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v
INORGANIC
S^e ~ ITS.
TRACE METALS
Trace metals may be present in natural groundwater or surface water.
The sources of these trace metals are associated with either natural
processes or man's activities. Two important natural processes contribut-
ing trace metals to natural water are chemical weathering and soil
leaching. The factors affecting the release of trace metals from primary
materials and soil and their solution and stability in water are solubility,
pH, adsorption characteristics, hydration, coprecipitation, colloidal
dispersion, and the formation of complexes. Decaying vegetation can also
affect the concentration of trace metals in water. Many plants are known
to concentrate various elements selectively. As a result, trace metals may
become available during the decay of the plants. Thus, the penetration
and movement of rainwater through soil may pick up these available
trace metals and affect the groundwater resource. Likewise, runoff
resulting from rainfall may transport trace metals to surface-water.
Mining and manufacturing are other important sources of trace metals
in natural waters. Several operations associated with the mining of coal
and mineral ores can lead to the discharge of wastewater contaminated
with trace metals or to the accumulation of spoiled material, which may
be leached of trace metals by rainfall and reach either surface or
groundwater. The discharge of industrial wastewater, such as that
generated by plating and metal-finishing operations, may also be the
source of trace metals in natural water.
205
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206 DRINKING WATER AND H"LTH
The treatment of raw surface or groundwater to make it acceptable for
public consumption may include the removal of trace metals. However,
trace metals may be added to water as a result of the treatment and the
subsequent distribution throughout a community. Depending on the
quality of the raw water and the quality desired in the finished (treated)
water, treatment may involve the use of chemicals, such as alum
(aluminum sulfate), lime, and iron salts. The chemicals used are usually
of commercial or technical grade with no exact composition, although the
American Water Works Association has established standards for most
chemicals used in the treatment of water supplies. Because of the
possibility of impurities in the chemicals, it is conceivable that trace
metals may be added to the water during treatment. A chemical itself,
such as alum, may also contribute to the trace metal content of the
finished water, depending on its solubility and the characteristics of the
water.
The occurrence of corrosion in the distribution system may also add
trace metals to finished water before it reaches the consumer. Common
piping materials used in distribution systems are iron, steel, cement
(reinforced concrete), asbestos cement, and plastic. Lead, copper, zinc,
aluminum, and such alloys as brass, bronze, and stainless steel may also
be used in addition to ferrous metals in pumps, small pipes, valves, and
other appurtenances. Trace metals may be contributed to the water
through corrosion products or simply by solution of small amounts of
metals with which the water comes in contact.
1 0
1 ~ ~ - ~
Trace Metals in Water Samples Collected in the Distribution
System or at Household Taps
The concentration of trace metals in water collected in the distribution
system or at household taps is more relevant with respect to the quality of
water being consumed by the public than is the raw water. The data in
Table V-1, taken from the community water supply survey involving 969
public water supplies, indicate the levels of several selected elements in
water samples collected in distribution systems. Chromium and silver
were present in microgram quantities, while cadmium, lead, and barium
were found to be in the milligram range (McCabe et al., 1970~.
The results of analyzing a number of tap-water samples, collected at
homes in Dallas, Texas, for trace metals are given in Table V-2. In the
unpublished report from which these data were taken, it was speculated
that the high iron concentration was due to the use of steel water mains in
the distribution system, whereas the high manganese concentration was
the result of accumulation of sandy sediment in the distribution system.
The high copper and zinc concentrations in the water samples were
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Inorganic Solutes 207
TABLE V-1 Concentrations of Selected Trace Metals in 2,595
Distribution Water Samples
Fraction of
Maximum Con- Samples
Limit,a centration, Exceeding
Element mg/liter mg/liter Limit, No
Barium 1.0 1.55 <0.1
Cadmium 0.01 3.94 0.1
Chromium (VI) 0.05 0.08 0.2
Lead 0.05 0.64 1.4
Silver 0.05 0.03 0
aUSPHS Dnnking Water Standards of 1962
(From McCabe et al., 1970)
believed due to the household plumbing. "Local influences" was the
reason cited for the high lead and nickel concentrations in the tap water.
Several studies have shown the combined eject of treatment and the
distribution system on the trace-metal content of the water reaching
consumers. A treatment plant handling 90 million gallons/day (90 mad)
and obtaining its raw water from the Allegheny River was studied with
respect to barium, copper, and nickel (Shapiro et al., 1960~. This
particular plant used sedimentation, slow sand filtration, and chlor~na-
tion. Water samples were collected for analysis before and after
chlorination and at a consumer's tap at a remote point in the distribution
system. Nickel and copper occurred in significantly higher concentrations
in the tap water compared with the treatment plant after chlorination
TABLE V-2 Concentrations of Selected Trace Metals in Household
Tap-Water Samples, Dallas, Texas
N Concentration, mg/liter
Element Samples Average Median Maximum Minimum
Cadmium 43 0.011 0.003 0.056 0.001
Chromium 36 0.004 0.003 0.020 0.001
Copper 43 0.037 0.029 0.164 0.004
Iron 35 0.093 0.088 0.274 0.031
Mercury 43 0.000115 0.000100 0.000885 0
Manganese 43 0.0037 0.004 0.008 0.001
Nickel 36 0.0109 0.010 0.023 0.005
Lead 43 0.0095 0.010 0.027 0
Zinc 43 0.0124 0.011 0.049 0.005
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208 DRINKING WATER AND H"LTH
TABLE V-3 Comparison of Concentrations of Several Trace
Elements in Raw and Tap Water of Three Cities in Sweden
Raw-Water
Concentration,
Element Halites
Malmo
Concentration Ratio, Tap; Raw
Stockholm
Goteberg
Barium 1-3 6.7 4.0 0.5
Cadmium 0.02~.3 2.5 0.5 1.0
Cobalt 0.1 0.7 1.0 3.0
Copper 2-13 0.5 0.2 0.4
Mercury 0.09~.4 1.1 1.0 1.0
Zinc 8-28 4.5 2.8 1.4
(From Bostrom and Wester, 1967)
100 ,ug/liter vs. 30 ,ug/liter for nickel and 4,000 ,ug/liter vs. 90 ,ug/liter for
copper. In the case of barium, the concentration was lower at the tap 40
,ug/liter vs. 90 ,ug/liter. The concentration of copper in water was higher
following chlorination (30 ,ug/liter before and 90 ,ug/liter after).
The effect of treatment and the distribution system on the concentra-
tion of trace metals was also studied in three cities in Sweden Mahno,
Stockholm, and Goteberg (Bostrom and Wester, 1967~. A comparison of
the raw and tap water concentration of six trace metals is shown in Table
V-3.
The change in concentration of several trace metals in raw, finished,
and tap water was studied in the Denver municipal system, which draws
its raw water from a variety of sources and uses five treatment plants that
are interconnected, which makes it impossible to determine the plant
from which a tap-water sample is derived (Barrett et al., 1969~. The
maximum: minimum ratio for most of the trace metals in the raw water
varied from 1.5: 1-6.5: 1; higher ratios were observed for aluminum, iron,
molybdenum, and zinc. A comparison of the concentrations of the trace
metals in the tap and finished water, based on ratios, shows that there
were both reductions and increases in the distribution system. As with the
raw waters, the concentrations of trace metals in the tap-water samples
showed considerable variation.
A distribution system in Seattle, Washington, was studied in an
attempt to determine the severity and location of the corrosion that was
known to be occurring (Danger, 1975~. The concentrations of several
trace metals were determined in the raw water and in two samples
collected at household taps. Standing samples were coldected as soon as
the tap was turned on; this represented water in contact with the
household plumbing at least overnight. Running samples collected after
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Inorganic Solutes 209
bleeding the line for 30 s represented water from the distribution main.
The corrosiveness of the system was recognized by the low phi and
hardness of the water. A comparison of the concentrations of iron,
copper, zinc, lead, and cadmium in the raw water with those in the
standing water confirmed the corrosiveness of the water. However, after a
comparison of the concentrations of the same trace metals in the standing
and running samples, it was concluded that most of the metal pickup was
occurring in the service lines connecting the distribution main to the
buildings and in the inside plumbing. It was also noted that the corrosion
products tested the trace metals correlated well with the materials in
contact with the water.
Trace Metals in Finished Water Supplies
A survey of the mineral content of the water served to customers (finished
water) in the 100 largest U.S. cities was made in 1962 (Durfor and Becker,
1964~. The highest, median, and lowest concentrations are listed in Table
V-4. The raw water used by these cities was either groundwater (wells and
infiltration galleries) or surface water (streams, reservoirs, and lakes). The
chemical quality of most groundwater supplies is stable, compared with
TABLE V-4 Maximum, Minimum, and Median Concentrations of
Constituents of Finished Water in Public Water Supplies of 100
Largest Cities in United States
Concentration, mg/liter
ConstituentHigh Median Low
Iron1.3 0.02 0.00
Manganese2.5 0.00 0.00
Magnesium120 6.25 0.00
Silica72 7.1 0.00
,ug/liter
Silver7.0 0.23 ND
Aluminum1,500 54 3.3
Barium380 43 1.7
Chromium35 0.43 o 2
Copper250 8.3 <0.61
Molybdenum68 1.4 ND
Nickel34 <2.7 ND
Lead62 3.7 ND
Vanadium70 <4.3 ND
ND, not detected.
(From Durfor and Becker, 1964)
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210 DRINKING WATER AND HEALTH
TABLE V-5 Frequency of Detection and Concentrations of Dissolved
Trace Metals in 1,577 Raw Surface Waters in the United States
(October 1, 1962-September 30, 1967)
Frequency of
Detection, Concentration, ,ug/liter
Element AS MinimumMaximum Mean
Zinc 76.5 21,183 64
Cadmium 2.5 1120 9.5
Iron 75.6 14,600 52
Molybdenum 37.7 21,500 68
Manganese 51.4 0.33,230 58
Aluminum 31.2 12,760 74
Beryllium 5.4 0.011.22 0.19
Copper 74.4 1280 15
Silver 6.6 0. 138 2.6
Nickel 16.2 1130 19
Cobalt 2.8 148 17
Lead 19.3 2140 23
Chromium 24.5 1112 9.7
Vanadium 3.4 2300 40
Barium 99.4 2340 43
(From Kopp, 1970)
that of streams, whose quality often varies seasonally and during flood
periods. The mineral content of impounded water is generally less than
that of water in streams.
In addition to the quality of the raw water, it is important to recognize
that water-treatment practices can affect the concentration of trace
metals in finished water. This can be seen from the data in Tables V-5 and
V-6. The concentrations of several trace metals in surface water of the
United States are summarized in Table V-5. Table V-6 gives values for
finished municipal water after treatment. This summary of analyses
performed on raw surface water and finished water indicates higher mean
concentrations of iron, zinc, lead, copper, and aluminum in finished
water. This broad comparison points to the possibility that trace metals
are added to water during treatment. Barnett et al. (1969) cited such an
instance in which the use of aluminum sulfate at a treatment plant
increased the aluminum concentration in the finished water by a factor of
5. Shapiro et al. (1962) observed, in a study of Pittsburgh tap water, a
considerable increase in the copper content between samples at the
water-treatment plant and those taken in the distribution system. Nickel
also showed a tendency to be higher in the distribution water samples
than at the treatment plant; however, the opposite was true for barium.
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Inorganic Solutes 211
In comparing the concentrations of several trace metals in raw water
taken from the Thames River and finished water at two treatment plants
using prechlor~nation, flocculation with alum, rapid sand filtration, and
postchlorination, it was found that treatment had no eject on the cobalt
concentration (Andelman and Shapiro, 1973~. However, as a result of
treatment, the concentrations of manganese and nickel in the finished
water decreased, whereas those of copper and cadmium increased.
In addition, 83 water-supply systems in EPA Region V were examined
for various organic and inorganic constituents (USEPA, 1975~. Region V
consists of Illinois, Indiana, Michigan, Minnesota, Ohio, and Wisconsin.
The water supplies examined were selected jointly by the EPA and the
states and consisted of 14 groundwater and 69 surface-water supplies.
The concentrations of metals in the raw- and finished-water supplies
included in the survey are summarized in Table V-7.
Occurrence of Trace Metals in Raw Water Supplies
In reporting the results of various water surveys, no attempt has been
made to distinguish between different analytical methods used that may
well have different sensitivities and precision.
TABLE V-6 Frequency of Detection and Concentrations of Trace
Metals in 380 Finished Waters in the United States (October 1,
1 962-September 30, 1967)
Frequency of
Detection. Concentration.,ug/liter
Element No MinimumMaximum Mean
Zinc 77.0 32.010 79.2
Cadmium 0.2 1212 12
Iron 83.4 21,920 68.9
Manganese 58.7 0.5450 25.5
Copper 65.2 11,060 43
Silver 6.1 0.35 2.2
Lead 18.1 3139 33.9
Chromium 15.2 129 7.5
Barium 99.7 1172 28.6
Molybdenum 29.9 31,024 85.9
Aluminum 47.8 31,600 179.1
Beryllium 1.1 0.020.17 0.1
Nickel 4.6 1490 34.2
Cobalt 0.5 2229 26
Vanadium 3.4 14222 46.1
(From Kopp, 1970)
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212 DRINKING WATER AND HEALTH
TABLE V-7 Metal Concentration Ranges in Raw- and Finished-
Water Supplies of 83 Cities in EPA Region V
Concentration, ,ug/liter
Element Raw Water Finished Water
Silver
Arsenic
Cadmium
Chromium
Copper
Iron
Magnesium
Manganese
Sodium
Lead
Selenium
Zinc
<0.2~.3
~ 1 .0-10.0
<0.2-12
<5.0-17.0
<5.0-200.0
<20-330
1 ,800~2,000
<5.0-760
1, 100-77,000
<2.0-30.0
<5.0
<5.~210
<0.2~.3
< 1 .0-50.0
<0.2~.4
<5.0~.0
<5.0-200.0
<20-1, 100
800~9,000
<5.0-350
1,000 91,000
<2.0-20.0
cS.O
<5.0~60
BARIUM
Barium was found in 99.4% of the surfacewater samples examined by
Kopp and Kroner (1967~. The range was 2-340 ,ug/liter, and the average
was 43,ug/liter.
BERYLLIUM
The maximum beryllium concentration observed in 1961 by Durum and
Haffty was less than 0.22 ,ug/liter in the Atchfalaya River at Krotz
Springs, Louisiana. Kopp and Kroner (1967) noted the presence of
beryllium in 5.4%of their samples, with concentrations ranging from 0.01
to 1.22,ug/liter and an average of 0.19,ag/liter.
CADMIUM
Groundwater contamination from electroplating operations has been
reported by Lieber (1954) to cause cadmium concentrations of up to 3.2
mg/liter. In Illinois surface waters, 10 of 27 sampling s rations on different
watersheds had cadmium concentrations below 10 ,ug/liter; the maxi-
mum observed by Ackermann (1971) was 20 ,ug/liter. Of 112 samples of
surface and groundwater in Canada examined, only four had detectable
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Inorganic Solutes 213
concentrations of cadmium, i.e., 10 ,ug/liter (Procter and Gamble, 1974~.
Kopp and Kroner (1967) reported that 2.5% of the surface-water samples
examined in their study contained cadmium at 1-120 ,ug/liter, with a
mean of 9.5 ,ug/liter. In a comprehensive study of U.S. rivers in 1974
(USGS, 1974), a maximum dissolved concentration of cadmium of 42
,ug/liter was reported for the Tanana River in Alaska. Durum et al. (1971)
reported cadmium concentrations of 1-10 ,ug/liter in 42% of the surface-
water samples examined, with only 4% above 10 ,ug/liter; the maximum
concentration was 130 ,ug/liter. High concentrations were reported to
occur in densely populated areas. Durum (1974) reported a distinct
regional pattern: areas with many pollution sources and higher rainfall
were higher in cadmium.
CHROMIUM
Durum and Hasty (1961) reported a range of concentrations for
chromium in U.S. rivers of 0.7 to 84 ,ug/liter Kopp and Kroner (1967)
detected chromium in 24.5% of the samples examined, with concentra-
tions ranging from 1 to 112,ug/liter and averaging 9.7,ug/liter. In a study
of surface and groundwater in Canada, all but two of 240 samples
examined were below 50 ,ug/liter (Procter & Gamble, 1974~. In 1974, a
maximum dissolved chromium concentration of 30,ug/liter was recorded
in water from the Pecos River, New Mexico; the Los Angeles River; and
the Columbia River, Oregon (USGS, 1974~. In a 1970 survey, 11 of 700
samples had chromium concentrations of 6 to 50 ,ug/liter, with none
exceeding 50 ,ug/liter (Durum et al., 1971~. Ackermann (1971) reported
chromium concentrations below 5 ,ug/liter for 18 of 27 river stations in
Illinois; the maximum was 50,ug/liter.
COBALT
The limit of solubility of cobalt in normal river water is approximately 5
,ug/liter, according to Durum et al. (1971), who reported that 37% of the
river-water samples examined contained cobalt at 1-5 ,ug/liter, with less
than 1% exceeding 5 ,ug/liter. A 1961 study showed a maximum of 5.S
,ug/liter in the Mississippi River at Baton Rouge (Durum, 1961~. A recent
survey detected a maximum of 17 ,ug/liter in the Kentucky River at
Lockport (USGS, 1974~. Kopp and Kroner (1967) found cobalt in 2.~% of
surface-water samples examined; the concentration ranged from 1 to 48
,ug/liter, with a mean of 17,ug/liter.
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214 DRINKING WATER AND HEALTH
COPPER
Copper has been observed to adsorb to colloidal material at alkaline pH
(McKee and Wolf, 1963~. Durum and Hasty (1961) found the maximum
copper concentration in the Susquehanna River to be 105,ug/liter. Kopp
and Kroner (1967) detected copper in 74.4% of the surface-water samples
examined; the concentration ranged from 1 to 280 ,ug/liter, with a mean
of 15 ,ug/liter. A recent survey detected a maximum of 40,ug/liter in the
North Platte River (USGS, 1974~. Analysis of 13 Canadian surface and
groundwaters including wells, rivers, and lakes-showed copper at 20-
860 ,ug/liter, the maximum being recorded in Lake Ontario (Proctor &
Gamble, 1974~. Copper in excess of 100 ,ug/liter was reported in 8 of 27
Illinois streams, with a maximum of 260 ,ug/liter (Ackermann, 1971~.
LEAD
Pickering and Henderson (1966) reported a maximum solubility of lead
of 500 ,ug/liter in soft water and 3 Igniter in hard water. Durum and
Hasty (1961) reported a maximum lead concentration of 55 ,ug/liter in
the St. Lawrence River at Levis, Quebec. In a more recent sampling of
727 U.S. sites, lead was found, at 1-50 ,ug/liter in 63% of the surface-
water samples examined (Durum et al., 1971~. However, lead was
detected less frequently at U.S. Geological Survey benchmark stations
than at locations in more developed areas.
In 1974, the Mississippi River at Vicksburg showed a maximum lead
concentration of 29 ,ug/liter (USGS, 1974~. Of 52 surface and groundwa-
ters examined in Canada, 50 were found to have less than 10,ug/liter; the
concentrations in the other two samples were 22 and 25,ug/liter (Procter
& Gamble, 1974~. In Illinois surface water, 25 of 27 river stations were
found to have lead below 50 ,ug/liter the other two had concentrations
greater than 50 ,ug/liter (Ackermann, 1971~. Kopp and Kroner (1967)
found lead at 2-140 ,ug/liter, with a mean of 23 ,ug/liter in 19.3%oftheir
surface water samples. Durum (1974) reported that the concentration of
lead in water, like that of cadmium, can be correlated with urbanization
and runoff.
MANGANESE
Durum and Haffty (1961) observed a maximum manganese concentra-
tion of 181-185 Igniter in two different surface waters. The median for all
samples was 20 ,ug/liter. Kopp and Kroner (1967) detected manganese in
51.4% of surface-water samples; the concentration ranged from 0.3 to
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Inorganic Solutes 215
3,230 ~g/liter, with a mean of 59 ,ug/liter. A maximum of 1,200 ,ug/liter
was detected in two different surface waters in 1974 (USGS, 1974~.
MERCURY
Durum et al. (1971) found dissolved mercury ranging from 0.1 to 4.3
,ug/liter in 7% of the surface-water samples examined; in some cases, total
mercury exceeded 5 ,ug/liter. According to a survey performed by Jenne
(1972), only 4% of the surface waters examined showed mercury in excess
of 10 ,ug/liter most of these were small lakes and reservoirs. The same
study reported that groundwater samples were below the limit of
detection for mercury. In 1974, the Rio De La Plata, Puerto Rico, was
observed to have a maximum dissolved mercury concentration of 2
g/liter, and the James River in Virginia showed 1.6 ,ug/liter (USGS,
1974~.
MOLYBDENUM
Durum and Hasty (1961) detected a maximum molybdenum concentra-
tion of 6.9 ,ug/liter in the Colorado River, Yuma, Arizona. In a more
extensive survey, Kopp and Kroner (1967) found molybdenum in 32.7%
of their surface-water samples; the concentration ranged from 2 to 1,500
,ug/liter, with a mean of 68,ug/liter.
NICKEL
A maximum nickel concentration of 71 ,ug/liter was observed in the
Hudson River at Green Island, New York (Durum and Hasty, 1961~.
Kopp and Kroner (1967) found nickel in 16.2% of surface-water samples:
the concentration ranged from 1 to 130 ,ug/liter, with a mean of 19
,ug/liter. In a study of 13 Canadian surface and groundwater resources,
only one sample was found to have nickel above the detection limit of 100
,ug/liter (Procter & Gamble, 1974~. In a study of Illinois surface-waters,
24 river stations had nickel concentrations below 50 ,ug/liter, and 3 had
concentrations of 50-530,ug/liter (Ackermann, 1971~.
SILVER
Samples containing silver at approximately 1 ,ug/liter were noted by
Durum and Hasty (1961) in the St. Lawrence River, Levis, Quebec, and
in the Colorado River, Yuma, Arizona. Of the surface-water samples
examined by Kopp and Kroner (1967), only 6.6% contained detectable
OCR for page 478
478 DRINKING WATER AND H"LTH
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Representative terms from entire chapter:
trace metals
