpected way. Initially
copper levels were lower at 72-hour than 24-hour standing time, however after 125 days the trend
reversed (Figure 34). At pH 8.5, stand time had a small impact on copper levels. 72-hour
samples tended to be 0.01 to 0.05 mg Cu/L higher at 72 hours for both brasses (not graphically
represented). Once again, copper leached from the pure copper coupon after 72 hours followed
the same pattern as 24 hours.

At pH 7.0, zinc leached from red brass was significantly higher (by approximately 1.0
mg/L) after 72 hours, more than doubling the zinc concentration (shown in Figure 36). Yellow
brass was also effected by stand time in the same fashion but at a higher scale. By the end of the
study, zinc levels leached from the yellow brass in 72 hours were more than double the levels at
24 hours (approximately 2.0 mg/L to 4.0 to 4.5 mg/L). Very small differences between 24- and
72-hour zinc concentrations leached from pure zinc were observed (shown in Figure 37). During
the first 125 days, zinc was actually lower in 72 hours, however, the trend reversed thereafter.

27



200 TM—T T T T T T T

3.0 mg PO,/L |
0.5 mg PO,/L 7

q 0.0 mg PO,/L }
150 |- i 4

°

175 |e

oe

125

100 |;

Lead, pg/L

75

50

25 |r

0 20 40 60 80 100 120 140
Elapsed Time, days

Figure 14. Effect of phosphate on lead leached from
85400 (yellow brass) coupon at pH 7.5.

59



Table A-2. Run 2: Cincinnati tap water, pH=7.0, 24 hour stand time

Study=Coupon
Analyte=Pb

Date _ Time, days C36000_C36000_C83600_C84400_C84500_C85200 C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

05/19/92 85 95.4 1586 102.9 1376 1145 286 44.6 14 475.6. 526.3 13 176.9
05/21/92 87 «95.9 175.7 1166 1384 1244 27.7 43.1 11 611.4 596.6 0.9 177.6
05/27/92 93 101.9 1715 115.6 165.9 1242 240 531 0.6 587.0 576.6 0.7 196.6
05/29/92 95 77.5 137.7 97.0 120.0 99.8 30.3 45.6 0.8 559.4 545.6 0.7 161.9
06/03/92 100 90.5 174.2 141.7 1744 1314 348 S41 1.9 777.5 832.4 05 224.8
06/04/92 101 80.4 1441 1089 129.9 102.9 261 44.7 0.2 503.4 481.7 -- -

06/09/92 106 ~ 1324 1043 135.9 1196 25.7 46.1 0.7 480.8 484.0 0.7 180.3
06/11/92 108 528 92.7 854 100.9 77.0 143 34.1 -0.9 357.2 367.5 -0.9 111.6
06/16/92 113. 584 95.6 107.7 144.0 139.9 -- 44.5 0.3 599.7 594.3 03 214.8
06/17/92 114 59.3 1195 1044 1320 135.7 27.1 42.7 0.8 612.2 609.1 0.7 184.7
06/18/92 115 59.4 116.0 991.3 116.5 103.3 24.1 40.0 1.1 519.9 501.3 0.5 163.0
06/23/92 120 - 121.5 100.7 157.3 -- 26.2 46.9 0.2 575.8 580.0 0.1 208.2
06/24/92 121. 543 ©=©100.0 983.4 -- - 22.1 39.0 0.4 459.1 449.5 0.1 133.3
06/25/92 12200 57.5 -- 89.0 141.4 -- 24.9 40.9 1.6 559.3 560.0 13 112.0
06/30/92 127) 580 112.2 966 148.9 -- 24.7 40.1 -0.1 606.1 583.2 2.0 1714
07/01/92 128 «59.1 109.0 992 1474 1241 261 S15 14 594.5 S911 14 145.3
07/02/92 129 «541 90.7 81.7 1228 1063 241 45.3 17 436.0 443.9 04 743
07/07/92 134 405 724 772 122.7 93.7 185 383 0.5 369.0 397.2 0.7 120.4
07/08/92 1350 41.60 «661.40 71.6) 119.1 92.6 19.7 381 0.2 426.7 422.0 0.1 139.8
07/14/92 141 365 57.3 70.7 1159 884 211 381 -0.4 378.2 381.4 O41 117.1
07/15/92 142 31.0 45.7 65.3 102.9 843 17.5 31.1 0.6 365.0 358.5 06 92.7
07/16/92 143 30.7 «945.2 67.5 105.1 81.1 17.9 30.9 0.4 425.8 374.6 0.7 116.6
07/22/92 149 -- 400 589 926 702 145 26.6 0.7 500.6 356.2 0.4 210.2
07/23/92 150 261 394 S589 103.2 79.7 168 26.8 ~ 0.8 410.7 406.4 0.1 103.7
07/28/92 155 30.1 47.1 89.7 142.2 113.0 202 30.7 0.6 468.0 449.9 14 152.8
07/29/92 156 29.9 453 97.2 1314 90.5 195 30.4 0.7 463.0 455.3 05 116.3

96



Copper, mg/L

3.0 po T T ¥ T T

T

1.5

°

pH 8.5
pH 7.0

0 20 40 60 80 100.

Time, days

Figure A-12. Brass Alloy C84400, Red Brass

159



Table A-17,

Study=Coupon

Run 2: Cincinnati tap water, pH=7.0, 72 hour stand time

Time, days C36000_C36000_C83600_C84400_C84500_C85200 C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

Analyte=Pb
Date

03/02/92 T-
03/09/92 14
03/16/92 21
03/30/92 35
04/06/92 42
04/13/92 49
04/20/92. 56
04/27/92 63
05/04/92 70
05/11/92 7
05/18/92 84
05/26/92 92
06/01/92 98
06/08/92 105
06/15/92. 112
06/22/92 119
06/29/92 126
07/06/92 133
07/13/92 140
07/20/92 147
07/27/92 154

177.2
237.6
205.3
169.3
113.3
118.3
104.7
109.0
98.7
113.8
102.8
91.5
78.8
74S
72.0
67.4
58.7
48.3
37.8
39.5

233.3 1688.6

169.4
199.2
222.0
189.1
185.9
208.5
211.2
204.5
182.3
191.8
197.5
160.9
151.6
143.0
138.0
119.7
104.1

76.9

58.3

58.6

447.1
320.1
235.7
175.8
150.7
160.9
152.0
141.4
146.7
148.7
134.6
124.4
127.1
123.0
119.4
107.3
108.2

96.1

88.1
109.6

899.5
313.3
306.2
234.7
187.0
170.1
197.9
204.1
172.3
176.0
184.5
177.8
162.7
181.7
163.6
163.2
158.5
161.9
156.0
147.2
176.6

1423.3

410.9
271.3
143.2
100.9

88.8
117.9
118.6
114.3
137.3
146.1
139.0

29.4
159.1
134.1

118

153.4
T24
89.3

102.4
741
52.9
53.6
45.1
36.5
29.5
28.8
30.2
29.8
32.7
26.1
26.6
24.3
25.9
23.7
214
22.7

321.7
105.8
68.6
35.7
29.5
25.9
32.2
35.0
37.7
38.6
44.8
45.2
45.9
52.8
43.6
43.1
44.3
47.6
44.9
39.2
37.0

3.8 1185.8
3.2 1024.6
-0.7 1688.2

13
0.5
0.2
12
0.5
0.7
10
0.7
12
1.0
11
0.2
0.6
0.7
0.6
-0.5
03 --

504.6
893.9
821.6
854.8
772.3
696.7
664.2
796.4
795.2
672.1
767.3
680.4
720.6
749.2
653.8
580.8

815.1
991.3

1512.3

494.1
876.0
848.0
836.4
T7117
684.9
713.8
TBO
784.0
689.9
748.2
659.0
693.4
717.6
661.3
570.0

0.8 710.5 727.5

3.0 1619.3
3.0 965.0
-0.9 939.5
0.6 $73.3
0.2 355.6
01 422.8
1.0 399.7
0.1 343.8
278.9
10 382.9
0.4 475.9
0.4 363.3
0.8 298.0
12 0.3
0.3 392.7
0.5 --
0.8 238.8
0.3 259.9
210.8



55. Jandel Scientific. Sigmastat User's Manual. Jandel Scientific, San Rafael, CA, (1992).
56. Glantz, S. A. Primer of Biostatistics. McGraw-Hill Inc., New York, (Third ed., 1992).

57. Daniel, W. W. Biostatistics: A Foundation for Analysis in the Health Sciences. John
Wiley and Sons, New York, (Fourth ed., 1987).

58. Natrella, M. G. Experimental Statistics. National Bureau of Standards Handbook 91,
United States Department of Commerce, Washington, D.C., (1963).

59. ASTM Designation: D4210-83; Standard Practice for Intralaboratory Quality Control
Procedures and a Discussion on Reporting Low-Level Data. American Society for Testing and
Materials (ASTM). (1983). ‘

60. Schock, M. R., Lytle, D. A. & Clement, J. A. "Effect of pH, DIC, Orthophosphate and
Sulfate on Drinking Water Cuprosolvency", Office of Research and Development, Cincinnati,
OH, EPA/600/R-95/085 (1995).

61. Edwards, M., Meyer, T. & Rehring, J. Effect of Various Anions on Copper Corrosion
Rates. Proc. AWWA Annual Conference, San Antonio, TX, June 6-10, 1993.

62. van Gaans, P. F. M. "WATEQX - A Restructured, Generalized, and Extended
FORTRAN 77 Computer Code and Database Format for the WATEQ Aqueous Chemical
Model for Tlement Speciation and Mineral Saturation, for Use on Personal Computers or
Mainframes". Computers & Geosciences, 15:6:843 (1989).

63. Trussell, R. R. & Wagner, I. "Corrosion of Galvinized Pipe". Ch. 3 In: Internal
Corrosion of Water Distribution Systems. AWWA Research Foundation/DVGW
Forschungsstelle, Denver, CO, (Second ed., 1996).

64. Pourbaix, M. Adlas of Electrochemical Equilibria in Aqueous Solutions. Pergamon Press,
Oxford, England, (1966).

65. Paulson, A., Benjamin, M. & Ferguson, J. "Zn Solubility in Low Carbonate Solutions”.
Wat. Res. , 23:1563 (1989).

66. Pisigan, R. A. J. & Singley, J. E. "Effects of Water Quality Parameters on the Corrosion
of Galvanized Steel". Jour. AWWA, 77:11:75 (1985).

67. Schock, M. R. & Wagner, I. "The Corrosion and Solubility of Lead in Drinking Water".
Ch. 4 In: Internal Corrosion of Water Distribution Systems. AWWA Research
Foundation/DVGW Forschungsstelle, Denver, CO, (1985).

37



3.5 i T T r T T T T T T T
¢ €84500 (red brass) |
C85400 (yellow brass)
24 hour stagnation
72 hour stagnation

Copper, mg/L

“0 20 40 60 80 100 120 140 160
Elapsed Time, days
Figure 34, Influence of stagnation time on copper

leached from a red and yellow brass coupons during
test run 2: pH=7.0.

79



ACKNOWLEDGMENTS

The authors wish to express particular thanks to Dr. Stanford Tackett for his initiation
of the study. We would also like to thank the following members of the USEPA staff: Herb
Braxton, Leslie Ostrozny, Kelly Mayhew, and Kenneth Kropp for daily operating and
sampling of the test system; Keith Kelty, James Doerger, James Caldwell, Louis Trombly, and
Patrick Clark for analytical support; and Thomas Sorg and James Owens for providing
editorial review of the document. And final thanks goes to Greg George, Steve Harmon, John
Damman, and Roger Rickabaugh of Dyncorp/Technology Applications, Incorporated and Kim
Brackett and Cory Demaris of IT Corp. for additional analytical support and technical
discussions.



TABLE OF CONTENTS

DISCLAIMER .. 1... eee nett ene ii
FOREWORD .. 1.011. tt eee ee eee eens iii
ABSTRACT . 0... cence eee eee iv
LIST OF TABLES .. 1.0.0... ee eee teen eee vii
LIST OF FIGURES .. 11.6. eee eee eens ix
ACKNOWLEDGMENTS .... 0.0... cee eee xii
INTRODUCTION . 2.10... ete eee eens 1
OBJECTIVES .. 1... 6... eee eee eens 1
BACKGROUND .. 2.1.66 e eee eens

Brass composition 2.2.0... 0 ee ee eee eee
Brass production procedures ............. 0.0.0. cece eee eee eee eee
Brass corrosion ..............

Dezincification ..........

Dissolution 6... eee eee

Dissolution controls

Lead release assessment from alloys in drinking water
Alternatives to the use of leaded brass... 0... 0.02 eee ee eee

TEST APPARATUS DESIGN AND OPERATION
Test apparatus ........ 20.0... 0...
Coupon material ..........0......0 000008
Coupon and test system cleaning procedures ... .
Operating procedures
Sampling ..............0...
Analytical procedures

Instrumentation
Quality assurance and quality control ......
Statistical data analysis and interpretation

RESULTS



cyt

Table A-36. Statistical comparisons of lead leaching trends using the Kruskal-Wallis one-way analysis of variance (ANOVA) on Ranks during test runs 1 to3. All
of the data sets showed that the trends were statistically different (P<0.0001). The table shows the proceeding pairwise multiple comparisons of lead leached from

individual alloys.
Test run #1 Test run #2 Test run #3
Pairwise multiple Pairwise multiple Pairwise multiple Pairwise multiple Pairwise multiple Pairwise multiple
comparison (p <0.05) comparison (p <0.05) comparison (p <0.05) comparison (p <0.05) comparison (p <0.05) comparison (p <0.05)
Statistical comparison over entire run*® after 60 days®® over entire run®# after 60 daysTM® over entire run*® after 60 days?"
€36000 (1) .vs. C36000 (2) no difference no difference different different no difference no difference
36000 (1) .vs. C83600 different different no difference different different different
€36000 (1) .vs. C84400 different different different different different different
€36000 (1) .vs. C84500 different different no difference different different different
€36000 (1) .vs. C85200 different different different different different different
36000 (1) .vs. C85400 no difference no difference no difference no difference no difference no difference
36000 (2) .vs. C83600 different different no difference no difference different different
C36000 (2) .vs. C84400 different different no difference no difference different different
€36000 (2) .vs. C84500 different different no difference no difference different different
C36000 (2) .vs. C85200 different different different different different different
€36000 (2) .vs. C85400 no difference no difference different different no difference no difference
C83600 .vs. C84400 no difference no difference no difference different no difference different
C83600 .vs. C84500 no difference no difference no difference no difference no difference different
C83600 .vs, C85200 no difference no difference different different different different
83600 vs. C85400 different different different different different different
€84400 .vs. C84500 no difference no difference different different no difference no difference
84400 .vs. C85200 different different different different different different
€84400 .vs. C85400 different different different different different different
€84500 .vs. C85200 different different different different different different
€84500 vs. C85400 different different different different different different
C85200 .vs. C85400 different different no difference no difference different different

F Failed Kolmorogov-Smimov test for normality (P<0.0001)
4 Student-Newman-Keuls Method for multiple comparisons

® Dunn's Method for multiple comparisons



14. AWWARE. Lead Control Strategies. AWWA Research Foundation and AWWA, Denver,
CO, (1990).

15. Cohen, A. "Copper and Copper Alloys: Innovative Applications of Castings, Forgings,
and Extrusions". ASTM Standardization News (October 1992).

16. Turner, M. E. D. "The Influence of Water Composition on the Dezincification of Duplex
Brass Fittings". Proc. Soc. Water Treat. Examin., 10:162 (1961).

17. Jester, T. C. "Dezincification Update". Jour. AWWA, 77:10:67 (1985).

18. Trethewey, K. R. “New Aspects of the Dezincification of Duplex Brasses in Sea Water.
Part 1: Free-Machining Brasses". J.N.S., 13:1:26 (1987).

19. Lucey, V. F. "The Mechanism of Dezincification and the Effect of Arsenic". British
Corrosion Journal, 1:9 (1965).

20. Horton, R. M. "New Metallographic Evidence for Dezincification of Brass by
Redispositon of Copper". Corrosion-NACE, 26:6:160 (1970).

21. Langenegger, E. E. & Robinson, F. P. A. "A Study of the Mechanism of Dezincification
of Brasses". Corrosion-NACE, 25:2:59 (1969).

22. Heidersbach Jr., R. H. & Verink Jr., E. D. "The Dezincification of Alpha and Beta
Brasses". NACE Corros. , 28:11:397 (1972).

23. Joseph, G. & Acre, M. T. "Contribution to the Study of Brass Dezincification".
Corrosion Science, 7:597 (1967).

24. Fink, F. W. "The Dezincification of Alpha Brass with Special Reference to Arsenic".
Trans. Electrochem. Soc., 75:441 (1939).

25. Langenegger, E. E. & Robinson, F. P. A. "The Role of Arsenic in Preventing the
Dezincification of Alpha Brass". Corrosion-NACE, 25:3:137 (1969).

26. National Association of Corrosion Engineers (NACE). Nace Basic Corrosion Course.
NACE, Houston, TX., (1979).

27. Turner, M. E. D. "Further Studies on the Influence of Water Composition on the
Dezincification of Duplex Brass Fittings". Proc. Soc. Water Treat. Examin., 14:81 (1965).

28. Tabor, L. E. "Effects of Softened Water on Equipment". Jour. AWWA, 48:3:239 (1956).

34



1000

100

Lead, pg/L

10

L n Hl L L n L n

0 20 40 60 80 100 120 140 160

Time, days

Figure A-6. Brass Alloy C84400, Red Brass

153


T T T

° 3.0 mg PO,/L 4
¢ 0.5 mgPO,/L |
5 0.0 mg PO,/L |

60 80 100 120 140

Elapsed Time, days

Figure 20. Effect of phosphate on copper leached from
C84500 (red brass) coupon at pH 7.5.



T T T T
3.0 mg PO,/L

0.5 mg PO,/L
0.0 mg PO,/L |

L 1 n 1

80 100 120 140

Elapsed Time, days

Figure 29. Effect of phosphate on zinc leached from
85400 (yellow brass) coupon at pH 7.5.



EPA/600/R-96/103
September 1996

STAGNATION TIME, COMPOSITION, pH, AND ORTHOPHOSPHATE EFFECTS
ON METAL LEACHING FROM BRASS

by

Darren A. Lytle and Michael R.Schock
Water Supply and Water Resources Division
National Risk Management Research Laboratory
Cincinnati, Ohio 45268

NATIONAL RISK MANAGEMENT RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268

&B Printed on Recycled Paper



Table A-S. Run 5: Cincinnati tap water, pHE7.5, 24 hour stand time

Study=Coupon
Analyte=Pb
Date__Time, days C36000 Pb free _C83600_C84400_C84500_C85200 C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

12/20/93 132 20.5 2.3 0.0 49.6 37.2 6.9 10.8 05 456.2 446.9 0.7 252.9
12/21/93 133 21.0 3.5 605 605 403 78 9.9 12 379.3 355.6 12 177.0
12/29/93 141 21.9 40 383 52.9 37.7 91 11.2 1.7 322.3 304.5 0.1 152.7
12/30/93 142 17.1 33 32.4 45.1 29.5 70 91 0.5 328.9 312.8 0.5 0.0

LOWER pH to 6.5
01/11/94 154 99.9 62 1388 2383 134.2 36.1 37.1 - 1356.8 1377.4 -0.9 530.4
01/13/94 156 109.3 44 89.8 -- 848 238 285 -0.4 1346.0 1359.3 -- 514.8
01/19/94 162 119.0 77° 1249 232.6 1301 341 35.6 -0.2 1862.6 1988.4 0.3 769.4
01/20/94 163° 111.5 6.0 107.1 .209.4 110.7 295 328 -0.5 1890.4 1977.3 19 731.9
01/25/94 168 107.3 64 97.2 2045 1114 316 35.8 -0.2 1563.5 1600.1 03 526.1
01/27/94 170 98.3 51 75.9 1591 794 23.3 31.2 0.8 1676.3 1683.2 -0.1 551.3
01/28/94 171 98.1 54 174.1 141.1 71.9 21.5 27.7 0.5 1595.4 1625.6 0.8 517.2
02/01/94 175 109.8 80 1024 199.2 112.3 31.3 38.2 0.6 1562.3 1621.9 08 569.6
02/03/94 177——«113.4 86 115.3 206.7 130.4 31.0 38.5 0.2 1674.8 1792.5 0.6 695.7

ADD PHOSPHATE=3.0 mg/L
02/08/94 182 - _ - 233.4 -- - - - 1708.8 1763.3 -- 750.7
02/11/94 185 -- - - - - - - - 945.9 907.2 ~ -
02/15/94 189 ~ - - - ~ - ~ - 1159.1 1683.5 -- 370.1
02/17/94 191 -- - - - - 3.9 47 -0.2 -- - 2.8 79.9
02/24/94 198 15.8 23 78 9.4 78 4.0 53 0.5 375.5 364.6 0.2 72.4
02/25/94 199 14.1 13 5.8 7.0 6.0 3.4 41 -0.8 337.3 352.0 -0.1 55.1

100



‘able A-22.

study=Coupon
lyte=Cu

Run 2: Cincinnati tap water, pH=7.0, 72 hour stand time

Date __ Time, days C36000_C36000_C83600_C84400_C8450__C85200_C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

92 0.026

98 0.228
105 -0.008
112 -
119 0.047
126 0.023
133 -0.033
140 0.050
147 0.044
154 0.059

0.214
0.133
0.146
0.154
0.149
0.086
0.131
0.085
0.104
0.096
0.651
0.108
0.078
0.088

0.075
0.051
-0.005
0.053
0.041
0.062

2.073
2.412
3,144
3.102
2412
2.041
2.240
2.252
2.078
1.886
2.208
1.808
1.543
1.484
1.592
1.667
1.588
1.357
2.284
1.614
1.927

3.141
2.364
2.756
2.864
2.208
1.604
2.139
2.287
2.346
1.956
0.001
1.815
1.836
1.885
1.863
1.854
1.911
1.630
2.008
1.897
2.234

1.753
1.441
2.609
2.732
2.161
1.734
2.210
2.363
2.156
1.926
0.003
1.821
2.031
1.852
1.829
1.749
1.807
1.483
1.976
1.928
2.085

0.123
0.211
0.399
1.089
1.127
0.911
1.088
1.221
1.037
0.905
0.039
0.924
0.990
0.983
1.011
0.950
0.920
0.878
1.108
1.426
1.177

123

0.595
0.334
0.324
0.347
0.398
0.370
0.528
0.638
0.664
0.651
0.042
0.717
0.924
0.882
0.850
0.852
0.803

0.896

0.010

1.155 --

3.712
3.849
3.133
2.563
2.847
2.713
2.121
2.208
0.012
2.078
1.738
1.651
1.545
1.489
1.487
1.603
1.606
4,949
0.998

-0.009
-0.016
0.015
0.031
0.039
-0.036
0.010
0.001
0.047
0.051
~0.020
-0.020
-0.005
0.005
-0.060
0.000
0.001
0.006
0.018

-0.001
0.005
0.032
0.016
0.020
0.024
-0.038
-0.028
0.003

-0.006

0.012
0.020
0.015
0.048

0.011
-0.104
013
-0.004



1000

100

Lead, pg/L

10

0 20 40 60 ‘80 100 .120 140 160
Time, days

Figure A-4, Brass Alloy C36000, Free Cutting Brass

151



ABSTRACT

Plumbing products made of brass and similar alloys are the only lead containing
materials still installed in drinking water systems and, by law, may contain up to 8% lead.
Brass ranges in metal composition depending on its application. Brass is composed of
approximately 60 to 80% copper, 4 to 32% zinc, 2 to 8% lead, * 6% tin, and trace amounts of
iron, tin, and cadmium. The relationship between alloy composition and resulting amounts of
metal leached from the alloy in drinking water has not been fully established. Better
understanding brass corrosion may provide information and guidance to the use of the safest
materials for the production of plumbing fixtures, and optimization of corrosion control
treatments.

This study examined the effect of alloy composition, pH, orthophosphate, and
Stagnation time on the metal leached from 6 different brasses and the pure metals that make-up
brass (lead, copper, and zinc) in Cincinnati, Ohio, tap water. Results demonstrated that the
amount of various metals leached from the alloys corresponded well with the alloy's .
composition. Leaching of metal components from brass were generally less affected by pH
than the pure metals. A pH of 7.5 and 0.5 to 3.0 mg/L orthophosphate significantly reduced
the amount of lead leached from the alloys initially, but had less impact as time continued.
Orthophosphate had a minimal impact on copper levels. The impact of stand time was
dependent on water quality and alloy composition. This report covers a period from August
1991 to January 1996, and work was completed as of December 1994.



Run 1: Cincinnati tap water, pH=8.3-8.5, 24 hour stand time

Time, days C36000_C36000_C83600_C84400_C8450__C85200 C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

0.098
0.061
0.069
0.030
0.027
0.035
0.036
0.015
0.020
0.010
0.030
0.010
0.020
0.010
0.020
0.020

0.075
0.046
0.045
0.030
0.021
0.031
0.033
0.016
0.003
0.020
0.030
0.010

0.010

0.020

0.010
0.020

-0.010

0.220
0.254
0.274
0.262
0.233
0.229
0.225
0.269
0.221
0.216
0.220
0.230
0.320
0.320
0.270

0.101
0.143
0.198
0.168
0.160
0.162
0.166
0.180
0.169
0.145
0.170
0.160
0.200
0.240
0.200
0.220
0.270
0.190
0.240
0.190
0.200
0.150
0.160
0.200
0.180
0.160
0.170
0.160
0.180
0.170
0.170
0.180
0.210
0.180
0.180
0.220
0.190
0.190
0.170
0.160
0.180
0.150
0.330
0.150
0.180
0.180
0.220
0.260
0.200
0.340
0.370

0.221
0.231
0.199
0.185
0.163
0.178
0.155
0.200
0.158
0.158
0.090
0.160
0.210
0.250
0.220
0.220
0.270
0.190
0.200
0.190
0.190
0.150
0.180
0.180
0.200
0.180
0.190
0.160
0.150
0.140
0.160
0.190
0.230
0.180
0.200
0.220
0.220
0.180
0.180
0.180
0.200
0.120
0.140
0.170
0.200
0.180
0.220
0.240
0.210
0.310
0.350

0.118
0.096
0.073
0.057
0.039
0.054
0.050
0.039
0.030
0.039
0.050
0.030
0.030
0.040

0.127
0.122
0.086
0.058
0.061
0,069
0.052
0.060
0.056
0.040
0.060
0.040
0.040
0.040
0.040
0.040
0.030
0.030
0.030
0.020
0.030
0.010
0.020
0.020
0.020
0.030
0.020
0.030
0.020
0.020
0.010
0.010
0.030
0.030
0.040
0.040
0.040
0.020
0.030
0.020
0.030
0.010
0.020
0.010
0.030
0.060
0.040
0.060
0.060
0.100
0.070

0.486
0.452
0.421
0.418
0.354
0.331
0.361
0.404
0.370
0.380
0.430
0.420
0.410
0.410
0.370
0.390
0.430
0.440
0.460
0.290
0.300
0.220
0.300
0.320
0,320
0.350
0.330
0.210
0.190
0.220
0.230
0.260
0.280
0.270
0.280
0.290
0.230
0.280
0.230
0.250
0.270
0.200
0,240
0.200
0.230
0.200
0.220
0.250
0.250
0.410
0.450

0.009 0.010 -0.006
0.005 0.005 0,006
0.011 0.003 0.004
0.008 0.008 0.008
0.010 0.013 -0.003
0.018 0.001 0.009
0.005 0.007 ° -0.010
-0.006 -0.004 -0.003
0.005 -- 0.002
0.010 -0.007 -0.006
0.020 0.030 0.010
0.010 0.010 --
-0.010 -- -

- 0.010 --
0.020 -- -
0.010 0.010 --

0.010 0.010 0.020
0.020 -- ~

0.010 -- -0.010
0.010 0.010 0.010
-0.010 -0.010 -0.010

0.000 0.000 0.000
0.000 0.000 0.000
0.010 -0.010
-0.010
~ 0.010
-0.010 --
-0.020 -0.030
0.010 --
0.010 0.010
0.010
-0.010
- 0.010
-0.010 --
-0.010 -0.010
0.010 0.010
om -0.010
-0.010 -0.010
0.030 0.030
0.020 0.020
0.010 --
0.010 0.020
0.020 0.020
0.020 0.020
0.010 0.010

0.011
0.002
0.005
0.009
0.005
0.006
0.004
-0.001
0.011
~0.004
0.010
0.010

0.010
0.020

0.020
0.010
-0.010
0.010
0.010

0.000
0.000

0.010
0.010
0.010
-0.010
-0.020
0.010



to a plateau which they stayed at for the remainder of the study. This pattern was believed to be
due to the slow dissolution of an oxide film thought to have formed on the coupon surface during
coupon atmospheric storage prior to study initiation. The film provided some corrosion
protection to the coupons initially, however, with time dissolved.and new films and equilibrium
conditions were established. The C36000 brass leaching trend decreased gradually during the first
60 days, after which the trend leveled off.

There was difficulty in accurately distinguishing or ranking leaching trends, with the
exception of the two C36000 brass coupons. The C36000 brass coupons stood out from the other
brasses in that significantly lower amounts of copper were leached from them. They contained
the least amount of copper of the brasses tested. The difficultly in detecting differences or ranking
copper leaching trends among the remaining brasses was due to the inconsistency or sporadicness
of the leaching trends despite strict control on pH leaching trends. This demonstrates that even
under well controlled laboratory conditions, a high degree of random variability occurred. The
cause (s) are difficult to determine since a number factors such as small water quality differences,
disturbance of the test apparatus, small stagnation time differences, and the dislodging of
particulate material could contribute to such behavior.

Copper levels generally remained between 1 to 2 mg/L of copper throughout the duration
of the study for the group of coupons. Similarly to test run 1, the amount of copper leached from
the pure copper coupon was initially higher than levels leached from brasses, however, rapidly
fell below those levels leached from the red brasses.

Trends were determined to be statistically different in most cases, leaching trends were
significantly different (P<0.05) (Appendix Table 37). However, leaching trends crossed over
each other frequently making it difficult to distinguish or rank trends. Good reproducibility of:
copper leached from the duplicate free-cutting brass coupons was found.

Zinc leached from brass coupons

Zinc leaching patterns followed a slightly different trend than lead and copper (Figure 8).
In almost all cases, zinc levels gradually fell with time, in most cases leveling off by
approximately 60 days. The amount of zinc leached from the coupons was directly dependent
upon the amount of zinc in the alloy. C36000 leached the most zinc, leaching as much as 2 mg/L
more than the next closest alloy, and averaged about 4 to 5 mg/L by the end of the study. The
levels leached from C36000 were nearly the same as the levels observed with the pure zinc
coupon. C85400 and C85200 brasses were next in order of leaching. The two yellow brasses
contained the next greatest amount of zinc. Zinc leached from them appeared to be still
decreasing at the end of the study. Red brasses C84500 and C84400 were next, and very close,
averaging around 0.5 mg/L and C83600 leached at <0.25 mg/L. In nearly all cases (after 60
days and over the entire study), zinc leaching trends were statistically different. Reproducibility
of zinc leached from the duplicate free-cutting brass coupons was good.

22



8.0 —— OO OI

r © (84500 (red brass) |
7.0 - vy 85400 (yellow brass)

L _—_24 hour stagnation
oe 72 hour stagnation _|

6.0
5.0

4.0

Zinc,mg/L

3.0

2.0

1.0

0.0

0 20 40 60 80 100 120 140 160
Elapsed Time, days

Figure 36. Influence of stagnation time on zinc
leached from a red and yellow brass coupons during
test run 2: pH=7.0.

81



500

SE T T T
C84500 (red brass) |
i v C85400 (yellow brass
é ——24 hour stagnation
72, hour stagnation

400 Fj

100

Wy, — pep RNA OR i PRE 0,

a rr ee
0 20 40 60 80 100 120 140 160

Elapsed Time, days

Figure 31. Influence of stagnation time on lead
leached from a red and yellow brass coupons during
test run 2: pH=7.0.

76



Wrought (forged) brass products are produced by mechanically forming the alloy to the
desired shape while the metal either still hot (700 to 850°C) and ductile, or at room temperature
(referred to as cold-working). Wrought alloys have not been remelted. Wrought brass offers
many advantages including high electrical and thermal conductivities, facilitating joining by
welding and soldering, good corrosion resistance, high strength and ductility, and excellent
machinability. Compared to cast products, wrought products have smoother surfaces, a faster
production time, greater freedom from porosity, and lower cost. Duplex brasses are easily
worked by hot pressing while alpha brasses tend to be stiff to work, even when hot. 16
Additionally, alpha brasses tend to crack during hard working if they contain small amounts of
impurities, especially lead (which is often added to improve machinability). Forging brass (60.0%
Cu, 38.0% Zn, and 2.0% Pb), alloy number C37700, is the most forgeable and therefore the most
common forged alloy. Forging is the method manufacturers prefer using to produce compression
fittings.

Brass corrosion

Dezincification

The majority of published research that has examined the effect of drinking water on brass,
bronze, and other zinc containing alloys is focused on the corrosion phenomena referred to as
"dezincification." _Dezincification has received special attention from the drinking water industry
primarily because of the physical and visible damage to plumbing systems that results, leading to
costly pipe failures and plumbing blockages. Dezincification of small valves and fittings in the

United States has not been nearly the problem it has in Great Britain and some other places in
northern Europe primarily because standard materials used in the U.S. tend to be low zinc
containing red brasses.’”

Dezincification is a specific form of dealloying or selective leaching corrosion. In the case
of dezincification, zinc is preferentially removed from the brass or other copper-zinc alloys.
Researchers have developed three main hypotheses to describe the mechanisms of zinc removal.
The first hypothesis, and generally more widely accepted, is that simultaneous dissolution of
copper and zinc occurs anodically, producing an electrolyte containing both copper and zinc,
followed by the redeposition of copper."*”° The second and less widely accepted hypothesis is that
zine is preferentially removed from the alloy, thus leaving a porous residue.” A third school of
thought is that a combination of the two occurs.” Depending on water composition and service
conditions, the dissolved zinc may react with carbonate or oxygen to form a crust of solid
corrosion products close to the corroded area. These corrosion products usually form smooth
mounds. Upon opening they show a structure made up of many hollow shells resembling the
appearance of a “meringue", giving rise to the term "meringue dezincification". This bulky by-
product causes home plumbing blockages which often present more of a problem than pipe failure
by corrosion. The remaining alloy is a porous, weakened, reddish residue that is susceptible to
failure.



Figure 1. Photograph of test system.



6.0
5.55 4
5.0
45
4.0
3.5
30F ° pH8.5 1
25+ 6 ¢ pH7.0 1
2.0
1.5

T

ot,

Zinc, mg/L

0 20 40 60 80 100 120 140 160
Time, days

Figure A-16. Brass Alloy C36000, Free-Cutting Brass

163



05 1.0 2.0 4.0 60 8.0 15.0

Standtime, hours

Figure 43. Copper stagnation profile for red
brass C84400.



80 100 120

Time, days

Figure A-15. Brass Alloy C85400, Yellow Brass



1.00 TM—T T_T T TTT T

LL 3.0 mg PO,/L J
0.90 0.5 mg PO,/L |
0.80 0.0 mg PO,/L |

oc e@0

0.70 4
0.60 - 4
0.50

Copper, mg/L

0.40
0.30

0.20 f
0.10 3

0.09 1+ 1 tt
0 20 40 60 80 100 120 140

Elapsed Time, days

Figure 22. Effect of phosphate on copper leached from
85400 (yellow brass) coupon at pH 7.5.

67



Differences in trends never exceeded 0.25 mg Zn/L. Figure 38 shows that at pH 7.0, yellow
brass leached the same amount of zinc as the pure zinc coupon at 72 hours (which is not different
from 24 hours). This suggested that the dissolution rate of zinc from brass was slowed by factors
such as surface area or alloy structure. At pH 8.5, stand time also had a significant impact on
zinc levels of coupon C85400 (shown in Figure 39) but at a lower magnitude than pH 7.0
(approximately 0.15 mg/L). The red brass did not appear to be significantly impacted by pH.
The pure zinc coupon was not affected by stand time at pH 8.5.

A preliminary study was conducted to further address the impact of stand time on the
metals leached from brass alloys. The study, operated identically to protocol previously
established, used test water described under the NSF faucet test protocol (pH= 8.19, DIC= 113.6
mg CIL, alkalinity= 501.7 mg CaCO,/L, free chlorine= 1.9 mg/L, and sodium= 220.0 mg/L).
Two brasses, yellow brass C85200 and red brass C84400 were each evaluated in duplicate.
Stagnation profiles were developed from samples taken following 30 minutes, 1, 2, 4, 6, 8, and
15 hours. Lead results suggested that stagnation profiles varied with alloy composition. Figure
40 shows that lead levels reached maximum levels as early as 30 minutes (following 2 months of
operation or "conditioning") for the yellow brass. This observation may have been associated with
the overall low amount of lead leached from the alloy. Figure 41 shows that lead leached from
red brass, however, was very much impacted by stagnation time. Lead levels appeared to still be
increasing up to 15 hours. These results suggest that the dissolution rate of lead is slowed down
by factors such as surface area or diffusion barrier films. These observations agree with
observations made between 24- and 72- hour standing samples.

Stagnation profiles for copper leached from both brasses (Figures 42 and 43) show that the
most rapid increase in copper levels occurred over the first 6 hours. The copper levels appeared
to still be slightly increasing after 15 hours. Similar observations were made with zinc stagnation
profiles, but continuing increases of zinc levels after 15 hours was not as apparent (Figures 44 and
45).

The results of this portion of the study showed that the dissolution rate of metals from
brass and pure metals is dependent on a combination of factors. Alloy characteristics and water
quality are clearly important. In terms of corrosion or dissolution rate, brasses likely will differ
from pure metals based on diffusion considerations. It is also reasonable to assume that for a
given corrosion rate, longer stand times would be required to reach higher metal levels in more
corrosive waters. But the question arises as to what happens to corrosion rates under changing
water qualities. For example, how does a change in pH, and subsequent distribution in chlorine
species, affect corrosion rates? Further, under typical drinking water conditions (and in this
study), two oxidants are present, dissolved oxygen and a disinfectant. How do the oxidants
interact and what happens to the corrosion rate when one is depleted? If both are depleted,
dissolution would cease. On the other hand, if an unlimited supply of oxidant and time were
available, metal levels leached from brass coupons would theoretically reach levels leached from
the pure coupons and chemical equilibrium. Unfortunately, it was impossible to determine
oxidant levels in the cells at the end of stagnation periods due to the small sample volumes used.

28



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Table A-11.

|Study=Coupon

Run 1: Cincinnati tap water, pH=8.3-8.5, 24 hour stand time

Time, days C36000_C36000 _C83600_C84400 C84500_C85200 C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

|Analyte=Zn
Date

08/14/91

08/15/91

08/16/91

08/20/91

08/21/91

08/22/91

08/23/91 10
08/27/91 14
08/28/91 15
08/29/91 16
08/30/91 17
09/03/91 21
09/04/91, 22
09/05/91 23
09/06/91 24
09/10/91 28
09/11/91 29
09/12/91 30
09/13/91 31
09/17/91 35
09/18/91 36
09/19/91 37
09/20/91 38
09/24/91 42
09/25/91 43
09/26/91 44
09/27/91 45
10/01/91 49
10/02/91 50
10/03/91 51
10/04/91 52
10/08/91 56
10/09/91 S7
10/10/91 58
10/11/91 59
10/17/91 65
10/23/91 A
10/25/91 73
10/30/91 78
11/01/91 80
11/06/91 85
11/08/91 87
11/13/91 92

Caornwne

0.64
0.61
0.61
0.51
0.43
0.38
0.35
0.31
0.22
0.41
0.36
0.35
0.48
0.49
0.45
0.27
0.41

0.23.

0.27
0.20
0.26
0.23
0.29
0.17
0.21
0.22
0.24
0.17
0.19
0.21
0.20
0.31
0.33
0.26
0.26
0.20
0.23
0.21
0.20
0.26
0.12
0.11
0.18

0.65
0.55
0.66
0.46
0.42
0.35
0.31
0.31
0.22
0.29
0.35
0.57
0.50
0.53
0.46
0.34
0.43
0.27
0.31
0.25
0.27
0.32
0.34
0.20
0.29
0.30
0.30
0.18
0.22
0.24
0.22
0.30
0.33
0.25
0.27
0.21
0.22
0.23
0.21
0.26
0.11
0.11
0.19

0.04
0.12
0.11
0.08
0.06
0.05
0.05
0.13
0.04
0.04
0.03
0.04
0.11
0.41
0.08
0.07
0.11
0.05
0.07
0.04
0.05
0.03
0.04
0.04
0.04
0.28
0.04
0.04
0.04
0.03
0.04
0.08
0.08
0.06
0.06
0.05
0.06
0.04
0.05
0.05
0.02
0.02
0.03

0.09
0.25
0.29
0.20
0.17
0.15
0.16
0.15
0.10
0.10
0.09
0.11
0.22
0.25
0.19
0.23
0.23
0.12
0.12
0.11
O11
0.08
0.08
0.10
0.09
0.09
0.12
0.09
0.11
0.10
0.09
0.17
0.18
0.13
0.13
0.11
0.12
0.09
0.09
0.11
0.05
0.12
0.09

0.06
0.22
0.27
0.20
0.15
0.12
0.16
0.15
0.10
O11
0.04
0.10
0.24
0.30
0.59
0.20
0.28
0.14
0.14
0.15
0.13
0.10
127
0.12
0.13
0.12
0.12
0.41
0.13
0.11
0.11
0.23
0.24
0.17
0.17
0.15
0.15
0.13
0.13
0.15
0.07
0.07
0.10

0.89
0.61
0.55
0.48
0.41
0.38
0.34
0.31
0.26
0.33
0.25
0.35
0.41
0.46
0.36
0.33
0.57
0.20
0.20
0.21
0.21
0.17
0.19
0.18
0.20
0.26
0.23
0.34
0.25
0.19
0.17
0.34
0.31
0.23
0.25
0.19
0.19
0.15
0.14
0.17
0.10
0.09
0.13

109

0.46
0.44
0.52
0.40
0.32
0.30
0.27
0.30 --
0.18 --
0.23
0.23 --
0.26
0.40
0.45 --
0.46
1.52
0.43
0.21
0.20
0.22
0.21
0.15
0.17
0.16
0.21
0.20
0.17 --
0.20
0.20
0.18
0.15
0.27
0.36
0.26
0.28
0.23
0.23
0.20
0.18
0.21
0.08 --
0.08
0.13 --

0.01
0.01
0.01
0.00
0.00
-0.00
0.00

0.01

0.01
0.01

0.02
0.08
0.06
0.01
0.01
0.02
0.01
0.01
0.01
0.01
0.02
0.01

0.01
0.01
0.01
0.02
0.03
0.02
0.01
0.02
0.02
0.01
0.01
0.01
0.01

0.01

0.01
0.01
0.01
-0.00
0.00
-0.00
0.00
-0.00

0.01

0.01
0.01
0.08
0.01
0.01

0.01
0.01
0.01
0.01
0.02

0.01 °

0.01
0.01
0.01
0.01
0.02
0.01
0.01
0.02
0.01
0.02
0.03
0.02

0.01
0.01

0.02
0.01
0.01
0.01
0.00

0.01
0.00

0.01

0.01
0.03
0.32
0.01
0.01

0.01
0.01
0.08
0.01
0.01
0.04

0.01
0.01
0.01
0.01
0.02
0.03
0.01
0.01
0.02
0.01
0.01
0.01
0.01
0.01
0.01
0.01

-0.01
11.25
831
6.08
3.38
2.73
2.56

1.94
1.89
1.86
3.08
1.74
1.57
137
0.93
0.79
0.49
0.52
0.42
0.40
0.39
0.41
0.30
0.28
0.85
0.25
0.29
0.32
0.25
0.27
0.29
0.35
0.26
0.25
0.24
0.21
0.19
0.14
0.22
0.11
0.10
0.14

0.07
0.06
0.05
0.05
0.01
0.02
0.02
0.01
0.01
0.01
0.02
0.01
0.02
0.01
0.01
0.27
0.11
0.02
0.01
0.14
0.01
0.01
0.03
0.01
0.01
0.01
0.01,
0.02
0.15
0.03
0.02
0.02
0.02
0.01
0.03
0.02
0.02
0.01
0.02
0.01
0.01
0.01
0.01


Table 5 (continued)
(e) Test run #5,

Lead, ug/L
Calcium, mg/L
Copper, mg/L.
Tron, mg/L
Potassium, mg/L
Magnesium, mg/L
Manganese, mg/L
Sodium, mg/L
Zinc, mg/L

Alkalinity, mg CaCO3/L
Sulfate, mg SO4/L
Chloride, mg/L |

Silica, mg SiO2/L
Nitrate, mg N/L
Ammonia, mg NH3/L
Phosphate, mg PO4/L
Dissolved oxygen, mg/L
Total inorganic carbon, mg C/L
Free chlorine, mg Clo/L
pH, pH units

<0.002
27.7
<0,003
<0.002
1.0

67
<0.0004
.9.0
0.01

17.9
43.8
24.0
13
0.69
<0.03
<0.02
SA
13.4
0.68
TA

45

<0.002
474
0.01
0.05

61

15.6
<0.0004
43.1
0.02

94,3
136.3

<0.02
38.9
0.00
0.01
3.9

113
<0.0004
25.1
0.01

57.2
100.8
35.0
3.0
1.05
<0.03
0.02
84
17.6
0.94
15,

<0.002
6.5
<0.003
0.007
0.8

3.1
<0.0004
10.4
0.03

22.4
23.4
5.8
1.6
0.23
<0.03
<0.02
16
3.4
0.15
0.1

<0.002
14
<0.003
<0.002
0.2

0.7
<0.0004
2.3
<0.001

5.0
5.6
52.0
0.3
0.08
0.06
<0.02
0.7
31.7
0.04
0.1

<0.002
42.5
<0.003
0.01

3.9

13.4
<0.0004



Table A-29. Run 4: Cincinnati tap water, pH=7.5, 0.5 mg PO4/L, 72 hour stand time

Study=Coupon
Anslyte=Zn

— Pate ‘Time, days C36000_C36000_C83600_C84400 €84500_C85200_C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

02/22/93 5 357 343 072 069 069 361 3.33 0.02 250 -0.01 845 -0.00
03/08/93 19 2.44 245 024 021 0.72 149 181 -0.00 0.32 -0.01 4.68 -0.00
03/22/93 33° «128 «641.76 «4009 019 O57 1.28 140 -0.00 0.22 -0.00 - -0.00
03/29/93 40 199 186 010 018 043 129 140 0.00 0.22 -0.00 3.72
04/05/93 47 232 215 0.08 024 O40 141 160 0.00 -0.00 2.80
04/12/93 54 «1.86 - - 018 032 42125 135 -0.00 0.25 000 231
04/19/93 61 178 161 010 0.19 0.29 109 125 0,00 0.22 -0.00 2.60
04/26/93 68 137 125 006 0.14 0.20 087 0.98 -0.00 0.15 -0.00 2.14
05/03/93 75 138 123 006 O13 018 084 091 0.00 015 -000 1.79
05/10/93 82 105 092 0.05 010 0.13 066 0.75 0.00 0.10 0.00 1.56
05/18/93 90 074 068 004 008 O11 058 065 -0.00 0.08 -0.00 1.17
05/24/93 96 089 082 004 O10 013 059 0.74 0.00 0.09 -0.00 1.13
06/07/93 110 (0.84 «4121 005 O11 0.13 0.55 0.77 0,00 0.08 0.00 1.24
06/21/93 124 —- 158 0.04 0.09 0.11 0.54 0.79 = -0.00 0.07 -0.00 1.38



Table 3, Analytical Methods Used for Chemical Analysis of Water Samples

Detection
Analysis Method Method Number Reference Limit (mg/L)
Metals
Calcium AA-Flame 7140 EPA 0.1
Magnesium AA-Flame 7450 - EPA! 2.0
Sodium AA-Flame 7710 EPA! 3.0
Potassium AA-Flame 7610 EPA} 0.25
Tron AA-Flame 7380 EPA 0.05,
Copper AA-Flame 7210 EPA! _ 0.02
Lead GFAAS 7421 EPAI 0.002
Zine AA-Flame 7950 EPA! 0.01
Manganese AA-Flame 7460 EPA! 0.01
Calcium: ICAP 200.7 EPAS 0.01
Magnesium ICAP 200.7 EPAS 0.025
Sodium ICAP 200.7 EPAS 0.025,
Potassium ICAP 200.7 EPAS 2.0
Copper ICAP 200.7 EPAS 0.003
Lead ICAP 200.7 EPAS 0.02
Zine ICAP 200.7 EPAS 0.001
Manganese ICAP 200.7 EPAS 0.0004
Silicon (as SiO.) ICAP 200.7 EPAS 0.053
Sulfur (as SO,-) ICAP 200.7 EPAS 0.045
Aluminum ICAP 200.7 EPAS 0.025
Tron ICAP 200.7 EPAS 0.002
Automated Potentiometric 4500-Cl D, Std. Methods? 1.0
Titration
Fluoride Automated Standard ~ Orion* <O1
Additions
Potentiometric ISE 340.2 EPAS 0.10
Orthophosphate Automated Colorimetric 1-2601-85 USGS? 0.02 (as PO,)
Total Phosphate. Automated Colorimetric 1-2600-85 uUsGs? 0.05 (as PO,)
Nitrate-N Automated Colorimetric A303-5173-00 Alpkem3 0.02 (as N)
Silicate Automated Colorimetric A303-5220-13 Alpkem3 0.4 (as SiO)
Sulfate Automated Turbidimetric 303-5220 Alpkem3 ~6.0 (as SO4)
Total Alkalinity Automated Potentiometric 9038, EPA! ~0.3 (as CaCO3)
Titration to Equivalence Point 2320 B46. Std. Methods? -
Others
Dissolved Oxygen Winkler (Azide Modification) 4500-0 D. Std. Methods? 0.50
Temperature - - - -
Ammonia Automated Colorimetric 350.1 EPAS 0.03
Total Inorganic
Carbon Coulometric Titration DS13-92 ASTMS <05
Total Chlorine DPD Colorimetric 8167 Hach? 0.02
Free Chlorine DPD Colorimetric 8021 Hach? 0.02
pH Closed-System Electrometric - EPA(DWRD)!9 ~

| USEPA, OSWER, SW846, Sept. 1986.
? Modified from methods for Determination of Inorganic Substances in Water & Fluvial Sediments, U.S.
Geological Survey Open-File Report, (85-495) 1985.

3 Alpkem Research, Inc., Clackamas, OR.

* Orion Research, Inc., Boston, MA.

5 USEPA, "Methods for Chemical Analysis of Water and Wastes,” EPA-60014-79-020 (1983),

S USEPA, "Methods for the Determination of Metals in Environmental Samples,” EPA-G0014-91-010 (1994).

‘7 "Standard Methods for the Examination of Water and Wastewater," 18% Edition (1992).

51994 Annual Book of ASTM Standards," section 11, volume 11.01 Water (I).

° Hach Company, Loveland, Co.

*© Drinking Water Research Division, USEPA, Internal Method. References: Journal AWWA 72:5:304(1980);
Schock & Lytle, Proc. AWWA WQTC (1994),

41°



3.0 mg PO,/L
0.5 mg PO,/L
a 0.0 mg PO,/L

80 100 120 140

Elapsed Time, days

Figure 25. Effect of phosphate on zinc leached from
83600 (red brass) coupon at pH 7.5:



24 hour stagnation
72 hour stagnation 1

“0 20 40 60 80 100 120 140 160

Elapsed Time, days

Figure 35. Influence of stagnation time on copper
leached from pure copper coupons during test run
2: pH=7.0.



29. Ingleson, H., Sage, A. M. & Wilkinson, R. "The Effect of the Chlorination of Drinking
Water on Brass Fittings". Journal of the Institute of Water Engineers and Scientists, 3:81
(1949).

30. Samuels, E. R. & Meranger, J. C. "Preliminary Studies on the Leaching of Some Trace
Metals from Kitchen Faucets". Water Research, 18:1:75 (1984).

31. Nielsen, K. Measurements and Test Procedure for Cadmium and Lead Pick up in the
Water from Drinking Water Installations. 7th Scandinavian Corrosion Conference, 1975.

32. Nielsen, K. "Control of Metal Contaminants in Drinking Water in Denmark". Aqua,
4:173 (1983).

33. Birden, H. H., Calabrese, BE. J. & Stoddard, A. "Lead Dissolution From Soldered Joints".
Jour. AWWA, 78:11:66 (1985).

34. Schock, M. R. & Neff, C. H. "Trace Metal Contamination from Brass Fittings". Jour.
AWWA, 80:11:47 (1988).

35. Gardels, M. C. & Sorg, T. J. "A Laboratory Study of the Leaching of Lead from Water
Faucets". Jour. AWWA, 81:7:101 (1989).

36. Landolt, D. "Contributions of Surface Analysis to Corrosion Science: Selective
Dissolution and Oxidation Phenomena in Alloy Corrosion". Surface and Interface Analysis,
15:395 (1990).

37. Paige, J. I. & Covino, B. D., Jr. Leachability of Lead from Selected Copper-Base Alloys
Used by the Plumbing Industry. NACE Corrosion/92, Nashville, TN, 1992.

38. Jones, D. A. “Polarization Studies of Brass-Steel Galvanic Couples". NACE Corrosion,
40:4:185 (1984).

39. Mattsson, E. & Histrat, K. "Lead Release from Leaded Copper Alloys in Tap Water".
Swedish Corr. Inst. Report 1986-02-28, (1986).

40. Specification of Requirements for the Suitability of Materials for Use in Contact with
Water for Human Consumption with Regard to Their Effect on the Quality of Water. Draft
for Development. DD 82! BSI:14 (1982).

41. Council directive relating to the quality of water intended for human consumption
(80/778/EEC). EC 1980:L229:11 (1980).



Run 5: Cincinnati tap water, pH=7.5, 72 hour stand time

299.2
82.7 23.7 275.7 . . 220.0
40.8 12.8 224.7 e . . 263.2
35.7 11.9 216.5 E . . 262.8
37.4 8.7 206.0 , 5 322.1
25.5 5.9 165.6 . 5 299.9
23.2 49 137.5 ! . . 461.1
19.8 46 136.1 | . 457.8
19.1 40 105.5 . A . 447.5
18.7 42 1013 x 5. F 421.2
15.8 26 74.0 . 5. . 385.1
18.6 5.2 88.6 . x . A724
14.9 25 54.5 s . . 380.8
15.2 24 45.2 . e 320.4
21.0 2.20 45.2 A . 406.5
22.9 3.6 44.8 f . 5 . 484.7
20.5 23 -- x x . . 456.2

122.0 88 110.8 218.1 . 5. 8 1743.5

188 -- 567.2
196 -- 206.6



Run 3: Cincinnati tap water, pH=7.5, 3.0 mg PO4/L, 24 hour stand time

Date __Time, days C36000_C36000_C83600_C84400_C8450__C85200_C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

08/14/92
08/19/92
08/20/92
08/21/92
08/25/92
08/26/92
08/27/92
09/01/92
09/02/92

4-

0.093
0.209
0.209
0.078
0.088
0.133
0.083
0.078
0.080
0.115
0.077
0.061
0.067
0.067
0.058
0.048
0.039
0.043
0.039
0.049
0.034
0.042
0.022
0.036
0.031
0.036
0.037
0.030
0.019
0.030
0.022
0.036
0.024
0.046

0.093
0.093
0.093
0.078
0.088
0.133
0.083
0.078

0.556
0.440
0.441
0.441
0.265
0.280
0.413
0.333
0.328
0.301
0.385
0.344
0.273
0.317
0.228
0.214
0.233
0.165
0.175
0.143
0.169
0.137
0.144
0.084
0.078
0.092
0.135
0.121
0.102
0.086
0.096
0.094
0.103
0.090
0.112

0.556
0.440
0.441
0.441
0.354
0.383
0.531
0.403
0.369
0.328
0.423
0.370
0.318
0.409
0.290
0.262
0.270
0.202
0.219
0.181
0.231
0.178
0.184
0.105
0.127
0.132
0.188
0.174
0.150
0.116
0.135
0.133
0.170
0.134
0.157

0.440
0.557
0.557
0.519
0.369
0.398
0.542
0.375
0.356
0.330
0.421
0.268
0.341
0.433
0.308
0.246
0.271
0.188
0.197
0.166
0.218
0.178
0.184
0.107
0.121
0.132
0.183
0.174
0.150
0.132
0.135
0.133
0.148
0.130
0.172

105

0.324
0.325
0.325
0.325
0.265
0.280
0.333
0.250
0.244
0.216
0.306
0.383
0.273
0.319
0.233
0.201
0.205
0.159
0.146
0.138
0.171
0.138
0.123
0.088
0.088
0.093
0.125
0.115
0.104
0.088
0.083
0.094
0.097
0.086
0.106

0.208
0.209
0.209
0.286
0.177
0.221
0.250
0.203
0.203
0.182
0.191
0.191
0.182
0.250
0.211
0.179
0.161
0.122
0.131
0.116
0.151
0.132
0.144
0.089
0.088
0.113
0.145
0.134
0.128
0.096
0.096
0.094
0.112
0.108
0.114

0.903
0.789
0.441
0.673
0.501 ~
0.575 --
0.667 --
0.494
0.494
0.457
0.517 --
0.472
0.432 --
0.570
0.395
0.312
0.294
0.211
0.241
0.183
0.232
0.200
0.205
0.123
0.141
0.153
0.211
0.193
0.176
0.133
0.156
0.152
0.156
0.138
0.180

0.019
0.011
0.019
0.011

0.004
0.018
0.016

0.001

-0.002
0.007
0.002
0.007

-0.002

-0.001
0.007
0,009

0.001

0.003
0.019
0.011
0.011

0.011
0.016

0.003

0.008
0.003
0.007
-0.002
0.001
0.009
0.003
-0.001

0.046
0.046
-0.046
0.115

-0.028
0.022

0.032

-0.002 -0.015

0.090
0.003
0.008
0.009
0.001
0.005
-0.010

-0.005

0.019
0.005
0.004

0.004 -0.028 0.011

-0.003
0.018

0.004
0.002
0.010
0.003
0.008
-0.009
-0.001
0.003
-0.001
0.000
0.001
0.005
0.005
-0.004
0.013
-0.003
0.014
0.003
-0.010
-0.004
0.001


Table A-14. Run 4: Cincinnati tap water, pH=7.5, 0.5 mg PO4/L, 24 hour stand time

Study=Coupon
Analyte=Zn

— Date Time, days 36000 _C36000_C83600_C84400_C84500_C85200_C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn.

02/05/93 0.72 0.76 013 014 026 0.29 044 0.12 0.07 0.08 2251 0.15
02/08/93 0.29 022 0.03 0.04 0.06 0.02 0.11 002 002 Oo 1.68 0.02
02/10/93 0.06 0.04 003 0.03 0.03 0.02 0.04 002 002 Oo 0.69 0.03
02/18/93 395 3.62 022 007 O15 559 3.69 O15 235 OK 8.90 0.01
02/19/93 348 334 030 017 045 352 283 003 169 -0. 768 0.01
02/23/93 3.67 351 034 032 033 2.66 246 001 158 0. 686 0.00
02/24/93 414 3.91 033 033 037 252 2.62 0.00 1.74 -0« 7.23 0.00
02/25/93 226 411 023 022 024 133 142 OJ 0.98  -0. 8.18 0.00
03/01/93 266 259 058 036 054 2.25 . 1.70 -0. 735 -0.00
03/02/93 134 129 016 0.13 021 093 092 O01 0.45 OL 717 (0.01
03/03/93 191 179 0.17 0.16 0.27 113 1.21 x 041  O4 6.62 0.01
03/04/93 184 175 014 O15 025 091 114 -O. 0.28  -0. 6.89 0.00
03/05/93 2.00 198 O44 016 028 097 122 -0. 0.26 -0. 745 -0.00
03/09/93 222 2411 O14 O17 038 113 129 OJ 0.24 © 04 725 0.00
03/10/93 150 145 O11 O15 033 0.74 090 -0. 0.16  -0. 6.57 0.00
03/11/93 222 245 013 O18 041 102 126 0. 0.21 O. 7.43 0.00
03/15/93 263 258 0.20 036 089 187 222 0. 0.35 -0. 0.00
03/16/93 168 153 0.08 0.20 035 082 092 OJ 0.17 O. 6.08 0.00
03/17/93 156 153 0.08 017 031 075 088 04 0.16 685 0.00
03/18/93 150 137 008 015 027 067 0.78  -0. 0.13 6.84 — -0.00
03/23/93 135 0.06 0.12 023 0.66 O71 OJ 0.14 0. 5.23 151
03/24/93 1.48 0.06 012 0.23 068 0.75 O4 0.14 6.15  -0.00
03/25/93 124119 «0.05 0.10 0.190.550.6101 O11 1 5.56 0.01
03/30/93 156 154 0.06 013 021 072 0.76 O1 0.14 O, 449 0.01
03/31/93 144 140 007 012 0.19 0.70 -0 0.13 -0. 5.13 0.00
04/01/93 187 1.85 0.14 0.21 ! 0.80  -0. 0.15 -O. 5.23
04/06/93 148 1.44 0.65 0.70 0, 0.14 Os 4.48
04/08/93 132 124 © 0, 011 016 057 0.60 -0¥ 0.12 -0. 4.61
04/15/93 1.37 . 0.12 016 056 0.63 0. 0.13 ON 4.02
04/20/93 128 = 1. . .. O14 051 0.55 . O11 0. 3.41
04/22/93 107 . 0.12 046 0.50 -0, 0.09 -0. 3.12
04/27/93 . . 0.10 044 047 O04 0.09

04/28/93 11401 K . 0.12 046 050 0. 0.10 0. 2.38
05/04/93 1200 1 . . 0.11 046 050 0. 0.10 O4 2.27
05/05/93 0.89 0 . . 0.09 038 0.43 -0, 0.07 -0. 1.92
05/11/93 0.94 0. . 010 041 046 oO. 0.09 Os 1.48
05/13/93 100 1. . 010 039 045 0. 0.08 04 1.72
05/19/93 O91 1 . 0.10 040 04 . . 131
05/20/93 078 0 . . 009 035 042 04 . . 1.24
05/25/93 068 0. X K 0.07 031 037 04 . . 1.05
05/27/93 097 1 . . 0.09 037 0.45 . . . 143
06/01/93 0.79 0. . . O15 0.63 0.84 04 . . 1.13
06/02/93 1.19 . . 0.11 037 046 04 . . 141
06/03/93 1.22 . x O11 035 044 0. . . 148
o6/0s/93 12300 1 . . 0.10 037 0.46 . . 137
06/10/93 . . . . 0.09 0.36 . . 158 0.00
06/14/93 . . . 0.11 048 067 0 . . 1.19 --
06/15/93 . 011 0.41 . . . 1.60 --
06/17/93 2 z . K 009 032 040 0 . . 150  -0.01
06/22/93 . . 0.10 0.35 . 1.70 0.01
06/24/93 / . 008 024 034-01 1.39 0.00



‘Table A-18.

Run 3: Cincinnati tap water, pH=7.5, 3 mg PO,/L, 72 hour stand time

Time, days C36000 C36000 C83600 C84400_C84500_C85200 C85400 Copper _Pure Pb Pure Pb Pure Zn Pb/Sn

Study=Coupon
Analyte=Pb
Date
08/17/92 7
08/24/92 14
08/31/92 21
09/08/92 29
09/14/92 35

2.0
0.6
0.9
1.0
0.6

1.0
1.6
11
12
0.8

53.0
25.0
17.6
12.7
11.9

36.0
16.1
10.8
73
TA

41.0
15.3
10.2
8.4
9.3

119

4.0
41
3.4
2.6
2.6

2.0 --
0.7
11
0.6
08

0.3
0.7
0.2
0.2

447.0
575.0
480.0
293.2
305.6

401.0 ~
363.8
360.0
313.9
304.4

84.0
0.4 117.2
“04 111.6
02 75.6
03 704



Table A-37. Statistical comparisons of copper leaching trends using the Kruskal-Wallis one-way analysis of variance (ANOVA) on Ranks during test runs 1 to 3. All
of the data sets showed that the trends were statistically different (P<0.0001). The table shows the proceeding pairwise multiple comparisons of copper leached from.
individual alloys.

Test run #1 Test run #2 Test run #3
Pairwise multiple Pairwise multiple Pairwise multiple Pairwise multiple Pairwise multiple Pairwise multiple
comparison (p <0.05) comparison (p <0.05) comparison (p <0.05) comparison (p <0.05) comparison (p <0.05) comparison (p <0.05)

Statistical comparison over entire run**® after 60 days" ® over entire run®* after 60 days**® over entire runTMTM® after 60 days”
rere on ee EE ON YS

€36000 (1) .vs. C36000 (2) no difference no difference no difference no difference no difference no difference
€36000 (1) .vs. C83600 different different different ‘different different different
€36000 (1) .vs. C84400 different © different different different different different
€36000 (1) .vs. C84500 different different different different different different
€36000 (1) .vs. C85200 no difference no difference different different different different
€36000 (1) .vs. C85400 no difference no difference different different different different
€36000 (2) .vs. C83600 different different different different different different
€36000 (2) .vs. C84400 different different different different different different
36000 (2) .vs. C84500 different different different different different different
— 36000 (2) .vs. C85200 no difference no difference different different different different
w& 36000 (2) .vs. C85400 no difference no difference different different different different
83600 .vs. C84400 no difference no difference no difference no difference no difference different
€83600 .vs. C84500 no difference no difference no difference no difference no difference different
83600 .vs. C85200 different different different different no difference no difference
83600 .vs. C85400 different different different no difference no difference no difference
84400 .vs. C84500 no difference no difference no difference no difference no difference no difference
C84400 .vs. C85200 different different different different no difference different
84400 .vs, C85400 different different different different no difference different
C84500 .vs. C85200 different different different different no difference different
C84500 .vs. C85400 different different different different no difference different
85200 .vs. C85400 no difference no difference no difference no difference no difference no difference

¥! Failed Kolmorogov-Smimov test for normality (P<0.0001)
® Failed Kolmorogov-Smimov test for normality (P=0.0024)
? Passed Kolmorogov-Smimov test for normality (P=0,3252)
4 Student-Newman-Keuls Method for multiple comparisons

® Dunn's Method for multiple comparisons



Table A-41. Quality control table showing standard reference material (SRM) analysis over the entire study period.

SRM recovery, % SRM recovery, %
Analyte Method* Min. Max. Mean Std, Dev. Range, mg/L. Analyte Method N_ Min Max Mean Std. Dev.__Range, mg/L.
Al ICAP 180 73.2 1280 1053 -9.2-—0.01040.100 Na AA 6 931 1010 96.2 2.6 —1,000-10.00
Al ICAP 127 829 1193 104.4 5,8 —_0.100-1.000 Na AA 60 © 93.8 107.9 103.2 2.7 ~—10.00-100.0
Al ICAP 126 939 1088 1023 23 —*1,000-10.00 Na ICAP 175 89.7 113.1 102.7 4.1—(0.100-1.000
Na ICAP 19 809 954 896 —-3.7_—*1.000-10.00
Ca AA 66 95.1 1075 1029 + 3.2-—10.00-100.0 Na ICAP 253° 90.1 «1148 1014 3.8 10.00-100.0
Ca IcaP 177 916 111.2 99.0 24 1.000-10.00 ‘Na ICAP 144 94.0 109.0 100.7 27 >100
Ca ICAP 345 917 1082 99.9 2.6 10.00-100.0,
Ca IcaP 52 964 109.2 1002.5 >100 NO; ALPKEMAA 221 79.2 122.0 101.1. = 7.2——(0.100-1.000
NO; ALPKEMAA M5 75.8 133.2981 —7.0—(1.000-10.00
Cl TITRATION «1479121049 100.2, 2.1 10.00-100.0 .
Pb AA 887 888 1221 993 © 43 0.010-0.100
Cu AA 436 88.0 120.8 99.2 3.7 0.100-1.000
cu ICAP 364 538 129.6 100.288 ~—0.010-0.100, PO, ALPKEMAA 2 91.7 100.0 95.8 += 5.9 —_0,100-1.000
cu ICAP 78 96.3 109.7 102.9 3.3.——(0.100-1.000 PO, ALPKEMAA 37 81.7 11S 98.7 7.4_—1.000-10.00
“cu ICAP $8 95.5 1059 998 = 1.7 —*1.000-10.00 PO, TECHNICONAA 109 917 116.7 993 5.5 0,100-1.000
PO, TECHNICONAA 79 95.2 106.3 100.5 21 1.000-10.00
F ISE 37 69.2 126.7 100.2 8.1—0.1001.000
wn OF JSE 15 828 113.1 98.584 ——*1,000-10.00 s IcaP 130 93.7 107.7 1014 © 3.2—‘1.000-10.00
Ra s ICAP 57 98.0 1068 100.7 19 — 10.00-100.0
Fe AA 336 86.5 109.8 99.3 3.5 0.100-1.000 SO, AUTOANALYZE 1 98.1 98.1 98.1 1.000-10.00
Fe ICAP 209 925 ©1523 103.7 -5.7—0.010-0.100 SO, AUTOANALYZE 163 821 1036 99.1. 2.8 ——‘10,00-100.0
Fe ICAP 250 94.3 120.6 101.8 3.4 0.100-1.000 SO, AUTOANALYZE 3 96.1 99.8 97.6 19 >100
Fe ICAP 320 933 ©1126 101.0 2.2 —1.000-10.00
Si ICAP 303 86.6 «103.1. 95.3 2.9 —1.000-10.00
K AA 79 88.6 110.6 99.6 4.4 ———0.100+1.000 SiO; ALPKEMAA 89 85.1. 116.8 97.0 5.5._—*1,000-10.00
K AA 7 93.2 uLi 103.6 42 1.000-10.00 SiO, ALPKEM AA 103 918 120.2 102.9 46 10.00-100.0
Mg AA 64 90.9 1049 101.3 3.4 —1.000+10.00 TALK TECHNICONAA 141 84.1 1280 100.2 4.0 10.00-100.0
Mg IcaP 177 90.6 1083 101.6 =. 28 =~ 0.100-1.000 TALK TECHNICONAA 35 95.0 1059 100.0 1.7 >100
Mg ICAP M42 938 = 108.4 100.028 ~——‘1.000-10.00
Mg ICAP 203 92.7 107.6 100.6 1.9 —_10.00-100.0 TIC COULOMETRY 315 926 1048 99.7 08 —10.00-100.0
Mg ICAP 52 96.2 1068 1004 = 23 >100
Zn AA 485 92.0 109.5 99.5 24 0.100-1.000
Mn AA 189 93.1 107.6 99.9 19 0.100-1,000 Zn ICAP 84 63.5 128.6 96.7 10.9 0.010-0.100
Mn ICAP 170 949 1136 1029 —3.0.—0,001-0.010 Zn ICAP 465 928 1159 1015 4.3 —_0.100-1.000
Mn ICAP 8 949 «110.9 101.5 3.6 —0.010-0.100 Zn ICAP 57 970 101.1 99.4 0.9 ——‘1.000-10.00
Mn ICAP 292 93.7 109.1 101.4 25 0,100-1.000
Mn ICAP 57 98.4 103.3 100.7 1.0 —_—1.000-10.00

* Methodologies detailed in Table 3

AAS- atomic absorption spectrophotometer

‘Adc autoanalyzer



FOREWORD

The U.S. Environmental Protection Agency is charged by Congress with protecting the Nation’s
land, air, and water resources. Under a mandate of national environmental laws, the Agency
strives to formulate and implement actions leading to a compatible balance between human
activities and the ability of natural systems to support and nurture life. To meet this mandate,
EPA’s research program is providing data and technical support for solving environmental
problems today and building a science knowledge base necessary to manage our ecological
resources wisely, understand how pollutants affect our health, and prevent or reduce
environmental risks in the future.

The National Risk Management Research Laboratory is the Agency’s center for investigation of
technological and management approaches for reducing risks from threats to human health and
the environment. The focus of the Laboratory’s research program is on methods for the
prevention and control of indoor air pollution. The goal of this research effort is to catalyze
development and implementation of innovative, cost-effective environmental technologies;
develop scientific and engineering information needed by EPA to support regulatory and policy
decisions; and provide technical support and information transfer to ensure effective
implementation of environmental regulations and strategies.

This publication has been produced as part of the Laboratory’s strategic long-term research plan.
It is published and made available by EPA’s Office of Research and Development to assist the
user community and to link researchers with their clients.

E. Timothy Oppelt, Director
National Risk Management Research Laboratory



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137



Table A-4. Run 4: Cincinnati tap water, pH=7.5, 0.5 mg PO4/L, 24 hour stand time

Study=Coupon
Analyte=Pb

02/05/93 39.8 2544.2 1691.0 1615.2 e 14.8 2733.8
02/08/93 y 56 1001 386 75.0 ! 5 5.0 208.7
02/10/93 66 314 119 144 . 56 38.9
02/18/93 137.0 1250.5 959.1 1075.7 . 78 14.4
02/19/93 385 313.4 760.9 348.4 1 5. 3.2 14
02/23/93 29.3 1389 1888 1084 2 % 0.1 41
02/24/93 33.0 1013 1435 77.7 a ¥ 0.6 47
02/25/93 192 725 962 54.8 0.6 28
03/01/93 244 76.1 105.2 55.5 5. 0.3 2.6
03/02/93 141 563 81.0 45.9 ! . 0.1 LS
03/03/93 13.0 431 773 405 y \ . 0.7
03/04/93 129 369 769 36.9 \. z 13
03/05/93 13.8 32.7 812 319 . . 0.8
03/09/93, 5 1830 385 77.9 37.3 5. : . 0.9
03/10/93 109 27.3 60.6 27.2 . . . 0.6
03/11/93 3. 92 266 49.2 24.6 . . . 0.6
03/16/93 84 295 52.9 y ; 17
03/17/93 91 255 39.2 x E . 0.6
03/18/93 i 60 210 32.1 . e ; . 0.1
03/23/93 62 163 25.2 x x . x 0.9
03/24/93 .f 6.2 27.2 . . . . 0.5
03/25/93 . 6.4

03/30/93 .! 8.2

03/31/93 5.7

04/01/93, fi 6.0

04/06/93 E 82

04/08/93 H 47

04/15/93 9.3

04/20/93 z 9.3

04/22/93

04/27/93

04/28/93 8.5

05/04/93 x 11.6

05/05/93 x 89

05/11/93 .: 10.9

05/13/93 e 19

05/19/93 . 10.8

05/20/93 E

05/25/93 16.6

0s/27/93 17.6

06/01/93 26.5

06/02/93 By 28.7

06/03/93 30.3

06/08/93 29.9

06/10/93 24.6

06/15/93

06/17/93 17.8

06/22/93 17.6

06/24/93 15.2



T T T
3.0 mg PO,/L |

0.5 mg PO,/L |
0.0 mg PO,/L

80 100 140

Elapsed Time, days

Figure 13. Effect of phosphate on lead leached from
85200 (yellow brass) coupon at pH 7.5.



Table 5 (continued)
(c) Test mn#3

Sunlyte.

Lead, pg/L
Calcium, mg/L
Copper, mg/L
Tron, mg/L
Potassium, mg/L.
Magnesium, mg/L
Manganese, mg/L.
Sodium, mg/L.
Zine, mg/L.

Alkalinity, mg CaCOg/L
Sulfate, mg SO4/L
Chloride, mg/L,

Silica, mg SiO2/L
Nitrate, mg N/L
Ammonia, mg NHg/L
Phosphate, mg PO4/L
Dissolved oxygen, mg/L
Total inorganic carbon, mg C/L
Free chlorine, mg Clo/L.
pH, pH units

(d) Test run #4.

Calcium, mg/L
Copper, mg/L,
Tron, mg/L
Potassium, mg/L
Magnesium, mg/L
Manganese, mg/L
Sodium, mg/L
Zine, mg/L

AJkalinity, mg CaCOg/L
Sulfate, mg SO4/L
Chloride, mg/L.

Silica, mg SiOo/L
Nitrate, mg N/L
Ammonia, mg NHg/L
Phosphate, mg PO4/L
Dissolved oxygen, mg/L
Total inorganic carbon, mg C/L
Free chlorine, mg Clo/L
pH, pH units

0.12
0.6
<0,003
0.01
0.11
0.36
<0.0004
11
<0.001

0.8
2.0
13
0.3
0.10
<0.03
13
0.21
0.28
0.12

0.40
3.0
0.00
0.01

0.3

0.9
<0.0004
2.5



1.50 pr T T T T T T T

1.25 + ° pH70 4

1.00 F J

0.75 F 4

Zinc, mg/L

0.50

é
:

0 20 40 60 80 100 120 140 160
Time, days

Figure A-18. Brass Alloy C84400, Red Brass

165



Table A-1. Run 1: Cincinnati tap water, pH=8.3-8.5, 24 hour stand time

Study=Coupon
|Analyte=Pb

Date ___Time, days_C36000 C36000 C83600_C84400 C84500 C85200 C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

08/14/91 1 300.7 356.2 399.2 376.7 335.1- 642.2 400.5 2.6 721.2 753.9 25 489.5
08/15/91 2 1488 175.0 244.0 258.5 200.0 257.7 153.6 0.9 929.2 1026.5 16 336.0
08/16/91 3 98.0 1265 1381 176.7 155.1 149.8 93.9 13 864.9 1189.9 13 304.5
08/20/91 T 7A 90.7 891 123.4 113.5 107.2 70.5 0.7 1994 151.1 0.1 244.3
08/21/91 8 585 770 667 940 932 838 52.8 0.3 646.3 201.8 0.1 244.4
08/22/91 9 S50 675 66.7 86.9 72.7 743 443 0.4 177.1 172.7 0.8 224.5
08/23/91 10 391 55.2 560 822 668 69.2 361 0.0 186.5 192.3 0.1 221.9
08/27/91 14 443 53.1 80.9 958 960 903 360 0.6 201.1 219.4 0.1 243.0
08/28/91 15 281 365 574 66.1 68.9 65.1 29.6 0.6 181.2 197.7 0.3 219.6
08/29/91 16 344 318 528 641 62.1 60.1 27.2 O05 176.9 191.8 03 208.5
08/30/91 17 282 ©6320 61.1 688 708 65.8 26.0 06 191.0 195.2 06 251.9
09/03/91 21 395 469 77.3 805 87.9 85.3 382 0.8 188.4 197.1 13.4 300.5
09/04/91 2225.9 288 736 842 1003 75.9 283 0.7 230.5 236.8 04 317.1
09/05/91 2300 24.2 © «26.7 89.1 97.0 131.1 84.9 30.2 11 260.6 274.2 18 449.8
09/06/91 24 212 232 803 844 111.7 77.3 282 0.7 241.0 260.0 0.3 427.8
09/10/91 28 15.2 17.0 692 113.0 1069 733 22.4 0.6 236.7 220.7 0.3 409.9
09/11/91 29 16.4 178 71.7 96.2 117.0 780 21.7 -0.0 251.4 254.9 0.1 469.6
09/12/91 30 128 135 594 75.2 89.6 59.6 13.3 0.2 177.6 179.8 0.1 157.9
09/13/91 31 8.5 96 31.6 63.3 75.7 519 13.2 0.5 177.5 181.7 -0.6 306.3
09/17/91 35 12.4 12.7 588 67.9 818 591 14.7 -0.4 213.6 215.8 -0.2 350.2
09/18/91 360 «115 114 570 712 749 55.8 12.5 -0.2 179.4 187.4 -0.2 395.7
09/19/91 37 10.4 11.0 465 59.3 625 49.0 11.6 0.2 169.5 181.7 0.3 343.1
09/20/91 38 10.1 106 45.6 575 60.0 513 11.5 -1.0 173.8 182.7 -1.2 323.8
09/24/91 42 9.7 102 471 723 72.9 55.2 12.1 0.9 174.5 174.3 -2.0 310.3
09/25/91 43 9.6 94 484 639 698 524 123 1.3 159.6 180.1 -14 353.0
09/26/91 44 9.0 90 425 616 574 41.7 7A 2.2 160.2 168.8 -1.9 311.0
09/27/91 45 85 82 440 623 625 44.9 9.6 13 186.0 176.2 15 259.1
10/01/91 49 6.7 68 405 574 662 47.8 11.5 0.1 156.9 153.0 -0.2 197.3
10/02/91 50 5.8 55 361 536 605 37.2 17 -0.2 151.3 150.1 -0.1 194.7
10/03/91 51 5.5 5.8 33.7 53.2 55.2 33.0 6.8 03 151.8 150.4 0.2 178.1
10/04/91 52 5.7 55 368 S599 585 344 79 03° 153.3 154.1 -0.2 168.2
10/08/91 56 73 65 465 73.6 79.3 43.5 91 0.4 190.7 192.2 0.3 243.6
10/09/91 57 6.6 70 46.6 74.0 82.4 40.0 9.7 0.3 187.9 183.8 -0.2 239.8
10/10/91 58 53 55 41.0 655 71.7 35.4 9.5 05 181.4 183.0 OS 212.1
10/11/91 59 5.8 54 499 73.1 779 40.3 9.6 -0.1 210.5 215.9 0.3 247.4
10/15/91 63 10.3 88 55.6 882 884 55.7 16.5 -0.2 237.2 257.2 0.0 311.6
10/17/91 65 53 50 380 574 587 29.0 8.4 -0.6 164.1 © 180.0 -0.8 123.7
10/23/91 710° (225 5.1 71.0 = 80.1 615 57.3 11.0 0.2 196.6 190.0 30.0 178.6
10/25/91 73 5.7 6.1 365 S06 484 25.9 31.2 0.2 199.6 173.3 0.3 153.7
10/30/91 78 41 272 323 495 70.7 21.7 5.4 0.6 217.4 181.5 -0.8 161.8
11/01/91 80 44 43 350 S15 475 21.0 5.9 -0.6 188.6 192.9 0.2 142.6
11/06/91 85 6.0 54 326 496 424 23.2 6.1 0.7 159.7 159.6 0.5 116.7
11/08/91 87 4.6 34 275 410 346 17.4 43 0.7 145.7 148.7 0.7 157.4

93



coupon. Asa group, the amount of lead leached at the completion of the study was approximately
8.5 ug/L. The brasses in this group were two of the three lowest lead containing brasses
evaluated. Lead levels dropped by approximately 90% over the remainder of the test run.

The “high" group consisted of the three red brasses: C83600, C84400, and C84500, and
yellow brass C85200. From 60 to 125 days, these brasses followed parallel lead leaching trends
but differed in magnitude by as much as 50 wg/L. C85200 brass leached the least amount of lead
in the group over this time period. The average lead concentration leached from the brasses in
the group during the last 21 days of the study was approximately 28 g/L. Lead levels dropped
by approximately 80% over the study period. There was no statistical difference among brasses
in this group (Appendix Table 36)

With the exception of the C85200 brass, the magnitude of lead leached from the brasses
corresponded well to the lead composition of the brass alloy after 60 days of leaching. In other
words, brasses containing greater amounts of lead tended to leach greater amounts of lead than
brasses containing lower amounts of lead. C85200 brass is a yellow brass and has a similar
composition as brasses in the low group. Based upon the similarity, it was expected that the
amount of lead leached from C85200 brass would have been similar to the amount of lead leached
from brasses in the low group. The difference between the two brasses is C85200 brass contained
slightly more copper and slightly less zinc than C85400 brass.

A white precipitate formed on several of the brasses. Upon close visual examination, it
was noted that the density of the coating increased as the zinc composition of the brass increased.
A nearly identical appearing but denser solid formed on the pure zinc coupon. Based upon the
visual examination, water chemistry, zinc solubility chemistry, and findings by others*®, the film
was believed to be basic zinc carbonate (hydrozincite). The film may have provided corrosion
protection by acting as a diffusion barrier and reducing the amount of lead leached from the
brasses. This observation could explain why more lead was leached from the lower zinc-
containing C85200 brass than expected.

Localized upward and downward patterns in the leaching trends were occasionally observed
in varying degrees throughout the test run. In most cases, the trends appeared to closely parallel
changes in water quality (pH and chlorine residual).

The pure lead coupons leached more lead than any of the brasses during all stages of this
test run. This observation demonstrated that the rate of lead dissolution from the brasses was
significantly hindered. Physical characteristics of the brass coupon surface such as exposed lead
surface area and the formation of corrosion deposits comprised of alloy materials other than lead
at the coupon surface were believed to be limiting factors.

Statistical comparisons of the lead leaching trends made over the entire test run and after
the lead trends appeared to stabilize (after 60 days) showed that the majority of trends were
significantly different (p<0.05) (Appendix Table 36). Good reproducibility between of lead

18



TIC bottle, were Nalgene® HDPE bottles. TIC samples were taken in 30 mL glass vials having
caps with conical polyethylene liners. Special care was taken to insure that no air or air bubbles
were trapped in the sample.

Analytical procedures

Unless otherwise specified, all chemicals used in this study were Analytical Reagent (AR)
grade. Deionized (DI) water was prepared by passing building distilled water through a Milli-Q
Plus® cartridge deionized water systemTM, having a resistivity > 18.2 MQ.

Glassware (excluding pipets) used for the preparation of standards and solutions was
cleaned using a 5% solution of Contrad 70°. The glassware was thoroughly rinsed with deionized
water. Reused glassware was immediately cleaned by soaking in 10% (v/v) concentrated HNO;
and rinsed with DI H,O. Glass pipets were cleaned by at least an overnight soaking in 5%
Contrad® solution, followed by rinsing with dilute AR-grade HCI in a plastic pipet washer. The
final rinse was a minimum of 8 total volumes of deionized water cycled through the pipet washer.
Air displacement micropipets with disposable tips were used for handling and transferring
solutions.

Ultrapure nitric acid, HNO,” was used to preserve samples. 0.15% of the sample volume
was the volume of nitric acid added to the sample (1.5mL/L). 6 N HCI® and 8 N NaOH® were
used to chemically adjust feed water pH. Sodium phosphate (Na,;PO,*H,O)® was used to adjust
the phosphate concentration in the feed water.

Instrumentation

Lead was analyzed with a Perkin Elmer Model 4000 Spectrophotometer® equipped with
a Model HGA 400 furnace programmer and AS 40 autosampler. Initially, all other metals were
analyzed with a Perkin Elmer Model 5000 Atomic Absorption Spectrophotometer and an AS 50
autosampler. After August 1, 1993, these metals were analyzed with a new Thermo Jarrel Ash®
61E® purged inductively coupled argon plasma spectrometer (ICAPS). The ICAPS was
implemented between test runs and improved detection limits of most metals analyzed (see Table
3). The change did not affect conclusions of the report since metals leached from the coupons
were well above the detection limits of both methodologies. Lead results, which did fall below
the detection limit, were not impacted because the method remained the same. The pH was

Millipore Corp., Bedford, MA.

© Ultrex, J. T. Baker Chemical Company., Phillipsburg, NJ.
© Mallinckrodt, Inc., Paris, KY.

© Fisher Scientific, Failawn, NJ.

© Perkin Elmer Corp., Norwalk, CT.

© Thermo Jarrel Ash Corp., Franklin, MA.



Table A-3.

Study=Coupon

Run 3: Cincinnati tap water, pH=7.5, 3 mg PO,/L, 24 hour stand time

Time, days C36000_C36000 C83600_C84400_C84500_C85200 C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

Analyte=Pb
Date
08/07/92
08/10/92
08/11/92 1
08/12/92 2
08/13/92 3
08/14/92 4
08/19/92 9
08/20/92 10
08/21/92 11
08/25/92 iS
08/26/92 16
08/27/92 17
09/01/92 22
09/02/92 23
09/03/92 24
09/09/92 30
09/10/92 31
09/16/92 37
09/29/92 50
09/30/92 Si
10/01/92 52
10/06/92 ST
10/08/92 59
10/14/92 65
10/16/92 67
10/21/92 72
10/22/92 73
10/27/92 78
10/29/92 80
11/03/92 85
11/10/92 92
11/13/92 95
11/17/92 99
11/19/92 101
11/25/92 107
12/01/92 113
12/03/92 115
12/08/92 120
12/10/92 122
12/15/92 127
12/17/92 129

313.2
203.6
19.0
44.0
5.7
11
1.0
1.0
1.0
11
1.0
2.0
13
0.7
0.7
0.4
0.6
1.0
13
18
2.0
11
0.7
0.6
0.8
0.7
0.8
03
0.7
0.5
0.2
0.5
-0.3
-0.8
0.1
0.2
0.6
0.5
0.6
0.0
0.6

127.3
63.0
15.0

40
19
75.2

1.0
0.5
2.0
1.0
1.0
11
15
0.4
0.7
0.9
18
21
19
14
0.6
0.6
0.8
0.7
0.6
0.3
12
0.8
0.2
0.6
-0.3
-0.9
-0.3
0.1
0.1
0.7
0.4
0.4
0.4

190.1
75.5,
535.0
415.0
79.9
48.0
43.0
26.0
20.0
18.0
16.0
15.0
13.1
11.0
8.6
111
10.2
10.5
16.0
16.5
14.2
17.4
13.9
20.0
18.8
26.3
20.2
24.8
22.9
23.1
29.2
27.6
23.8
33.8
23.1
24.8
22.6
20.6
19.8
27.3
19.8

292.9
78.8
1251.0
428.0
72.3
67.2
23.0
16.0
13.0
11.3
10.0
10.0
8.6
TA
6.0
1S
6.4
6.8
8.5
8.5
6.6
Vd
5.2
7.6
79
9.6
8.1
79
14
1d
10.2
10.2
8.1
5.6
8.5
92
9.0
8.1
6.9
9.5
TA

290.9 84.2
78.5 36.4
581.0 246.0
650.0 33.0
79.9 713
6.0

35.0 4.0
26.0 4.0
17.0 3.0
12.4 3.0
12.0 3.0
11.0 3.0
10.4 3.6
10.2 24
5.7 21
7.0 23
23 V7
S.A 2.8
6.1 3.1
69 48
5.5 2.5
79 27
5.0 1.6
-0.4 -0.4
6.2 2.0
8.6 2.9
65 24
17 18
8.1 25
11.2 19
9.5 19
10.4 27
8.8 15
6.8 0.7
8.7 17
10.3 21
87 18
9.2 2.4
8.1 19
10.7 44
8.5 23

97

74.8
38.0
47.0
8.0
3.2
2.0
1.0
1.0
0.7
1.0
1.0
1.0
11
0.5
1.0
0.6
0.9
0.5
14
1.4
0.9
11
0.7
13
0.7
0.9
0.4
0.2
19
0.1
0.1
0.9
2.0
-0.2
0.1
0.1
0.4
0.4
0.8
0.7
0.5

4.1 1773.0 6075.0

12.0
2.0
1.0
0.3
10

1.0
0.1

12
0.4
0.1

1.0

0.3
0.3
14
0.4
0.7
0.5
-0.1
0.7
0.1
03
-0.4
-0.5
0.7
0.3
-0.5
0.9
0.5
-0.3
0.1
-0.5
0.4
0.6
0.2
0.2
-0.4

192.0
2636.0
781.0
478.4
611.0
643.0
388.0
456.7
283.0
287.0
373.9
272.5
207.7
198.5
233.1
204.0
149.6
146.2
119.4
104.0
135.5
86.1
86.2
94.1
98.5
84.9
1L4
105.3
92.2
118.7
133.5
95.2
78.1
92.1
88.5
86.9
100.5
81.1
108.2
88.8

619.0
422.0
453.0
362.7
405.0
355.0
305.0
320.4

291.0
343.9
259.8
221.0
211.9
236.8
250.2
200.9
312.2
210.9
149.7
177.7
119.4
124.5
118.3
128.3
19.1
13.8
114.6
0.0
139.0
138.2
99.4
78.5
82.9
79.4
713
96.4
79.1
100.5
88.8

12.5
40.0
2.0
1.0
0.3

0.9
0.2
-0.1
0.4
0.2
0.1
0.2
11
0.4
0.8
0.5
0.1
0.3
0.7
0.1
-0.2
-0.4
0.6
-0.3
-0.5
0.1
0.6
-0.5
0.0
02
0.5
1.0
0.4
-0.3
0.2

592.0
234.0
109.0
61.8
44.5
91.0
133.0
171.0
147.9
70.0
123.0
87.1
125.0
65.3
56.4
57.9
72.5
54.3
69.9
60.1
51.4
76.1
51.6
71.9
58.5
69.0
57.5
37.0
573
58.8
64.7
70.8
57.9
42.9
58.4
78.5
62.2
70.7
62.4
83.4
59.7


60 80 100 120 140 160

Time, days

Figure A-7. Brass Alloy C84500, Red Brass



3.0 pr 5 T T T

°o =pH8.5
2.57 ° = pH7.0 q
2.0 7
a)
&
we LSP 7
s
Lo)
1.07

Time, days

Figure A-10. Brass Alloy C36000, Free Cutting Brass

157



Copper, mg/L

0 2 40 60 80 100 120 140 160

Figure A-14. Brass Alloy C85200, Yellow Brass

161



stabilize. Brass composition had little impact on final lead levels (levels observed at the
termination of the test runs) when orthophosphate was present at 0.46 and 2.8 mg/L.

Lead levels measured when phosphate was present were similar to those observed for the
same alloy at pH 8.5. Based on results of the control test run, the impact of pH (7.5 versus 8.5)
on lead levels leached from the brasses lessened relative to pH 7.0 test run results.

The impact of orthophosphate on pure lead was different than the brasses. Lead response
was more typical of that described by lead solubility relationships."““"* Orthophosphate clearly
reduced lead levels leached from pure lead (Figure 15). The highest orthophosphate dose was
most effective in reducing lead concentration, lowering lead levels to near 100 g/L by the end
of the test run. The 0.5 mg/L orthophosphate dose was also effective at reducing lead levels, but
to a lesser degree than the higher orthophosphate dose (final lead levels were about 200 ug/L).
This result demonstrated the importance of sufficient orthophosphate dosing in obtaining optimal
lead control benefits. Without orthophosphate addition, lead levels were near 300 pg/L at the end
of the test run (130 to 140 dasys). Orthophosphate concentration did not have the same impact
on stabilization time of the brasses. Orthophosphate had an immediate impact on lead reduction
and stabilization, while without orthophosphate lead levels started high and dropped to stabilized
levels by approximately 60 days.

Similar observations were made with lead leached from the 60:40 Sn:Pb solder coupon
(Figure 16). The final lead levels were not as high and the benefit of orthophosphate was not as
dramatic, but trends and patterns were nearly identical to the results of the pure lead test.

The impact of orthophosphate on copper leached from the brasses was more difficult to
interpret (Figures 17 to 22). Copper levels leached from red brass C83600 and C84400 were 0.2
to 0.4 mg/L lower when orthophosphate was present. Copper leached from similar copper
containing C84500 brass, however, was not impacted by orthophosphate. Copper leached from
the yellow brasses and the C36000 coupons was lower by as much as 0.1 mg/L when
orthophosphate was not present. Orthophosphate had little impact on copper leached from pure
copper (Figure 23). The results are confusing but do suggest that in some cases orthophosphate
(at pH 7.5) can provide some benefit in reducing copper dissolution from brass. Some insight into
the observations can be found in recent work suggesting that orthophosphate is most beneficial at
reducing copper levels at lower pH values (< 7.0) on new materials. The research shows that
minimal reduction in copper solubility at pH 7.5 is realized from the addition of orthophosphate.

The impact of orthophosphate on copper at pH 6.5 was briefly explored as an extension.
to test run 5. After 142, days the pH was lowered from 7.5 to 6.5 for 23 days. Copper leached
from the pure copper coupon immediately increased to more than 1 mg/L and averaged 1.2 mg/L
over the period. At 182 days, 3.0 mg/L orthophosphate was added. The run was continued for
an additional 17 days. The copper levels were initially sporadic, jumping between 0.67 and 2.3
mg/L, but averaged only 0.36 mg/L for the last two sampling events. This brief investigation was

26



5.0 T ¥ T T T T T

4.54 iN °o 6pH8.5 4
° pH7.0

4.0F 4

3.0

Zinc, mg/L

2.0 F 4

0 20 40 60 80 100 120 140 160
Time, days

Figure A-20. Brass Alloy C85200, Yellow Brass

167



‘able A-10. Run 5; Cincinnati tap water, pH=7,5, 24 hour stand time

Date __Time, days C36000_Pb free _C83600_C84400_C84500_C85200_C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

08/03/93 0.014 0.001 0.096 0.054 0.084 0.026 0.014 0.114 0.013 0.003 0,008 0.003
08/11/93 1 0.072 0.202 0.360 0.342 0,125 0.067 0.123 0.857 0.004 0.006 0.001 0.001
08/12/93 2 0.052 0.298 0.361 0.288 0.290 0.067 0.116 1.097 0.003 0.006 0.003 0,002
08/13/93 3 0.045 0378 0.415 0.275 0.423 0.085 0.110 1.333 0.003 0.002 -0.001 0.002
08/17/93 7 0.037 0.902 0.509 0.401 0.683 0.100 0.096 1.491 0.004 0.002 0,000 0.002
08/18/93 8 0.015 0.944 0.482 0.440 0.732 0.109 0.111 1.357 0.004 0.002 -0.001 0.001
08/19/93 9 0.033 0.947 -- 0.511 0.774 0.121 0.104 1.304 0.003 0.001 -0.002 -0.001
08/20/93 10 0.042 0.949 0.530 0.551 0.805 0.139 0.104 1.216 0.004 0.004 0,002 0.003
08/24/93 14 0.023 0.813 0.529 0.570 0.660 0.161 0.070 0.903 0.011 0.006 0.003 0.004
08/25/93 15 0.019 0.717 0.531 0.581 0.639 0.161 0.091 0.785 0.010 0.013 0.001 0.001
08/26/93 16 0.019 0.699 0545 0.631 0.653 0.206 0.081 0.742 0,008 0.007 0.004 0.004
08/27/93 17° (0.014 0.633 0512 0.612 0.627 0.205 0.086 0.656 0,008 0.002 -0.002 -0.001
08/31/93 21 0.014 0.612 0510 0.657 0.624 0.198 0.081 0.604 0.010 0.005 0.001 0.003
09/01/93 22 0.016 0.513 -- 0.554 0.576 0.187 0.080 0.492 0.052 0.005 0.002 0.006
09/02/93 23 0.013 0.435 -- 0.493 0.515 0.165 0.073 0.401 0.006 0.004 0.001 0.004
09/07/93 28 0.007 0.807 0.584 0.813 0.756 0.234 0.156 0.935 0.010 0.006 0.002 0.002
09/08/93 29 0.012 0.505 0.439 0.568 0.574 0.134 0.091 0.493 0.010 0.007 0.002 0.005
09/09/93 30 0.011 0.421 0.391 0.477 0.495 0.131 0.082 0.402 0.008 0.006 0.001 0.003
09/10/93 31 (0.008 0.368 0.352 0.416 0.427 0.114 0.070 0.348 0.009 0.005 0.001 0.004
09/14/93 35 0.008 0.725 0.592 0.837 0.780 0.200 0.175 0.788 0.015 0.007 0.002 0.004
09/15/93 36 0.009 0.337 0.384 0.501 0.449 0.092 0.092 0.400 0.013 0,007 0.002 --

09/16/93 37° «(0.008 0.298 0.338 0.424 0377 0.081 0.080 0.312 0,009 0.005 0.000 0.003
09/20/93 41 0.005 0.557 0.500 0.721 0.618 0.158 0.162 0.660 0.009 0.005 0.001 0.002
09/21/93 42 0,006 0.358 0.403 0.539 0.436 0.085 0.093 0.406 0.009 0,006 0.002 0.004
09/23/93 44 0,002 0.287 0.355 0449 0.357 0.073 0.071 0.325 0.004 -0.001 -0.005 -0.004
09/24/93 45 0,002 0.271 0.331 0.430 0.337 0.070 0.069 0.309 0.002 0.003 -0.003 -0.001
09/29/93 50 0.006 0.310 0.399 0.464 0.396 0.079 0.093 0.386 0.009 0.004 0.001 0.002
09/30/93 S1 0,005 0.279 0.362 0.409 0.349 0.072 0.084 0.340 0,006 0.005 0.001 0.003
10/04/93 55 0.005 0.477 0,544 0.638 0.573 0.141 0.148 0.644 0.006 0.006 0.002 0.002
10/05/93 S56 0,005 0.300 0.425 0471 0.388 0.077 0.084 0.388 0.007 0.005 -0.000 0.001
10/07/93 58 0.007 0.246 0.452 0.510 0.351 0.074 0.071 0.368 0.005 0.004 0,000 0.004
10/12/93 63 0.003 0.452 0.594 0.709 0.549 0.136 0.126 0.647 0.005 0.005 0.001 0.003
10/14/93 65 0.006 0.245 0.398 0.466 0.313 0,060 0.060 0.324 0.008 0.005 0.001 0.003
10/18/93 69 0.003 0.417 0.599 0.780 0.496 0.126 0.129 0,605 0.005 0.004 0.000 0.001
10/19/93 70 0.006 0.177 0.310 0.379 0.234 0.054 0.063 0.279 0.007 0.006 0.002 0.004
10/21/93 72 0.004 0.259 0.436 0.567 0.321 0.071 0.094 0.383 0.004 0.003 0.001 -0.000
10/22/93 73 0.008 0.180 0.328 0.417 0.234 0.053 0.065 3 0.013 0.003 --

10/25/93 76 0.008 0.280 0.452 0.608 0.325 0.087 0.107 0.028 0.003 0.001
10/26/93 77° =0.006 0.157 0.293 0,392 0.205 0.049 0.058 0.006 -- 0.003
10/28/93 79 0.005 0.134 0.276 0355 0.171 0.045 0.043 0.007. 0.005 0.005
11/01/93 83 0.008 0.290 0.494 0.657 0.330 0.101 0.111 0.002 -- 0.000
11/02/93 84 0.006 0.160 0.345 0.442 0.202 0.053 0.068 0.005 -- 0.002
11/04/93 86 0.002 0.126 0.290 0.372 0.160 0.043 0,052 0.004 0.001 0.002
11/05/93 87 0.003 0.125 0.278 0.351 0.144 0,041 0.048 0.004 -- 0.003
11/08/93 90 0.006 0.208 0.402 0.553 0.238 0.079 0.097 0.004 0,001 0.001
11/09/93 91 0.005 0.139 0.355 0.436 0.172 0,049 0.060 0.003 0.002 0,002
11/15/93 97 0.005 -- 0.538 0.710 0.308 0.110 0.130 0.005 0,002 0.002
11/16/93 98 0.003 0.139 0.324 0.405 0.164 0.049 0,059 0.001 0.001 0.002
11/18/93 100 0.010 0.113 0.256 0.327 0.135 0.044 0.049 0.006 0.008 0.011
11/19/93 101 0.008 0.105 0.241 0.313 0.115 0.042 0.038 0.005 0.002 0.001
11/22/93 104 0.007 0.182 0.370 0.465 0.182 0.065 0.069 0.004 0.003 0.005
11/23/93 105 0.013 0.124 0.311 0.395 0.152 0.051 0.057 0.005 0.005 0.002
11/30/93 112 0.008 0.156 0.406 0.512 0.199 0.063 0.076 0.003 0.001 0.004
12/02/93 114 0.002 0.142 0.354 0.439 0.142 0.050 0.056 0.000 0.001 -0.002
12/03/93 115 0.002 0.117 0.329 0.420 0.141 0.049 0.061 0.262 -0.001 0.002 0.001 0,001
12/06/93 118 0.005 0.205 0.467 0.625 0,206 0.086 0.104 0,389 0.003 0.002 -0.000 0.001
12/07/93 119 0.005 0.116 0.298 0.386 0.130 0.051 0.055 -- 0.003 0.004. 0.002 0.001
12/09/93 121 0.004 0.107 0.292 0.394 0.124 0.048 0.057 0.231 0.004 0.003 0.004 0.002

107



Table A-27. Run 2: Cincinnati tap water, pH=7.0, 72 hour stand time

Study=Coupon
Analyte=Zn

Date _ Time, days C36000 C36000 C83600 C84400 C84500 C85200 C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

03/02/92 T- 115 143° 228 4159 807 5.98 004 004 002 516 0.02
03/09/92 14 6.75 6.05 1.03 180 215 579 597 003 002 003 3.43 0.03
03/16/92 21 659 621 0.95 198 193 586 616 0.02 001 -0.00 3.30 -0.00
03/23/92 28 22 - - ~ - - ~ - ~ - ~ -

03/30/92 35 647 633 059 162 181 440 608 002 001 O01 553 0.01
04/06/92 42 5.20 5.04 046 1.35 154 333 495 0.03 0.02 002 3.77 0.02
04/13/92 49 491 S515 052 150 1.70 347 510 -0.00 -0.01 -0.01 3.62 -0.00
04/20/92 56 590 742 039 135 159 335 624 -0.03 -0.05 -0.05 421 -0.04
04/27/92 63 5.27) 581 031 111 132 3.003 527 -0.04 -0.04 -0.04 4.63 -0.04
05/04/92, 7 S11 5.15 031 1.04 129 2.92 4.75 -0.03 -0.04 -0.04 4.01  -0.05
05/11/92 77 S49 553 O45 131 154 346 501 003 014 001 422 0.01
05/18/92 84 S548 S48 034 114 136 339 492 -0.06 -0.06 -0.06 4.29 -0.07
05/26/92 92 510 S11 040 1.20 138 3.27 464 -0.04 -0.04 -0.03 3.82 -0.03
06/01/92 98 481 5.03 0.28 0.91 107 263 439 -0.04 0.06 -0.05 4.29 -0.04
06/08/92 105 5.25 «5.62 0.32 :1.13 135 3.16 494 -0.03 -0.03 -004 444 -0.04
06/15/92 112 «550 S41 0.31 1.05 124 2.97 5.20 -0.03 -0.04 -0.04 448 -0.03
06/22/92 119 509 524 031 099 122 300 444 0.11 -0.03 -0.04 428 -0.03
06/29/92 126 554 539 0.28 1.00 117 284 467 -0.04 -0.06 -0.05 4.73 -0.06
07/06/92 133 445 «64.70 §=90.27 0.92 104 248 3.99 0.00 0.00 0.00 4.23 0.00
07/13/92. 140 522 495 0.30 117 126 3.02 498 -0.03 -0.00 5.71 -0.04
07/20/92 147 403 4.64 0.31 1.03 113° 261 3.47 0.01 - 5.36 0.00
07/27/92 154. 6.17 6.07 0.40 138 150 356 5.07 0.01 0.00 554 0.01

128



5.0 T T r q T T T T
o 6pH=8.5
° pH=7.0
=f 4
=)
= 4
ov
L L L ns

“0 20 40 60 80 100 120 140 160

Time, days

Figure A-22. Pure copper

169



60 80 100 120 140

Elapsed Time, days

—o— C36000 —®— €84500
—o— C36000 —*®— C85200

—v— C83600 —4— C85400
—w*— C84400 —@— Pure zinc

Figure 5. Zinc leached levels from brass and pure
zinc coupons during test run #1, pH =8.5.



Table A-7. Run 2: Cincinnati tap water, pH=7.0, 24 hour stand time

Study=Coupon
Analyte=Cu

Date ___Time, days C36000 _C36000 C83600_C84400 C8450 __C85200 C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn.

06/16/92 113 0.075 Ox 1.492 1.759 1.759 1171 1,251 -0.009 -0.010 -0.022 -0.025
06/17/92 114 0.048 0. 1.271 .! 1505 1.074 1.180 1.088 -0.039 -0.069 -0.072 -0.049
06/18/92 0.070 0. 1131 1. 1.527 0.942 1.021 0.728 -0.040 -0.037 -0.009 -0.008
06/23/92 -0.038 0. 1504 1. 2.186 1.253 1313 1.340 -0.060 -0.008

06/24/92 1.138 0.870 0.972 0.939 -0.020 -0.020

06/25/92 1.240 1.601 0,939 1.104 0.840 -0.020 -0.022

06/30/92 1325 1 1.620 0.965 1.030 0.735 -0.052 -0.020

07/01/92 1.652 1.917 1.031 0.338 1.191 -0.013 -0.014

07/02/92 0.919 1.206 0.742 0.840 0.482 -0.003 -0.005

07/07/92 1.032 1.218 0.679 0.708 0.737 -0.020 -0.008

07/08/92 0.992 1.189 0.627 0.656 0.512 0.013 --

07/09/92 .L 1.423 1.533 0.909 0.980 0.947 0.009 -0.006

07/14/92 .f 1.257 1.506 0.883 0.886 0.923 0.011 0.005

07/15/92 . 5 1.844 1.993 1.136 1.211 1.178 0.007 0.007

07/16/92 .f . 1.348 1.443 0.832 0.900 0.861 0.021 0.013

07/21/92 .( . 1.305 1454 0.812 0.778 0.815 0.012 0.006

07/22/92 . . 1.153 . 1300 0.691 0.728 0.622 0.007 0.015

07/23/92 . . 1.822 1.378 0.901 0.983 0.837 0.024 0.025

07/28/92 . 2.039 2.462 1.751 1.604 1.119 -0.001 0.017

07/29/92 . 1.464 1586 0.875 0.729 0.697 -0.003 0.013



60 80 100 120 140

Elapsed Time, days

Figure 23. Effect of phosphate on copper leached
from C122 (pure copper) coupon at pH 7.5.



Zinc leached from brass coupons

Zinc leaching trends (shown in Figure 5) behaved differently from those observed for both
copper and lead in that there were not groups of distinct leaching trends. Zinc levels leached from
the brasses were a function of the percentage of zinc in the brass throughout the entire study. Zinc
concentrations appeared to slightly decrease over the first two weeks. They stabilized after about
60 days in the concentration range of about 0.05 to 0.30 mg/L. Zinc leachate concentrations
fluctuated slightly throughout the study. As was the case for copper, fluctuations often appeared
to correlate with changes in background water chemistry (i.e., pH and chlorine residual).

‘The pure zinc coupon leached as much as 11.3 mg/L at the start of the study, but dropped
rapidly to about 0.32 mg/L after 40 to 50 days. By the end of the study, the amount of zinc
leached from the pure zinc coupon was lower than the amount leached from the yellow brasses
and nearly the same as the red brasses. As was the case for copper, there appeared to be a zinc
content threshold where the alloy took the leaching qualities of pure zinc. The zinc composition
of the alloy was low relative to copper content and the pure zinc coupon. Despite this condition,
zinc dissolution rates were not hindered and in some cases appeared to even be slightly enhanced.
A simple explanation would be that the amount of zinc in the alloy and at the alloy surface in
contact with the water were sufficient to avoid kinetic limitations. A more complex theory would
be that the selective removal of zinc from the alloy, possibly enhanced by galvanic interactions
among other elements within the alloy, contributed to the observations. Of course these
explanations are speculative; thoughts made by the authors. Without a detailed scientific
investigation on the electrochemical interactions between the elements that make up brass and a
high degree of knowledge of the structure of brass alloys (which were well beyond the scope of
this project), a valid scientific explanation cannot be given.

Statistical analysis of zinc leaching data showed that nearly all case comparisons were
statistically different (Appendix Table 38). Zinc leaching trends observed after 60 days showed
that duplicate coupon (C36000) were not statistically different.

Test run #2
Extraction water quality

Table 5b summarizes the extraction water quality used during test run 2. The pH of the
tap water was strictly controlled at an average of 7.01 with a standard deviation of 0.05 by the
addition of HCl and/or NaOH. Sulfate levels were lower during this test run than the first by
approximately 50 mg/L, averaging 68 mg SO,/L. Free chlorine was also lower during this test
run than the first, averaging 1.4 mg/L with a standard deviation of 0.28 mg/L. Measured TIC
and DO averaged 12.6 mg C/L and 8.9 mg O,/L, respectively.

20



fal

1.0 2.0 4.0 60 8.0 15.0

Standtime, hours

Figure 41. Lead stagnation profile for red brass
84400.



INTRODUCTION

Water sampling and monitoring requirements described in the Lead and Copper Rule
(LCR)"® specify that one liter first-draw water samples must be collected at selected consumer's
taps following at least 6 hours of stagnation. Lead service lines, tin:lead solder, and brass fixtures
are considered major contributors of lead to that one liter sample. The practice of using lead pipe
and lead-based solders in home plumbing systems was eliminated in 1986.* In addition, all pipes
and fittings were required to be constructed of "lead-free" material which, by legal definition,
contain less than 8% lead.

The metal composition of brass ranges from approximately 60 to 80% copper, 4 to 32%
zinc, 2 to 8% lead, < 6% tin, and trace amounts of iron and other alloying elements depending
on its application. Therefore, by previous definition, plumbing products constructed of brass and
similar alloys such as faucets and valves are considered "lead-free" and are the only lead-
containing components still permitted for use in drinking water systems. For this reason,
understanding the major influences upon and mechanism(s) of metal release from brass and
techniques to control that release are important in meeting LCR requirements and limiting metal
exposure to consumers.

The effect of water quality (i.e. pH, dissolved inorganic carbon [DIC], sulfate, chloride,
free chlorine, dissolved oxygen, etc.) on the solubility of the primary metals that make-up brass
(Cu, Zn, and Pb) has been explored to varying degrees by numerous investigators and is generally
understood. However, predicting the dissolution of metals from an alloy is likely more
complicated than solubility relationships alone, and may be influenced by many factors including
alloy composition, structure, and surface area. As an example, initial work conducted by British
researchers’ indicates that the amount of lead leached from brass and lead containing alloys is
independent of the percentage of lead in the alloy. Other researchers® theorize that dezincification
of zinc-containing alloys can result in increased lead surface area which results in increased lead
dissolution. Developing a better understanding of the control aspects of brass corrosion will
provide additional guidance to water utilities, consultants, and governmental agencies on strategies
to reduce lead release into drinking water.

OBJECTIVES

The initial purposes of this multi-year research project was to establish relationship(s)
among the composition of six brass alloys and the metal (Cu, Zn, and Pb) concentrations leached
from them in Cincinnati (Ohio) tap water and to provide insight into brass corrosion control
measures. The same water quality effects on the metals leached from the major pure metal
components of brass (Cu, Zn, and Pb) were also explored. The project was expanded to include
the evaluation of the impact of pH (7.0 and 8.5) and a non-zinc containing orthophosphate
chemical (dosed at 0.5 and 3.0 mg PO,/L) at pH 7.5 on metal leached from brasses, lead, copper,
zinc, and 60:40 Sn:Pb solder. Also, the effect of stagnation period on metal(s) leached from the



5.0 T T r T T T T T r T

e
eoy

Zinc, mg/L

0.9 eb a
0 20 40 60 80 100 120 140

Elapsed Time, days

Figure 24, Effect of phosphate on zinc leached from
C36000 (free-machining brass) coupon at pH 7.5.

69



3.0 mg PO,/L
0.5 mg PO,/L
2 0.0 mg PO,/L |

60 80 100 120 140

Elapsed Time, days

Figure 30. Effect of phosphate on zinc leached from
pure zinc coupon at pH 7.5.



LIST OF FIGURES

Number Page

1. Photograph of test system. 46

2. Schematic of individual test loop. 47

3. Lead leached from brass coupons during test run #1, pH =8.5. 48

4. Copper leached from brass and pure copper coupons during test 49
run #1, pH =8.5.

5. Zinc leached levels from brass coupons during test run #1, pH =8.5. 50

6. Lead leached from brass coupons during test run #2, pH =7.0. 51

7. Copper leached from brass and pure copper coupons during test 52
run #2, pH =7.0.

8. Zinc leached from brass coupons during test run #2, pH =7.0. 53

9. Effect of phosphate on lead leached from C36000 brass coupon at pH 7.5. 54

10. Effect of phosphate on lead leached from C83600 (red brass) coupon at pH 55
75.

11. Effect of phosphate on lead leached from C84400 (red brass) coupon at pH 56
75.

12. Effect of phosphate on lead leached from C84500 (red brass) coupon at pH 57
7.5.

13. Effect of phosphate on lead leached from C85200 (yellow brass) coupon at 58
pH 7.5.

14. Effect of phosphate on lead leached from C85400 (yellow brass) coupon at 59
pH 7.5.

15. Effect of phosphate on lead leached from pure lead at pH 7.5. 60

16. Effect of phosphate on lead leached from 60:40 Sn:Pb solder coupon at pH 61
75.

17. Effect of phosphate on copper leached from C36000 brass coupon at pH 7.5. 62

18. Effect of phosphate on copper leached from C83600 (red brass) coupon at 63

19. Effect Fonosphate on copper leached from C84400 (red brass) coupon at 64
20. Effect FP moaphate on copper leached from C84500 (red brass) coupon at 65
21. Effect a mosphate on copper leached from C85200 (yellow brass) coupon at 66
22. ~~ Effect OP noophate on copper leached from C85400 (yellow brass) coupon at 67
23. Effect Fonosphate on copper leached from C122 (pure copper) coupon at pH 68
24. ~~ Effect of vihosphate on zinc leached from C36000 brass coupon at pH 7.5. 69

ix



Table A-7.

Run 2: Cincinnati tap water, pH=7.0, 24 hour stand time

Time, days C36000_C36000_C83600_C84400 C8450 _C85200 C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

Study=Coupon
|Analyte=Cu
Date.

02/20/92

02/21/92

02/25/92 1
02/26/92 2
02/27/92 3
02/28/92 4
03/03/92 8
03/04/92 9
03/05/92 10
03/06/92 11
03/10/92 15
03/11/92 16
03/12/92 17
03/13/92 18
03/17/92 22
03/18/92 23
03/19/92 24
03/20/92 25
03/25/92 30
03/26/92 31
03/27/92 32
03/31/92 36
04/01/92 37
04/02/92 38
04/03/92 39
04/07/92 43
04/08/92 44
04/09/92 45
04/14/92 50
04/15/92 51
04/16/92 52
04/17/92 53
04/23/92 59
04/24/92 60
04/28/92 64
04/29/92 65
04/30/92 66
05/01/92 67
05/05/92 7
05/06/92 72
05/07/92 73
05/12/92 78
05/14/92 80
05/19/92 85
05/21/92 87
05/27/92 93
05/29/92 95
06/03/92 100
06/04/92 101
06/09/92 106
06/11/92 108

0.012
0.006
0.501
0.352

0.367
0.103
0.125
0.149
0.215
0.203
0.244
0.254
0.241
0.228
0.277
0.209
0.239
0.202
0.236
0.398
0.262
0.438
0.389
0.380
0.194
0.165
0.225
0.144
0.187
0.210
0.260
0.110
0.118
0.089
0.127
0.153
0.114
0.073
0.167
0.207
0.080
1.448
0.095
0.110
0.052
0.100
0.115
0.096
-0.020
0.102

0.001
0.014
0.572
0.388
0.376
0.375
0.367
0.319
0.317
0.356
0.319
0.326
0.317
0.324
0.309
0.306
0.236
0.241
0.268
0.244
0.468
0.400
0.413
0.444
0.439
0.223
0.194
0.244
0.182
0.218
0.234
0.249
0.077
0.121
0.192
0.214
0.153
0.118
0.073
0.225
0.245
0.225
0.048
0.175
0.210
0.064
0.212
0.216
0.192
0.047
0.102

0.035
0.008
0.428
1.176
1.331
1.197
1.600
1365
1.618
1.741
1.844
1.674
1.731
1.826
2.266
1.823
1.812
1.923
1.876
1.872
2.914
2.262
2.346
2.456
2.571
1.794
1.780
1.394
1.680
1.610
1.570
2.748
2.644
1.624
1.385
1,921
1.253
1315
1.677
1.331
1.319
1.331
0.019
1.316
1.392
1.350
1.186
1.588
1.154
1.116
1.016

0.036
-0.005
0.991
1.832
2.167
1.975
2.019
1.523
1.643
1.872
1.876
1.705
1.762
1.725
2.295
1.798
1.813
1.847
1.849
1.818
2.921
2.427
2.401
2.621
2.314
1.952
1.809
1.457
1.880
1.710
1.730
2.684
2.761
1.826
1.553
1.672
1.436
1.508
1.928
1.500
1.523
1.500
0.057
1.434
1.741
1.675
1.406
1.917
1.346
1.484
1321

0.016
-0.001
0.387
1.179
0.970
0.939
1.044
0.874
0.876
0.991
1.191
1.180
1.331
1.332
2.012
1.642
1.657
1.722
1.852
1.887
2.867
2.565
2.086
2.756
2.609
2.058
1.905
1.486
1.980
1.810
1.800
2.900
2.730
1.862
1.623
2.584
1.528
1.669
2.025
1.570
1.561
1.570
0.061
1.447
1.749
1.679
1.410
1.986
1.346
1.454
1.321

-0.004
-0.006
0.111
0.131
0.205
0.313
0.349
0.394
0.441
0.478
0.495
0.654
0.716
0.750
0.921
1.013
1.031
1.147
1.300
1.278
2.400
1.775
2.035
1.942
1.933
1.341
1.368
2.782
1.270
1.300
1.260
1.957
1.212
1.233
1.070
1.255
1.070
1.139
1317
1.138
1.131
1.138
0.065
0.959
1.188

1.042°

0.983
1.405
0.962
0.882
0.847

103

0.004
-0.008
1.007
0.808
0.854
0.803
0.556
0.509
0.557
0.600
0.543
0.623
0.631
0.652
0.508
0.541
0.491
0.590
0.501
0.514
0.889
0.719
1.058
0.966
1.099
0.728
0.841
0.840
0.834
0.973
1.009
1.717
0.611
0.970
1.008
1.251
1.665
1.174
1.042
1.241
1.135
1.241
0.080
0.963
1.424
1.260
1.104
1,612
1.154
0.954
1.016

-0.002
0.015
0.669
0.698
0.882
1.013
1.186
1.262
1.310
0.221
0.946 --
3.029 --
3.200
3.042
3.766
3.141
3.170
3.301
3.043
2.497
3.950
3.468
4.473

0.006 --
-0.018 -0.017
0.006 0.008
0.010 0.004
0.006 -0.007
0.004 -0.012
0.012 0,005
0.016 0.026
0.036 0.020
0.008 0.011
0.005
0.018

-0.008 -0.059

0.133 -0.067
-0.026 -0.111
0.042 0.017
0.025 0.004
0.004 0.006

3.587 -0.035 -0.033

3.283
2.530
2.031
0.738
2.020
1.890
1.940
3.021
3.144
1.837
1.570
1.643
1.445
1.523
1.788
1.444
1.448
1.444
0.083
1.270
1.516
1.486
1.108
1.519
1.026 ~
1.059
0.881 --

0.047 0.105
-0.037  -0.079
0.012 0.006
0.009 0.010
-0.010 -0.005
0.003 -0,000
0.001 0.004
0.007 0.048
0.085 0,054
-0.048 -0.042
-0.066 -0.062
-0.012 -0.017
-0.031  -0.031
-0.075 -0.039
-0:034 0.000
0.043 0.045
0.048 0.019
0.043 0.045
2.832 3.034
-0.013  -0.009
-0.059 -0.053
-0.005 0.008
0.008 0.013
0.025 -0.003

-0.021 -0.051

-0.010
-0.015
-0.003
-0.008
0.002
-0.002
0.001
0.019
0.031
0.006
0.001
0.002
0.003
0.030
0.007
-0.058
-0.069
0.008
0.064
-0.103
0.009
0.036
-0.014
-0.057
0.059
0.024
-0.001
-0.003
-0.021
0.003
-0.000
0.053
0.013
-0.026
-0.025
-0.021
-0.063
0.059
0.004
0.048
0.057
0.048
2.873
0.008
-0.010
0.012
0.053
0.001

0.047

-0.009
-0.013
-0.009
-0.005
0.004
-0.001
0.027
0.012
0.032
~0.009
0.010
0.003
0.002
0.007
-0.016
-0.057
-0.089
0.011
-0.091
~0.065
0.035
0.015
-0.012
0.055
0.041
0.021
0.007
-0.002
-0.016
0.000
-0.004
0.093
-0.008
-0.020
-0.054
0.031
0.031
0.055
0.039
0.056
0.061
0.056
2.182
0.022
~0.042
0.017
0.057
0.005
0.032
0.043


6.0 T T T T T T T
! ;

3.0 mg PO,/L
0.5 mg PO,/L
5.0 fr 0.0 mg PO,/L

oe

Zinc, mg/L

0 20 40 60 80 100 120 140
Elapsed Time, days

Figure 28. Effect of phosphate on zinc leached from
C85200 (yellow brass) coupon at pH 7.5.

73



Table A-S.

Run 5: Cincinnati tap water, pH=7.5, 24 hour stand time

Study=Coupon
Analyte=Pb
Date __Time, days C36000 Pb free _C83600_C84400_C84500_C85200 C85400_ Copper Pure Pb Pure Pb Pure Zn Pb/Sn
08/02/93 rinse -- 5.1 97 10.2 8.8 8.6 2.9 17 3.2 167.6 22 38.6
08/03/93 rinse 5.4 0.2 11.0 13.9 9.3 2.6 0.4 0.4 0.0 14.6 00 43.9
08/11/93 1 396.5 189.3 708.3 816.7 444.5 424.3 436.3 44 623.0 944.7 13 783.6
08/12/93 2 246.0 84.9 303.5 328.1 4184 168.2 205.2 11 426.8 614.2 1.0 798.3
08/13/93 3 2082 441 215.4 215.4 343.2 133.4 173.9 11 340.8 377.9 13 580.3
08/17/93 7 1764 270 2145 188.9 319.0 113.5 171.7 0.8 267.7 281.5 0.8 472.4
08/18/93 8 48.0 21.3 210.6 186.9 315.0 121.3 163.9 1.0 279.6 340.6 0.2 485.9
08/19/93 9 114.2 18.0 -- 186.5 325.9 129.4 153.7 0.7 320.6 364.0 0.5 360.7
08/20/93 10 101.3 18.2 229.5 203.0 316.1 122.9 142.8 0.2 317.4 346.5 0.3 349.9
08/24/93 14 (62.7 16.4 192.4 171.1 240.5 91.9 102.9 05 274.6 327.5 03 380.6
08/25/93 15 49.4 11.4 183.1 192.9 229.8 76.2 97.7 0.9 278.2 316.7 1.6 226.9
08/26/93 16 42.2 9.7 1764 169.6 244.7 72.4 94.2 0.8 297.0 301.6 0.1 330.1
08/27/93 17 39.4 9.9 203.2 187.0 261.0 71.4 104.2 0.2 330.1 361.9 -0.1 370.2
08/31/93 21 38.7 99 185.7 162.2 217.2 58.0 84.2 0.5 312.0 335.0 04 281.8
09/01/93 22 2 33.7 78 - 153.5 2076 486 75.9 -0.7 302.3. 327.9 -0.9 274.6
09/02/93 23 33.0 77 150.4 187.4 425 65.0 0.1 308.7 322.5 03 260.2
09/08/93 29° 37.7 8.6 1876 168.4 190.7 50.2 70.0 1.1 324.2 346.2 0.5 403.9
09/09/93 300. 27.6 53 151.6 135.5 157.5 36.1 54.0 -0.1 290.5 317.0 +03 251.9
09/10/93 31 24.4 44 137.1 1256 147.7 29.9 50.8 -0.6 338.7 3413 -0.7 267.6
09/15/93 360 (34.1 218 151.4 142.6 1543 32.3 56.5 0.8 340.3 359.8 22.3 -
09/16/93 37° 21.2 40 1366 114.8 137.5 22.8 40.8 0.2 302.1 325.7 -0.6 248.2
09/21/93 42 21.4 4.1 130.3 113.5 1393 25.2 464 0.3 335.3 327.4 0.6 271.6
09/23/93 44 19.2 3.0 1184 107.9 120.7 17.8 33.4 -0.1 348.4 340.2 -0.3 263.0
09/24/93 45 19.3 25 109.2 107.4 116.3 16.9 31.7 -0.4 345.0 332.4 0.0 256.5
09/29/93 50 20.6 3.6 4.0 40 113.4 18.7 2.0 0.6 350.4 329.7 0.4 256.4
09/30/93 Si 18.4 28 105.3 98.5 116.0 15.7 30.5 05 353.8 338.5 03 263.5
10/05/93 5620.9 42 1114 105.1 106.0 17.8 34.2 0.7 349.7 348.3 0.3 248.4
10/07/93 58 17.7 3.1 110.5 105.5 133.3 14.1 28.3 0.2 347.9 338.1 -0.2 267.7
10/12/93 63 19.1 5.2 147.1 137.1 37.3 27.0 50.7 04 445.3 482.4 0.2 350.1
10/14/93 65 14.6 33 94.2 90.8 92.2 15.4 28.0 0.6 355.5 325.0 -0.1 241.9
10/19/93 70 13.8 28 82.0 78.9 73.3 14.0 26.3 0.2 295.8 296.5 -0.6 206.5
10/21/93 72 15.8 3.5 89.8 92.9 99.7 15.1 28.1 0.1 361.5 354.3 O.1 242.2
10/22/93 73 12.6 22 72.5 75.2 74.4 118 23.5 0.2 309.7 303.8 0.1 0.0
10/26/93 77 11.7 2.3 68.7 65.0 62.2 11.0 19.6 0.5 292.3 267.4 0.0 197.5
10/28/93 719 10.9 23 59.0 65.3 62.2 9.7 15.8 -0.2 293.7 304.6 0.4 184.9
11/02/93 84 12.1 23 65.7 75.4 66.9 10.7 18.7 0.6 289.3 283.1 -0.1 173.4
11/04/93 86 111 18 S15 60.1 52.4 9.2 14.9 0.9 298.5 285.3 03 179.3
11/05/93 87 10.0 1.8 47.0 52.4 45.8 8.0 13.2 0.1 272.3 268.5 03 174.2
11/09/93 91 11.1 2.5 69.2 69.9 53.4 8.8 13.4 -1.7 311.5 307.5 -2.2 185.7
11/16/93 98 11.1 2.2 51.6 66.3 59.6 115 14.3 03 298.2 280.1 11 --
11/18/93 100 10.7 2.0 36.6 45.9 40.6 78 9.9 0.5 284.3 262.1 0.6 1541
11/19/93 101 9.6 20 374 41.9 36.6 76 8.6 -0.1 270.1 266.8 -0.1 149.2
11/23/93 105 13.3 1.6 40.2 48.2 44.8 1A 11.2 -0.7 286.6 276.6 -0.2 162.9
12/02/93 114 11.9 3.7 30.9 47.3 34.3 6.9 9.0 04 325.7 311.0 -0.1 178.8
12/03/93 115 12.0 14 29.7 452 3314 6.1 8.7 0.3 357.5 298.7 03 175.9
12/06/93 118 21.0 2.2 45.2 67.0 54.7 10.0 13.7 -0.6 406.5 397.9 -0.4 254.6
12/07/93 119 15.6 26 328 495 383 TA 10.0 0.4 305.1 286.6 06 162.4
12/09/93 121 13.7 2.6 27.5 42.3 29.2 63 Vd 0.7 343.2 332.3 05 168.9
12/13/93 125 22.9 3.6 44.8 67.8 55.5 10.2 14.1 0.5 484.7 498.9 03 291.9
12/14/93 126 16.1 1.7 30.4 426 33.7 6.0 V7 05 302.8 302.2 0.3 154.5
12/16/93 128 12.8 08 20.6 34.9 21.7 41 5.7 -0.4 298.7 194.4 0.2 152.6



T r T T T

© 84500 (red brass},
v €85400 (yellow brass)
___.24 hour stagnation / |

72 hour stagnation

60 80 100 120 140

Elapsed Time, days

Figure 39. Influence of stagnation time on zinc
leached from a red and yellow brass coupons during
test run 1: pH=8.5.





Copper, mg/L

Elapsed Time, days

—o— C36000
—o— C36000
—w— C83600
—v¥— C84400

—TM— C84500
—TM— C85200
—4— C85400
—@— Pure copper

Figure 7. Copper leached from brass and pure
copper coupons during test run #2, pH =7.0.



60 80 100 120 140
Elapsed Time, days

—o— C36000 —m— C84500
—o— C36000 —m— C85200
—¥— C83600 —4— C85400
—w— C84400 —@— Pure lead

Figure 3. Lead leached from brass and pure
lead coupons during test run #1, pH =8.5.



"Pre-leaching" lead from the alloy has been considered. Prior to distribution, the brass
product would be exposed to an aggressive metal extraction solution, perhaps an acidic solution.
The solution would extract or dissolve the lead from the brass surface, therefore reducing lead the
amount of lead exposed to the water. The process, which could be described as an "aging"
technique, may eliminate initial high water lead levels from exposure to new brass products. This
solution, however, has considerable drawbacks including cost, and handling and disposal issues
associated with the production of a hazardous, lead-containing extraction solution.

Researchers at AT&T Bell Laboratories have been exploring properties of copper alloys
substituting bismuth for lead as a solution to lead contamination from leaded brasses."* They have
found that copper alloyed with bismuth coupled with a ductility-enhancer such as phosphorous,
indium, or tin, machines as well as leaded alloys. These studies have been conducted at the
laboratory-scale and full-scale implementation issues remain unresolved.

Some manufacturers have been advertising nearly true "lead-free" (advertised to contain
trace amounts of lead as a contaminant) brass or bronze alloys as possible substitutes for the lead-
containing ones. Leadfree Faucets Inc.® claims to have developed a method for producing faucets
from aluminum bronze (<0.05% Pb).“ Currently the company produces the faucets solely for
components of point-of-use devices. Another company, NIBCO®, has used a brass that contains
bismuth as a substitute for lead in their cast brass products.’ The bismuth-brass alloy was
patented and licenced by IMI Yorkshire Fittings Limited® of the United Kingdom. The alloy
contains 2.7% bismuth and < 0.25% lead.** While these truly lead-free materials show promise,
introducing bismuth to drinking water in the distribution system remains an unexplored issue.
Currently, however, no faucets are being made from lead-free alloys on a large scale.

TEST APPARATUS DESIGN AND OPERATION
Test apparatus

The test apparatus consisted of a large water reservoir (100 gallon Nalgene® tank)
connected to 12 parallel test loops by 1/2" inside diameter (ID) Schedule 80 polyvinyl! chloride
(PVC) pipe. Test water contained in the reservoir was recirculated in the tank by a PVC pipe
recirculation line and magnetic drive pump system. The water was fed to the loops by a separate
magnetic drive pump and line. All pump components in contact with the water were constructed
of metal-free materials. Water that had passed through the loops was discharged to a waste drain.

Each test loop was constructed of a variety of PVC Schedule 80 and high density
polyethylene (HDPE) valves, fittings, and pipe. The systems each contained a 3-way valve, a

“ Leadfree Faucets, Inc., Chagrin Falls, OH.
© NIBCO, Inc., Elkhart, IN.
© [MI Yorkshire Fittings LTD., P.O. Box 166, Leeds, LS1 1RD, UK.

10



Table 1. Extraction water used in the Nordtest??

Method 1:

Reagent

Weight added*

NaCl
Na,SO,
CaCO,
CO, gas
Air

Method 2:

Reagent

50 mg

50 mg

50 mg
until CaCO, is dissolved;
then until pH=7.0 (+/-0.1)

Weight added

NaCl
Na,SO,
Ca(OH),
CO, gas
Air

50 mg

50 mg

37 mg
until pH < 5; then
until pH=7.0 (+/-0.1)

* weight dissolved in 1 liter of test water



Table 5. Extraction water quality.

Lead, ug/L
Calcium, mg/L.
Copper, mg/L.
Tron, mg/L
Potassium, mg/L
Magnesium, mg/L
Manganese, mg/L
Sodium, mg/L
Zinc, mg/L

Alkalinity, mg CaCO3/L
Sulfate, mg SO4/L
Chloride, mg/L

Silica, mg SiO2/L
Nitrate, mg N/L
Ammonia, mg NH3/L
Phosphate, mg PO4/L
Dissolved oxygen, mg/L
Total inorganic carbon, mg C/L
Free chlorine, mg Clo/L
pH, pH units

<0.002
34.7
<0.02
<0.05
23

94
<0.01
14.8
<0.01

43.5
104.0
39.0
2.4
<0.02
<0.03
<0.02
na

na
0.65
8.04

0.04

Lead, g/L
Calcium, mg/L.
Copper, mg/L.
Tron, mg/L
Potassium, mg/L
Magnesium, mg/L
Manganese, mg/L
Sodium, mg/L
Zinc, mg/L

Alkalinity, mg CaCO3/L.
Sulfate, mg SO4/L
Chloride, mg/L

Silica, mg SiO2/L
Nitrate, mg N/L
Ammonia, mg NH3/L
Phosphate, mg PO4/L
Dissolved oxygen, mg/L
Total inorganic carbon, mg C/L
Free chlorine, mg Clo/L.
pH, pH units



3.0 mg PO,/L
0.5 mg PO,/L
0.0 mg PO,/L

i

80 100 40

Elapsed Time, days

Figure 27. Effect of phosphate on zinc leached from
84500 (red brass) coupon at pH 7.5.



OL=HS “Aiyend s21e44 BopENT ZoNy,

‘THILTIEO
26/9TEO
‘colET/EO
‘c6IZT/EO
TOITTIEO


‘able A-26.

Run 1: Cincinnati tap water, pH=8.3-8.5, 72 hour stand time

Time, days C36000_C36000_C83600_C84400_C84500_C85200 C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

iStudy=Coupon.
[Analyte=Zn
Date
08/19/91 6
08/26/91 13
09/09/91 27
09/16/91 34
09/23/91 41
09/30/91 48
10/07/91 55
10/15/91 63
10/21/91 69
10/28/91 16
11/04/91 83
11/25/91 104
12/02/91 111
12/09/91 117
12/16/91 125
12/30/91 139

0.59
0.34
0.47
0.32
0.40
0.30
0.39
0.37
0.30
0.20
0.35
0.29
0.39
0.50
0.73
0.27

0.56
0.40
0.61
0.49
0.47
0.38
0.39
0.37
0.33
0.23
0.35
0.26
0.34
0.49
0.73
0.26

0.09
0.05
0.06
0.05
0.05
0.04
0.07
0.07
0.05
0.04
0.05
0.05
0.06
0.08
0.10
0.04

0.22
0.15
0.19
0.16
0.15
0.13
0.17
0.15
0.13
0.08
0.12
0.14
0.16
0.20
0.28
0.09

0.17
0.12
0.23
0.22
0.18
0.20
0.22
0.20
0.16
0.10
0.17
0.17
0.18
0.21
0.30
0.10

127

0.54
0.40
0.39
0.39
0.43
0.28
0.38
0.34
0.25
0.18
0.22
0.22
0.27
0.31
0.50
0.23

0.43
0.31
0.47
0.36
0.35
0.29
0.35
0.45
0.33
0.22
0.29
0.30
0.37
0.46
0.71
0.28

0.01
0.01
0.01
0.21
0.01
0.02
0.02
0.02
0.02
0.01
0.01
0.01
0.01
0.02
0.03
0.01

0.01
-0.00 --

0.19
0.01
0.02
0.02
0.02
0.03
0.01
0.01
0.01
0.02
0.03
0.02
0.02

0.01

0.02
0.01
0.01
0.03
0.02
0.02
0.02
0.01
0.01
0.01
0.01
0.01
0.01
0.01

5.94
3.16
138
0.85
0.34
0.33
0.23
0.24
0.24
0.15
0.18
0.18
0.18
0.25
0.33
0.12

0.04
0.02
0.02
0.59
0.04
0.02
0.02
0.02
0.02
0.01
0.01
0.01
0.01
0.01
0.01
0.01


The resistance of an alloy to dezincification does not change significantly until the zinc
content is greater than 15%; after which the possibility for dezincification increases. Arsenic
(typically up to 0.1% As) added to alpha brass effectively inhibits dezincificationTMTM, however,
does not prevent dezincification of greater zinc-containing duplex brasses. Antimony and
phosphorous in amounts of 0.02 to 0.05% have also been used to safeguard against dezincification
attack in alpha brasses.”°

Many researchers have studied the effect of water quality parameters on dezincification.
Turner showed that chloride and carbonate hardness contents were major factors influencing
"meringue" dezincification."*”” He found that in waters where the pH was above 8.3 and the
chloride concentration was high relative to temporary bicarbonate hardness, dezincification
occurred. He developed the “Turner” Diagram relating chloride concentration and temporary
hardness to suitability for resistance to dezincification. Lime softening converts water that does
not support dezincification to one that does by increasing the pH and lowering the temporary
hardness. Other factors identified in controlling dezincification include: percent zinc in alloy,
electrolyte condition of water, galvanic couples or electric currents, and the availability of oxygen
and other chemicals in water.

Tabor” examined bronze (copper alloy in which zinc or nickel is not the major alloying
elements) valve stems from the city of Los Angeles water distribution system that had failed as
a result of dezincification. He discovered that in cases where bronzes containing high zinc
contents were being used with water that had been softened with lime, dezincification was
common. Through experimentation using a galvanic bronze-iron cell, he discovered that generally
the higher the zinc content of the bronze, the greater the chance of dezincification. In the case
of alloys with low zinc content (less than 15% zinc), zinc and copper acted as a unit, with iron
providing the cathodic protection. In alloys with high zinc content (greater than 20% zinc), the
zinc and copper acted independently of each other, with zinc being anodic to the iron and copper
being cathodic. The zinc rapidly dissipated because of the irons inability to provide protection.
There appeared to be a transition zone between a zinc content of 15 to 20% where dezincification
may or may not occur. Other findings indicated that the dezincification process may be increased
with oxygen content in system, water velocity, temperature, and deposits built-up on the material
surface.

Ingleson et al.” conducted experiments to examine the effect of chlorination on ball valves
made of cast and hot-pressed brass (single alpha-phase brass containing 2 to 3% lead). They
concluded that the presence of up to 0.4 mg/L of free chlorine increased the rate of
dezincification. They also concluded, however, that the impact of chlorine was low relative to
the impact of variations in water composition.

Dissolution

Dissolution refers to the dissolving of the metals composing the alloy into the solution in
contact with the metal. As mentioned, the majority of past brass corrosion research has focused

5



Table A-28. Run 3: Cincinnati tap water, pH=7.5, 3.0 mg PO4/L, 72 hour stand time

Study=Coupon
Analyte=Zn

Date __Time, days C36000_C36000_C83600 C84400_C84500_C85200 C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

08/17/92 7 200 164 029 068 034 139 160 -0.02 -0.00 -0.00 694 0.01
08/24/92 14 1.73 168 041 057 0.40 1.07 134 -0.00 -0.01 0.00 630 -0.01
08/31/92 21 1.91 190 047 047 042 115 146 -0.01 -0.01 -0.01 2.48  -0.00
09/08/92 29° 1.43 142 030 037 0.31 0.85 112  -0.00 -0.01 -0.01 1.94 -0.00
09/14/92 35 1.41 148 021 031 0.30 0.79 117 0.00 -0.00 -0.00 233 -0.00

129



.<—— Upper Manifold
Nipple, 1/2 " HDPE

Check Valve

Nipple, 1/2" HDPE
Reducer Coupling, 1/2"X1/4", PVC

Labcock, 1/4", PVC, MPT X MPT

ha —— Labcock, 1/4", MPT
Tee, 1/4", PVC

Sample Cell, Teflon

Tubing, Teflon, 1/4"
[ J
———— Stopcock, Teflon, 3-Way
ie) . "
Hq Tubing, Teflon, 1/4'
e —————— Rotameter, 1/4" Couplings
______. Tubing, Teflon, 1/4"
——————Connector, 1/4" FPT to 1/4" Tubing
——— Reducing Nipple, 1/2" X 1/4", HDPE
& —__— Needle Valve, 1/2", PVC

Nipple, 1/2" HDPE
———— Bottom Manifold

Figure 2. Schematic of individual test loop (not to scale).
47



Lead leached from brass COUPONS «6... eee eee eee
Copper leached from brass coupons ......-++++++ oe
Zinc leached from brass COUPONS «6... eee eee
Test rum #2... eee ene
Extraction water quality... 6. cece
Lead leached from brass coupons... 6... ++ eee
Copper leached from brass coupons .........++-+
Zinc leached from brass coupons .........++
Impact of pH on metal leached from coupons
BYQSS COUPONS 6. ee
Lead COUPONS 2... eee
Copper COUPON ©. eee ccc eee teen
ZiNC COUPONS «6. ee ee ee eee
60:40 tin:lead solder COUPONS ©... eee eee ene
Impact of orthophosphate on the metal leached from coupons
Extraction water quality... 6... eee eves
BYrQSS COUPONS 66.6. eee
Impact of stagnation time on metals leached
Evaluation of low-lead alloy .. 1... 0.20... cee cece teenies
Impact of sulfate on copper dissolution ............- 050s eee eee eeee

DISCUSSION AND CONCLUSIONS ......-.-- 00 e ee eee eee eee eee 29

vi



wl

40 60 80 100 120 140 160

Time, days

Figure A-19. Brass Alloy C84500, Red Brass



pH 8.5

pH 7.0

80 100 120 140 160

60

20

Time, days

Figure A-8. Brass Alloy C85200, Yellow Brass

155



1.00 TT

L 3.0 mg PO,/L |
0.90 L 0.5 mg PO,/L
0.80 + 0.0 mg PO,/L

a @0o

0.70
0.60 +
0.50
0.40 ff)

Copper, mg/L

0.30 #
0.20

0.10

9.09 ee
0 20 40 60 80 100 120 140

Elapsed Time, days

Figure 19. Effect of phosphate on copper leached from
84400 (red brass) coupon at pH 7.5.

64



leaching of duplicate free-cutting brass coupons was observed (i.e., no statistical difference was
observed).

Copper leached from brass coupons

Copper leaching trends were similar to those observed for lead in that two groups, a "high"
and a "low", were established (Figure 4). The major difference was that the division into trend
groups took place at the beginning of the test run.

The high group consisted of the three red brasses: C83600, C84400, and C84500. Unlike
lead leaching trends, a relatively constant amount of copper (approximately 0.22 mg/L) was
leached from the brasses in the high group throughout the entire test run (Appendix Table 37).
The leaching patterns and copper levels of the high group brasses were nearly identical throughout
the entire test run. These results showed that smaller differences in copper composition in similar
alloys did not translate into significant differences in copper leaching levels.

The low group of brasses consisted of C36000, C85200, and C85400 which were also the
brasses that contained the lowest percentage of copper. The copper leaching trends among these
brasses were also nearly identical. Copper levels gradually decreased over the first 20 to 40 days
followed by a leveling off trend at a concentration of approximately 0.03 mg/L. No statistical
differences between trends in this group were discovered (Appendix Table 37).

After approximately 120 days, the pure copper coupon leached nearly the same amount
of copper as the red brasses. This showed that there was a critical alloy composition in which the
brass alloy took on the leaching properties of pure copper.

A number of gradual concentration peaks and valleys were observed in the copper leaching
trends. The gradual change in copper levels was characteristic of a response to fluctuations in
extraction water quality rather than the collection of dislodged particulate material which would
result in single random copper spikes. A review of the extraction water chemistry during periods
of peaks and valleys frequently showed a relationship between pH and copper concentration. For
example, in one instance over a 35-day period (from 95 to 130 days into the test run), the pH of
the extraction water gradually dropped from approximately 8.7 to'8.2 (Appendix Figure F1). A
corresponding increase or inverse pattern was seen in copper levels. This was especially evident
with the high group brasses, where copper levels more than doubled during this time period.
Similar relationships were not always obvious or apparent as this particular case. A number of
factors such as coupon age and water quality probably impact the occurrence and degree of such
relationships.

In most cases, trends within groups were not statistically different from each other. Also,
duplicate copper (C36000) was not statistically different over the entire test run or after 60 days,
which demonstrated good experimental reproducibility (Appendix Table 37).

19



0.30 r T T T r T T r T T
o 3,0mg PO,/L |
¢ 0.5 mg PO,/L
0.25 2 0.0 mg PO,/L
0.20 ;
3
a
5 0.15 7
5
v0
0.10 1
0.05 fa, ;
0.00 tg mga Ono ew,
0 20 40 60 80 100 120 140

Elapsed Time, days

Figure 17. Effect of phosphate on copper leached from
36000 (free-machining brass) coupon at pH 7.5.

62



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138



3.0 mg PO,/L |
0.5 mg PO,/L ||
0.0 mg PO,/L {

140

Elapsed Time, days

Figure 10. Effect of phosphate on lead leached from
83600 (red brass) coupon at pH 7.5.



1, Clean milled specimens (Cu, Zn, solders, and brasses) by ultrasound in 0.5%
Triton X-100® surfactant for 5 minutes. Clean each coupon individually in a
small glass beaker (containing Triton X-100®) surrounded by water. Following 5
minutes of ultrasonic treatment, discard the cleaning solution and rinse the metal
coupon with distilled water. Repeat the ultrasonic cleaning procedure for an
additional 5 minutes after replacing Triton X-100® with distilled water.

2. Soak copper and brass coupons individually in 1:4 HCl for 30 minutes at room
temperature. Rinse the coupons thoroughly with distilled water and dry with a
KimwipeTM.

3. I£ the lead coupons are covered with a dark coating, sand the surfaces clean
with fine emery cloth or sand paper (e.g. special emery grinding paper, grit 0,
designated for metallography). Polish with a paper towel. Ultrasonic cleaning in
distilled water may be used to remove any solid particles adhering to the coupon,
but it is probably unnecessary. If ultrasound is used, 30 seconds to 1 minute is
sufficient. Longer times result in.attack of the Pb metal surface.

4, Finally, rinse the coupons in acetone and air dry. They may be used
immediately or stored in a desiccator for later use.

Prior to starting the study, the entire experimental system was cleaned with a 5% solution
of Contrad 70° detergent. The solution was recirculated through the feed tank and rinsed

through the loops for 10 to 20 minutes. The solution was then held in the cells (empty cells), as
if coupons were being tested, for 24 hours. Next, the entire system was drained and the procedure
was repeated. The system was thoroughly rinsed with Cincinnati tap water until the Contrad®
solution was satisfactorily removed. The preceding steps were repeated using 0.15% HNO,
solution in place of the detergent except that after 24 hours standing, the acid solution held in the
test cells was analyzed for metals (Pb, Cu, Zn, Fe, and Sn). The acid cleaning steps were
repeated until standing metal levels were consistent with background Cincinnati tap water metal
levels. The cleaning procedure was also used to clean the system before the start-up of new water
quality tests. Analysis of the acid cleaning solution showed that metals were adsorbed onto the
surface of the test loop components during a test run, and several acid rinses were required to
remove the contamination before re-starting.

Operating procedures

The daily operating procedure of the test system was as follows:

© Curtis Matheson Scientific, Inc., Houston, TX.
® Buehler LTD., Evanston, IL.
© Godax Laboratories, Inc., New York, NY.

12



But, one could theorize how the results would be affected if one or both oxidants were depleted.
Clearly the results pointed out the complexities of the role of stagnation time, and oxidant type
and levels on metal levels. Also, the results demonstrated the difficulty associated with comparing
metal levels measured in corrosion control studies and field samples under non-equilibrium
conditions to each other and solubility model predictions based on equilibrium conditions.

Evaluation of low-lead alloy

An evaluation of the lead and other composite metals leached from a low-lead containing
brass® was made during test run 5 (pH=7.5). The nominal composition of the alloy as reported
by the manufacturer was 85% copper, 4% tin, 3% bismuth, and less than 0.2% lead. Figure 46
shows that despite low lead composition, significant amounts of lead leached from the coupon
initially. However, within a short period of time, lead levels dropped to near instrumental
detection limit (2 pg/L). No detectable bismuth was leached from this coupon at any stage of the
test run. The instrumental detection limit for bismuth was 0.025 mg/L.

* Impact of sulfate on copper dissolution

Although the impact of sulfate on copper corrosion was not stated as an objective of this
study, background sulfate levels, theoretical considerations, and observations made over the test
tuns warrants brief discussion. Figure 47 (taken from Schock et al.) shows copper levels (after
concentrations were considered stable) leached from the pure copper coupons during all 5 test runs
superimposed on a solubility diagram. The theoretical curves correspond to average DIC and
orthophosphate concentrations during the respective runs. The figure also includes the computed
solubility line for Cu,(OH),SO,H,O, which is in closer agreement to the experimental data at
higher pH values. Although this observation was not made under controlled experimental
conditions, it does suggest that sulfate may impact copper dissolution. Clearly more
experimentation needs to be done to clearly identify the role of sulfate on copper corrosion.

DISCUSSION AND CONCLUSIONS

The results of this study showed that the amount of lead leached from brass was generally
dependent on the amount of lead in the brass from pH 7.0 to 8.5. The more lead in the alloy, the
greater amount of lead leached from the alloy. In nearly all cases, the highest lead levels leached
from the brasses during the first two weeks of exposure and decreased at the fastest rate during
this period. New coupon surfaces and a thin layer of excess lead smeared over the coupon surface
as a result of coupon machining were believed to contribute to this observation. At PH 8.5, the
concentration of lead leached from the brasses “leveled off" after 60 to 70 days. Under more
corrosive conditions (pH 7.0), lead levels were still decreasing slightly at the end of the test run
(155 days). The pure lead coupon leached considerably more lead than the brasses which

® Nibco, Inc., Elkhart, IN.

29



7 T
Test run 1
Test run 2
Test run 3
Test run 4

opadeq

Chlorine, mg/L

0.0

0 20 40 60 80 100 120 140 160
Time, days

Figure A-2. Free chlorine variation of test waters
during each test run

149 .



Copper, mg/L

0 20 40 60 80 100 120 140 160
Elapsed Time, days

—o— C36000 —#— €84500
—o— C36000 —=— C85200
—v¥— C83600 —4— C85400

—v— C84400 —@— Pure copper

Figure 4. Copper leached from brass and pure
copper coupons during test run #1, pH =8.5.

49



measured with a Orion Model EA 940 pH meter® and an Orion Ross Sure-FloTM electrode. Free
and total chlorine were analyzed with a Hach DR/2000 spectrophotometerTM, TIC was analyzed
by a coulometric procedure on a UIC Model 5011 CO, coulometer® with Model 50 acidification
module, operated under computer control. A complete list of analytes and analytical methods is
shown in Table 3.

Quality assurance and quality control

Laboratory quality assurance (QA) procedures for analytical precision and accuracy for all
samples followed procedures established by the Treatment Technology Evaluation Branch (TTEB)
for all research studies. QA practices include requirements for analysis of duplicates and spikes
of samples comprising more than 10% of the sample load, and verification of instrument
calibration and some interference checking through external certified reference standards at
multiple times during each analytical run. The exact location and frequency of different types of
quality control spikes, standards, blanks, and duplicates, along with accuracy requirements, are
specified in those documented procedures for each type of analysis. They cannot be generalized
because the precision and accuracy expectations vary with the type of instrument used and the
levels of the analyte encountered in the different experiments.

Quality control charts for the major analytes are given in Appendix Tables 39 to 41for QA
samples analyzed during the study period. Duplicate difference, spike recovery, and standard
recovery information is presented for analyte concentration ranges.

Statistical data analysis and interpretation

Differences in metal leaching trends where determined using several statistical approaches.
Data normality was determined by the Kolmorogov-Smirnov Test. In most cases of this study,
data distributions were not normal (at 95% confidence), suggesting the use of the following non-
parametric statistical data interpretation techniques. The Kruskal-Wallis One Way Analysis of
Variance (ANOVA) on Ranks was used to demonstrate differences in metal leaching trends from
coupons. The Kruskal-Wallis Test is necessary when (a) determining if three or more groups are
affected by a single factor (e.g. brass composition), and (b) samples are not normally distributed
or do not have equal variances. Since ANOVA statistics only indicate whether two or more
groups are different, the Student-Newman-Keuls method and the Dunn's method were used to
make multiple comparisons between all possible group pairs. The Student-Newman-Keuls test is
used when group sizes are equal and Dunn's test is used when group sizes are unequal. All
Statistical comparison tests were made at 95% confidence (P=0.05), that is to say with 95%
confidence that the groups differ significantly. In the few cases were the data were normally

© Orion Research, Inc., Boston, MA.
® Hach Company, Loveland, CO.
© UIC Inc., Joliet, IL.

15



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24 hour stagnation
72 hour stagnation

1 4 1 n 1 1 L 1 1 i n 1

“0 20 40 60 80 100 120 140 160

Elapsed Time, days

Figure 37. Influence of stagnation time on zinc
leached from pure zinc coupons during test run
2: pH=7.0.



80 100 120 140 160

Time, days

Figure A-17. Brass Alloy C83600, Red Brass



42. National Sanitation Foundation (NSF). Drinking Water System Componants- Health
Effects. NSF International Standard Number 61, Section 9, 1994.

43, Dudek, F., J. Phone conversation with Frederick J. Dudek, University of
Chicago/Argonne National Laboratory. (1993).

44, Wright, W. Phone conversation with Walter Wright, President, Lead Free Faucets Inc.
(1993).

45, Showman, R. Experiences with Lead-Free Brass in the Manufacture of Cast Valves and
Fittings. Proc. American Water Works Association Annual Conference, New York, New
York, June 19-23, 1994.

46. Stevens, J. W. Letter from Mr. J.W. Stevens of the World Health Organization Center for
Drinking Water and Water Pollution Control to Michael R. Schock, USEPA, NRMRL,
WSWRD, TTEB. (1993).

47, Anonymous. Microwave Digestion of Lead Turnings. Application Note NM-5 (Metals
and Mining) CEM Corp., P.O. Box 200, Matthews, NC. 28106 (1990).

48. Anonymous. Microwave Digestion of Pb:Sn Solders. Application Note NM-4 (Metals and
Mining) CEM Corp., P.O. Box 200, Matthews, NC. 28106 (1990).

49. Rains, T. Personal communication. ACS Spectroscopy Short Course, Pittsburgh
Conference, New Orleans, LA. (1991).

50. Gilman, L. Microwave Sample Preparation Manual. Table 8, Acid Selection Guide,
Aqua Regia. Application Note NM-4 (Metals and Mining) CEM Corp., P.O. Box 200,
Matthews, NC 28106 (1989).

51. Lytle, D. A., Schock, M. R. & Tackett, S. Metal Corrosion Coupon Study
Contamination, Design, and Interpretation Problems. Proc. AWWA Water Quality Technology
Conference, Toronto, ON, Nov. 15-19, 1992.

52. ASTM Standard G31-72. American Society for Testing and Materials (ASTM). (1983).

53. ASTM Method 2688-83 Method B, Coupon Test. American Society for Testing and
Materials (ASTM). (1983).

54, USEPA. “Handbook for Analytical Quality Control in Water and Wastewater
Laboratories", U.S. Environmental Protection Agency, Environmental Monitoring and
Support Laboratory, Cincinnati, OH, EPA-600/4-79-0019 (1979).

36



T T T T

* 84500 (red brass)

v C85400 (yellow brass
24 hour stagnation
see 72 hour stagnation

resneracennsnagg RF ton,
ee 7
i 1 poy

60 80 100 120 140

Elapsed Time, days

Figure 32. Influence of stagnation time on lead
leached from a red and yellow brass coupons during
test run 1: pH=8.5.



Figure A-21. Pure lead



T T T T
3.0 mg PO4/L

0.5 mg PO4/L
0.0 mg PO4,L

40 60
Elapsed Time, days

Figure 9. Effect of phosphate on lead leached from
36000 (free-machining brass) coupon at pH 7.5.



T T r T
24 hour stagnation
72 hour stagnation

400

200

0) 1 n 1 1 i n 1 4 1 i 1 i 1
0 20 40 60 80 100 120 140 160

Elapsed Time, days

Figure 33. Influence of stagnation time on lead
leached from pure lead coupons during test run
2: pH=7.0.



Table A-13. Run 3; Cincinnati tap water, pH=7.5, 3.0 mg PO,/L, 24 hour stand time

Study=Coupon
Analyte=Zn

Date _Time, days C36000_C36000_C83600 _C84400_C84500 C85200 C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

08/07/92 458 349 0.17 0.24 0.60 194 3.11 -0.02 0.01 0.00 24.81 -0.01
08/10/92 454 0.99 0.02 007 0.09 047 027 -0.04 0.01 001 084 0.02
08/11/92 1 199 1.72 0.00 009 0,05 1.74 1.98 0.05 0.00 -- 11.69 -0.00
08/12/92 2 466 206 002 031 0.02 179 2.21 -0.02 0.01 -0.00 873 -0,00
08/13/92 3 2.90 143 0.07 0.41 0.18 1.15 1.70 -0.00 -0.00 -0.00 7.19 -0.00
08/14/92 4 = 2.03 193 010 039 0.33 1.24 1.72 -0.05 -0.01 -0.00 7.49 -0.00
08/19/92 9 2.74 195 033 065 059 1.17 185 -0.01 -0.00 -0.00 1037 ~-0.00
08/20/92, 10 222 138 016 035 040 0.77 146 0.03 0.00 0.00 9.79 0,00
08/21/92 11 1.90 149 0.22 038 0.31 0.82 121 -0.01 0.00 001 738 -0.00
08/25/92 15 1.06 104 022 026 0.21 0.61 0.72 -0.03 0.00 -- 5.22 0.00
08/26/92 16 141 143 0.21 0.23 021 068 0.89 - 002 -0.01 0.00 457 0.01
08/27/92 17 1.64 172 0.27 031 030 0.89 110 -0.01 -0.01 -0.01 3.58 -0.00
09/01/92, 22 107° 116 018 023 0.23 065 084 0.00 0.00 0.00 2.72 0.01
09/02/92 23 1.05 110 012 019 0.20 060 078 -0.01 -0.00 -0.00 2.80 -0.00
09/03/92 24 098 104 O11 018 O18 O55 0.71 -0.00 -0.01 -0.01 2.76 -0.01
09/09/92 30 112 1.26 O17 0.23 025 068 0.87 ~ -0.00 -0.01 253 -0.00
09/10/92 31 0.99 112 «60.13 «0.19 0.58 = 0.20 0.79 0.00 -0.01 = -0.01 2.57 -0.00
09/16/92 370,99 106 010 018 019 055 074 0.00 -0.00 -0.00 2.23 0.00
09/29/92 50 1.54 175° 012 030 032 0.75 116 -0.00 -0.01 -0.01 3.02 -0.00
09/30/92, 51 1.07 121 006 O15 019 054 0.81 0.00 -0.00 -0.00 231 -0.00
10/01/92 521.04 114 004 010 017 048 0.76  -0.00 -- -0.00 1.84 0.00
10/06/92 S57 60.84 60.98 004 014 017 036 055 -0.00 -0.01 -0.00 243 0.06
10/08/92 590.74 «= 0.81 = 0.02, 0.09 0.13 0.27, 045-001 -0.00—--0.01 1.98  -0.00
10/14/92 65 075 083 0.03 O11 O18 0.31 0.45 -0.00 -0.01 -0.01 205 -0.00
10/16/92 67 =60.64 «860.70 = 0.01 007) 0.10 019 036 -0.00 -0.01 -0.01 1.92  -0.01
10/21/92 72 0.75 083 0.02 009 O11 0.23 0.43 -0.00 -0.01 -0.00 202 -0.00
10/22/92 73 0.63 0.71 0.01 0.07 0.08 0.19 036 -0.01 -0.01 -0.01 1.70 -0.00
10/27/92 78 0.63 0.71 0.02 008 0.09 018 0.36 0.00 0.00 0.00 182 0.00
10/29/92 80 O51 050 001 0.04 005 0.11 0.24 = -0.01 0.00 -0.00 113 0.04
11/03/92 85 048 052 0.00 0.04 0.005 011 0.26 -0.00  -0.00 -- 137 -0.01
11/05/92 87 057 068 001 005 0.06 013 033 -0.01 -0.01 -0.00 148 -0.01
11/10/92 92 0.76 087 001 008 009 019 044 -0.00 -0.02 -0.01 1.86 -0.00
11/13/92 95 075 086 001 007 007 0.16 040 -0.00 -0.01 -0.01 1.75 -0.00
11/17/92 99 068 0.78 O01 007 007 014 0.38 -0.00 -0.01 -0.00 1.60 0.00
11/19/92 101 069 074 O01 0.05 006 013 034 -0.00 -0.01 -0.01 138  -0.00
11/24/92 106 066 «600.73 0.01 007 007 013 0.35 0.00 -0.00 -0.01 1.60 -0.00
11/25/92 107. 0.59 0.66 001 006 0.06 0.12 032 0.00 -0.00 -0.00 1.58  -0.00
12/01/92 113 0.69 068 0.01 0.07 0.08 0.12 0.32 0.00 -0.00 -0.01 1.71 0.00
12/03/92 1150.61 0.62 0.01 0.06 0.06 0.10 0,27- ~ - 1.64 0.00
12/08/92 120. 0.70 0.72 O01 006 007 012 0.32 -0.00 -0.01 -0.00 1.69 -0.01

113



Table A-15. Run 5: Cincinnati tap water, pH=7.5, 24 hour stand time

Study=Coupon
Analyte=Zn

11/23/93 10S . .

11/30/93 112 «1.87 .. . . .. . . 0.01
12/02/93 1141.60 .f . . . . . . . 0.01
12/03/93 115 .( . . . . . . .{ 0.01
12/06/93 118 .: . E . . .( 0.01
12/07/93 1191.32 .( B . . . . 0.01
12/09/93 121-0 1.43 . . . . . . 0.01
12/13/93 125 2.19 . . . .’ . . . 0.02
12/14/93 1261.39 . . . B . . . 0.01
12/16/93 128 «117 5 . . . .( . 0.00
12/20/93 13200 «75 . . . . .( . 0.01
12/21/93 133 «1.70 . . . . . . 0.01
12/29/93 1411.44 . . . . . . 0.01

LOWER pH to 6.5
12/30/93 1421.20 . . . 0.01
01/11/94 154 6.33 .. . . .. . x . . 0.01 8.40
01/13/94 156 5.91 .. . . . E . .( . 0.01 8.21
01/19/94 162 6.38 . . . . . . . . 0.01 = 7.89
01/20/94 163 6.35 5 . . . .! ‘ . . 0.01 754
01/25/94 168 6.40 . . . . . F . 0.01 1.78
01/27/94 170 6.28 B . y . . . .( . 0.01 8.13
01/28/94 171 6.06 . . . . . .( . 0.01 788
02/01/94 175 7.50 . . . . . . . 0.02 9.00
02/03/94 177871 . Fs . . 0.02 892
02/07/94 181 ~

ADD PHOSPHATE=3.0 mg/L
02/08/94 182 8.80 i 0.02 7.30
02/11/94 185 4.22 B . . . .{ .{ 0.01 6.10
02/15/94 189 = 7.86 . . . 0.03 13.46
02/17/94 191 4.39 . - ~
02/24/94 198 2.60 . 0.01 4.00
02/25/94 199 2.44 . 0.01 3.82



Impact of pH on metal leached from coupons
Brass coupons

- The influence of pH on metal dissolution from the alloys and pure metals was evaluated
by comparing metal levels leached from the coupons exposed during test runs 1 and 2 (Appendix
Figures F3 to F24). The results showed that the three red brasses all behaved similarly with
respect to the influence of pH on lead levels leached. As expected, the water considered to be
most corrosive towards lead, the lower pH water, leached the most lead from the red brass
coupons. This was particularly evident with C83600 and C84400 coupons, where a difference
between the two pH leach trends of approximately 100 wg Pb/L was maintained throughout the
duration of their respective studies. The influence of pH on lead leached from C84500 was not
as significant and at one stage, between 20 and 60 days, appeared to be insignificant. The most
notable difference was that C84500 brass contained the most zinc of the three red brasses tested.
As a group, the red brasses contain the most lead, nearly doubling the lead content of the yellow
brasses.

The two yellow brasses (C85200 and C85400) exhibited different lead leaching responses
to pH than the red brasses. Interestingly, lead leached from C85200 (Appendix Figure F8)
showed pH had no visual impact on lead concentration while the impact of pH on lead leached
from C85400 (Appendix Figure F9) brass was small (10 ug Pb/L) relative to the red brasses. The
major compositional differences between the red and yellow brasses are red brasses contain more
lead but far less zinc. These observations suggest that the dissolution of lead from brass was not
solubility controlled, otherwise lead levels would be higher at pH 7.0 due to higher lead solubility.

The differences between the amount of lead leached from C36000 (Appendix Figure F4)
at pH 7.0 and 8.5 fell between differences observed with yellow and red brasses. Lowering the
PH to 7.0 increased lead levels significantly (by approximately 30 4g Pb/L) but not to the degree
observed with the red brasses. Free-cutting brass contains the most zinc of all the brasses tested
and contains less lead than the red brasses and more lead than the yellow brasses.

Copper leaching levels were significantly higher at the lower pH for all brasses except
36000 brass. The difference was greater amongst the red brasses, and (Appendix Figures F11
to F15) with copper levels being more than 1.5 mg/L higher at pH 7.0. The difference between
copper leached from the coupons at pH 8.5 and 7.0 appeared to widen as the percentage of copper
in the alloy increased. Free-cutting brass leached the least copper and the differences between
copper leached at pH 7.0 and 8.5 was insignificant.

Zinc leaching levels were significantly higher at the lower pH for all brasses. As with
copper, the difference between zinc leached at pH 8.5 and 7.0 appeared to increase (Appendix
Figures F16 to F20) as the percentage of zinc in the alloy increased. The largest difference was
seen with the free-cutting brass (which contained the most zinc) and the smallest difference was
red brass C83600 which contained the least zinc.

23



T T
Test run 1
Test run 2
Test run 3
Test run 4
Test run 5

LL To Py TL Wy ge

n n L L 1 1 L

20 40 60 80 100 120 140

Time, days

Figure A-1. pH variation of test waters during each test run



r T
1400 ° pH
1200 | |
1000 J

800 | 4

Lead, pg/L

600

400

200

0 20 40 60 80 100 120 140 160
Time, days

Figure A-24. 60:40 Sn:Pb Solder

171



LIST OF FIGURES (continued)

Number

A-l,

pH variation of test waters during each test run

Free chlorine variation of test waters during each test run
Ortho-phosphate concentrations during test runs 3, 4, and 5
Lead leached from brass C36000 at pH 8.5 and 7.0

Lead leached from brass C83600 at pH 8.5 and 7.0

Lead leached from brass C84400 at pH 8.5 and 7.0

Lead leached from brass C84500 at pH 8.5 and 7.0

Lead leached from brass C85200 at pH 8.5 and 7.0

Lead leached from brass C85400 at pH 8.5 and 7.0
Copper leached from brass C36000 at pH 8.5 and 7.0
Copper leached from brass C83600 at pH 8.5 and 7.0

. Copper leached from brass C84400 at pH 8.5 and 7.0
. Copper leached from brass C84500 at pH 8.5 and 7.0
. Copper leached from brass C85200 at pH 8.5 and 7.0
. Copper leached from brass C85400 at pH 8.5 and 7.0
. Zinc leached from brass C36000 at pH 8.5 and 7.0

. Zinc leached from brass C83600 at pH 8.5 and 7.0

. Zinc leached from brass C84400 at pH 8.5 and 7.0

. Zinc leached from brass C84500 at pH 8.5 and 7.0

. Zinc leached from brass C85200 at pH 8.5 and 7.0

. Lead leached from 60:40 Sn:Pb solder at pH 8.5 and 7.0
. Lead leached from pure lead at pH 8.5 and 7.0

. Copper leached from pure copper at pH 8.5 and 7.0

. Zinc leached from pure zinc at pH 8.5 and 7.0

Page

148
149
150
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171



‘Table A-30, ‘Run 5: Cincinnati tap water, pH=7.5, 72 hour stand time

Study=Coupon
Analyte=Zn

Date __Time, days C36000_C36000_C83600_C84400_C84500_C85200_C85400_ Copper Pure Pb Pure Pb Pure Zn Pb/Sn

08/16/93 6 168 152 032 099 195 143 139 0.01 001 001 616 0.01
08/23/93 13° «1.76 «(0.81 «60.43 O81 1.67 2.31237 001s «01s s1.48— (0.01
08/30/93 20 163 065 040 080 129 227 244 001 001 001 064 0.01
09/07/93 28 0.67 «041 0.29 058 0.76 124 172 001 001 001 046 0.01
09/14/93 35° 106 036 025 059 068 099 199 0.01 001 001 078 0.01
09/20/93 41 104 030 020 049 054 080 171 0.01 001 001 072 0.01
10/04/93 55 155 030 018 065 047 091 “167 001 001 001 134 0.01
10/18/93 69 178 0.29 0.17 061 039 106 162 002 0.01 0.01 162 0.01
10/25/93 76 175 019 012 040 023 075 099 002 0.04 002 125 0.01
11/01/93 83 190 022 014 047 024 0.93 114 0.02 002 002 147 0.02
11/08/93 90 173 016 0.10 033 016 063 077 002 001 002 127 0.02
11/15/93 97 211 031 O15 O51 023 101 123 002 001 O01 171 0.01
11/22/93 104 150 0.13 008 027 O11 050 048 0.01 001 001 129 001
12/06/93 1182.12 0.16 «0.10 0.33 0.12 -0.58-—0.68-Ss«002-s«O01s—s«iss.71—S(0.
12/13/93 125° 219 0.21 013 039 016 0.73 083 0.02 001 002 161 0.01
12/20/93 132. «1.75 (0.18 - 033° 0.13 0.60 0.66 0.02 001 001 168--
LOWER pH to 6.5

01/31/94 174 7.90 055 034 100 041 197 430 002 001 001 682 0.03
ADD PHOSPHATES3.0 mg/L

02/14/94 188 426 0.28 009 0.28 018 087 196 001 001 001 562 0.01
02/22/94 196 655 046 012 038 0.21 170 337 0.02 0.00 000 644 0.01

131



139

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Table A-39. Quality control table showing duplicate sample analysis differences over the entire study period.

Difference, mg/L Difference, mg/L
Analyte __Method* ‘Max. Mean Std Dev Range, mg/L. Analyte Method N_~ Min _Max,__Mean Std Dev _ Range, mg/L.
Al ICAP 15 0.0010 0.0141 0.0052 0.0036 —_0.010-0.100 Na AAS 15 0.0000 1.4408 0.4702 0.4304 10,00-100.0
Al ICAP 10 0.0002 0.0140 0.0069 0.0050 _0.100-1.000 Na ICAP 25 0.0360 1.4613 0.3420 0.3399 10,00-100.0
Ca AAS 15 0.0000 2.8754 0.5201 0.7728 ~—_10,00-100.0 NO; ALPKEMAA —- 3. 0,0000 0.0100 0.0033 0.0058 —_0.001-0.010
Ca IcaP 25 0.0186 0.7754 0.2735 0.1915 10.00-100.0 NO, ALPKEMAA = 210,000 0.0600 0.0124 0.0161 —_0.100-1.000
NO, ALPKEMAA = 17 (0,0000 0.1400 0.0506 0.0448 ~—_1.000-10.00
Cl TITRATION ~—1-—(0,8000 0.8000 0.8000 1.000-10.00
Ci TITRATION — 11. 0.0000 3.0400 0.5982 0.9516 —_10,00-100.0 Pb AAS 395 0.0000 0.0058 0.0003 0.0005 _0,001-0.010
Pb AAS 228 0.0000 0.0138 0.0009 0.0015 0.010-0.100
cu AAS 93 0.0000 0.0931 0.0070 0.0130 0,001-0.010 Pb ‘AAS 250 0.0000 0.0542 0.0056 0.0083 _0,100-1.000
Cu AAS $1 0,0000 0.0600 0.0088 0.0129 —_0.010-0.100 Pb AAS 12 0.0077 0.1706 0.0555 0.0625 —_1.000-10.00
cu ‘AAS 84 0.0000 0.5121 0.0182 0.0594 0,100-1.000 Pb ICAP 9 0,0006 0.0140 0.0048 0.0043 0,001-0.010
cu AAS 46 0.0000 1.0061 0.1442 0.2553 1,000-10.00 Pb ICAP 8 0.0006 0.0202 0.0115 0.0055 0.010-0.100
Ca IcaP 10 0.0000 0.0011 0.0003 0.0004 —_0.001-0.010 Pb ICAP 8 0.0038 0.0239 0.0102 0.0070 —_0.100-1.000,
cu ICAP 30,0008 0.0011 6.0009 0.0002 0.010-0.100
cu IcaP 11 0.0007 0.0111 0.0044 0.0034 0.100-1.000 - ~~ PO, + ALPKEMAA —.2-_0,0000 0.0000 0.0000 0.0000 0.001-0.010
cu ICAP 10,0080 0.0080 0.0080 1,000-10.00 PO, ALPKEMAA — 30.0000 0.0000 0.0000 0.0000 —_0.010-0.100
PO, ALPKEMAA — 10.0000 0,000 0.0000 1.000-10.00
F 1 0.0080 0.0080 0.0080 0.100-1.000 PO, TECHNICON AA 7 0.0000 0.0100 0.0014 0.0038 —_0.001-0.010
PO, TECHNICON AA 10 0.0000 0.0100 0.0020 0.0042 0,010-0.100
5 Fe AAS 141 0.0000 4.1330 0.0674 0.3523 0,001-0.010 PO, TECHNICON AA 5 0.0000 0.0000 0.0000 0.0000 —_0.100-1.000
u“ Fe AAS 81 0.0000 0.4320 0.0402 0.0673 0,010-0.100 PO, TECHNICONAA 5 0.0000 0.5500 0.2380 0.2319 —_‘1.000-10.00
Fe AAS 18 0.0120 0.5016 0.1378 0.1316 0.100-1.000
Fe ICAP 14 0.0000 0.0047 0,0013 0.0014 —_0,001-0.010 8 ICAP 25 0.0004 0.2964 0.0949 0.0816 —_10.00-100.0
Fe ICAP 10 0.0000 0.0038 0.0011 0.0011 0.010-0.100 SO, UTOANALYZE 9 0.0000 4.9000 1.0071 1.5659 —_10.00-100.0
Fe IcaP 1 0.0008 0.0008 0.0008 0.100-1.000 SO, UTOANALYZE 1 29,860 29.860 29.860 >100
K AAS 30,0009 0.0028 0.0016 0.0010 0.010-0.100 SI ICAP 25 0.0346 0.0154 0.0102 —_1.000-10.00
K AAS 29 0,000 0.2144 0.0473 0.0601 —_1.000-10.00 SiO, ALPKEMAA = 27 0.8200 0.1107 0.1845 1,000-10.00
K ICAP 20 0.0077 0.8398 0.2800 0.2262 —_1,000-10.00
TALK TECHNICON AA 12 0.0383 0.3427 0.1758 0.1024 —_10.00-100.0
Mg AAS 10 0.0000 0.6054 0.1490 0.2285 —_1.000-10.00
Mg AAS 5 0.0098 0.0607 0.0282 0.0198 —_10.00-100.0 TIC COULOMETRY 9 0.0600 1.0000 0.2389 0.2919 —_10,00-100.0
Mg IcaP 20 0.0065 0.1831 0.0842 0.0598 —_1,000-10.00
Mg ICAP 5 0.0090 0.0821 0.0373 0.0345 —10.00-100.0 Zn AAS 90 0.0000 0.0561 0.0048 0.0086 —_0,001-0.010
Zn AAS. 28 0.0001 0.0224 0.0053 0.0056 0.010-0.100
Ma AAS 90 0.0000 0.0650 0.0066 0.0124 —_0,001-0.010 Zn AAS 65 0.0000 0.1880 0.0110 0.0274 0,100-1.000
Mn AAS 6 0.0000 0.0324 0.0113 0.0123 0.010-0.100 Zn AAS 70 0.0000 2.5939 0.0698 0.3091 —_1.000-10.00
Mn TcaP 25 0.0000 0,0005 0.0001 0.0001 —_0.001-0.010 Za ICAP 9 0.0000 0.0017 0.0006 0.0006 —_0,001-0.010
Zn ICAP 6 0.0000 0.0033 0.0008 0.0013 0.010-0.100
Zn ICAP 6 0.0001 0.0019 0.0008 0.0008 —_0.100-1.000
Zn ICAP 4 0.0133 0.0181 0.0155 0.0020 1,000-10.00
¥ Methodologies detailed in Table 3

AAS. atomic absorption spectrophotometer
AA; autoanalyzer



68. Schock, M. R. Treatment or Water Quality Adjustment to Attain MCL's in Metallic
Potable Water Plumbing Systems. Plumbing Materials and Drinking Water Quality:
Proceedings of a Seminar, Cincinnati, OH, May 16-17, 1984, (1985).



LIST OF FIGURES (continued)

Number

25.
26.
27.
28.
29.

30.
31.

32,
33.
34,
35.
36.
37.
38.
39.
40.
41.
42.
43.
44,
45.

46.
47.

Effect of phosphate on zinc leached from C83600 (red brass) coupon at pH
75.

Effect of phosphate on zinc leached from C84400 (red brass) coupon at pH
75.

Effect of phosphate on zinc leached from C84500 (red brass) coupon at pH
75.

Effect of phosphate on zinc leached from C85200 (yellow brass) coupon at
pH 7.5.

Effect of phosphate on zinc leached from C85400 (yellow brass) coupon at
pH 7.5.

Effect of phosphate on zinc leached from pure zinc coupon at pH 7.5.

Influence of stagnation time on lead leached from a red and yellow brass
coupon during test run 2: pH=7.0.

Influence of stagnation time on lead leached from a red and yellow brass
coupon during test run 1: pH=8.5.

Influence of stagnation time on lead leached from pure lead coupons during
test run 2: pH=7.0.

Influence of stagnation time on copper leached from a red and yellow brass
coupon during test run 2: pH=7.0.

Influence of stagnation time on copper leached from pure copper coupons
during test run 2: pH=7.0.

Influence of stagnation time on zinc leached from a red and yellow brass
coupon during test run 2: pH=7.0.

Influence of stagnation time on zinc leached from pure zinc coupons during
test run 2: pH=7.0.

Influence of stagnation time on zinc leached from a red and yellow brass,
and pure zinc coupons during test run 2: pH=7.0.

Influence of stagnation time on zinc leached from a red and yellow brass
coupon during test run 1: pH=8.5.

Lead stagnation profile for yellow brass C85200.

Lead stagnation profile for red brass C84400.

Copper stagnation profile for yellow brass C85200.

Copper stagnation profile for red brass C84400.

Zinc stagnation profile for yellow brass C85200.

Zinc stagnation profile for red brass C84400.

Lead leached from "lead-free" brass during test run 5: pH=7.5.

Comparison of theoretical and observed copper levels for all test runs.



predominant. The exposure time required to receive the greatest lead exposure from brass
depends on the alloy composition and water quality. In "corrosive" water and with red brasses,
highest lead levels may not be obtained until beyond 15 hours of stagnation. Lead and Copper
Rule requires at least 6 hours standing time, which does not necessarily represent the worst case
scenario. In addition poor metal level reproducibility in samples taken from the same location
could be attributed to differences in stagnation time.

It is important to stress that the conclusions of this study were based on tightly managed
laboratory experiments with identically machined coupons in several closely controlled waters
using consistent, reproducible operating procedures. Extrapolation of the results to field
conditions where alloys are subjected to the distribution system should be done with some caution.
For example, brass faucets encounter mechanical operation which may effect metal levels by
influencing leaching trends or physically dislodging protective films. Physical features of alloy
fixtures are also likely to play a role in the degree which metals leach from them in the
distribution system. While results of this study suggest that reducing the amount of lead in a brass
faucet or other plumbing fixture or valve will reduce the lead levels at the tap, the significance
of the reduction will likely depend on the role of these other parameters.

FUTURE NEEDS

More research is needed on exploring the degree variables other than metal solubility
influence the metals leached from alloys. Specifically, the variables that should be studied are:

alloy machining and finishing techniques; faucet structure; water flow pattern, velocity, and
pressure through faucet structures; mechanical operation; fixture age; and stagnation time. Kinetic
issues related to the impact of oxidants (type and concentration) on metal dissolution rates also
needs to be further addressed. This study focused on the impact of 24- and 72-hour stand times
on metal levels, but more work at lower stand times would be more relevant to home occurrence
of metals in tap water samples and the Lead and Copper Rule monitoring program.



Table A-12, Run 2: Cincinnati tap water, pH=7.0, 24 hour stand time

Study=Coupon
Analyte=Zn

Date __ Time, days C36000 C36000_C83600_C84400_C84500_C85200_C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

05/19/92 85 3.81 3.70 010 037 0.45 165 2.78 -0.03 O01 -005 4.44 -0.04
05/21/92 87 421 468 O11 045 0.61 151 2.81 -0.05 -0.06 -004 5.41 -0.05
05/27/92 93 421 420 012 043 051 179 3.01 -005 -0.06 -0.06 4.89 -0.04
05/29/92 95 369 387 012 040 049 217 245 -0.03 -0.04 -0.04 455  -0.03
06/03/92 100 478 5.06 012 047 O58 153 287 -0.07 -0.07 -0.07 636 -0.05
06/04/92 3.78 3.84 009 039 O48 120 243 -0.04 -0.03 -0.05 4.73 -0.04
06/09/92 417 389 O11 040 046 145 254 -0.04 -0.04 -0.04 452 -0.04
06/11/92 3.75 3.79 009 037 044 117 2418 -0.03 -0.03 -003 4.46 -0.04
06/16/92 490 539 O11 040 0.49 2.80 -0.05 -0.03 -0.04 5.62 -0.04
06/17/92 3.91 448 010 038 050 189 234 -0.05 -0.04 -0.04 5.08 -0.04
013 «4.03 «041 039 050 1.36 2.27 0.09 -0.03 -0.02 4.70 -0.03
450 422 010 O41 047 144 255 -0.06 -0.05 -0.05 538 -0.04
3.62 3.56 0.07 112 2.00 -0.04 -0.06 -0.06 4.73 -0.06
4.02 3.76 009 048 056 113 219 -0.05 -0.06 -0.03 5.29 -0.05
425 3.91 010 037 0.44 131 245 -0.02 -0.05 -0.05 5.13  -0.02
07/01/92 3.60 3.57 0.10 036 0.43 113 039 -002 0.01 000 5.04 -0.02
07/02/92 3.59 3.25 010 036 042 1.00 1.81 -0.01 -0.00 000 4.46 -0.03
07/07/92 3.55 3.25 010 038 0.43 112 2.006 -0.01 0.00 0.01 4.25 -0.01
07/08/92 355 3.25 012 038 0.43 1.00 1.74 0.00 -0.00 -001 545 -0.04
07/09/92 4.06
07/14/92 4.25 0.13 047 #052 132 2.44 -0.02 -0.00 -0.00 5.03 0.03
07/15/92 4.08 0.12 0.42 048 1.03 1.66 0.01 001 000 462 0.01
07/16/92 0.85 0.13 0.42 047 108 1.79  -0.03 -0.00 5.18 0.00
07/21/92 4.47 0.14 047 0.61 127 194 001 001 001 5.06 0.01
07/22/92 434 0.12 O41 046 1.05 161 -0.03 0.00 0.00 4.77 0.01
07/23/92 3.95 0.12 040 048 1.07 1.60 -0.01 -~ 0.00 4.44 0.00
07/28/92 5.14 0.15 047 0.65 132 248 -002 001 O01 481 0.01
07/29/92 458 0.16 046 O48 1.29 1.77 - 0.01 O01 5.06 0.01



sample holding cell, and tubing made of Teflon®. The holding cell was sized to tightly hold one
1"x2"x1/8" metal coupon® in order to maximize the ratio of coupon surface area to volume of
water in contact with the coupon. The coupon surface area was 4.75 in? and the volume of water
was 26 mL, resulting in a surface area to volume ratio of 0.18 in’?/mL. Figure 1 isa photograph
of the test system and Figure 2 is a schematic of an individual test loop.

Coupon material

Six differently composed brass coupons, plus, a pure copper, pure zinc, pure lead, and
60:40 Sn:Pb solder coupon were simultaneously tested. One brass and the lead coupon were
tested in duplicate to evaluate material and procedural variability. The brass coupon compositions
are given in Table 2. The brasses used were chosen because they represent common materials
used to manufacture brass faucets and other fixtures used in drinking water systems. Several
coupon finishes were available from the coupon supplier: 120 grit, milled, and glass bead finishes.
The 120-grit finished coupons were chosen for this study because it was the finest finish available
and was presumed to give the most consistent coupon surface.

The compositions of the brass coupons were reported by the coupon manufacturer as
percentage ranges. In many cases, relatively wide composition ranges, such as those given for
lead, overlapped among different brasses. The nature of the study, however, required more
definitive metal coupon compositions.

For the purposes of this study, the chemical composition of the coupons was assumed to
be relatively uniform for the batch, and throughout each coupon. Subsamples consisting of
approximately 0.1 grams of material cut from the corners of unused coupons from the same batch
were used for the chemical analysis. Microwave digestion procedures were used to digest pieces
of the lead coupons”, Sn:Pb solder coupons, and copper, zinc, brass coupons”. The digestates
were analyzed for lead, copper, zinc, iron and tin by flame atomic absorption spectroscopy and
results have been included in Table 2.

Coupon and test system cleaning procedures

Problems with coupon contamination, lead to the development of a thorough coupon pre-
cleaning procedure." The cleaning procedure was, in part, a combination of two American
Society for Testing and Materials (ASTM) coupon wash procedures: designations G31-72° and
D2688-83". The procedure used and recommended for cleaning new metal coupons to be exposed
to static leach testing was as follows:

® Metal Samples, Inc., Munford, AL.



on dezincification and unfortunately in nearly all of those cases metal leaching levels or dissolution
was not addressed. Information pertaining to metal dissolution from brass alloys is typically
general.

Samuels and Méringer” evaluated short-term metal leaching from 8 kitchen faucets in 4
different types of water and aqueous fulvic acid. The study involved measuring metal
concentrations in standing water samples taken from inverted water faucets for two 24-hour stand
periods. Results showed that lead as well as copper, zinc, chromium, and cadmium leached in
varying amounts depending on the type of faucet used and the leach solution.

Nielsen*"? found that lead could be picked up in water from household plumbing fixtures
composed of brass such as water meters and mixer fittings, and main and stop valves composed
of gunmetal (copper alloy containing 5% Pb).

Birden et al.?3 found lead contamination in copper pipe loop systems constructed of no lead
containing parts other than brass compression fittings. Lead leaching was attributed to the lead
in the brass used to make the fittings.

Schock and Neff** obtained data from a 2-year field and laboratory study that implicated
brass valves and fittings as potentially significant sources of lead, copper, and zinc in drinking
water. The field study indicated that'new chrome plated sampling faucets on pipe loops in
galvanized and copper systems were associated with 125 mL water samples that exceeded the lead
maximum contaminant level which was 0.05 mg Pb/L at the time of the study. As a result, they
conducted trace metal leaching experiments on six new sampling taps using an inverted faucet
technique. The tests were performed using deionized and Champaign (Illinois) tap water (3
faucets for each tap water). Samples following 24-hour dwell times were taken every 2 days for
2 weeks. The samples were analyzed for lead, cadmium, zinc, iron, and copper. The faucets
subjected to deionized water leached about 100 mg Pb/L and dropped off rapidly to less than 10
mg Pb/L at the end of the 2 weeks. Faucets subjected to Champaign tap water initially leached
approximately 1 mg Pb/L and dropped to less than 0.3 mg Pb/L at the end of 2 weeks.

Gardels and Sorg® also evaluated metal leaching from faucets. They used a different metal
extraction approach than the fill and dump scenario implemented by the previous investigators.
They mounted 12 different faucets upright to a manifold system connected to a pressure activated
pump and water storage reservoir. In this position, the faucets were operated under pressure in
a similar fashion to how they would be used in a home. Leaching tests were conducted with
deionized and Cincinnati (Ohio) tap waters over a 9 month period. Standing water samples were
taken at a variety of standing times and sampling schemes. Samples were analyzed for lead,
copper, zinc, iron, chromium, and cadmium. Results indicated that lead leached from new cast
brass faucets could contribute lead to drinking water in excess of 10 pg/L. They showed that as
much as 75% of the lead leached from common kitchen faucets could be collected in the first 125
mL of water from the faucet; more than 95% of the lead was collected in the first 200 to 250 mL.



A-10.
A-I1.
A-12.
A-13.
A-14,
A-15.
A-16.
A-17.
A-18.
A-19.
A-20,
A-21,
A-22.
A-23.
A-24,
A-25.
A-26.

LIST OF TABLES

Extraction water used in the Nordtest

Metal composition of test coupons used in leach study
Analytical methods used for chemical analysis of water samples
Test run conditions

Extraction water quality: test run #1

Extraction water quality: test run #2

Extraction water quality: test run #3

Extraction water quality: test run #4

Extraction water quality: test run #5

Lead, Run 1, pH=8.3-8.5, 24-hour stand time

Lead, Run 2, pH=7.0, 24-hour stand time

Lead, Run 3, pH=7.5, 3.0 mg PO,/L, 24-hour stand time
Lead, Run 4, pH=7.5, 0.5 mg PO,/L, 24-hour stand time
Lead, Run 5, pH=7.5, 24-hour stand time

Copper, Run 1, pH=8.3-8.5, 24-hour stand time

Copper, Run 2, pH=7.0, 24-hour stand time

Copper, Run 3, pH=7.5, 3.0 mg PO,/L, 24-hour stand time
Copper, Run 4, pH=7.5, 0.5 mg PO,/L, 24-hour stand time
Copper, Run 5, pH=7.5, 24-hour stand time

Zinc, Run 1, pH=8.3-8.5, 24-hour stand time

Zinc, Run 2, pH=7.0, 24-hour stand time

Zinc, Run 3, pH=7.5, 3.0 mg PO,/L, 24-hour stand time
Zinc, Run 4, pH=7.5, 0.5 mg PO,/L, 24-hour stand time
Zinc, Run 5, pH=7.5, 24-hour stand time

Lead, Run 1, pH=8.3-8.5, 72-hour stand time

Lead, Run 2, pH=7.0, 72-hour stand time

Lead, Run 3, pH=7.5, 3.0 mg PO,/L, 72-hour stand time
Lead, Run 4, pH=7.5, 0.5 mg PO,/L, 72-hour stand time
Lead, Run 5, pH=7.5, 72-hour stand time

Copper, Run 1, pH=8.3-8.5, 72-hour stand time

Copper, Run 2, pH=7.0, 72-hour stand time

Copper, Run 3, pH=7.5, 3.0 mg PO,/L, 72-hour stand time
Copper, Run 4, pH=7.5, 0.5 mg PO,/L, 72-hour stand time
Copper, Run 5, pH=7.5, 72-hour stand time

Zinc, Run 1, pH=8.3-8.5, 72-hour stand time

vii

39
40
41
42
43
43

44

45

93
95
97
98

101
103
105
106
107
109
111
113
114
115
117
118
119
120
121
122
123
124
125
126
127



Table A-23. Run 3: Cincinnati tap water, pH=7.5, 3.0 mg PO4/L, 72 hour stand time

Study=Coupon
Analyte=Cu

Date ___Time, days C36000_C36000_C83600_C84400 C8450 __C85200_C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

08/17/92 7 0.093 0.093 0.285 0.208 0.324 0.170 0.131 0.864 0.011 0.011 -0.046 -0.005
08/24/92 14 0.108 0.078 0.392 0.437 0.497 0.302 0.257 0.751 0.016 0.016 -0.060 0.009
09/31/92 21 0.083 0.083 0.375 0.500 0.500 0.333 0.208 0.833 0.021 0.014 -- 0.007
09/08/92 29 0.077 0.077 0.308 0.397 0.410 0.256 0.179 0.731 0.019 0.019 -- 0.006
09/14/92 35 0.086 0.049 0.318 0.395 0.435 0.283 0.171 0.526 0.010 0.011 0.048 0.012



Table A-6. Run 1: Cincinnati tap water, pH=8.3-8.5, 24 hour stand time

Study=Coupon,
Analyte=Cu

Date __ Time, days C36000_C36000 C83600_C84400_C8450__C85200_C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

12/18/91 127 ~ 0.010 0.160 0.180 0.170 0.040 0.050 0.210 0.010 0.010 0.010 0.010
12/20/91 129 0.020 0.020 0.260 0.270 0.270 0.040 0.080 0.320 -- 0.010 0.010 0.002
12/22/91 131 0.010 0.010 0.170 0.190 0.160 0.020 0.060 0.180 -0.004 0.004 0.005 --

01/02/92 142 -0.020 -0.020 0.190 0.200 0.180 0.010 0.040 0.260 -0.020 -0.030 -0.020 -0.020
01/03/92 143 -0.030 -0.030 0.180 0.200 0.190 0.002 0.020 0.260 -0.005 -0.010 -0.020 -0.020

102



800 r T T T T T T

° 3.0 mg PO,/L |
700 ¢ 0.5 mg PO,/L 7
2 0.0 mg PO,/L
600 7
500 7
a
= 4
3 400 [ |
Oo
300 + 1
200 + Ww |
100 Hawk oo
r¢) 4 1 i n i 1 L i 4 1 4
0 20 40 60 80 100 120 140

Elapsed Time, days

Figure 16. Effect of phosphate on lead leached from
60:40 Sn:Pb solder coupon at pH 7.5.

61



distributed, The Kruskal-Wallace one way ANOVA test on ranks was used to demonstrate
differences in leaching trends.** All statistical calculations were made using SigmastatTM® (version
1.0) statistical software. Detailed and understandable statistical procedure descriptions can be
found in S.A. Glantz's Primer of Biostatistics®* and W.W. Daniel's Biostatistics: A Foundation
for Analysis in the Health Sciences’ or any other acceptable statistical reference.

Data outliers (data points that fell well beyond the majority of set measurements and
reasonable expectations) were occasionally encountered. The first approach used to treat data
outliers was to look for an assignable cause (e.g., a misidentified sample bottle or a leaking
coupon holder cell). Quality assurance data from analytical test runs, laboratory log books, and
bottle labels were examined for errors and documented problems. Where an explanation for a
suspected outlier could not be found, the data was tested statistically according to the United States
Department of Commerce National Bureau of Standards® for the case where the population mean
and standard deviation are known at a confidence level of 90% (P=0.10). Identified outliers were
recorded, however, were not included in statistical analysis and graphical representations.

RESULTS

Table 4 is a summary of the general water quality conditions and time periods of each "test
run" of the study for future reference. Test runs were continued until metal leaching “trends”
visually "leveled-off" or their slopes approached zero. The terminology “metal leaching trends”
is used in this report to describe the curve of metal concentration leached from a coupon over a
time frame (study period). Unless otherwise noted, the following results refer to samples collected
following approximately 22- to 24-hour stagnation times. Raw metal analysis and extraction water
quality data is compiled for all test runs in Appendix Tables 1 to 35. Values less than analytical
detection limits including negative numbers are presented in the tables. Since those values
represent real instrumental outputs, it has been recommended that they are retained for statistical
calculations. Tables 5a to Se summarize the extraction water qualities used in each test run.

Test run #1
Extraction water quality

Non-chemically adjusted Cincinnati tap water was used in test run 1. Asa result, larger
than desired pH fluctuations (0.18 pH units standard deviation) were observed throughout the test
run. The solubility of copper, in particular, is strongly impacted by pH® and even small pH
fluctuations (0.1 pH units) have been shown to considerably influence copper solubility.*' The
mean sulfate concentration (116.3 mg SO,/L) was higher during this test run than in others.
ResearchersTM*! have suggested that sulfate negatively impacts copper corrosion at pH values above
approximately 7.5 and may be beneficial at lower pHs in new systems. The mechanism(s),

© Jandel Scientific, San Rafael, CA.



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brasses, lead, copper, zinc, and 60:40 Sn:Pb solder was examined. Finally, metals leached from
a "lead-free" brass were briefly explored.

The experiments were conducted using standard 1"x2"x1/8" metal coupons and a "fill-and-
dump" test protocol in chemical variations of Cincinnati tap water. Conclusions were based on
graphical and statistical data interpretations.

BACKGROUND

A growing public awareness about the toxicity of lead has brought about the question of
the contribution of lead by leaded brass plumbing fixtures and faucets to drinking water. A recent
preliminary lead and copper rule survey’ of 46 large systems and 7 medium and small systems
conducted by the Association of Metropolitan Water Agencies stated: “By far the major reason
is or is suspected to be lead leaching from new (newer) faucets and fixtures.", referring to
reported causes of high lead values in drinking water samples. As the public grows more familiar
with the issues concerning safe drinking water, pressure on legislators to reduce or even ban the
use of lead (and other contaminants) in plumbing products may grow.

In California, the Natural Resources Defense Council and the Environmental Law
Foundation filed a complaint with the California Superior Court on December 15, 1992. The
complaint stated that a number of major faucet manufacturers marketed faucets that leach lead into
the drinking water at levels exceeding the limit of 0.5 ug/L set under the State’s Proposition 65
Standard.* The lawsuit targeted 13 major faucet manufacturers. The case was settled in August
of 1995 when a number of major manufacturers agreed to meet stipulations which included
warning labels and a lead reduction program.”

In a similar situation, the Environmental Defense Fund, Natural Resources Defense
Council, and the California Attorney General recently filed suit under California Proposition 65
against four manufacturers of submersible water pumps.'° Some of these pumps, which are used
to draw water from private wells, are constructed with brass components and, as a result, can
provide a point source of lead contamination.

Brass composition

Brasses are defined as copper alloys that contain zinc (5 to 40% Zn) as the principal
alloying element with or without other alloying elements, such as tin, iron, aluminum, nickel, and
silicon. Brass can be subdivided into three main families: copper-zinc alloys; copper-zinc-tin
alloys (tin brasses); and copper-zinc-lead alloys (leaded brasses)."

Zinc is added to copper to increase tensile strength. The tensile strength of the alloy
increases significantly with increasing zinc concentration up to 20% zinc, whereas further zinc
addition only slightly increases tensile strength. Brasses containing more than 20% zinc are
referred to as “yellow brass,” while brasses containing less than 15% zinc are referred to as “red

2



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Lead leached from brass coupons

Figure 6 shows lead leaching trends from the six brass coupons (and one duplicate C36000
coupon) and duplicate pure lead coupons during this test run. The greatest amounts of lead leached
from the coupons during the first 14 days of the run, with levels dropping off rapidly during this
period. The relative amount of lead leached from the brass during this period was generally
dependent on the amount of lead in the brass. The magnitude of lead leached from the brasses
during the first 14 days differed by as much as 300 g/L among the brasses.

From 14 to approximately 40 days, the lead leaching trends began to level off. During this
period, lead trends aligned themselves in the direction and order they would follow for the
remainder of the study. Alignment appeared haphazard initially, with trends overlapping and
following no distinct pattern. By 40 days, the patterns established a clear position and direction.

From 40 days to the end of the test run, the tendency of the majority of the lead leaching
trends was to slightly decrease. Yellow brass C85200 was the exception in that the decrease was
more apparent. Also, C85400 brass, oddly, exhibited a gradual increasing lead leaching trend
before finally leveling off. C85400 is a yellow brass containing the most zinc but the least lead
of the brasses tested. The most plausible explanation was the theory that zinc dissolution
subsequently lead to the exposure of additional lead surface sites resulting in increased corrosion
rates °, However, for this theory to hold, similar observations should be observed with similarly
composed brasses which was not the case for C85200 brass.

A distinct set of trend groups like those observed in test run 1 did not develop during this
test run. In some cases, lead concentrations observed at the end of this test run were one order
of magnitude greater than levels observed for the same coupon during the test run 1. By the end
study, trends tended to be evenly separated by roughly 10 to 50 ug/L. The percentage of lead
leached from brass was directly related to the amount of lead in the alloy (i.e., the more lead in
the alloy the more lead leached from the brass). As was the case in test run 1, the pure lead
coupons leached more lead than any of the brasses.

Statistical comparisons of the leaching trends made over the entire test run and following
the period after 60 days show that approximately half of the trends are significantly different at
the 95% confidence interval (Appendix Table 36). Trends that are not significantly different are
mostly of the same group or brass type, yellow or red brasses. The duplicate C36000 trends were
significantly different over the entire study and after 60 days were significantly different which
was, in part, probably due to the high lead levels leached from the coupons.

Copper leached from brass coupons

Copper leaching trends differed from lead leaching trends in that copper levels did not start
out extremely high, followed by a rapid drop and gradual leveling off (shown in Figure 7). With
the exception of C36000 brass, the trends gradually increased over the first 60 days of the test run

21



80 100 120 140

Time, days

Figure A-11 Brass Alloy C83600, Red Brass



05 10 2.0 40 60 80 15.0

Standtime, hours

Figure 45. Zinc stagnation profile for red brass
C84400.



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Zinc,mg/L

“0 20 40 60 80 100 120 140 160

Elapsed Time, days
¢ C€84500 (red brass)
» C85400 (yellow brass)
y Pure zinc
——24 hour stagnation
72, hour stagnation

Figure 38. Influence of stagnation time on zinc
leached from a red and yellow brass, and pure
zinc coupons during test run 2: pH=7.0.

83



brass." Zinc is soluble in copper, and when added to copper to produce brass, up to 35% of the
zinc will dissolve to form an alpha solid-solution (alpha brass). When still more zinc is added,
a second or beta, solid-solution is formed. Brasses with 35 to 40% zinc consist of mixtures of
these two solutions and are referred to as alpha-beta or "duplex" brasses. Duplex brasses are
cheaper and easier to fabricate than alpha brasses. However, they are susceptible to
dezincification, a form of corrosion that will be discussed in more detail later in the paper.

Lead is added to brasses to improve machinability of the alloy and make castings pressure
tight by filling the voids created as the casting cools. Lead is insoluble in copper-zinc alloys and
therefore during solidification, lead precipitates and forms a dispersion of second phase particles
or globules both at the grain boundaries and within the matrix. The globules serve to improve the
alloy's machinability by acting as chip breakers, reducing tool clogging and allowing increased
cutting speed.'? Lead is found in brass from 0.1 to 12.0%", however, brasses most commonly
used in household fixtures contain 1.5 to 7.5% Pb'*. The reference standard for machinability is
“free-cutting" or "free-machining" brass, composed of 61.5% Cu, 3% Pb, and 35.5% Zn. This
alloy, designated C36000, is given a reference machinability rating of 100% and is the standard
to which all other brasses are related. Lead offers little effect on corrosion resistance of the alloy.

Tin is added to brass to improve corrosion resistance (particularly impingement or erosion
attack), and increase the tensile strength and hardness of the alloy. In addition, tin significantly
increases the resistance of the alloy to attack by acidic media and the tendency for dezincification.
Admiralty alloy is a tin brass extensively used as condenser tubing. Admiralty brass is made by
adding 1% tin to cartridge brass (70% Cu, 30% Zn). Approximately 3 to 5% tin is often added
to red or semi-red brasses to increase the strength and hardness of the alloys.

'

A variety of other elements may be added in small quantities to enhance properties of the
alloy. For example, arsenic, antimony, and phosphorous are added to certain brasses to inhibit
dezincification. Aluminum is added to provide corrosion resistance and color enhancement and
nickel is added as a whitening agent.

Brass production procedures

Brass plumbing fixtures and faucets are most commonly formed by either cast or wrought
Processes. Cast brass products are made by pouring melted alloy (ingot, virgin metal, or scrap)
into a mold and allowing it to cool. Castings offer corrosion resistance, high thermal and
electrical conductivities, and good wear qualities. Casting permits the production of irregular and
complex internal and external shapes, such as those often seen in faucets. The production of these
products may not be practical by forming or machining processes. The major market for cast
products in the United States in 1991 was plumbing and heating; 108 million pounds and 26% of
the market.'° The dominant cast alloys were identified as C84400 (75%) and C83800/C84800
(25%).



sd
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10 2.00 40 60 8.0 15.0

Standtime, hours

Figure 44. Zinc stagnation profile for yellow brass
C85200.



Table A-1. Run 1: Cincinnati tap water, pH=8.3-8.5, 24 hour stand time

Study=Coupon
Analyte=Pb

Date Time, days _C36000_C36000 _C83600 C84400_C84500_C85200_C85400_Copper Pure Pb Pure Pb Pure Zn

11/13/91 92 6.0 58 35.3 554 45.9. 23.7 TA 13 2005 201.5 0.7
11/20/91 99 74 58 385 570 523 261 83 0.8 219.4 217.5 -0.0
11/22/91 5.1 41 312 482 43.5 18.5 5.1 0.2 783 78.7 -0.0
11/27/91 8.5 70 42.7 488 45.1 19.1 7.2 3.0 198.6 2011 27
12/04/91 76 62 41.3 62.7 57.0 225 85 2.7 257.5 244.4 2.6
12/06/91 83 70 369 S11 460 20.6 8.6 3.2 182.1 205.8 3.4
12/08/91 11.2 8.0 480 69.2 59.9 30.5 2.5 229.3 316.8 25
12/11/91 8.7 90 363 51.8 46.9 20.2 8.7 2.7 222.0 252.6 29
12/18/91 7A 61 29.5 31.6 29.2 208 8.0 3.1 195.1 191.6 3.3
12/20/91 85 70 318 356 342 20.6 V7 2.7 194.6 218.2 24
12/22/91 82 67 244 313 , 289 241 8.4 24 211.0 233,5 24
01/06/92 81 23.8 32.7 30.8 28.6 8.8 2.1 251.0 262.1 2.0



Table A-11. Run 1: Cincinnati tap water, pH=8.3-8.5, 24 hour stand time

Study=Coupon
Analyte=Zn

Date ___ Time, days C36000_C36000_C83600_C84400 C84500 C85200_C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

11/20/91 99 023 024 004 O11 O14 O17 0.19 O01 O01 002 016 0.02
11/22/91 017 4016 0.04 007 009 O12 O13 O01 001 O01 013 0.01
11/27/91 106 «600.25 «0.22 0.05 0.10 0.14014 0.16 S001 0.01001 0.18001
12/04/91 033° 031 006 O15 O18 018 020 001 O01 O01 0.24 0.01
12/06/91 025 0.22 005 O10 O11 O14 O17 O01 001 0.03 0.20 0.01
12/11/91 0.60 057 012 0.24 028 027 037 0.02 001 O01 041 0.02
12/18/91 0.21 0.22 005 008 009 015 019 0.01 - 0.02 0.22 0.02
12/20/91 039 039 0.09 016 O19 023 029 0. 0.02 O01 031 0.02
12/22/91 0.28 0.27 003 010 009 019 0.25 0.01 001 0,19 --

01/02/92 033 033 006 014 014 0.25 0.32 0.01 001 0.16 0.02
01/03/92 034 032 006 014 016 O21 0.24 0.02 002 020 0.04



400

350
300
250

200

Lead, pg/L

150

100

50

Elapsed Time, days

Figure 12. Effect of phosphate on lead leached from
C84500 (red brass) coupon at pH 7.5.

57



1.00 T T T_ T 7 T T T

[ © 3.0mg PO,/L |
0.90 L © 0.5 mg PO,/L
0.80 2 0.0 mg PO,/L |

Copper, mg/L

0 20 40 60 80 100 120 140
Elapsed Time, days

Figure 18. Effect of phosphate on copper leached from
C83600 (red brass) coupon at pH 7.5.

63



that the dissolution of lead increased with the percentage of lead for all of the alloys tested with
the exception of yellow brasses. They found that temperature generally had little effect on
increasing the amount of lead leached from the alloys, but may have slightly reduced the lead at
higher temperature. They also found that lead leached from the brass alloys decreased by a factor
of 2 to 200 times over 14 days of testing.

Jones** used electrochemical polarization methods to study the galvanic corrosion of steel
coupled to brass. He found that alloy composition (copper and zinc) was important in determining
the anode and cathode. When the copper-zinc alloy contained more than 40% copper, the alloy
behaved electrochemically like pure copper in that the alloy acted as the cathode. But when the
copper content fell below the critical value of 40%, the alloy behaved as pure zinc, acting as a
sacrificial anode when coupled with steel.

The internal structure of brass products contribute to metal dissolution concentrations and
rates. Faucets, for example, are relatively complex in that bends, angles, and touching metal
components are often incorporated in their design. These areas represent locations for erosion
corrosion. Faucets and valves are also subject to physical wear associated with opening and
closing valves, which may increase metal levels by causing increased fresh surface exposure or
by contributing occasional particulate contamination.

Lead release assessment from alloys in drinking water

Several countries have developed metal extraction tests to evaluate the metal release from
alloy plumbing materials in contact with drinking water. Mattsson and Eistrat® have presented
a European summary of metal extraction tests for some materials used in drinking water plumbing
systems. The "Nordtest" was the first, and probably most recognized, method used for assessing
the potential for lead, cadmium, and other metal release by materials used in drinking water
systems.?! The Nordtest method has been adopted by Scandinavian countries.

The Nordtest procedure is basically carried out as follows: The test specimen (e.g. fitting,
valve, or pipe) is degreased with methanol. Flowing tap water is then rinsed through the specimen
for one hour. Next, the outlets of the sample are capped with polyethylene plugs and the
specimen is filled with synthetic test water (composition shown in Table 1). The test water is
replaced 7 times over a 10-day test period (at 1, 2, 3, 4, 7, 8, 9, and 10 days). Water samples
are taken on the 9" and 10" days and analyzed for lead, cadmium, and other metal pick-up.
Noting the sample volumes and metal concentrations over the 2-day sample period, the metals
extracted from the specimen are calculated. The obtained values are believed to be representative
of maximum metal pick-up in a first draw sample in home installations and can therefore be
related to accepted drinking water standards.

The British Standard Institution (BSI) has also established set procedures and requirements
for the suitability of materials used in contact with drinking water.” The test procedure is similar
to the Nordtest, but differs in the comparison against test limits. The BSI method uses separate

8



20 40 60 80 100 120 140 160

Time, days

Figure A-5. Brass Alloy C83600, Red Brass



200 T 7 T T

150 |r 7

Elapsed Time, days

Figure 46. Lead leached from "lead-free" brass during
test run 5: pH=7.5.

91



During the first three test runs, the Nalgene® tank was filled with approximately 30 gallons
of Cincinnati tap water. Water pH was chemically adjusted, if necessary, by adding 6 N HCl or
8N NaOH. The tank recirculation pump was in continuous operation during the make-up of the
feed water to assure complete mixing and dispersement of chemical additives. In the last two test
tuns, the water was determined to be stable enough (i.e., did not significantly change chemically)
that the storage tank was filled to 80 gallons and that water was used over the following several
days. The free chlorine residual and pH was checked daily and chemically adjusted as necessary
to meet standards. Free chlorine residual was maintained by adding sodium hypochlorite solution
(4 to 6% available chlorine).

After the water was prepared, all valves in the loops were opened to the waste drain. The
feed pump was activated. Test water was flushed through the loops simultaneously at a flow rate
of approximately 0.15 L/min for a brief rinse period of 5 to 10 minutes for total flow of
approximately 10 gallons. The valves in the loops were then closed, holding the water in the cells
in contact with the metal coupons. The water was held in the cells for approximately 22 to 24
hours during weekdays (Monday thru Friday) and 72 hours over weekends (Friday thru Monday).
Next, the cells were sampled by opening the labcock above the cell to the air and then opening
the 3-way Teflon® stopcock below the cell while simultaneously holding a 60 mL Nalgene®
HDPE sample bottle below the stopcock sample port. Air admitted through the top stopcock,
allowed the leach water to drain by gravity into the sample bottle. The total sample volume was
only about 26 mL, most of which was contained in the Teflon® sample cell. The valves were then
closed and newly prepared source water was again flushed through the cells, as mentioned,
repeating the procedure. Initially, sampling from the cells was conducted daily. After several
weeks of operation, sampling was reduced to 3 times per week (two 24-hour samples and one 72-
hour sample). Water was flushed through the cells daily (Monday to Friday), even when sampling
was not done. Air was in contact with the metal coupons for a short period of time; however, the
coupon surface was not exposed long enough to completely dry.

Test runs were generally terminated after approximately 150 days. Termination was based
on apparent stabilization of metal leaching levels. At the end of each test run, the coupons were
removed from the cells, the system was cleaned as previously described, new coupons were
installed, and the study was repeated with a different extraction water.

Sampling

Water samples taken in 60 mL bottles from the sample cells, as mentioned, were preserved
in 0.15% ultrapure HNO, and analyzed for lead, copper, zinc, iron, and tin. Free chlorine, total
chlorine, and pH were measured daily and dissolved oxygen was measured weekly in the tank feed
water. These parameters were measured immediately, prior to fresh water being fed to the loops.
Additionally, three feed water samples were taken: a 250 mL 0.15% HNO, preserved sample for
background metal analysis (Ca, Cu, Fe, K, Mg, Mn, Na, Pb, and Zn); a 250 mL sample for
background wet chemistry analysis (alkalinity, Cl, NH;, NO;, PO,, SiO,, and SO,); and a 30 mL
sample for total inorganic carbon (TIC) analysis. All sample bottles, with the exception of the

13



Table 4. Test run conditions

Test Run #_ Date

Conditions

8/14/91-1/6/92
2/25/92-7/29/92
8/11/92-12/17/92

2/18/93-6/24/93

8/11/93-2/25/94

Cincinnati tap water; no chemical adjustment

Cincinnati tap water; adjusted to pH of 7.0 with 6 N HCl
Cincinnati tap water; adjusted to pH of 7.5 with 6 N HCl
and PO,” adjusted to 3.0 mg/L* with sodium phosphate
Cincinnati tap water; adjusted to pH of 7.5 with 6 N HCl
and PO,? adjusted to 0.5 mg/L* with sodium phosphate
Cincinnati tap water; adjusted to pH of 7.5 with 6 N HCl



Copper, mg/L

1.0 T T

0.9 #1

T

0.5
0.4 F
0.3 L
0.2 L
0.1 L
0.0 [

05 1.0

2.0 40 60 8.0 -15.0

Standtime, hours

Figure 42, Copper stagnation profile for yellow

brass C85200.

87



60.40 tin:lead solder coupons

Solder coupons exhibited unexpected leaching trend results (Appendix Figure F24).
Initially, over the first week of the study, the coupon exposed to the PH 7.0 test water leached the
most lead. The lead levels dropped off rapidly, then leveled off and stabilized after about 70
days. High levels were also observed initially with the pH 8.5 test water, however, not to the
degree observed with the pH 7.0 water.

Impact of orthophosphate on the metal leached from coupons

Extraction water quality

Tables Sc to Se summarize the quality of extraction water used in test runs 3, 4, and 5.
With the exception of sulfate in run 5 and phosphate, water qualities were generally similar in
composition. The pH was tightly maintained at 7.5 because orthophosphate is most effective at
reducing lead solubility in a pH range of approximately 7.3 to 7.7. Orthophosphate averaged 2.8,
0.46, and <0.02 mg PO,/L in test runs 3, 4, and 5, respectively. A non-zinc containing
orthophosphate chemical was used to avoid potential questions, confusion, and interpretation
difficulty associated with separating the well-documented influence of orthophosphate and
potential impact of zinc, as suggested by some, on metal leached from the brasses.

Brass coupons

Figures 9 to 14 show the effect of orthophosphate on lead leached from the brass coupons.
The most notable impact of orthophosphate on lead levels was on the rate at which lead was
reduced. Orthophosphate reduced the time (days) for lead levels to stabilize. The highest
orthophosphate dose (2.8 mg/L) caused lead levels to drop rapidly and stabilize in all brasses.
The lead levels by the end of the test run were generally low (< 10 ug/L) and in some cases less
than analytical detection limits (2 »g/L). Reducing the orthophosphate concentration to 0.5 mg/L,
increased the time for lead levels to stabilize by as much as 50 days, but had little impact on final
Jead concentrations. In most cases, lead levels leached from coupons exposed to the control water
(0.0 mg PO,/L) appeared to still be decreasing after 140 days. Interestingly, lead levels leached
from the yellow and free-machining brasses eventually dropped to approximately the same
stabilized lead levels observed in the test runs where orthophosphate was added (Figures 9, 13,
and 14). Although this observation did not quite hold true for all of the red brasses (Figures 10
to 12), their lead leaching trends were still decreasing at the termination of the test run. If the test
Tuns were carried out longer, lead levels may have eventually dropped to the stabilized levels
observed in the phosphate test runs. It was concluded that the biggest role of orthophosphate on
lead leached from brass was as an “aging accelerator’.

The alloy composition also impacted the amount of time required for lead levels to
stabilize. Generally, the more lead in the alloy, the longer time required for lead levels to

25



80 100 120 140 160

Figure A-13. Brass Alloy C84500, Red Brass



Table A-24.

Study=Coupon
Analyte=Cu

Date.

Run 4: Cincinnati tap water, pH=7.5, 0.5 mg PO4/L, 72 hour stand time

Time, days C36000_C36000_C83600_C84400_C84500 C85200 C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

02/22/93
03/08/93
03/22/93
03/29/93
04/05/93
04/12/93
04/19/93
04/26/93
05/03/93
05/10/93
05/18/93
05/24/93
06/07/93
06/21/93

5
i9
33
40

0.093
0.056
0.023
0.012
0.020
0.023
0.024
0.037
0.023
0.022
0.021
0.017
0.010

0.123 0.551
0.056 0.517
0.023 0.475
0.019 0.504
0.034 0.427
0.023 --
0.024 0.473
0.023 0.356
0.009 0.334
0.022 0.285
0.021 0.229
0.017 0.244
0.010 0.239
-0.001 0.266

0.356
0.457
0.393
0.408
0.420
0.394
0.379
0.311
0.299
0.250
0.208
0.230
0.232
0.247

0.617
0.317
0.311
0.381
0.447
0.394
0.424
0.357
0.318
0.271
0.229
0.237
0.253
0.254

0.054
0.197
0.167
0.205
0.244
0.205
0.227
0.199
0.186
0.167
0.132
0.144
0.169
0.168

0.271
0.297
0.249
0.266
0.285
0.227
0.250
0.206
0.213
0.188
0.146
0.157
0.176
0.209

1385 0.174 -0.002 -0.002 --

1.039 0.658 0.003 -0.004
0.845 0.516 0.003 0.003
0.882 0.543 0.001 0.001
0.935 -- - -

0.765 0.525 0,004 0.004
0.738 0.518 0.010 0.011
0.562 0.403 0.011 -0.004
0.504 0.400. 0.005 0.004
0.402 0.312 0.008 0.008
0.333 0.257 -

0.349 0.271 -0.000 -0.008
0.351 0.282 -0.001 -0.008
0.356 0.291 0.012 -0.014

0.004
0.003
0.001
0.001
0.004
0.004

0.003
0.007
0.008

-0.008

-0.007
0.006



evaluations for pipes and fittings. Lead extracted from pipe specimens should not exceed the limit
specified in the European Economic Community (EEC) Directive on water quality for human
consumption.“ For fittings, 5% of the determined amount shall not exceed this limit.

Recently in the United States, a voluntary standard was developed by the National
Sanitation Foundation International (NSF) located in Section 9 of ANSI/NSF Standard 61
(@rinking Water System Components- Health Effects)” pertaining to the leaching of metals from
mechanical plumbing devices. The standard establishes an extraction protocol for assessing lead
and other metal leachability from plumbing products in contact with drinking water. The
procedure describes a protocol for washing and conditioning the components. The devices are
then exposed to the extraction water (pH=8, alkalinity =500 mg CaCO,/L, and Cl,=2 mg/L) for
19 days using a static "fill-and-dump" test protocol. Samples are collected after days 3, 4, 5, 10,
11, 12, 17, 18, and 19 following a 16-hour dwell time and analyzed for lead. The data is
normalized, taking into account factors such as water volume and surface area. In the case of
lead, the data is statistically manipulated and compared to a maximum allowable level of 11 pg
Pb/L. The comparisons serve as a means of accepting or rejecting plumbing products for
certification under this standard.

Alternatives to the use of leaded brass

A variety of potential alternatives to the use of leaded brass alloys exist. Products could
be redesigned to reduce internal surface area or alternative casting processes could be used. The
internal surface of the product could be coated with a lead-free material. Faucets constructed of
plastic or faucets with plastic water channels could be used.

Another potential solution is to reduce or eliminate the amount of lead used in brass
plumbing fixtures and faucets. Some researchers and manufacturers have marketed alternative
alloying materials that enhance the machining properties of an alloy as well as lead does. Others
have investigated processes to produce materials of lower lead content for construction of fixtures.

Initial work conducted at the Argonne National Laboratory supported by the U.S.
Department of Energy investigated the selective removal of lead from brass and bronze scrap
melt.” A major source of cast brass is recycled copper base scrap (primarily old automobile
radiators) in the form of ingots. The production of cast products from recycled scrap material
provides founders with an energy conservative, cost-effective alternative material source to
primary ores. However, the scrap typically contains high amounts of lead (more than 7 to 8% Pb)
and requires the addition of virgin materials to meet lower lead standards. The researchers have
investigated vacuum distillation as a means to selectively "pull-off" or remove lead from the
recycled melt. This process is based on vapor pressure differences among materials in the melt.
The process has shown promise under laboratory conditions, but cost effectiveness remains an
issue.



20 40 60 80 100 120 140 160
Elapsed Time, days

—o— C36000 =m C84500
—o— C36000 i C85200
—w¥— C83600 —4— €85400
—¥— C84400 —@— Pure zinc

Figure 8. Zinc leached from brass and pure
zinc coupons during test run #2, pH =7.0.



Table A-21. Run 1: Cincinnati tap water, pH=8.3-8.5, 72 hour stand time

Study=Coupon,
Analyte=Cu

Date _ Time, days C36000_C36000_C83600_C84400_C8450__C85200 C85400_Copper Pure Pb Pure Pb Pure Zn Pb/Sn

08/19/91 6 0.050 0.051 0.249 0.149 0.176 0.065 0.075 0.461 -- 0.002 0.002 0.003
08/26/91 13° 0.028 0.036 0.251 0.163 0.182 0.057 0.070 0.354 0.007 0.008 0.009 0.010
09/09/91 27 = =©0.020 0.020 0.270 0.220 0.220 0.040 0.060 0.470 0.010 0.010 -- 0.010
09/16/91 34 0.020 0.020 0.220 0.200 0.210 0.020 0.040 0.370 -- ~ -0.010 --
09/23/91 41 ~ 0.230 0.200 0.230 0.040 0.040 0.370 -- - - ~
09/30/91 48 -0.010 -0.010 0.170 0.190 0.190 0.020 0.030 0.320 -- - - -
10/07/91 55 -- ~ 0.220 0.200 0.220 0.020 0.020 0.300 -0.010 -0.010 -0.020 -0.020
10/21/91 69 -0.010 0.010 0.210 0.210 0.250 0.040 0.040 0.280 -- 0.010 0.010 --
10/28/91, 76 0.010 0.020 0.170 0.180 0.190 0.030 0.050 0.240 0.010 0.010 -- ~-
11/04/91 83 0.010 0.010 0.220 0.210 0.230 0.030 0.030 0.330 -- - - -
11/25/91 104 0.020 0.020 0.260 0.260 0.240 0.040 0.060 0.290 0.030 0.030 0.010 0.030
12/02/91 111 0.020 0.030 0.280 0.300 0.260 0.050 0.070 0.330 0.010 0.020 0.010 0.020
12/16/91 125 0.010 0.010 0.360 0.370 0.350 0.060 0.120 0.500 0.010 0.010 -- -
12/30/91, 139 0.004 0.005 0.160 0.180 0.150 0.030 0.060 0.210 -0.020 -0.010 -0.010 -0.010



Table A-9. Run 4: Cincinnati tap water, pH=7.5, 0.5 mg PO4/L, 24 hour stand time

Study=Coupon
Analyte=Cu

Date __ Time, days C36000_C36000_C83600_C84400_C84500_C85200_ C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

02/05/93 0.263 0.241 0.475 0.373 0.839 0.365 0.329 0.314 0.088 0.088 0.110 0.103
02/08/93 0.088 0.103 0.132 0.132 0.176 0.088 0.096 0.183 0.067 0,074 0.074 0.088
02/10/93 0.410 0.110 0.118 0.110 0.118 0.110 0.110 0.110 0.110 0.110 0.099 0.106
02/18/93 0.193 0.193 0.518 0.193 0.294 0.070 0.171 0.367 0.143 -0.00 -0,00 -0.00
02/19/93 0.164 0.193 0569 0. 0.326 0.081 0.241 0.631 0.177 -0.00 0.005 0.005
02/23/93 0.177 0.216 0.623 0. 0.656 0.137 0.452 0.282

02/24/93 0.196 0.229 0.728 0. 0.767 0.276 0.535 0.336 -0.00 -0.00 -0.00
02/25/93 0.117 0.156 0.489 0. 0.515 0.216 0.336 0.276 «-0.00  -0.00 -0.00
03/01/93, 0.057 0.057 0.496 0. 0.569 0.117 - 0.376 -0.00 -0.02 -0.00
03/02/93 0.056 0.057 0.369 0.361 0.128 0.201 0. 0.461 0.001 0.001 0.001
03/03/93 0.081 0.101 0501 0. 0.441 0.181 0.281 0. 0.561 0.002 0.004 0.004
03/04/93 0.085 0.085 0.473 0.400 0.208 0.268 0. 0.570 0.011 0.011 0.005
03/05/93 0.093 0.113 0.557 0. 0.437 0.263 0.316 0. 0.637 -0.00 -0.00 -0.00
03/09/93 0.096 0.096 0.577 0. 0.410 0.296 0356 0. 0.677 0.002 -0.00 -0.00
03/10/93 0.073 0.072 0.407 0. 0.276 0.194 0.235 0. 0.467 -0. -0.01  -0.01
03/11/93 0.076 0.089 0.560 0: 0.376 0315 0.336 0. 0.623 -0. 0.01 -0.01
03/15/93 0.030 0.031 0.666 0. 0.353 0.217 0.319 0.771 -0.00  -0.00
03/16/93 0.056 0.056 0.483 0. 0.341 0.239 0.2870. . -0.00  -0.00
03/17/93 0.063 0.077 0.463 0. 0.341 0.239 0.266 0. |. -0.00 0.00
03/18/93 0.056 0.056 0.422 0. 0.300 0.215 0.249 0: . 0.002 0.002
03/23/93 0.043 0.043 0.413 0. 0.310 0.208 0.249 0. . . -0.00 0.00
03/24/93, 0.053 0.053 0.401 0. 0319 0.217 0.251 0. . . -0.00 0.00
03/25/93 0.046 0.053 0.340 0.278 0.176 0.196 0. . . -0.00  -0.00
03/30/93 0.042 0.042 0367 0. 0.367 0.245 0.258 0: . . 0.001
03/31/93 0.040 0. 0.386 0.325 0.223 0.223

04/01/93 . 0.386 0.284 0.277 0: .

04/06/93 . 0.244 0.244 0. ; 0.001
04/08/93 . 0.284 .0.197 0.190 0. . . . 0.001
04/15/93 . . . 0.322 0.221 0.199 0. . . . 0.004
04/20/93 . 0.305 0.195 0.196 0. . K 0.005
04/22/93 x |. 0. 0.257 0.167 0.167 0. . . 0.005
04/27/93 . ! 0.270 0.180 0.165

04/28/93 . 0 0.243 0.180 0.166 . -0.00
05/04/93 0.031 0. |! 0.252 0.182 0.167

05/05/93 0.041 0. . 0.229 0.159 0.145 0. .

05/11/93 0.042 0. / 0.25 0.167 0.167 0. |! 0.015
05/13/93 0.056 0. . 0.243 0.180 0.153 .

05/19/93 0.020 0. . 0.216 0.147 0.133 0: . 0.003
05/20/93 0.038 0. . 0.192 0.137 0.131 0. . . -0.00
05/25/93 0.012 0. . 0.162 0.119 0.105 0. . . . -0.00
“05/27/93 0.034 0. ! 0.183 0.181 0.160

06/01/93 0.032 0. ! 0.223 0.160 0.188 0. . .

06/02/93 105 0.032 0. . 0.202 0.160 0.160 0; . . 0.011
06/03/93 106 0.032 0. .. . 0.197 0.155 0.134 0. . . 0.009
06/08/93 11 0.014 -0. . 0.204 0.142 0.121

06/10/93 113. 0.001 . . 0.211 0.151 0.128

06/14/93 117 0.002 0.239 0.153 0.168

06/15/93 118 0.224 0.146 0.139

06/17/93 120 -0.00 0.000 0.210 0.147 0.147

06/22/93 125 0.003 0.003 0.218 0.153 0.153

06/24/93 127° 0.003 0.003 0.101 0.154 0.088 0.104

106



Table A-10.

Study=Coupon
AnalytesCu

12/13/93
12/14/93
12/16/93
12/20/93
12/21/93
12/29/93
12/30/93

LOWER pH to 6.5
01/11/94
01/13/94
01/19/94
01/20/94
01/25/94
01/27/94
01/28/94
02/01/94
02/03/94

125
126
128
132
133
141
142

154
156
162
163
168
170
471
175
177

Run 5: Cincinnati tap water, pH=7.5, 24 hour stand time

0.006
0.006
0.007
0.005
0.032
0.008
0.008

0.031
0.037
0.029
0.030
0.030
0.039
0.033
0.040
0.041

ADD PHOSPHATE=3.0 mg/L

02/08/94
02/11/94.
02/15/94
02/17/94
02/24/94
02/25/94

182
185
189
191
198
199

0.027
0.017
0.036
0.021
0.015
0.014

0.251
0.127
0.102
0.210
0.146
0.180
0.129

0.435
0.383
0.620
0.504
0.459
0.431
0.430
0.577
0.745

1.280
0.366
0.722
0.252
0.214

0.545
0.337
0.270
0.408
0.427
0.392

1.488
1.269
1.728
1.457
1.330
1.232
1.168
1.510
1.783

2.302
0.721
1.479

0.361

0.691
0.418
0.366
0.590
0.507
0.534
0.451

1.623
1.379
1.916
1.586
1379
1.316
1.225
1.585
1.871

2.362
0.824
1.562

0.373

0.184 0.318 0.339

0.143
0.115
0.203
0.166
0.173
0.147

0.578
0.481
0.737
0.576
0.542
0.484
0.429
0.601
0.735

1.128
0.398
0.804

0.188
0.157

0.252
0.189
0.392
0.320
0.338
0.263

1.177
0.960
1.475
1.152
1.165
1.087
1.007
1.331
1.688

2.349
0.673
1.633

0.003
0.003
0.015
0.007
0.008
0.003

0.008
0.004
0.007
0.003
0.004
~0.001
0.001
0.005
0.006

0.007
0.002
0.003

0.004
0.003
0.001
0.007
0.002
0.002
0.006

0.006
0.005
0.007
0.002
0.005
-0.001
0,003
0.005
0.006

0.007
0.001
0.006

0.143 0.132 0.387 0.004 0.007

0.118 0.119 0.343

0.004

0.004

0.002
0.001
0.002
0.003
0.006
0.009
0.003

0.003
0.002
0.001
0.001
0.001
~0.003
-0.005
0.004
0.002

0,002
0.000
0.001
0.002
0.000

0.002
0.001
-0.001
0.002
-0.005
-0.006
0.003
0.002

0.003
-0.001
0.000
0.003
0.004



A-27.
A-28.
A-29.
A-30.
A-31.
A-32.
A-33.
A-34,
A-35.
A-36.
A-37.
A-38.
A-39.

A-40.

A-41,

LIST OF TABLES (continued)

Zinc, Run 2, pH=7.0, 72-hour stand time

Zinc, Run 3, pH=7.5, 3.0 mg PO,/L, 72-hour stand time

Zinc, Run 4, pH=7.5, 0.5 mg PO,/L, 72-hour stand time

Zinc, Run 5, pH=7.5, 72-hour stand time

Run 1, Extraction Water Quality, pH=8.3-8.5

Run 2, Extraction Water Quality, pH=7.0

Run 3, Extraction Water Quality, pH=7.5, 3.0 mg PO,/L

Run 4, Extraction Water Quality, pH=7.5, 0.5 mg PO,/L

Run 5, Extraction Water Quality, pH=7.5

Statistical Comparisons of Lead Leaching Trends

Statistical Comparisons of Copper Leaching Trends

Statistical Comparisons of Copper Leaching Trends

Quality control table showing duplicate sample analysis differences
over the entire study period.

Quality control table showing spike recovery analysis over the
entire study period.

Quality control table showing standard reference material (SRM)
analysis over the entire study period.

viii

128
129
130
131
132
134
136
138
140
142
143
144
145

146

147



I
=H
=)
3
3
4

05 10 2.00 40 60 80 15.0

Standtime, hours

Figure 40. Lead stagnation profile for yellow brass
C85200.



suggested that corrosion rates of brass were hindered. Slight fluctuations in leaching trends were
often associated with pH fluctuations in the extraction water.

The impact of pH on the amount of lead leached from brass was dependent on the amount
of lead in the brass. In higher lead containing red brasses, more lead leached from the brasses at
pH 7.0. This observation followed expected lead solubility response to pH and was also observed
with the pure lead coupon. As the amount of lead in the alloy decreased, however, the impact of
pH on the amount of lead leached from the alloy decreased to the point were there was little or
no impact on the yellow brasses.

Orthophosphate tended to act as an “aging accelerator” in that it's most significant role on
lead leached from brass was to reduce the time required for lead levels to stabilize. This was
clearly the case with the yellow brasses and was believed to eventually be the case for red brasses
given longer time or usage. Lead levels dropped and stabilized most rapidly with 3 mg/L
orthophosphate followed by the 0.5 mg/L dose, and the 0 mg/L dose. The pure lead and solder
coupons responded to orthophosphate more according to solubility predictions (orthophosphate
reduced final lead levels). Lowest lead levels were observed at 3 mg/L, followed by 0.5 and 0
mg/L. The amount of lead in the alloy impacted the time required for lead levels to level off as
well. As the amount of lead increased, the trends shifted to the right or took longer to stabilize.
The role of alloy composition on final lead levels also decreased when orthophosphate was
present.

The amount of copper leached from the brasses at pH 8.5 was also clearly related to alloy
composition. It appeared that red and yellow brasses acted as two groups. The red brasses
leached the most copper and by the end of the study were leaching as much copper as the pure
copper coupon. It was hypothesized that at some critical copper content, the alloy takes the
leaching properties of pure copper. Copper levels were relatively stable throughout the entire
study. At pH 7.0, copper levels were sporadic and difficult to order. Copper levels increased
over the first 60 days of the study and leveled off. Once again, some red brasses leached as much
copper as the pure copper coupon. The amount of copper leached from the alloys was strongly
influenced by relatively small fluctuations in pH.

The impact of pH on copper levels increased with increasing pH. Largest differences in
copper levels between pH 7.0 and 8.5 were observed with pure copper and the red brasses. The
difference decreased as the copper composition decreased. Lower copper levels were observed
at pH 8.5.

The impact of orthophosphate was obvious. In some cases, copper levels leached from
some alloys when orthophosphate was present were slightly lower, however the opposite
observation was made in other cases. It was believed that pH 7.5 was borderline to receive copper
benefits with orthophosphate. Preliminary investigation suggested that orthophosphate may
provide benefit to copper corrosion at pH 6.5.



>
&
g
z
a
g
[=")
:
o

i J 1 a fZ| pee yo |

Test run 3
Test run 4
Test run 5

Time, days

Figure A-3. Ortho-phosphate concentrations
during test runs 3, 4, and 5



Date

Run 1: Cincinnati tap water, pH=8.3-8.5, 72 hour stand time

Time, days _C36000 C36000_C83600 C84400 C84500 C85200 C85400 Copper Pure Pb Pure Pb Pure Zn Pb/Sn

08/19/91
08/26/91
09/09/91
09/16/91
09/23/91
09/30/91
10/07/91
10/21/91
10/28/91
11/04/91
11/25/91

6
13
27
34
41
48
SS
69
76
83

104

92.9
65.2
30.5
18.5
16.4
13.1
10.2
8.2
6.8
9.4
10.3
93
9.7

105.9
74.3
314
19.0
18.5
12.7
23.9

73
5.8
79
83
8.1
76
6.6

136.4
85.9
90.2
62.3
64.9
51.3
56.4
49.5
45.1
49.4
48.6
54.9
40.2
24.9

167.7
105.0
90.4
76.4
86.4
66.5
92.6
76.1
60.7
78.3
79.4
84.2
58.8
318

134.2
95.1
125.3
93.5
102.0
718
98.2
69.0
50.1
68.7
66.4
69.7
50.0
273

131.6
99.6
93.6
72.4
83.3
61.8
59.7
45.0
33.3
36.2
29.5
18.9
37.8
29.8

95.2
54.4
35.9
20.6
20.1
13.7
13.7
13.5

87
10.3
10.4
13.2
13.3

9.7

0.2
-0.9
0.2
-0.3
-2.3
0.1
0.0

6.7
0.3
15
28
2.6
21

1131.3 1256.0

203.8
230.8
211.1
224.7
185.4
212.6
215.7
205.3
239.8
278.1
293.4
347.3
268.2

251.5
238.7
218.7
244.2
194.8
232.4
254.1
227.7
284.4
360.1
358.6
394.1
287.3

0.4
0.5
0.2
-0.5
-2.4
-0.6
-0.2
-1.0
-0.6
0.5
18
0.3
2.4
2.2

322.9
309.9
333.3
361.3
444.4
293.1
362.6
219.4
171.4
216.4
200.7
145.3
497.3
301.8



10.0000 ———
Theoretical Solubility
Run I (DIC=14, pH=8.5)
— - Run 2 (DIC=13, pH=7.0)
-- Run 3 (DIC=14, 0-PO,=2.8, pH=7.5)
+++ Run 4 (DIC=I1, 0-PO,=0.5, pH=7.5)
—:— Run 5 (DIC=18, pH=7.5)

Experimental Data
Run 1
Run 2
Run 3
Run 4
Run 5

Figure 47. Comparison of theoretical and observed copper levels for coupon study.

92



REFERENCES

1, Drinking Water Regulations; Maximum Contaminant Level Goals and National Primary
Drinking Water Regulations for Lead and Copper. Final Rule; correction. Fed. Reg.
56:135:32112 (July 15, 1991).

2. Maximum Contaminant Level Goals and National Primary Drinking Water Regulations for
Lead and Copper. Final Rule. Fed. Reg. 56:110:26460 (June 7, 1991).

3. Drinking Water Regulations: Maximum Contaminant Level Goals and National Primary
Drinking Water Regulations for Lead and Copper. Final Rule; correcting amendments. Fed.
Reg. 57:125:28785 (June 29, 1992).

4. Public Law 99-339. Safe Drinking Water Act Amendments of 1986 (1986).

5. Oliphant, R. J. & Schock, M. R. “Copper Alloys and Solders". Ch. 6 In: Internal
Corrosion of Water Distribution Systems. AWWA Research Foundation/DVGW
Forschungsstelle, Denver, CO, (Second ed., 1996).

6. USEPA. "Seminar Publication: Control of Lead and Copper in Drinking Water", U.S.
Environmental Protection Agency, Office of Research and Development, Washington, D.C,
EPA/625/R-93/001 (May, 1993).

7. Association of Metropolitan Water Agencies. Bulletin #92-35, Lead and Copper Rule
Monitoring. (1992).

8. Water Policy Report. (1992).

9. News Release. National Resources Defense Council. "Faucet Settlement to Affect 90% of
U.S. Market". (1996).

10. News Release. Environmental Defense Fund and National Resources Defense Council.
"Many Pumps in Private Wells Pose Lead Threat; Env. Group. Attorney General File Suit".
(1994).

11. Copper Development Association (CDA). Standards Handbook:Cast Copper and Copper
Alloy Products, Part 7- Alloy Data. CDA, New York, (1978).

12. Plewes, J. T. & Loiacono, D. N. "Free-Cutting Copper Alloys Contain No Lead".
Advanced Materials and Processes, 140:4:23 (1991).

13. Uhlig, H. The Corrosion Handbook. John Wiley and Sons, New York, (1948).

33