This report is the result of a
literature search. The contents
do not necessarily reflect the views
and policies of the Environmental
Protection Agency, nor does mention
of trade names or commercial
products constitute endorsement
or recommendation for use.
> A ^
RECOMMENDED UNIFOSM
EFFLUENT CONCENTRATIONS
EPA Region III
Enforcement Division
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Chapter
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CONTENTS
Topic
Preface
Arsenic
Barium
Biochemical Oxygen Demand and Suspended Solids
Cadmium
Chlorine Residual
Chromium
Copper
Cyanide
Fecal Coliform
Fluoride
Hydrogen lon-Acidity-Alkalinity
Iron
Lead
Manganese
Mercury
Nickel
Oil and Grease
Phenol
Phosphorous
Selenium
Setteable Solids
Silver
Surfactants
Turhidity
Zinc
Appendix
Page
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20
30
75
89
93
115
136
155
157
167
172
189
208
219
242
254
274
299
319
334
337
352
364
370
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PREFACE
This report is intended to meet the immediate needs of many
programs of the Environmental Protection Agency. The information
can be used by the professional staff of the Permits Branch in
drafting industrial wastewater permit conditions, by the professional
engineering and legal personnel of the Enforcement Division in seek-
ing solutions to clean up the industrial, municipal and combined
municipal-industrial discharges into our nation's surface waters, by
Air and Water Programs Division in establishing effluent requirements,
by the engineering staff of the Municipal Facilities Branch in approv-
ing plans and grants for municipal wastewater treatment systems, and
by the administrative personnel in accomplishing the programs and
objectives of the EPA.
The objectives of this work are to define the sources of certain
pollutants, their effects within the aquatic environment for speci-
fied uses and the level of technology for treatment which is currently
available and ecomically within reason and to recommend a uniform
effluent level for the parameters covered. As such, very little
dependence is made for the dilution effect. Rather, the ability of
the waters to dilute pollutants is reserved for the many uncontroll-
able discharges such as surface runoff. Similarly, the toxicity of
a pollutant on fish and aquatic life under a limited duration of one
hour maximum is given more consideration than the effect of the pollu-
tant during extended exposure.
In identifying the sources of each pollutant, both natural and
manmade sources, outside and within the immediate scope of EPA programs,
have been included. While there are many areas which need further
investigation, the reader should at least gain a feeling for the
magnitude of the problem.
Discussions of the effects of the pollutants within the aquatic
environment include the following: a) the impact on man, domestic
animals and wild life through consumption of water and food, b) the
impact on man, domestic animals and wildlife by direct contact in
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surface waters, c) the impact on plants by irrigation, d) the impact
on fish and other aquatic life by direct contact, taking into
account the duration of the exposure, the physical, chemical and
biological characteristics of both the discharge and receiving waters
as well as the concentration effect within the food chain.
The currently available methods of treatment have been described
with respect to the influent loading, the achieved effluent concen-
tration(s), and both the capital and operating cost. The heretofore
nebulous description of treatment efficiency, in terms of percent
removal, has been avoided wherever possible. The stoichiometry of
chemical treatment processes is discussed in general terms.
The recommended uniform effluent concentrations are based on
currently achievable concentrations for the particular waste under
the worst waste condition reported. Many wasteloads are currently
treatable to lower levels than those recommended as the uniform level.
In fact, almost all wasteloads including even the worst, can be
treated so that the average effluent concentrations will be lower
than the recommended uniform concentration. The uniform effluent
concentration is defined as the arithmetic average concentration
(weight per unit volume - milligram per liter - mg/1) over a one
hour period. Ideally, this should be measured by continuous composite
sample proportional to the instantaneous flow, for a one hour period.
Due to practical and economical limitation ,however, the following
are considered as acceptable alternatives.
1. At least 50% of the grab samples, collected at evenly
spaced time intervals during any one hour period, should be less than
the recommended concentration.
2. No single grab sample should exceed the recommended con-
centration for Hazardous Materials by more than 50 percent
3. No single grab sample should exceed the recommended
concentration for any parameter by more than 100 percent.
In all situations the uniform effluent recommendations of this
report apply to the treated process wastewaters prior to dilution
with non-process or cooling waters.
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Every pollution problem must be evaluated on a case-by-case
basis. This report defines an effluent level which can be reached
now by almost all dischargers. In many cases the discharge levels
can be much lower. In all situations the most stringent levels must
be used, be they federal, state or local regulations.
SUMMARY OF RECOMMENDATIONS
Max. Stream Cone
Parameter*
Arsenic
Cadmium
Chromium
Lead
Mercury
Barium
Copper
Iron, Total
Iron, Dissolved
Manganese
Nickel
Selenium
Silver
Zinc
Cyanide
Fluoride
Oil and Grease
Phenolics
Phosphorus
Settleable Solids
Surfactants
Suspended Solids
BOD5
Total Chlorine
to Protect
Water Uses
0.010
0.010
0.050
0.010
none
1.0
0.02
0.1
0.1
0.05
0.5
0.010
0.003
1.0
0.01
1.0
0.3
0.001
0.01
none
0.5
none
none
0.002
Effluent
Unif.Eff.Cone.
0.050
0.100
0.100
0.100
0.005
2.0
1.0
2.0
1.0
0.1
1.0
0.010
0.100
1.0
0.025
1.5
10.0
1.0
2.0
0.2
1.0
30.0
30 - 75
0.1
Concentrations
Max.
0.075
0.150
0.150
0.150
0.005
4.0
2.0
3.0
2.0
0.2
2.0
0.020
0.100
2.0
0.050
1.5
10.0
2.0
4.0
0.4
2.0
30.0
90.0
0.2
Design
Goal
0.030
none
none
0.010
none
< 1.0
0.03
< 1.0
< 0.3
0.05
< 0.5
< 0.010
< 0.010
0.1
none
0.5 - 1.0
1.0 - 2.0
0.1
< 1.0
none
< 0.5
15
none
Residual
* All units are mg/1 except ml/1 for settleable solids
111
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•
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CHAPTER I-ARSENIC
_2
Arsenic is found in most natural waters as arsenate (AsO, )
or arsenite (AsO~ ), occurring in sea water mainly as arsenite.
Mineralogically, it may occur as elemental arsenic but it is usually
found as the arsenides of the true metals or as pyrites. It is oxi-
dized and recovered as a byproduct in the smelting of many ores.
Table 1-1 lists some of the naturally occurring levels of arsenic in
the environment. A number of industrial sources of arsenic also
exist. These are summarized in Table 1-2 with the approximate con-
centrations to be expected in the various effluents.
ENVIRONMENTAL EFFECTS OF ARSENIC
Effect on Man
From a review of literature dealing with the biotic responses
to arsenic and its pharmacology it is apparent that arsenic compounds
can elicit a variety of responses from living organisms depending on
its form, concentration and mode of exposure. In general the effects
include chronic and acute syndromes and possible carcinogenicity. It
M
is a cumulative poison in most life forms due to its low excretion
• rates. Schneider (83) reports that the human body constantly accumu-
lates arsenic and that normal blood levels range from 0.2-1.0 mg/1
• of arsenic. Lambou and Lira (55) have reported that arsenic toxicity
_ decreases in the following order depending on the mode of entry into
•
the body-arsenides, arsenates, colloidal arsenic, atoxyl and cacodyl.
Arsenicals (pesticides) also act locally as mild and slow corrosives.
They systematically relax the capillaries and increase their permea-
bility, thus creating inflammation.
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The fatal dosage of arsenic compounds may vary with the
solubility of the preparation. Table 1-3 summarizes the human tox- •
icity data available on arsenic. Lambou reports that trioxide is •
toxic at 5-50 mg and is usually fatal at 0.06-0.18 g (55). McKee
and Wolf (66) report that arsenic concentrations of 0.21 mg/1-10.0 mg/1 •
are sometimes poisonous to human beings; on the other hand concentra-
tions of 0.05 mg/1-0.2 mg/1 in drinking water can be safe for human V
consumption. The mortality rate of acute clinical arsenic poisoning «
has been reported to be 50-75% (55). Acute arsenic poisoning results
in violent gastroenteritis which resembles cholera. It may also cause •
skin eruptions and liver or heart damage. The chronic or subacute
symptoms include weakness, loss of appetite, gastrointestinal dis- f
turbances, hoarseness, coughing and laryngitis, peripheral neuritis, «
occasional hepatitis and skin disorders. *
Schneider (83) reports that arsenic consumed in domestic water fl
supplies would not be carcinogenic, a statement supported by Lambou
and Linn (55). However, McKee and Wolf (66) report several incidents •
of cancer which may be attributable to consumption of arsenic in water.
1
It is possible that the form of the compound may be the controlling •
factor. Potentially recognized possible sites of carcinogenic effects IB
in humans are the skin, lung and liver. Other suspected sites include
the mouth, esophygus, larynx and bladder (55). •
Effect on Fish and Other Aquatic Life
_„ _i
summarized in Tables 1-4 and 1-5. These tables give the toxic and M
tolerable levels found by various researchers. Some organisms have
been found to concentrate arsenic from the surrounding water. Marine •
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TABLE 1-1
CONCENTRATION OF ARSENIC IN NATURAL ENVIRONMENT
Source Concentration Reference
Soils up to 500 mg/kg (83)
Earth crust 1.8 mg/kg (55)
U.S. surface water 0.01-0.1 mg/1 (55)
Sea water 0.003 mg/1 (6)
Normal blood 0.2-1.0 mg/1 (83)
Molluscs, Coelenterates up to 0.3 mg/kg (83)
and Crustaceans
Marine plants (highest up to 30 mg/kg (83)
in the Brown algae)
Marine animals 0.005-0.3 mg/kg (83)
Shellfish over 100 mg/kg (66)
Fish oils (15 species): Average 11.8 mg/1
Range 1.20-60-10 (33)
3
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TABLE 1-2
SOURCES AND SOME KNOWN CONCENTRATIONS
IN INDUSTRIAL WASTEWATERS
Source
Manufacture of
Parisgreen
Calcium meta-arsenate
Insecticides (Arsenical)
Industrial or municipal discharge
of pre-soak household detergent
Laundry products (currently available)
Laundry detergents discharged into Kansas
sewage system
OF ARSENIC
Concentration Reference
362 mg/1 (76)
(as anArsenious
oxide)
up to 70 mg/1 (55)
up to 36 mg/1 (55)
0.002-0.01 mg/1 (15)
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Mineral rock; waste from industry and mining mean-0.034 (15)
activity; residues from pesticides in major
U.S. River Basins (1962-7)
Herbicides and pesticides manufacture
Glassware and ceramic products
Tannery operations
Fish processing plant
Sulfuric acid made from sulfide ores
Acid mine drainage (active and abandoned
mines)
Fly ash scrubber drainage
Storm runoff from power plant
Metallurgical industry
4
max -0.336
significant amount (61)
of arsenic compound
(76)
(76)
(76)
(55)
(55)
(55)
(55)
(61, 76, 55)
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plants, specifically brown algae, have been found to contain con-
centrations up to 30 mg/1. Accumulations of up to 0.3 mg/1 have
been reported in some molluscs, coelenterates , and crustaceans. Some
reported accumulation factors are shown in Table 1-6.
TABLE 1-3
TOXIC EFFECTS OF ARSENIC ON HUMANS
Form
Undefined
Undefined
Elemental
Trioxide
Trioxide
Sodium
Arsenite
Undefined
Undefined
Undefined
Undefined
Undefined
Undefined
Undefined
Undefined
Cone (or Dose)
130 mg
130 mg
Ingest ion of un-
specified concentra-
tions
5-50 mg
60-180 mg
325 mg
Prolonged ingestion
at low cone .
Non-oral dose
Oral, drinking water
Normal exposure to
workers in arsenical
industry
0.21 mg/1
0.3-1.0 mg/1
0.4-10.0 mg/1
12 mg/1
5
Effects Reference
Lethal (59)
Severe poisoning; (59)
cumulative toxic effect;
small eruptions on hands
and soles of feet, sometimes
developing into cancer;
possible liver damage and
heart ailments, causal
factor for Hoff's disease.
Sub-acute and acute (59)
symptoms
Toxic (55)
Fatal (55)
Lethal (66)
Chronic, sub-acute symptoms (59)
positive, epidermal cancer (59)
possible carcinogen to skin (66)
and liver.
no significant increase in (59)
cancer mortality.
poisonous over a long period (66)
of time
(66)
(66)
Death (66)
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The Green Book reports that arsenic is moderately toxic to plants and
highly toxic to animals, especially as AsH., (6). They also report
that fish food organisms can tolerate an application rate of 2 mg/1 •
of As_0_. A level of 15 mg/1 has been reported to be toxic to certain
1
fish eggs, including Lepomis macrochirus and Micropterus dolomieui. m
The eggs of these two species survived 7 and 6 days, respectively m
following exposure. The effluent from nuclear reactors may contain
appreciable concentrations of arsenic-76 which may be concentrated •
somewhat in the aquatic food chain (55).
bottom muds or even in plankton (55). Should further study confirm «
this hypothesis it would amplify the importance of controlling arsenic
in effluents wherever the soluble phosphorous concentration is suffi- •
cient to produce a heavy aquatic growth.
Effect on Plants and Animals ^
Arsenic at very low concentrations appears to stimulate plant •
growth, however, the presence of any excess soluble arsenic will re-
duce crop yields. The mode of action appears to be the destruction •
of chlorophyll. McKee and Wolf (66) report that old orchard soils in !•
the state of Washington were found to be unproductive when a concentra-
tion of 4 to 12 mg/kg of arsenic trioxide, was reached in the top soil. •
They also reported that fruits and vegetables, however, have been
found to contain arsenic compounds due to natural conditions alone (66). |
Table 1-7 summarizes some effects of arsenic on specific species of
plants.
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Sickness and death of cattle have been reported to result
from consumption of arsenic naturally present in water supplies (66)
The lethal dose of arsenic is believed to be approximately 20 mg/lb
of animal weight. The dosages of arsenic toxic to various animals
are given in Table 1—8. Arsenic has been used in drinking water to
counteract selenium poisoning in cattle, pigs, dogs and rats.
CONCENTRATIONS OF ARSENIC
Type of
Organisms
fish
pike perch
bleak
carp
eels
crabs
bass
minnows
crappies and bluegills
minnows
Chironomus
fish food organisms
pink salmon
fish
bass
bass, bluegills, crappies
mussels
f latworms
TABLE 1-4
TOXIC TO FISH AND AQUATIC
Concentration of
Arsenic (mg/1)
1.1
1.1-2.2
2.2
3.1
3.1
4.3
7.6
11.6
15
17.8-234
Concentration of Arsenic
trioxide (mg/1)
1.96
2-4
5.3
10
10
10
16
40
7
ORGANISMS (66)
Time of
Exposure
2 days
3 days
4-6 days
3 days
11 days
10 days
36 hours
8 days
10 days
3-16 days
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CONCENTRATIONS OF
Type of Organism
pike perch
fish
bleak
fish
carp
eels
crabs
fish
bass
trout
minnows
chironomus larvae
food organisms
bass, bluegills,
fish
mayfly nymphs
some zooplankton
trout, bluegills,
sea lamprey
fish
coho salmon
fish
mussels
trout
insect larvae
minnows
TABLE 1-5
ARSENIC TOLERATED BY FISH AND AQUATIC ORGANISMS (66)
Concentration of
Arsenic, mg/1
0.7-1.1
0.76
1.1-1.6
1.5-5.3
2.2
2.2
3.1
5.3
6.0
7.6
13.0
Concentration of
Arsenic trioxide mg/1
1.9
2
crappies 2-6
2-7
3-14
5
5
5
5-10
7
8
10
10-20
17.1
8
Time of
Exposure
48 days
11 days
1-7 days
13 days
13 days
90 days
24-148 hours
232 hours
30 days
1 hour
~
1-7 days
24 hours
— _
15-30 minutes
24-148 hours
1 month
1 hour
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TABLE 1-6
I
ACCUMULATION OF ARSENIC IN AQUATIC ORGANISMS (55)
I
Organism Concentration Factor
Benthic Algae 2000
™ Mollusc (muscle) 650
• Crustacean (muscle) 400
m Fish (muscle) 700
Various species seaweed 200-600
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TABLE 1-8
CONCENTRATIONS OF ARSENIC TOXIC TO
Species
Laboratory
animals
Dog
Swine
Sheep, goat,
horse
Cow
Rats, Mice
Chickens
Fowl
Guinea Pigs
Mouse
Laboratory
animals
Laboratory
animals
Rats
(cancer sensi-
tive strain)
Dose Form
5-100 rag/kg arsenic
100-200 mg/kg
500-1000 mg/kg
10,000-15,000 mg
15,000-30,000
15.1-214 mg/kg Arsenic
Trioxide
324 mg
50-100 mg
14-30 mg/kg
5 mg/1 for life Sodium
(0.50 mg/kg/day) Arsenite
0.5 mg/kg/day
2.5 mg/kg/day
0.1 ml of 1%
lanolin suspension
in paranasal
sinuses (3 times) .
n
ANIMALS
Effects Reference
Lethal (66)
Toxic (55,66)
Toxic (55,66)
Toxic (55,66)
Toxic (55,66)
96hr. LD(50) (66)
Lethal in 24hr. (66)
Toxic (55,66)
Lethal (105)
Significant de- (105)
crease in survival
and longevity
Change in condi- (105)
tioned reflexes
Morphological (105)
changes in blood and
impairment of kidney
function; cumlative
in organs
11 of 20 developed (105)
a total of 15 tumors
of 7 types. Control:
8 of 20 developed
a total of 8 tumors
of 4 types
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TABLE 1-9
ARSENIC TREATMENT METHODS AND REMOVAL EFFICIENCY
Concentration mg/Jl
Treatment Initial Final %Removal
Lime Softening 0.2 0.03 85
Charcoal Filtration 0.2 0.06 70
Ferric Sulfide 0.8 0.05 94
Filter Bed
Coagulation with 25.0 5 or less 80 or more
Ferric Sulfate
Coagulation with 3.0 0.05 98
Ferric Chloride
Precipitation with 0.6
Ferric Hydroxide
Precipitation with 362 15-20 94-96
Ferric Hydroxide by (as Arsenic (as Arsenic
Ferrous Sulfate & Oxide) Oxide)
Lime Coagulation
with Settling only
Ferrous 0.8 0.05 94
Sulfide Filter
Bed, Bone Carbon &
Settling
Ferrous 0.5 trace
Sulfide Filter Bed,
followed by Sand &
Coke Filtration
Chemical 0.05-0.5 80-95
Coagulation,
Sedimentation, and
Filtration
Activated Sludge 0.0028+0.0004 0.0010+0.0005
Removal /Biomass 0.040 +0.01 0.0228+0.009
0.133 +0.023 0.056 +0.01
12
References
(55,76)
(76)
(76)
(76)
(76)
(76)
(76)
(76)
(76)
(97)
(103)
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• TREATMENT TECHNOLOGY - ARSENIC REMOVAL
Currently available treatment technology consists of cold-lime
| softening and the more standard procedures of coagulation, settling
m and filtration. Complexation of the arsenic compounds with heavy
metals has been reported as a potential removal mechanism not only in
• the above processes, but as a third treatment method.
The 1970 works of Magnusen et al, reviewed and discussed by
^ Lambou and Lim (55)and Patterson and Minear (76) show that lime soften-
« ing will reduce an initial arsenic complex concentration of 0.2 mg/1
to approximately 0.03 mg/1, thus achieving an 85% removal. Simple
IB filtration through a charcoal bed can reduce arsenic from 0.2 mg/1 to
a final effluent level of 0.06 mg/1 of arsenic (55,76). Arsenic re-
• moval has also been accomplished by passage of the wastewater through
— a ferrous sulfide filter bed followed by bone carbon settling and
™ filtration (76). Coagulation with iron salts (ferric sulfate, ferrous
B sulfate, ferric chloride) and subsequent rapid sand or multi media
filtration of the ferric hydroxide precipitate is another arsenic
• removal process (76). When the arsenic bearing wastewaters are acid,
lime is normally used to adjust the pH to alkaline conditions (pH = 10).
' Arsenic compounds have been reported to be removed upon sedi-
A ments. Lund (61) proposes that arsenic may be precipitated from
wastewaters bearing heavy metals by complexation of the arsenic with
• the heavy metal ions. He has reported approximately 90% removal of
the initial arsenic concentration by complexation with heavy metals,
• when the heavy metals were removed by chemical precipitation.
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This complexation of arsenic compounds appears to be one of the
mechanisms involved in the ferric hydroxide precipitation. •
A tabulation of the currently available methods for treating g|
arsenic compounds and their degree of removal is given in Table 1-9.
The cost of arsenic removal will be similar to that of routine water •
treatment. The chemical cost associated with this method will be
that of the coagulant and lime needed for precipitation. A summary 0
of treatment processes, their effectiveness and cost, by Weston (97) m
has shown the capital cost (in millions of dollars) to be approxi-
mately 0.3 for a one MGD facility, 1.3 for a ten MGD plant, and 4.6 W
for a fifty MGD facility. These cost estimates do not include the
cost of sludge or lime disposal. f
Three figures illustrating the treatment cost for arsenic are •
included here (76) . Figure 1-1 indicates the total cost of treatment
by coagulation, sedimentation and rapid sand filtration. Figure 1-2 •
gives the operating cost for lime neutralization and, Figure 1-3
shows the capital cost for 21.0 MGD lime neutralization plant. •
In summary, it has been shown that coagulation, sedimentation, •
and filtration are the most common and effective means of treating
arsenic bearing wastes. Where the arsenic wastewaters are acidic, •
pH adjustment to alkaline conditions will be required for effective
removal. The cost of treatment will depend on the volume of wastes •
to be treated and their initial water quality parameters, especially flj
the acidity.
14
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f
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f
Figure 1-1
Total cost of treatment by coagulation, sedimentation and
rapid sand filtration. Cost includes capital investments for 30
years at 4%, labor, power, chemicals, maintenance and repair, and
heating of building (76).
Q
W
H
3
o
o
o
w
p-l
H
tr>
o
H
o
H
100
10
Note:
Dashed lines represent probable
range of costs; solid line
represents average cost.
I I I
.1
1.0
FLOW IN MILLION GAL. PER DAY
10
15
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Figure 1-2
Operating costs for lime neutralization,
including sludge dewatering by vacuum filtration (76)
o
o
•1VO OOOT/3 'SISOD
16
o
o
o
00
e
O SH
O M
O O
O
O
O i-t
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Figure 1-3
Capital cost for a 1 MGD lime neutralization
plant, including sludge disposal (76).
o
o
o
o
o
o
S,OOOT $ 'ISOO IVIIdVD
17
a)
O
tn
cfl
B
ex
a,
P
o
o
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SUMMARY AND RECOMMENDATIONS
I
The following conclusions can be drawn from the above data.
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1. Arsenic and arsenic compounds are apparently tolerated by man
and other organisms at the levels found normally in the en-
vironment except in a few locales with high arsenic contain-,
ing mineralogy.
2. The above review indicates that arsenic compounds are cumu-
lative throughout the entire food chain and are possibly con-
centrated upon bottom sediments. While man, fish, plants, and
wild life are capable of tolerating most natural arsenic con-
centrations all are sensitive to toxic effects at relatively
low dosage.
3. Currently available treatment for arsenic and arsenic compounds
is capable of maintaining an effluent concentration of 0.05 mg/1.
While higher effluent concentrations are reported for some
wastes, filtration of the settled effluent should be capable of
maintaining a final concentration of 0.05 mg/1.
4. Further literature review and research is needed to define the
best available treatment technology.
I
Arsenic and arsenic compounds may be contributed to the
| aquatic environment, and to its food chains, by the precipitation of
_ arsenic-bearing atmospheric particulates. This represents a source
~ of arsenic uncontrollable by effluent standards, and necessitates
• the strictest possible limits on the controllable effluents. It is
essential that the concentration of arsenic compounds in our nation's
• waters be kept to an absolute minimum. Even with minimum achievable
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levels in receiving waters, arsenic may still be concentrated to a
certain degree upon bottom sediments. This of itself necessitates
the use of filtration where arsenic is a potential problem in a dis- I
charge.
It is, therefore, recommended that a uniform effluent limit of |
0.05 mg/1 be adopted at this time. When improved treatment technol- «
ogy becomes available, it should be applied to maintain arsenic
levels at the lowest level possible. An arsenic concentration of •
0.05 mg/1 should be safe for human consumption.
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Salts of barium
CHAPTER II-BARIUM
are found naturally in soils and unweathered
rock, hence, small concentrations are found in rivers and sea water.
Barium salts are used
ceramics, rubber, dye,
(66,76).
Table II-l shows
The range in drinking
as 3.0 mg/1.
Table II-2 is a
extensively in the metallurgical, glass and
explosives, concrete, and paint industries
some naturally occurring levels of barium.
water is from less than 0.0006 mg/1 to as high
list of the most commonly used barium salts in
agricultural and industrial establishments. Also listed in that
1
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1
1
table is the maximum solubility of the salt between 10°C and 90°C
(61,66).
ENVIRONMENTAL EFFECTS
Effect on Man
OF BARIUM
The alkaline earth metal, barium, and its salts are toxic to
man, animals, fish and
II-3 lists some of the
other aquatic life in varying degrees. Table
toxic levels of various salts. Unlike other
metals and toxic substances, barium has been studied extensively
with respect to toxicity levels and time of exposure. It can be seen
that a dose of 550-600
mg of barium is fatal to man.
The salts of barium are muscle stimulats, especially of the
1
1
1
heart. Barium acts by
constricting the blood vessels creating an
increase in blood pressure. Barium sulfate when aspirated may cause
granuloma of the lung
and other sites in man. It is further reported
20
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that deposition of insoluble forms of barium in sufficient amounts
at localized sites may cause chronic irreversible changes in tissues
(94).
According to McKee and Wolf (66) , the fact that barium is ex-
creted more rapidly than calcium indicates that there is little
chance of a cumulative effect within the human body. Actual studies
confirm that barium does not accumulate in the bone, muscle, kidney,
or other tissue (66,94).
TABLE II-1
NATURALLY OCCURRING LEVELS OF BARIUM (59)
Source
Various River Basins
Rivers, selected
N. Atlantic Slope Basin
Drinking Water
Cone.
0.015 -
0.009 -
0.010 -
0.0006 -
.090 mg/1
.152 mg/1
0.150 mg/1
3.000 mg/1
21
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1
1
TAB
COMMONLY USED
Lt LL-i
BARIUM SA1
Salt Solubility
1
1
|
1
|
•
1
1
1
1
1
1
1
1
1
Barium Acetate
Barium Carbonate
Barium Chloride
Barium Nitrate
Barium Sulfate
Barium Silica Fluoride
* Industry Use is defined as
588 g/.l
22 mg/1
393 g/.l
50 g/1
1.15 mg/1
260 mg/1
follows:
1. Natural rock weathering
2. Chemical industry
3. Dry and Tanning
4. Textiles
5. Paint
6. Electronic
7. Pyrotechnic
8. Petroleum
9 . Rubber
10. Glass
11 . Metal Manufacture
22
Industry Use*
3, 4, 5
1, 2
2, 3, 4, 5
6, 7, 8
2, 3, 4, 5, 9
10, 11
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On the basis of the threshold limiting values in industrial M
atmospheres, an estimate of the amount adsorbed into the bloodstream,
and daily consumption of two liters of water, it is estimated that •
consumption of barium should be limited to 2.0 mg/1 (66). McKee and
Wolf (66) and the Drinking Water Standards (94) have recommended a |
limit of 1.0 mg/1 to provide a safety factor and to allow for possible «
accumulation in the body. *
Effect on Plants
According to the data provided by McKee and Wolf, barium is
I
present in most soils, however, it is not utilized by most plants.
Barium is considered to be poisonous to them (66) . •
Effect on Fish and Other Aquatic Life ^
The lethal concentration of barium in fish and aquatic life
varies according to the form in which it is found. The lethal con- •
centration limit of barium for sticklebacks is 400 mg/1 (66). Gold-
fish have a concentration factor of approximately 150 for barium. •
While none of the other data reviewed indicates that other fish or •
aquatic life concentrate barium, it should be considered as a possi-
bility. |
A review of the effect of various barium salts on fish and
aquatic life as reported in McKee and Wolf is summarized below (66): •
Barium acetate at a concentration of 5 mg/1 was found •
to have no effect on rainbow trout, bluegill sunfish,
and sea lamprey during a 24-hour exposure. •
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Barium carbonate was found to have a 96-hour TLm greater
than 10,000 mg/1 for mosquito fish. However, it was
noted that the limiting solubility of barium carbonate
is 22 mg/1.
Barium chloride is reported to have harmed the nervous
system of young silver salmon after a 72-hour exposure
at a concentration of 50 mg/1. Barium chloride in Lake
Erie water at 20-25°C was found to have threshold con-
centrations of 12 mg/1 for Leptodora kindtii and 29 mg/1
for Daphnia magna. Barium chloride was also found to have
a lethal concentration of 10 mg/1 on the aquatic plant,
Elodea canadensis, and 11.1 and 14.3 mg/1 on two differ-
ent species of snails.
Barium nitrate has been found to be lethal in concentra-
• tions of 20 mg/1 for two species of snails, 10 mg/1 for
Elodea canadensis and 200 mg/1 for goldfish. In investi-
M gations of Lake Huron water at 12°C, a 24-hour exposure
to Barium nitrate at a concentration of 5.0 mg/1 had no
* effect on rainbow trout, bluegill sunfish, or the sea
B lamprey.
Barium sulfide at a concentration of 5.0 mg/1 was investi-
• gated in Lake Huron water at 12 C and no effect on rain-
bow trout, bluegill sunfish, or the sea lamprey was indi-
™ cated after a 24-hour exposure.
• On the basis of the above data, McKee and Wolf recommended a
maximum concentration of 5.0 mg/1 of barium for fish and other
• aquatic life (66).
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TREATMENT TECHNOLOGY - BARIUM REMOVAL •
While there is not an extensive amount of literature available _
on the treatment of barium, Patterson and Minear (76) and Weston (97) ™
have proposed the following methods for barium removal. The most •
likely method, according to both sources, is coagulation and precipi-
tation of barium as barium sulfate. Weston indicates that filtration I
may be desirable for effluent polishing. Precipitation with sodium
and ferric sulfate have also been reported as effective. Patterson •
and Minear pointed out that maximum theoretical solubility of barium •
sulfate is 1.4 mg/1 (as barium). Ferric sulfate has been effectively
used in removing the finer non-settleable barium sulfate precipitate •
and could eliminate the need for final filtration.
Other methods reported by Patterson and Minear include the use •
of adsorption by activated carbon, ion exchange, and electrodialysis. •
While no efficiency was reported for adsorption on activated carbon,
an operating cost of 20 centsper thousand gallonswas given. Removal I
of barium from nuclear waste was reported as 99.99% efficient and an
efficiency of 99% removal from non-nuclear wastewaters was achieved. •
Electrodialysis similarly was reported as 99.9% efficient in the re-
moval of barium.
While little cost data are available, Weston has indicated that •
coagulation and precipitation of barium with sodium sulfate followed
by settling and filtration is capable of achieving a final barium •
effluent concentration of 1-2 mg/1 at a capital cost of $200 per •
thousand gallons for a 1 MGD plant; $128 per thousand for a 10 MGD
plant, and $92 per thousand gallons for a 50 MGD plant. In relation •
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to the capital costs of a typical secondary sewage treatment facil-
• ity, these capital costs range from 3-6 times less.
I SUMMARY AND RECOMMENDATIONS
_ On the basis of the data discussed above, the following state-
ments can be made:
• 1. It is apparent that barium may be found in the industrial
wastewater from several industries including, but not
• limited to, metallurgy, glass manufacture, textiles and
_ dyes, vulcanization of rubber, paints, tanning, embalming,
* electronics, pyrotechnics, and radioactive wastewaters.
fl 2. Barium is toxic to man, animals, fish and aquatic life.
3. Based on the known toxicity to man, the maximum allowable
• concentration should be 1.0 mg/1. Based on barium's
_ toxicity to fish and aquatic life, barium should not be
* discharged in concentrations greater than 5.0 mg/1.
• 4. Treatment by coagulation, precipitation, and filtration
has been reported to reduce barium concentrations to an
I effluent level of 1-2 mg/1. Treatment by activated
carbon, ion exchange, and electrodyalisis has been re-
™ ported to have high percentages of removal (over 99%).
• Removal of barium from industrial wastes by coagulation,
precipitation, settling, and filtration are achievable
• at capital costs 3-6 times less than the cost of a
typical secondary sewage treatment facility.
On the basis of the above statements, it is recommended that a
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maximum uniform effluent criteria for barium be set at a concen-
tration of 2.0 mg/1. Where an industrial or a municipal discharge
containing barium is located immediately upstream from a domestic
water supply intake, it is recommended that treatment be employed
to maintain effluent concentration below 1.0 mg/1.
TABLE I1-3
TOXIC EFFECTS OF BARIUM ON MAN AND ANIMALS (105)
Compd
Ba"
BaCO.
3
BaC03
BaC03
BaCO,,
3
BaC03
BaC03
BaC03
BaC03
BaCl_
2
BaCl2
BaCl2
BaCl2
BaCl2
BaCl2
BaCl2
BaCl2
Ba F0
Species
Human
Human
Rabbit
Rat
Rat
Rat
Mouse
Rabbit
Guinea Pig
Human
Rat
Dog
Mouse
Rat
Dog
Horse
Rabbit
Guinea Pig
Dose_
500-600 mg
800 mg
170-300 mg/kg
50-200 mg/kg
800 mg/kg
1,480+340 mg/kg
200 mg/kg
170-130 mg/kg
1,000 mg/kg
100 mg/kg
250 mg/kg
90 mg/kg
7-14 mg/kg
355-533 mg/kg
90 mg/kg
800-1,000 mg/kg
170 kg
350 mg/kg
Effect
Lethal
LD
LD
50
50
Lethal
LD50
LD50
Lethal
LD
50
LD50
Lethal
LD
50
27
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TABLE II-3
TOXIC EFFECTS OF BARIUM ON MAN AND ANIMALS (105)
Compd
Ba
Species
Human
BaCl Rat
C12 Rabbit
Dose
Chronic Effect
vaso-constriction
elevation of BP,
muscle stimulant,
especially heart
changes in conditioned
reflexes, slight
tissue structure
changes slight decrease
in cholinesterase
activity
5, 2.5, +1 mg/kg/day Decrease in
13.2 mos. cholinesterase
activity at 5 mg/kg.
No changes at other
doses.
None reported
20 mg/kg/day
10 mg/kg/day
for 6.5 mos.
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TABLE
TOXIC EFFECTS OF BARIUM ON
Salt
BaCl2
BaCl2
BaCl,
l
BaCl.
2
BaN03
BaN03
BaN03
BaCO
BaCl2
BaCl2
BaCl2
BaCl2
BaN03
BaCl2
BaCl2
Species
Silver Salmon
Silver Salmon
Plants (Elodea)
Snails
Snails
Tinea vulgaris 10
Snail
Elodea
Goldfish
Gambusia af finis 10
Daphnia magna
Daphnia magna
Gambusia affinis 3
Rana sp. (eggs) 24
Gasterosteus aculeatus
Mosquito fish
Young eels
29
II-4
FISH AND AQUATIC LIFE
Concentration, mg/1 Reference
158 72 hr LD90 (66)
282 100% kill in 23 hrs. (66)
10 Lethal threshold (66)
11.1 Lethal threshold (66)
14.3 Lethal threshold (66)
,000 Lethal threshold (66)
20 Lethal threshold (66)
10 Lethal threshold (66)
200 Lethal threshold (66)
,000 Lethal threshold (15)
83 immobilization threshold (15)
(.48 hrs)
29 immobilization threshold (15)
(64 hrs)
,200 Lethal threshold (15)
,430 Lethal threshold (15)
400 Lethal threshold (15)
1640 96 hr. TL (66)
m
2083 36 hr. TL (66)
m
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1
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•
1
1
1
1
1
1
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CHAPTER III
BIOCHEMICAL OXYGEN DEMAND AND SUSPENDED SOLIDS
IDENTIFICATION OF THE PARAMETERS
Biochemical oxygen demand (BOD) and suspended solids (SS) are
two of the most commonly used parameters to describe effluent quali-
ties.
The decay of organic matter washed into streams during a rain-
fall will exert a BOD. Natural erosion may result in a suspended
solids concentration. In addition to natural sources, domestic and
industrial wastewater discharges also contain substantial amounts of
BOD and suspended solids. Various sources and concentrations found
in the material studied are summarized in Table III-l.
BOD
The BOD test is a measurement of the oxygen required by living
organisms (bacteria) to decompose organic material under aerobic con-
ditions. It is a laboratory procedure, which is intended to represent,
in a controlled environment, that which would occur under normal stream
conditions. The oxygen demand is exerted by three classes of mater-
ials: carbonaceous organic material, that which is utilized by
bacteria under aerobic conditions as a source of food; nitrogenous
organic material (or oxidizable nitrogen of nitrite, ammonia, and
organic nitrogen) that which serves as food for the specific
Nitrosomonas and Nitrobacter bacteria; and reducible inorganic
compounds (such as ferrous iron, sulfite, and sulfide).
30
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TABLE
SOURCES OF BOD AND
Source Flow (MGD)
Domestic Waste
Strong
Medium
Weak
Digester
Supernatant
Digester
Supernatant
Food Industry
Cannery, Soup
Dairy, Cheese .0072
Dairy, Cheese .0072-. 072
Seafood
General Fish
Processing
Bottom Fish
Processing
Fish meal:
cooling water
process water
Herring Pump
Water
Stickwater 56
Rendering
Waste
Salmon .04 3-. 046
Cannery
III-l
SUSPENDED SOLIDS
BOD (mg/1)
300
200
100
616
840-1380
1530-2220
2700-3440
1726
192-640
621
1005
,000-112,000
42,000
3660-3900
31
SS (mg/1)
500
300
100
17,100
740
263
2200-3020
19,700
508-4780
Reference
(ID
(11)
(11)
(80)
(80)
(43)
(84)
(84)
(87)
(87)
(87)
(87)
(87)
(87)
(87)
(87)
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
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1
1
1
1
1
1
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1
•
1
1
1
•
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1
1
TABLE
SOURCES OF BOD AND
Source Flow (MGD)
Salmon . 33
Cannery
Salmon .011-. 66
Curing
Transport
Flume
Water
Waste
Flume
Tuna
Processing
Fruits &
Vegetables
Citrus Plant 2.0
Cannery Waste:
(screened)
Pear 0.01-1.87
Peach 0.30-2.02
Apple 0.43-0.60
Municipal- 2.0
Cannery
Meat Processing
Poultry
Poultry
Packing House
Slaughterhouse
Slaughterhouse 0.0235
Petrochemical
Industry
Mixed Chemicals
Refinery, Detergent
Alkylate
Refinery, Butadiene,
Butyl Rubber
III-l (Cont.)
SUSPENDED SOLIDS
BOD (mg/1)
3860
173-3082
200-1150
100-2200
895
840-2400
1170
1600-2040
860-1810
950-1390
141-424
1000
150-2400
712
400-3000
200- 800
1700
10-250,000
1950
345
225
32
SS (mg/1)
2470
40-1824
400
100-2100
1091
770
830
470-540
100-1500
530
230-2000
930-3000
27-60
121
110
Reference
(87)
(87)
(87)
(87)
(87)
(61)
(53)
(35)
(35)
(35)
(46)
(98)
(61)
(25)
(61)
(61)
(50)
(44)
(45)
(45)
(45)
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The five-day BOD as determined in the laboratory, generally
represents from 44%-94% of the ultimate BOD, depending on the rate B
constant (K). Recent investigations of pulp and paper mill waste
papers, however, have indicated that due to the extremely low rate B
of biological attack on lignin, less than 50% of the ultimate BOD is •
found in the 100 day period (77).
The BOD,, test is performed at a constant temperature of 20°C, B
which is well within the range of natucal stream temperature. Similar-
ly, the dilution water used is enriched and buffered with potassium, B
phosphate, calcium, magnesium and ammonium salts solutions to main- •
tain favorable nutrient and pH conditions throughout the test.
SUSPENDED SOLIDS
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The 13th edition of Standard Methods (1) defines suspended solids B
(non filtrable) as that portion of material in a liquid sample which
is retained on a filter. In general terms, suspended solids may be B
considered to be the colloidal material or the difference between
total solids and dissolved material.
Standard Methods points out that the principal factors involved B
in the analytical procedure are: the chemical and physical nature
of the material in suspension, the pore size of the filter, the area B
and thickness of the filter mat, and the amount and physical state
of the material being retained on the filter. Because the residue •
determination is subject to several variables it does not have the •
accuracy of some analytical procedures. The temperature at which
the residue is dried is important because the weight of the sample B
may be increased or decreased accordingly. For example, volatili-
33
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zation of organic matter, water of crystallization and gases from
• heat-induced chemical decomposition may be responsible for losses
_ in weight, while oxidation and absorbed atmospheric moisture may
™ cause a gain in weight.
I ENVIRONMENTAL EFFECTS OF BOD AND SUSPENDED SOLIDS
• The basic effect of both suspended solids and BOD discharges
on receiving waters is (1) the reduction of the dissolved oxygen
• level in the receiving waters through immediate and short term
oxygen demands, (2) the deposition of solids which through decompos-
| ition of benthic deposits exert a continuous oxygen demand and (3)
m the concentration of toxic compounds. Biological flocculation can
cause solids to settle out in streams, creating sludge banks, septic
• conditions, odors and general unsightliness. While BOD may enhance
the growth of some viruses and bacteria, it will have a deleterious
| effect on other aquatic organisms, through depletion of the dis-
•| solved oxygen in the stream. The concentration effect of some trace
metals such as arsenic, cadmium and mercury is discussed in other
• chapters.
I
The presence of biological suspended solids and associated BODr
• is an indicator of the potential presence of pathogens. It is
recommended (6) that domestic water supplies have a dissolved oxygen
• level of 4 mg/1 on the average, and never less than 3 mg/1. High
• concentrations of 6005 reduce the dissolved oxygen of the stream
and thus indicates the presence of organic pollution. Suspended
34
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Effect on Man
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I
solids are easily monitored continuously and can be used to control
possible turbidity and trace metal concentrations. •
Effect on Plants
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There is insufficient information available on which to base
definite limits on BOD or dissolved oxygen levels for irrigation I
water (6). It is noted, however, that the utilization of waters «
having high BOD or COD values are capable of aggravating conditions, *
by further depletion of the available oxygen and by production of I
conditions in the soil which may reduce trace metals. When the dis-
solved oxygen level is decreased, elements such as iron and manganese •
may be reduced to the more soluble divalent forms. Reduced forms of
some metals are toxic.
It is known that suspended solids are capable of interfering H
with the flow of water in conveyant systems and other structures.
In general, suspended solids are known to precipitate and settle •
when the velocity decreases to two feet per second. Suspended solids
can decrease the storage capacity of reservoirs and create excessive •
abrasion on structures, pipes and pumps. Suspended solids can cause •
crust formations on soils, thereby reducing the infiltration rate and
the emergence of seedlings. The beneficial use of BOD and suspended •
solids, however, have been well documented with respect to the
irrigation of sandy soils of low organic matter. The effect of BOD •
and suspended solids on soils and plants varies with respect to the •
permeability and type of soil which receives the discharge.
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•
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Effect on Domestic Animals and Wildlife
For animals and wildlife (as for man) , it is important to
• control BOD and suspended solids to maintain an adequate dissolved
oxygen level in the water and to insure a minimum concentration of
• disease producing organisms. Areas used by waterfowl, for example,
• must be kept aerobic to surpress Botulinus organisms which have been
reported to have killed millions of waterfowl (6).
Effect on Fish and Aquatic Organisms
• As with many pollutants, the discharge of BOD and suspended
solids to receiving waters has a major impact upon the fish and
Jj aquatic life present in those waters. The discharge of raw domestic
M sewage and certain improperly treated industrial discharges (such
as from paper and pulp and sugar industries) have been shown to
stimulate growth of Sphaerotilus bacteria. Heavy growths of
Sphaerotilus are well known for fouling fishing lines, clogging nets,
| and generating unsightly conditions. The metabolic demands of both
_ living and decomposing Sphaerotilus impose a high BOD load on the
* stream. Large populations of Sphaerotilus may render the habitat
B noxious to animals, thereby excluding desirable fish and inverte-
brates.
• Most of the research concerning oxygen requirements for fresh
water organisms deal with fish (6), however, it is logical to assume
• that a requirement for fish would also serve the rest of the aquatic
• community. On the basis of investigations of the various effects of
low dissolved oxygen on fish life, it was recommended (6) that for
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I
diversified warm water biota, including game fish, the daily dis-
solved oxygen concentration whould be greater than 5 mg/1. Due to •
expected daily and seasonal fluctuations, a dissolved oxygen level
between 4 and 5 mg/1 can be withstood for short periods, though. •
Similarly, for cold water biota the dissolved oxygen concentration
should be near saturation. It is noted that this is especially •
important in spawning areas, where the dissolved oxygen concentration •
should not be less than 7 mg/1 at any time. On the basis of support-
ing growth and propagation of trout, salmon and other cold water I
species of the biota, a dissolved oxygen concentration of at least
6 mg/1 should be provided at all times. With respect to dissolved •
oxygen levels of small and large oligotrophic lakes, it was recommended •
that the hypolimnion not contain less than 6 mg/1 oxygen at any time.
Investigations of the marine environment revealed that satis- •
factory survival and growth of marine organisms are supported by a
dissolved oxygen level ranging between 5 and 8 mg/1. Studies on •
marine animals have shown that a dissolved oxygen level less than 1.25 •
killed most of the marine test animals within a very few hours. It
was therefore recommended that the surface dissolved oxygen concen- •
tration of coastal waters be not less than 5 mg/1, except for natural
variations (6). With respect to estuaries and tidal tributaries, it •
was recommended that the dissolved oxygen level should not be less m*
than 4.0 mg/1 at any time, except for natural variations.
TREATMENT TECHNOLOGY - BOD AND SUSPENDED SOLIDS
I
In reviewing current engineering text, one is readily cognizant B
that flowing streams have an ability to recover from biological load-
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37
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• TABLE III-2
RELATIVE EFFICIENCIES OF SEWAGE TREATMENT (37)
I
Percent Removals
Treatment Operation or Process BOD SS
Fine Screening 5-10 2-20
Plain Sedimentation 25-40 40-70
Chemical Precipitation 50-85 70-90
• Trickling filter preceded and followed 50-95 50-92
by plain sedimentation
• Activated sludge preceded and followed 55-95 55-95
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by plain sedimentation
Stabilization ponds 90-95 85-95
38
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ings. The ability to utilize self purification of streams as a
safety factor, has been aptly discussed by Fair, Geyer & Okun (37). |
Their report includes the following quotation: "The removal of 90-95% •
of the suspended solids, BOD, and COD of wastewaters before the
discharge of effluents into receiving waters is not considered enough, •
nor is a subsequent natural purification of receiving waters for reuse
by man accepted as sufficiently rigorous to assure the safety and |
palatability as well as the general usefulness of such waters." We «
are thus faced with the question of not what can the river take and
survive, rather, what can be done with currently applicable technology •
within reasonable cost to enhance the quality of our resources.
Removal of BOD and suspended solids from industrial and muni- |
cipal wastewaters may be achieved by physical, chemical and biological •
operations and/or processes or a combination of all three. The re-
spective removal efficiencies which one can anticipate from various •
treatment operations and processes are summarized in Table III-2 from
Fair, Geyer and Okun (37).* As may be seen from the table the greater J|
efficiency of both BOD and suspended solids removal is achieved .
through biological processes. A report by Stewart (92) on the various *
modifications of activated sludge indicates that biological processes •
may be loaded over a wide range with respective degrees of removal.
A tabulation of the twelve more common modifications of the activated •
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* One should realize, however, that when the data in this table
were prepared, many of the newer process and operation modi-
fications were not in use. •
39
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• sludge process are summarized in Table III-3.
In addition to the standard procedures of Tables III-2 and 3,
• treatment technology for BOD and suspended solids removal during the
• last several years has made substantial improvements. Among these
are the tube settlers, microscreens, ultrafiltration, multi-media
• filtration, upflow clarifiers, and moving bed filters. A summary of
these improvements and their effectiveness for removal of BOD and
m suspended solids, in the form of additional treatment steps and as
• substitutes for secondary type treatment, is given in Table III-4
from the work of Convery (26) and the EPA Technology Transfer Manual
• on Suspended Solids Removal (23).
Suspended solids are associated not only with biological process
• waste, but also with chemical treatment. As a great deal of the
• suspended solids are found in the colloidal state, one should consider
the mechanisms of removal which are described by Nemerow (72) and
• Rich (78,79). Colloidal solids may be removed by chemical coagula-
tion, neutralization of the electrical charge, and adsorption. Re-
| moval of colloidal solids by chemical coagulation requires the forma-
« tion and precipitation of insoluble metal hydroxides and oxides or
interaction with organic polymers having charged sites. Neutraliza-
• tion of the electrical charge involves lowering of the zeta potential
and/or neutralization of the colloidal charges with an excess of
| oppositely charged ions. In the presence of an excess of oppositely
» charged ions, hydrous oxides are formed which enhance both chemical
coagulation and adsorption. Adsorption is a surface phenomenon in
• which organic and/or inorganic matter is adsorbed on a material.
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TABLE III-3
EFFICIENCY OF ACTIVATED SLUDGE MODIFICATIONS (92)
Process
Extended Aeration
Conv. Activated Sludge
Tapered Aeration
Step Aeration
Activated Aeration
Contact Stabilization
Hatfield Process
Kraus Process
High Rate
Modified Aeration
Rapid Bloc
Supra Activation
Loading Factor
Lb. BOD/Day/1000 cu. ft.
20
35
35
50+
50+
70
70+
100
100
100
150+
400 •
41
Percent Removal
BOD 5
75-85
95+
95+
90-95
80-85
85-90
85-90
85-90
60-75
60-75
90-95
55-65
1
1
1
1
I
1
1
•
•
1
1
1
1
1
1
1
1
1
1
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I
Good adsorbents have active or activated surfaces with a high
• surface to volume ratio.
In addition to the interrelationships of chemical coagulation,
| neutralization, and adsorption processes for the removal of colloidal
M solids, a polishing step such as rapid and/or multi-media filtration
is beneficial. Other methods utilized for the removal of suspended
• solids include flotation and microscreening.
From the above discussion, it is apparent that BOD and suspended
solids may be removed from municipal and industrial wastewaters.
_ Typical percentages of BOD removal range from 75-95%. Suspended
* solids removal in terms of percentage is found to parallel the
I percentage removal of BOD. Likewise, as the suspended solids are re-
duced, so are the levels of many other pollutants. A summary of the
I data found in the literature with reapect to industrial waste and
_ information from "Deeds and Data" (4) is shown in Figure Ill-i. It is
™ apparent from the data plotted in Figure Ill-i that a relationship
• does exist between the effluent BOD and effluent suspended solids
levels. In a well designed and operated biological treatment system,
• the soluble portion of the BOD in the effluent will be extremely small
with respect to the portion of BOD which is associated with the sus-
• pended solids. Thus, by removal of the suspended solids after
• biological treatment and clarification, one can expect that not only
will the suspended solids be greatly reduced, but the BOD will also
• be reduced.
By referring to Figure Ill-i it is apparent that for a biological
• effluent with a suspended solids level of 60 mg/1, a BOD of approxi-
mately 80 mg/1 would be expected, however, it could possibly range
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1
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between 50 and 120. In the lower portion of the figure, the suspended
I solids appear to vary more widely than does the BOD. This indicates
_ that at a lower range of BOD one is speaking almost strictly of a
* soluble BOD which has not been removed by biological treatment, rather
• than one associated with suspended solids. It also appears that as
the suspended solids approach zero, the remaining BOD is soluble and
I not suspended. It, therefore, appears logical to conclude that should
_ the waste with a suspended solids level of 60 mg/1 and a BOD level of
~ 80 mg/1 be further treated for the removal of suspended solids to a
• level of 20-30 mg/1, the associated BOD will also be removed with
only the soluble BOD remaining. From the figure, a residual BOD of
• 10-30 mg/1 could be expected.
In consideration of the data shown in Figure Ill-i, and the
' achievable final effluent levels associated with suspended solids, the
• soluble portion of the BOD in the effluent may be expected to vary
with respect to the activated sludge or other biological treatment
I process. For example, a treatment plant utilizing a high rate bio-
logical system could have a substantially greater amount of soluble
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BOD in the effluent than one using the contact stabilization or
extended aeration modification of activated sludge.
TREATMENT SUMMARY:
From the above discussions, it is apparent that the technology
does exist for the removal of BOD^ and SS. It is rather a matter of
the application of the technology. Some industries as shown in the
_
• previous section, have accepted the challenge and are currently
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achieving treated effluents with 8005 less than 30 mg/1 and SS less
than 30 mg/1. I
It is recognized that, in general, biological processes lose
their peak efficiencies during cold winter weather. They are capable I
of maintaining a final effluent of less than 75 mg/1, however. As •
streams naturally have higher D.O. levels, due to greater oxygen
transfer in the winter, slightly higher 8005 loadings may be handled I
without creating problems. Weather, however, does not affect the
impact of suspended solids on the receiving waters. Therefore, the |
suspended solids level of all discharges should be maintained below _
30 mg/1 year around.
It is also recognized that natural conditions such as, surface I
runoff may add significant loads of suspended materials on the receiv-
ing waters. This must not be an excuse to add further to the problem |
through industrial and municipal discharges. Rather, it is the reason _
and need to improve management practice of agricultural lands, urban
storm runoff, etc. I
SUMMARY AND RECOMMENDATIONS •
On the basis of the literature reviewed and the above discussions,
the following conclusions are cj^awn. •
1) Material which exerts a biochemical oxygen demand and I
suspended solids are found in surface waters from many
natural and man-made sources. I
2) The major impact of BOD is through the depletion of oxygen
in the receiving waters. •
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45 I
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3) Suspended solids exert an impact on the receiving waters
by creating sludge banks, general unsightliness, acting
as an adsorbent for toxic chemicals, destroying of/'fish
spawning grounds, creating excessive wear on transport
facilities, and by depleting the storage capacities of im-
_
* poundments.
I 4) Domestic water supplies should contain neither BOD nor SS
as both can be associated with disease producing organisms
I and virus.
5) Waters used on plants should not contain excessive amounts
• of BOD or SS.
I 6) Sandy soils may be used effectively for waste disposal.
The extent of this use depends upon the organic content of
• the soil and its permeability.
7) BOD and SS must be kept to a minimum to insure adequate
' dissolved oxygen to suppress Botulinus organisms.
• 8) BOD and SS must be maintained at minimum levels to ensure
adequate dissolved oxygen for fish and aquatic life in both
• fresh and marine waters.
9) The technology currently exists to remove 5 day BOD and SS
• to effluent concentrations less than 30 mg/1, each.
• 10) Cold temperatures may decrease the performance of biological
treatment processes. However, an effluent level of 75 mg/1
• should be attainable by biological means during cold weather.
11) Removal of suspended solids from biologically treated waste
effluents will also remove the associated BOD of the flocculant
solids.
46
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_
™
12) Effluent BOD5 below 20 mg/1 will most likely be in a dis-
solved state and may not be further removed with SS unless
treated further.
13) Removal of collodial suspended solids from chemically •
treated wastewaters is often necessary to maintain low
effluent levels of trace metals. I
14) The removal of oil and grease residuals after biological
treatment can be improved through better suspended solids •
removal . •
On the basis of these conclusions and the text of this report, it is
recommended that the following effluent limits be adopted: •
guspended Solids; Maximum level of 30.0 mg/1 at all times.
Biochemical Oxygen Demand-5 Day: The BOD,- shall not exceed •
a 24 hour average of 30 mg/1 for three (3) consecutive days, except •
during winter when the 24 hour average shall not exceed 75 mg/1 for
three (3) consecutive days •
For EPA Region III it is recommended that "winter" apply to the
months of December through February in the southern area and November I
through March in the northern most areas. •
It is further recommended that the 6005 not exceed a concentration
of 90 mg/1 at any time. I
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CASE STUDIES OF BODS & SS REMOVAL
• A. Food Industry
A new addition to the realm of biological treatment processes
m is the BIO-DISC. The BIO-DISC system consists of closely spaced,
• round discs mounted on a horizontal shaft. Functionally, it combines
the principles of trickling filters and activated sludge. It has been
• reported by Antonie (10) to be effective both in pretreatment and as a
secondary treatment process. Treatment efficiencies BOD,--removal are
I5
summarized in Table III-5. As a biological process it is capable of
mm achieving a final BOD5 effluent in the range of 17-55 mg/1.
In treating dairy cheese waste for a cheese factory in Hilbert,
• Wisconsin, in a two stage aerobic "Cavitator" system, Schulze (84)
reported the following efficiencies:
| 1. A BOD 5 concentration of 840-1380 mg/1 was reduced to an
_ effluent of 12-18 mg/1. The loading was 80 Ib. BOD/D,
™ detention 20 hr. and flow 7200 GPD.
• 2. A BOD5 concentration of 1530-2220 mg/1 was reduced to an
effluent of 15-29 mg/1. The loading was 140 Ib BOD/D,
| detention 12 hr. and flow 7200-72,000 GPD.
_ A report by Soderquist, et^ aJL. (87) discussed the treatment of fish
™ processing wastes by coagulation, flotation, and activated sludge.
• Clarification with 4000-5000 mg/1 F-FLOK coagulant on Salmon process
waste reduced total solids from approximately 2000 mg/1 to about 800
• mg/1. Eighty to 92% of the protein was also recovered by this method.
Breaking of fish oil emulsions with clay, lime, alum, and ferric
• chloride has been reported as 75% effective in BOD removal. The
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chlorination required prior to sedimentation reduced suspended solids
to about 200 mg/1 and BOD to 400 mg/1. Flotation with coagulant aids I
on salmon processing wastes was also reported as partially effective
in BOD and solids removal. The results are summarized in Table III-6. ••
An activated sludge pilot plant treating fish process waste reduced •
suspended solids from 320 mg/1 to 12-70 mg/1, BOD5 from 1000 mg/1 to
5-27 mg/1, and Total N from 70 mg/1 to 35-51 mg/1. I
By utilizing spray irrigation on terraced land, Gilde (43) reports
that food processing waste from Campbell Soup Company was treated to •
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the following effluent characteristics.
Mean Concentration, mg/1
Parameter Wastewater Effluent
Total Suspended Solids 263 16
Total Organic Carbon 264 23
BOD5 616 9
Total Phosphorus 7.6 4.3 I
Total Nitrogen 17.4 2.8
I
The design criteria from the Paris, California, study (43) included
a slope recommendation of greater than 2% but less than 6%, with a •
150-175 foot zone between the sprinklers and the effluent collection
berm. The application rate was 0.25 inch per day in winter and 0.50 •
inch per day in summer. The plots were planted with Reed Canary grass.
In a recent report on fruit processing waste, Exvelt 35 reported •
that raw waste loads in the range of 860-2040 mg/1 BOD^ can be reduced •
by aerobic treatment to an effluent of less than 10 mg/1 when the
unit is loaded at 0.5 mg BOD removed/mg MLVSS-Day. •
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TABLE III-5
BIO-DISC OPERATING EFFICIENCY (10)
WASTE WATER
Dairy :
Fresh
Septic
Brewery:
Bakery :
Septic
Combined Domestic &
Industrial
Distillery:
Piggery: Septic
BOD 5 Cone,
Influent
1000
1100
850
600
2000
1200
600
800
500
mg/1
Effluent
300
30
55
17
300
30
350
480
30
40
50
Percentage
REMOVAL
70
97
95
98
50
95
85
80
95
95
90
Residence
TIME, hr.
0.3
2.5
5.0
2.9
0.2
0.5
2.8
2.2
1.1
0.7
2.2
52
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TABLE III-6
FLOATATION WITH COAGULANT AID (87) ON SALMON WASTE WATERS
BOD TS SS
COAGULANT INF. EFF. INF. EFF. INF. EFF.
Alum 47 mg/1 - - 5400 1560
11 " 2290 1200
Ferric Chloride 60 mg/1 - - 5580 2400
" •• •• _ 2860 950
" " 133 mg/1 - - 1800 1180
F-FLOK 1000 mg/1 - - 5900 1200
Aluminum Hydroxide 75 mg/1 1775 425 2685 1505 640 1305
Zetol A 1 mg/1 1275 381 2441 1625 697 200
Alum 375 mg/1 plus 2833 633 4268 2162 1993 397
lime 75 mg/1
53
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It is apparent from Exvelt's report that good solids removal
is manditory for low BOD in the effluent. The results of Exvelt's
studies are summarized in Table III-7 below. The new plant was put
• into operation between the 1968-69 season. The last 3 data sets are
the most significant.
m Graham and Filbert 46 have reported that a combined municipal
• cannery waste with a combined 8005 concentration of 141-424 mg/1 has
been reduced to an effluent of 16 mg/1 or less, 96 percent of the time.
• Treatment consists of aeration basins with sludge return, clarification,
and chlorination. They also report an effluent of 3.2 mg/1 orthophos-
• phate (as PO.) which was a reduction over the influent. The average
• flow was 2.0 MGD.
In treating slaughterhouse waste, Hopkins and Dutterer (50)
• noted a BOD-j removal from 1700 mg/1-10 mg/1. The 23,499 GPD plant
utilized screening grease separation by air flotation and skimming,
I agitition, activated sludge, chlorination, and ponding.
« Merrill 68 reported settleable solids removal from 3788 and 3339
mg/1 to 561 and 38 mg/1, respectively from frozen meat packing wastes.
fl Treatment by air flotation of grease, alum (A12(SQ ) ) coagulation
extended aeration, clarification and chlorination yielded a final
I effluent of 17 mg/1 (85-95% removal).
A poultry processing plant in West Germany is reported by
_
Wieferig 98 to have reduced 1000 mg/1 BOD. from its wastewater to
I an effluent of less than 25-30 mg/1. Treatment consisted of surface
aeration after removing fat, feathers and solids.
I
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TABLE
AEROBIC TREATMENT OF
III-7
CANNERY WASTE (35)
Screened Waste
Fruit
Processed
A. Aerated
1967 Pear
1967 Peach
NOV
1967 Apple DEC
JAN
1968 Apple FEE
Flow
MGD
Lagoon Ef]
1.03
1.36
0.60
0.52
B. Activated Sludge;
1968 Pear
1968 Peach
MAR
1968 Apple APR
MAY
1969 Peach
1969 Pear
1969 Apple
C. Contact
1969 Pear
0.21
0.30
0.40
2.02
1.87
0.43
BOD
mg/1
Eluent ;
2040
1810
1230
950
Cost
2040
1810
1390
860
1600
1190
Stabilization;
1.58
2150
c
Effluent
COD BOD COD SS
mg/1 mg/1 mg/1 mg/1
Cost $0.041/#BOD Removed
3050
2150
1520
1400
$0.061/#BOD
3050
2150
1830
1510
2290
1500
370 1040 770
340 - 830
190 760 540
110 620 470
Removed
250 490 375
360 - 370
130 570 470
20 120 66
9 55 15
5 28 11
Cost $0.067/#BOD Removed.
2910
IB
4 23 6
1
1
1
1
1
1
1
1
1
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1
1
1
1
1
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I
_ Camp (25) ,in describing in-house changes for a poultry process
™ in Florida, reported that by improving plant operating practices
flT the average flow rate was decreased from 422 gpm to 357 gpm. The
BOD,, was also reduced from 712 mg/1 to 263 mg/1. Improvements in-
• eluded cleaning of traps and separators, reducing spills and improv-
ing dry clean-up procedures prior to wash down.
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_ Following the inplant reductions a treatment plant was designed and
™ constructed to use segregated wastewater collection, surface settling,
• extended aeration, final settling and a four acre polishing pond.
Operation record revealed a final clarifier effluent of 15 mg/1 BOD^
• maximum, 8 mg/1 average (98.5-99.5% removal) and a suspended solids
_ level of 10 mg/1 maximum, 6 mg/1 average. The polishing pond effluent
™ showed a BOD^ of 8 mg/1 maximum and 3 mg/1 average.
B. Petrochemical Industry
• The treatment of various petrochemical wastewaters was reported
by Gloyna and Ford (44,45). Tables 111-8,9,10 and 11 smmarize their
V findings on BOD- removal efficiencies by activated sludge, trickling
filters, aerated lagoons, and waste stabilization ponds, respectively.
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C. Pulp and Paper Industry
A review of recent literature indicates that while activated
sludge is the major method of treating pulp and paper wastewaters,
chemical treatment is being tested in full scale facilities with
• success. In treating 125 kg/ton BOD by anerobic fermentation and
aeration, Grishina and Izotova (47) report that the BODq was reduced
from 1000 mg/1 to 20 mg/1. The effluent COD remained high, however,
« and a BOD:M:B ratio of 100:3:0.5 was necessary.
Dobolyi 29 reported a final affluent of 25 mg/1 BOD and 430
• mg/1 COD for an intergrated mill pulping straw by the Kraft process.
The waste was pre-treated by coagulation with 400 mg/1 Fe 90, and 600
mg/1 Ca(OH) prior to biological treatment. In using activated sludge
64
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.a c -. W
PM
CO
0)
CO 0) rH
o
4J W CO
CO 0)
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on a Kraft mill waste, Ganczaruzyk (40) reported BOD
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I
and vegetable tanning waste contain 1000-1500 mg/1 BOD_; 2000-8000
• mg/1 COD, and total Kjeldahl nitrogen of 150 mg/1. Treatment by an
anerobic-aerobic lagoon yielded an effluent with 20-330 mg/1 BOD
• (200 mg/1 aver.), 300-1700 mg/1 COD (900 mg/1 aver.), and total
• Kjeldahl nitrogen of 100 mg/1 (aver.). In a similar study, Parker
(25)reported the treatment of vegetable tannery waste by activated
• sludge. The results of his study are summarized in Table 111-13.
They show the affect of different loadings and detention.
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E. Textiles
M A report by the A.D. Little Company (60) discussed the treatment
_ of textile wastes. The SRWL for BOD5 was reported to range from 270-
™ 1000 mg/1. Very little removal of total dissolved solids is accom-
tf plished by conventional activated sludge, extended aeration or lagoons.
Total dissolved solids of the textile waste reported ranged from 500-
• 3000 mg/1. The effectiveness of biological treatment on textile
wastes is summarized in Table 14.
F. Steel Industry
| In a 1954 paper on the treatment of flue dust waste from the
^ U.S. Steel Fairless Works, Henderson and Baffa 49 reported that
primary thickening, flocculation with lime, followed by clarification
V is capable of reducing the influent suspended solids from 2000 mg/1
to less than 50 mg/1.
• In treating combined once through cooling water and concentrated
^ coolant wastes at a 12:1 ratio, Armco (2 )f ound the following oil
™ removals with 195 mg/1 alum, 43 mg/1 lime, 32 mg/1 clay, and 1 mg/1
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TABLE 111-12
*
EFFLUENT QUALITY & COST (62)
Cumulative
BOD COD SS COLOR TDS Cost
PROCESS mg/1 mg/1 mg/1 (Units) mg/1 C/1000 GAL
Influent 284 1600 440 2000 1450
Primary Eff 277 1440 38 2000 1450 3 to 4
Biological
Aerated Lagoon 63 700 50 1800 1450 902
Activated Sludge 20 410 20 1800 1450 10
Massive Lime 15 400 20 200 1200 20
Sand Filtration 10 400 1 200 1200 23
Carbon Absorption 2 10 1 10 1100 23
Ion Exchange nil 5 1 nil nil 77
*
Based on 1969 ENR Const. Cost
Example Discharge of 24.3 MGD.
69
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TABLE 111-13
EFFLUENT DATA FOR BLENDED BATE POOL & TANNINS FROM Parker (75)
PARAMETER
Flow, GPM
Detention, days
BOD Load, lb/1000 ft 3/D
% BOD Removed
% COD Removed
BOD5, mg/1
COD, mg/1
ORG-N, mg/1
NH~N, mg/1
j
TKN, mg/1
TS, mg/1
TDS, mg/1
TVS, mg/1
SS, mg/1
Set. S., ml/1
PH
T. Sulf., mg/1
TP, mg/1
AVE. RAW
WASTE I
15
49.6
1.8
97
76
1043 35
4470 1135
40.6 15
47.1 25
87.8 40
9190 6000
6500 5500
2710 900
539 500
15.1 20+
6.0 7.0
1.5 0
6.83 2.3
70
II
20
37
2
96
65
47
1650
30
28
59
7600
6600
1100
900
40
7
0
7
PHASE
III
33
.4 16.2
.4 4.5
84
42
187
2740
36
34
70
2500
1400
1000
500
3
.2 7.3
0
.7 5.6
IV
69
7.8
9.4
67
38
270
2930
18
18
36
2000
800
1400
500
1
7.1
0
5.8
V
127
4.2
17.3
63
37
315
3000
25
43
68
2400
1200
1200
450
2
6.8
0.4
3.6
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TABLE 111-14
BIOLOGICAL TREATMENT OF TEXTILE WASTE FROM A. D. Little (60)
TREATMENT PROCESS
a) Modified Activated
Sludge-Cotton & Polyester
b) Extended Aeration -
Cotton & Polyester & Rayon
c) Extended Aeration -
Printing
d) Extended Aeration -
Cotton & Polyester & Rayon
e) Extended Aeration -
Polyester & Synthetics
f) Extended Aeration -
Cotton
g) Activated Sludge -
Cotton & Synthetics
h) Extended Aeration -
Polyester & Rayon
i) Aerated Lagoon -
Wool
j) Aerated & Natural Lagoons -
Average of 8 Plants Fabric
Unknown or Cotton & Nylons
with Dyeing and Finishing
BOD
SRWL - EFF
760-120
450-85
650-45
560-75
450-65
570-33
,. , 600-25,
t0 {1000-75}
300-50
164-64
360-45
SS_
SRWL - EFF
105-270
50-25
175-50
200-75
25-25
. ,100-5 ,
t0 {300-70}
112-121
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Parameter
Total Oil, mg/1
BOD5, mg/1
COD, mg/1
Suspended Solids, mg/1
SRWL
1276
893
6320
770
Effluent
76
57
441
55
% Removal
91
93
89
93
™ cationic polymer.
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The report also concluded that the pH needed to be maintained above
• 6.0 for efficient treatment and that flow equalization was an
absolute must.
• The cost of treating combined once through cooling water and
• concentrated coolant oily waste was between $0.046-0.051/1000 gallons
of waste. Treatment included coagulation and air flotation. Although
I the recovered oil scum had no potential as fuel oil, it was sold to
municipalities for use as road oil (2) .
G. General.
The performance of surface-aerated basins on BOD- removal prior
to clarification has been summarized by Beychok (L8). Table 111-15
shows some of his data.
72
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TABLE 111-15
INDUSTRIAL WASTE TREATMENT by SURFACE AERATED BASINS (18)
Industry
Pulp & Paper
Pulp & Paper
Oil Refinery
Pulp & Paper
Pulp & Paper
Petrochemical
Pulp & Paper
Pulp & Paper
Pulp & Paper
Textiles
Distillery
Fiberglass
Oil Refinery
Petrochemical
Oil Refinery
Wood Treating
Cannery
Cannery
BOD, mg/1
Inf Eff
254 93
239-93-33
85.5-57-45
225-119-78.5
225-62-40.5
600 90
131 92
526 95
402 74
200 100
550 94
933-98-78.5
270 72
2500 200
160-120-40
2200 200
360 21
980 50
Remarks
Single Basin
Two Basins in series
" " No Nutrients
" " w/Nutrients
Two Basins in Parallel
Single Basin
Two Sections in Series
Single Basin
Single Basin
Single Basin
Two Basins in Series
n ii n ii
Single Basin
Two Basins in Series
Single Basin
Lit. Rev.
73
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Further treatment of effluents of this quality would be needed
• prior to discharge. However, application of one of the methods de-
scribed in the previous section could easily provide an effluent
• with a BOD5 and SS of less than 30 mg/1 each.
• While BODr per se is not associated with trace metals and
hydroxide sludges, suspended solids are. In this regard, filtration
I of settled chemically treated wasteswaters is often necessary to
maintain desired effluent levels for the trace metal.
I
In treating electroplating wastes, McDonough and Steward 64
reported that the use of the Lancy Intergrated treatment system
I
yielded a final effluent of less than 10 mg/1 suspended solids.
• In testimony to the Illinois Pollution Control Board (97)
Weston cited filtration as a polishing step in the removal of
W arsenic, barium, calcium, copper, iron, manganese, nickel, and zinc.
•I As discussed in the chapter on "Oil and Grease," the removal of
biological floe and suspended solids by filtration from biological
• effluents will improve the removal of oils. For further details
refer to the individual chapters for the parameter in question.
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CHAPTER IV-CADMIUM
SOURCES OF CADMIUM
Cadmium, like many other metals, occurs naturally in soil,
fresh and salt waters, consequently in our food and bodies.
+2
In the natural aquatic environment it occurs as soluble Cd
salts, soluble inorganic and organic complexes and insoluble pre-
cipitates. At a pH of greater than 7, cadmium hydroxides and car-
bonates will precipitate.
Friberg ej^.al. (39) report that cadmium in the environment is
particularly associated with zinc, lead and copper concentrations.
In areas not known to be polluted with cadmium, natural conditions
in the soil are reported to be less than 1 ppm. Normal levels of
cadmium in food are reported to be less than 0.05 ppm. Similarly,
McKee and Wolf (66) have reported that a normal concentration of
cadmium for many plant and animal tissues is about 1 mg/kg. Table
IV-1 lists some naturally occurring concentrations of cadmium.
While cadmium is normally present in the environment, its
concentration in water is being increased by many industrial discharges.
Since it is associated with the refining of zinc, lead, copper, and
the alloying of copper, lead, silver, aluminum, and nickel, it is
very likely that cadmium pollution started as early as the first use
of any of these metals. Industrial activities which contribute to
increased concentrations of cadmium are shown in Table IV-2. Friberg
ert.al. (39) also reported that the burning of oil and waste and scrap
metal treatment may contribute to the cadmium concentration. Their
work also showed that agricultural fertilizers, either as chemicals or
as sludge from sewage treatment plants, contain cadmium which may be
75
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TABLE IV-1
NATURALLY OCCURRING CONCENTRATIONS OF CADMIUM
Source Concentration Reference
Soils* 1 mg/kg (39)
Food (normal level) 0.05 mg/kg (39)
Many plant and animal 1 mg/kg (66)
tissues
Some natural waters 0.010 mg/1 (39)
Sea water 0.08 mg/1 (6 )
Marine plants 0.4 mg/1 (6 )
Marine Animals 0.15-3mg/l (6 )
3
Air (Manhattan Yearly mean 0.023 mg/m (39)
3
Air (non-urban New York) Yearly mean 0.003 mg/m (39)
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TABLE IV- 2
INDUSTRIAL SOURCES AND CONCENTRATIONS OF CADMIUM
Cadmium
Industrial Source Concentration (mg/1)
Alkaline accumulators
Automobile heating control 14-22
manufacturing
Ceramic manufacturing
Chemical Industries
Pigment Works
Textile printing
Plastics
Lead mining
Acid drainage 1,000
Metallurgical alloying
(on copper, lead, silver,
aluminum, and nickel)
Plating
Plating rinse waters 15 average
(large installations) 50 maximum
0.5 GPH drag-out 48
2.5 GPH drag-out 240
Plating bath 23,000
Electroplating waste <2-4
77
Reference
(39)
(76)
(61,66,76)
(61,76,66)
(76,39)
(61,76,66)
(39)
(76)
(61,66,76)
(76)
(14)
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released to the aquatic environment. Lund (61) reported that cadmium A
is a by-product of nuclear reactor operations. Salts of cadmium
are also used in insecticides and as anti-parasitic agents. •
ENVIRONMENTAL EFFECTS OF CADMIUM
Effect on Man and Animals
78
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Table IV-3 lists the physiological effects of cadmium upon
animals. The consumption of water containing cadmium has been found 9
to result in cumulative poisoning in mammals. McKee and Wolf (66)
have reported that cadmium tends to concentrate in the liver, kidneys, •
pancreas and thyroid of humans and animals. _
In general, for humans there are two principal mechanisms of •
absorption: respiration and ingestion (39). For this report the •
primary concern is the gastrointestinal mode of ingestion. Friberg
e^.a.1^. (39) reported that in human newborns, the total body content I
of cadmium is small, less that .001 mg. Their studies, and those
which they reviewed, indicated that the placenta of the mother apparent- m
ly acts as a shield to the fetus, even for those mothers who had been •
exposed to excessive cadmium concentration prior to the child's birth.
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flj The concentration of calcium has been found to play an important
role in the assimilation of metals from the intestines. While the
I hardness of the water itself is not the most important factor, a low
calcium diet has been shown to allow up to 50% more concentration of
• cadmium in the liver and kidneys of rats. Similarly, a low protein
• diet, irrespective of the calcium content within the diet, was found
to give considerably higher levels of cadmium in the kidneys, livers,
• and whole bodies of rats.
Friberg ^.a^. has shown that cadmium in the human body may
V cause hypertension and arteriosclerotic heart disease, bone damage,
• sterilization, liver, and renal damage.
Cadmium together with vanadium has also been correlated with
• mortality by heart disease. Bone damage can occur under relatively
short periods of exposure to only moderate concentrations of cadmium
V when the calcium content of the individual's diet is low. The report
m by Friberg et.aJ^. also concluded from studies on animals that cadmium
and cadmium compounds can give rise to malignant tumors. With respect
• to the potential carcinogenic effect of cadmium on man Friberg
stated, "the carcinogenic evidence of cadmium in human beings is by
0 no means conclusive as yet but fully motivates further and intensive
m studies in groups exposed industrially as well as those through food
and ambient air".
• Normal daily intakes of cadmium in human diets as reported
by Friberg jet.al.. (39) varied between 0.004 and 0.06 mg in five
| different countries studies. Table IV-4 gives suggested maximum
M cadmium concentration in drinking water.
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TABLE IV-3
PHYSIOLOGICAL EFFECTS OF CADMIUM UPON ANIMALS
Species
Human
Human
Human
Human
Rabbits
Dogs
Hamster
Dose Effect
150 mg/kg Lethal in 1.5 hrs.
14.5 mg Nausea and vomiting
From water - Disorders of renal
"High cone." function, "Itai itai"
disease
From water Hypertension linked to
and food increased retention of
Cd in kidneys
0.3-0.5 g/kg 0/16 animals with
0.1-50.0 ppm tumors
in drinking
water
0.15-0.3 mg/kg Fatal
High Positive teratogenicity
80
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Reference |
(66)
(66) I
(39) *
(39) •
(39) I
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(39)
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Friberg, et_.a\^. (39) concluded from experiments on animals
that an absorption rate of less than 10% of the actual oral dose
would be normal and that in most cases a 2% absorption could be ex-
pected. However, there were large individual variations. In con-
sidering the absorption for a "standard man" with an estimated 50
years intake, they estimated a normal absorption rate between 3 and 8%.
They recommended, however, that an absorption rate of 10% should be
considered as quite possible until clarified by further studies. The
research indicated that normally the highest concentration of cadmium
will be found in the kidneys. Based upon experiments on animals,
Friberg £t_-al_. has determined that a concentration of about 200 ppm
wet weight is a critical concentration in the renal cortex. At an
assumed 10 percent absorption rate over a fifty year period, for
example, a daily consumption of 0.05-0.075 mg/1 cadmium would result
in renal dysfunction. (At a 5% absorption rate over the same period
of time a daily consumption of 0.1-0.15 mg/1 would have the same result.)
Friberg et^.al^.concluded that a concentration of 0.01 mg/1 in a water
supply would contribute little to the daily intake of man (assuming
the standard consumption of 1-2 liters of water per day). A con-
centration of 0.02 mg/1, however, would increase the cadmium con-
sumption from 0.02-0.04 mg per day. This then approaches a critical
concentration at a 10% absorption.
In discussing the possible biological half-life of cadmium in
man, Friberg, .et_.al.. (39) concluded "...it is conceivable that cadmium
will be retained for many years in man once it has been absorbed.
This is supported by findings in autopsies of workers which indicate
81
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a very slow decrease in liver levels after exposure ceased." ^
Effects on Plants
82
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Friberg _e_t_.al_. (39) identified rice and wheat as two food
products which are capable of concentrating cadmium from the soil.
In general, they found that wheat accumulated cadmium to a slightly
greater extent but both concentrations were around 1 ppm. Rice •
and wheat grown in most parts of the world will normally contain less
than 0.1 ppm of cadmium in the grain. 9
I
Effects on Fish and Other Aquatic Life
Table IV-5 shows that the acute lethal level of cadmium with
respect to fish varies from a low of 0.01-10 mg/1, depending upon •
the organism, the hardness of the water, the temperature, and the
•
time of exposure. McKee and Wolf (66) and others (15) show that cadium
toxicity increases with water softness for all the forms of fish life •
studied. As hardness increases, thereby increasing the chance of a
higher calcium diet for aquatic life, the toxicity of the cadmium •
compounds decreases. Several authors have reported a synergistic •
effect with respect to toxicity of cadmium compounds in the presence
of zinc, copper, selenium, and cyanide (6,15,66). •
In investigating the concentrations of cadmium in seafood,
Friberg et..a.L (39) reported that oysters from the East Coast of the •
United States contain 0.1-7.8 ppm (wet weight) whereas West Coast •
oysters contain only 0.2-2.1 ppm (wet weight).
Cadmium, like other trace metals, has been reported to be con- •
centrated upon suspended particles and in bottom sediments (39) .
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• In the literature reviewed by Friberg et^.al^. (39) one particular
case indicated that 500 meters downstream from a factory discharging
• cadmium, only 0.004 mg/1 of cadmium was found in the water, while
80 mg/1 (dry weight) was found in the bottom sediments. Thus, we
I must be aware that even the lack of detection of cadmium in the
« surface water does not preclude the possibility of relatively high
cadmium concentrations being available to biota of the stream.
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TABLE IV-4
CADMIUM STANDARDS PROMULGATED (66)
• Maximum
Agency Cone.(mg/1)
• U S.P.H.S. Drinking Water Stds. in the U.S.-1962 Mandatory 0.01
1961 WHO European Std. for Drinking Water Excessive 0.05
9 USSR Max. Permissible Cone, in Reservoir Waters General Sanitary 0.01
I
Surface Water Criteria for Public Water Supplies Permissible 0.01
in the U. S.
83
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ENVIRONMENTAL
Species
Daphnia
magna
Daphnia
magna
Flathead
Minnows
Flathead
Minnows
Flatworm
Goldfish
Strickleback
TABLE IV-5
EFFECTS OF CADMIUM UPON FISH AND AQUATIC ORGANISMS
Dose Effect Reference
0.10 mg/1 Threshold (66)
as CdCl0
2
0.0026 mg/1 Immobilization (66)
as CdCl2
0.90 mg/1 Toxic in Soft water (15)
as CdCl2
5.0 mg/1 Toxic in Hard water (66)
as CdCl2
2.7 mg/1 Toxic (6)
as CdN03
0.0165 mg/1 Very sensitive in (66)
as CdCl_ Soft water
in 8.5 to 18 hrs.
0.20 mg/1 Lethal (6,66)
as Cd
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Where cyanide or other complexing agents are not present, the
cost of removing cadmium may be expected to be equivalent to that of
conventional treatment involving coagulation, settling, rapid sand or
multimedia filtration. As with many metal wastes, filtration is very
important in removing the slow settling metal hydroxide floe. The
total cost of treatment by coagulation, sedimentation, and filtration
has been described in the report on arsenic.
The new system described by Patterson and Minear for precipi-
tation of cadmium, for small electroplating wastes, is the Kastone
process. Hydrogen peroxide is added to the wastewaters, which
oxidizes the cyanide and forms an oxide of cadmium simultaneously.
The cadmium oxide is claimed to be more easily removed than the cadmium
hydroxide. This treatment system is believed to be suitable for plants
with low flows. Filtration is still advisable.
Ion Exchange
The ion exchange process concentrates the cadmium, making
recovery amenable. Patterson and Minear reported the recovery value
of cadmium to be between $1.20-$6.00 per thousand gallons for a
solution concentration of 50-250 mg/1 (as cadmium). The recovered
value of cadmium may be capable of offsetting the additional treatment
cost within one-half to two years. Patterson and Minear did warn,
however, that ion exchange is unsuitable for the recovery of cyanide
solutions. No specific applications of ion exchange recovery of
cadmium cyanide solutions were found.
On the basis of pilot plant work, reported by Patterson and
Minear, removal of cadmium by a cation exchanger was 99% efficient,
85
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and 99.9% efficient by a cation plus anion exchange column. The
initial concentration was reported as a trace quantity. On this |
basis, one can only assume that the final effluent would be in the _
zero mg/1 range prior to breakthrough. ™
In summary, it is apparent that cadmium has a significant B
environmental impact upon man, other animals, and aquatic life. It
has been shown that the toxicity of cadmium will vary with the presence I
of calcium and protein in the diet of mammals and possibly that of —
fish, and with the presence of other trace metals. It has also been •
shown that once cadmium is absorbed by the human body it is retained. B
For this reason, Byerrum, as reported in McKee and Wolf (66), suggested
that cadmium concentrations should not be allowed to exceed 0.1 mg/1. I
TREATMENT FEASIBILITY - CADMIUM REMOVAL
I
A detailed review of current technology of cadmium removal has
been prepared by Patterson and Minear (76) and others (46,61,66). In B
general, cadmium may be removed by ion exchange or chemical precipi- •
tation. Cadmium carbonate and cadmium hydroxide are insoluble under
alkaline conditions and are therefore easily precipated. It is also B
technically feasible to remove concentrated sources of cadmium by
electrolytic or evaporative recovery. A new process for low flows |
has been discussed by Patterson and Minear (76). _
Chemical Precipitation
The chemical precipitation of cadmium is dependent upon the B
pH of 8, an effluent of 1.0 mg/1 may be expected; whereas at a pH of 10, m
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f a final effluent of 0.1 mg/1 may be expected. In Patterson and
« Minear's review, they stated that when iron is present in the waste
with cadmium, "precipitation will yield complete removal" at a pH
• of only 8.5.
Complexing agents such as cyanide, as found in electroplating
| waste, must be removed before cadmium can be precipitated. Fortunately,
_ cyanide may be readily removed allowing for cadmium precipitation.
™ Patterson and Minear report the cost for removing complexed cadmium
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can be expected to be equal to that of cyanide removal.
SUMMARY AND RECOMMENDATIONS
The review of cadmium as a waste, its impact, and treatment has
provided the following information:
1. Cadmium exists naturally in the soil and in the water but
_
* industrial and agricultural discharges contribute sub-
• stantial loads when untreated.
2. Like arsenic, cadmium is concentrated and becomes cumulative
• in man, animals, and plants. Cadmium is toxic to animals
_ and aquatic life.
* 3. Cadmium acts synergistically in the presence of other
B metallic ions increasing its toxicity.
4. Cadmium causes poor bone mineralization in humans with low
I calcium diets. Cadmium can cause liver and renal damage
in man and animals. It has also been shown that with low
• calcium diets cadmium accumulation in the liver was about
• 50% more than in the kidneys of test animals. Cadmium
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causes chronic kidney damage in man under continuous exposure,
possibly as low as 0.012-0.020 mg/day. Cadmium levels were also •
shown to be higher in test animals when their diet was low in protein.
Cadmium contributes to cardo-vascular disease in man. I
5. Trace amounts of cadmium in water may concentrate on
bottom sediments as much as 20,000 times the concentration •
in the water. •
6. There appear to be technically feasible methods to reduce
cadmium levels in wastewaters to levels lower than 0.1 mg/1. I
However, further study and research is needed to confirm
the actual level which is currently obtainable by these m
methods. •
It is readily apparent that the effluent level of all cadmium
It is desirable that an effluent level for cadmium be set at 0.10 ^
mg/1. Furthermore, it is recommended that literature reviews and
research in this area be supported and continued to investigate other •
currently feasible methods of treatment, and to determine obtainable
effluent levels for all discharges. |
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CHAPTER V-TOTAL CHLORINE RESIDUAL
• The major discussion on the effects of chlorine residuals in
the aquatic environment is a report by Brungs (20). It is important
• to note that Brungs work is directed at safe total chlorine residuals
in surface waters. The references cited within this report are listed
• in Brungs' report.
• Brungs has documented that the uniform total residual chlorine
level in surfacfe waters should not exceed 0.002 mg/1 to protect most
• aquatic life. Intermittent discharges from certain facilities such as
from power plant chlorination processes for slime removal, should
B not cause the receiving waters to reach a total residual chlorine
•j concentration of 0.1 mg/1 for more than 30 minutes, nor 0.005 mg/1
for more than 2 hours.
• When consulted on this report, Brungs (21) stated that he is
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continuing to document his studies. With respect to potentially safe
effluent levels of total chlorine residuals, Brungs stated that a
reasonable maximum level would be 0.1 mg/1. The stream, however, should
never contain more than 0.002 mg/1. Therefore, discharges which will
• be diluted from a concentration of 0.1 mg/1-0.002 mg/1 within 30
minutes could be tolerated provided the entire cross section of the
| stream is not affected. Brungs stressed that a channel past the dis-
_ charge must be maintained if fish life is to exist in the stream.
™ Waters containing as little as 0.001 mg/1 total residual chlorine are
•j avoided by rainbow trout.
Data on the effects of chlorine residuals over continuous and
• intermittent periods of exposure are summarized in Table V-l.
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RESULTS OF BRIEF EXPOSURES OF FISH TO TOTAL RESIDUAL CHLORINE
Species
Misc
Misc
trout fry
chinook salmon
white sucker
brook trout
smallmouth bass
rainbow trout
rainbow trout
finger ling
rainbow trout
fathead minnows
fathead minnows
yellow perch
yellow perch
largemouth bass
largemouth bass
brook trout
brook trout
brook trout
brook trout
* TL50 = median
Effect Endpoint
initial kill
erratic swimming
lethal
first death
lethal
median mortality
median mortality
slight avoidance
lethal
lethal
TL50*
TL50
TL50
TL50
TL50
TL50
mean survival
time
mean survival
time
mean survival
time
mean survival
time
tolerance limit.
Time
15 min.
6 min.
instantly
2.2 hrs
Residual Chlorine
Concentration (mg/1)
0.28
0.09
0.3
0.25
30-60 min. 1.0
90 min.
15 hrs.
10 min.
2 hrs.
4-5 hrs.
1 hr.
12 hrs.
1 hr.
12 hrs.
1 hr.
12 hrs.
8.7 hrs.
14.1 hrs.
20.9 hrs.
24 hrs.
0.5
0.5
0.001
0.3
0.25
0.79
0.26
0.88
0.494
0.74
0.365
0.35
0.10
0.05
0.005
Brungs'
References
Truchan, 1971
Truchan, 1971
Coventry, et.al
1935
Holland, et.al.
1960
Fobes, 1972
Pyle, 1960
Pyle, 1960
Sprague &
Drury, 1969
Taylor &
James 1928
Taylor &
James, 1928
Arthur, 1972
Arther, 1972
Arther, 1972
Arther, 1972
Arthur, 1972
Arthur, 1972
Dandy, 1967
Dandy, 1967
Dandy, 1968
Dandy, 1967
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• It is fully recognized that many state agencies either recommend
or require minimum total residual chlorine levels in treated effluents.
•i The states in Region III which currently require chlorination and/or
a chlorine residual in at least some of their discharges are as
follows :
| (1) Delaware - All domestic wastewaters must be chlorinated.
•j (2) Pennsylvania - Effluent must be disinfected.
(3) Virginia - 2.0 mg/1 chlorine residual must be maintained
for discharges into some waters.
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™
(4) West Virginia - Chlorination is required of all dis-
charges 12 months of the year. (34)
™ Requirements for states in other regions are also reported in
H a summary of federally approved water quality standards. (34).
TREATMENT METHODS
Wastewaters are disinfected primarily to control bacteria and
• the organisms which are pathogenic. Indicators such as fecal coliforms
are used for controlling the efficiency of the disinfection process.
| The means of attaining low levels of these indicator organisms is
M presently being reevaluated and many questions are arising as to the
proper choice for disinfecting, be it chlorine, ozone, or other
• biological, physical, or chemical processes. Two promising processes
are briefly discussed below.
| "Closed-loop chlorination" has been reported by Thomas and
« Brown (93) to be an economical and effective means of controlling the
rate of chlorination. According to the authors, closed-loop chlorin-
• ation is applicable to any waste treatment facility. While the unit
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costs about $5,000 it rapidly offsets the cost of manpower needed .
to do the same job. Thomas and Brown stated that "financially, it
is imperative that closed-loop chlorination equipment be provided to Ij
replace the four men who otherwise would be required to give effective
chlorination. The cost of closed-loop chlorination equipment can be •
recovered in two to three months by payroll savings. Obviously, _
additional maintenance will be required; but this will be small - in ™
the range of one hour a week to one hour a day". •
The use of ozone for disinfection is also a possible alternative.
It is widely reported to be in use in Europe and is gaining acceptance •
in the U. S.
IECOMMENDATIONS
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On the basis of the above discussion and the report by Brungs
(20) ,a maximum total chlorine residual in surface waters of 0.002 mg/1
is recommended.
Where currently permissible under state and local laws and •
regulations, it is suggested that all discharges contain not more than
0.10 mg/1 total residual chlorine, or where possible maintain a stream |
level at less than or equal to 0.002 mg/1 after a 30 minute mixing
period.
As an interim measure to limit the chlorine residual in a dis-
charge, it is recommended that the discharge not contain more than
0.2 mg/1 total chlorine residual above that required by state or •
local law and/or regulation.
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CHAPTER VI-CHROMIUM
Unlike most toxic trace elements, chromium is not commonly en-
• countered in the natural environment. Trace amounts of chromium have
been found in food (66). However, this is only expected for food
• cooked in a stainless steel utensil. Trace amounts found from this
source are not known to have any physiological effects upon man.
• Chromium has been found in trace amounts in soil and plants, however,
• there is no evidence that this chromium level is either detrimental
or beneficial for plant nutrition.
• Chromium may be found, apparently due to natural conditions, in
sea water at a concentration of 0.00005 mg/1. Marine plants may con-
| tain chromium at concentrations of 1.0 mg/1, and marine animals between
0.2 and 1.0 mg/1 (6).
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Chromium is found in hexavalent and trivalent forms. The tri-
+3
valent form (Cr ) normally consists of the hydrated or complexed cation
in water. The prevalent forms of hexavalent chromium (Cr ) include
-2 -2
chromate (CrO, ) and dichromate (Cr 0 ). Chromium trioxide, a hexa-
. valent form, is also referred to as "chromic acid" or "chromic acid
™ anhydride".
i ry
I Divalent compounds (Cr ) tend to oxidize to the trivalent form.
The hexavalent chromium salts of sodium, potassium, and ammonium are
• quite soluble. As a result, for removal one normally considers reducing
_ hexavalent chromium to the trivalent form. This may be done by heat,
* organic matter, or by reducing agents such as sodium metabisulfite.
• The trivalent chromic salts are soluble only as chloride, nitrate, and
sulfate, and the hydroxide and carbonate chromic salts are quite
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insoluble.
The industrial sources of chromium reported by Lund (61), Nemerow I
(72), and others are shown in Table VI-1. The most common sources are
electroplating, metal finishing, tanning of leather, and cooling tower |
effluents. McKee and Wolf also reported prevalent sources of hexa- •
valent chromium to include annodizing of aluminum, the manufacture of
paints, dyes, explosives, ceramics and paper. Hexavalent chromium is •
more prevalent in these effluents, although some trivalent chromium may
be present. Trivalent chromium salts are used as mordants in textile I
dying, in the ceramic and glass industry and in photography. _
The major source of chromium in our surface waters appears to be ™
from industrial and municipal discharges which contain industrial wastes I
rather than from natural sources.
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ENVIRONMENTAL EFFECTS OF CHROMIUM
Effect on Man
The toxicity of chromium compounds in man is quite high. In 1946 •
the U.S.P.H.S. Drinking Water Standards set a maximum allowable limit
of 0.05 mg/1. A justification for this limit at that time was that •
it was the current limit of detection. It was not set as a result of •
physiological effects. The 1962 Drinking Water Standards retained the
same 0.05 mg/1 limit. I
Evidence indicates that man neither needs nor benefits from
chromium salts in his diet. Chromium salts are rapidly and completely •
eliminated when ingested orally. It was reported that a Long Island •
family of two adults and two children revealed no abnormalities after
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TABLE VI-1
SOURCES OF CHROMIUM
Sources Type Concentration mg/1 Reference
Chrome Plating Cr03~3 4,170,000 (61)
Plating Waste Cr+6 0-555 (72)
Total 0-612
Electroplating Total 11-41 (14)
a.-}
Electroplating Cr 140 (76)
IBM Plant Cr+6 1300 (76)
Metal Finishing Total 1-700 (16)
Brass & Copper CrO 70-96.9 (96)
Wire Mill ^
Cr 27 (96)
+f\
Acid Bath Waste Cr 122-270 (76)
Cr+3 37-282 (76)
Tannery Wastes Total 30-70 (72)
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consuming hexavalent chromium of 1.0 to 25.0 mg/1 in their drinking
water for a three year period. Another investigation reportedly found |
mild nausea from consumption of water with 5 mg/1 on an empty stomach. «
Consumption of water with 2.5 and 3.5 mg/1, however, failed to produce
any symptoms. McKee and Wolf concluded that man apparently may consume •
5.0 mg/1 hexavalent chromium with no deleterious physiological effects.
However, concentrations above 1.5 mg/1 may cause color and taste •
problems. _
While the salts of trivalent chromium are not believed to be physio- •
logically harmful, large doses of chromate may lead to corrosive effects •
in the intestinal tract and to nephritis. Approximately 0.5 grams of
potassium bichromate has been reported to be toxic. •
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Effect on Plants
I Chromium is shown to be toxic to plants (6,66) at concentrations
m of 3.4 mg/1 or above. Table VI-2 summarizes toxicity data.
Effect on Animals
I A limit of 0.05 mg/1 for chromium in water used for stock watering
has been proposed, but there apparently is little justification for the
I level (6).
McKee and Wolf report that the maximum non-toxic level in the
drinking water of white rats is 500 mg/1 as hexavalent chromium (66).
I They also reported that a drinking water concentration of 500 mg/1 of
potassium chromate would not affect the utilization of food by rabbits
I but that 10,000 mg/1 of zinc chromate has markedly interfered with the
• digestion. The concentration of 5 mg/1 of chromium in conjunction with
11 mg/1 of selenium caused an increase in mortality among rats.
I In other works reported by McKee and Wolf, white rats were fed
potassium chromate at a dosage of up to 11 mg/1 for one year. Other
| test rats received up to 25 mg/1 of chromium as potassium chromate
M and 25 mg/1 as chromic chloride. The study indicated that there was
no significance in the difference of weight, food intake, water con-
I sumption, or blood analysis from the experimental group. However, the
report did show that a concentration above 5 mg/1 chromium was detected
| in all tissues, especially in the spleen. As a result, McKee and Wolf
« recommended that the concentration of chromium be maintained at or
™ below 5 mg/1 for all stock and wild life for watering purposes.
• Effect on Aquatic Life
It is readily apparent that the lethal and toxic concentrations of
_
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Form
Trivalent
Potassium
Bichromate
Potassium
Bichromate
Potassium
Bichromate
Trivalent &
Hexavalent
TABLE VI-2
CHROMIUM TOXICITY TO PLANTS (66)
Concent ration, mg/1
3.4-17.3
5
10
15-50
Plant
Various
Oat
Oat
Oat
Sensitive
Effect
Slightly Toxic
Slight Chlorosis
Marked Chlorosis
Reduced Growth
Adverse
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all forms of chromium vary with the species (66). Table VI-3 summarizes
the experimental evidence available. McKee and Wolf report a general
toxicity limit for fish of 5 mg/1. [A threshold toxic concentration
for small prawn was reported to be less than 5 mg/1. Lower forms of
aquatic life are much more sensitive to chromium compounds (66).]
Under a two (2) year exposure oysters showed a chromium toxicity of
0.01-0.012 mg/1 (6).
• McKee and Wolf have also reported that fish are capable of with-
standing from 10 mg/1 to over 500 mg/1 of various chromium compounds,
| depending on the time of exposure without detrimental effect. They
• noted that lower forms of aquatic life are capable of withstanding a
chromium concentration of 5.0 mg/1 for up to one hour without detri-
• mental effect.
McKee and Wolf have reported that algae are capable of concentrat-
Jj ing radioactive chromium 100 to 500 times. Similarly, Van den Berg and
_ Daum (95) indicated that recent studies on a cooling water chromium
discharge showed that chromium is concentrated in fish. Their investi-
• gat ion showed that the concentration within the fish is increased as
both the total chromium concentration in the water, and time increased.
H While under continuous exposure, fish have shown detrimental effects
to concentrations of 1.0 mg/1, while they are capable of survival
™ with no significant damage at concentrations of 10 or more mg/1 for
• short periods of time. Total chromium concentrations whould be maintained
at 0.05 mg/1 for aquatic life under continuous exposure. They are
I capable of withstanding short exposures of up to 5.0 mg/1 for as much
one hour. Other factors such as temperature, pH, the species, the
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TABLE VI-3
TOXICITY OF CHROMIUM TO FISH
AND AQUATIC ORGANISMS (66)
Target Organism
Brown Trout
Carp
Silver Salmon
Silver Salmon
Rainbow trout
Goldfish
Bluegills
Bluegills
Trout
Bluegills
Trout
Trout
Bluegills
Bluegills
Young eels
Young eels
Sticklebacks
Sticklebacks
Sticklebacks
Young eels
Minnows
Daphnia magna
Daphnia magna
Microregma
Navicula
Navicula
Daphnia magna
Scenedesmus
E. Coli
Grammarus pulex
Snail
Midge fly larvae
Snail
Polycelis nigra
Daphnia magna
Scenedesmus
Microregma
Polycelis nigra
Cr Form
hexa-
hexa-
hexa-
hexa-
hexa-
hexa-
hexa-
hexa-
hexa-
hexa-
hexa-
hexa-
hexa-
hexa-
hexa-
hexa-
tri-
tri-
tri-
tri-
tri-
hexa-
hexa-
hexa-
hexa-
hexa-
hexa-
hexa-
hexa-
hexa-
hexa-
hexa-
hexa-
hexa-
tri-
tri-
tri-
tri-
Concentration mg/1) Effect
5.2
7.1
10.0
17.8
20.0
35.3
A5.0
50.0
50.0
70.0
100.0
150.0
103.0
145.0
130
520
1,
2,
2,
5.2
40.0
0.016
0.05
0.21
0.21
0.25
0.51
0,
0.
1.4
17.3
25.0
40.6
148.0
42.0
5.0
37.0
75.0
.3
.0
.4
.7
.7
toxic
unharmed
freshwater, toxic
seawater, toxic
toxic, 18°C
unharmed
tolerated 20 days
toxic limit, 30 days
killed within 33 hrs
toxic limit, 1 week
24 hr. TLm
killed in 6 hrs.
96 hr. TLm
24 hr. TLm
tolerated 50 hrs.
killed 5-12 hrs.
survived 1 week
survived 2 days
lethal limit
survived avg. of 187
survived 6 hrs.
toxic threshold
killed in 6 days
toxic threshold
softwater TLm
hardwater TLm
toxic threshold
toxic threshold
toxic threshold
total mortality
softwater TLm
unharmed
hardwater TLm
toxic threshold
toxic threshold
toxic threshold
toxic threshold
toxic threshold
TOO
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• hardness of the water, and possibly the valence of chromium may also
influence its toxicity (66).
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TREATMENT TECHNOLOGY - CHROMIUM REMOVAL
I
The currently available methods of chromium treatment consist of
I a reduction-precipitation process, a modification known as the Lancy
Integrated System, and Ion Exchange. Other methods which have been
B researched by the Battelle Memorial Institute will be discussed, as
• well as the effects of chromium on biological treatment.
The theory and practice of treating chromium bearing plating wastes
• is presented in Nemerow (72) and Gurnham (48). The basic process con-
sists of alkaline-chlorination, reduction, and precipitation followed
by neutralization. Control of pH is very important, as is the time of
reaction.
Alkaline Chlorination
Many chromium bearing plating wastes may also contain cyanide.
This waste must be reduced and acidified to convert the hexavalent
chromium to the trivalent form prior to precipitation. As chromium
I cannot be reduced until all of the cyanide is removed, the alkaline
chlorination process is used for cyanide removal. The details of this
• method are discussed in the chapter on cyanide.
• Reduction and Precipitation
After removal of cyanide from combined wastes, or upon separating
I chromium plating wastes, the hexavalent form of chromium must be reduced
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to the trivalent form to permit precipitation. To accomplish this,
sufficient free mineral acid is added to the waste to reduce the I
chromium by maintaining a pH of 3.0 or lower. After reduction of the
chromium, alkali, usually in the form of a lime slurry, is added to |
neutralize the acid and then precipitate the trivalent chromium. One
of the methods used to reduce the hexavalent form of chromium to tri-
valent is the addition of ferrous sulfate. Nemerow (72) summarized I
the chemicals needed to remove one mg of chromium as follows: 16 mg
of copperas (ferrous sulfate), 6 mg sulfuric acid, and 9.5 mg lime, •
The chemical reactions will normally produce 2 mg of a chromic hydrox- _
ide and 0.4 mg of a ferric hydroxide sludge. In addition, about 2 mg ™
of calcium sulfate will be produced, part of which may also precipitate. I
Disposal of these sludges is a major unsolved environmental problem.
Neutralization •
In many plating waste operations the oxidized cyanide and reduced •
chromium wastes will be combined with the other wastes, which may con-
tain metals, oil, and grease, for subsequent and perhaps final treatment. •
If the combined waste is still acidic, a lime slurry can be added to
neutralize and precipitate the metals. This reaction normally produces |
a large and heavy coagulant sludge. H
A 1968 report by the Battelle Memorial Institute (16) listed the
following two conventional methods for chromium removal: I
1. Hexavalent chromium may be reduced by the addition of sulfur
dioxide, sulfates, and ferrous sulfate. The process is common |
among intermediate and large plants. The process involves re-
duction of the hexavalent chromium to the trivalent form under
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• low pH (2.0-3.0) followed by precipitation of the trivalent
form with alkali. Clarification is mandatory for efficient
• removal of the trivalent chromium, copper, nickel, and iron
when waste pickle liquor is used for the reduction step.
I 2. Precipitation of the hexavalent chromium may be achieved direct-
• ly by the addition of barium salts. While this method is re-
portedly effective, the sludge (BaCrO.) is highly toxic which
• poses a solid waste hazard.
In Patterson and Minear (76), it is indicated that the reduction
I
of hexavalent to trivalent chromium is not always 100% complete. The
• efficiency will depend upon the time allowed for reduction, the pH of
the reaction mixture, the concentration, and type of reducing agent
I employed. They noted that an initial hexavalent concentration of 140
mg/1 can be reduced to a total of 0.7 to 1.0 mg/1 as hexavalent chromium,
| using sodium bisulfite as a reducing agent. As the use of sodium bi-
_ sulfite can cause odors and corrosion, it is often replaced by sulfur
™ dioxide. Patterson and Minear reported that the use of sulfur dioxide
I at an IBM plant achieved total removal of as much as 1,300 mg/1 of
hexavalent chromium. The pH of the waste was decreased to 2 with a
• total detention time of 90 minutes. Other reports indicated that the
use of sulfur dioxide is much more efficient in the reduction hexavalent
™ chromium than the bisulfite (76).
• In discussing the precipitation of the trivalent form of chromium,
it was indicated that the most effective pH range is from 8.5 to 9.5.
I This is the point of minimum solubility of the chromic hydroxide sludge
formed by the precipitation of trivalent chromium (76). The most common
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alkali used is calcium hydroxide or other forms of lime.
At the previously mentioned IBM plant, a final effluent concen- |
tration of 0.06 mg/1 as total chromium was obtained. It was also noted m
that a coagulant aid (Separan NP-10) was used to improve the precipita-
tion and sedimentation characteristics of the chromic hydroxide. •
In several of the plants discussed by Patterson and Minear, it
was shown that filtration of the final effluent following sedimenta- |
tion improved the overall removal of chromium. For one waste, sand _
filtration reduced the initial chromium concentration of 1.3-4.6 mg/1
to a final concentration of 0.3-1.3 mg/1 (as total chromium). Most of I
this chromium was reported to exist as the soluble hexavalent form
rather than the trivalent chromium. I
The efficiency of the reduction, neutralization, and precipitation
of chromium, reported in various works investigated, are summarized in
Table VI-4.
TABLE VI-4
THE REMOVAL OF CHROMIUM BY
REDUCTION, NEUTRALIZATION, AND PRECIPITATION
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Concentration, mg/1 •
+6 ~
Source Initial as Cr Effluent, as Total Reference
Electroplating 10 0.6 (17) I
Electroplating 140 1.0 (76)
IBM Plant 1,300 0.06 (76) I
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I A modification of the standard reduction precipitation process
known as the Lancy Process has been reported by Lund (61). Lancy's
| batch or continuous treatment system follows the parameters of the
_ standard reduction precipitation process. The one basic difference
~ is in automation. A pH meter and an ORP controller are utilized to
I modify the quantities of the chemicals entering the reaction tank.
The Lancy integrated system is an extension of the normal process.
• In the integrated system, a chemical process solution (lime) is used
to remove the dragout film and droplets containing the harmful chemical
• compound prior to recycling. The treatment solution is then recircu-
• lated between various wash tank stations and a reservoir where the
metal hydroxides are precipitated. Lund reports that effluent quali-
• ties from the Lancy batch treatment or continuous flow through system
are 0.1 mg/1 chromium, and 0.01 mg/1 chromium for the integrated treat-
I ment system. Mr. Ivan Whittman, of Lancy Laboratories, has indicated
• to this author that the integrated system has been successfully imple-
mented in plants with design flows ranging from 25 gallons per minute
• (gpro) to greater than 500 gpm design flows. McDonough and Stewart (64)
reported that the Lancy integrated treatment system used by the S. K.
| Williams Co. of Wauwotosa, Wisconsin, was capable of achieving a total
• chromium concentration of zero during several years of operation.
Other parameters of interest, obtained by the S. K. Williams Company,
• are a final effluent with a pH of 6.5 to 9.5, cyanide concentration of
none, copper less than 0.50 mg/1, nickel less than 1.0 mg/1, iron less
| than 0.50 mg/1, and settleable solids less than 10 mg/1. (Editorial
Note: The 13th edition of Standard Methods (1) does include a method
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whereby settleable solids may be reported in terms of mg/1. This apparent-
ly is what has been used here.) •
Ion Exchange •
The 1968 Battelle Report (16) indicated effective chromium removal
by ion exchange and evaporation in concentrated waste streams. Similar- •
ly, Patterson and Minear's review on the treatment of hexavalent and tri-
valent chromium indicates that cation exchange can be applied to remove |
trivalent chromium, and an anion exchange may be employed for the re- •
moval of hexavalent chromium (76) . Upon exhaustion of an anion exchange
column, it may be regenerated with sodium hydroxide to elute sodium •
chromate. The sodium chromate may then be passed through a cation ex-
change column to recover purified chromic acid. If recovery of the •
chromic acid is not desired, the concentrated regeneration waste of the _
exchange column may be treated by the reduction-neutralization-precipita- ™
tion method. Patterson and Minear, like the Battelle Report, indicated •
that the ion exchange process will not only produce reusable water, but
may prove to be economically feasible where the waste is highly concen- I
trated, and/or where the cost of water is high.
One of the reports reviewed by Patterson and Minear indicated that •
ion exchange was both economically and technically feasible for wastes fl
containing chromate ion concentrations up to 200 mg/1, and that chromate
concentrations greater than 500 mg/1 were suitable for evaporative re- •
covery.
There are two possible alternatives in the treatment technology •
for trivalent chromium by ion exchange. First, passing concentrated •
chromic acid baths through a cationic resin removes metallic contaminants
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such as iron, aluminum, and trivalent chromium from the chromic acid,
thus allowing reuse of the chromic acid solution. Second, dilute rinse
• waters can be passed through mixed bed resins to remove both the cationic
trivalent and anionic hexavalent forms, allowing for the complete re-
• use and recycle of the rinse water.
In the testimony of Weston (97) before the Illinois Pollution Con-
| trol Board it was stated that an effluent of 0.03 mg/1 is currently
_ obtainable by the use of ion exchange for hexavalent chromium waste.
™ A report by Driver (30), indicates that as little as 1 mg/1 of chromium
B is now being discharged in the cooling waters used by City Service
Company, Buttle Rubber Plant at Lake Charles, Louisiana. This plant
• previously had discharged significant amounts of chromium in their
cooling water. By the use of ion exchange, this particular City Service
B plant is currently recovering the chromate from the rinse water. The
chromium is recycled to the cooling towers for further use.
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Miscellaneous
Another process reported by Patterson and Minear is that of
evaporative recovery. One of the references cited indicated that a
plating waste rinse water with only a few mg/1 of chromic acid could
• be concentrated to over 900 mg/1 by evaporative recovery (76). Patterson
and Minear also indicated that the evaporative recovery was suitable
| for waste containing over 500 mg/1 of chromate.
« Other methods researched and reported by Battelle in 1971 (17) for
™ electroplating wastes are summarized in Table Vl-5.
• The final treatment method investigated for this report was that
of biological processes. A report by Stanley consultants (91) and a
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TABLE VI-5
POTENTIAL METHODS FOR CHROMIUM REMOVAL
Form
Concentration, mg/1
Initial Effluent
+6
Cr
K2Cr20?
Cr
+6
100
100
1000
1000
100
10-100
10
0-10
0-10
0-5
0-4
0.04-0.70
Method
Ion Floatation
Carbon Adsorption, pH 2-3,
4.0 GPM/ft
Carbon Adsorption, pH 2-3,
5.0 GPM/ft
Liquid-Liquid Extraction
108
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1965 PHS study (5) on the interaction of heavy metals indicate a maxi-
• mum reliable potential of approximately 50% removal of various trace
• metals. The report by Stanley on tannery wastes indicated that aero-
bic lagoons were capable of reducing initial total chromium concentra-
• tion from 11 to 9 mg/1. Activated sludge was found capable of reducing
an initial chromium concentration of 60 mg/1 to 4 mg/1 (91). The PHS
I study (5) investigated the effects of chromium, copper, zinc, and
• nickel in four full scale treatment plants receiving combined municipal-
industrial wastes. This study indicated that chromium intake levels
• varying from 0.8 to 3.6 mg/1 would be reduced to 0.2 amd 2.5 mg/1 re-
spectively. The PHS study indicated that hexavalent chromium concentra-
H tions up to 0.5 mg/1 could be almost completely removed. Concentrations
« of 2 mg/1 in the raw waste will show at least some small quantity of
chromium in the effluent. Concentrations of 5 mg/1 and higher were
• found to pass through the biological system.
In summary, it is apparent that chromium can be removed efficiently
• to a level of 1 mg/1 by currently available and utilized methods. With
_ proper control the levels may be reduced to 0.01 mg/1 or less. It has
™ also been shown that ion exchange is currently functional even on large
• volumes of chromium bearing wastes such as cooling water. While the City
Service report indicated a chromium breakthrough point of 1 mg/1, it is
• believed that adequate control of such an operation could reduce this
break point level to much lower levels. The testimony of Weston (48)
• indicated that the more commonly practiced procedures of alkaline reduc-
• tion, chemical precipitation, and sedimentation are capable of providing
an effluent of 0.06 to 4 mg/1 for trivalent chromium, and 0.7 to 1 mg/1
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for hexavalent chromium.
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Cost of Treatment
The literature review by Patterson and Minear (76) and the testi- |
mony of Weston (97) provide a reasonable idea of the relative capital _
and operational costs of treating hexavalent and trivalent chromium by ™
the various methods. Table VI-6 summarizes the capital cost data pro- •
vided in the two references.
Similarly, the operating costs of treating both hexavalent and •
trivalent chromium as shown in the report by Patterson and Minear are
summarized in Table VI-7.
In summary, it is apparent that chromium is no more expensive to
remove from wastewaters than many of the other elements and trace metals.
In fact, with a cost of about $1.00 per thousand gallons for reduction •
and precipitation of chromium, it may be cheaper in some areas than the
cost of the water supply, making it beneficial to institute recycling, •
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SUMMARY AND RECOMMENDATIONS
The following generalizations can be made on the basis of the information •
discussed above.
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1. Chromium exists only at very low levels in nature.
2. Industrial sources are capable of contributing up to 4.17 kg/1
if untreated.
3. Man reportedly can consume up to 3.5 mg/1 of chromium through •
his drinking water without known detrimental effects.
4. Animals and wildlife can consume up to 5.0 mg/1 in their drink- |
ing water without known detrimental effects.
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TABLE VI-6
CAPITAL COST FOR CHROMIUM TREATMENT
Form Method Flow
Hex Reduction & 1 MGD
Precipitation
Hex Reduction 6. 10 MGD
Precipitation
Hex Ion Exchange 100 gpm
Hex Ion Exchange 1 MGD
Hex Ion Exchange 10 MGD
Hex Ion Exchange 50 MGD
Tri Precipitation 0.2 MGD
Capital Cost
$ 200,000
700,000
40,000
300,000
3,000,000
4,600,000
224,000
Reference
(97)
(97)
(76)
(97)
(97)
(97)
(76)
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Form
Hex
Hex
Hex
Hex
Hex
Hex
Hex
Tri
Tri
Tri
Tri
Hex
Hex
TABLE VI- 7
OPERATION COST - CHROMIUM REMOVAL (76)
Method Flow, gpm Cone, mg/1
Reduction & 100 120
Precipitation
Reduction & 70 50
Precipitation
Ion Exchange - 50
Ion Exchange 100 50-100
Evaporation 0.5-2
Evaporation 2.0-5
Evaporation 5.0-10
Precipitation (Lime Cost) - 2000
Precipitation (Lime Cost) - 1000
Precipitation 0.2 MGD
Ion Exchange
Reduction & 73 2300
Precipitation
Ion Exchange 73 2300
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$/1000 Gal. •
< 1.00
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1.00
-.„,.
0.68 •
10.00
5.00 I
2.50
2.50 1
1.25 «
0.80
0.16-0.24 1
$33. 19 /Day
1
$12. 44 /Day Net.
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5. Plants subjected to chromium concentrations below 3.4 mg/1
showed no toxic effects.
6. The threshold of toxicity to fish is about 5 mg/1 of chromium
for continuous exposure. However, ranges of 10 >.to 50 mg/1 are
tolerable for short periods of exposure (days).
7. The lower forms of aquatic life have a limiting toxicity of
0.050 mg/1 or less under continuous exposure. Under short
periods of exposure (up to one hour), levels of 5.0 mgm/1 are
tolerable.
8. Both algae and fish appear to be capable of concentrating
™ chromium, while it is reported that other life forms rapidly
expel chromium ingested by the oral route.
9. Current treatment methods are capable of obtaining an average
total chromium concentration of 0.06 mg/1 or less. However,
even processes such as ion exchange have breakthrough concentra-
tions of 1.0 mg/1.
10. The costs of construction and operation of chromium treatment
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facilities are comparable with the costs of treating other metals.
• It was apparent in reviewing the material cited, that one of the
• major causes for residual total chromium found in effluents is the incom-
plete reduction of hexavalent chromium to the trivalent form, which pro-
• hibits complete precipitation. However, the batch-flow through system
discussed by Lund (61) indicates that with proper monitoring and instru-
| mentation the standard reduction precipitation process is fully capable
M of reaching a total chromium level in the effluent of 0.1 mg/1. Other
reports showed that filtration may also be needed to more fully control
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the total system. It is, therefore, felt that with proper controls in
instrumentation, a final effluent concentration of 0.1 mg/1 as total |
chromium is currently achievable.
As chromium in both the hexavalent and trivalent forms has been
shown to be toxic, especially to the lower forms of aquatic life, it is •
recommended that a uniform effluent limit of 0.1 mg/1 be established
cognizant that processes such as the Lancy Integrated Process are current- _
ly in full scale operation yielding effluents of 0.01 mg/1 or less as ~
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total chromium.
It is admitted that the basis for these recommendations is a
limited amount of material, particularly with respect to health hazards. •
It is recommended that further studies be done in this area, especially
to confirm the potential concentration effect of chromium within fish ™
and other aquatic life. •
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CHAPTER VII-COPPER
Copper is found naturally in the aquatic environment in the
form of copper salts, inorganic or organic (soluble forms) complexes
or precipitates. Table VII-1 shows the concentration of copper in
• nature and industrial-domestic uses of copper and its salts. Most
mining of copper oxide ores is done in the states of Arizona, Michigan,
• Montana, Nevada, New Mexico and Utah. (48) Copper smelting and plat-
• ing is done throughout the country, while copper and brass manufactur-
ing takes place in the northeastern quarter of the nation. The major
• sources of copper as described by Patterson and Minear (76) include metal
processing, pickle and plating bath waste, brass and copper metal work-
ing waste, jewelry manufacturing, alkaline Benberg rayon process, and
acid mine drainage. Copper and its salts are also used in the electri-
cal and plumbing fields where conductivity or corrosion resistance is
important, in dye, printing, tanning pigment, pyrotechnic and photo-
graphic processes, and in human and veterinary medical preparations (66).
A review of the literature indicates that the concentration of cop-
_ per in discharges from various industrial processes ranges to a high
™ of 44,000 mg/1. A summary of various concentrations of copper found
• in wastewaters has been compiled in Table VII-2.
Copper is also known for complexing, especially with cyanide.
• This is discussed in greater detail in the chapter on cyanide and
its removal. A tabulation of copper concentrations found in complex
cyanide plating waste is given in Table VII-3 taken from the work of
Nemerow (72).
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Source
Surface Water
Ground Water
Sea Water
INDUSTRIAL
Metallic Copper:
Copper Chloride:
CuCl2 2H20
Copper Nitrate:
Cu(NO») 3H 0
Copper Sulfate:
CuSO, &
CuSO, 5H.O
TABLE V1I-1
NATURAL SOURCES OF COPPER
Concentration mg/1 Reference
up to 0.05 (66)
12 (Av.) (66)
0.03 (Av.) (83)
& OTHER USES OF COPPER AND ITS SALTS (66)
Cooking utensils, electrical industry, pipes,
roofing, and other uses where conductivity or
corrosion resistence are important.
Electroplating of aluminum, manufacturing of
indelible inks , mordant in dyes and pringing
fabrics.
Pyrotechnics, textile dying and printing,
photography, insecticides and electroplating.
Most common salt of copper. Extensive use
for tanning, dyeing, electroplating, process
engraving, pigment manufacturing.
Human medicine as fungicide, bacteriocide.
astringent, and irritant.
Veterinary medicine as emetic, anthihelminthic ,
and treatment of anemia.
116
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TABLE VII-2
CONCENTRATIONS OF COPPER IN PROCESS WASTEWATERS
„ Copper Concentration _, ,.
Process r ,.. Reference
"8/1
APPLIANCE MANUFACTURING
Spent Acids 0.6 - 11.0 (76)
Alkaline Wastes 0-1.0 (76)
AUTOMOBILE HEATER
Production 24 - 33 (28 Ave) (76)
BRASS INDUSTRY
Brass Dip 2-6 (76)
Brass Mill Rinse 4.4 - 8.5 (76)
Tube Mill 74 (76)
Rod & Wire Mill 888 (76)
Rolling Mill 34 (76)
Bichromate Pickle
Tube Mill 13.1 (76)
Rod & Wire Mill 27.4 (76)
Rolling Mill 12.2 (76)
Copper Rinse 13 - 74 (76)
Brass Mill Rinse 4.5 (76)
Brass & Copper Wire Mill 75 - 174 (96)
Pickle Rinse Waters 70 @ 0.5 MGD (48)
800 @ 0.02 MGD (48)
Pickle Bath Dump 10,000 (48)
Pickling Bath Waste 4,000 - 23,000 (72)
Bright Dip Waste 7,000 - 44,000 (72)
BUSINESS MACHINE CORP.
Plating Wastes 2.8 - 7.8 (4.5 Ave) (71)
Pickling Wastes 0.4 - 2.2 (1.0 Ave) (71)
COPPER MILLS
Mill Rinse 19 - 74 (76)
Plating Rinse Water 5.2 - 41 (76)
Tube Mill Waste 70 (Ave) (76)
Wire Mill Waste 800 (Ave) (76)
PLATING & METAL PROCESSING
Metal Processing 204 - 370 (76)
Plating Wash 20 - 120
Plating Wash 0-7.9 (76)
Rinse Waters up to 100 (20 Ave) (76)
4 Plating Operations 6.4 - 88 (76)
Electroplating Waste 0.2 - 10.0 (14)
Cyanide-Copper Waste 18 (16)
Plating Waste 6 - 300 (72)
SILVER PLATING WASTES
Silver Waste 3 - 900 (12 Ave) (71)
Acid Waste 30 - 590 (135 Ave) (71)
Alkaline Waste 3.2 - 19 (6.1 Ave) (71)
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TABLE VII-3
COMPLEXED COPPER-CYANIDE PLATING WASTES (72)
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Rinse water Copper concentration(mg/1) •
Plating Bath @ Dragout rate @ Dragout rate of 2.5 gph
Cu Cone, (mg/1) of 0.5 gph fl
51,500 107 535 K
12,400 2.8 14
30,000 62 310 •
21,000 44 220
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ENVIRONMENTAL EFFECTS OF COPPER
While small concentrations of copper are beneficial and
actually necessary for man and animals, higher concentrations of
copper create taste and odor problems and are detrimental to various
industrial uses of water, plant life, stock and wildlife, fish and
other aquatic life.
Effect on Man
A review of the PHS Drinking Water Standards (94) indicates
that copper is essential and beneficial to man. Man has a daily re-
quirement of 2.0-3.0 mg/1 for adults and approximately 0.1-2.0 mg/1
for preschool children (66,94). It was reported, however, that a con-
centration of 1-5 mg/1 of copper will impart an unpalatable taste in
the water. A "small" dose of copper may be non-toxic, while a "large"
dosage may produce emesis, and prolonged oral administration may result
in liver damage. On the basis of the above, the Public Health Service
recommended a desirable level of 1.0 mg/1 of copper for domestic water
supplies.
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A review of McKee and Wolf indicates that copper has a definite
physiological function in the circulatory system of man. It is not
known to be a cumulative poison but is normally excreted through the
urine at approximately 1.0 rag/day with excess amounts being excreted
through the feces. It is a necessary factor in the utilization of
iron by blood-forming organs.
McKee and Wolf (66) report that "doses of 60-100 mg taken by
mouth cause symptoms of gastroenteritis, with nausea and intestinal
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irritation, but doses of 10-30 mg have not caused poisoning even when
as "small" and "large" in the PHS Drinking Water Standards. Table VII-4 •
shows threshold levels for copper in drinking, agricultural and indus-
trial water supplies •
McKee and Wolf also reported that the limiting factor of copper
in domestic water supplies is its taste. The threshold concentration is |
in the range of 1-2.0 mg/1 while a level of 5-7.5 mg/1 copper makes .
the water completely undrinkable. This latter point is also discussed
by Schneider (83). McKee and Wolf also noted that a concentration of •
1 mg/1 copper has been found to react with soap producing insoluble
green curds. It has also been known to produce blue-green staining on •
porcelain fixtures. _
Effect on Irrigation Water and Plant Life
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McKee and Wolf report that minute quantities of copper are bene-
ficial and essential for plant growth. However, concentrations in the
range of 0.17-7.20 mg/1 have been found to be toxic to sugar beets and
barley grown in nutrient solution. Similarly a 20 mg/1 concentration •
is toxic to tomatoes, 0.1 mg/1 to orange and mandarin seedlings, and
0.5 mg/1 or higher to flax. Copper concentrations as low as 0.1 mg/1 |
may be toxic to plants grown in nutrient solutions (6). A tolerance _
limit of 0.2 mg/1 copper is recommended for water irrigated sands *
which are very low in organic matter, for all other types of soil •
a safe limit of up to 5 mg/1 is suggested. Table ¥11-5 summarizes
the toxic concentrations of copper to plants. •
120
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TABLE VII-4
THRESHOLD LEVELS FOR COPPER IN
POTABLE, AGRICULTURAL AND INDUSTRIAL
Threshold
Level mg/1
Drinking Water 1
General Ind. Water Supplies 5
Textile Water Supplies 0.5
Beverages* (ready-to-drink 2-7
and carbonated)
Irrigation 0.1
Water Irrigated Sand Soils 0.2
Other Soil 5
Fresh Waters 0.02
Marine Waters 0.05
* British Ministry of Agriculture
TABLE VI 1-5
TOXIC
WATER SUPPLIES
References
(66)
(66)
(6)
(66)
(66)
(6)
(6)'
(66)
(66)
CONCENTRATION OF COPPER TO PLANTS (66)
Species
Sugar beets
Barley -
Tomatoes
Oranges and mandarin
seedlings
Flax
121
Concentration mg/1
0.17 - 7.20
2.0
0.1
0.5
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Effect on Stock and Wildlife
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The Green Book reports that concentrations of iron and copper
in milk, as low as 0.1 mg/1, have been found to contribute to the
development of oxidized flavors. However, a concentration of 1.0 mg/1
copper was recommended for stock watering (6). On a similar note, •
McKee and Wolf reported that small amounts of copper are beneficial
for the hemoglobin count and growth in rats. Copper is beneficial |
to the growth of suckling pigs and is believed necessary to prevent _
scouring and wasting diseases in cattle and sheep. *
In general it would appear that copper at a concentration of f|
approximately 1 mg/1 is not detrimental to animal wildlife, however,
higher concentrations may be. •
Effect on Fish and Other Aquatic Life •
The effect of copper on fish and aquatic life varies not only
with respect to various species, but also with respect to water quality. |
Table VII-6 summarizes the toxic and synergistic effects of copper «
with respect to various water quality parameters.
As summarized in Table VII-7, it is apparent that there is a I
broad range of copper toxicity for various aquatic species (both
riarine and fresh). Most forms of fresh water fish are capable of •
withstanding a copper concentration of 0.10 mg/1 or greater. Other
forms of fresh water aquatic life have substantially greater sensi- *
tivities to copper down to approximately 0.002 mg/1. Toxicity to tt
marine life, on the other hand, generally falls within a range of
0.05-0.1 mg/1. It has been reported that copper is less toxic in •
river water than in lab tests. In addition to being highly toxic to
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many forms of aquatic life, copper is concentrated by fish and
aquatic life. A summary of this data is shown in Table VII-8.
While one species of algae has been shown in Table
a relatively high concentration factor for copper, copper
of copper sulfate has long been utilized for the control
VII-8 to have
in the form
of algae in
farm ponds, reservoirs, etc. Table VII-9 shows that various species
of algae have a comparatively high sensitivity to copper
TABLE VII-6
SUMMARY OF SYNERGISTIC EFFECTS
AND COPPER
Parameter Effect
Hard Water toxicity decreased to range
of 0.1-1.0 mg/1 Cu.
Soft Water Cu. toxicity increased to 0.015-3.0 mg/1
range
Zinc @ 8 mg/1 alone killed fish as did copper @ 0.2 mg/1
Zinc (§1.0 mg/1 & copper @ 0.025 mg/1
also killed fish
Chlorine toxicity of Cu. increases
Cadmium toxicity of Cu. increases
Sodium nitrite toxicity of Cu. was decreased
& Sodium
nitrate
Copper toxicity of cyanide decreased
Alkalinity toxicity of Cu. decreased
Acidity toxicity of Cu. increases
Temperature toxicity of copper sulfate decreased
2.5% for each oc below 15 °C.
Mercury toxicity of Cu. increases
1?1
sulfates.
Reference
(66,83)
(66,83)
(6,15,83)
(66)
(66)
(66)
(66)
(6,66)
(66)
(6,66)
(6)
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TABLE VI I- 7
TOXIC OR HARMFUL COPPER
CONCENTRATIONS
Species
Barnacles
Mytilus edulis
Oys ters
Soft Clam
(Mya arenaria)
Giant Kelp
(Macrocystis
pyrifera
Red tide organism
(Gymnodinium breve)
Generally: bacteria &
Mi c roo rg ani sms
Oyster Larvae
Young eels
Blue gill sunfish
(softwater)
Rainbow Trout
(Lake Huron)
Sea Lamprey
Daphina magna, young
Cyclops vernalis
Mesocyclops leuckarti
Diaptomas oregonensis
Hemacheilus barbatulus
Nereis sp. (warm)
FOR FISH & OTHER AQUATIC
Concentration
mg/1
10-30 in 2 hours
0.55 in 12 hours
0.1 - 0.5
0.5 in 3 days
0.1 in 2-5 days
0.05
0.1 - 0.5
0.1 - 0.5
0-13 for 50 hrs. as
CuCl2 2H20
1.25 96 hr. TLm
5.0 in 10 hrs . as
CuCl2 2H20
5.0 in 12 hrs. as
CuCl0 2H00
2 2
0.027 as CuCl
2.7
1.9
0.0024
0.20 in 24 hrs.
0.1 (threshold)
124
LIFE
Reference
(6,66)
(6,66)
(6)
(6)
(6,66)
(6)
(66)
(66)
(66)
(66)
(66)
(66)
(66)
(in Lake Erie
water @ 20-25°C)
(15)
(15)
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TABLE VII- 7 (con't)
TOXIC OR HARMFUL COPPER
CONCENTRATIONS FOR FISH & OTHER AQUATIC LIFE
Concentration
Species mg/1 Reference
Carcinas maenas 1-2 (threshold) (15)
(shore crab)
Leander squilla 0.5 (threshold) (15)
(prawn)
Crayfish, young 0.125 - 0.6 (15)
Salmo gairdnerii 0.4 - 0.5 (15)
FISH MAXIMUM CONCENTRATION
tolerated as CuSO,
4
Perch 0.5 (66)
Black bass and 0.8 (66)
bluegills
Sunfish 1-35 (66)
Black bass 2.00 (66)
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An additional effect of copper in surface waters, as reported by
McKee and Wolf is its interference with BOD determinations and the |
self-purification process of streams. A concentration as low as «
0.01-0.5 mg/1 will interfere with BOD and self-purification rates (66). ™
Other investigators reviewed by McKee and Wolf, however, indicated fl
that a concentration of 0.4 mg/1 did not interfere with self-puri-
fication and that a copper concentration of 8.4-35 mg/1 might be •
needed to cause a 50% reduction in BOD,.. In this case it appears that
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the water quality may have affected the results of the reported in-
vestigations. •
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TREATMENT TECHNOLOGY-COPPER REMOVAL
Precipitation
One of the oldest and most common methods of treatment of
copper bearing wastewater is precipitation of copper hydroxide at
alkaline pH conditions. Copper hydroxide has a minimum solubility |
within the pH range of 9.0-10.3. It is also reported to have a «
solubility of 0.01 mg/1 at a pH of 10 (76). The theoretical level *
is Seldom obtained due to poor settling, incomplete reactions, and I
the influence of other ions within the solution. Generally, lime
is utilized to maintain proper pH conditions. Table VII-10 shows •
the efficiency of this and other processes, with and without fil-
tration. *
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TABLE VII-8
CONCENTRATION OF COPPER IN FISH & AQUATIC LIFE
Species C. F. Reference
Plankton 1,000-5,000 (6)
Algae (Ochromonas) 1,840-3,040 (66)
Sphaerotilus 3,890 (66)
Marine bacteria 990 (66)
Marine invertebrates, 5,000 (66)
soft parts
Fresh water fish 50 (66)
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TABLE VII-9
TOXICITY OF COPPER SULFATE TO ALGAE
Species
BLUE-GREEN ALGAE Toxicity Reference
GREEN ALGAE
Arkistrodesmus
Chlorella
Closteriums
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Cylindrospremum 2.0-4.0 mg/1 Toxic (15)
Anabaena for 28 days
Anacystis •
Calotnrix ™
Nostoc
Oscillatoria
Plectonema
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Oocystis
GREEN ALGAE
Scenedesmus
Stigeoclonium _
Zygnema •
GREEN FLAGELLATE AND YELLOW ALGAE
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Chlamydomonas
Pandorina
Tribonemas M
Gomphonema •
Navicula
Nitzschia
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Anabaena 0.09 Cone, mg/1 (66)
Beggiatoa 5.0
Chara 0.2-5.0
Cladophora 1.0
Cladothrix 0.2
Conferva 0.4
Nauicula 0.7
Oscillatoria 0.1-0.4
Scenedesmus 5.0-10.0
Spirogyra 0.05-0.3 •
Ulothrix 0.2 •
Volvox 0.25
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TABLE VII-10
COPPER TREATMENT EFFICIENCIES
Process
Lime Neutralization and
settling
Line Neutralization settling
& Filtration
Cyanide destruction
w/ sodium hypochlorite
Coag. w/ferric chloride
w/filtration of eff
Lancy Batch Treat
Lancy Integrated
Lancy Integrated
Carbon adsorption of
copper cyanide complex
Process change -
Velco Brass & Copper Co.
Process Modification
Recovery
Ion Exchange
Electrolytic Recovery
CONCENTRATION
Initial
33
204-385
unknown
unknown
10-20
general
previous
eff 0.2-2.5
general
14-18
30
electroplating
electroplating
electroplating
98
75-124
40
unknown
1.02
26
129
mg/1
Final
less than 1.0
0.5 (ave.)
0.2-2.5
0-1.2 (0.15-.19 ave)
1-2
0.2-2.5
0.2-0.5
0.5
0.005-0.5 (Lab scale)
0.16-0.3 (full scale)
1.5-2.0
0.15
less than 0.5
less than 1.0
0.25-0.35
0.9
none
0.03
0.0 in 11 days
Ref .
(76)
(76)
(76)
(76)
(76)
(97)
(76)
(97)
(76)
(76)
(61)
(61)
(64)
(U)
(96)
(76)
(48)
(76)
(76)
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Copper-Cyanide Wastes
A new method involving complexed copper cyanide wastewaters
utilizes the destruction of cyanide by sodium hypochlorite followed
by a pH adjustment and coagulation-precipitation with ferric chloride •
and lime, and subsequent filtration. Table VII-10 shows the processes
efficiency. •
Lancy Process •
The Lancy Integrated System theoretically is capable of achiev-
ing an effluent of 0.15 mg/1. Table VII-10 shows process efficiency |
of the Lancy System. •
In practice, McDonough and Steward (64) reported an effluent
copper concentration of less than 0.50 mg/1 with the Lancy integrated •
system. Lund (61) describes the Lancy system which utilizes counter-
current rinsing with a chemical solution (lime) that is then recycled |
after sedimentation. .
Carbon Adsorption
Battelle (14) reported complex cyanide-chromium removal from I
electroplating waste by carbon adsorption. Their report indicated
that carbon adsorption of complexed cyanide from electroplating waste "
was most effective with nickel and copper complexes and at a pH of 10. •
The cost of removing cyanide by complexing with nickel or copper by
carbon adsorption and recovery,, after previous contact with cadmium •
or zinc, was in the range of 2C-40C per pound of cyanide treated.
|
Recovery Processes
Copper can be economically recovered from the wastewaters under •
certain situations. One of the, methods which may be utilized as a
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• recovery step is process modification. According to Patterson and
Minear (76) the use of counter current rinsing for one company allowed
• direct return of their rinse flow to their plating bath as evapo-
rative makeup water. The counter current rinsing for this plant re-
jf duced their rinse water flow volume from 480 gph to only 16 gph.
_ This scheme reduced their total copper discharge from 40-0.9 mg/1.
The Velco Brass and Copper Company, of Kenilworth, New Jersey (96)
• has reduced its copper effluent by converting a former sulfuric-
chromic acid and ammonium bifluoride-chromic acid pickle to a sul-
• furic acid, 2-5% hydrogen peroxide pickle (with stabilizing agents).
_ The result has been a reduction in copper in the discharge from 175-
™ 124 mg/1 to 0.25-0.85 mg/1. Velco (96) reports that by the use of
• a neutralizing agent chemical rinse following a sulfuric acid-hydrogen
peroxide pickle dip, the copper count content of the rinse water can
be maintained at 0.1 mg/1. At present, the cost of their pickling
treatment and recovery process is $156.00 per operating day (or $194.00
per operating day including amortization costs). This compares to
their previous cost of $195.00 per operating day, which does not in-
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elude cost of treatment. Their current treatment recovery cost is
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only $46.72 per day or $.62 per ton of copper wire produced.
Table VII-10 shows the efficiency of other recovery processes
including evaporative recovery, ion exchange and electrolytic recovery.
Evaporative recovery has been practiced for over 20 years (76).
Patterson and Minear indicate, however, that some form of pre-concen-
tration may be needed for this process to be economical.
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Ion exchange, according to Patterson and Minear, may be an
I
economical means of removing copper from dilute wastewaters. One
of the articles reviewed by them indicated that ion exchange was I
successfully used from a wastewater containing only 1.02 mg/1 copper,
at a flow rate of approximately 0.80 gallons per square foot per minute. •
Gurnham (48) reports that the Inspiration Consolidated Copper •
Company of Arizona utilizes electrolytic recovery for their copper
sulfate waste to completely eliminate the discharge of copper in their •
wastewaters. He also reported that the rate of recovery of copper
from this facility is about 40,000 tons per year. A pre-concentration |
step may be necessary for this type of operation (76) . •
A review of Table VII-7 indicates that while some processes
such as ion exchange and electrolytic recovery may be capable of re- •
ducing the copper concentration to the range of 0.030 mg/1, destruc-
tion processes are currently capable of maintaining effluent levels |
of 1.0 mg/1. Proper pH control followed by good clarification for
removal is needed to reach a lower concentration.
A review of the capital and operating and maintenance cost in •
Tables VII-11 and 12 would indicate that the operation of a plant
utilizing lime neutralization and sedimentation might be more eco- |
nomical if filters are utilized. Further confirmation of this data _
is necessary prior to using this as a general assumption. It is ™
apparent, however, in reviewing the capital and operating costs that I
both figures are in line with the cost of removing other metals from
wastewaters. •
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SUMMARY AND RECOMMENDATIONS
After a review of the above discussions and referenced data,
the following can be stated.
1. A concentration above 0.05 mg/1 in surface waters and above
0.03 mg/1 in sea water is considered to be from man-made in-
dustrial sources. Industrial waste discharges of copper have
been reported to vary anywhere from trace levels up to as high
as 44,000 mg/1.
2. Copper is an essential element in both man and animals. While
copper at rather high concentrations may be toxic to man and
animals it will produce an unpleasant taste to the point of
being completely unpalatable long before it has a toxic effect.
The 1962 Drinking Water Standard of 1.0 mg/1, appears to be
appropriate for human beings.
3. Industrial water supplies may utilize waters containing copper
up to 5 mg/1. However, the textile industry is reported to
have problems with waters containing as little as 0.5 mg/1.
4. Water containing as much as 5 mg/1 copper used for plant irri-
gation normally does not create problems. However, for sandy
soils very low in organic matter, copper may be damaging to
plants at a concentration of 0.1 mg/1.
5. The water supply for stock and wildlife has been shown to be
beneficial if it contains some copper. However, it is recommended
that it not exceed a concentration of 1.0 mg/1.
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6. Fresh water fish have been shown to tolerate a concentration
as high as 0.14 mg/1. Other fresh water organisms, however, |
have a toxicity to copper reportedly as low as 0.002 mg/1. •
Marine aquatic life has a general toxicity range starting at
0.05 mg/1. Various forms of aquatic life including fish and •
lower forms are known to have concentration factors ranging
from 50-5000 C.F. The toxicity of copper is known to increase |[
in the presence of zinc, chlorine, cadmium, and mercury in .
acid waters and at temperatures above 15°C. Conversely, the *
toxicity of copper decreases as water hardness increases, cal- I
cium concentration, and alkalinity increase, and as the concen-
trations of other previously mentioned metals decrease. It has •
also been found to decrease in the presence of sodium nitrate _
and sodium nitrite and also when the temperature is below 15°C. ™
7. Copper sulfate is known to be toxic to algae and is used for H
their control. Effective concentrations range from 0.07 to
10 mg/1. I
8. Ca rent achievable tre tment is capable of maintaining a maxi-
mum effluent level of 1.0 mg/1. Various recovery processes are •
currently capable of reducing copper cown to the 0.03 mg/1 •
range on an average. The cost of both initial installation
and operation of treatment facilities.is well within the range •
of treating other metals.
On the basis of the above summary, it is recommended that a
uniform effluent limit of 1.0 mg/1 be adopted for all wastewater dis- •
charges of copper. It is further recommended where copper is of
particular concern to the preservation of fish and aquatic life and |
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1
1
1
1
1
1
1
1
1
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1
1
1
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where an industrial discharge will not receive dilution by other dis-
charges within the same industry or by rapid mixing or use of a
diffuser in the stream, that the industry remove copper to the best
obtainable level that is economically possible. On the basis of the
literature reviewed for this report the value of copper should offset
some of the economic problems of more complete treatment.
TABLE VII-11
CAPITAL COST FOR COPPER REMOVAL
Cost/
Process Flow Cost 1000 Gal. Reference
Lime Neutralization
and settling $9,200 (76)
" 1 MGD $ 100,000 100 (97)
10 MGD 600,000 60 (97)
50 MGD 2,600,000 52 (97)
Lime Neutralization 1.5-2.0 800,000 400-530 (76)
Settle & Filter
1 MGD 300,000 300 (97)
" 10 MGD 1,300,000 130 (97)
50 MGD 4,600,000 92 (97)
TABLE VII-12
OPERATION MAINTENANCE COST FOR COPPER TREATMENT (76)
Process Cost/1000 Gal.
Lime Neutralization and sludge dewatering $3.50 (1951)
Lime Neutralization and settling 3.59 (1957
Assumed " 1.62 Rinse waters
only
2.85 Total
Lime Neutralization 5-9C for 1 MGD
settlings & filtration 11-20C for 10 MGD
Recovery Value :
of copper waste $0.60-$3.00 @ 100-500
of brass waste $0.20-$1.20 @ 40-250
135
mg/1
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CHAPTER VIII-CYANIDE
• Cyanide is found in the wastes of several industries (14,16,
48,61,66,67,72). These include the extraction of ore, gold mining,
.
•
•
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photographic processing, coke plants and blast furnaces, manufacture
of synthetics, electroplating and metal finishing, and pickle liquor
waste, as well as other chemical industries. The major source of
cyanide in industrial wastewaters is probably the waste from coke
plants, non-ferrous plating baths and plating rinse waters. Various
concentrations reported in the literature have been summarized in
Table VIII-1.
• From this table it is apparent that the concentrations of cyanides
• in plating baths may be expected to vary from 20,000-100,000 mg/1.
The concentration of cyanides found in plating rinse waters is highly
• dependent upon the rate of drag-out. Concentrations are reported from
10-1500 mg/1. Nemerow (72) indicated cyanide concentrations of various
• plating baths and rinse waters as functions of the complexing metal
and two different drag-out rates. This data has been summarized in
Table VIII-2.
• In addition to hydrogen cyanide and cyanide salts, cyanide may
also appear in discharges as the sodium or potassium salts of cyanate,
• thiocyanate, ferro and ferric cyanides and also as cyanogen chloride
• (66) . Although concentrations are customarily expressed in terms of
mg/1 of cyanide ion, the actual form present is a function of pH. Be-
cause hydrogen cyanide (HCN) is a weakly dissociated acid, it will be
present mainly in the undissociated form at a pH less than 8. In Figure
VIII-1 the relative proportions of CN and HCN are shown as a function of
pH. Below a pH value of 7 less than one percent of the total is present asCN.
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Above a pH value of 10, 87
percent is present as the
This relationship is important because HCN is a more
thi- Ion. Therefore, even
critically dependent on pH
CONCENTRATIONS OF
Source
Plating Baths
Plating Rinse Waste
Coke Plant Crude Liquor
to Ammonia Still
From Ammonia Still
for a given concentration,
•
TABLE VIII-1
cyanide ion (66).
toxic entity than
toxicity will be
CYANIDE IN INDUSTRIAL WASTE WATERS
Concentrations, mg/1
48,000-100,000
21,800- 57,000
10- 700
39- 1,500
28- 72
20- 100
10- 100
TABLE VI I I- 2
Reference
(76)
(72)
(76)
(16)
(14)
(48)
(48)
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COMPLEXED CYANIDE PLATING WASTE
CYANIDE
Plating Bath
28,000 w/Cu
57,700 w/Cd
48,900 w/Zn
47,500 w/Cu & Zn
21,800 w/Ag
CONCENTRATIONS, MG/L (72)
(Rinse Drag-Out
0.5 gph
58
120
102
99
45
137
@)
2.5 gph
290
600
510
495
225
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-1 -2 -3
CYANIDE CONCENTRATION-MOLE
137B
-6
-8
'•Z,
a
J.-H
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• The relative toxicities of a nickel-cyanide complex are such that a pH
drop from 7.8 to 7.5 increases the toxicity tenfold and a drop from 8.0
• to 6.5 increases the toxicity a thousand fold (6). Adjustment to the
optimum pH is also an important facet of the treatment of cyanide as
• will be discussed later. Direct sunlight on effluents containing the
• otherwise less toxic ferric and ferro cyanides is also of great import-
ance (16) .
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ENVIRONMENTAL EFFECTS OF CYANIDE
Effects on Man
I The toxicity of cyanide in man is well documented but at relative-
ly high concentrations. It is acknowledged in the 1962 Drinking Water
• Standards (94) that the 0.2 mg/1 CN standard for rejection of a water
_ supply is based on the treatability of cyanide and a safety factor of
* 100 rather than its toxicity to man. Other recognized standards of
H 0.01 to 0.2 mg/1 are based on fish toxicity rather than toxicity to
man (94).
• The toxic effects of cyanide on man are summarized in Table VIII-3.
McKee and Wolf (66) indicate the average fatal dose of hydrogen cyanide
• for man is 0.7 to 3.5 mg/kg of body weight. A fatal dose for a 165 Ib.
• man would then be 52-260 mg of HCN.
The maximum safe intake level of cyanide is believed to be about
18 mg/day, part of which may come from natural and industrial exposures
(66). An odor threshold of 0.001 mg/1 may make water unpalatable before
toxic effects are important.
McKee and Wolf (66) also report that the body normally ingests
small amounts of cyanide e.g., by consumption of members of the cabbage
™ 138
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family. Small portions of ingested cyanide will be exhaled and the
remainder will be rapidly converted by the liver to the
toxic sulfur compound
slowly in the urine.
, thiocyanate which is eliminated
relatively non-
irregularly and
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Cyanide, therefore, is a non-cumulative toxin and
small doses can be disposed of continuously by the body
toxifying mechanisms.
TABLE VIII-3
's natural de-
ORAL TOXICITY OF CYANIDE FOR MAN
Dose
0.001
2.9 - 4.7 tng/day
10 mg single dose
Response
Odor threshold
Non-injurious
Non-inj urious
<18 mg/day total intake Maximum safe ingestion
19 mg/day in water
50-60 mg single dose
Calculated from threshold
limit in air as safe
Fatal
Reference
(66)
(94)
(94)
(66)
(94)
(94)
Effect on Domestic and Wild Animals
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With reference to stock and wildlife, McKee and Wolf indicate that
hydrogen cyanide and
animals. A hydrogen
sodium cyanide have been found to
cyanide concentration of 103 mg/1
be toxic to
has been found
to be fatal to cows and ducks. Otherwise toxic and lethal dosages of
hydrogen cyanide and
McKee and Wolf report
sodium cyanide are summarized in Table VIII-4.
that for sheep the toxic dose of
hydrogen cyanide
is 1.05 mg/kg of body weight, while the toxic concentration of sodium
cyanide is 4.15 mg/kg of body weight.
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TABLE VIII-4
TOXIC EFFECT OF CYANIDE ON DOMESTIC ANIMALS (66)
Animal Dose of__HCN
Cow 0.39 - 0.92 grams
Sheep 0.04 - 0.10 grams
Horse 0.39 grams
Dog 0.03 - 0.04 grams
TABLE VIII-5
TOXIC EFFECTS OF CYANIDE ON FISH AND OTHER AQUATIC ORGANISMS
Organism
Trout
Blue gills
Bullheads
Brook trout
Rainbow trout
Fish
Rainbow trout
Bluegill sunfish
Trout
Trout
Bluegill sunfish
Rainbow Trout
Fish
Adult chub
Trout
Adult Chub
Trout
Carp
Daphnia magna
Cricotopus bicinctus
Mayorella palestinensis
(from McKee & Wolf)
CN~ Cone, (mg/1)
.02
.4
.5
0.05
0.07
0.1
0.1-0.2
0.12-0.18
.126
.15
.18
.2
.2
.33
.42
.50
1.0
10.0
.34
3.2m
130
(66)
Time of
Exposure
27 days
96 hrs.
96 hrs.
120-126 hrs.
74 hrs.
1 day
1-2 days
96 hrs. TL
170 min. m
4.8-6.4 min.
24 hr. TLm
11 min
150 min.
2.5 hr.
4 min.
141 min.
20 min.
1.5 hrs.
48 hrs.
—
—
Effect
survived
survived
survived
lethal
overturned
overturned
MLD
—
overturned
overturned
—
LD-50
lethal
lethal
overturned
MLD
lethal
MLD
lethal
survived
lethal
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The literature reviewed did not contain any mention of the poten-
tial effect of toxicity of cyanide on plant life.
Effect on Fish and Aquatic Organisms •
The major impact of cyanide on the aquatic environment is its
toxicity to fish and other forms of aquatic life. It is again noted •
that the effect of pH is a significant factor. McKee and Wolf report •
that an innocuous concentration of cyanide at a pH of 8 may become
detrimental if the pH is lowered to 6 or less. They further report •
"In natural streams, cyanides deteriorate or are decomposed by bacterial
action, so that excessive concentrations may be expected to diminish •
in time." (66) McKee and Wolf also indicated that from 90 to 95 per- •
cent of the cyanides in waters have been found to be removed by per-
colation of wastewaters through soil columns. Greater removal was •
obtained in soils rich in organic matter.
The toxicity to fish and other aquatic organisms is summarized in I
Table VIII-5. The Report of the Committee on Water Quality Criteria •
indicates that the toxicity of cyanide to diatoms was found to vary very
little with respect to temperature (6). McKee and Wolf on the other •
hand indicate that the toxicity of cyanide to fish has been found to
increase at elevated temperatures. They report that a rise of 10 C
produced a 2 to 3 fold increase in the toxicity of cyanide. Other •
factors which have an effect on the toxicity of cyanide, as reported by
McKee and Wolf, include dissolved oxygen and the presence of certain •
metals. McKee and Wolf and the "Green Book" (6,66) indicate that a
low dissolved oxygen level may increase the toxicity of cyanides. ||
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• Trout were exposed at 17 C to a concentration of 0.105 mg/1 of cyanide.
This level was found to be toxic in 8 hours at 95 percent oxygen satura-
I tion, in 5 hours at 73 percent saturation, and only 10 minutes at 45
percent saturation. With respect to the presence of metals, nickel
may complex with the cyanide decreasing its toxicity, especially at
higher pH values. Zinc and cadmium on the other hand, have been found
-3 -4
to increase toxicity. Iron cyanide complexes (Fe(CN), ' ) are normally
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• less toxic than simple cyanides (1,66). However, McKee and Wolf have
reported that under exposure to direct sunlight the previously assumed
I harmless concentration of 2000 mg/1 (under diffuse light) of potassium
ferric cyanide or potassium ferrocyanide become toxic at concentrations
• of 0.5 to 2.0 mg/1. A potassium ferrocyanide concentration of 2.0 mg/1
• under direct sunlight resulted in a cyanide concentration of 0.36 to 0.48
mg/1 which killed fish in 0.5 to 1.5 hours.
• A general recommendation of 0.025 mg/1 has been proposed by the
Aquatic Life Advisory Committee of the Ohio River Valley Sanitation
H Commission, according to McKee and Wolf, as the limit for being unsafe
• to fish and aquatic life. They further indicated that proper chlorina-
tion under neutral or alkaline conditions is capable of reducing cyanide
• to a level far below the recommended limit. The acute oral toxicity of
cyanogen chloride, which is the product of chlorinating hydrogen cyanide,
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would be 1/20 that of the hydrogen cyanide alone.
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TREATMENT TECHNOLOGY - CYANIDE REMOVAL
chromium and cyanide removal is highly dependent upon the method select-
ed, the waste volume, the concentration, the degree of recovery and the
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The 1968 report the Battelle Memorial Institute (16) discussed
I he following live conventional methods for cyanide removal from B
plating waste:
(1) Oxidation by chlorine gas - complete removal •
(2) Oxidation by hypochlorites - complete removal
(3) Conversion to cyanate by chlorine gas followed by precipita- •
tion and clarification
(4) Conversion to cyanate by hypochloride
(5) Conversion to Ferrocyanide by ferrous sulfate - effluent I
obtained, 5-10 mg/1
They also reported seven newer methods which were being investi-
gated at that time for cyanide removal. These include: •
(1) Complex formation with polysulfides to form sulfocyanates
(2) Destruction by potassium permanganate p
(3) Oxidation to cyanate by ozone _
(4) Oxidation to cyanate by hydrogen peroxide
(5) Complexation by nickel salts to highly stable nickel cyanide I
(6) Biological oxidation
(7) Irradiation, dialysis, reverse osmosis, and electrolytic •
reduction.
In the 1968 report, Battelle also reported that ion exchange and evapora-
tion have proven feasible for detoxification and recovery of cyanide in •
more concentrated waste streams. They indicated that the cost of
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value of that recovered, whether it is a batch or continuous opera-
tion, and the chemical cost.
According to the recent investigation by Patterson and Minear
(76),
the three most frequently employed practices for cyanide removal are
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destruction of cyanide by chlorination, electrolytic decomposition,
ozonation. Table VIII-6 summarizes some typical treatment plant
characteristics .
TABLE VIII-6
SUMMARY OF TREATMENT EFFECTS ON CYANIDE
[CN~] mg/1
Method of Treatment Flow Influent Effluent
Chlorination 2500-3000 gals/hr - 0.1
Chlorination 2000 gals/mo 32.5 0.0
Chlorination 4- Sulfuric - 700 0.0
Acid Hydrolysis
45,000 -
Electrolytic Decomposition - 100,000 0.1-0.4
Ozonation 500 gals/min 25.0 0.0
Lancy Integrated System - - 0.02
Chlorination
Destruction of cyanide by chlorination may be accomplished by
and
Ref .
(76)
(76)
(76)
(76)
(76)
(61)
either
the direct addition of chlorine gas or by the addition of sodium hypo-
chlorite, thus saving on hydroxide. The selection of the method is
one
of economics. Chlorine gas is about half as expensive as hypochlorite
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treatment. However, it is also much more dangerous to handle and the
equipment costs are higher.
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The destruction of cyanides by chlorination may be carried out in _
either batch or continuous operations. In the batch operation, suffici-
ent amounts of sodium hydroxide are added to the waste to raise the pH I
to approximately 10.5. Chlorine is then added at a constant rate with
the simultaneous addition of more sodium hydroxide to maintain the pH •
above 10.5. This oxidizes the cyanide to the cyanate which is less _
toxic. Continuation of the addition of chlorine will completely oxidize ^
the cyanide to the harmless forms of nitrogen and carbon dioxide. To •
accomplish this, chlorination is continued without the further addition
of sodium hydroxide. I
This may also be done by acid hydrolysis. Acid hydrolysis however,
must take place at a pH of 2 to 3 which usually necessitates the addition •
of sulfuric acid and then subsequent neutralization of the acidic waste •
prior to discharge. This method for complete destruction of cyanide
has both advantages and disadvantages. The main disadvantage is that I
back neutralization increases the total dissolved solids level of the
effluent. The main advantage of this process is that cyanate will be H
destroyed within about 5 minutes contact time. •
Complete destruction of cyanide may also be obtained as mentioned
by continuation of chlorination alone. The rate of the reaction, how- •
ever, is relatively slow (up to 24 hours) if the pH remains greater
than 10. However, if the pH of the waste is reduced to between 8 and |
8.5, the cyanate oxidation can be completed within about 1 hour. One •
problem encountered in the total oxidation of the cyanate by chlorine
alone is that an excess amount of chlorine must be added to prevent •
liberation of the highly toxic cyanogen chloride gas.
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I This same process may be carried out on a automated continuous
system. The feed mechanisms for adding chlorine and sodium hydroxide
• are often controlled by pH meter and an oxidation-reduction potential
recorder-controller.
H As reported by Gurnham (48) the theoretical requirements for the
• destruction of 1 pound of cyanide are 2.7 pounds of chlorine and 3.1
pounds of sodium hydroxide for the first step of the reaction. The
I total theoretical chemical requirement is 6.8 pounds of chlorine and
3.7 pounds of sodium hydroxide per pound of cyanide. However, it has
• been found in practice that approximately 8 pounds of chlorine are re-
• quired per pound of cyanide destroyed.
As reported by Patterson and Minear (76) several manufacturers have
I developed small package treatment systems for the destruction of cyanide
by chlorination. They indicated that the capacity of these units range
| from 800 gallons of waste per hour containing a maximum of 450/mgl of
im cyanide, to units capable of handling 1,800 gallons per hour with a
maximum cyanide content of 350 mg/1. The cost of a unit with the
I capacity of 800 gallons per hour was reported by Patterson and Minear
to be $15,000 for the complete unit. Patterson and Minear further re-
| ported that larger cyanide destruction units require individually
_ tailored treatment systems. They reported that one unit utilizing a 2
step process has been constructed to handle 1.5 MGD.
• Patterson and Minear also described the efficiency of these units.
One unit, treating from 2,500 to 3,000 gallons per hour of cyanide
• waste, achieved a final effluent of 0.1 mg/1. Similarly, an IBM plant
utilizing alkaline chlorination followed by acid hydrolysis, reduced a
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700 mg/1 cyanide concentration to 0 mg/1 cyanide plus cyanate.
Another plant described by Patterson and Minear was a General •
Electric Metal Plating operation in Erie, Pennsylvania. They had a •
waste containing an average cyanide content of 32.5 mg/1. It was
treated on a batch basis at the rate of 2,000 gallons per month, and B
obtained a final concentration of cyanide in the effluent of 0.0 mg/1
as cyanide. |
Electrolytic Decomposition •
Patterson & Minear reported that waste containing high concentrations
of cyanide are most effectively treated by electrolytic decomposition. •
The concentrated cyanide waste is subjected to electrolysis at a tempera- _
ture of approximately 200 F for several days. When the system is first ™
started, the cyanide will be completely broken down to carbon dioxide I
and ammonia with cyanate as an intermediate. However, as the process
continues, the waste electrolyte becomes less capable of conducting •
electricity and the reaction may not be completed. It is further stated
that the residual cyanate which may be formed will then require chlorina- •
tion for further destruction. They reported that this system, with de- •
tention of 1 to 18 days, is capable of reducing initial cyanide concen-
trations ranging from 45,000-100,00 mg/1 to final cyanide concentrations I
of 0.1 to 0.4 mg/1.
One of the problems which has been encountered with the electroly- •
tic destruction process, as reported by Patterson and Minear, has been •
the presence of sulfate in the waste. In removing cyanide concentra-
tions of 695 to 750 mg/1, heavy scaling at the anode prevented further I
electrolysis.
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• Ozonation
More recent literature, as reported by Patterson and Minear, indi-
• cates that ozonation might offer the cheapest method of destroying cya-
nide. They reported that cyanide complexed with zinc, nickel, and
Jj copper was easily destroyed. However, a cobalt-cyanide complex was
_ found to be resistant to treatment by ozonation. Patterson and Minear
™ indicated that the Boeing Airplane Metal Working plant in Wichita,
I Kansas, has reported complete destruction of cyanide from a 500 gallon
per minute waste stream initially containing 25 mg/1 cyanide.
• Miscellaneous
• As reported in Lund (61), the patented process for treating electro-
plating waste known as the Lancy system is also capable of obtaining low
• cyanide concentrations from plating waste. He states that a batch
treatment is capable of obtaining a 0.5 mg/1 effluent while the inte-
• grated system theoretically is capable of obtaining an effluent of 0.02
• mg/l of total cyanide. In a report of a full scale operation utilizing
the Lancy integrated system, McDonough and Stewart (69) have reported a
• total effluent cyanide concentration of "none" after several years of
operation at an electroplating facility in Wisconsin.
| A 1971 report by the Battelle Memorial Institute (14), discussed
_ investigations of several new processes which they have investigated
for removal of complexed cyanide. They reported that carbon absorption
• of complexed cyanide from electroplating waste was most effective with
nickel and copper complexes at a pH of 10. Other methods investigated
• and reported by Battelle included flotation, liquid-liquid extraction,
_ centrifugation followed by extraction, and carbon absorption with recovery.
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Their work was aimed at the recovery of the heavy metals associated
with the cyanide, and the final effluent concentrations of cyanide
obtained are substantially higher than those reported by other methods.
Cost of Treatment |
The cost of treating cyanide wastewaters by the various methods •
has been summarized in Tables VIII-7 and VIII-8 below, Table VIII-7
gives the capital cost and Table VIII-8 the operating and maintenance •
costs. From these tables, it is apparent that the cost of treating
cyanide bearing wastewaters is dependent not only on the process which |
is utilized, but also on the volume of waste treated, and the concen- H
tration of cyanide in the wastewaters. Additional cost data other than
that summarized in these tables is shown in the report by Patterson and •
Minear (76) and in the last chapter of this report.
On the basis of the cost data by Weston (97), as shown in Table |
VIII-7 the total destruction of cyanide by chlorination under alkaline _
conditions is comparable with the cost of removing metals from industrial ™
I
wastewaters.
In remarks before the State of Illinois Pollution Control Board re-
garding the establishment of effluent criteria, Currie (27) stated that •
several industrial witnesses, representing firms with cyanide problems, _
endorsed the proposed Illinois Pollution Control Board limit of 0.025 '
mg/1 for total cyanide. He further reported that while the work of •
Patterson and Minear and the testimony by Weston indicated that chlorin-
ation, among other methods, is currently capable of achieving cyanide I
effluent levels of zero, the great bulk of their evidence supported the
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maximum effluent concentration of 0.025 mg/1. Such an effluent limit
effluent limit.
will give some leeway for minor operational upsets versus a 0.0 mg/1
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On the basis of the above discussions, the following conclusions •
arc drawn:
(.1) The major sources of cyanide from industries are electroplat- •
ing and metal finishing, coke plants and blast furnace waste •
from the steel industry. Concentrations of cyanide from in-
dustrial waste may be expected to vary from 10 to as high as •
100,000 mg/1. The higher concentrations are from plating bath
waste of the electroplating and metal finishing industry. Im- •
proved plant housekeeping and the reduction of rinse water •
drag-out from plating solutions can substantially reduce the
concentration of cyanide in the wastewater. •
(2) The toxicity of a cyanide waste is a function of its pH. How-
ever, at the pH of most natural waterways most of the cyanide B
will be present as undissociated HCN, the more toxic form. «
Due to its natural detoxification mechanisms, the human body
can safely ingest up to approximately 18 mg/day of cyanide. •
(3) Cyanide is reported to have an ordor threshold of 0.001 mg/1.
(4) The human body reportedly exhales some of the cyanide ingested •
and the liver converts most of the remainder to the less toxic _
form of thiocyanate which it then expels through the urine. ™
(5) Fish appear to be the organisms most sensitive to cyanide. flj
The cyanide concentrations should not exceed 0.025 mg/1 for
the preservation of fish life. •
(6) Wastewater treatment technology, as currently practiced, is
achieving a final effluent level of 0.0 mg/1 of cyanide by at >•
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at least three methods.
(7) The cost of achieving these levels is within the range of
• the equivalent cost of removing trace metals from the waste-
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waters.
On the basis of the above conclusions and discussions, it is recom-
mended that a uniform effluent limit be established at 0.025 mg/1 for
cyanide. It is felt that such a limit is immediately achievable. It
• is one which will allow for minor operational difficulties, and it is
within economic reason. This limit is recommended on the basis of the
| preservation of fish life. It is also recognized that if chlorination
• is utilized for the destruction of cyanides then adequate controls will
be needed to meet the criteria which is set forth under a separate
V chapter on maximum total chlorine residuals.
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CHAPTER IX-FECAL COLIFORM
As defined in the Drinking Water Standard (94), fecal coliforms
ar" considered an indicator of recent fecal pollution. The fecal
coliform group consists of Escherichia cp 11 . E_. coli are character-
M
istically found in both human and animal intestines. As such, they
• are an indicator of the presence of disease producing organisms.
The sanitary significance of fecal coliforms has been aptly dis-
cussed in the work of Geldreich (41) and in other literature (1,6,
66,94). Therefore, no general discussion will be presented in this
report.
As the most immediate effect of fecal coliforms in surface
waters is on recreational use, the recommendation of this report is
for the preservation of this use.
With respect to the treatability of wastes containing fecal
coliform, substantial reductions will be obtained by biological,
chemical and physical treatment. Assurance of low levels is normally
I
achieved by some form of disinfection.
RECOMMENDATION
• To preserve the recreational utilization of surface waters, it
is recommended that during the months of May through October all dis-
• charges not contain more than 400 fecal coliform bacteria per 100 ml
sample at any time. This level is set to assist the maintenance of
| stream standards of200/100 ml for contact recreational use.
— It is recommended that during the remainder of the year, November
* through April, that discharges not contain more than 2000/100 ml
fecal coliform. This level is set to assist maintenance of stream
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standards of 1000/100 ml for non-contact recreational use.
Lower levels are not recommended at this time for the •
following reasons: g|
(1) Fecal coliform are found in surface waters due to
natural, urban, and agricultural runoff. Therefore, •
municipal and industrial discharges are not the
only contribution and in some cases not the major 0
contributor. •
(2) The chapter on chlorine shows that excessive amounts of
residual free and/or combined chlorine are not •
beneficial.
Our objective, therefore, is to remove the disease producing
organisms through more complete biological, chemical, and physical •
treatment rather than re]ying upon disinfection by chlorination.
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CHAPTER X-FLUORIDE
Fluorine, the most reactive non-metal, is never found free in
• nature, but occurs as the univalent anion, fluoride, in sedimentary
rocks as fluorite or fluorspar (calcium fluoride), and in igneous
• rocks as cryolite (sodium aluminum fluoride).
_ Major industrial fluoride discharges are from electroplating,
™ insecticides, steel and aluminum manufacture, glass and ceramics
fl manufacture and fertilizer wastes (76) . Disinfection of brewery
apparatus, wood and mucilage preservation and fertilizer manufacture
• contribute additional fluoride. (61,66,76).
Fluoride as HF is now scrubbed from stack gases as a result of
™ tighter air pollution control laws. Fluoride effluent discharges occur
• from stack effluent scrubbing in phosphoric acid production, steel
mills, and chemical plants among other industries (6). Fluoride is
• added to drinking water and therefrom eventually discharged in domestic
wastewater.
• Concentrations of fluoride found in industrial discharges, vary
• from a low of trace levels to 107-145 mg/1 for aluminum reduction
plants to a high of 1000-3000 mg/1 for glass manufacture (76).
ENVIRONMENTAL EFFECTS OF FLUORIDE
A low concentration of fluoride is beneficial to man and
animals and possibly even fish. Beyond the fine line denoting bene-
A fit, fluoride can be damaging, toxic or, in high enough concentra-
tions even lethal.
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Effect on Man
ized in Table X-2.
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Concentrations of the fluoride ion between 0.8 and 1.5 mg/1
have been shown to be beneficial in reducing tooth decay (1,66). •
Concentrations of up to 5 mg/1 are reported not to produce any harm-
ful effects other than occasional mottling (66). A comparison of •
mortality rates has failed to show any increase in nephritis, heart
disease or cancer to be associated with low fluoride levels. Sodium
fluoride does have a slight salty taste, but less so than sodium •
chloride (66).
Higher concentrations of fluoride are reported to be detrimental m
to man. The concentrations and effects are summarized in Table X-l.
Fluoride also affects industrial uses of domestic water. It is
reported that 1 mg/1 fluoride in water used for wet milling corn can •
be concentrated to 6 mg/1 in steep water, and 5 mg/1 in corn syrup.
Malt syrup made with similar water may contain up to 8 mg/1 fluoride. 0
Fluoride concentrations from 1-5 mg/1 also seem to stimulate yeast «
activity in the fermentation of malt (66).
Effect on Plants •
Fluoride uptake from water is restricted by a combination of
elements in soil, a soil pH above that required for uptake, and by ™
plant root discrimination against fluoride. Concentrations up to B
10 mg/1 in irrigation water have been found to cause no direct damage
to various plants. Concentrations of 100 mg/1 and more have caused •
plant damage, however (66). Some of the reported research is summar-
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•
1
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Effect on Domestic Animals and
The toxic threshold for animals
The effects on animals are analogous
in fighting tooth decay but damaging
Wildlife
is reported to be 1.0 mg/1 (66).
to those on man, ie., beneficial
at higher concentrations.
Table X-3 gives some typical dose response relationships for a number
of species.
Wolf and McKee also reported that for cows consuming water with
500/mg/l fluorides, their milk only contained 0.5 mg/1
1
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TABLE X-l
EFFECTS OF EXCESSIVE FLUORIDE IN
Concentration, mg/1
0.8 - 1.5
1.7 - 1.8
1.0 - 2.0
2.0
3 to 6
4.4 - 12
6.0
8-20
11.8
20 (rag/day)
115
180
2000
159
DRINKING WATER (1,66)
Effects
Threshold for mottling of teeth
50% of children have mottled teeth
Mild to moderate mottling
Dental mottling and weakening of
teeth structure
Severe dental mottling
Chronic fluorosis and skeletal
system damage
Tooth enamel pitted and chipped
Bone changes expected
Chronic fluorine intoxication
in adults
Crippling fluorosis after
20 years
Sub - lethal in drinking water
Toxic to man in drinking water
Lethal dose in drinking water
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FLUORIDE
Species
Peach, tomato, buckwheat
Peach and buckwheat
Sprouting of beans
Buckwheat
TABLE X-2
1
EFFECTS ON PLANTS (66) |
Cone of F
10
100
100
180
, mg/1
- 150
Peach, tomato and buckwheat 200
Buckwheat and peach
Large bean plants
FLUORIDE EFFECTS
Species
Cattle
Sheep
Mice
Cattle
Cattle, Rats
Cattle
Hogs
Cattle
Young Cattle
Hamsters
Sheep
Sheep
Rabbits
360
1000
TABLE X-3
IN DRINKING
Cone . of
1.0
1.0
1.4 - 4.5
0.4
1.
3
6-16
18
25 - 100
50
60
120
200
160
WATER OF
F~, mg/1
mg/1
mg/1
mg/1
mg/kg
mg/kg
mg/kg
mg/1
mg/1
mg/1
mg/1
mg/day
mg/day
mg/kgm
Effect
No injury
Severely injured in
three days
Inhibited
Did not injure at pH 5.5
Killed in a short time
Injurious even at pH 6.5
Stunted growth
ANIMALS (66)
Effect
Harmless
Fluoride poisoning
Teeth mottling
No mottling
Mottling of teeth
Bone damage and death
Severe mottling
Increasing fluorosis
Teeth lesions
Dental fluorosis in 10
weeks
Affected teeth and bones
Threshold for general
health
Lethal
VM
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Effect on Fish and Aquatic Life
I
Fluorides, like many other elements, are most damaging at lower
• concentrations on fish life. Wolf and McKee reported direct toxic
effects of fluoride ions toward fish life. They also noted a relation-
ship between fluorides and fish teeth condition. Whether it is bene-
ficial or detrimental was not indicated, however. The levels toxic
to fish are summarized in Table X-4. The fluoride concentration toxic
• in soft water was found to be approximately 75% of that toxic in hard
water in a study reported in the Water Quality Data Book, Volume III
V (15). Salmo gairdnerii exhibited a 21 day LD^Q of 8.5 mg/1 fluoride
• (15).
A 1966 study postulated that rainbow trout are more sensitive
V to fluoride ions at higher temperatures. The LC,-,. were given as
follows: 5.9-7.5 @ 45°F and 2.6-6.0 @ 55°F. (15).
fj Other forms of aquatic life, including lobsters, Daphnia,
H protozoa and rotifers among others, are apparently less sensitive to
fluoride than are fish. The toxic levels ranged from greater than 4.5
fl mg/1 for lobsters to 270 mg/1 for Daphnia, and up to 1000 mg/1 for
protozoa and rotifers (66).
m TREATMENT TECHNOLOGY - FLUORIDE REMOVAL
M Excessive concentrations of natural fluoride ions have been re-
moved successfully for many years in the water treatment industry.
• The three most common methods of reducing low (less than 10 mg/1) con-
centrations of fluoride to the 1.0 mg/1 range are:
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TABLE X-4
EFFECTS OF FLUORIDE ON FISH (15,66)
Species
Eggs
Trout
Minnows
Unspecified
Carp
Goldfish
it
Rainbow Trout
Mosquito Fish
Tinga vulgaris
Goldfish
Cone, of F , mg/1
1.5
2.3 - 7.3
2.6 - 6.0
2.7 - 4.7
5.9 - 7.5
7.7
64
75 - 91
100
120
358
419
678
1000
1000
Effect
Slowed and poorer hatching
TL at 18°C in soft water
m
TL at 13°C in soft water
m
TL
m
TLm at 7.5°C in soft water
Unharmed in one hour
10 day TLm
Survived over 4 days
Killed in 4 days
Toxic in soft water
96 hr TLm in turbid water
lethal
Killed in 12-29 hrs. in
soft water
Killed in 60-102 hrs. in
hard water
162
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(1) Coprecipitation, magnesium in lime - soda softening
M (2) Coagulation with alum and lime in low magnesium hardness
waters
• (3) Adsorption on activated alumina (76).
H For industrial wastes having fluoride concentrations up to
3000 mg/1, Patterson and Minear (76) report that lime coagulation at
fl a pH of 11 is normally used. The calcium fluoride precipitate has a
theoretical maximum solubility of about 8 mg/1 at a pH of 11, but is
I noted for its slow formation. As a result long detention periods are
_ required. Addition of excess lime followed by settling, recarbonation,
™ and resettling are often needed to obtain a 10-20 mg/1 effluent with
• a pH suitable for discharge (61,76).
Other technically feasible treatments include fluoride removal
• on synthetic and natural (processed bone and bone char) hydroxy apatite,
and ion exchange on natural and synthetic zeolites. While both Weston
• (97) and Patterson and Minear report obtainable effluent levels of
M 0.5-1.5 mg/1 with hydroxy apatite, Patterson and Minear report that
this method has been abandoned in most plants due to the excessive cost.
• Similarly, while an effective strong cation exchange resin has
been developed for fluoride removal, overall treatment and chemical
• costs are reported as excessive (76).
• The effectiveness of the various treatment processes for fluoride
removal are shown in Table X-5. In general, the capital costs for lime
• treatment, alum coagulation and magnesium softening will follow general
water treatment costs. Weston reports the capital costs for an alum
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TABLE X-5
EFFECTIVENESS OF FLUORIDE REMOVAL (76,97)
Fluoride Concentration, mg/1
Process Initial Final
Lime Addition 1000 - 3000 20
Lime Addition 1000 - 3000 7 - 8 *
Lime Addition 500 - 1000 20 - 40
Lime Addition - 10
Alum Coagulation 3.6 0.6-1.5
Alum Coagulation 1
Hydroxy apatite
Beds
Synthetic 12-13 0.5-0.7
Synthetic 10 1.6
Bone char 6.5 1.5
Bone char 9-12 0.6
Unspecified 0.5-1.5
Alumina Contact Beds 8 1
Alumina Contact Beds 20-40 2-3
Alumina Contact Beds 9 1.3
Magnesium softening 3-4 0.8-0.12
164
Reported
Application
Industrial
Industrial
Industrial
Industrial
Municipal
Industrial
Municipal
Municipal
Municipal
Municipal
Industrial
Municipal
Industrial
Industrial
Municipal
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1
1
1
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11
*
1
1
1
1
1
1
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coagulation plant yielding a final fluoride effluent of 1.0 mg/1
as $100,000 for 1 MGD, $600,000 for 10 MGD, and $2,600,000 for 50 MGD.
SUMMARY AND RECOMMENDATIONS
(1) Fluoride is found naturally in sedimentary and igneous rock
• formations. These contribute to natural fluoride ion con-
centrations found in surface waters of those areas.
« (2) Fluoride ions are added to surface waters by a number of
M industrial discharges. The use of water scrubbing due to
air pollution controls of gaseous discharges of fluoride
• has added more industries to the list of aqueous fluoride
dischargers.
W (3) Fluoride ions at a concentration of 0.8-1.5 mg/1 in water
m are beneficial to man, some industries, and animals.
(4) Fluoride concentrations above 2.0 mg/1 may be detrimental
• to man, while fluoride concentrations above 10 mg/1 in
water are definitely damaging to man, industrial uses and
| plant life, and presumably to animals.
» (5) Fluoride concentrations above 1.5 mg/1 are damaging to fish
eggs and fluoride concentrations above 2.3 mg/1 are toxic
V to trout and other species of fish.
(6) High levels of fluoride ion in industrial wastes can be
• reduced from 3000 mg/1 to 10-20 mg/1 by lime coagulation
_ and precipitation.
™ (7) Industrial wastes bearing less than 40 mg/1 fluoride can
IB be treated by one of the more economical processes to a
final effluent level of 0.5-1.5 mg/1. Other technically
V feasible treatment methods exist but are reported to be
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less economical.
On the basis of the present information, a uniform effluent |
criteria is difficult to justify at this time. It is recommended, ^
however, that an effluent level of 1.5 mg/1 be adopted for fluoride
where justified on the basis of water use. It is recognized that B
two stage treatment will be necessary for industries with wastes con-
taining high levels of fluoride to maintain a 10 mg/1 effluent. ^
Attainment of 1.5 mg/1 level will not damage the use of water for man, —
animal, plants, industry uses, fish or other aquatic life. ™
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166 g
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^ CHAPTER XI-HYDROGEN ION - ACIDITY - ALKALINITY
f Acidity and alkalinity are quantitative measures of the respec-
_ tive abilities of a water to neutralize strong bases and strong acids
~ to an arbitrarily designated pH or indicator endpoint. The pH is an
H expression of the intensity of the acid or alkaline condition of a
solution. It is defined as the negative of the logarithm (base 10)
I of the hydrogen ion activity.
^ The most commonly chosen titration endpoints are the methyl
™ orange (pH of 4.5) and phenolphthalein (pH of 8.2-8.4) although in
• special cases a potentiometric titration may be performed to a pH of
particular interest (1). The method of determining a particular acid-
• ity or alkalinity is to titrate with .02N NaOH or .02N H SO, respec-
tively. Table XI-1 lists the various parameters obtained by the
• titrations. For unpolluted natural waters relatively simple relation-
M ships exist between the parameters of Table XI-1 and the concentrations
of hydroxide, bicarbonate, carbonate and hydrogen ion. The relation-
• ships are handled by Sawyer and McCarty (81).
By the classifications in Table XI-1, the methyl orange acidity
• consists chiefly of mineral acids, and some neutralization of weak
• organic and inorganic acids. Phenolphthalein acidity is attributed to
the bulk of the weak acids in solution, especially carbon dioxide and
• bicarbonate in addition to the methyl orange acidity. Similarly, the
phenolphthalein alkalinity may be taken as the neutralization of free
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hydroxyl ions and some weak bases. The methyl orange alkalinity will
be the sum of the phenolphthalein alkalinity and the major portion of
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LOG CONCENTRATION DIAGRAM FOR CARBONATE
FIGURE XI-1
168
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(U
O
C
O
CJ>
c
o
c
Q)
CO
O
-------
1
1
1
1
1
1
1
1
1
1
the alkalinity due to weak organic and weak inorganic bases.
TABLE XI-1
Parameters Manner Obtained
Methyl-orange acidity (mineral) Titration to methyl orange end-
point with 0.02N NaOH
Phenolphthalein acidity (total) Titration to phenolphthalein end
point with 0.0 2N NaOH
Methyl orange alkalinity (total) Titration to methyl orange end-
point with 0.02N H SO
Phenolphthalein alkalinity
(Hydroxyl plus one-half carbonate) Titration to phenolphthalein end'
point with 0.02N H0SO.
2 4
In clean natural waters simple sum and difference relationships
between hydroxyl, bicarbonate, carbonate and hydrogen ion can be
written to express the various free and total acidities and alkalini-
ties (81). Their relationships to pH are illustrated in Figure XI-1.
In polluted waters and in domestic and industrial wastes these re-
lationships no longer hold. These discharges will contain large
amounts of non-carbonate acidities and alkalinities, including weak
organic acids (e.g. acetic, p^ opionic and humic) and their salts,
weak inorganic acids and theii salts (borates, phosphates), ammonia,
i i j i i
and hydrated heavy metals (Fe , Al ) . In these cases the acidity
and alkalinity indicate how w>^ may expect a particular water to react
to acid or alkaline influences, but tell us little of the chemical
composition of the solution itvolved.
169
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specific ions at various pH concentrations are treated in the indi-
vidual chapters.
RECOMMENDATIONS
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Both acidity and alkalinity are expressed as mg/1 of CaCO,., imply-
ing that the acidity would be neutralized by this amount of CaCO or
that the alkalinity is equivalent to this amount of CaCO.,.
Effects of Hydrogen lon-Acidity-Alkalinity •
The literature more than adequately supports the need to main- _
tain pH levels in surface waters between about 6.0-9.0 for the pro- ™
duction and well-being of aquatic organisms. Due to the interde- •
pendence of pH, acidity and alkalinity, it is desirable to maintain
a minimum buffering capacity. In particular, the pH of primary con- •
tact recreation water should be between 6.5 and 8.3 (6). When the pH
is outside this range the buffering capacity (i.e., balance between •
acidity and alkalinity) becomes more important. A brief computation •
of pH requirements is shown in Table XI-2.
Within the pH range of 6-8, toxicities are attributable to the •
specific anions or cations involved. The synergistic effects for
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The pH of all discharges shall not be less than 6.0 nor more than
9.0. An exception to this ruling will be permitted if the receiving
water has a natural pH outside of this range. In this case, the pH of
the discharge shall not be less than that of the receiving water, when •
the natural pH is less than 6.0 nor greater than that of the receiv-
ing water when the normal pH is higher than 9.0. •
It is further recommended that in the interest of maintaining a
minimal carbonate-bicarbonate buffering capacity, no discharge shall ™
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contain less than 20 mg/1 of alkalinity as CaCO_.
TABLE XI-2
DESIRABLE pH RANGES (6,66)
REMARKS
MAN
Drinking Water
Primary Contact Recreation
ANIMALS
Farmstead Water Supplies
INDUSTRIAL PROCESSES
Brewing
Confectionary
Food Canning and Freezing
Laundering
Oil-well Flooding
Rayon Manufacturing
Steel Making
Tannery Operations
PLANT LIFE
Irrigation water, Permissible
Irrigation water, Desirable
Aquatic Plants
Plankton Production, Optimum
FISH, MARINE, AND ESTUARY ORGANISMS
Most Resistant Species
Trout, Tolerance Range
Trout, Toxic Limit
Perch, Toxic Limit
Most Fresh Water Fish, Tolerance
Optimum for Fish Eggs
Marine and Estuary Organisms
Marine and Estuary Limits
Shellfish
pH RANGE
6.0 - 8.5
6.5 - 8.3
5.5 - 9.0
6.5 - 7.0
7.0 minimum
7.5 minimum
6.0 - 6.8
7.0 minimum
7.8 - 8.3
6.8 - 7.0
6.0 - 8.0
4.5
5.5
7.0
7.5
9.0
8.5
9.2
8.4
4.0 -10.1
4.1 - 9.5
4.8 - 8
4.6
6.5
9,
8.4
6.0 - 7.2
Ambient + 0.
6.7 - 8.5
7.0 - 9.0
171
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CHAPTER XII-IRON
+3 +2
H Iron is found in both the ferric (Fe ) and in the ferrous (Fe )
forms in the environment. The form in which iron is found depends upon
m the pH, dissolved oxygen concentration and complex forming agents pre-
sent in the water. At a pH of approximately 7.8, and in the presence
• of oxygen, the soluble ferrous iron will be oxidized to ferric iron
_ which will then be readily hydrolyzed to form an insoluble precipitate,
™ ferric hydroxide. Table XII-1 shows some naturally occurring concentra-
• tions of iron.
There are several industrial sources of iron which are of signific-
I ance. Table XII-2 summarizes concentrations from primary sources of
iron-bearing industrial wastewater. Steel mill pickle liquor is the
• largest source of high concentrations of iron. Acid mine drainage,
• while not yielding as high a concentration as waste pickle liquor, may
add substantially greater volumes of iron to surface waters. Other in-
• dustrial wastewaters containing significant iron concentrations are the
chemical, dyeing, ceramic, ink, printing, metallurgical, cannery,
• tannery and textile industries. Paint pigments contain iron salts and
iron salts are wasted after use as coagulants in water and wastewater
treatment processes.
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172
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TABLE XII-1
CONCENTRATION OF IRON IN NATURE
Source Cone.(mg/1 as Fe) Reference
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Surface water in U. S. 0.0-0.4 (99) ^
98 U. S. Rivers 0.02-3.0 (99) •
Dissolved mineral matter 0.01-0.950 (99) •
Weathering of rock, acid waters, etc. 0.001-1.67 (99)
Surface waters in coal mining area 3-1520 (72) •
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173 •
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1
TABLE XII-2
INDUSTRIAL SOURCES &
Industry
Steel Mills
Waste pickle liquor
Waste (Continuous) Liquor
Waste (Batch) Liquor
Pickle bath rinse
Pickle bath rinse
HC1 pickle liquor
Mine Drainage
Ferrous iron
Total iron
West Virginia
Motor Vehicle Assembly
Body assembly
Vehicle assembly
Metal Processing
Appliance manufacture
Automobile heating controls
Appliances :
Mixed waste
Spent acids
Alkaline waste
Chrome plating
Plating waste
Brass pickle liquor
Brass bright dip waste
Metal Plating
174
CONCENTRATIONS OF IRON
Concentration
mg/1 (form)
70,000 (Total Fe)
130,000-160,000 (FeSO,
150,000-220,000 (FeS04
200-5,000 (Total Fe)
300-4,500 (FeSO.)
4
210 (Fe"1"1")
36
0.2-22,360,126-157
3-1,520
4
3
0.09-1.9
1.5-31
0.2-20
25-60
Trace
40
4_i-
3.58 (Fe )
100-210 (Total)
30-360 (Total)
1.2-21
Reference
(76)
) (48)
) (48,72)
(76)
(72)
(3)
(76)
(72,76,99)
(72)
(76)
(76)
(76)
(76)
(76)
(76)
(76)
(76)
(14)
(72)
(72)
(72)
-------
ENVIRONMENTAL EFFECTS OF IRON
The concentration of iron in waters is significant to man,
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industry, stock, wildlife, fish and aquatic life.
Effect on Man •
Current limits for iron in domestic water supplies are based on •
taste considerations rather than toxicity (94). As little as 0.1 mg/1
may impart an unpalatable taste depending upon the form in which it is •
found (66). Aesthetically, iron is known to stain laundry at a con-
centration of only 0.3 mg/1 (94). |
The Drinking Water Standards states that the iron permitted in «
public water supplies (after control to prevent objectionable taste
or laundry staining) "...constitutes only a small fraction of the •
amount normally consumed and is not likely to have any toxicological
significance." The normal daily nutritional requirement for man is 1-2 |
mg. Man's normal diet contains from 7-35 mg per day. ^
Effect on Industrial Water Supplies
Table XII-3 shows that more stringent iron requirements have M
been set for several industries than for domestic water supplies.
Effect on Irrigation, Stock and Wildlife Watering •
The presence of iron in irrigation waters is reported to be of •
little importance. Iron is an essential constituent in the diet of
animals. If the iron concentration is too high, however, cows may •
not consume enough water, which adversely affects their milk production
(66).
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TABLE XII-3
IRON TOLERANCES FOR INDUSTRIAL USE
CONCENTRATION ,
Camp (24)
0.5*
0.5*
0.2*
0.1*
-
0'.2*
;es 0.2
Industries
0.2*
0.1*
-
0.2*
0.2*
0.2*
-
-
issing
0.2*
1.0*
0.2*
0.1*
0.1*
0.005*
0.0
0.2*
0.25
0.25*
1.0*
0.2*
mg/1
McKee & Wolf (66)
_
0.5
0.2
0.1-1.0
-
-
0.1-0.2
0.1-0.2
-
trace
0.2
0.2
0.2-1.0
0.1
-
0.1
-
0.3
0.2-1.0
0.1
0.1
_
0.0-0.05
0.1-2.0
0.1-1.0
-
-
-
Water Quality
Criteria (6)
.
0.5-14
-
-
0.01-1.0
-
0.3
0.1
-
-
-
0.2
-
-
1.0
1.0
-
-
1.0-0.3
0.1-1.0
-
-
__
-
0.1-50
0.1-0.3
0.1
0.1
-
Industry
Air Conditioning
Cooling Water
Baking
Breweries
Boiler Feed
Canneries
Carbonated Beverages
Chemical & Allied
Confectionery
Distilling
Electroplating
Food, General
Ice
Laundry
Oil Well Flooding
Petroleum
Photographic Processing
Plastics, Clear
Pulp & Paper
Ground Wood
Kraft Pulp
Soda & Sulfite
Highgrade Papers
Rayon (Viscose)
Pulp Production
Manufacture
Tanning
Textiles
General
Dyeing
Wool Scouring
Cotton Bandage
*Applies to iron and manganese individually or to their sum.
176
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Effect on Fish and Other Aquatic Life
Iron can have a major impact on fish and other aquatic life. The •
toxicity of iron to fish is dependent upon the pH and the buffering •
capacity of the water. Very little iron normally remains in solution
in buffered water, or a water with a pH above 8. As a result iron hydrox- •
ides are deposited on the gills of fish, which is believed to irritate
and block their respiratory channels. In addition, the heavy ferric •
hydroxide precipitate is believed to smother fish eggs on the stream •
bottoms. At a lower pH and in unbuffered waters, iron may have a direct
toxic effect on fish and other aquatic life (66). •
Table XII-4 reveals that iron may be toxic and interfere with fish
life at concentrations as low as 0.2 mg/1 in unbuffered, low pH waters •
over extended periods. Table XII-5, however, shows that well buffered •
waters with higher pH (high hardness) may support fish life at iron con-
centrations as high as 10-50 mg/1 for exposure times ranging from 1 hour •
to 96 hours. Most fish are capable of surviving longer periods of ex-
posure at an iron concentration of 0.7-1.0 mg/1, provided that the water |
is well buffered and has a pH near neutrality (66). «
An iron concentration exceeding 0.2 mg/1 has been found to create
problems due to the growth of the iron bacteria Crenothrix, Gallionella, •
and others. These iron bacteria utilize iron as a source of energy and
store it in their microbial protoplasm (66). It is also apparent from p
the works of McKee & Wolf that fish and other aquatic life are capable _
of concentrating iron. Investigations utilizing radioactive iron Fe-59 "
have been reported to have concentration factors ranging from 720 to JB
200,000. The concentration factors reported by McKee & Wolf are
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1
1
1
1
1
•
1
1
1
1
^^H
1
1
1
1
1
1
1
summarized in Table XII-6.
TABLE XI I- 4
TOXIC OR HARMFUL CONCENTRATIONS (mg/1) OF IRON FOR FISH LIFE (66)
Form of Iron Concentration Species of Fish Type of Time of
mg/1 Water Exposure
Iron 0.2 three types of-
fish
Iron 0.9 carp pH 5.5
or less
Iron 1-2 pike, tench, pH 5.0-6.7
Fed 0.6 goldfish tap
Iron 10 rainbow trout 5 min.
FeCln 1.2 stickleback tap 6 days
J
FeCl 4.35 goldfish tap 3 days
Fe90_ 2.0 trout , salmon,
roach
FeK (S0,)2 14 young eels
Fe (SOJo 0.716 shiners, carp, distilled 12-24 hrs
FeCl 13 young eels 50 hrs.
FeSO 2.9 shiners, suckers, distilled 4-24 hrs.
carp
Iron 1.28 fish distilled 24 hrs.
178
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Form of Iron
Iron
FeC13
FeCl3
Ke2(s04)3
FeCl2
FeS04
FeSO.
4
FeSO.
q.
TABLE XII-5
IRON CONCENTRATIONS FOUND NOT HARMFUL
TO FISH LIFE (66)
Concentration Species of Fish Type of Time of
m^/l Water Exposure
0.7 good fish fauna supported
in 95%
waters
1.0 sticlebacks taps 10 days
5.0 young eels - 50 hrs.
5.0 rainbow trout, Lake Huron 24 hrs.
bluegill sunfish,
sea lamprey
10 goldfish hard water 96 hrs.
5 carp, shiners, - 24 hrs.
suckers
17.1 minnows - 1 hr.
50 bass, bluegills - 7 days
50 trout - 24 hrs.
179
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1
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1
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1
••
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1
1
1
1
1
1
1
1
TABLE XII-6
CONCENTRATION FACTORS FOR RADIOACTIVE IRON (Fe-59)
IN FISH & AQUATIC LIFE (66)
Organism C.F.
Phytoplankton 200,000
Invertebrates, skeleton 100,000
Filamentous algae 100,000
Insect larva 100,000
Algae, non-calcareous 20,000
Invertebrates, soft parts 10,000
Fish 10,000
Flagellate, Rhodomanas 7,500
Flagellate, Ch 1 amy d omona s_ 6,000
Diatom, Nitzschia 5,533
Vertebrates, skeleton 5,000
Diatom, Navicula conf . 4,220
Alga, Ochromonas 1,550-4,480
Vertebrates, soft parts 1,000
Flagellate, Platymonas 720-1,030
180
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Treatment Technology for Iron Removal
The primary method for iron removal is the conversion of ferrous ™
iron to the ferric state, followed by precipitation of ferric hydroxide •
n( n pll of approximately 7.8, where the solubility of ferric hydroxide
is at a minimum. This method of iron removal has been used for many •
years in treatment of municipal water supplies. As reported by Patterson
and Minear (76), waters with a high concentration of iron are usually •
found to have a high concentration of carbon dioxide. In the removal •
of carbon dioxide by aeration, the ferrous iron is converted to ferric
iron. Lime is frequently utilized to maintain the pH at the desired •
level for maximum precipitation of the ferric hydroxide.
Fair, Geyer and Okun (37), and Patterson and Minear (76) note that •
insoluble iron oxide frequently exists in suspension as a fine colloidal •
dispersion which resists sedimentation due to its small particle size,
when precipitated at a pH of 9. A very Io\> specific gravity makes it •
difficult to remove by sedimentation without prolonged detention times
or filtration. A summary of iron removal efficiencies currently obtained B
in various industries is given in Table XII-7. While greater than H
than 1 mg/1 total iron remained in the effluents noted in Table XII-7
for sedimentation only, a filtration step held other effluents to less •
than 0.5 mg/1.
It is also worth noting that some companies are capable of recover- |
ing byproducts from waste sulfuric acid pickle liquor. Byproducts re- _
covered by some companies include copperas with ferrous sulfate; copperas *
with sulfuric acid; ferrous sulfate with sulfuric acid; ferric sulfate •
with sulfuric acid; ferric iron with sulfuric acid; iron powder; ferric
oxide,; ferric oxide with aluminum sulfate. Nemerow also stated that •
181
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183
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I
regeneration is possible when hydrochloric acid is used as a pickle
•
•
•
•
•
I
liquor. The Braw-Knox-Ruthner process is one such recovery method (72).
An additional method of treatment reported in both Nemerow (72)
and Patterson and Minear (76) is the use of deep well disposal. However,
as this does not reportedly enter surface waters, it is not considered
•
here as a treatment process for setting an effluent criteria.
One other process described by Patterson and Minear (76) is the
"Walker Process". The system consists of distributing the wastewater,
after restabilization, over graded anthracite coal which accomplishes
aeration of the wastewater. The bed surface is reported to contain
•
residual iron hydroxide which acts as a catalyst for the oxidation of
• the ferrous iron to the ferric form, followed by precipitation of ferric
hydroxide. The units need periodic back washing with subsequent solids
• removal and disposal.
im The final method of iron treatment reported in the literature is
that of combining waste sulfuric acid pickle liquor with chromate waste-
• waters from cleaning operations. Combinations of the acid pickle liquor
with the chromate waste are utilized to reduce the chromium hexavalent
| form to the chromium trivalent form. Then both the iron and the chromi-
H urn are precipitated by lime. Effluents of 0.5 mg/1 total soluble iron
and 0.05 total chromium have been reported (76).
• A summary of the capital costs reported in the literature reviewed
for iron removal is summarized in Table XII-8 below.
| As indicated from this tabulation, the costs vary substantially
_ according to the process utilized and the capacity of the facility.
Similarly, a summary of the operating and maintenance costs for various
methods of iron removal and neutralization is given in Table XII-9.
184
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TABLE XII-8
CAPITAL COST FOR IRON REMOVAL
Capital Cost
Method Flow MDG Million Dollars
Chemical Coagulation
Settling & Filtra-
tion 1.0 0.3
Settling & Filtra-
tion 10.0 1.3
Settling & Filtra-
tion 50.0 4.6
Neutralization, coag- 0.06 0.1
ulation , settling
(HC1 Pickle Liquor) 0.1 1.0
HC1 Pickle Liquor 0.1 4.0
w/ Recovery)
Walker Process 2.7 0.05
Total Iron: Foundry
Waste by Coagulation &
Filtration 7.5 134
185
$/1000 Gal Ref.
300 (97)
130 (97)
92 (97)
1670(8 hr. (76)
flow)
10,000 (72)
40,000 (72)
18.5 (76)
0.0178 (76)
1
1
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1
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1
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1
1
1
1
1
1
-------
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1
1
1
1
1
1
1
1
••
1
1
1
1
1
mf
1
TABLE XII-9
OPERATION AND MAINTENANCE COST FOR IRON REMOVAL & NEUTRALIZATION
Method Flow,
Neutralization (w/Lime
Equalization, and
Sludge Dewatering
0
0
1
1
1
10
10
50
0.
W/Limestone
Neutralization w/Lime -
W/Limestone
W/Soda Ash
Neutralization ($5-$10
Neutralization W/Lime
or Limestone 0.
Regeneration of HC1 0.
Pickle Liquor
Total Iron: Foundry 7.
Waste by Coagula-
tion & Filtration
MGD $/1000 Gal
assumed) ,
.5 15
.5 29
.5 108
.0 25
.0 26
.0 103
.0 12.5
.0 20
.0 11
06 0.02
20
0.032
0.0591
0.268
per 1000 Ib. acid)
1 20
1 8800
5 23.28
186
C/tng/1
Acidity ,mg/l Acid/1000 Gal
500 3.0
1000 2.9
20000 0.5A
500 5.0
1000 2.6
20000 0.51
500 2.5
1000 2.0
500 2.2
Steel Mill
pickle liquor
0.0052
0.010
0.0486
HC1 Pickle
liquor
Gross Cost
Ref .
(76)
(76)
(76)
(76)
(76)
(76)
(76)
(76)
(76)
(76)
(76)
(99)
(99)
(99)
(72)
(72)
(72)
(76)
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SUMMARY AND RECOMMENDATIONS
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(1) Iron exists in both ferric and ferrous forms in nature. The ferrous B
iron may be rapidly converted to the ferric state at a pH greater
than 7. •
(2) The sources of iron from industrial waste are numerous. Their concen-
trations range from trace quantities to 220,000 mg/1 as ferrous sul- •
fate. •
(3) The effect of iron on man is basically aesthetic. Water with an iron
concentration greater than 0.3 mg/1 will stain domestic laundry. I
(4) Many industrial uses require water containing less than 0.1 mg/1
of iron in order to maintain product quality. •
(5) Iron is directly toxic to fish life through precipitation of ferric •
hydroxide within the respiratory system of the fish and on the
stream bottoms, smothering fish eggs. •
The toxic concentration will depend upon the pH and the buffering «
capacity of the waters. As the water hardness, the buffering capacity
and pH decrease, and the toxicity has been found to increase. •
The concentration of iron by fish and other aquatic life ranges
from 700 to 200,000 times the external aqueous level. •
(6) Present technology is capable of removing dissolved iron from waste- _
water to concentrations of 1.0 mg/1 or less and removing total iron ™
from wastewater to concentrations of 2.0 mg/1. •
(7) Capital costs for facilities needed to remove iron are generally
equivalent to or below the cost of secondary treatment facilities. •
However, the cost may be substantially increased when neutralization
is involved for efficient conversion of the ferrous iron to the
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• ferric state.
(8) The operating costs for the removal of total iron from foundry
• wastewater are expensive. However, they are comparable with the
operating costs of neutralizing other acid iron-bearing wastewaters.
On the basis of present information, it is recommended that a uni-
• form effluent criteria of 1.0 mg/1 be adopted for dissolved iron and
2.0 mg/1 be adopted for total iron.
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• 188
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CHAPTER XIII-LEAD
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Lead occurs naturally in the environment as a primary metal and
I in limestone and galena (PbS) deposits, Table XIII-1. The aquatic
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forms of soluble lead are Pb or its complexions. At basic pH,
| hydroxide and carbonate precipitates are readily formed.
_ Lambou and Lim (56) report that while there are 500 companies
* in the United States which mine, smelt, and refine lead, 65% of the
I total output is by seven companies. In addition, 96% of all domestic
lead mines are located west of the Mississippi River. The industries'
• statistics for 1964 through 1968, as reported by Lambou and Lim,
indicate that 89% of the lead is mined in Missouri, Idaho, Utah, and
™ Colorado - 47% being mined in Missouri alone. Tables XIII-2 and 3 show
the United States lead production from 1964-1968 and lead consumption
in 1968 and 1969.
• Secondary production from the recovery melting and smelting of
scrap lead is done by 200 companies within the United States. However,
•I over 50% of this production is done by the American Smelting and
• Refinery Company and the National Lead Company. Gurnham (48) has in-
dicated that the secondary lead recovery production is as large in
• tonnage as is the primary lead production. Its potential, however,
from the industrial waste viewpoint, is much greater. He reported
• that 50 of the largest plants are located on the seacoast and near
• the Great Lakes. Recovery of lead from storage batteries, for example,
has the potential problem of antimony and antimonial lead alloys,
• the discarding of unwanted waste products by burning, as well as the
high toxicity of the lead itself.
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TABLE XIII-1
NATURAL SOURCES OF LEAD
Source Concentration Reference
TABLE XIII-2
U. S. LEAD PRODUCTION* (56)
1964 1965 1966 1967 1968 5 Yr.Avg.
Domestic Ores (recoverable 286.0 301.1 327.4 316.9 359.2 318.1
lead content)
Primary Lead (refined) 449.4 418.2 440.7 379.9 467.3 431.1
Secondary Lead (lead 541.6 575.8 572.8 553.8 550.9 559.0
content) 1285.6 1301.7 1352.1 1259.7 1396.9 1319.2
Thousands of tons
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Industrial effluent concentrations, commercial uses and common
lead alloys are shown in Table XIII-4. •
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Limestone & Galena Deposits 0.4-0.8 mg/1 (66) •
Surface & Ground Water Trace to 0.04 mg/1, 0.01 avg. (66)
Sea Water 0.003-0.03 mg/1 (6) |
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Antimonial Lead (primary 8.6 6.6 11.2 9.1 19.5 11.0
lead content)
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NOTE: Lower figures for 1967 reflect the results of an industry-wide
strike. •
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ENVIRONMENTAL EFFECTS OF LEAD
A review of the tabulated data indicates that while lead may
be present to some extent in our natural environment, the basic impact
on the environment is from its utilization in numerous commercial
products, particularly in leaded gasoline. Lead may enter the environ-
ment in liquid, or solid waste discharged from industrial production
or in exhaust from consumption of leaded fuel. It then can be returned
to the earth by rain or snow.
McKee and Wolf (66) have reported that lead is foreign to the
human body and has no known nutritional value. The total intake of
lead must be considered in evaluating its impact on man as it may
enter the body through food, air, tobacco smoke, water, and other
beverages . While the exact level at which the human body accumulates
lead over the amount excreted has not been definitely established,
McKee and Wolf report that it is probably between .3 and 1.0 mg/day.
Table XIII-5 gives the effect of different lead concentrations on man.
Effect on Man
Lead is a cumulative poison which tends to be concentrated in
the bone. McKee and Wolf reported that since the sensitivity to lead
differs considerably with individuals, a safe level of lead cannot
be definitely stated. "Typical symptoms of advanced lead poisoning
are constipation, loss of appetite, anemia, abdominal pain, tender-
ness, pain, and gradual paralysis in the muscles, especially of the
arms. A milder and often undiagnosed form of lead poisoning also
occurs in which the only symptoms may be lethargy, moroseness,
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TABLE XII1-3 —
LEAD CONSUMPTION IN THE UNITED STATES BY PRODUCT (56) ™
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Includes lead content of leaded zinc oxide and other pigments. _
(Short
Product
Metal Products:
Ammunition
Bearing Metals
Brass & Bronze
Cable Covering
Caulking Lead
Casting Metals
Collapsible Tubes
Foil
Pipes, Traps, & Bends
Sheet Lead
Solder
Storage Batteries:
Battery grids, posts, etc.
Battery Oxides
Terne Metal
Type Metal
Pigments:
White Lead
Red Lead and Litharge
Pigment Colors
Other *
Chemicals:
Gasoline Antiknock Additives
Miscellaneous Chemicals
Miscellaneous Uses:
Annealing
Galvanizing
Lead Plating
Weights and Ballast
Total
Other, unclassified uses
Grand Total**
tons)
1968
82,193
18,441
21,021
53,456
49,718
8,693
9,310
6,114
21,098
28,271
74,074
250,129
263,574
1,427
27,981
915,500
5,857
86,480
14,163
3,234
109,734
261,897
629
262,526
4,194
1,755
389
16,768
23,106
17,924
1,328,790
1969
79,233
17,406
21,512
54,203
44,857
9,918
12,484
5,881
19,407
25,818
72,626
280,386
302,160
1,583
25,660
973,134
6,617
79,898
14,670
1,201
102,386
271,128
602
271,736
4,252
1,797
406
17,368
23,813
18,287
1,389,358
** Includes lead which went directly from scrap to fabricated products.
192
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TABLE XIII-4
CONCENTRATION OF L£AD IN INDUSTRIAL WASTEWATER (56)
Source Concentration
Engine Parts Plant 2.0 - 140.0 mg/1
Plating Bath Rinse Water 0- 30 mg/1
Lead Mining Operations 0-.04 mg/1
COMMERCIAL USES OF LEAD (56)
Compound Major Commercial Uses
1. Lead Metal, Pb: Found chiefly alloyed with antimony, tin, or copper.
2. Litharge, PbO: Used especially in storage-battery manufacturing.
3. Red lead, Pb.,0.: Used in paints and storage batteries.
4. Lead dioxide, PbO?: Used in chemical industry.
5. Lead carbonate, 2PbCO Pb (OH)2: White lead, used in paints.
6. Lead sulfate, PbSO,: A paint pigment.
7. Lead titanate, PbTiO : A paint pigment.
8. Lead acetate, Pb(C?H-0_)9: The most common water-soluble compound
^- J *— i- f -| -.
of lead.
9. Lead arsenate, Pb_(AsO_): A common insecticide.
10. Lead chloride, PbCl: Probably formed when fluxes are used with
heated lead.
11. Lead silicate, PbSiO : Present in glasses and vitreous enamels.
12. Lead chromate, PbCrO,: Used in yellow and green pigments.
13. Lead borate, Pb (BO ) : Employed in certain plastics.
14. Lead sulfide, PbS: Occurs naturally as galena.
15. Lead tetraethyl, Pb(C2H ) : Used in gasoline.
COMMON LEAD ALLOYS (56)
Solder: lead and tin; 50 - 80% lead.
Type metal:lead, tin, antimony; 60 - 90% lead.
85 - three 5 bronze: copper, tin, lead, zinc; 5% lead.
Bearing bronze: copper, lead, zinc; 15 - 20% lead.
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constipation, flatulence, and occasional abdominal pains". (66)
Continuous consumption and exposure to low concentrations of lead
create a cumulative toxicity of greater significance than exposure to
occasional small doses. •
TABLE XII1-5
EFFECTS OF LEAD ON MAN (66)
Form Concentration Remarks
0.1 mg/1 Chronic poisoning for
hypersensitive persons
The pharmacological and physiological mechanisms of lead
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Lead, Total 0.33 mg/day Avg. American Intake
" .01-0.03 mg/day Avg. Am. Intake from water
" 0.1-0.6 mg/day Dangerous over lifetime
" 0.042-1.0 mg/1 Reported Pb poisoning I
" 0.01 -0.16 mg/1 Reported non-poisonous
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poisoning have been reported by Lambou and Lim (56) . They reported
that the salts of lead are known to precipitate proteins, thereby •
acting as local astringents. While their acute toxicity is low, they
are absorbed over long periods of time to produce cumulative effects. •
Lambou and Lim also report, "Chronic lead poisoning is especially •
dangerous because it develops insidiously, and is often not recognized
until it is far advanced. The symptoms involve the nutrition, the •
blood, the nervous and muscular structures, apparently independently.
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• Eventually there may be degradation of the kidneys and other organs."
The physiological mechanisms involved with lead toxicity include a
• paroxysmal phenomena resembling flocculation and the alteration of the
calcium level of the blood.
™ Lambou and Lim (56) also reported the toxicity of lead compounds
• to be influenced by the solubility of lead within body fluids, the time
of contact with the body fluids, the quantity ingested, inhaled, or
• absorbed, and the quantity present within the circulatory system at
any given time.
• The degree of toxicity of various lead compounds, as consumed
• through oral ingestion, in decreasing order are as follows: lead
arsenate, lead carbonate, lead monoxide, and lead sulfate. Other lead
• compounds of similar but lower degrees of toxicity, again in descend-
ing order are metallic lead, lead chromate, red lead, lead dioxide,
| lead phosphate, and lead sulfide. Lambou and Lim indicated that
m there is definite evidence, from experiments with both man and animal,
that lead has injurious effects on the germ cells of both male and
• female. The effects may be passed maternally through the fetal blood
during gestation. A report of Cantarow and Trumper (1945), reviewed
by Lambou and Lim, indicated that it has been repeatedly demonstrated
that lead will pass through the placenta into the fetal tissues.
This has been reported to increase the incidence of epilepsy, muscular
spasms, convulsions, and other nervous disturbances in the child (56).
In conjunction with the effects on humans, Lambou and Lim re-
ported an investigation of persons working in a Japanese storage
battery plant with the following two conclusions:
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1. The rate of sterility was approximately twice as high
among those exposed to industrial lead concentrations. •
2. 8.2% of the group had pregnancies ending in premature •
or stillborn births while the control group, not exposed
to the industrial lead poisoning, averaged 0.2%. •
The present lead standards based upon physiological effects on
humans are shown in Table XIII-6.
Effect on Plants and Animals
I
Available data on the effects of lead on non-aquatic plants _
and animals are summarized in Table XIII-7 ™
Lambou and Lim comment that "animals and birds are also subject H
to chronic lead poisoning, and show practically the same symptoms as
man. An interesting effect of lead pollution can be demonstrated in •
water fowl mortality due to lead poisoning. Twelve million pounds
of lead shot are expended annually over the nation's best water fowl •
habitats. The shot remains there relatively unchanged. Water fowl •
frequently ingest these shots and die of lead poisoning. Annual
mortality has been estimated at roughly one million birds. For •
aquatic fowl ingestion of lead shot is doubly dangerous because approx-
imately 0.5% of arsenic is added" (56). I
Effect on Fish and Aquatic Life •
The toxicity of lead to fish and other forms of aquatic life
has been well documented by McKee and Wolf. While the toxicity of jj
lead may vary with respect to the lead salt considered, it may ^
definitely be stated that it is very toxic and is concentrated within ™
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the fish flesh. The degree of toxicity has been reported to vary
with respect to the total hardness, the calcium ion concentration,
the concentration at which it is present in the water, and the level
of dissolved oxygen.
TABLE XIII-6
PRESENT LEAD STANDARDS PROMULGATED BASED ON HUMAN EFFECTS (94)
A. Physiologically Safe
(1) Lifetime
(2) Short period, few weeks
B Harmful
(1) Borderline
(2) Toxic
(3) Lethal
Concentration
.05 mg/1
2-4 mg/1
2-4 mg/1, for 3 mo.
8 -10 mg/1, several weeks
Unknown, probably
15 mg/1, several weeks
TABLE XIII-7
EFFECTS OF LEAD ON PLANTS AND ANIMALS (66)
Species Concentration Remarks
Oats, Potatoes 1.5 - 25 mg/1 (lead nitrite) Growth stimulation
Oats, Potatoes 50 mg/1 (lead nitrite) Detrimental
Sugar beets 51.8 mg/1 (lead) Injurious
Cattle
Farm animals
18 mg/1 (soft water)
0.5 mg/1
Lead Poisoning
Maximum safe limit
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The toxicity of lead as total lead and as various salts has
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been summarized in the work of McKee and Wolf, and is shown in
Table XII1-8. It is apparent that toxic effects are observed at •
concentrations as low as 0.01 mg/1.
I
Lambou and Lira reported the investigations of Pringle et al.
on the concentration effect of lead in shellfish. The concentration
in the shellfish increases with the concentrations in water on a 1:1
ratio. The depletion rates for lead in oysters increased as the ex- I
posure decreased below a level of 0.05 mg/1. Above the level of
I
0.05 mg/1, the depletion rate remained relatively constant. A summary
of investigations of lead concentrations in shellfish from Atlantic
coast waters and Pacific coast waters is shown in Table XII1-9.
The work of Lambou and Lim indicates that lead is concentrated •
in various species of the aquatic environment (56). A compilation
of concentration factors for various organisms is summarized in |
Table XIII-10. g
McKee and Wolf reported an investigation of water hardness
I
versus the concentration of lead in solution. It was found that with
a total hardness of 14 mg/1 (CaCO ), that precipitation of the lead
•
by calcium carbonate occured as the lead concentration reached 9 mg/1. •
When the total hardness was increased to 53 mg/1 (as calcium carbon- _
ate), the maximum concentration of lead which would remain in solution ™
was approximately 1.6 mg/1. Schneider (83) reported a similar low H
toxicity for lead in waters containing 50 mg/1 hardness as calcium
carbonate. High concentrations of calcium carbonate are therefore •
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TABLE XIII-8
TOX1CITY OF LEAD TO AQUATIC LIFE (66)
Species Form Concentration,
Aerobic bacteria Lead, Total 1.0
ii it n 5
Flagellates U'J
ii ii 05
Infusoria
Bacterial Decomposition " " 0.1-0.5
" " 0 1 - 0.2
Fish
Sticklebacks " " °'1 ~ °'2
Trout, 48 hours " " °'62
Daphnia magna " Chloride 0.01- 1.0
Fresh water fish " " °'33
Stickleback " Nitrate 0.16
Minnows, Stickleback " " °-53
& brown trout
ii ii i ?5
Microregma
Escherichia coli " " lt3
Bluegill sunfish " Tetraethyl 0.20
(Lepomis Macrochirus)
199
me/ 1 Remarks
Toxic
Toxic
Toxic
Inhibition
Toxic or
Lethal
Toxic or
Lethal
No visible
Harm
Deleterious
ii
Death
ii
Deleterious
11
Min. Safe
Cone.
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TABLE XIII-9
LEAD IN SHELLFISH FROM ATLANTIC COAST WATERS
(MAINE THROUGH NORTH CAROLINA) AND IN
THE PACIFIC OYSTER (WASHINGTON) (56)
Lead Concentration in Tissue
(mg/kg, wet tissue*)
Species and Location
Atlantic Coast (Maine through North
Carolina)
Eastern Oyster
Northern Quahaug
Softshell Clam
Surf Clam
Blue Mussell (Narragansett Bay,
R. I.)
Common Rangia (Pongo River,
N. C.)
Channeled Whelk (Narragansett Bay
R. I.)
Pacific Coast (Washington)
Pacific Oyster
Range
0.10 - 2.30
0.10 - 7.50
0.10 -10.20
Average
0.47
0.52
0.70
0.20
0.20
0.20
3.20
0.20
Shucked, drained meats were homogenated, lyophilized, wet
digested, diluted, and read by atomic absorption.
200
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TABLE XI11-10
CONCENTRATION FACTORS FOR ORGANISMS STUDIED (56)
Organism
Phytoplankton
Mollusk (Whole animals)
Zooplankton
Ocean Fish: Hard Tissue
Soft Tissue
Fresh Water Fish: Hard Tissue
Soft Tissue
Clams & Oysters: Soft Tissue
Channeled Whelk
Brown Algae
Softshell Clam
Northern Quahaug
Eastern Oyster
Common Rangia
Surf Clam
Blue Mussel
Mo Husk-Muscle
Pacific Oyster
Concentration Factor
40,000
4,000
3,000
5,400
35
1,400
15
1,050
1,100
700
230*
170*
160*
70*
70*
70*
40
70*
Assumed dissolved lead concentration of 3 ug/1 in seawater.
Hard Tissue on basis of ash weight of bone.
Soft Tissue on basis of live weight.
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capable of reducing the toxicity of lead by removal of the lead from
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solution. I
McKee and Wolf also reported that investigations by the Cali-
fornia Water Pollution Control Research Board indicated that the
toxicity of lead on rainbow trout increased with a reduction of the
dissolved oxygen. A factor of 1.0, 0.95, 0.85, or 0.71 should be
applied to the lethal or toxic concentration of lead as the percent •
of saturation for dissolved oxygen decreases as follows: 100%, 80%, 60%
and 40%. |
In summary, it has been shown that lead is toxic at low levels _
to man, animals, fish, and other aquatic life. As even low concen- ™
trations of lead are concentrated within the blood system and bone •
structure of man, animals, fish, and other aquatic life, it is imper-
ative to control any discharge of lead into the aquatic environment. •
TREATMENT TECHNOLOGY
I
In the previous sections it has been noted that the carbonate
and hydroxide forms of lead are relatively insoluble. It has also •
been shown that a total hardness of 53 mg/1 (as calcium carbonate)
alone is capable of reducing the soluble lead to a concentration of •
approximately 1.6 mg/1. Lime precipitation is therefore as one process •
by which lead may be removed from solution. This is supported by
Weston (97) who states that chemical precipitation and sedimentation •
is currently capable of producing an effluent concentration of 0.1-
1.4 mg/1. As described by Patterson and Minear (76), precipitation |
of lead as lead carbonate or lead hydroxide yields tremendous savings
in the overall cost of treatment. Table XIII-11 outlines the treatment
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TABLE XIII-11
TREATMENT OF LEAD IN INDUSTRIAL WASTEWATERS
Method Initial Cone. Effluent Cone. Reference
Total Hardness 1.6 mg/1 (66)
53 mg/1 (CaCO ) (soluble Pb)
C.P.S. * 0.1-1.4 mg/1 (97)
2.0 - 140 mg/1 Trace (76)
(Lime) 0.31 mg/1 0.1- mg/1 or less (76)
" 66.1 mg/1 (Pb Tetraethyl) Trace (76)
(FeS04)
(pH 10.4-10.3 45 mg/1 (Inorganic Pb) 1.7 mg/1 (76)
Lancy Batch Process - 0.5 mg/1 (61)
Lancy Integrated Process - 0.01 mg/1 (61)
Ion Exchange .055 mg/1 0.0015 mg/1 (76)
126.7-140.8 mg/1 0.02-.53 mg/1 (76)
* Chemical Precipitation and Settling.
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of lead in industrial wastewater.
Patterson and Minear reported that the cost of removing lead I
by chemical precipitation is similar to that of removing other metals.
The cost of treating lead is shown in Table XIII-12. While direct |
cost figures were shown in the literature reviewed for ion exchange, •
it was felt that the net cost would be based on the recovery of the
lead. Otherwise the construction and operating cost would be similar •
to that for hexavalent chromium removal.
In summary, it has been shown that lead is readily treatable I
by precipitation to a final effluent level of 0.1 mg/1 provided that _
proper controls are available and the plant is efficiently operated. ™
It is recognized that filtration might be required to control the sus- •
pended solids which could contain a substantial concentration of lead.
It is also apparent that ion exchange, and processes such as the Lancy I
Integrated System are capable of reaching final effluent levels of
0.01 mg/1 or less. The Lancy Integrated System is currently an •
achievable treatment process for plants with a total discharge in the •
range of 25-500 gpm. It is difficult, however, to estimate its
economic feasibility for larger facilities. It is felt that ion ex- I
change is currently more in the realm of "best available treatment"
than "currently applicable treatment." In the utilization of a •
process such as ion exchange, one must remember that the regeneration •
brines must ultimately be disposed of.
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TABLE XIII-12
COSTS FOR TREATMENT OF LEAD BY PRECIPITATION
Type
Metal Plating Ind.
Metal Plating Ind,
1 MGD
10 MGD
Precipitation
by FeSO.
Capital
Operations
$l,108/thousand gal. $.80/thousand gal
$1.62/thousand gal.* $.62/thousand gal.
$100,000
$600,000
4.2% of Total
Treatment of
Wastewater
Reference
(76)
(76)
(97)
(97)
(76)
* Amortized Capital Cost, interest rate and period of amortization
were not reported.
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SUMMARY AND RECOMMENDATIONS
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In general the following statements can be made relative to
lead in the environment: •
1. Lead occurs naturally in the aquatic environment up to _
concentrations of 0.8 mg/1 with average levels of 0.01 mg/1 ^
in surface and ground waters. I
2. Lead is cumulative in man, animals, fish and wildlife.
3. A total intake of 0.1 mg/1 in water or a total of 0.6 •
mg/day may cause lead poisoning for hypersensitive persons
although man excretes lead to a degree. •
4. Fish and aquatic life are capable of concentrating lead •
from 40-40,000 times the background aquatic levels. Fish
and aquatic life are sensitive to lead concentrations in I
the range of 0.01-0.1 mg/1. Lead toxicity may be reduced
in hard waters and/or in the presence of high dissolved •
oxygen. •
5. Lead is currently treatable by available means to an
effluent level of 0.1 mg/1 for all discharges at a cost •
comparable to the removal of other trace metals. Current
achievable treatment will remove lead from some wastewaters |
with flows up to 1 MGD at final effluent concentrations •
of 0.01 mg/1 at a reasonable cost. Ion exchange may
yield final effluent concentrations as low as 0.0015 mg/1. •
Implementation of this process on a full scale, however,
needs to be proven prior to its adoption as a best available •
method. _
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I On the basis of the above review, it is recommended that a
mm uniform effluent criteria of 0.10 mg/1 be adopted. It is further
recommended that an average effluent concentration of 0.01 mg/1 of
I lead be the objective of all wastewater bearing lead up to a flow
rate of 1 MGD.
| It is recognized that the recommended, presently obtainable
_ effluent level of 0.1 mg/1 lead may not protect all of the aquatic
life under continued exposure. It has been shown, however, that
I even the more sensitive aquatic life species are capable of withstand-
ing higher concentrations in the 0.1 mg/1 range for short durations.
• It has further been shown that this level would at least meet the
recommendation of McKee and Wolf for maximum levels in the drinking
™ water for man's consumption. It is also noted that this is below the
• level recommended for short periods of exposure in man's drinking
water by the U. S. Public Health Service Drinking Water Standards.
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CHAPTER XIV-MANGANESE
Manganese ores are very common and are widely distributed, in
I o | *•>
I both the manganous, Mn , and manganic, Mn forms. The oxides,
carbonates, and hydroxides of manganese are only sparingly soluble in
• water and, therefore, manganese ions are not found in natural surface
_ waters above 1.0 mg/1 (66).
™ Common industrial uses of manganese are in steel alloy, dry
• cell battery, glass and ceramics, paints and varnishes, ink and dyes,
match and fireworks industries. The manganous form of manganese is
• generally used in dyeing operations, disinfection, linseed oil driers,
electric batteries, dyeing porcelain, glazing, varnishes, and in
B special fertilizers. The permanganate ion (MnO.) is used as a strong
• oxidant which is normally reduced to insoluble manganese dioxide (66).
Due to their similar chemical properties, manganese is often
• found in the presence of iron. Gurnham (48) reports that clarified
wastewaters of the iron mining industry after milling, flotation, and
• agglomeration, contain as much as 27.6 mg/1 of manganese. Another
•j similarity between iron and manganese is that manganese oxides are
known for creating brown or black stains on porcelain fixtures,
• laundry items, and fine papers. In contrast to iron, however, Fair,
Geyer and Okun (37) , report that the manganous form of manganese
| oxidizes rather slowly to the insoluble manganese dioxide form, while
M iron is rapidly oxidized from the ferrous to the ferric state. Oxi-
dation of manganese requires approximately 90 minutes at a pH of 9.3
• and approximately 60 minutes at a pH of 9.5.
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ENVIRONMENTAL EFFECTS OF MANGANESE
Manganese is an essential nutrient for man, animals and plants. •
In general, manganese is not toxic to aquatic life except in concen- _
trations exceeding 25 mg/1 (66). The main objection of high concen- ™
trations of manganese in surface waters is aesthetic and economic •
damage by staining and forming of deposits. The presence of manganese
has been found to hinder many industrial water uses. •
Effect on Man
toxicity to humans near Tokyo and Manchukuo (66). However, they point
out that in these isolated circumstances the concentration of manganese
I
The 1962 Drinking Water Standards (94) reports two reasons for
limiting the concentration of manganese in drinking water. These are: I
(1) to prevent aesthetic and economic damage and (2) to avoid any
possible physiological effects from excessive intake. A domestic con- |
sumer may find a brownish color imparted to laundered goods, and an •
objectionable taste to beverages such as coffee and tea by waters con-
taining manganese. •
With respect to the possible physiologic effects, the Drinking
Water Standards reported hepatic cirrhosis in rats treated with very |
large dosages however, neurological effects of manganese have not been _
reported to result from oral ingest ion by man or animal. McKee and
Wolf indicated that slight toxic effects to high concentrations of fl
manganese have been reported (66). For example, manganese may be toxic
in a concentration of 0.5-6.0 g/kg body weight when administered to I
rabbits daily. McKee and Wolf cite a few instances of manganese
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was far higher than the amount that would normally be tolerated
aesthetically in drinking water.
The Drinking Water Standards (94) indicate that the average
™ consumer could tolerate concentration of manganese of 0.01-0.02 mg/1
• for aesthetic reasons. However, a recommended drinking water standard
of 0.05 mg/1 was set.
• McKee and Wolf (66) reported that manganese salts will impart
a metallic taste to water at concentrations ranging from 0.5-20 mg/1.
• They also indicated that manganese in excess of 0.15 mg/1 has been
• found to cause turbidity problems. Manganese has also been known to
promote growth of some microorganisms in reservoirs filters, and dis-
• tribution systems. It will also coat the sand particles in rapid sand
filters in water treatment plant, promoting the formation of mudballs
• and clustered sand particles, reducing the overall efficiency of the
• filter.
Effect on Industrial Water Supplies
In general, manganese ±s undesirable in water used for many
industries. Table XIV-1 indicates the limit of tolerance of manganese
in certain industries.
Effect on Plants
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McKee and Wolf (66) reported that manganese is essential for the
• growth of plants, apparently as an enzyme activator. Manganese has
• been used to enrich soil which stimulates plant growth (6,66). On the
other hand, manganese has also been found to be toxic under some
• conditions. Manganese toxicities have been reported at a concentration
of 0.5 mg/1 (6). The toxicity depends upon the various plant species
I
and conditions of nutrient imbalance.
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TABLE XIV-1
INDUSTRIAL WATER SUPPLY LIMITS FOR MANGANESE AND IRON, mg/1
Industrial Use
Air Conditioning
Baking
Brewing, Light & Dark
Canning
Carbonated Beverages
Confectionary
Cooling Water
Distilleries
Dyeing
Food Processing
Ice
Laundering
Milk Industry
Pulp & Paper
Groundwood
Kraft pulp
Soda & Sulfite
Highgrade paper
Fine paper
Kraft paper, Bleached
" " Unbleached
Photography
Plastics (clear)
Rayon & Viscose
Pulp production
Manufacturing
Tanning
Textiles, General
" Dyeing
" Wool Scouring
" Bandages
Mn
Mn & Fe
References
0.5
0.2
0.1
0.2
0.2
0.2
0.2
0.2
0.5
0.1
0
0.2
0.2
0.2
0.03-0.1
0
0.1-0.5
0.1
0.05
0.05
0.05
0.1
0.5
0
0.02
0.03
0.02
0.2
0.1 -0.25
0.25
1.0
0.2
0.5
0.2
0.1
0.2
0.2, 0.1
0.2
0.2
0.2
0.5
0.1
0
0.2
0.2
0.2
0
1.0
0.2
0.1
0.1
0.1
0
0.02
0.05
0
0.2
0.1 -0.25
0.25
1.0
0.2
(24,66)
(24,66)
(24,66)
(24,66)
(24,66)
(24)
(45,66)
(66)
(45,66)
(24)
(66)
(24,66)
(24,66)
(66)
(24)
(24)
(24,66)
(24,66)
(24,66)
(24,66)
(24)
(24)
(24)
(24)
(24,66)
(24,66)
(24,66)
(24,66)
(24,66)
(24,66)
(24,66)
(24,66)
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McKee and Wolf (66) have also reported that manganese injury
• has been found to be intensified in the presence of molybdenum,
vanadium, and nitrate and diminished in the presence of cobalt, iron,
• molybdenum, aluminum, a phosphorus deficiency, ammonium and ammonium
nitrate. It is believed that nearly all species of plants are capable
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of tolerating up to 2 mg/1 of manganese (6).
Effect on Domestic Animals and Wildlife
Manganese has been found to be an essential nutrient for
animals. McKee and Wolf (66) reported that a deficiency in manganese
produces ovarian disfunction, testicular degeneration, poor lactation,
lack of growth, bone abnormalities, and disturbance of the central
• nervous system. Manganese may have been partly responsible for the
occurrence of infectious enemia in horses at a concentration far above
M what would be expected in a normal water supply.
• Effect on Fish and Other Aquatic Life
McKee and Wolf (66) report that manganese and its salts are
• generally toxic to fish and aquatic life at a concentration greater
than 25 mg/1. Permanganates, are much mora toxic to fish than the
B manganous salts, however. They have been found to kill fish at con-
• centrations of 2.2-4.1 mg/1 as manganese. Fortunately, the per-
manganates are readily reduced to insoluble manganese dioxide under
• natural water conditions.
The conclusions and recommendations of McKee and Wolf (66)
I
summarizing the limits of manganese in different types of water
supplies are given in Table XIV-2.
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TABLE XIV-2
RECOMMENDED LIMITS OF MANGANESE IN WATER SUPPLIES (66)
Water Supply
Domestic
Industrial
Irrigation
Stock Watering
Fish & Aquatic Life
Concentration (mg/1
0.05
0.05
0.50
10.00
1.00
TABLE XIV-3
PROCESSES FOR MANGANESE REMOVAL (76)
Process Comments
Aeration
Chlorine and Hypochlorite
Oxidation
Adjustment of pH
Catalysis
Ion Exchange
Chlorine Dioxide
Manganese Dioxide or
Potassium Permanganate
Direct Potassium Permanganate
Addition
Slow and ineffective below pH 9.
Not particularly effective for
organically bound manganese.
Lime soda type treatment gives
removal at pH 9.5.
Copper ion enhances air oxidation.
Effective for small quantities of
iron and manganese. Resins quickly
fouled by iron and manganese oxides.
Rapidly oxides manganese to the
insoluble form, but expensive.
Regeneration, green sand and filter
process. Economic disadvantage of
requiring excess permanganate.
Requires sand filtration
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TREATMENT TECHNOLOGY - MANAGANESE REMOVAL
Drinking Water Standards (94) indicate that manganese is
difficult to remove to residual concentrations of much less than 0.05
mg/1. Manganese removal has been practiced for many years in the treat-
• ment of municipal water supplies and industrial process waters. In
general, the technology consists of the removal of the soluble manga-
£ nous ion as an insoluble precipitate. Since many wastewaters contain
_ both manganese and iron, the methods utilized in iron removal are
* appropriate for the removal of manganese. The one difference is that
• a pH of 9-9.5 is needed for removal of manganese while a pH of 7.5-8.5
is needed for the removal of iron (37,66). Patterson and Minear (76)
• have summarized the effective processes for removal of manganese in
Table XIV-3.
• As reported in Patterson and Minear (76) , chemical oxidants to
• assist conversion of the manganous ion to insoluble manganese have
been used although this has also caused problems with filtration. The
• formation of manganese floes with strong oxidants has been found to
clog slow sand filters. They indicated that utilization of chlorine,
• followed by lime coagulation, and rapid sand filtration was effective
• in the removal of manganese, at an initial concentration as high as
5.7 mg/1. They also reported that for effective oxidation of manganese,
• a free chlorine residual of 0.5 mg/1 was required. The oxidation
utilized 1.29 mg of chlorine per mg of manganese oxidized.
• The use of ion exchange for iron and manganese removal was also
mm reported by Patterson and Minear (76) . They indicated that the
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advantages of ion exchange process are: s smaller capital investment
than for coagulation filtration, up to 4 times greater flow rates, ™
smaller plant requirements, and simpler operation. A disadvantage •
of this process is that the brine utilized to regenerate the ion
exchange unit creates a major disposal problem since the manganese I
is found to remain in a soluble form in the brine. An additional
drawback is that an absolute anaerobic condition must be maintained •
in the ion exchange unit to prevent the manganese being oxidized by •
the air and forming a precipitate which will clog the ion exchange bed.
In summary, it has been reported by both Patterson and Minear •
(76) and Weston (97) that it is possible to obtain a final effluent
concentration of 0.05 mg/1 of manganese. Table XIV-4 summarizes the |
efficiencies of various units. Table XIV-5 indicates the capital •
costs and Table XIV-6 shows the operation and maintenance costs. The
operation and maintenance cost and the capital investment for the •
removal of manganese is well within the range of the cost for removing
other metals. |
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1
1
••
1
1
1
1
1
1
•
1
1
1
1
1
1
1
1
TABLE XIV- 4
TREATMENT EFFICIENCY FOR MANGANESE REMOVAL
Process
Chlorination and lime coagulation
and filtration
Permanganate oxidation and
filtration
Permanganate oxidation plus
sodium alginate
Permanganate oxidation and
filtration
Lime coagulation, settling and
filtration
Greensand filter
Ion exchange
* Iron - mg/1 in parenthesis (however
216
Concentration, mg/1
Influent Effluent Reference
5.7 split flow (76)
used
1.0 0.05 (76)
0.35 0.02 (76)
0.05 (97)
0.05 (97)
1.7 0.0 (76)
1.7(37)* 0.1(0.5)* (76)
1.0(53) 0.0(0.3)* (76)
1.3(52)* 0.0(0.1)* (76)
, unspecified)
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TABLE XIV-5
CAPITAL COST FOR MANGANESE REMOVAL
Process Flow Cost
Chemical coagulation, settle 1.0 MGD 300,000
and filter 10.0 MGD 1,300,000
50.0 MGD 4,600,000
Chlorination, settle and 1.0 MGD 300,000
filter 10.0 MGD 1,300,000
50.0 MGD 4,600,000
Aeration, lime coagulation, * 75,000
settle filter and recarbonate
Greensand filter * 26,000
Reference
(97)
(97)
(97)
(97)
(97)
(97)
(76)
(76)
* Treating the same flow and wastes (however, unspecified).
TABLE XIV-6
CHEMICAL COST FOR MANGANESE REMOVAL (76)
Process Cost/1000 Gallons
Lime coagulation and 2.1
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SUMMARY AND RECOMMENDATIONS
flj (1) Manganese is normally iround with iron in the nature.
(2) Manganese is found in several industrial wastewaters.
• (3) Manganese is a basic and essential nutrient to man, plant and
animal life. Manganese damages plants only at concentrations
above 2 mg/1. Manganese at a concentration below 10 mg/1 has
no adverse effect on animals.
I
(4) Manganese is not toxic to fish and aquatic life until the
• concentration approaches the 1-2 mg/1 range in the stream.
(5) Current technologies are capable of removing manganese to less
than 0.05 mg/1 with reasonable costs.
(6) The major problem of manganese in surface waters is aesthetic.
• Based on the above summary, it is recommended that a uniform
effluent criteria be established at concentration of 0.10 mg/1 for
I
manganese.
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CHAPTER XV-MERCURY
Mercury was not widely recognized as a water pollutant until
• 1966 when Irukayama reported on the 1953 mercury pollution incident
in Japan. Since that date, mercury has moved to the forefront as one
B of the most closely watched pollutants being discharged into our
_ nation's waters. The major sources of mercury discharges are summar-
™ ized in Table XV-1. All of these sources are discussed in a recent
• publication by Selikoff (85).
Chlor-alkali plants are reported to discharge from 51-85 grams
I of mercury per ton of chlorine produced. It was also noted that prior
to the recognition of mercury as an important pollutant this figure
™ may have been much higher (85).
• The use of mercurial catalysts to convert acetylene to acet-
aldehyde resulted in losses of mercury estimated at 300 kg/yr for one
• plant in Sweden (85). Discharge concentrations for mercury slimicides
utilized in the pulp and paper industries have not been reported in the
I literature although their usage is extensive.
• The agricultural usage of mercury in pesticides has been re-
ported to amount to not less than 2100 metric tons per year. Of this
V amount, 400 tons per year have been attributed to use within the
United States.
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TABLE XV-1
MAJOR INDUSTRIAL SOURCES OF MERCURY POLLUTION
Mercury pigments and impregnating agents
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Chlor-Alkali Plants
Slimicide Treatment of Distribution Systems •
Fungicide Treatment of Seed Grains
Combustion of Fossil Fuels ™
Disposal of mercurial antiseptics (hospital, laboratories, dental
clinics)
Disposal of mercury containing switches, rectifiers and measuring •
devices (thermometers, barometers fluorescent tubes, mercury lamps, •
batteries, etc.)
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1
Processing of some raw materials (e.g. coal, carbon, chalk,
phosphates, pyrites). •
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Coals in the United States contain mercury in concentrations
• from a few parts per billion to several parts per million. Based on
an estimated average of one part per million, the annual consumption
• of 500 million tons of coal per year would contribute 1,000,000 pounds
• of mercury per year to the environment. This value does not include
mercury contributed from the refinement and use of crude oil products
• which may contain even higher concentrations of mercury (85).
Mercury occurs naturally in the form of the mineral cinnabar, a
I mercury sulphide, and rarely, as the free element. These forms may
*m be leached or volatilized into the water and air environments, pro-
viding a low but constant background (66).
• Both air pollution and natural sources of mercury must be con-
sidered in evaluating the total exposure of man and animal. Table
J| XV-2 summarizes both the total world consumption of mercury and United
» States trends (85),
Lambou reports that mercury is usually discharged in one of the
• five forms listed in Table XV-3 (54). The reactions and inter-
conversions these forms may undergo are illustrated in Figure XV-i.
£ Experimental work has confirmed that metallic mercury can be easily
_ oxidized to divalent mercury under the conditions often found at the
* bottoms of lakes and streams. Under reducing conditions, metallic
fl mercury is stable and remains in the sediment as a reservoir which
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may be converted years later to the divalent form.
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TABLE XV-2
TOTAL WORLD PRODUCTION OF MERCURY AND TRENDS IN THE U. S. (85)
Total world production
Trends in uses of mercury
in U. S.
Agricultural use
Amalgamation
Catalyst manufacture
Dental (c)
Electrical equipment
Chlor-alkali plants
Laboratory use (b)
Industrial controls (b)
Paints
Paper and pulp
Pharmaceuticals
Other uses (d)
Not accounted for (e)
1968 (a)
(tons)
9,836
130
10
73
116
746
663
75
202
401
16
16
302
12
2863
Sources and export of
Mercury in U. S.
U.S. domestic mines 1097
Imported 910
GSA sales to industry ( :) 745
GSA transfers to govt.
agencies 68
GSA transfers to inter-
National redevelopment 91
Redistilled (g) 316
Secondary recovery (h) 402
GSA stock 86
Exported 289
1969 (a)
(tons)
10,885
102
7
112
116
710
788
78
265
370
21
27
368
42
3006
1090
1164
117
380
402
539
19
Estimated
1974-1975 (b)
(tons)
101
9
89
144
863
869
79
351
407
9
25
226
3172
NOTE: These values do not include any mercury held by General Services
Administration or Azomic Energy Commission.
a. U.S.D.I. Bureau of lines, USGS 1968 1969 (Mercury).
b. Trends in Usage of fercury, National Materials Advisory Board,
National Research Council, Washington, D.C.
c. Includes redistilled mercury.
d. Includes purchases for expansion and new chlor-alkali plants.
e. Mercury, chiefly from secondary recovery - uses not specified.
f. General Services Administration
g. This mercury is from other sources and is given additional
purification.
h. This mercury is recovered from battery scrap, dental amalgrams
and other reprocessed sources.
222
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TABLE XV-3
THE FORMS OF MERCURY PRESENT IN INDUSTRIAL DISCHARGES
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^ L. Inorganic divalent mercury - Hg
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2. Metallic mercury - Hg°
3. Phenyl mercury - C,H Hg
• 4. Methyl mercury - CH Hg
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I 223
5. Alkoxy-alkyl mercury - CH 0-CH2CH-2Hg+
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FIGURE XV- i
POSSIBLE INTERCONVERSIONS OF MERCURY COMPOUNDS
IN NATURAL AQUATIC ENVIRONMENTS (102) _
Hg
Hg
Removal and retention by
living systems
224
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TABLE XV-4
MERCURY RESIDUES IN GRAIN AND FRUIT UNTREATED AND
TREATED WITH PHENYL MERCURY FOLIAM SPRAY (85)
Mercury (ppb)
Commodity Untreated Treated
Rice 20-100 100-700
Mandarin orange
Skin 10-50 30-240
Pulp 10-40
Apple
Skin 10-50 70-310
Pulp 10-50 30-130
TABLE XV-5
MERCURY IN FOODS (85)
Nanograms/gram
Food Country (range)(pp+)
Haddock United States 17-23
Herring Baltic states 26-41
Apples United Kingdom 20-120
Apples New Zealand 11-135
Pears Australia 40-260
Tomatoes United Kingdom 12-110
Potatoes United Kingdom 5-32
Wheat Sweden 8-12
Rice Japan 227-1000
Rice United Kingdom (imports) 5-15
Carrots United States 20
White bread United States 4-8
Whole milk United States 3-10
Beer United States 4
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Both phenyl and alkoxi-alkyl mercury have been reported to under- _
go conversion to methyl mercury through inorganic divalent mercury •
(54). •
Divalent mercury has a strong affinity for organic muds and
has been shown to be biochemically methylated in the benthic sediments. •
Two products are possible from this reaction, monomethyl and dimethyl
mercury. The monomethyl form is accumulated by aquatic organisms, •
while the dimethyl form is apparently lost through evaporation to the •
atmosphere. High pH favors the formation of the dimethyl form. The
methylation of mercury is not only rapid but is also reported to be •
enhanced by anaerobic conditions (85) .
In Sweden, regardless of the nature of the mercury pollutant, |
only methyl mercury has been found in fish, indicating that a methyl- •
ation of mercury compounds also takes place in the fish itself (54) .
Jernelov (102) found that the mucus on pike is able to convert inor- •
ganic bivalent mercury almost completely into methyl mercury within
a short period of 2-4 hours. |
Mercury in natural aquatic systems is apparently converted to «
the methylated form regardless of the form in which it was intro-
duced. In reviewing the impact of mercury on the environment it will •
be seen that not only is this form the most toxic, but it is also the
form most easily retained by living creatures.
ENVIRONMENTAL EFFECTS OF MERCURY
Effect on Man
I
Prior to 1963, it was reported that adults could safely consume •
water containing from 4-12 mg of mercury per day and that a fatal
226
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dose of mercury from such water would be about 75-300 mg/day (66).
It is now believed that water is not the critical mode of ingestion
For man. Exposures of the general populace to toxic concentrations
I
ol mercury is likely to result from the consumption of contaminated
• fish and possibly other food and not directly through water or air.
The tragic outbreaks of the so-called Minanata disease in Japan have
™ been attributed to the long term consumption of fish which had con-
• centrated methyl mercury from polluted waterways (85). Such a mech-
anism is extremely important in nations like Japan where the normal
• diet of the population contains a high percentage of fish and sea-
food.
m There have been other incidents of mercurial poisoning in Iraq,
• Pakistan and Guatemala where farmers receiving fungicide treated
seed grain ate the seed instead of planting it. Table XV-4 illus-
• trates the variation of mercury content between treated and untreated
food stuffs. Table XV-5 gives the mercury residues found in a number
| of food products from a variety of world markets.
• The potential contamination of fish and shellfish is obviously
critical in determining the hazards associated with mercury dis-
• charges. Recognition of the natural methylation of mercury in the
environment and the concomitant biological magnification in success-
J| ive predators requires setting criteria at the lowest feasible level
_ if we are to maintain the safety of commercial fisheries.
* It is difficult to calculate threshold levels for toxic effects
• on humans due to the intermittent nature of the exposure in the re-
ported cases of chronic mercury poisoning. For acute, single dose
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exposures mercuric chloride and all the organomercurials tested _
fell into the extremely toxic catagory, (LD,_n, are between 5 and ™
J \J S
50 mg/kg). The levels of mercury contamination necessary to induce •
chronic poisoning have not been reported in the literature. This
is due to the difficulty of ascertaining the eating habits of the •
affected individuals and problems inherent in relating mercury con-
centrations ingested to mercury concentrations in fish caught after 9
the incident. The situation is further complicated by the fact that •
there can be several weeks delay between the ingestion of the critic-
al amount of mercury and the onset of symptoms. This could result •
in acute cases being diagnosed as chronic. The symptoms of alkyl
mercury poisoning are indicative of damage to brain tissue and are •
in many cases irreversible. •
Prenatal and postnatal exposures are also of importance.
Acute and chronic exposures can be readily passed through the pla- •
cental barriers to the fetus and also to infants through the mother's
milk. Studies in both man and animals indicated a concentration of ||
mercury within the fetal blood about 20% higher than that in the •
mother (54). Silikoff reports that the concentration may be 30%
higher in the fetal red blood cells than in the red blood cells of •
the mother (85).
Children born of mothers exposed to methyl mercury have been j|
found to suffer from symptoms approaching a cerebral palsy like «
disease. The disease varies in severity from mild to moderate spas- *
ticity and ataxia, to severe intellectual retardation, seizures, B
and evidence of generalized brain damage.
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Lambou reports that about 15% of the total body accumulatin
• of methyl mercury is found within the brain cells. It was found
_ that neurological symptoms begin to manifest themselves when the
* brain cells contain about 0.020 rag/gram (20ppb) of mercury in the
B wet tissue in the brain.
The threshold mechanism appears to be due to the number of
• damaged brain cells rather than the methyl mercury threshold. Rapid
damage of many brain cells could clinically be reported erroneously
• as the methyl mercury threshold (54).
• The alkyl mercury compounds have also been reported to damage
gametes prior to fertilization and to increase the frequency of
• chromosone breaks in Swedish fishermen whose blood levels of methyl
mercury were higher than the general population. These elevated
W levels were attributed to their high dietary intake of fish (102).
I Effect on Mammals and Birds
Reports indicate that many mammals and birds are affected by
mercury poisoning through the consumption of contaminated fish.
Study of the Minanata incident shows that cats had been dying before
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humans were noticably affected. Experimentally, cats have been killed
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by feeding them fish and shellfish containing 5.7 ppm mercury. Both
acute and chronic toxic concentrations of methyl mecuric chloride
have been reported for cats and rats. The toxic concentrations for
cats have been found to be between 10-50 mg/kg. Most acute cases
of poisoning had received a 20 mg/kg oral dose and chronic effects
were noted at a concentration of 1 mg/kg per day. Similarly, rats
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have been shown to be acutely poisoned at concentrations of 20 mg
mercury per 100 grams delivered orally and to show chronic effects •
of poisoning after oral dosages of 1-2 mg/100 gm/day (85). •
The retention time of methyl mercury in the tissues of various
species tested varied widely. The experimental half-lives are shown •
in Table XV-6.
The toxic concentrations of methyl mercury to birds have been |
found to be about the same as those for laboratory mammals, approx- m*
imately 12-20 mg/kg. The mercury residue found in the liver and
kidney of birds killed experimentally with treated seed ranged from •
30-130 ppm for pheasant, 70-115 ppm for jackdaws, and 50-200 ppm for
magpies. In pheasants, it was also found that the level in the mus- g
cles ranged from 20-45 ppm. Liver and kidney residues of approxi- «
mately 30 ppm seemed to be associated with the onset of critical *
symptoms in the subject birds. A normal level would be less than •
1 ppm (85) .
Toxicity to secondary consumers is also of concern. It was •
found that goshawks and ferrets died within 2-3 weeks after eating _
hens which had fied from methyl mercury poisoning. It was also ™
found that hawks and owls which had eaten seed-eating prey with con- •
centrations up to 140 ppm had died with levels of 300 ppm. Deaths
of secondary consumers can be expected as the result of successive •
concentration of mercury levels through lower trophic levels (85).
Methyl mercuric chloride has been placed in the acute toxicity •
ranking of organic chemicals found in fresh water as determined by •
the LD,.,, in mammals using oral administration. It ranks number 2
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TABLE XV-6
BIOLOGICAL HALF TIMES OF METHYL-MERCURY RESIDUES
Species Approximate Half-Times (days)
| IN VARIOUS SPECIES (101)
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Mouse 8
Rat 16
Young dogs 20
• Squirrel Monkey 65
Man 70
Seal 500
Poultry 25
Molluscs 700
Crab 400
Pike 700
Flounder 1000
Eel 1000
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B (a) Half-Times is the Time for excretion of 1/2 body burden.
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• 231
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with the concentration of 099 mg/kg, and as number 11 in the range
of 100-199 mg/kg. Two other organic mercury compounds have also •
been listed in the ranking of acute toxicity of potential organic
pollutants as determined by the LD _ in mammals using oral admin- •
istration. They are ranked as number 55th Diethyl mercury at a •
concentration of 50-99 mg/kg; and, as number 96th ethyl mercuric
chloride at a concentration of 200-299 mg/kg (59). •
Effects on Fish and Other Aquatic Life _
McKee and Wolf report that mercuric ions are considered to be
highly toxic to all forms of aquatic life (66). A concentration of •
mercury within the range of 0.004-0.02 mg/1 (as mercury) has been
reported to be harmful to fresh water fish. Table XV-7 summarizes •
the toxic concentrations of the various forms of mercury to various _
species of fish and aquatic life. ™
A concentration of 1.0 mgl of mercury, as mercuric chloride, tt
has been found to reduce the rate of oxygen utilization in BOD tests
by 80%. Mercuric chloride has also been shown to increase in tox- •
icity from 0.02-0.2 mg/1 for sewage organisms. The mecuric metals
which form the most insoluble sulfides have been found to be the
most toxic (15). Mercuric compounds were found in a study in Denmark
to be concentrated by pike. A mercury content of 0.07 ppb was found
to be concentrated within pike as much as 3,000 times (102). •
Concentrations of methyl mercuric chloride in waters receiving
acetaldehyde plant wastes have been reported at 14.4 mg/1 and con- V
centrations of mercury in fish varied from 9-88 mg/kg of dry weight
(60).
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TABLE XV- 7
TOXIC CONCENTRATIONS OF MERCURY
Adapted From McKee and
Form Conc.,mg/l
Mercury Chloride 0.008
(as Hg) 0.01
" 0.01
0.011
0.02
0.15
0.2
0.03
0.03
Mercuric Cyanide 0.02
(as Hg)
0.15
" " 0.20
0.16
Mercuric Nitrate 0.015
(as Hg(N03)2
0.015
1.00
Mercuro-Organics 0.02-1.4
0.02-1.4
Phenylmercuric acetate 0.01
Mercuric acetate 0.02-0.05
Phenylmercuric acetate 0.005-0.01
233
ON AQUATIC LIFE
Wolf (66)
Species Remarks
Sticklebacks Injury or kill
Sticklebacks " "
Minnows " "
Sticklebacks Threshold
Guppies Injury or kill
Microregma Threshold
Escherichia coli "
Scenedesmus "
Daphnia magna "
Daphnia magna "
Scenedesmus "
Escherichia coli "
Microregma "
Isopod 1st Response
Fish (Stickleback) "
Polychaete " "
Minnows Fatal
Shiners "
Young Salmon Max. Safe Cone
" " " " "
Daphnia pulex " " "
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A temperature effect on mercury toxiclty has also been reported
by Lambou (54) . An investigation of the toxicity of various organic
mercury compounds to fingerling channel catfish is summarized in the
Table XV-8.
TABLE XV-8
TOXICITY OF ORGANIC MERCURY COMPOUNDS ON
FINGERLING CHANNEL CATFISH (54)
TLm in mg/1
Chemical Temperature 24 hrs. 48 hrs. 72 hrs 96 hrs.
°C
Phenylmercuric 19 4.1 3.4* 3.3 3.3
acetate
Pyridylmercuric 24 3.8 0.49
acetate
Ceresan M (a) 19 1.8 1.8 1.6 1.6
Lignasan (b) 19 2.0** 2.2 1.7 1.3
Tag 10% solution (c) 20 1.5 0.78 0.60 0.58
* At 45 hours
** At 28 hours
(a) Ethyl mercury p-toluene sulfonanilide, 7.7 percent (total
mercury as metallic, 3.2 percent)
(b) Ethylmercuric phosphate, 6.25 percent
(c) Phenylmercuric acetate, 10 percent.
910.
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Effect on Plants
• It has been reported that a concentration of 0.5 mg/1 mercury
added as mercuric chloride caused a 50% inactivation of photosyn-
• thesis in giant kelp during a four day exposure, and that a concen-
• tration of 0.1 mg/1 decreased photosynthesis by 15% in one day, with
complete inactivation after four days (6). A minimum lethal concen-
• tration of mercuric salts has been reported in the range of 0.9-60
mg/1 for phytoplankton.
I Selikoff reported that the organic compounds of mercury may
M produce genetic mutations and chromosomal aberrations in certain
systems of plants (85).
£ TREATMENT TECHNOLOGY
_ A review of current literature in the field of industrial waste
™ treatment (48,61,72) indicates that very little is known or reported
• on the treatment and control of mercury waste discharges. The report
by Lelikoff (85) and more recent works indicate that control of a
• mercury discharge is feasible at least from the production of chlor-
alkali.
m Selikoff reported on nine process and housekeeping changes that
• were able to produce a tenfold decrease in mercury discharges from
chlor-alkali plants in Sweden (85). These procedures, current and
• planned, are listed below.
1. Cooling the hydrogen gas to less than 0° at 2 atm of
•I pressure and returning condensate to decomposer
2. Returning condensate obtained by cooling chlorine gas to
the brine solution.
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3. Separating waste streams and using epoxy on concrete floors
to prevent entrapment of mercury
4. Enlarging and improving sedimentation basins. •
5. Filtering wastewater through activated charcoal.
6. Treating wastewater with disulfide and subsequent |
coagulation, sedimentation and filtration. .
7. Treating waste by means of ion exchange, probably after
pre-treatment by another method. I
8. Improving procedures for reactivating cell anodes.
9. Recirculating all water used in production. •
A summary of the improvements made in the mercury discharge •
from a chlor-alkali plant in Sweden is presented in Table XV-9.
In testimony presented to the Illinois Pollution Control Board, |
R. F. Weston indicated that total mercury could be reduced by ion M
exchange to a total effluent level of 0.002-0.005 mg/1 (97). He also
estimated the capital cost to be $1.2 million for a 10 MGD treatment •
facility, or $120/1000 gallons.
A recent report (9) indicates that mercury may be reduced in J|
the atmosphere at chlor-alkali plants to a level of one ppb or as ^
low as 6 mg/metric ton of chlorine produced. One of the techniques *
developed by B. P. Chemical Company consists of a process which I
washes the mercury laden vent gases in hydrogen with a solution of
sodium hypochlorite and sodium chloride at a pH of about 9-10.5. •
It was reported that the chloride ion keeps the mercury in solution
as a complex salt. Mercury is then recovered by blending of the •
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scrubber solution with a brine, which then enters an amalgam cell,
or electrolytic or chemical reduction process.
• The B. P. Chemical Company process was reported to have an
installation cost of approximately $665,000 for a 60,000 metric ton
| facility in England. The operating costs were reported not to ex-
_ ceed $250 per year for the scrubbing chemicals used and an annual
maintenance cost of $7,000 per year.
• A second process has been developed by Monsanto Company Enviro-
Chemical Division. Their process utilizes the adsorption of mercury
• onto a specially formulated adsorbent. After complete utilization
_ of the adsorbent, Monsanto Envir-Chem states that the canisters
™ containing the adsorbent may be returned to them for disposal. Re-
B portedly, they have two processes for disposing of the mercury con-
taining adsorbents which do not contribute to environmental pollution.
• A review of the report prepared for EPA by General Technology
Corp. (42) on the waste of the inorganic chemical alkali and chlorine
• facilities indicates an average wastewater discharge of 20,000 gallons
• per ton of chlorine produced in a chlor-alkali plant. This flow fac-
tor of 20,000 gallons per ton of chlorine produced can be applied to
• the data shown above in Selikoff's report. The data then indicate
that mercury concentration for the new plant at Stenungsund, 1969,
• would equal 0.0362 mg/1 and technically possible mercury levels by
• 1970 would range from 0.0070-0.01466 mg/1. This data compares
favorably with that of Weston who indicated an achieveable level of
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0.002-0.005 mg/1.
Mr. Frank Hall of the Enforcement Division of EPA, Headquarters
has indicated that an effluent level of 0.1 pounds of mercury per
day has successfully been obtained through various legal actions on
several chlor-alkali plants in recent years. This maximum effluent
criteria of 0.1 pounds per day can not be applied indiscriminately
to other types of mercury discharges. However, it has been defined
as technically feasible for plants utilizing either the B. P. or
Monsanto processes as discussed above (9) .
TABLE XV-9
MERCURIAL DISCHARGE FROM CHLOR-ALKALI PLANTS IN SWEDEN (85)
Loss of mercury (g/ton of chlorine)
Range New plant at technically
Loss to Aug. 1967 Stenungsund, 1969 possible in 1970
Water 30-40 0.55 0.01-0.1
H2 gas 5-10 0.4 0.01
Alkali 1-10 0.8 0.01-0.5
Ventilation 15-25 1.0 0.5
Total 51-85 2.75 0.53-1.11
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SUMMARY AND RECOMMENDATIONS
1. The largest single man made source of mercury is the production
• of chlorine in chlor-alkali plants. There are, however,
numerous other industrial and commercial sources of mercury
I pollution.
« 2. Mercury is toxic in all forms, but in the aquatic environment
it is converted to its most toxic form, methyl mercury. In
• the form of methyl mercury it may be rapidly absorbed by fish
and other forms of aquatic life. Mercury is subject to biolog-
• ical magnification, that is, increasing residue concentrations
_ in the higher trophic levels.
™ 3. The principal danger to man is from the ingestion of mercury
B contaminated fish and foodstuffs. Such ingestion may cause
genetic, nerve, or barin damage and/or death. An additional
• concentration effect in fetal blood and tissues is noted.
Methyl mercury accumulates so well that repeated minute intake
™ during a prolonged period can kill or create permanent dis-
• ability.
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4. The fatal dose of mercury for man could range from 75-300
mg/day.
5. Mercury has been found to be 20% higher in the fetal blood
of mammals than in the mother
6. A mercury concentration of 0.5-0.9 mg/1 has been reported as
the lethal concentration to plant life.
7. Organic mercury may produce genetic mutations and chromosomal
aberrations in plants.
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8. Secondary poisoning by mercury in birds and mammals if of •
importance.
9. Harmful concentrations of mercury for fresh water fish have f
been found to be within the range of 4-20 ug/1 —
10. Methyl mercury chloride ranks as the second most toxic ™
organic chemical to animal life through injection by the B
oral route.
11. Chlor-alkaLi plants are capable of achieving effluent levels I
below 0.1 Lb/day with existing technology, and levels of 0.002-
0.005 mg/1 are feasible in treated discharges. •
It is the public policy of the Environmental Protection Agency •
as stated by the Administrator, Mr. William Ruckelshaus, that there
should be no man-made discharges of mercury. An appropriate inter- •
pretation of Mr. Ruckelshaus1 statement would mean a non-detectable •
concentration of mercury.
On the basLs of the above conclusions, it is readily apparent •
that mercury should be maintained at an absolute minimum level. It
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is recognized that for some industries this may necessitate a change
of product, or of materials and/or processes utilized. It is recom-
mended that an interim maximum uniform effluent criterion of 0.005
mg/1 be adopted for all discharges. It is further recommended that •
a maximum total discharge of 0.1 pounds/day be adopted for all chlor-
alkali plants. f
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• It cannot be overstressed that our objective is to reach a
total non-existent discharge of mercury into the aquatic environment.
| Therefore, our objective is a non-detectable concentration of mercury
• in all surface and ground waters. Currently, the limit of detection
of mercury by flameless atomic adsorption, as described in W.Q.O.
I Methods for Chemical Analysis of Water and Wastes, April 1971 is
ten nanograms per liter (0.000010 mg/1).
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• 241
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CHAPTER XVI-NICKEL
Natural aquatic concentrations of nickel are found as the
• divalent nickel ion or its complexes. Nickel is leached from its
ores and minerals. Nickel salts are noted for their solubility and
B characteristic green color. Table XVI-1 gives the concentrations
of nickel found in nature.
INDUSTRIAL SOURCES
The primary source of nickel pollution in surface waters is
_ the metal plating and metal finishing industry. The second major
* source is the manufacture of nickel-copper alloys known as monels.
• Most monels consist of 63-67% nickel and 30% copper. Other nickel
copper alloys known as cupro nickel consist of more than 50% copper
• (24). Various concentrations found in these industrial wastewaters
are summarized in Table XVI-2. Other industrial uses of nickel are
in the manufacture of synthetic ink, brown ceramic colors and the
• dyeing and printing of fabrics.
In discussing the disposal of nickel bearing wastewaters,
• Nemerow (72), reported that nickel concentrations discharged to
municipal sewers should not contain Tiore than 2-5 mg/1 nickel. He
reported that 2.0 mg/1 will be toxic to the bacteria utilized in
sludge digestion.
ENVIRONMENTAL EFFECTS OF NICKEL
Effects on Animals and Plants
Tables XVI-3 and XVI-4 summarize the toxic concentration of
nickel to certain plants and animals. While the U. S. Public Health
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Drinking Water Standards (94) do not have a limit on nickel, Water
Quality Criteria Data Book Volume 2 (105) indicates that the
Russians have placed a maximum permissible concentration at 0.1 mg/1
TABLE XVI-1
CONCENTRATION OF NICKEL IN NATURE (6)
Sources* Concentrations
* Nickel sources as their salts.
McKee and Wolf report that while there is no data on the toxicity
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Seawater 0.0054 mg/1
Marine Plants Up to 3 mg/1 •
Marine Animal 0.4025 mg/1
Serpentine Rocks 400-5,000 mg/kg •
Natural Soil 5-100 mg/kg •
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of nickel to man, it is believed to be Jow. They did indicate,
however, that nickel in the water supply may hinder the growth of •
the liver in amphibia, reptiles, birds, and mammals (66).
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TABLE XV I- 2
CONCENTRATION OF NICKEL IN CERTAIN INDUSTRIAL
Source
Plating wastewaters
Plating and pickling
operation
Metal finishing waste
Electroplating waste
* Flow of 100 gpm
** Flow of 50 gpm
Concentration (mg/1)
11.3 mg/1 avg.
5.0-35 mg/1 range*
12.6 mg/1 avg.
6.0-32 mg/1 range**
30-300 mg/1
5.0-58 mg/1
TABLE XVI-3
TOXIC CONCENTRATION OF NICKEL TO CERTAIN
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Plants
Flax (water culture)
Horse beans and corn
Citrus plants
Sugar beets
Tomatoes
Potatoes
Oats
Kale
* with molybdenum,
Toxic Level
0.5 mg/1*
any cone .
unspecified
injurious level
15.9-29.4 mg/1**
symptoms were reduced
WASTEWATERS
Reference
(72)
(72)
(16)
(14)
PLANTS
Reference
(66,6)
(66)
(66)
(66)
** grown in a nutrient solution sand culture
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TABLE XVI-4
TOXIC CONCENTRATIONS OF NICKEL TO CERTAIN ANIMALS
Animals Cone. Effect Reference
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Biological Sludge 2.0 mg/1 toxic (72)
Rats 5.0 mg/1* increased mortality (66) m
Cats & dogs (4-12 mg of Ni(Ac) or non toxic (59) •
NiCl2 per kg of body •
weight) over 200 days _
* Nickel in drinking water with a selenium solution (11 mg/1
cone.) - Synergism suggested. B
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• Effect on Fish and Other Aquatic Life
One study reviewed by McKee and Wolf indicated that nickel
I may be more toxic to fish than iron or manganese. However, they
also reported that fish were found living in waters polluted with
| mine effluent containing 13-18 mg/1 of nickel. In general, McKee
mm and Wolf report the nickel is less toxic to fish and river crabs
than copper, zinc, brass, or iron.
• McKee and Wolf reported that nickel readily combines with
cyanide to form a nickel cyanide ccmplex which is relatively stable.
• One Ni-CN complex with a concentration as high as 100 mg/1 (as cyanide)
_ was found to be not harmful to fish life if moderately alkaline
* conditions prevailed. A review of the data presented in the Water
fl Quality Data Book, Volume 3 (42) indicates that nickel, as nickel
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chloride, is much more toxic to fish and aquatic life in soft water
than it is in hard water: 4-5 mg/1 nickel chloride is toxic in soft
water while 24-42 mg/1 is toxic in hard water.
With respect to marine plant life, a nickel concentration of
2.0 mg/1 has been found to cause a 50% reduction of photosynthesis
I
in kelp (15). On a similar note, McKee and Wolf report that a con-
• centration of 2.5 mg/1 of nickel oxide from nickel sulfate in a
water culture has caused plants to wilt and die.
• As noted in Table XVI-4, Nemerow (72) indicated that 2.0 mg/1
• of nickel is toxic to the sludge digestion process. McKee and Wolf
report that a nickel concentration of 3.6 mg/1 as nickel sulfate
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has caused a 50% reduction in the oxygen utilization in synthetic
sewage. m
In summary, little is known about the toxicity of nickel to •
man. Nickel's toxicity to plant life has been noted as well as its
effect on certain animals and wildlife. The presence of nickel, for •
example, may have a hindering effect on the growth of the liver but
the actual toxic concentration has not been reported. Sticklebacks •
are known to have a lethal limit of 0.8 mg/1 of nickel while other •
forms of fish and aquatic life appear to have greater resistance to
nickel toxicity. In general, it has been found that nickel is more I
toxic to aquatic life in soft water than in hard water.
TREATMENT TECHNOLOGY - NICKEL REMOVAL
I
Process modification and good housekeeping to reduce accidental fl
spills and to reduce dragout loss of nickel from plating bath solu-
tions have been recommended by both Nemerow (72) and Patterson and •
Minear (76). After waste reduction and in plant process changes, _
an economical treatment system can be utilized for nickel destruction •
(i.e., precipitation and disposal) or recovery of higher concentra- •
tions of nickel, possibly followed by destruction of diluted wastes.
Destructive Treatment •
Nickel forms an insoluble precipitate, nickel hydroxide, which •
is effectively removed at a pH of about 9.5 or above. Nickel
hydroxide has a minimum theoretical solubility of 0.01 mg/1 at a I
pH of 10. While the removal of nickel as nickel hydroxide is most
effective at a high pH, little efficiency is gained above a pH of |
10 (76). -
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• Both Patterson and Minear (76) and Weston (97) report that
the addition of lime is effective in raising the pH to the desired
I level for the precipitation of nickel hydroxide. They indicate
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that the nickel in most wastewaters can be effectively reduced to
a final effluent of less than 1.0 mg/1.
A modification of the normal lime coagulation, precipitation,
sedimentation process is the Lancy Process as reported by Lund (43).
As mentioned in other reports on electroplating wastes, the Lancy
system (integrated process) utilizes a chemical solution (lime) to
rinse the dragout plating solution from the material. The chemical
solution is allowed to precipitate the metals which are then recycled,
I
Recovery Processes
• Patterson and Minear report that the processes currently used
for the recovery of nickel are countercurrent rinsing, direct reuse,
• ion exchange, evaporative recovery, electrolytic recovery, and re-
• verse osmosis. The more usually employed methods are countercurrent
rinsing and direct reuse both of which reduce the total volume of
• the flow, concentrating the nickel within the waste thereby reducing
the cost of nickel recovery. Patterson and Minear reported that
I nickel bearing wastes ranging in concentrations from 100-900 mg/1
• have an estimated recovery value of $.80-$7.00 per thousand gallons.
Patterson and Minear gave one example where the use of counter-
H current flow with multiple rinse tanks allowed for direct reuse of
the nickel plating solution dragout and resulted in a final nickel
I concentration of only 0.9 mg/1 in the final rinse (76).
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As reported by Patterson and Minear, the other most commonly I
utilized means of recovery which does not necessitate further treat-
ment, is the use of ion exchange. Their data indicated that the B
additional cost of ion exchange was rapidly offset by the value of •
the nickel recovered. However, they did not discuss the treatment or
further disposal of the regeneration waste from the ion exchange unitfl
The remaining three recovery processes reported by Patterson
and Minear, evaporative recovery, electrolytic recovery, and reverse I
osmosis, all necessitated further nickel removal from the diluted •
wastewaters following nickel recovery prior to disposal. In general,
it would appear that these processes are feasible for recovering highH
concentrations of nickel. The wastewaters from these facilities
with a residual nickel concentration of approximately 20-30 mg/1, |
can be treated by lime coagulation, precipitation, and sedimentation mt
to a final effluent of less than 1.0 mg/1.
A summary of the various treatment piocesses and their effi- I
ciencies is given in Table XVI-5. The initial installation cost of
various methods of treating nickel for either destruction or re-
covery are summarized in Table XVI-6 and the chemical and operating _
costs for the treatment units are given in Table XVI-7. ™
From the standpoint of treatment feasibility and economics, I
both recovery of concentrated nickel bearing wastes and destruction
of lower concentrations of nickel bearing wastes are achievable. •
Selection of the most appropriate method of destruction and/or
recovery naturally needs to be evaluated on an individual basis by
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the industry. The value of recycled nickel, however, will be an
incentive to reduce the volume of nickel bearing
facilitating nickel recovery and/or destruction.
TABLE XVI-5
REMOVAL EFFICIENCY OF NICKEL FROM INDUSTRIAL
Nickel Concentration, mg/1
Process Initial Final
Lime coagulation
100 1.5 @ ph
with filtration 0.1 - 1.9
with filtration 21 0.09- 1.9
35 0.4
w/Separon NP-10 39 0.17
(Plating Waste) 15 0.5
Lancy Batch Electroplating 3-4
Lancy Integrated " 0.5
Lancy Integrated " Less than
Ion Exchange 870 Complete
60,000 Reclaimed
Recovery & Destruction
Evaporative recovery High
Electrolytic recovery,
& Reverse Osmosis 20 - 30
followed by Lime
coagulation 20-30 1.0
250
wastewater thereby
WASTEWATERS
Reference
= 9.9 (76)
(97)
(76)
(76)
(76)
(76)
(66)
(66)
1.0 max (64)
Removal (76)
(76)
(76)
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TABLE XVI-6
I
Process
Lime Coagulation
Evaporation
Recovery
Reverse Osmosis
CHEMICAL
Process
Lime Coagulation
Recovery Value
Ion Exchange
Evaporation
Recovery
1
Capital Cost/
Flow Cost 1000 Gal. Reference
1
0.45 MGD 187,000 $1,108 (1966) (76)
1.0 MGD 300,000 300 (1971) (97)
10.0 MGD 1,300,000 130 (1971) (97) •
50.0 MGD 4,600,000 92 (1971) (97) •
400 GPH 45,000 _
50 GPH 5,000- 6,000 6.42 - 7.71 •
500 GPD 10,000-20,000 •
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TABLE XVI-7 |
COST FOR NICKEL REMOVAL OR RECOVERY (76) __
1
Initial Operation Recovery
Ni cone, (mg/1 Cost Value B
1
35 SOc/1000 gal @ 0.45 MGD •
150 - 900 $0.80-7.00/1000 _
gal. J
52«?/lb. nickel
recovered •
— (400 GPH $100,000/yr.
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SUMMARY AND RECOMMENDATIONS
On the basis of the literature reviewed and the above discussions,
the following can be stated:
1. Nickel is found in natural soils at concentrations ranging from
• 5-100 mg/kg and in serpentine rock at concentrations of 400-
5,000 mg/kg.
2. Nickel is present in several industrial wastes, predominately
mm from metal finishing and plating industries.
3. Little is known of its toxicity to man and no limit has been set
• for nickel in the 1961 Drinking Water Standards. In general,
the toxicity of nickel to man is believed to be very low.
• 4. Nickel is toxic to plants, and naimals. The lowest toxic level
_ reported was C.5 mg/1 (water culture) to flax.
5. Nickel may hinder the growth of the liver in animals; the con-
• centration has not been reported in the literature reviewed.
6. Nickel complexes with cyanide, however, it is reported as not
• toxic to fish life at a concentration of 100 mg/1 (as cyanide)
in alkaline waters. The lowest toxic concentration to fish has
• been reported for the stickleback fish at 0.8 mg/1. The toxicity
• of nickel decreases by a factor of approximately 7-10 in soft
water as compared to hard waters.
I 7. Nickel is economically recovered from concentrated waste streams,
sometimes at a profit. Therefore, treatment cost of nickel may
I be substantially less than that for treating and removing other
• metals.
8. Nickel is removed from solution by precipitation with lime to a
• final effluent concentration of less than 1.0 mg/1.
• 252
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While nickel is substantially less harmful to most forms of life
than many of the other trace metals, it is toxic to plants and po-
tentially toxic to animals and fish life. On the basis of the above •
review it is recommended that a uniform effluent concentration be
set at 1.0 mg/1 as nickel. Should future studies indicate nickel to |
be more toxic than is currently reported, it is recommended that the •
effluent level be adjusted.
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CHAPTER XVII-OIL AND GREASE
Oil and grease covers a broad spectrum of substances. In this
| report we are speaking not only of lubricating oil, vegetable oils
_ and grease but the large group known as hexane extractables.
There are many definitions of what constitutes oils and
I greases. Patterson and Minear (76) define oil and grease as that
material extracted from wastewaters using hexane. Hexane solubles
I include such materials as waxes, fats, soaps, fatty acids, lubricants,
cutting fluids and other light and heavy hydrocarbons. Other sub-
™ stances extracted in hexane include primary petrochemicals such as
• ethylene and propylene, and such intermediates as xylene, ammonia,
methanol, ethanol, butanol, ethyl-benzene and some chlorinated hydro-
• carbons.
The American Petroleum Institute (API) classifies oil waste as
• follows: (1) light hydrocarbons including light fuels, (2) heavy
• hydrocarbons, crude oils and tars, (3) lubricants and cutting fluids,
(4) fats and fatty oils originating from food processing (76).
• The sources of oils and grease are primarily industrial and are
listed in Table XVII-1. The volume of industrial discharges contain-
• ing oil may vary from small trickles to millions of gallons per day
• discharged from steel mills, for example. Similarly, the concentra-
tions may vary from minute traces up to 24,400 mg/1 reported for sea-
• food stick water.
The presence of oils and greases in water is of great
B aesthetic concern to man. Oils and their soluble products are also
of concern because of their toxicity to fish and other aquatic life.
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Concentration, mg/1 •
'*"» t~ o 1 TT-mii 1 o -I -f- -i arl J?^-frO'VOTtr»tS ^™
TABLE XVI1-1
INDUSTRIAL WASTEWATER
OIL & GREASE SOURCES AND CONCENTRATIONS
PRIOR TO TREATMENT
Source Total Emulsified Reference
Oil Refinery: 4-13 — (44) •
Refinery, Detergent 73 — (45) |
Alkylate
Petro Chemical: 42-8,000 — (44) I
P.C. Sour Water 500 — (44)
P.C. Mixed Chemicals 547 — (45)
P.C. Phenols, Cresols Trace — (45) •
Steel Mills: 1276 — (2)
Coolant Water 14,600 3,494 (2) •
Cold Rolling 700 200 (76) |
Hot Rolling 20 (76)
Cooling Waters 100-5,000 (76) _
Meat Packing: 600-2000 (1200 typical) (48)
Catch Basin effluent 420 ~ (48) •
Slaughter, cut, cook 2180 — (48) •
Bacon 370 -- (48)
Salami 320 — (48)
Ham, Pork, Sausage 200 — (48) •
Beef, lard 2350 — (48) •
Vat Wash, etc. 240 — (48)
Sausage grind & mix 330 — (48) •
Smoked meat 970 — (48) |
Seafood;
Herring Pump Water 4,500 — (87)
Stick Water 4,200-24,400 — (87)
Sardine Rendering 5,700 — (87)
Salmon Cannery 250 — (87)
Tuna Processing 287 — (87)
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ENVIRONMENTAL EFFECTS OF OIL AND GREASE
Effects on Man
• The basic objection to the presence of oily material centers
_ around one of aesthetics and safety. As noted in McKee and Wolf
™ (66), the immediate impact of oil is: "a) spoiling of beaches, and
fl| coastal resorts; b) destruction and injury of seabirds; c) the
fouling of boats, fishing gear and quays; d) the risk of fire in
• harbors and other enclosed areas; and e) damage to marine flora
and fauna''. Recently, incidents have been reported of oil spills
• causing not only aesthetic damage but damage to fish and other
• aquatic life, plus potential damage to the entire area if oil-covered
waters become ignited. Some specific problems caused by oil and
• grease are turbidity, films, irridescence, and increased difficulty
in the treatment for potable water. With respect to toxicity, Mckee
• and Wolf reported, "It appears, therefore, that hazards to human
• health will not arise from drinking oil polluted x^aters for they will
become aesthetically objectionable at concentrations far below the
• chronic toxicity level."
• Effects on Industrial Water Supply
Oil in industrial water supplies becomes important from two
• aspects. First, serious damage has been reported when boiler feed
water contains only a few parts per million of oil. Oil deposits
• within the boiler tuve surfaces may prevent proper heat transfer,
_ and cause overheating and failure of the metal. Second, the taste
™ and odor from oily materials within the water supply have a noxious
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effect on products which are prepared for human consumption. Oil in
tremely low.
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the water used for the manufacture of paper and cement has also been
reported to detract from the quality of the product. •
Effects on Animal and Birds
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Effects on animals and livestock are both scant and inconclu-
sive. However, consumption of oily water may produce some laxative
effect (66). Anyone who has ever had any association with an oil
spill, will be well aware of the detrimental effects of oil on birds. •
There are many well documented attempts to save birds from the pit-
falls of oil spills. Once a bird comes into physical contact with •
oil, the oil penetrates the bird's plumage, resulting in the bird los- •
ing its natural insulation to cold and, for those birds which normally
fly, its ability to take flight. Even with the desperate attempts •
of many volunteers to save water fowl, the rate of survival is ex-
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Effects on Plants
McKee and Wolf report that aromatic solvents, of petroleum
origin at concentrations up to 300 mg/1 have been used to control |
weeds along irrigation ditches with no detrimental effect on crops _
subsequently irrigated from the ditches. However, they also report ™
that oil pollution may be partially responsible for the loss of large B
areas of eel grass along the American and European coasts. They
concluded, "Where large areas of eel grass have disappeared there •
has been a great decrease in mollusks and crustaceans, wild fowl
have moved elsewhere, and coastline erosion has often followed." •
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Effects on Fish
The discharge of oily wastes to receiving waters has its major
impact through its effect upon fish life. McKee and Wolf report that
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free oils or emulsion have been found to adhere to the gills of fish
I reducing oxygen transfer (See Table XVII-2.) They also note the coat-
ing of algae and plankton with oily waste which removes them from
• the food web. Settled deposits may coat the bottom destroying the
• benthic organisms and interfering with spawning. Oxygen transfer
at the air-water interface is hindered and photosynthesis may be
• affected by a surface coating of oil. Lastly, McKee and Wolf report
a toxic effect of oils directly on fresh water fish at concentrations
• as low as 0.3 mg/1 (6). Toxic reactions to petrochemicals are reported
• at concentrations from 12-97 mg/1.
To repeat, discharge of oily wastes has been shown to be of
• significance in the production of tastes and odors in drinking water.
It has also been shown of even greater significance to the fish and
| aquatic life, through direct toxicity, reduction of oxygen transfer,
reduction of photosynthesis, and deleterious affect on the food chain
balances.
• Oils and greases are also a matter of aesthetic concern,
accounting for the destruction of beaches and tidal areas. Oils
• foul boats and fishing gear and cause fire damage and property losses.
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TABLE XVI I- 2
EFFECTS OF OIL AND GREASE
Waste Receptor
Source Affected Effect
Petroleum Man Taste
Raw Petroleum Man Odor
Mineral Oil Man Taste
Mineral Oil Man Odor
Gasoline Man Taste
Gasoline Man Odor
Aromatic Solvents Grasses Weed
Control
Crude Oil Fish Toxic
Petrochemicals Man Toxic
259
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Cone, (mg/1) Reference
1.0 - 2.0 (66) •
0.1 - 0.5 (66)
2.5 (66) §
5.0 (66) _
0.005 (66) •
0.010 (66) •
300 (66)
0.3 (6) |
12.97 (44,45)
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• TREATMENT TECHNOLOGY - OIL AND GREASE REMOVAL
A review of current literature on the removal of oils and
• grease, from various industrial waste sources, indicates the use of
several levels of treatment. Primary treatment, consisting basically
• of gravity separation with skimming, is normally capable of achieving
m effluent levels of 10-250 mg/1 of oils. Secondary treatment, consist-
ing of chemical and physical separation, is capable of achieving
• effluent levels of 5-150 mg/1. Biological treatment is capable of
producing a final effluent level of less than 2 mg/1, provided the
| waste has been pre-treated by either physical or chemical-physical
• means and depending upon the characteristics of the oil or grease.
The primary treatment of oil wastes takes advantage of the dif-
• ference in specific gravity between oils and greases and that of water.
The basic principle involves gravity separation in a container of
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sufficient size to allow the free oils and greases to rise to the
surface where they are skimmed off. Three factors which determine
the efficiency of gravity separation are: (1) the rate of rise of
• the oil and grease, (2) the type and concentration of emulsion and
(3) the hydraulic loading of the separator. Patterson and Minear
m (76) reviewed the work of Wallace et.al. who indicated that from 60-
_ 70% of the free oil and grease may be removed in a 30-40 minute time
span. From this work, it appears that the maximum efficiency by
gravity separation would be approximately 75% removal, over a two
hour or longer detention time. A 1967 report on the Cost of Clean
Water for the Petroleum Industry (7) indicates that the American
Petroleum Institute (API) separator is capable of removing from
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60-99% of the free floating oil, but it is not applicable to emul-
sified oil removal. |
Similarly, the work of Gloyna and Ford (44,45) reported the ^
efficiency of four common methods for physical removal of oily wastes
from the petrochemical industry. These are summarized in Table XVII-3. IB
While the gravity separation of oils and grease is directed
only at the free floating portion, chemical and physical separation •
is directed at total removal. Oily emulsions may be broken by chem- ^
ical, physical, or a combination of chemical and physical means. ™
According to Patterson and Minear, chemical methods are most exten- l|
sively used in the treatment of oily wastewaters. The Cost of Clean
Water report (7) noted that chemical and physical treatment of API •
separator effluent can remove from 60-95% of the floating oil, and
from 10-90% of the emulsified oil. It was reported (7) that chemical •
coagulation and sedimentation are capable of removing 60-95% of the •
floating oil and 50-90% of the emulsified oil.
In treating combined wastewater consisting of once through •
cooling water and concentrated coolant waste at a 12:1 ratio, ARMCO
(2) found the oil removals listed below using 195 mg/1 of alum, •
43 mg/1 of lime, 32 mg/1 clay, and 1 mg/1 of a cationic polymer. m
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TABLE XVI I- 3
REMOVAL OF OIL FROM PETROCHEMICAL WASTE
BY GRAVITY SEPARATION (44,45)
Oil Concentration, mg/1
Process Influent Effluent
Circular Clarifiers 7,000-8,000 125
108 20
108 50
Impounding 3,200 10-50
Parallel 200-400 10-40
API Separator 220 49
90-98 40-44
50-100 20-40
42 20
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Parameter SRWL*(mg/l) Effluent % Removal _
Total Oil 1276 76 91
BOD5 893 57 93
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COD 6320 441 89
Suspended Solids 770 55 93 •
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The report concluded that pH values must be maintained above «
6.0 for efficient treatment, and that flow equalization is an abso-
lute must. •
Emulsion breaking of fish oils with clay, lime, alum, and
ferric chloride has been reported by Soderguist, e.t_.al^(87) to be Jj
75% effective in the removal of BOD. This reference also indicated _
that chlorination was required prior to sedimentation of the emulsion *
to control a rather pungent odor condition. 9
In treating concentrated coolant waste ARMCO (2) reported that
cationic polymers were found to be effective in breaking oil emul- •
sions at total oil concentrations of 14,600 mg/1, and emulsified oil —
of 3,494 mg/1. Emulsions were, however, found to be very sensitive *P
to dosage and temperature. The optimum temperature was found to be 4
between 100 and 150°F. Batch treatment of the concentrated coolant
water reduced the total oil level to 730 mg/1, and the emulsified •
oil concentration to 175 mg/1.
Acidification of oily waste has also been found to be bene- •
ficial in breaking oil emulsions. Soderguist, ej^.a^. reported that •
the acidification of oil fish waste followed by flotation was
capable of reducing the fish oil from over 24,000 mg/1 to an effluent •
* SRWL = Standard Raw Waste Load g
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concentration of 80 mg/1 total.
Other treatment efficiencies reported in the literature for
the removal of emulsified and total oil from various effluents are
given in Table XVII-4.
TABLE XVII-4
REMOVAL BY CHEMICAL COAGULATION
Waste Influent Effluent
Chemical Source mg/1 mg/1 Reference-
Alum, lime, Steel mill
clay, polymer coolant 1276 76 (2)
Alum, lime, Fish oils (75% BOD (87)
ferric chloride Removed)
Lime, alum Oil refinery (95% BOD (76)
Removed )
Soda ash, lime Ball & Roller 302 28
polymer Bearing Plant
Alum, Meat packing 1944 142 (76)
Air flotation
As reported in Patterson and Minear, coagulation with iron
salts has been generally effective for de-emulsifying oil waste.
However, breaking of emulsions by acidification has generally been
found to be more effective wince a Tiassive hydroxide sludge will not
be formed. In addition, emulsion breaking by the addition of alum
and iron salts also adds large quantities of inorganic salts to the
effluent, which may creat an additional pollution problem by increas
ing total dissolved solids.
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The physical emulsion breaking methods commonly used include
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heating, centrifugation, filtration, and air flotation. Patterson
and Minear report that centrifugation is normally most efficient •
when applied to oily sludges, rather than to typical dilute oil waste-
waters. 9
Filtration has been found to be effective in treating steel •>
mill waste containing up to 230 mg/1 of emulsified oil (76). The re-
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moval efficiency of high rate filtration and diatomaceous earth fil-
tration is summarized along with the capital operating cost in Table
XVII-5 as reported in Patterson and Minear (76). •
The third type of oil and grease removal is the combination of -m
chemical coagulation and/or acidification with air flotation. In a
review of Patterson and Minear's work, it is readily apparent that •
flotation has been used predominately as a method of removing emulsi-
fied oils from petroleum and petrochemical industrial wastewaters. Jg
The report on the Cost of Clean Water for the petrochemical industry «
(7) has indicated that air flotation, both with and without chemicals,
is a standard procedure for manu refinery and petrochemical industries. •
Air flotation without chemicals effectively removes 70-95% of the
floating oil and 10-40% of the emulsified oil. Flotation with chem- •
icals yields efficiencies of 75-95% and 50-90% for floating and emul- _
sified oils, respectively. In summary of the works reported by ~
Patterson and Minear, Table XVII-6 indicates the improved efficiency •
of flotation with coagulants, over flotation without them.
While not as widely used as gravity separation and chemical- •
physical means, biological treatment is also applicable to the removal
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of oil and grease from wastewaters. Patterson and Minear report that
oil and grease laden waters from food processing plants have been
treated bidogically. Further works reviewed by Patterson and Minear
indicated that an anaerobic lagoon achieved an 84% removal of grease
during one 4 day sampling period. The grease in the raw waste
ranged from 425-1,270 mg/1 while an effluent grease concentration was
reported at 69-147 mg/1. Another article also reviewed by Patterson
and Minear indicated an 99% reduction of oil from a refinery waste
oxidation pond which had initial and final oil concentration of 154
and 18 mg/1 respectively.
In a report of the treatment of oily materials by activated
sludge, Hydro-science (51) concluded that a system continuously ex-
posed to oily wastes is capable of handling a load of 0.1 Ib of hexane
I
extractables per pound of mixed liquor suspended solids (MLSS). This
corresponds to an oil concentration of 50 mg/1 for MLSS or 2,000 mg/1
and 75 mg/1 for the MLSS of 3,000 mg/1, etc. Barnhart (of Hydro-
science) (13) stated that a well operated activated sludge system is
capable of reducing oil and grease from 50-75 mg/1 to a 1-2 mg/1
effluent. He stressed that good operation and uniform sludge wasting
V was essential. Filtration of the effluent may be needed to maintain
the 1-2 mg/1 oil level due to sludge carry over.
| Gloyna and Ford (44,45) remarked on the ability of activated
M sludge to maintain low oil levels in the treatment of petrochemical
waste. An activated sludge treatment of refinery, natural gas,
• liquids, chemical specialities, and sanitary sewage had an effluent
oil concentration of 0.5 mg/1. In the treatment of refining process
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Treatment
HRFb
Coagulant
HRF & DE°
TABLE XV I 1-5
FILTRATION OF EMULSIFIED OILY WASTE (76)
Effluent3 Capital Operating
Oil, mg/1 Cost, $ Cost, $/Day
20 750,000 300
& HRF 10 775,000 372
5 1,000,000 440
aRaw Waste: 230 mg/1 Emulsified Oil @ 3,000 gpm
K
HRF -.High
rate sand and gravel filter
CDE: Diatomaceous earth filtration of HRF effluent
Floation
62%
70%
79%
70-80%
TABLE XVII-6
PERCENT REMOVAL OF OIL & GREASE BY
COAGULATION AND AIR FLOTATION
FROM REFINERY WASTE (76)
Alone Float .W/Coagulants Dosage
94% 25 mg/1 Alum
95% Polymers & Clay
87% 25 mg/1 Alum
up to 90% 30-70 mg/1 Alum
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• waste, they reported an oil removal of 75-85% efficiency, with the
effluent containing only 1-2 mg/1 of oil. Similarly, a final effluent
0 concentration of 1 mg/1 was reported in the activated sludge plant
M greating waste from methylene and acetylene production.
^ ARMCO (2) reported the cost of breaking the emulsified oils
• by batch treatment with a cationic polymer at $2.24-$7.70 per thousand
gallons of waste depending upon the characteristic of the oil treaied.
f| They also reported that if the recovered oil was of fuel oil quality,
^ the net cost of oil removal was only 4.8-8.5 cents per gallon of oil
* recovered. ARMCO also reported the cost of treating the combined
• once through cooling water with concentrated coolant oily waste.
They found that for this combined waste the operation cost ranged
I from $0.046-$0.051 per thousand gallons of waste. The treatment in-
_ eluded floculation and air flotation. Although the recovered oil had
™ no potential as fuel, it was utilized by local municipalities as road
oil. Other cost data available in the literature are summarized in
Table XVII-7 and XVII-8.
• In summary, petroleum refinery wastes are likely to contain much
more free oil than emulsified oil. Industrial waste sources such as
• steel mills, metal finishing, electroplating, food production,
JV tanneries, textiles will contain more emulsified oils. As a result
the large producers of refined oils and other petrochemicals are
• able to achieve a 1-2 mg/1 total effluent oil concentration much
more readily than are some of the smaller processes which have to
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handle emulsified oils. One should not infer, however, that low oil
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TABLE XVII-7
CAPITAL COSTS FOR REFINERY OILY WASTE TREATMENT (7)
Process
API Separator
Air Flotation
Flow, MGD
3.0
7.5
15.0
3.0
7.5
15.0
Capital Cost-, $
46,500
105,000
210,000
111,500
222,750
371,250
Cost $/MGD
15,500
14,000
14,000
37,167
29,700
24,750
ANNUAL MAINTENANCE AND OPERATING COSTS FOR REFINERY
OIL WASTE TREATMENT (7)
Process
API Separator
Air Flotation
Flow, MGD
3.0
7.5
15.0
3.0
7.5
15.0
M & 0 Cost $/Yr.
23, )00
36, )00
55, )00
37, )00
74, )00
117, 750
Cost $/MGD
7,667
4,800
3,667
12,333
12,333
7,850
269
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TABLE XVII-7 (Con't)
CAPITAL COSTS FOR 'TREATMENT OF MEAT PROCESSING OILY
WASTES (8)
Process Flow, MGD Capital Cost, $ Cost, $/MGD
Gravity Separator 0.125 12,000 96,000
0.54 35,000 64,815
1.68 250,000 14,881
Air Flotation 0.125 *
0.54 60,000 111,111
1.68 150,000 89,285
* Not Reported
ANNUAL MAINTENANCE AND OPERATING COSTS FOR TREATMENT
OF MEAT PROCESSING OILY WASTES (8)
Process Flow, MGD M & 0 Costs, $/Yr. Cost $/MGD
Gravity Separator 0.125 1,000 8,000
0.54 10,000 18,519
1.68 18,000 10,714
Air Flotation 0.125 *
0.54 13,000 24,074
1.68 30,000 11,905
* not reported .
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concentrations cannot be achieved in wastewaters containing a large
9 percentage of emulsified oils. From the above data, it is apparent
•I that even some of the worst emulsified oils may be broken down by
acidification or coagulation followed by a physical treatment step
• which would lend them to further reduction by biological treatment.
SUMMARY AND RECOMMENDATIONS
I
The following conclusions are drawn on the basis of the liter-
• ature reviewed:
1. Oil and grease are found naturally but only in very low con-
| centrations, and only in marine waters. A large potential
. exists for adding oil and grease through discharges to sur-
face waters from many industries, and the concentrations range
• from trace amounts up to 24,4000 mg/1.
2. Large concentrations of emulsified oils are found in steel
• mills, meatpacking, seafood handling, textile mills and
tannery wastes.
™ 3. The major hazard of oily wastes in the aquatic environment
W is to fish and other aquatic life. Concentrations of 0.4 ml/1
(about 0.3 mg/1) of crude oil have been found to be toxic to
• some fresh water fish. Waters containing oil and/or grease
become aesthetically objectionable to man long before they
9 become health hazards. Minute concentrations of oil wastes
• may conglomerate or precipitate and form oily sludge on the
bottoms of receiving waters and smother benthic life. At a
• later time the sludge may be released to the water environment.
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4. Oils and grease may be removed progressively by gravity
separation, chemical and physical means and biological treat- 0
merit. The degree of treatment necessary to reach any given m
level will depend upon the degree of emulsification and the
individual characteristics of the hexane soluble material. •
5. Capital costs for oil removal appear to approximate the cost
for unit processes of standard design, e.g. clarifiers, ||
oxidation ponds, flocculators, etc. Chemical costs will vary
with the waste characteristics.
On the basis of treatment technology it appears that oily •
waste can be removed to an average effluent concentration of 1-2 mg/1.
Varying degrees of emulsification reduce the efficiency and the •
reliability of chemical and biological processes. It is therefore ' •
recommended that a maximum uniform effluent criteris of 10 mg/1 be
adopted for all wastewaters containing oil and grease. I
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CHAPTER XVIII-PHENOLS
As noted by Patterson and Minear (76), phenols includes a
wide range of organic compounds. According to "Standard Methods",
(1) phenolics include phenol, chlorophenols, both ortho-and-meta-
substituted, and parasubstituted phenols, in which the substitution
is a carboxyl, halogen, methoxy or sulfonic acid group. In terms of
I
effluent quality, the term phenolics includes a general group of
• similar compounds which have been derived from or include "phenol",
the monohydroxy derivative of. benzene. Discussion of phenols in this
I report includes those phenolics which evidence characteristic proper-
M ties of phenol when in solution. Phenol (known as carbolic acid) is
somewhat soluble in water. Most other phenols are insoluble in water.
• Phenols are colorless, but are easily oxidized and can be colored by
oxidation products.
The major industrial sources of phenolic waste are listed in
Table XVIII-1, along with typical concentration values. It is evident
from Table XVIII-1 that industrial affluent concentration of phenolics
• can vary from very low concentrations of 17 mg/1 to extremely large
concentrations of 12,000 mg/1
I
ENVIRONMENTAL EFFECTS OF PHENOL
Effect on Man
One of the major concerns to man from phenolics in the aquatic
• environment is the taste and odor problem found in drinking water.
When phenolic compounds are present in chlorinated waters a strong
medicinal odor is often present. This odor results from the formation
of a series of chlorophenols. For example, phenol can combine with
274
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chlorine to form 2 or 4 chlorophenol, 2,4-dichlorophenol and 2,4,6- «|
trichlorophenol. These compounds can cause taste and odor problems
in drinking at trace concentration (less than 1 mg/1). It was •
shown by McKee and Wolf (66) that taste and odor threshold concen-
trations for non-chlorinated phenols can vary from 0,01-60 mg/1 £
with the general threshold value of 1 mg/1, while chlorinated phenols M
have taste and odor threshold concentrations ranging from 0.002-1.0
mg/1 with a general threshold level of 0.002 mg/1. See Table XVIII-2 I
for threshold value of the different chlorophenols.
Because of the above values, in 1962 USPHS established a drink- •
ing water standard of 0.001 mg/1 based on taste and odor threshold ._
levels rather than on toxicity. These low threshold concentrations ™
make phenolic compounds undesirable by both domestic and industrial Ift
users of water, since the unpalatable taste is passed on to food and
beveragess. I
Man has little to fear from toxicity related problems in drink-
ing water due to the large amounts needed to produce harmful effects. ™
McKee and Wolf (66) report that ingestion of concentrated solutions •
of phenol will result in severe pain, renal irritation, shock and
possible death. A total dose of 1.5 grams is needed to be fatal. It I
is unlikely that this large quantity could be consumed in drinking
water because such concentration are much higher than taste consider- 9
ations will allow. •
Table XVIII-3 lists the characteristics of phenolic waters.
The BOD and COD data for many phenolics are presented along with the •
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TABLE XVIII-1
PHENOL CONCENTRATIONS REPORTED
IN
INDUSTRIAL WASTEWATERS
Source Concentration, mg/1
Coke Ovens
Weak ammonia liquor ,
without dephenolization 400-12,
Weak ammonia liquor,
with dephenolizer 4.5 -
Wash oil still wastes 30 -
Final cooler water
Pure still
Combined waste 6.4
Oil Refineries
Sour water 65 -
General wastewaters 40 -
Detergent alkylate
Butadiene, Butyl rubber
Post - stripping
General (catalytic cracker) 40 -
Mineral Oil wastewater
Petroleum products
Petrochemical
General petrochemicals 50 -
Mixed organics 10 -
Benzene refineries
Nitrogen works
Tar distilling plants
276
000
332
150
105
72
185
80
160
17
80
50
100
25
600
• 50
210
250
300
Reference
(48,71,76)
(76)
(48)
(71)
(71)
(71)
(44,45,76)
(76)
(44,45)
(44,45)
(76)
(76)
(76)
(44,45)
(76)
(44,45)
(76)
(76)
(76)
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TABLE XVIII-1 (Con
I
't)
PHENOL CONCENTRATIONS REPORTED |
IN
••
INDUSTRIAL WASTEWATERS
Source Concentration, mg/1 Reference 11
Synthetic resins, Phenol 4,
Formaldehyde, Fatty Acids
Glycerol, Phtholic acids,
Maleic acids, Pentacrythritol,
H. C. solvents
Aircraft maintenance 200 -
Other
Rubber reclamation 3 -
Orion manufacture 100 -
Plastics factory 600 - 2,
Fiberboard factory
Word carbonizing
Phenolic resin production 1,
Stocking factory 6,
Nylon
Phenol, Cresols production 280 -
277
500 (44,45) J
400 (76) •
10 (76) 1
150 (61,76) m
000 (76)
150 (76) |
500 (76)
600 (71,76) |
000 (76) •
(44,45)
500 (44,45) J
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theoretical oxygen demand. Taste and odor and human toxicity data
™ are presented where known.
I Effect on Fish and Other Aquatic Life
• McKee and Wolf report that fish are affected two ways: (1) by
direct toxicity, and (2) by tainting of the fish flesh. They point
• out that there are many difficulties in determining the detrimental
effects of phenolic compounds. "The reported lethal concentrations
M vary widely not only because of the common variables such as species,
_ temperature, time of contact, dissolved oxygen and mineral quality
™ of water but also because of synergistic and antagonistic effects of
H other substances in the water." It was also reported that a combin-
ation of phenolics in a waste is generally more toxic than pure
• phenol along.
A review of the literature (15,45,59,66) on the toxicity of
• phenols indicates that each phenolic has its own lethal limit which
• has little relation to the time of exposure. There is a wide spectrum
of toxic levels and considerable overlapping between the lethal
I or damaging concentration among species. McKee and Wolf report that
the24, 48, 96 hour TLm concentration for fish is in the range of 10-
• 20 mg/1 at 20°C. Generally speaking, the threshold level for fish
• however, is in the range of 1.0 mg/1. Selected phenolic TLm's are
shown in Table XVIII-4.
• In conclusion the toxicity of phenol and related compounds
I
toward fish varies with respect to several important parameters.
Toxicity increases when the D.O. or hardness of the water decreases,
the temperature increases and when there is a combination of the
preceding effects.
I
278
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TABLE XVIII-2
TASTE AND ODOR THRESHOLD
CONCENTRATION AT 25°C (66)
Geometric Mean Threshold mg/
Compound
Phenol
2-chlorophenol
4-chlorophenol
2 ,4-dichlorophenol
2 ,6-dichlorophenol
2 ,4 ,6-trichlorophenol
Taste
1.0
0.004
1.0
0.008
0.002
1.0
Odor
1.0
0.002
0.25
0.002
0.003
1.0
279
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TABLE XVII1-3
CHARACTERISTICS OF PHENOLIC WASTES (61)
BOD COD Theoretical T&O* Toxic**
PHENOLIC Ib/lb Ib/lb P.P. Ib/lb mg/1 mg/1
Phenol 1.6 2.4 0.15 0.1 - 1.5
Acetophenone 0.17
Catechol 1.89 1.89
o-Cresol 1.6 2.4 2.52 0.65 0.5
m-Cresol 1.7 2.3 2.52 0.7 0.5
p-Cresol 1.45 2.52 0.5
p-Cumylphenol 2.6 2.8
Dibutylphthalate 0.43 2.24
Methylphenylketone 0.5 2.5
Morpholine Nil 2.6
Naphthalene 0 3.0
1, 4-Naphthaquinone 0.8 2.1 0.3
2-Naphthol 1.7 2.55
B-Naphthol 1.8 2.5 2.55 1.3
Pyridine 0.02 3.03 0.8 1,000
Quinoline 0.7
Resorcinol 1.15 1.89
2,4,6-Trinitrophenol 0.92 0.98
Xylene 0 3.16 2.2 22
1,3,4-Xylenol 1.5 2.62
1,3,5-Xylenol 0.82 2.62
* Taste and odor threshold is tentative
* * Toxicity threshold based on fish, species not specified
280
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The second major effect of phenolic waste on fish and other
• aquatic life is tainting of the flesh. McKee and Wolf report that
mixed phenolic substances are the most troublesome. The chloro-
•i phenols are known to produce bad taste in fish flesh at concentra-
• tions which are far below the lethal or toxic dosages. Mineral oils,
carbolated oils, and other light oils which are usually part of the
I phenolic waste, reportedly have a great bearing on the tainting of
fish flesh.
A report by Gloyna & Ford (45) indicates that phenols and
M other nonchlorinated phenolic compounds have been found to taint
fish flesh at concentration of 1.0-10.0 mg/1. However, their report
• also indicates that chlorinated phenols may taint fish flesh at con-
centrations as low as 0.005 mg/1.
B McKee and Wolf report that phenolic compounds are less toxic
•| toward lower forms of aquatic life (fish food organisms) than they
are towards fish. A review of their data indicates that a concen-
• tration of 1 mg/1 has been found to limit photosynthesis in the
Platymonas organism, and threshold effects on several other organ-
jf isms including Daphnia have been observed at concentrations greater
« than 1 mg/1. Toxicity of some selected phenolics to Chlorella
pyrenoidosa is shown in Table XVIII-5.
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In summary McKee & Wolf indicated that the following concen-
trations of phenol would not interfere with the respective beneficial
uses of water:
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TOXICITY OF
TO
Organic Chemical
Phenol
Phenol
Cresol
Cresol's (ortho,meta,
o-Bromophenol
m ,p-Bromophenol
o-Chlorophenol
m , p-Chlorophenol
2 ,4-Dichlorophenol
2 ,4,5-Trichlorophenol
Pentachlorophenol
Xylenols
Nitrophenols
o-Aminophenol
m , p-Aminophenols
Hydro quinone
TABLE XVII 1-5
SOME SELECTED PHENOLICS (44,45)
CHLORELLA PYRENOIDOSA
Toxic Cone.
(mg/1)*
1,060
233
800
para) 148-171
78
36
96
40
21
1.5
0,001
49-81
9-14
47
140
178
Ref. (as desig-
nated in the
work of
Gloyna & Ford)
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50
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50
50
50
50
50
50
50
50
50
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50
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* Based on 50% REduction in Chlorophyll Content
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(1) Domestic water supply - 0.001 mg/1
(2) Irrigation - 50.0 mg/1
(3) Stock watering - 1000.0 mg/1
(4) Fish and aquatic life - 0.2 mg/1
TREATMENT TECHNOLOGY-PHENOL REMOVAL
^ A review of the current literature (45,48,71,76) indicates
* that methods are available for removing phenolic wastes from a wide
• range of concentrations to almost any level desirable. For some of
the more difficult wastes, however, several steps of treatment may
• be necessary to reach a given level. The matter of practical eco-
nomics, rather than technical capability, is the limiting factor and
™ may have some bearing on the so-called currently achievable level.
• Patterson and Minear (76) indicate that the method of selection for
phenolic removal and its efficiency may depend on the overall com-
• position of the wastewater. They report that it is normally necessary
to remove both oil and heavy metals prior to removal of phenolics
w from the wastewater. In general, however, currently available tech-
• nology is being successfully utilized for efficient phenolic removal.
As shown in Table XVIII-1 the industrial waste loading of
• phenolics varies from low to extremely high concentrations. As a re-
sult, the treatment technology discussed below will be under the
• categories of recoverable phenolics, biological and other processes
for intermediate phenolic removal, and polishing steps.
Recoverable Phenolics
• Patterson & Minear report that high concentrations of phenol
in a waste stream allow for economical recovery. The phenolic
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recovery value reported by Patterson and Minear is 20c/ton of coal
process, for coke plant ammonia liquor, as of 1969. There are cur- 0
rently many methods available for the removal of up to 99% of the •
phenol from high concentration wastewaters. However, even at this
high level of removal, a substantial amount of phenolic compounds re- •
main in the effluent.
In discussing phenolic removal from phenol resins, Nemerow I
(71) stated that single stage phenol extraction will remove approx- —
imately 96% of the phenols and 100% of the formaldehyde present. ™
Other methods discussed by Nemerow include lagooning and thermal in- fl|
cineration. No efficiencies were reported.
Gurnham's (48) review of phenolic waste treatments discussed •
the use of liquid extraction, vapor-phased dephenolization, and bio-
logical treatment. Countercurrent liquid-liquid extraction, on a ™
coke plant's waste, was said to reduce the phenolic content of the •
crude ammonia liquor from 1500-2000 mg/1 to a 10-30 mg/1 level.
Gurnham also reported that the use of two stage Podbielniak centri- •
fugal extractors on ammonia liquor yielded an efficiency of 99% re-
moval and that with vapor phased dephenolization processes followed W
by treatment with 10% caustic solution efficiencies of 95-98% removal
were obtainable.
Table XVIII-6 gives a summary of currently available phenolic •
recovery processes from concentrated wastewaters. While the effluent
data presented below represents well over 95% removal, in most cases |
the final effluent concentration still remains substantially high.
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TABLE XVIII-6
PHENOLIC RECOVERY FROM
CONCENTRATED WASTES
Phenol Concentration, mg/1 Percent*
Process Influent Effluent Removal Ref.
Benzene-Caustic
Dephenolization process 3,000 210-240 93 (76)
Counter-Current Podbielniak
Extractors 2,000 100 95 (48,76)
Single-stage Phenolic
Extraction 1.600 64 96 (71)
IFAWOL Dephenolization
Process (Carl Still) 4,000 40 99 (76)
Pulsed Column
Extractors 2,200 30 98.6 (71)
Steam Evaporation 1,500-2,000* 30-100* 98.5 (48)
Liquid-Liquid Extractors 1.500-2,000* 10- 30* 98.5 (48)
Caustic Recovery 1,500-2,000* 30-100* 99.5 (76)
Keppers Light Oil Extraction 1,500-2,000* 10- 30*
* Influent load assumed from Table XVIII-1 and Effluent based
on referenced percent removal.
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Gloyna and Ford (45) have reported that phenols may be removed
by solvent extraction with the efficiency depending on the solvent •
used as shown in Table XVIII-7.
Biological and Other Processes for Intermediate Level Treatment
From an economic standpoint it is expensive to recover phenolics •
from industrial wastes which contain phenolics in concentrations of
less than 500 mg/1. As a result, biological processes including M
lagoons, oxidation ditches, trickling filters, and activated sludge _
have been reported for this level of treatment (48,76). ™
In Gurnham's (48) discussion of phenolic treatment, he reports tt
that activated sludge and trickling filters individually have reduced
phenolic waste from 800 mg/1 to effluents containing 1 mg/1 or less. •
Certain precautions are recommended for satisfactory operation, such
as a wastewater feed of nearly constant composition, a temperature ™
above 70; a pH near neutrality, a storage capacity of 5 or more days, •
the addition of nutrient phosphorus, and the absence of tars and oils.
On a similar note, Patterson and Minear have indicated that the •
success of biological treatment of phenolic wastes depends on the
toxicity of other contaminants in the water to micro-organisms used V
in the biological process. •
While it has been reported that biological processes are ami-
able to phenolic wastes at corcentrations of 5-500 mg/1, Table XVIII-8 •
from the works of Patterson ard Minear indicates that biological
processes have been used successfully for concentrations up to twice |
this value in full scale plants, and up to the 4000 mg/1 range on a
287
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pilot plant scale. The affectiveness of biological treatment on
phenolic bearing petroleum wastewaters is summarized in Table XVIII-9. •
Other methods which have been utilized for moderate level
phenolic waste streams include chemical coagulation, chemical oxida- |
tion, and gas stripping followed by incineration. In Patterson & M
Minear's review on phenolic treatment, it was indicated that coagula-
tion with alum and iron salts has been utilized. It was also found •
that 10-20 percent of the phenolics starting at an initial concentra-
tion of 100-125 mg/1, were removed. One piece of literature reviewed £
by Patterson and Minear, however, suggested that chlorination plus ^
coagulation with lime would result in almost 100% removal of phenolics,
at a cost of $1.25-$1.50 per thousand gallons of waste treated. •
In Nemerow's (71) discussion of phenolic removal from rubber
waste, he stated that chlorination is very effective if sufficient I
time is given for the reaction. Similarly, Patterson and Minear ^
have reported that extremely high concentrations of chlorine must ™
be added to effect complete removal of phenolics. In addition, it flj
was found that this must be done at a pH of 7 or less, to prevent
the formation of toxic chlorophenols. •
Patterson & Minear reported on the use of ozone and chlorine
dioxide for successful oxidation of phenol. Although ozone was re- •
ported as being an efficient treatment process, operating and cap- •
ital costs are extremely high. It was reported that 1.5-2.5 parts
of ozone are required per part of phenol for effective removal, but •
effluents of down to 0.003 mg/1 were obtainable.
291
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I
Patterson & Minear also reported on the use of hydrocarbon
| stripping, followed by incineration for the removal of phenol. The
a cost of this operation will be discussed later in this section.
Polishing Steps in Phenolic Removal
• As shown above, biological treatment is generally capable of
_ reducing phenol concentrations down to 1-2 mg/1, or less. While
™ not reported in any of the recent text reviewed for phenolic waste
• treatment, Patterson and Minear report that Phenol removal is cur-
rently achievable to below the 0.1-1.0 mg/1 level.
• The ozone treatment previously disregarded for higher levels
of phenolic waste is much more effective and economical as a polisher
• process. Another process utilized in polishing is activated carbon.
• The work of McPhee and Smith, as discussed by Patterson and Minear,
indicates that a good grade of activated carbon should have the capac-
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ity of removing 0.09 mg phenol for every 20 mg of activated carbon.
By utilizing activated carbon, phenolic waste concentrations of 0.020
mg/1 can be reduced to a final effluent level of 0.005 mg/1.
On the basis of the above treatment processes, from the recover-
able range of phenolic waste, to the intermediate range, to the polish-
• ing process, it becomes apparent that a phenolic effluent anywhere
from 100 mg/1 down to 0.005 mg/1 is currently, technically obtainable.
I
COST OF PHENOLIC TREATMENT
• As reported in Patterson & Minear the cost associated with the
treatment of phenolic waste appears to be well within the range of
equivalent cost for water and wastewater treatment processes. Table
XV1II-10 has been prepared from the various data reviewed by Patterson
292
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TABLE XVI I 1-9
SUMMARY OF BIOLOGICAL TREATMENT
OF PHENOLIC - PETROCHEMICAL
WASTE (44)
Product and/or FLOW Phenol Cone, mg/1
Process MGD INF. EFF. Treatment
Refinery, Natural Gas
Liquids, Chemical Activated
Specialities, Domestic wst. 4.87 0.05 Sludge
Sour Waters 0.43 65 0.065 TF & AS
Refining Process 0.51 33 0.5 Activated
83 Sludge
Petroleum Products 0.27 25 1 A,S.
Synthetic Resins 4,500 1.5 Two Stage
Phenol, Formaldehyde, Trickling
Organic Acids, H. C. Solvents Filter
293
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and Minear. As noted in Table XVIII-10 the costs for the individual
treatment processes and their respective flows have been compared
to what has been termed by Weston (97) a typical secondary treatment
facility. While the costs for some of the recovery processes appear
• to be high, one must remember the value of recovered phenol.
As summarized in Table XVIII-11 the recovery value of phenols
B by the Barrett recovery process has been reported to be in the range
M of $400,000 per thousand gallons (76). Patterson and Minear further
state that "capital costs decrease from lower removals. Assuming
• an inflow of 5,000 mg/1 and allowing an effluent concentration of
50 mg/1 lowers the capital cost of $150,000 for a 1 MGD plant and
$70,000 for a 0.01 MGD plant. Increasing effluent phenols concen-
tration to 500 mg/1 (90% removal) reduces the 0.01 MGD cost to $60,000.
Reduced recovery value is associated with decreased recovery." Phenol
• recovery from this process offsets any operating costs. A quick
estimate of multiple treatment facilities including a recovery step
• followed by activated sludge, and possibly even a polishing step,
_ would indicate that the total operating costs could be very close to
* zero. The total capital costs appear well within the realm of the
fl equivalent secondary treatment facility.
Operational costs from the works of Patterson & Minear have
• also been summarized and shown in Table XVIII-12. These data indi-
cate that the typical operating costs, with the exception of the two
• chlorination steps, are well below the equivalent costs of removing
• trace metals.
In conclusion, it is apparent that the technology currently
• exists to remove phenols to very low residual levels at costs which
294
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I
SUMMARY AND RECOMMENDATIONS
are comparable to those of equivalent secondary treatment facilities.
It is of particular significance that a two stage process, consisting |
of a recovery stup for initial phenol reduction followed by a bio- M
logical system, should be capable of achieving a final effluent con-
centration of less than 1 mg/1. It is also apparent that where •
needed, technology exists to reduce phenol levels even lower.
I
On the basis of the above, the following conclusions have been flj
drawn:
1. Phenolics include a broad group of organic compounds and are •
prevalent in many industrial discharges. Industrial waste
phenolic sources range in concentration from a few mg/1 to 9
12,000 mg/1. •
2. Phenolic compounds are responsible for taste and odor
problems and tainting of fish flesh. The> can also be toxic •
to certain fish at low concentrations.
3. A stream criterion of 0.001 mg/1 is based upon the threshold V
odor concentration in domestic water supplies for chlorinated •
phenolics. A stream criterion of 0.2 mg/1 is needed to pro-
tect fish life. •
4. Current technology is capable of removing phenolics from
industrial and municipal discharges to a level of 1 mg/1 or 0
less by biological treatment or a combination of recovery •
steps followed by biological treatment. Polishing steps on
biological treatment effluent are capable of producing a •
final effluent with a phenolic concentration of 0.003-0.005 mg/1.
297
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• On the basis of the above statements, it is recommended that
a uniform effluent criterion of 1.0 mg/1 be adopted for all
•I phenolic waste discharges. This recommendation recognizes that data
• provided within this report indicates that some biological treatment
plants are not currently meeting this condition. However, as has
• been discussed and documented above, biological treatment processes
are capable of reaching much lower levels. It is also recognized
| that the recommended discharge criterion of 1.0 mg/1 could cause
M some taste and odor problems if a discharge is located immediately
(within a 1000: 1 dilution zone) above a domestic water supply intake,
• It is further recommended that, where the local situation in-
dicates that the stream water quality criterion of 0.001 mg/1
• phenolics would be violated by a current industrial or municipal dis-
_ charge, an effluent level of 0.010 mg/1 be adopted. In addition, an
average operating condition for a typical process day should be in
B the range 0.003-0.005 mg/1 on the basis of current technology.
It is further recommended that any new industrial discharge,
• on the basis of current technology alone, should meet an effluent
criterion of 0.010 mg/1.
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CHAPTER XIX-PHOSPHORUS
Due to the present interest in phosphate as a possible limit-
I
ing nutrient in algal blooms and concomitant eutrophication problems,
sources of phsophorus have been well delineated in the literature.
Elemental phosphorus does not occur in nature, but rather is found
as phosphates in several minerals and as the soluble, inorganic
anion in water. Because of its important role in energy transfer
in biochemical cycles, it is also found in a wide variety of
organic compounds.
McKee and Wolf (66) state "...it is a constituent of fertile
soils, plants, and the protoplasm, nervous tissue and bones of
animal life. It is an essential nutrient for plant and animal
growth, and like nitrogen, it passes through cycles of decomposi-
tion and photosynthesis. It combines directly with oxygen, sulfur,
hydrogen, the \ alides, and many metals."
Naturally occurring inorganic forms of phosphorus are listed
_ in Table XIX-1. Phosphate minerals are formed by the precipitation
™ of ions from super-saturated solution or, in the case of carbonate-
• apatite, by the active replacement of carbonate with phosphate in
previously formed minerals. These minerals represent the natural
I reservoir of phosphate in the environment.
The form of phosphate in solution is controlled by the pH.
• The log concentration of phosphate versus pH is shown in Figure
• XlX-i. It can be readily seen than at normal pH levels (6-8) the
greatest percentage of the phosphate will be present as H«PO or
299
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HPO . This relationship is controlling regardless of the "form
Chlor Apatite Ca, (pOJ3
Hydroxy Apatite Ca (P°A)O OH
Carbonate-Apatite (Francoilite) Ca (PO , CO , OH) F
Anion Forms
Monbasic Phosphate H?POA
Dibasic " H P0.
4
Tribasic " PO"
4
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in which the phosphate is introduced, except for the tripoly and
pyrophosphates. In these cases, the kinetics of conversion to
orthophosphate are low enough to permit residual concentrations
of the compounds. It is the fully dissociated P0,~ form which •
TABLE XIX-1
I
NATURALLY OCCURRING INORGANIC FORMS OF PHOSPHORUS (66,73)
Mineral Forms Chem-Formula •
Fluor-Apatite (Apatite) Ca
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Pyrophosphate P?^-, •
Hexametaphosphate (P0n),
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Tripolyphosphate p^°in •
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ill ii ill lit
LOG CONCENTRATION DIAGRAM DESCRIBING PHOSPHATE EQUILIBRIA
FIGURE XIX - i
301
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is reported to be the most readily available for biological utili-
zation (72,73).
Phosphorus is found in untreated domestic wastewaters at con-
centrations ranging from 5 to 40 mg/1 with typical wastes averaging
about 10 mg/1 (as P) (19,67). Typical secondary treated municipal
effluents contain from 1 to 12 rag/1 (as P) (19,26,67). Phosphorus
removal in secondary plants depends upon the type of treatment .
Industrial sources of phosphorus are listed in Table XIX-2.
Other sources of phosphorus in surface waters include agricultural
runoff from feed lots, fertilized acreage and natural organic
decayed matter found in general erosion materials.
ENVIRONMENTAL EFFECTS OF PHOSPHORUS
Effects on Man
For many years polyphosphates have been used in low concentra-
tions in boiler waters to reduce corrosion and control scale. At
these low concentrations phosphorus is not known to have any physio-
logical significance. Phosphorus compounds are, however, undesirable
in high concentrations (450 mg/1) in water used to prepare foods.
They have a buffering action on the stomach acids (6) . Hexameta-
phosphates are converted to phosphoric acid in the low pH environ-
ment of the stomach (see Figure XIX-1) . High concentrations can
cause both vomiting and diarrhea. The safe oral dose is recommended
not to exceed 50 mg/1. Other detrimental effects of phosphorus in-
clude interference with coagulation and f locculation. As noted in
302
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TABLE XIX-2
SOURCES OF PHOSPHORUS IN WASTEWATERS
Industrial Source
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Potato Processing I
Fertilizer Manufacture
Metal Finishing Wastes •
Flour Processing _
Dairy Wastes (PO°IO)
Commercial Laundries (PO ~ (PO.),) •
4 j D •
Slaughterhouse Wastes (P 0 _)
Cooling Water (P0,=) I
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Boiler Slowdown (H2PO , PO, )
Petrochemical Plants
Detergent Manufacture (PO,~, P70 )
Textiles (PO,~)
Tanneries (P(l,~) •
Baking Powder Manufacture (H^PO. )
Medicine (Laxative)(HPO ~) •
Photography (PO ~) •
Paper Mills '~" =^
Water Treatment (PO , P 0 , P.,0 ) •
Oil Well Drilling (P00 )
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the section on surfactants, tripoly-and pyrophosphate concentra-
tions of 0.5 to 1.5 mg/1 are known to have interfered with water
treatment (66).
Phosphates are also noted for affecting the aroma of beer
and its resistance to bacterial action (66).
Effect on Irrigation
Phosphorus is an essential nutrient for plants. Because of
this phosphorus has a generally beneficial effect at levels normal-
ly found in treated effluents or in surface streams. However,
waters having a phosphorus concentration of 6C mg/1 can contribute
to iron chlorosis in blueberry plants (66).
fl Effect on Fish and other Aquatic Life
Phosphate is of little importance as a compound directly toxic
• to fish and aquatic life. Levels necessary to produce a direct
toxic effect are several orders of magnitude higher than the levels
• which would produce severe eutrophication problems. Once phosphorous
• enters the eco-system, however, it may theoretically exert an oxygen
demand of 160 mg per 1 mg of organic phosphorous prior of complete
• oxidation (6).
Elemental phosphorus is quite toxic. McKee and Wolf report
that colloidal phosphorus (as P ) has a 48-hour TLm of 0.105 mg/1
for bluegill sunfish. However, this form represents a relatively
minor percentage of normally encountered wastes.
Because phosphate is actively incorporated into the tissues
and protoplasm of all living creatures, concentration factors of
4,900-13,600 for algae, 30,000-165,000 for fish and up to 850,000
304
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for spirogyra are routinely found above the background level.
For this reason the release of radio-active phosphorus must
be strictly controlled regardless of form.
TABLE XIX-3
DIRECT TOXIC EFFECT OF PHOSPHORUS
Target Organism P-Form Cone. Level Test
Effect Ref
Man
Man
Food Crop
(Blueberry)
PO,
(P°3>4
PO,
Bluegill
450 mgm/1 Used in Buffers (6)
food prep. stomach
acid
50 mg/1 Ingestion Vomiting, (66)
diarrhea
60 mgm/1 Used as Complexed (66)
irrigation iron re-
water suiting in
iron chlor-
osis
Colloidal Immersion 48 hr. TLm=(66)
Dispersion [0.105 mgm/1]
A more widely recognized effect is the role of phosphorus as
a contributing nutrient in algae blooms. Massey and Robinson (63)
report that phosphorus is one of 15 elements which may limit growth
of algae. Other elements noted in the literature include iron,
sodium, nitrogen, carbon, potassium, magnesium, calcium, manganese,
silicon (for diatoms), sulfur (as sulfates) , and oxygen (6,63).
Of the elements listed, phosphorus and carbon are the two most
significant (63).
305
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•
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While nitrogen is significant in discharges, some algae can fix
atmospheric nitrogen, making its control as the limiting element
highly questionable.
I
It was not until works by Kuenzel , King, and Kerr and
• associates were known that carbon was openly considered a limit-
ing element (63). This is an additional reason for the effluent
• criteria recommended for BOD and SS (see Chapter III of this
• report) .
Phosphates still must be considered one of the possible
• limiting elements in algal blooms due either to their threshold
values or synergistic effects which are neither known or fully
• understood. As such, it is reported that from 0.009 mg/1 to
• 0.015 mg/1 phosphorus can be the limiting concentration (6,63).
In addition, it is stated (6) that detention of waters has been
found to reduce phosphorus concentrations. It is theorized that
this may be due to phosphorous uptake by organisms and/or by
precipitation. On the basis of data available in 1967-68 it was
recommended (6) that total phosphorus concentrations not exceed
•
0.10 mg/1 in flowing streams or 0.05 mg/1 in ponds or reservoirs
TREATMENT TECHNOLOGY-PHOSPHORUS REMOVAL
Treatment technology for the removal of phosphorus has re-
cently been reported in the literature in substantial volume. The
_
EPA has commissioned the compiling of a "Process Design Manual for
H Phosphorus Removal" by Black & Veatch, Consulting Engineers (19).
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As this manual adequately reviews the current state of the art ,
the individual mechanisms of the various processes will not be |
discussed in this report. Rather, the efficiencies and costs _
of the various methods will be emphasized with respect to achieve-
ment levels. In general, the methods which have been reported as •
effective include the following:
(1) Coagulation prior to primary clarification, utilizing •
alum and/or lime, generally known as Phosphate Extrac- _
tion Process (PEP) . '
(2) Utilization of an up-flow clarifier filtration (solids •
contact) with coagulation either before or after
biological treatment and filtration. I
(3) Post biological coagulation with alum and/or lime.
(4) Moving bed filters with coagulation. B
(5) Activated sludge and other biological processes. •
(6) Biological - Chemical treatment, i.e., the addition of
coagulants directly to the activated sludge system. •
(7) Coagulation and precipitation with metallic salts and
polyelectrolyte. H
(8) Reverse osmosis. •
(9) Adsorption on activated bentonite.
(10) Ion exchange. •
(11) Adsorption and uptake by "Activated Algae".
Removal efficiencies reported for the various procedures and |
capital costs, operation costs and amortized operation costs are •
summarized in Tables XIX-4 and XIX-5 respectively.
307
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SUMMARY AND RECOMMENDATIONS
• In General the following statements can be made relative to
phosphorus and phosphates in the environment.
• 1. There are both natural and man contributed sources of
_ phosphate in nature. There can be no zero background
™ for phosphorus because it is an essential nutrient of
• all plant life. In Those areas where the water is devoid
of phosphorus little aquatic life will be present.
• 2. The largest contributors of phosphorus to surface and
ground waters are domestic wastewaters and agricultural
™ runoff. Domestic wastewaters contain between 5 and 40
• milligrams per liter and average about 10 milligrams per
liter. Concentrations of phosphorus in agricultural
• runoff can be several hundred milligrams per liter.
3. In the normal pH range of most streams (6 to 8) the major
• ionic forms are dibasic phosphate and monobasic phosphate,
form in which the phosphate was introduced into the water.
• 4. Phosphate concentrations are of more significance to fish
and aquatic life than to man, animals and plants. Fish
| have demonstrated a 48 hour TLm to 0.105 mg/1 of elemental
• colloidal phosphorus. On the other hand, phosphate concen-
trations below 50 mg/1 do not appear to have any significant
• effects on man, animal or plants. Some forms of aquatic
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that is, H?PO, and HPO . This is irrespective of the
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life are capable of concentrating phosphorus up to
850,000 times the background concentrations of the |
aquatic environment. mm
5. High concentrations of phosphate may interfere with
water treatment. Concentrations as low as 0.5 to 1.5 •
milligrams per liter have been demonstrated to inter-
fere with treatment. |
6. The nature of algal blooms is still being investigated _
and debated. Phosphorus and carbon are widely recognized
as being important limiting elements with respect to II
algae blooms. Concentrations as low as 0.009 milligrams
per liter of phosphate have been reported as limiting to I
algal growth. Other studies indicate somewhat higher
concentrations to be the limiting level of phosphate. •
7. Current technology can effect a reduction of phosphorus •
to 1-2 mg/1 as phosphorus. The cost of removing phosphorus
varies with the process and the size of the plant. Several •
processes have been shown to be effective.
On the basis of the present information, a unifrom effluent •
criterion is difficult to justify at this time. It is recommended, •
however, that where stream and impoundment levels are at or above
0.10 or 0.050 milligrams per liter respectively that all municipal •
and industrial discharges in the zone of influence uniform effluent
criterion of 2.0 mg/1 as phosphorus. 0
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When the EPA adopts a policy that all municipal discharges,
as well as industrial discharges, must meet a uniform effluent
• criterion for phosphorous, a 2 mg/1 (as P) concentration is
recommended. Until such a policy is developed, it is preju-
| dicial to levy an effluent criterion on either industry or domestic
M discharbes alone. The phosphorus limitation, like all criteria,
must be equally applied to all effluents.
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CHAPTER XX-SELENIUM
Selenium is primarily found in soil as elemental selenium, ferric
selenite Fe?(SeO_)_, calcium selenate Ca~ (SeO,).,, and organic selenium
compounds. Selenium is often found in association with sulfur. Con-
centrations as high as 30 mg/kg of selenium have been found in the
soils of South Dakota and Wyoming.
Lakin (104) states that, "The selenium content of surface waters
is a function of pH of the waters as well as its presence in the drain-
age system Selenium is quantitatively precipitated as a basic ferric
selenite at pH 6.3-6.7. At a pH of about 8, selenite may be oxidized
to the soluble selenate ion." Table XX-1 shows the naturally occurring
forms of selenium in the environment with some indication of the magni-
tude of their abundance.
Selenium is used industrially in its elemental form and as several
salts. Table XX-2 shows the industrial sources of selenium. Selenium
may also be expected in trace quantities from municipal sewage contain-
ing industrial wastes, as well as directly from industrial waste dis-
charges. A review of the literature has indicated only a few concentra-
• tions of selenium which may be found in various wastewaters. A secondary
sewage effluent has shown 0.023 mg/1 of selenium (104).
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TABLE XX-1
NATURAL SOURCES OF SELENIUM IN THE ENVIRONMENT (104)
Sources
Crustal Abundance
Soil
Sea Water (ave.)
River Water (ave. of 9)
Goal
Petroleum
Air (U.S.A.)
Form
elemental
ferric selenite (pH 4.5-6.5)
calcium selenate (pH 7.5-8.5)
organic
H Se (Bacterial Action)
Diethyl Selenide Gas
Se and SeO,, particulate
from (coal & oil uses)
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Quantity
0 . 5 ppm
0.1-1,200 ppm
0.00009 mg/1
0.0002 mg/1
3 ppm
0.2 ppm
8 million
released/yr.
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TABLE XX- 2
INDUSTRIAL SOURCES OF SELENIUM
1) paint manufacturing
2) dye manufacturing
3) glass production
• A) rectifier and semiconductor manufacturing
5) photoelectric cells and other electrical apparatus production
• 6) supplement to sulfur in the rubber industry
• 7) component of alloys
8) insecticides manufacturing
9) wastewaters from copper ore refineries
10) incinerator quench water used to cool fly ash when paper is
1i burned (0.005-0.023 mg/1) [76]
11) incinerator residue quench water. (.003 mg/1) [76]
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ENVIRONMENTAL EFFECTS OF SELENIUM
municipal waste discharges.
Effect on Man
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Selenium is an essential nutrient to man and other animals in trace
quantities but it is detrimental and toxic at higher concentrations.
Selenium tends to concentrate in plants and lower forms of aquatic life- •
possibly without immediate toxic effects. However, when it is ingested
by fish, man or animals, it can have toxic effects. Since the concentra- j|
tion of selenium in the soil is relatively difficult to control, it is —
important to regulate the amount of selenium in all industrial and ^
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The Drinking Water Standards (94) report that selenium is now
recognized as being toxic to both man and animals. They also report
that selenium, like arsenic, may have permanent effects. For example,
selenium is noted for increasing the incidence of dental caries in man, •
and is a potential carcinogen. As a result, in 1962 the Drinking Water
Standards' criteria for selenium was reduced from its previous value of H
0.05 mg/1 to 0.01 mg/1. Concentrations in excess of this amount were tm
determined to be grounds for rejection of the water supply. The World
Health Organization European Drinking Water Standards (1961) state an •
excessive limit of 0.05 mg/1. The USSR maximum permissible concentra-
tion for drinking water is set at 0.01 mg/1. |
McKee and Wolf (66) report, "Proof of human injury by selenium is »
scanty and definite symptoms of selenium poisoning have not been identi-
fied; but it is widely believed that selenium is highly toxic to man." •
Table XX-3 reviews the effects of selenium on man. McKee & Wolf reported
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THE EFFECT OF SELENIUM OF MAN (105)
Selenium Form Cone. Level Effect
undefined 2-4 rag/kg minimum lethal dose
undefine 5-7 mg/1 in food harmful to liver
5-7 mg/1 in water increased suscept-
ability to dental
caries, Gastro-
intestinal distur-
bances, icterus
undefined from seleniferous high rate of dental
areas caries ; tendency for
increased malocclu-
sion and gingivitis
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that mild chronic selenium poisoning has been observed in humans living
in areas where the selenium concentration of the soil is relatively high. •
They also reported that selenium, as hydrogen selenide (H_Se), at a con-
centration of 0.2 ppm, has caused toxic symptoms as an air pollutant. m
Nevertheless, it is interesting to note in the McKee and Wolf report
I
that selenium in trace amounts is known to be an essential nutrient
for animals including man although very little is known about the •
mechanisms of its beneficial action.
McKee and Wolf report that selenium salts are rapidly and efficient- £
ly absorbed through the gastrointestinal tract, and are largely excreted w
in the urine. The highest retention of selenium within the human body
is found in the liver and kidneys. Selenium appears to act by maintain- •
ing the catalytic properties of the enzyme glutathione peroxidase which
catalyzes the decomposition of hydrogen peroxide. The intake of selenium |
through food rather than water appears to be the basic problem for man. _
The extreme tolerance limit of selenium in foodstuffs is reported at ™
4.0 mg/kg with a safer limit of 3 mg/kg. The U. S. Food and Drug Ad- 9
ministration, however, has placed a "zero" tolerance limit on selenium
in fruits and other edible crops for human consumption. I
Selenium has been found to be capable of protecting rats against
mercury poisoning, a fact which is potentially encouraging to humans •
since high concentrations of selenium have also been found along with •
high concentrations of mercury in foods such as tuna fish (100).
Effect on Animal Life
As noted above, the presence of selenium in trace amounts is bene- •
ficial to animals. It is reported that a deficiency of selenium in
animal diets may result in white muscle disease, while an excess amount •
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of selenium has been known to cause "blind staggers" and "alkali disease'
I (6). A concentration of up to 24 mg/kg in the vegetation consumed by
^ livestock will produce the "alkali disease". This involves a lack of
™ vitality, a loss of hair, sterility, lameness, and possibly death from
anemia and malnutrition. Table XX-4 reviews the effects of selenium on
animal life.
• McKee and Wolf reported that any vegetation containing 5.0 mg/kg
of selenium has been found to be dangerous to livestock, while fodder
4B has been found to cause selenium poisoning with concentrations as little
IB as 1 mg/kg. They report that the tolerance limit for livestock is about
4 mg/kg in their feed.
• Chronic and acute selenium poisoning has been reported to occur
naturally among cattle, sheep, horses, pigs, and poultry where the
• selenium concentrations in the soil were naturally high. While McKee
«• and Wolf report that water containing 0.4-0.5 mg/1 of selenium is
generally non-toxic to cattle, this concentration of selenium in the
• water may contribute to selenium poisoning initiated through the feed.
Effect on Plants
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It has been reported that plants containing 4 to 5 mg/kg of selenium
are considered to induce toxic symptoms in animals (6). They indicated
that this level of selenium could result in many crops due to a selenium
• level of 0.05 mg/1 in irrigation waters.
Plants may be affected by selenium due to its presence in the soil
as well as its presence in water. Concentrations ranging from 1-6 mg/kg
have been found in the top eight inches of soil in many areas (66).
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Species
Rat
Sheep
Livestock
Mouse
Rat
Mouse
Rat
TABLE XX-4
THE EFFECT OF SELENIUM ON ANIMAL LIFE (105)
Selenium Form Cone. Level Effect
Undefined 0.012 rag/kg Near sub-threshold
Undefined 0.4 mg/kg Stimulated the inhi-
bitory process of brain
cortex up to 10-20 days
Undefined Anemia, liver damage &
icterus
Se (SeO^) 3 mg/1 for life Significant increase in
growth rate
Se (SeOl) 3 mg/1 for life Most animals died young
Se (SeO~) 3 mg/1 for life Significant decrease in
growth rate
Se (SeO°) 3 mg/1 for life Significant increase in
longevity. Increase in
serum cholesterol; no
effect on serum glucose,
blood pressure or on
aortic plaques
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The ability of plants to concentrate selenium depends on the species,
the age of the plant, the season of the year, and the concentration of
• the soluble selenate ions in the root zone of the plant the pH and
electrode potential of the soil. In soils of pH 7.5 to 8.5 selenium
| exists in the form of the selenate ion which is readily available to
_ plants (104).
McKee and Wolf report that plants under certain circumstances can
• absorb relatively high concentrations of selenium without apparent
damage to the plant itself. For example, a weed (Astragulus) can con-
• tain as much as 4,500 mg/kg of selenium. Other plants grown in selenif-
^ erous soils have been found to contain as much as 1,610 mg/kg of
™ selenium. Plants reported to have high concentrations of selenium in-
• elude wheat, up to 63 mg/kg, and onions, up to 17.8 mg/kg. Wheat has
been directly damaged by a concentration of 30 mg/kg of sodium selenate
• in the soil. The presence of chemically similar sulfates have been
found to diminish both the uptake of selenium and its toxicity to the
• plant itself.
• Effect on Fish and Other Aquatic Life
While McKee and Wolf report that generally selenium has been found
|| to be toxic to fish and aquatic life in concentrations of 2.0-2.5 mg/1,
• they also report that concentrations considered to be safe for human
beings, over a period of weeks have been found toxic to fish. While
• no concentration was specified, one would assume that this concentra-
tion is in the range of 0.01 to 0.05 mg/1. Barnhart, as cited by
Battelles' Columbus Laboratories' report (15), indicated that selenium
(possibly acting in synergism with other ions such as uranium or zinc)
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TABLE XX-5
EFFECTS OF SELENIUM ON PLANTS (66)
Selenium Concentration (mg/1)
0.00 - 0.10
0.11 - 0.20
0.21 - 0.50
Over 0.50
Remarks
No plant toxicity anticipated.
The water would be usable, how-
ever, long-term accumulations
should be carefully monitored.
Toxic accumulation within plants
is probable.
Water would be unsuitable under
any condition for plants.
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— was believed to be responsible for a fish kill in Colorado. The fish
* killed included black bullhead, bluegill, channel catfish, large-mouth-
flj ed bass, rainbow trout, white crappie, and yellow walleye. This work
indicated that arsenic was also found in the lake. Samples of the
• flora and fauna in the lake were found to contain greater than 300 ppm
of selenium. The report concluded that it was believed that selenium
• has been passed up through the food chain to the fish which then
accumulated the element to lethal concentrations.
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I TREATMENT TECHNOLOGY FOR THE REMOVAL OF SELENIUM
^ As noted by Patterson and Minear (76) very little has been report-
ed in the literature on the levels of selenium in industrial wastewaters
• or its treatment. A review of the literature (58,76) and personal dis-
cussions with Dr. O'Connor (74) indicate that the most logical and
|| efficient means of removal of selenium is by ion exchange. The litera-
^ ture, reviewed by Patterson and Minear, indicated that selenium is
most likely to occur in the anionic form in an aqueous solution.
• Linstedt (58) reported that only 0.9 percent of the selenium was re-
moved by a cation exchange column while a cation and anion exchange
• column removed 99.7 percent of the selenium concentration. Linstedt,
et al. concluded their work by stating that the most effective removal
' method for selenium, which they had investigated on a bench scale, was
• the use of a strong acid-weak base ion exchange unit. The removal
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efficiencies of the processes investigated by Linstedt et al are
summarized below in Table XX-6.
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TABLE XX-6
BENCH-SCALE REMOVAL OF SELENIUM BY ADVANCED WASTE TREATMENT (58)
Process
Initial Feed
Lime Coagulation &
Settling
Cation Exchange
Cation & Anion Exchange
Cumulative Removal by
Sand Filtration
Activated Carbon
Cation Exchange
Anion Exchange
% Removal
16.2
0.9
99.7
9.5
43.2
44.7
99.9
Concentration mg/1
Approx. 0.0128
0.0107
0.0127
0.00009
0.0116
0.00727
0.00708
0.00001
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Similarly Weston (97) recommended to the Illinois Pollution Control
Board a combined cation and anion ion exchange unit for the removal of
dissolved selenium. However, no cost data or achievable effluent con-
centrations were provided. Patterson and Minear included within their
report two figures showing the chemical and amortization costs of a
weak base ion exchange system.
Currie, in his summary, commenting on the adoption of an effluent
criteria for selenium for the Illinois Pollution Control Board (27),
made the following comment:
Because of the toxicity of selenium, it it desirable to adopt an
effluent standard, even in the absence of conclusive evidence as
to the removal technology, in order to protect legitimate water
uses.
Dodge testified that the very strict 0.01 unit standard was obtain-
able. Since a somewhat higher level is acceptable for aquatic life,
Dodge suggested the standard of 1.0 units, recognizing both that
higher control may sometimes be necessary to protect public water
supplies and that we may later discover, in a variance proceeding,
more information as to the treatability that may result in a re-
examination of the standard.
As reported in Patterson and Minear, the work of Linstedt and his
co-workers indicated that the common method of lime coagulation, settling,
and sand filtration was found to be ineffective in removing selenium
from the wastewaters investigated. On the other hand, discussions with
Dr. O'Connor (74) indicate that one of the co-authors of the original
work, Carl P. Houck, reported that the precipitation of selenium has been
effective. According to O'Connor, Houck's article reported the recovery
of selenium by its adsorption on a ferric hydroxide sludge at a pH of 8,
and by the utilization of ferric alum as a coagulant. Other methods
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proposed by O'Connor, which bear investigation for selenium removal ^
include: precipitation with a ferric salt, ion exchange on duplicate *
matter such as clay, reverse osmosis, and distillation. V
It is apparent that little full-scale work on selenium removal has
been reported in the literature. On the basis of the bench-scale work, I
the question remains as to what final effluent level can be obtained at
higher initial concentration.
SUMMARY AND RECOMMENDATIONS
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1. It is apparent that selenium is both an essential nutrient to
man and other animals in trace quantities, and is detrimental
and toxic at higher concentrations.
2. Selenium is found naturally in the soil and in water and V
artificially in industrial and municipal discharges. It is
capable of being concentrated in plants and lower forms of •
aquatic life, possibly without immediate toxic effects. How- ^
ever, upon ingestion and accumulation in fish, man and animals, ~
toxic concentrations are reached. This is a major hazard of •
selenium toxicity to man.
3. Selenium is also toxic to plants and fish directly, but at •
higher concentrations.
4. Bench-scale treatment has reduced selenium from an initial con-
centration of approximately 0.012 mg/1 to a final effluent of
less than 0.1 ug/1 by anionic ion exchange.
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• 5. While effluent levels have not been reported, it appears that
selenium may also be removed from wastewaters by coagulation
fl with ammonia hydroxide or ferric alum at a pH of approximately
M 8. The selenium ion is removed with the ferric hydroxide pre-
cipitate.
• 6. As the concentration of selenium in the soil is difficult to
control, especially when it is due to natural causes, it is
| of extreme importance to control the amount of selenium in all
• industrial and municipal waste discharges.
It is recommended that a uniform effluent criteria of 0.01 mg/1
• be adopted at this time. It is further recommended that the investiga-
tions and literature review of the treatment technology for the removal
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of selenium from wastewaters be continued.
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CHAPTER XXI-SETTLEABLE SOLIDS
At one time settleable solids were discharged to waters
mostly because no treatment was provided. Today, any plant
• providing primary treatment will remove most of the settleable
fractions. More insidious than the deliberate discharges of
£ untreated wastes is the uncontrolled discharge of urban and
M farm runoff resulting from a myriad of projects. Table XXI-1
is a compilation of the sources of settleable solids.
• Settleable solids may be contributed in discharges from
both municipal and industrial waste treatment facilities. They
| include inorganic and organic materials. Inorganic components
_ may include but will not be limited to: sand, silt, and salts
from natural runoff and mining operations; gravel washing, dust,
I and fines from coal washeries; and loose soils, from agricultural
land, highway runoff, and construction projects. The organic
• fraction would normally be expected to include settleable
^ materials such as grease, oils, tars, fats, fiberous material
™ such as you might expect from paper mill, and synthetic plastic
• production; saw dust, hair, grease, and other various settleable
materials from sewers. In addition, any treatment process utiliz-
ing clarification and precipitation of metallic hydroxide or
carbonate sludges, will also contain settleable solids if not
properly clarified.
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TABLE XXI-1
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SOURCES OF SETTLEABLE SOLIDS
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1. Natural Runoff
2. Mining Operation •
3. Sand and Ground Quarries •
4. Highway and Construction Projects
5. Combined and Storm Sewer Discharges I
6. Untreated Industrial Wastes
7. Untreated Municipal Wastes
8. Filter Backwash
ENVIRONMENTAL EFFECTS OF SETTLEABLE SOLIDS
I
Settleable Solids have also been shown to contain high con- •
centrations of trace metals which, if not removed, can be very
toxic to the beneficial uses of the water. Various investigations •
reported in other sections have shown that some of these trace •
metals once absorbed upon settleable solids, and particulate
matter, may at a later date be leached from the solids by changes •
in water quality and/or by the benthic aquatic life or the biota
of the receiving water. |
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Effects on Fish and Aquatic Organisms •
Settleable solids have adverse effects on fisheries by cover-
ing the bottom of streams or receiving water with a blanket of •
material that destroys both the bottom flora and fauna, and the
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• strata necessary for the spawning of fish. These deposits may
contain organic material which depletes the oxygen supply,
• creating an anaerobic condition which causes production of
hydrogen sulfide, carbon dioxide, methane, and other gases (6).
TREATMENT TECHNQLOGY-SETTLEABLE SOLIDS REMOVAL
I
It has been well documented that adequate clarification will
I remove settleable solids from both industrial and municipal waste
treatment facilities. The clarification process has also been
considered to be a basic primary step of treatment and, therefore,
can be considered as a minimum step in treatment well within
economic means.
It is recommended that a uniform effluent criteria for
settleable solids, as specified in "Standard Methods", not exceed
I 0.2 ml/1. This criteria will meet the minimum guidelines as
established in Water Quality Criteria (6).
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CHAPTER XXII - SILVER
Silver is found naturally in its metal state, combined with ores,
or as a salt. As an ore, silver appears as Argentite, Ag^S; Horn silver,
AgCl; Proustite, Ag^AsS ; and Pyrargyrite, Ag3SbS3 (66). Silver is
• also reported to be a by-product in the mining of lead, copper and
zinc (74). The nitrate salt is the most soluble form followed by the
J[ sulfate. The chloride, sulfide, phosphate and arsenate salts are
practically insoluble. Table XXII-1 lists some natural and industrial
sources of silver.
Table XXII-2 lists industrial uses of silver. Silver has been
used as a disinfectant, especially in Europe. While 0.015 mg/1 of AgO
• was reported as effective on some bacteria, it reacts slowly and is ex-
pensive (37). Concentrations of 20 mg/1 had no effect on some viruses
™ and 1000 mg/1 was non toxic to Endameoba histolytica. It was reported
• as ineffective and hazardous for swimming pool use (24,37).
Nemerow (14) indicated that due to the value of silver most in-
• dustries will utilize complete recovery processes t3 remove the silver
from the waste prior to discharge to any receiving waters. He cited
™ the examples of one silver plating plant spending $120,000/year to re-
• cover $60,000 worth of silver by evaporation. Eastman Kodak companies
recover 100% silver by the common methods of metallic replacement,
• electrolysis and chemical precipitation.
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KNVI KONMENTAL EFFECTS OF SILVER
As diacuased in the Drinking Water Standards (94) , the intention-
al addition of silver to water as a disinfectant is of primary
concern. The chief effect on man is cosmetic, consisting of a per-
manent blue-grey discoloration of the skin, eyes and mucous membranes
(argyria) . It has been shown that plant and marine life are capable
of concentrating silver above the ambient concentrations found
TABLE XXII-1
NATURAL SOURCES OF SILVER
Source Concentration Reference
Sea Water 0.0003 mg/1 (66)
Fresh Water, N.E. Basin 0.0019 mg/1 (mean) (59)
Municipal Water Supplies Up to 0.05 mg/1 (66)
INDUSTRIAL SOURCES OF SILVER
Source Concentration Reference
Industrial Waste Water 130 - 564 mg/1 (76)
Silver Plating 51 mg/l(@0.5 gph)* (14)
Rinse Waters 255 mg/l(@2.5 gph)* (14)
* Drag-out rates
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TABLE XXII-2
USES OF SILVER
Form Use Reference
Ag, metallic Jewelry (66)
Silverware
Alloys
H
Electroplating
• Food & Beverage Industry
AgNO_ Photographic Industry (66)
Ink Manufacturing
» Electroplating
* Coloring of Porcelain
I Antiseptic
Agl Cloud Seeding (74)
I AgO Disinfectant (24,37)
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in the water (6). Vegetables cooked in silver bearing waters have
also been found to concentrate silver (6). Silver is also toxic to
fish and aquatic life.
Effect on Man
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The chief effect on man is argyria. While the amount of colloi-
dal silver required to produce argyria is not precisely known, the •
amount of silver from injected Ag-arsphenamine which produces argyria
is any amount greater than 1 gram of silver or 8 grams of Ag- •
arsphenamine. The Drinking Water Standards point out that most common _
salts of silver may produce argyria when ingested by the mouth or ™
through injection. It was also noted that individuals concurrently •
receiving bismuth medication have been found to develop argyria more
readily. •
The Drinking Water Standards state that silver has an affinity
for elastic fibers. It is primarily excreted from the body by the ™
liver. Silver within the body is chiefly transported by the blood •
stream in which it is carried by plasma proteins in the red blood
cells. Once silver is fixed in the body tissue, negligible excretions •
will occur through the urine. Table XXII-3 shows the effects of
silver on animals. m
On the assumption that all silver ingested is deposited in the •
integument, the authors of the Drinking Water Standards calculate
that a concentration of 0.01 mg/1 could be ingested for a life time •
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at a rate of two liters o> water per day without reaching the concen-
• tration of 1 gram of silver. Similarly, they stated that 0.05 mg/1
of silver could be consumed for 27 years without exceeding the silver
• deposition of 1 gram. McKee and Wolf point out, however, that this
• does not allow for the consumption of silver through foods such as
mushrooms, or for concentration in cooked foods as discussed above.
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Effect on Plants
• Both the Drinking Water Standards and the work of McKee and Wolf
indicate that silver is concentrated within food. In particular,
• McKee and Wolf note that mushrooms are known to have a very high con-
centrations of silver. The Drinking Water Standards report that any
^ vegetable belonging to the family Brassicaceae such as cabbage, turnups,
• cauliflower and onions is capable of concentrating silver which might
be found in the cooking water. As a result, the silver content of
• several liters of water could be ingested through the consumption of
these vegetables when cooked. It was also pointed out that there is
a probably increase in the absorbtion rate of silver in the presence
of sulfur compounds in food.
Effect on Fish and Other Aquatic Life
The toxicity of silver, silver nitrate, and silver sulfate has
been reported in the literature. It has been summarized in Table
XXII-4.
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In general, silver salts are reported as toxic to fish
and aquatic life at concentrations ranging from 0.003 to 0.4 mg/1.
It appears that most forms of fish and aquatic life are capable of
surviving a concentration of less than 0.1 mg/1 for at least one
day. Some species
of marine animals and plants are capable of con-
centrating silver as much as 1-3 mg/1 from a
of 0.0003 mg/1. (6)
It, therefore, appears
silver may be concentrated in fish and other
sea water concentration
logical to assume that
aquatic life. If this
is true, man and other mammals can then receive silver not only by
direct consumption
grown or cooked in
Species
Man
Man
Rat
Rabbit
of water, but also through the ingestion of food
silver bearing water.
TABLE XXII-3
EFFECTS ON ANIMALS
Concentration (or Dose)
1 g Ag, injected
10 g Ag, ingested
400-1000 ug/1
0.25 mg/kg/day (11 mo.)
342
Remarks Reference
Argyria (66)
Lethal (105)
Pathologic changes (94)
of kidneys, liver &
spleen
Effect on immunologi- (105)
cal capacity, condi-
tioned reflexes,
vascular , nervous fie
glial tissue of
encephalon & medulla
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
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1
1
1
1
1
•1
1
1
^•P
1
1
1
1
1
1
1
1
TABLE XXII-4
SILVER TOXICITY TO FISH AND
Species Ag Concentration Form
mg/1
Salmon fry 0.04 AgNCL
Salmon fry 0.44 AgNO.,
Young eels 0.2 AgNO_
Guppies 0.0043 Ag
Sticklebacks 0.003 AgNO
Sticklebacks 0.004 AgNO_
Sticklebacks 0.01 AgNO.,
3
Sticklebacks 0.1 AgNO
Daphnia magna 0.1 Ag
Daphnia magna 0.03 Ag
Daphnia magna 0.0051 AgNOQ
- — - — • •- — ,3
Tadpoles 0.1 Ag
Lebistes retiolatus 0.01 Ag
Adult barnacles 0.04 Ag SO,
343
AQUATIC LIFE
Remarks
Some killed
Killed
Max tolerated
24 hour
LD50
Lethal @ 15-18°C
1 wk survival
4 days survival
1 day survival
Killed
Med. threshold
Immobilization
Killed
Killed
90% killed
Reference
(66)
(66)
(66)
(66)
(15,66)
(66)
(66)
(66)
(15)
(15,66)
(15,66)
(15)
(15)
(15)
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behind.
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TREATMENT TECHNOLOGY - SILVER REMOVAL
Due to the value of silver, most of the treatment technology for |
its removal from waste waters is centered around its recovery. In «
addition to the previously mentioned recovery value of silver noted
by Nemerow (14), Patterson and Minear (76) report that even dilute tt
wastewaters ranging from 50 - 250 mg/1 of silver have a net recovery
value of $1.60 to $9.00 per thousand gallons. The basic methods for I
the recovery of silver fall into the four broad categories of precipi- _
tation, ion exchange, metallic replacement, (reduction exchange) and ™
electrolytic recovery. Their respective efficiencies are summarized B
in Table XXII-5.
Precipitation I
Precipitation of silver from solution normally utilizes the low
solubility of silver chloride. Patterson and Minear report that •
silver chloride has a maximum solubility of 1.4 mg/1 (as silver ion) •
provided silver chloride complexes are not formed. As most other metal
ions in conjunction with chloride are soluble, it allows for silver •
recovery from mixed metal waste without prior waste stream segrega-
tion. Under alkaline conditions, the precipitation of hydroxides of •
other metals occurs along with silver chloride. Patterson and Minear •
report that acid washing other precipitates allows for the removal
of the contaminating metal ions, leaving the insoluble silver chloride •
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As reported by Nemerow, silver is often found in cleaning wastes
• in conjunction with cyanide. Cyanide must be removed prior to the
precipitation of silver as a silver chloride. This may be achieved
• by oxidation of cyanide with chlorine which then releases chloride
• ions into solution allowing for the precipitation of silver chloride
directly. Patterson and Minear pointed out, however, that in the
•
event that cyanide concentrations greatly exceed that of silver, high
chlorine concentrations may result from the cyanide oxidation, there-
I by greatly reducing the effectiveness of this removal procedure.
mm With respect to recovery of silver from photographic solutions,
Patterson and Minear described the use of magnesium sulfate and lime
• in solutions containing high levels of organic acids, the use of sul-
fide to precipitate silver in the form of silver sulfide, and the use
| of hydrosulfide to precipitate both free silver and silver sulfide.
m Ion Exchange
" As one would expect due to the selective solubility of various
B silver salts, ion exchange has been found very useful in the recovery
of silver from dilute photographic wash waters and plating rinse
| waters. (See Table XXII-5)
Patterson and Minear reported the use of a series of cation and
»• anion exchange columns for the recovery of silver cyanide from plat-
• ing rinse waters. While no final effluent levels were given, they
did report that for one plant approximately 280 mg of silver were re-
• covered for each liter of wastewater passed through the ion exchange
columns .
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Method
TABLE XXII-5
TREATMENT FOR SILVER IN WASTEWATER
CONTAINING CYANIDE
Silver Silver
Concentration mg/1 Effluent Concentre- Ref,
tion mg/1
*Chl & P, bench scale
Chi & P, full scale
Chi & P, full scale
Chi, pH to 6.5,coag.
with ferric chloride
& lime, settle,pH to
8.0 & resettle)
Chi & pH (coag. with
ferric chloride &
lime & settle)
Ion Exchange
(a) Cation
(b) Anion & Cation
Ion Exchange
Metallic Replacement
*Chl - Chlorination
P - Precipitation
105-250
130-585
0.7 - 40
0.055
0.055
1-3.5
0.0-8.2
1-3
0.1 or less
0.1
0.0078
0.0046
Trace
95% Removal
(76)
(76)
(97)
(76)
(26,97)
(58)
(58)
(59)
(76)
346
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•
•
•
•
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One work reviewed by Patterson and Minear indicated that there
may be problems in recovering silver from resins, making the re-
covery of silver by ion exchange uneconomical for photographic waste.
Another author indicated the use of an electrolytic process to re-
move silver from the ion exchange resin regenerant. (76)
I
Metallic Replacement
Metallic replacement, otherwise known as reductive exchange,
consists of the precipitation of silver onto another metal. In order
to form the silver precipitate, the silver ion must be substituted
by another metal ion. Iron and zinc are common substitutes. Nemerow
(72) reported that this is one of three methods recommended by the
Eastman Kodak Company for the recovery of silver from photographic
waste. Similarly, Patterson and Minear report the use of metallic
replacement by silver plating plants. However, as the silver is re-
placed, the zinc and iron released must be removed from the waste-
ap
water by further treatment
Electrolytic Recovery
Nemerow also reported electrolytic recovery as a recommended
method by Eastman Kodak for the recovery of silver. Patterson and
• Minear report that hagh wastewater concentrations are needed for the
method to be effective. They indicated that most silver bearing
wastewaters do not have sufficient concentration of silver to make
the process feasible. They stated that while some units have been
347
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effective at silver concentrations ranging from 100 to 500 mg/1,
they have only noted consistent success in reducing silver from •
concentrations ranging from 5000 mg/1 down to 500 mg/1. The cost
of such a unit has been estimated to be as little as 400 dollars. •
In summary, it is apparent that the value of silver makes it •
amenable to recovery processes at a net gain for the industry. Due
to the low capital cost, it would appear that electrolytic recovery j§
would be a first step for very high concentrations of silver waste- M
waters. Thereafter, the use of ion exchange, or precipitation with
the chloride ion, would appear to be more feasible. While the effi- •
ciency of full scale ion exchange unit has not been reported in the
literature reviewed, it has at least been shown in bench scale tests j[
that very low effluent levels are obtainable. One must consider, _
however, the additional treatment steps which may be necessary for
the destruction of the regenerate. This also appears to be the majbr I
problem for the metallic exchange treatment process. Generally, the
recovery of silver by precipitation with chloride ion would appear I
the most feasible and it has been shown on the full scale process to _
achieve a final effluent concentration of less than 0.1 mg/1. Table ™
XXII-6 reviews the costs for treatment of silver in wastewater. •
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Method
TABLE XXII-6
COST FOR TREATMENT OF SILVER IN WASTEWATER
CONTAINING CYANIDE
Cost in $10QO/mgd
P & S (chloride)
Chls P & S (ferric
chloride and lime)
Ion Exchange
Electrolytic Re-
covery
P = Precipitation
S = Sedimentation
Chl= Chlorination
$1000
$ 610
$210
$710
$.18/lb Ag recovered
$1.75
$400 capital cost
(rate of flow not specified)
Reference
(97)
(97)
(97)
(97)
(76)
(76)
(72)
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SUMMARY AND RECOMMENDATIONS
350
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On the basis for the above discussion and literature review, I
the following conclusions are drawn:
(1) Silver is found in the marine environment due to natural •
causes. Marine plants and animals contain silver above
the ambient concentration of their water environment.
(2) Considering only the consumption of silver in drinking •
water, the safe concentration of silver should be less
than O.lmg/1. |
(3) Some vegetables are capable of concentrating silver from M
water in which they are cooked, thereby providing an
additional source of silver to man. Mushrooms concen- •
trate silver during growth.
(4) A silver concentration above O.lmg/1 is toxic to fish £
even for short durations. A silver concentration as .
low as 0.003 mg/1 is toxic to stickleback fish under ™
extended exposure. I
(5) While industrial waste concentrations may be relatively
high, the value of silver makes removal by recovery I
economically attractive. Silver may be recovered by
precipitation with the chloride ion, ion exchange, metallic •
ion exchange, and electrolytic recovery. Due to its low •
capital cost, electrolytic recovery is most advantageous
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for concentrations of silver in the range of 5000 mg/1.
| For silver bearing wastewaters with a silver concentra-
• tion from less than 5 to 600 mg/1 the most effective
treatment process appears to be precipitation and re-
I covery by the chloride ion. At concentrations in the
range of 50 to 250 mg/1 silver has a net recovery value
| in the range of $1.60 to $9.00 per thousand gallons of
_ wastewater.
(6) Treatment of silver bearing wastewaters by chlorination,
• ferric chloride coagulants, pH adjustment, and settling
is capable of obtaining a final effluent concentration
| of less than 0.1 mg/1.
_ (7) Due to the value of the recovered silver, the next cost
of silver recovery and treatment is substantially less
• than that of treating any other metal.
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On the basis of the above conclusions, it is recommended that an
interim effluent level be adopted at 0.1 mg/1. It is recognized
that this level is above the maximum level for drinking water of 0.050
• mg/1 and that, possibly, ion exchange is capable of obtaining a 0.050
mg/1 effluent level as a maximum condition. On the basis of the current
• data available however, the interim level should be adopted immediately.
• As soon as a methodology is available for a 0.050 mg/1 effluent level,
such a level would be recommended. In all cases, a final objective of
• 0.010 mg/1 should be kept in mind.
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CHAPTER XXIII SURFACTANTS
H Surfactants are synthetic organic chemicals which have a high
residual water affinity at one end of the molecule and a low
• residual affinity at the other. In discussing surfactants it
is actually the methylene blue-active substances to which this
9 chapter is addressed. These include not only the well known
• alkyl benzene sulfonates (ABS) and linear alkyl sulfonates
(LAS), but many inorganic and organic compounds which may
• interfere with methylene blue. According to the 13th Edition
of Standard Methods (1), "Organic sulfonates, sulfonates,
• carboxylates, phosphates , phenols - which complex methylene
• blue - and inorganic cyanates, chlorides, nitrates, and thiocyan-
ates - which form ion pairs with methylene blue - are among the
• positive interferences. Organic materials, especially amines
which compete with the methylene blue in the reaction can cause
I low results. Positive errors are much more common than negative
• when determining anionic surfactants in water."
Common sources of ABS and LAS are shown in Table XXIII-1.
• While many major industrial sources exist, municipal sewage
contains a significant amount of surfactant.
| In 1965, industry responded to the pressure to improve the
_ treatability of surfactants by switching from ABS to LAS. The
* basic difference between ABS and LAS is the organic structure
H and, thereby, the biodegradability. ABS consists of a branched
alkyl group generally attached to a non-terminal carbon which is
• more difficult to decompose through biological means than LAS
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which has
a straight chain alkyl group.
TABLE XXIII-1
MAJOR SOURCES OF SURFACTANTS AND REPRESENTATIVE CONCENTRATIONS (59)
A. Major
Sources
Laundries
Car washes
Textile industry
Tanneries
Canning operations
General industrial clean-up operations
Municipal wastes
B. Commonly Found ABS Concentrations in Water
AGENT
ABS
ABS
ABS
ABS
ABS
ABS
LAS
Source Location Concentration
Detergent - industrial waste 0.6 mg/1
Surfactants Italy-surface 3.5-100 mg/1
waters
Anionic detergent Czechoslovakia .5 mg/1
Synthetic detergent Wisconsin well 10 mg/1
Synthetic detergent River and water 0.14 mg/1
supplies in 32 (average)
U. S. cities
Sewage In various U.S. 4-45 mg/1
cities
Sewage U.S. Cities 1-15 mg/1
353
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ENVIRONMENTAL EFFECTS OF SURFACTANTS
Effect on Man
With respect to effects on man, Borneff (as reported in
• McKee and Wolf (66)) indicates that water supplies containing
synthetic detergents are capable of dissolving carcinogenic
• compounds. Borneff concluded, "Drinking water obtained from
_ rivers subject to contamination with wastewater containing
™ detergents must be considered injurious to health" (66).
• Volume 1 of the Water Quality Data Book (59) states that the
maximum ABS concentration which produces no harmful effect in
• mammals over long periods is 0.5 mg/1. This concentration also
produced no organoleptic effects when administered for long
• periods. The major difficulties created by detergents and other
• surfactants in domestic water supplies include those of foaming,
turbidity, interference with treatment, and the production of
• tastes and odors. Under favorable conditions a concentration of
0.5-1 mg/1 of surfactants may cause a light foaming condition.
• It is interesting to note that the tendency of ABS to cause foam-
• ing is greatest in clean water and decreases progressively as
the pollutional load is increased. Similarly, the foaming power
• and stability of the foam are greater at a pH of 3 and of 9 than
near neutrality (66).
Synthetic detergents in general, at a concentration of 3 to
•| 5 mg/1, have been found to interfere with coagulation and floe
formation at water treatment plants (66).
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With respect to taste and odor conditions, an off taste in
clean water has been reported in the ABS range of 1 to 40 mg/1.
The work of Filicky et al . is summarized in Table XXIII-2 indicates
the minimum perceptible (taste and odor) concentrations for various
surface active agents. It is apparent that the minimum perceptible
concentration varies with chemical compositions of the surfactants
in solution. Chlorination of waters containing detergents may
accentuate the unpleasant tastes and odors (66) .
TABLE XXIII-2
MINIMUM CONCENTRATION OF A DETERGENT REQUIRED TO PRODUCE A PERCEP-
TIBLE TASTE AND ODOR, ALSO, TASTE AND ODOR THRESHOLD VALUES OF A
5 mg/1 DETERGENT CONCENTRATION (AFTER FILICY , et al.) (66).
Minimum Threshold
Concentration Value of Type of
Surface-Active Perceptible 55 mg/1 Taste or
Agent (mg/1) Concentration Odor
Taste Results
Alkyl aryl sulfonate 0.6 8 Limey, chemical
Alkyl aryl sulfonate 0.6 13 Chemical, soapy
Alkyl sulfate 3.0 2 Solvent
Alkyl sulfonate 1.4 4 Bitter, soapy
Sulfonated amide 2.5 2 Chemical, soapy
Odor Results
Alkyl aryl sulfonate 0.7 7 Limey, chemical
Alkyl aryl sulfonate 0.3 I/ Soapy
Alkyl sulfate 0.2 25 Aromatic, solvent
Alkyl sulfonate 0.3 21 Kerosene, soapy
355
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1
1
1
1
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1
1
1
1
1
1
1
1
1
1
1
1
1
TABLE XXIII-2 (cont)
Minimum Threshold
Concentration Value of Type of
Surface-Active Perceptible 55 mg/1 Taste or
Agent (mg/1) Concentration Odor
Sulfonated amide 2.0 3 Chemical, soapy
Effect on Domestic Animals and Wildlife
McKee and Wolf indicate that water containing surfactants has
been found to dissolve the protective oil coating on water-fowl, there-
by causing the feathers to become water-logged. They report that
livestock will refuse to drink water containing surfactants. Small
doses of surfactants put in the water supply of poultry is believed
responsible for a rapid weight gain or loss; for example, a concen-
tration of 5 mg/1 sodium oronite was reported to give a 5 percent
increase in the weight of baby chicks. Water Quality Data, Volume 1,
lists surfactants within the acute toxicity ranking of organic
chemicals found in fresh water. These values are tabulated in
Table XXIII-3 according to their effect upon mammals.
Effect on Plant Life
McKee and Wolf found there were conflicting opinions as to
the effects of surfactants on plants. One report they studied
noted that a coating of LAS has a harmful effect upon the develop-
ment of spinach, carrots, endive, lettuce and tomatoes. This was
reportedly caused by a disturbance of the humidity balance within
the soil, which allowed the soil to drain too rapidly. However,
356
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a second report showed that surfactants are believed to promote
water retention and retard penetration. On the basis of this
conflict, no immediate conclusions can be drawn regarding the
effects of surfactants on plant life.
Water Quality Criteria (6) indicates that within the marine
environment detergents have been found to be more toxic in saline
waters than in either fresh waters or tidal estuaries. The
photosynthesis of marine kelp has been reported to be decreased
by 50 percent after a 96 hour exposure to a surfactant concentra-
tion of 1.0 mg/1.
TABLE XXIII-3
SURFACTANT TOXICITY TO MAMMALS (66)
Species
Human
Human
Dog
Pigs, young
Pigs, young
Pigs, young
Rats
Guinea pig
Guinea pig
Rat
Mice
Substance Cone. Level (or Dose)
LAS 100 rag/day (4 mo.)
ABS 100 mg/day (4 mo.)
ABS 1000 mg/day (6 mo.)
ABS .1% in water (79 days)
ABS .2% in water (79 days)
ABS .4% in water (79 days)
ABS 500 mg/1 (2 years)
ABS 2000 mg/1 (6 mo.)
LAS 2000 mg/1 (6 mo.)
LAS 1.4-1.5 gm/kg
LAS 2.8 gm/kg
357
Effect
no toxic effect on 6 men
no effect
no effect
no effect
stimualted growth
no effect
no effect
slight toxic effect
slight toxic effect
LD50 (single dose)
LD50 (single dose)
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Effect on Fish and Other Aquatic Life
The effects of surfactants on fish and aquatic life are
relatively well documented (6,66,59). The presence of surfactants
in concentrations up to 0.14 mg/1 are generally not toxic to fish
• and other aquatic life for short periods of time (66). However,
trout reportedly have avoided waters containing as little as
| 0.001 mg/1 (59).
im Most of the earlier works in the literature dealt primarily
with the effects of soaps and the ABS type surfactants, while the
• recent references include the effects of LAS surfactant as well.
In general, McKee and Wolf show that the toxic concentrations of
| various ABS type surfactants, in either hard or soft water, vary
« from 3.6 to 5.6 mg/1 as a 96 hour TLm. They also indicate that
™ while the toxicity of ABS type surfactants is greater in hard
• water than in soft water, a decrease in the water temperature can
make the surfactants just as lethal in soft water as in hard water.
H McKee and Wolf report concentrations of 5 mg/1 of various detergents
_ as having a lethal effect upon tadpoles, stickleback, roach, carp,
' and Daphnia. A concentration of 3 mg/1 of well oxygenated clean
fl water was found to produce a 50 percent mortality for rainbow
trout within a 12 week period.
• Table XXIII-4 indicates the varying degrees of toxicity of
alkyl aryl sulfonates including ABS for different time exposures
™ to various aquatic organisms. In comparison, Volume I of the new
• EPA Data Book has indicated a 96 hour TLM concentration for linear
ABS (LAS) for three species: bluegill fingerling, 0.6 to 3.0 mg/1;
I flathead, 3.5 mg/1; and flathead (eggs), 3.4 mg/1 in 24 hours.
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Recommended stream criteria for surfactants are summarized in
Table XXIII-5. While these are applicable as stream criteris,
one must not consider the appropriateness of a unilateral
application as effluent criteria without considering the current
treatability of surfactants found in today's discharges.
TABLE XXIII-4
EFFECT OF ALKYL-ARYL SULFONATE, INCLUDING ABS, ON AQUATIC ORGANISMS (6)
Organisms
Trout
Bluegills
Fathead minnows
Fathead minnow fry
Pumpkinseed sunfish
Salmon
Yellow bullheads
Emerald Shiner
Bluntnose minnow
Stoneroller
Silver jaw
Rosefin
Common shiner
Carp
Black bullhead
"Fish"
Trout sperm
Daphnia
Concentration
(mg/D
Time
5.0
3.7
5.0
4.2
3.7
0.86
16.0
5.6
17.0
2.3
13.0
11.3
3.1
9.8
5.6
1.0
7.4
7.7
8.9
9.2
9.5
17.0
18.0
22.0
6.5
10.0
5.0
20.0
7.5
26 to 30 hours
24 hours
24 hours
48 hours
30 days
90 days
96 hours
96 hours
96 hours
7 days
3 months
3 days
10 days
96 hours
96 hours
96 hours
96 hours
96 hours
96 hours
96 hours
96 hours
96 hours
24 hours
96 hours
Effect
Death
TLm
Gill pathology
TL
TLm
Sa?e
TL
Gill damage
Reduced spawning
TLm
TLm
Gill damage
Mortality
Histopathology
TLm
TLm
TLm
Min. lethality
Damage
TL
359
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TABLE XXIII-4 (cont)
Concentration
Organisms
Lirceus fontinailis
Crangonyx setodactylus
Stenonema ares
Stenonema heterotarsale
Isonychia bicolor
Hydropsychidae (mostly
cheumatopsyche).
Orconectes rusticus
Goniobasis livescens
Snail
Chlorella
Nitzchia linearis
Navicula seminulum
(mg/1)
10.0
.s 10.0
8.0
16.0
le 8.0
16.0
8.0
.y 16.0
32.0
16.0
32.0
16.0
32.0
18.0
24.0
3.6
5.8
Time
14 days
14 days
10 days
10 days
10 days
10 days
9 days
12 days
12 days
9 days
9 days
12 days
12 days
96 hours
96 hours
23.0
Effect
6.7 percent survival
(hard water)
0 percent survival
(hard water)
20-33 percent survival
0 percent survival
40 percent survival
0 percent survival
0 percent survival
37-43 percent survival
20 percent survival
100 percent survival
0 percent survival
40-80 percent survival
0 percent survival
TLm
TLm
Slight growth reduction
50 percent growth re-
duction in soft water
50 percent reduction in
growth in soft water
TABLE XXIII-5
CRITERIA FOR SURFACTANT CONCENTRATION CONTROL
Concentration
(1) 0.5 mg/1 ABS
(2) 3.6 to 5.6 mg/1
(2b) 0.6 to 3.5 mg/1
Effects
Max. dosage which produces no
long term effects in mammals.
Ref.
(59)
TLm, LAS threshold limit for 96 hrs.(66)
96 hr TLm for LAS on Bluegill (59)
fingerling flatheads, flathead eggs.
(3) ABS - 1/7 of 48 hr. TLm Recommended stream cone.
LAS - .2 mg/1 or 1/7
of 48 hr. TLm
(4) 1.0 mg/1
(5) 0.5 mg/1
Taste and odor and foaming
problems.
Max. desirable cone, for human
consumption.
360
(6)
(66)
(66)
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TREATMENT TECHNOLOGY-SURFACTANT REMOVAL
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As the form of detergents and synthetic surfactants has changed
over time, so has the reason for treatment. The early approach to •
treating wastes containing soaps was to handle them as other wastes _
with high BOD. In time, soaps were replaced by the ABS synthetic ™
type which reduced BOD levels from industrial processes substantially. I
As mentioned previously, the pressure has been applied to the
detergent industry to convert to the more readily degradable LAS I
type surfactants. At this time the state-of-the-art is centered
around what form of soft detergents and what type of builders are •
most appropriate. Should the builder be high or low in phosphates? •
If phosphates are not used, what is a suitable substitute which is
still effective as a cleansing agent, but is not toxic or harmful I
in some other means?
While the type of soap or detergent has been varying with time, •
the basic treatment processes remain biological treatment and •
chemical coagulation. Nemerow (71) indicates that chemical coagula-
tion with alum yields a 90 percent removal of soap BOD from textile •
mills. He also states (72) that theoretically detergents may be
removed to a level of approximately 0.2 mg/1 by a combination of |
coagulation, filtration and adsorption. Table XXIII-6 lists the «
approximate efficiency of various treatment methods for mixed ABS-
LAS and only LAS type detergents. I
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TABLE XXIII-4 (cont)
Concentration
Organisms
Lirceus fontinailis
Crangonyx setodactylus
Stenonema ares
Stenonema heterotarsale
Isonychia bicolor
Hydropsychidae (mostly
cheumatopsyche).
Orconectes rusticus
Goniobasis livescens
Snail
Chlorella
Nitzchia linearis
Navicula seminulum
(mg/1)
10.0
.8 10.0
8.0
16.0
le 8.0
16.0
8.0
y 16.0
32.0
16.0
32.0
16.0
32.0
18.0
24.0
3.6
5.8
Time
14 days
14 days
10 days
10 days
10 days
10 days
9 days
12 days
12 days
9 days
9 days
12 days
12 days
96 hours
96 hours
23.0
Effect
6.7 percent survival
(hard water)
0 percent survival
(hard water)
20-33 percent survival
0 percent survival
40 percent survival
0 percent survival
0 percent survival
37-43 percent survival
20 percent survival
100 percent survival
0 percent survival
40-80 percent survival
0 percent survival
TLm
TLm
Slight growth reduction
50 percent growth re-
duction in soft water
50 percent reduction in
growth in soft water
TABLE XXIII-5
CRITERIA FOR SURFACTANT CONCENTRATION CONTROL
Concentration
(1) 0.5 mg/1 ABS
(2) 3.6 to 5.6 mg/1
(2b) 0.6 to 3.5 mg/1
Effects
Max. dosage which produces no
long term effects in mammals.
Ref.
(59)
TLm, LAS threshold limit for 96 hrs. (66)
96 hr TLm for LAS on Bluegill (59)
fingerling flatheads, flathead eggs.
(3) ABS - 1/7 of 48 hr. TLm Recommended stream cone.
LAS - .2 mg/1 or 1/7
of 48 hr. TLm
(4) 1.0 mg/1
(5) 0.5 mg/1
Taste and odor and foaming
problems.
Max. desirable cone, for human
consumption.
360
(6)
(66)
(66)
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TREATMENT TECHNOLOGY-SURFACTANT REMOVAL
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As the form of detergents and synthetic surfactants has changed
over time, so has the reason for treatment. The early approach to I
treating wastes containing soaps was to handle them as other wastes _
with high BOD. In time, soaps were replaced by the ABS synthetic *
type which reduced BOD levels from industrial processes substantially. I
As mentioned previously, the pressure has been applied to the
detergent industry to convert to the more readily degradable LAS I
type surfactants. At this time the state-of-the-art is centered
around vrtiat form of soft detergents and what type of builders are •
most appropriate. Should the builder be high or low in phosphates? •
If phosphates are not used, what is a suitable substitute which is
still effective as a cleansing agent, but is not toxic or harmful •
in some other means?
While the type of soap or detergent has been varying with time, I
the basic treatment processes remain biological treatment and •
chemical coagulation. Nemerow (71) indicates that chemical coagula-
tion with alum yields a 90 percent removal of soap BOD from textile •
mills. He also states (72) that theoretically detergents may be
removed to a level of approximately 0.2 mg/1 by a combination of |
coagulation, filtration and adsorption. Table XXIII-6 lists the •
approximate efficiency of various treatment methods for mixed ABS-
LAS and only LAS type detergents. •
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SUMMARY AND RECOMMENDATIONS
On the basis of the literature review, the following conclusions
• have been drawn:
(1) The term surfactants for this report includes all methylene
I blue-active substances which would be included by the
_ Standard Method. While LAS is more prevalent in today's
™ wastewaters, ABS is till used in some industrial operations.
I (2) The major effect of surfactants in water is their
tendency to cause foaming, taste, and odor problems.
• Foaming has been found to decrease as the pollution load
in the stream is increased and as the pH approaches
• neutrality.
• (3) Any taste and odor problem is usually found at and above
a surfactant concentration of 1.0 mg/1 and chlorination
• of surfactant bearing wastewaters accentuates the taste
and odor.
• (4) The maximum desirable concentration of surfactants in
• water for human consumption is 0.5 mg/1.
(5) Some plants have been found to be sensitive to surfactant
• concentrations in excess of 1.0 mg/1. For fish and other
aquatic life toxicity of ABS ranges from approximately
I 3.0 to 6.0 mg/1. For fish and other aquatic life toxicity
• of LAS ranges from 0.6 to 3.5 mg/1.
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(6) Theoretically, detergents may be removed to a level
of approximately 0.2 mg/1 by coagulation, filtration I
and absorption. •
(7) Biological treatment or sand filtration is capable of
removing 85% of the surfactants, measured as BOD. •
On the basis of the foregoing, it is recommended that a
uniform effluent criterion of 1.0 mg/1 be established for all |
surfactants, as measured by the methylene blue technique, provided »
that no foaming is observed at the discharge or immediately down-
stream. It is further recommended that all dischargers be •
informed that their average surfactant concentration should be
in the range of 0.5 mg/1.
TABLE XXIII-6
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TREATMENT METHODS FOR SURFACTANTS (57) •
Method ABS AND LAS Efficiency Efficiency |
Biological: ( % removal as BOD) ( % removal as BOD)
Trickling Filter 52 77 •
Activated Sludge 67 86 •
Lagoon 71
Sand Filtration 85 I
Note: The softer LAS surfactant is easily degraded biologically while •
the harder ABS is not easily treated. •
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CHAPTER XXIV-TURBIDITY
SOURCES OF TURBIDITY
_ Turbidity is a physical parameter which expresses the optical
* properties of fine suspended matter in solution. This matter may
I be suspended material such as clay and silt, or organic matter,
bacteria, plankton or similar organisms.
• The analytical procedures for measuring turbidity vary from
a crude visual comparison to comparisons with standard solutions
" of a kaolinite suspension using sophisticated light scattering
• measuring devices. The nepthelometric method consists of measur-
ing the intensity of light scattered at 90° to the light source.
I The Jackson candle method uses a standardized bees wax candle
to measure the image of the flame as it passes vertically through
• a sample. It is the standard against which all other methods are
• based. Results are given in Jackson Turbidity Units (JTU).
To further confuse the issue the Nephelometric method uses
• turbidity free water to dilute samples having a turbidity greater
than 40 Jackson Turbidity Units (JTU) (1). By now it should be
I apparent that the measurement of turbidity is subject to several
• variables. The procedures, however, are not the only source of
variations. All methods of measuring turbidity are subject to
• false readings by the presence of debris, coarse sediments,
gas bubbles, vibrations, "true color" and the individual
I optical properties of the particular material in suspension.
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ENVIRONMENTAL EFFECTS OF TURBIDITY
Effect on Man
Effect on Man
I
Colloidal mica, for example will give highly erroneous readings
in comparison to many other materials. I
Turbidity is present in most municipal and industrial _
discharges. Of particular note, however, are industries which *
use or manufacture large quantities of starch; clays; mineral flj
substances such as zinc, iron, and manganese; fibers and sawdust;
and eroded soils. Of special interest are the pulp and paper, •
mining, dredging, and logging industries (66).
I
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The primary influence of turbidity in water used for human •
consumption is aesthetics. Turbidity, however, may be due to
toxic trace metals, or disease producing bacteria and virus. I
Therefore, the turbidity limit has been set at 5 JTU in the •
Drinking Water Standards (94).
I
The presence of turbidity in water used for food preparation, B
beverages, and high quality products is noted in the literature (66).
Certain industries where turbidity is likely to have a deleterious I
effect are: ice making, laundries, beverage, and brewing, textiles,
pulp and paper, steam boilers, and turbine operations. •
A summary of the water quality needs of several industries is
shown in Table XXIV-1.
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TABLE XXIV-1
TURBIDITY LIMITS FOR INDUSTRIAL WATER SUPPLIES (66)
INDUSTRY
Beverages
Food Products
Breweries
Boiler Feed Water
Pulp and Paper
Alkaline Pulps
High Grade Paper
Fine Writing and Book Paper
Unbleached Kraft Paper
Bleached Kraft Paper
Groundwood Paper
Textiles
Nitrocellulose
Rayon
Cotton
Cotton (Callaway mills)
Baking
Cooling Water
Ice Making
Tanning
JTU
1-2
10
1-10
1-20 (Lowest for high
pressure)
25
5-25
10
100
40
50
0.5
1
25
0.3-0.5
10
50
1-5
20
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TABLE XXIV-2
AVERAGE FATAL TURBIDITIES FOR FISH (66,6) •
I
Species of Fish Ave. Exposure, Days Turbidity, JTU
Rock Bass 3.5 38,250 g
Channel catfish 9.3 85,000
Pumpkin seed sunfish 13.0 69,000 •
Largemouth 7.6 101,000 •
Golden shinner 7.1 166,000
Black bullhead 17.0
222,000 I
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Effect on Fish and Other Aquatic Life
Turbidity may affect fish and aquatic life in four ways: (1)
light penetration is decreased thereby decreasing photosynthesis
and productivity of fish food organisms; (2) high concentrations •
of particulate matter can damage sensitive organs (e.g. gills);
(3) it may interfere with normal predation and feeding patterns; |
and, (4) by excluding light, turbidity can modify the temperature _
structure of impoundments (66).
Direct reduction of fish productivity occured as the turbidity •
exceeded 25 JTU, and bottom organisms decreased from 249/sq ft to
36/sq ft due to silting (66). Aquatic insect productivity dropped g
by 85% below drag line operations. Studies have demonstrated a _
41.7% drop in fish yield as turbidity increased above 25 JTU. When •
turbidity reached 100 JTU, the fish yield was only 18.2% of that in ij
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clear ponds (less than 25 JTU). Similar reductions were found
• in plankton volumes. (Buck as reported in 6 and 66).
im While Wolf and McKee report that fish thrive in waters with
turbidities of 200 to 400 JTU, direct lethal effects to eggs are
• found above 1000 JTU within 6 days. Some of the average
turbidities found to be fatal to fish are summarized in Table
| XXIV-2. In general, as turbidity approaches 20,000 JTU, harmful
mm effects are observed even in adult fish (66).
It is recommended that turbidity in the receiving water due
• to a discharge should not exceed 50 JTU in warm water streams,
25 JTU in warm water lakes and 10 JTU in cold water streams, cold
• water or oligotrophic lakes (66).
I
TREATMENT TECHNOLOGY-TURBIDITY REMOVAL
I
The removal of turbidity is closely associated with the removal
• of suspended solids. When the turbidity of a particular wastewater
• is due to colloidal material, it can be removed by coagulation,
sedimentation, and filtration.
SUMMARY AND RECOMMENDATIONS
• On the basis of the above discussion, the following statements
can be made:
• 1. Turbidity is a readily observable physical characteristic
(not a pollutant itself) and the analytical procedures for turbidity
• are subject to internal and external variables.
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2. Materials which cause turbidity are found in both
naturally occuring and industrial discharges. Turbidity is •
objectionable in domestic water supplies for aesthetic reasons •
above a level of 5 JTU and is generally objectionable in water
supplies because it is an indication of possible toxic and •
disease producing materials.
3. Many industries require waters with low turbidities •
(less than 10 JTU) for product quality reasons. •
4. Materials which have turbidity in surface waters reduce
fish and aquatic life production, water temperatures, and light •
penetration. Materials causing a turbidity above 1000 JTU begin
to have direct lethal effects on fish reproduction, and above |
20,000 JTU begin to harm adult fish. _
5. Turbidity levels in surface waters should be maintained
at or below 50 JTU in warm water streams; 25 JTU in warm water I
lakes, and, 10 JTU in cold water streams, and cold or oligotrophic
waters. |
On the basis of the review it is recommended that a uniform •
maximum effluent level of 50 JTU be adopted. It is further recommended
that lower effluent levels be adopted when necessary to maintain the •
desirable receiving water quality of Summary No. 5 above. m
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CHAPTER XXV-ZINC
+2
Zinc occurs in the natural aquatic environment as soluble Zn
salts, soluble inorganic and organic complexes and insoluble
precipitates. At basic pH's, the hydroxides and carbonates
are readily formed. Zinc occurs naturally and is abundant in
• rocks and ores in some areas. Table XXV-1 outlines several
naturally occuring zinc levels in the environment. The litera-
B ture contains references to zinc in the ores of lead, copper and
-------
Water Standards that several enzymes are dependent upon zinc (62) .
Zinc deficiency has cuased growth retardation that is overcome
only by an adequate daily intake through the consumption of food
and water. Pre-school age children have been found to require
0.3 milligrams of zinc per kilogram of body weight as a daily
requirement. The daily adult intake is reported to be 10-15
milligrams, with an excretion averaging about 10 milligrams
daily through the feces and 0.4 milligrams through the urine (94).
Table XXV-2 shows other zinc concentrations that affect man.
McKee and Wolf reported that zinc bearing water should not be used
in acid drinks, such as lemonade, due to the possible formulation
of zinc citrate and other organic zinc compounds that may be
poisonous.
TABLE XXV- 1
NATURAL OCCURRING ZINC LEVELS IN THE ENVIRONMENT
Source Zn Concentration Reference
Most Plants 1-10 mg/kg (66)
Cereals as high as 140 mg/kg (66)
Sea Water 0.01 mg/1 (6)
Marine Plants as high as 150 mg/1 (6)
Marine Animals 6-1500 mg/1 (6)
371
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TABLE XXV-2
INDUSTRIAL ZINC BEARING WASTE WATERS
Process
Zinc Mining
Mine drainage
Metal Processing
Pickle bath waste
Bright dipwastes
Copper Mill Rinse Waters
Brass Mill Rinse Waters
Brass Mill Pickle Waste
Brass Mill Rinse Waste
Plating
General @ 100 gpm discharge
@ 50 gpm discharge
w/CN complex
Plating bath
@ 0.5 gph drag-out
@ 2,5 gph drag-out
Plating waste
General
General
General
Zinc
Brass
Zinc
Brass
General
Silver Plating
Silver bearing wastes
Acid waste
Alkaline
Rayon Wastes
General
Automotive Ind.
General
Average
1450
0.25 9
5-220 65
0.5-5.1 2.2
250-1000
1-12 16/100 cars
Reference
(45)
4300-41,400
200-37,000
0.8-13.0
2.6-10.7
36-374
10-20
3.1
7.4
(71,72)
(71,72)
(65)
(65)
(96)
(48)
7.0-215
1.0-1.7
39-82
2.4-13.8
55-120
15-20
70-150
11-55
70-350
10-60
7.0-215
46.3
1.0
33,800
70
350
8.2
15
46.3
(71,72)
(71,72)
(71,72)
(71,72)
(71,72)
(72)
(76)
(76)
(76)
(76)
(76)
(76)
(76)
(76)
(71 per 76)
(71 per 76)
(71 per 76)
(76)
(72)
372
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TABLE XXV- 3
ENVIRONMENTAL EFFECT OF ZINC UPON MAN
Effect Zinc
Gastrointestinal
irritant
Milky appearance to
drinking water
Greasy film on
drinking water
(after boiling)
Taste threshold in
spring water
Taste threshold in
distilled water
No known detrimental
effects
ii it
Nausea & fainting
Zinc may be eroded from
Concentration (mg/1)
675-2280
30
5.0
27.2 (as ZnSO )
17.6
11.2 to 26.6
23.8 to 40.8
30
Reference
(62)
(66)
(66)
(66)
(66)
(66,94)
(66,94)
(66,94)
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zinc plated galvanized pipes and may
appear in high concentrations in domestic water supplies. The
Drinking Water Standards state that a dissolution
produce a concentration of 5
rag/1. This would be
of zinc could
accompanied
by a cadmium concentration of approximately 0.01 mg/1, and a
lead concentration of approximately 0.05 mg/1. As
1946 Drinking Water Standard
desirable level of 5 mg/1.
a result , the
of 15 mg/1 was reduced to a maximum
This level allows for
373
the provision
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of zinc, needed for the daily intake, while minimizing taste
• problems and the format ion-'"d€ an oily, filfii on. boiled water.
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Effect on Plants
I
McKee and Wolf reported that while small amounts of zinc
They reported that a deficiency of zinc has been found to cause
|t- -".,>.... i , „,
poor growth and dwarfing of the leaves of fruit trees and causes
are needed for nutrition by most crops, zinc is found to be toxic
\«. „ f s ,
t* ' „' -I
when the nutritional value is exceeded by a very snail amount.
01 - '
ilttorosis in- c'drn. Zinc' is' present in most plants at a, ,cpi)
tion of 1 to 10 mg/kg and as high as 140 mg/kg in ;pe,rea^&i, ^•;<\^-..\i
M Table XXV-1. Table XXV-4 outlines other environmental effects of
-zvLr^c on plants ,and algae.. '; ..' •.-•',•: ?H.:- ~ r ': **
Effect on Domestic Animals and Wildlife
Animals, like man, require-small amounts of zinc in their daily
diets. The acidic effects of '^inc ini.the drinking;wager for animals
is apparently of little concern. Table XXV-5 summarizes the effects
of zl^dl^i animals.
Effect on Fish and Other Aquatic Life
_ .O'ji.lM/i... :<, %-n, .'••.:>,'. . ,. i,,. ':; ^ _ T _ (,
• ,.-,...:3,",rn/;?ii' The*"'s^h-§itJivity of fish and aquatic life to zinc has been found
• ••';. :a\- -.;,..: .>>,.-...
to vary v;ith the species, age and condition of the fish as well as
^B - • * - • ' ' -' ; ,.i>;,, > . ' j - ' ,^ - - - .
• the physical characteristics significant in determining the toxic
• effects of zinc are the hardness of the water, the calcium and
magnesium concentrations, the pH, the temperature, and the concentra-
• tion of dissolved oxygen.
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TABLE XXV-4
TOXIC EFFECTS ON PLANTS
Type of Plant (66)
Orange & Mandarin seedlings
Flax
Water hyacinths
Oats
Plankton (6)
Nitzchia cinearis
(soft water, 44 mg/1 CaCO-
Navicular seminulum
(soft water, i.e. 44 mg/1 CaCO_
Zinc Concentration (mg/1)
3
5
10
25-100 (as ZnSO,)
22°0
4.29
4.05
27°C
1.59
2.31
30°C
1.32
3.22
TABLE XXV-5
EFFECTS ON ANIMALS AND WILDLIFE (66)
Type of Animal
Pigs
Laying hens
Rats
Zinc Concentration (mg/1)
1,000 (in milk)
Effect
lameness and malnutrition
10,000 (in drinking water) Reduced egg production,
less water consumption,
loss of body weight
50 (in drinking water) No harmful effect
375
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From the toxicity data in Table XXV-6 it is apparent that
• the toxicity of zinc to fish life is substantially reduced as the
hardness of the water is increased. It is also apparent that the
• toxicity may decrease slightly with an increase in temperature.
• There is some discrepancy as to whether it is water hardness, as
CaCO , or whether it is the concentration of calcium and magnesium
• (reported CaCO ) which controls the toxicity of zinc. While most
of the studies on the toxicity of zinc on fish life report varia-
• tions in relation to water hardness, a report (15) on the toxicity
fli of zinc to plankton referred to the concentration of calcium and
magnesium as the critical factors. Results of the study are
• summarized in Table XXV-4. It is interesting to note from this
study that the toxicity of the zinc increased rather than decreased
|H with an increase in temperature for plankton rather than decreased
M as shown in most of the fish studies.
A review of the literature indicates that copper may have a
•
synergistic effect on the toxicity of zinc. McKee and Wolf reported
that 1 mg/1 of zinc in the presence of 0.025 rag/1 of copper was as
£ toxic to fish life as 8 mg/1 of zinc alone. Similarly, the work of
_ Sigler et al. , as reported in the water Quality Criteria Data Book
Volume 3 (25) indicates that a concentration of 0.6 mg/1 of zinc in
I the presence of 0.048 mg/1 of copper was toxic to salmon in soft
water. In hard water, McKee and Wolf reported that the threshold
• concentration of a mixture containing 0.56 mg/1 of zinc and 0.44
_ mg/1 of copper was about that which was to be expected assuming no
™ synergism. One is therefore lead to conclude that copper may have
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a synergistic effect with zinc only in soft waters (15-20 mg/1
CaCO,).
3
TABLE XXV-6
as
TOXICITY OF ZINC ON FISH LIFE AND EFFECT OF HARDNESS, TEMPERATURE
& pH CONCENTRATIONS, mg/1
Temperature °C
Species Water 18-20 30
Lepomis Soft 2.9 - 3.8 1.9 - 3.6
Macrochirus Hard 10.1 - 12.5 10.2 - 12.2
" Soft 2.86 - 3.75 0.9 - 2.10
" Hard 6.60 - 9.47 6.18 - 9.50
Physa Soft 0.79 - 1.27 0.62 - 0.78
Heterostropha Hard 2.66 - 5.57 2.36 - 6.36
(pond snail)
Pimephales Soft 0.96
Prumelas Hard 33.4
Zepomis Soft 5.46
macrochirus Hard 40.9 -
Bluegill Sunfish Soft 2.9 - 3.8 1.9 - 3.6
" Soft 4.2
" Hard 10.1 - 12.5
11 Hard 12.5 - 12.9
Flathead Soft (50 mg/1) 4.9 @ pH = 8
Minnow Hard (200 mg/1) 32.3 @ pH = 6
Ref.
(15)
(15)
(15)
(15)
(15,66)
(15,66)
(15)
(15)
(15)
(15)
(66)
(66)
(66)
(66)
.0 (15)
.0 (15)
According to McKee and Wolf, the toxicity of zinc salts is also
increased as the concentration of dissolved oxygen decreases.
effect of dissolved oxygen on zinc toxicity is the same found
copper, and phenols. They reported a lethal concentration at
The
for lead,
60%
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saturation to be about 85% the lethal concentration at 100% saturation.
377
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McKee and Wolf reported that zinc may also be dangerous to
•
oysters in small concentrations. In large amounts, it has been
known to impart a blue-green color. They reported that snails
have a toxic limit of 1.0 mg/1 zinc in natural waters. McKee and
Wolf report that zinc, like several other metals, has been found to
mm
be concentrated by various forms of aquatic life. Studies with
• radioactive Zn , indicate concentration factors to range from a
low of 290 to a high of 200,000.
TREATMENT TECHNOLOGY- ZINC REMOVAL
Removal of zinc from industrial wastewater, plating wastes in
V particular, may be greatly enhanced by good housekeeping, spill
prevention plans, recycling, and countercurrent rinsing. Zinc wastes
• are more amenable to treatment following concentration of wastewater
and a reduction of total flow. The removal of zinc from industrial
™ wastewaters is normally carried out either by chemical coagulation
• and precipitation, or by a recovery step.
• Precipitation
As zinc hydroxide has a limited solubility above a pH of
• approximately 8.8, it may effectively be removed from wastewaters
under alkaline conditions. Lime is normally used to raise the pH,
H due to its availability and low costs. In acidic industrial wastes,
_ which may be high in sulfates, calcium sulfate will also be precipi-
tated with the zinc hydroxide, forming large volumes of sludge. As
I a result, the cost of treating wastes with high sulfate concentrations
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may be substantially greater due to sludge disposal.
Since zinc bearing wastewaters also often contain substantial I
concentrations of cyanide and chromium, the cyanide must be oxidized
following reduction of the chromium from the hexavalent to the |
trivalent form prior to precipitation of zinc and other trace metals. «
The efficiency of zinc removal by chemical precipitation is summarized
in Table XXV-7. •
The works of Patterson and Minear (76) discussed a new process
by DuPont which utilizes hydrogen peroxide, catalyst and stabilizers •
to oxidize cyanide and promote the formulation of metal oxide in lieu
of the hydroxide. As the oxide of metals are most amenable to filtra- •
tion, lower final effluent levels might be obtainable. A full-scale V
changeover of this type has been described in the literature (96). The
Velco Brass & Copper Company of Kennelworth, New Jersey, converted a •
former sulfuric chromic acid or ammonium bifluoride-chromic acid pickle
to a sulfuric acid-hydrogen peroxide pickle with stabilizer agents. As •
a result, their previous zinc discharges of 36-375 mg/1 have been re- •
duced to their current level of 0.08-1.6 mg/1. This process has re-
duced their previous costs of $195 per day without treatment to $194 •
per day for total operating cost plus amortized installation costs. A
summary of the capital costs for zinc removal by lime coagulation and •
precipitation is summarized in Table XXV-8. With respect to the operat- •»
ing costs, Patterson and Minear reported that for the General Electric
plant referred to in Table XXV-7, treating 30,000 gallons per day the •
cost was $3.79 per 1,000 gallons. Other operational costs reported by
Patterson and Minear were as low as $.34 per 1,000 gallons. •
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TABLE XXV- 7
EFFICIENCY OF ZINC REMOVAL BY CHEMICAL PRECIPITATION
Zinc Concentration
Process Initial mg/1 Effluent
Zinc coag. & precip. General 0.5-2.5
& settle 20 Less than 1.0
10-20 1-2
55-120 Less than 1.0 (av.)
Copper Brass 0.5-2.5
fabrication
Plating wastes 3-4
Lancy integrated Plating wastes 0.5
Zinc coag. & Precip. General 0.1-0.3
Settle & Filter Copper-Brass 0.1-0.5
fabrication
2.2-6.5 (16 ave.) 0.02-0.23
380
Reference
(97)
(76)
(48)
(76)
(76)
(61)
(61)
(97)
(76)
(76)
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TABLE XXV-8
CAPITAL COST OF ZINC REMOVAL
Cost,
$/1000
Process Flow Cost, $ Gal. Ref.
Lime coag. & precip. 1 MGD 100,000 100 (97)
& settle 10 600,000 60 (97)
Lime coag., precip. 1 MGD 300,000 300 (97)
settle & filter 10 MGD 1300,000 130 (97)
50 MGD 4600,000 108 (97)
(1957) 0.3 MGD 276,000 9200* (76)
*Includes vacuum filter cost of $30,000
Recovery Process
While precipitation, ion exchange, evaporation, and simple
process modifications may be utilized for the recovery of zinc,
Patterson and Minear have indicated the following: "Unless other
process modifications are necessary, or extremely high levels of
zinc are present and minimal purification of recovered material is
required, zinc recovery is generally not economical."
In contrast with the report of Patterson and Minear, the works
of McGarvey, et al. (65) state, "the recovery and disposal of copper
and brass alloy metals from washwaters prior to discharge in the
stream might be accomplished successfully by employing high capacity
ion exchanges such as Amberlite, IR-120. Either the sodium or
hydrogen cycle may be used..." Further analysis of this study
381
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indicated that copper, zinc and chromium could be precipitated
• from the chloride regenerate and recovered by chemical means,
or they could be wasted. While Patterson and minear report that
V recovery of zinc is generally not economical, or as economical
• as lime precipitation, they report that recovery by evaporation
resulted in substantial savings for one plant. Evaporative
• recovery preceded by process modifications reduced a total of
3,000 gallons an hour to 50 gallons an hour. It also resulted
| in chemical savings of more than $18,000 a year. By following
« the breakpoint formula presented in the report of Patterson and
Minear it is apparent that zinc recovery might be beneficial for
• large operations with concentrated zinc wastes. It is also
questionable whether Patterson and Minear had compared the cost
J| of recovery with simple precipitation and sedimentation or
« whether they hac. included the additional cost of filtration. The
reports by McGa'/vey and Patterson and Minear do agree on one point.
• Zinc may be recovered from precipitates by dissolution with acid.
It is also apparent that the total cost of treatment facilities
£ may be recovered from precipitates by dissolution with acid. It
_ is also apparent that the total cost of treatment facilities may
* be substantially reduced by a reduction in the volume of waste-
B water to be discharged.
In summary, zinc concentrations in waste waters can be reduced
• by lime coagulation precipitation and sedimentation to a final
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effluent concentration of up to 2.5 rag/1 and may be further reduced •
to a maximum concentration of 0.5 mg/1 by filtration.
SUMMARY AND RECOMMENDATIONS
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On the basis of this discussion the following statements can I
be made about zinc:
1. Zinc is abundant in rocks and various metal ores. The
marine environment contains 0.01 mg/1 of zinc in water, up to
150 mg/1 in marine plants, and from 6 to 1,500 mg/1 in marine
animals, apparently due to natural causes. •
2. Major industrial sources of zinc bearing wastewaters are
mining and smelting of zinc, metal alloys, and plating operations. |
3. Zinc is a necessary nutrient to man, animals, and plants •
in limited amounts. Surface waters used for irrigation of plants
should not contain more than 5 mg/1 zinc due to damaging effects. •
Zinc concentrations in surface waters should be less than 50 mg/1
for animal and wildlife watering.
4, Domestic water supplies should not contain more than 5 mg/1
zinc for aesthetic reasons.
5. Zinc toxicity varies with respect to the species, age, and •
condition of fish as well as the water hardness, pH, dissolved
oxygen, and other trace metal concentrations. The presence of •
copper will increase the toxicity of zinc in soft waters. Most
forms of fish and aquatic life can withstand short exposure (at •
least one hour) to a zinc concentration of 1.0 mg/1 in both soft •
I
383 •
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• and hard waters. Reductions in the dissolved oxygen of surface
waters will increase the toxicity of zinc.
I 6. Zinc bearing industrial wastewaters can currently be
treated by lime coagulation, precipitation, settling, and possible
^ filtration to a maximum effluent level of less than 1.0 mg/1. The
• cost to reach an effluent level of 1.0 mg/1 is within a reasonable
economic range, compared to removing other pollutants.
• On the basis of the above discussion, it is recommended that
a uniform effluent level for zinc be established at 1.0 mg/1. In
V applying this effluent limit to industrial and municipal dis-
• charges, consideration must be given to the concentration of other
trace metals such as copper and their synergistic effects. With
• respect to average operating conditions, of a zinc removal treat-
ment process, the effluent should only contain a zinc concentra-
• tion in the range of 0.1 to 0.5 mg/1.
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APPENDIX
A: References A-l — A-9
B: Water Quality Criteria Recommendations B-l — B-9
• for Total Residual Chlorine in Receiving
Waters for the Protection of Freshwater
Aquatic Life by W. A. Brungs and Staff
C: Capital and Operating Costs C-l
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REFERENCES
1. American Public Health Association, 1971. STANDARD METHODS; for
the Examination of Water and Waste Water. APHA, AIWA, WPCF.
New York, N. Y. 13th ed. 874p.
2. Armco Steel Corporation, 1970. Treatment of Waste Water-Waste Oil
Mixtures. WPCRS 12010 EZV 02170.
3. Armco Steel Corporation, 1971. Limestone Treatment of Rinse Waters
from Hydrochloric Acid Pickling of Steel. EPA, WPCRS 12010
DUL 02/71.
4. Anom. "Deeds and Data." JWPCF. 40:7:1358, 40:11:1953, and 41:5:836.
5. Anom. 1965. "Interaction of Heavy Metals and Biological Sewage
Treatment Processes." USDHEW, PHS. Environmental Health Series
999-WP-22. 1965.
6. Anom. 1968. Water Quality Criteria: Report of the National Technical
Advis o ry Commi 11ee. FWPCA. 1968. Pub. No. 0-287-250. 234pp.
7. Anom. 1967. The Cost of Clean Water: Vol III. Industrial Waste
Profiles, No. 5. Petroleum Refining. U. S. Department of the
Interior, Washington, D. C., 1967.
8. Anom. 1967. The Cost of Clean Water: Vol. Ill Industrial Waste
Profiles, No. 3. Meat Products. U. S. Department of the
Interior, Washington, D. C., 1967.
9. Anom. 1972. "Technology: Cell Systems Keep Mercury from Atmosphere.'
Chemical and Engineering News. February 14, 1972. (Also February
21, 1972 issue.)
10. Antonie, R. L., 1971. "The Bio-Disc Process News Technology for the
Treatment of Biodegradable Industrial Waste Water." In Water-1970;
Chemical Engineering Progress Symposium Series 107: Vol 67:1971
pp 585-588.
11. Babbitt, H. E., and E. R. Baumann, 1958. Sewerage and Sewage Treat-
ment . John Wiley and Sons, Inc., New York. 790p.
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21. Brungs, W. A., 1972. Personal Communication.
22. Bunch, R. L., 1971. "Factors Influencing Phosphorus Removal by
Biological Treatment." IN: Water-1970: Chemical Engineering Pro-
gress Symposium Series 107: Vol 67:1971. L. K. Cecil, ed. pp 90-94.
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REFERENCES (CONT.)
12. Barker, J. E., Foltz, V. W., and R. J. Thompson, 1971. "Treatment of
Waste Oil: Waste Water Mixtures." IN: Water-1970: Chemical
Engineering Progress Symposium Series 107; Vol 67:1971. L. K.
Cecil, ed. pp 423-427.
13. Barnhart, E., personal communication, January 1972. (Hydroscience •
Inc., 363 Old Hook Road, Westwood, New Jersey.)
14. Battelle Columbus Laboratories, 1971. An Investigation of Techniques •
for Removal of Cyanide from Electroplating Wastes. EPA, WPCRS *
12010 ELE: 11/71:87 pp.
15. Battelle's Columbus Laboratories, ed., 1971. Water Quality Criteria |
Data Book Volume 3: Effects of Chemicals on Aquatic Life. EPA, WPCRS
18050GWV 05/71. _
16. Battelle Memorial Institute, 1968. A State-of-the-Art Review of Metal *
Finishing Waste Treatment. WPCRS 12010 EIE 11/68.
17. Battelle Memorial Institute, 1971. An Investigation of Techniques •
for Removal of Chromium from Electroplating Wastes. EPA:WPCRS
12010 EIE 03/71:91 pp. •
18. Beychok, M. R., 1971. "Performance of Surface-Aerated Basins." IN:
Water-1970: Chemical Engineering Progress Symposium Series 107: _
Vol 67:1971. L. K. Cecil, ed. pp 322-339. •
19. Black and Veatch, Consulting Engineers, 1971. Process Design Manual
for Phosphorus Removal. EPA, Program No. 17010 GNP, October 1971. •
20. Brungs, W. A., 1971. "Water Quality Criteria: Recommendations for
Total Residual Chlorine in Receiving Waters for the Protection of •
Freshwater Aquatic Life." Submitted to Francis T. Mayo, Regional •
Administrator, EPA, Region V, December 20, 1971.
I
23. Burns and Roc, Inc., 1971. Process Design Manual Jror Suspended Solids M
Removal. EPA, Program No. 17030 GNO, •
24. Camp, T. R., 1963. Water and its Impurities. Reinhold Publishing
Company, New York. 1963. 355p. I
A-2
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REFERENCES (CONT.)
25. Camp, W. S., 1969. "Poultry Processor Meets Challenge of Increased
Waste Load." Water and Sewage Works. 116:9IW 24-26 September 1969.
26. Convery, J. L. , 1970. Treatment Techniques for Removing Phosphorus
from Municipal Waste Waters. EPA, WPCRS:17010 01/70. 35pp.
27. Currie, D. P., 1971. "Effluent Criteria: Opinion of the Board."
Newsletter #36, 11-15-71. State of Illinois Pollution Control
Board.
28. Datagraphics, Inc., 1971. Projected Waste Water Treatment Costs in
the Organic Chemicals Industry (updated). EPA, WPCRS. No. 12020
GND 07/71, 161p.
29. Dobolyi, E., 1970. "Laboratory Model Experiments on the Chemical
and Biological Purification of Waste Water from the Dunary'varos
Paper Mill." Papiripar (Hung.) 14:2:39; Bull. Inst. Paper Chem.,
41:4:3345. (1970) TJS[: "Annual Literature Review" JWPCF 43:6
June, 1971.
30. Driver, W. J., 1971. "Where We Stand." Carrints, MCA March-April,
1971.
31. Eberhordt, W. A., and J. B. Nesbitt, 1968. "Chemical Precipitation
of Phosphorus in a High-Rate Activated Sludge System." JWPCF:
40:7:1239-1267. July 1968.
32. Eckenfelder, W. W., and D. J. O'Connor, 1961. Biological Waste
Treatment. Pergamon Press. New York. 299p.
33. Ellis, M. M., Westfull, B. A., and M. D. Ellis, 1941. "Arsenic in
Fresh-Water Fish." Ind. En&. Chem. 33:10:1331-1332 October, 1941.
34. EPA, 1971. Disinfection. EPA, OWP, Division of Water Quality
Standards, Washington, D. C., May 1971.
35. Esvelt, L. A., 1970. "Aerobic Treatment of Liquid Fruit Processing
Waste. IN: Proceedings: First National Symposium on Food Pro-
cessing Wastes. FWQA, WPCRS 12060:04/70:119-143.
36. Eye, J. D., 1970. Treatment of Sole Leather Vegetable Tannery Waste.
WPCRS 12120 WPD-185 09/70.
A-3
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REFERENCES (CONT.)
37. Fair, G. M., Geyer, J. C., and D. A. Okun, 1968. Water and Waste
Water Engineering. Volume 2, "Water Purification and Waste Water
Treatment and Disposal." John Wiley and Sons, Inc., New York.
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38. Ferguson, J. F., Jenkins, D., and W. Stumm, 1971. "Calcium Phosphate m
Precipitation in Waste Water Treatment." IN: Water-1970: I
Chemical Engineering Progress Symposium Series 107: Vol 67:1971.
L. K. Cecil, ed. pp 279-287.
39. Friberg, L., Piscator, M., and G. Nordberg, 1971. Cadmium in the »
Environment. EPA, Nat. Tech. Inf. Serv. No. PB 199 795. April,
1971. •
40. Ganczarczyk, J., 1968. "Protection of Surface Waters in Poland
Against Pollution by Effluents from Pulp and Paper Mills." Centre ^
Beige Etude Doc. Eaux. (Belg.) (CEBEDEAU), 21:291:23; Bull. Inst. •
Paper Chem. 40:10:9045 (1970) "Annual Literature Review" JWCPF *
43:6 June, 1971.
41. Geldreich, E. E., 1966. Sanitary Significance of Fecal Co11forms •
in the Environment. U. S. Department of the Interior, FWPCA,
Pub. No. WP-20-3 122p. •
42. General Technology Corporation, 1971. "Industrial Waste Study of
Inorganic Chemical, Alkalies and Chlorine." (EPA Draft Report- _
Unpublished.) •
43. Glide, L. C., 1970. "Food Processing Waste Treatment by Surface
Filtration." IN: Proceedings: First National Symposium on Food •
Processing Waste. FWQA, WPCRS 12060:04/70:311-326. |
44. Gloyna, E. F. and D. L. Ford, 1970. The Characteristics and Pollu- g
tional Problems Associated with Petrochemical Wastes, Summary •
Report, FWQA, WPCRS 12020: 2/70.
45. Gloyna, E. F. and D. L. Ford, 1970. The Characteristics and B
Pollutional Problems Associated with Petrochemical Wastes, Detail- B
ed Report, FWPCA, WPCRS 12021:2/70.
46. Graham, J. L. and J. W. Filbert, 1970. "Combined Treatment of |
Domestic and Industrial Waste by Activated Sludge." IN: Proceed-
ings : First National Symposium on Food Processing Wastes. FWQA, _
FWQA, WPCRS 12060:04/70:91-117. •
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REFERENCES (CONT.)
47. Grishina, E. E. and K. M. Izotova, 1969. "Anaerobic Fermentation
of Waste Waters from the Production of Wood-Fiber Board." Ochistka
Proizved. Stachnykh Vod (USSR), 4:165, Chem. Abs. 73:6:28625p
48. Gurnham, F. C., 1965. Industrial Waste Water Control, Academic
Press, New York. 1965 476p.
49. Henderson, A. D. , and J. J. Eaffa, 1954. "Wt.ste Disposal at a Steel
Plant Treatment of Flue Dust Waste." JSED, ASCE 80:494:9-54:1-8.
50. Hopkins, E. S., and G. M. Dutterer, 1970. "Liquid Wastes Disposal
from a Slaughterhouse." Water & Sewage Works, 117:7:lW-2. July,
1970.
51. Hydroscience, Inc., 1971. The Impact of Oily Materials on Activated
Sludge Systems. EPA, WPCRS 12050 DSH:03/71:110pp.
52. Johnson, E. L. , Beeghly, J. H., and R. F. Wukasch, 1969. "Phosphorus
Removal with Iron and Polyelectrolytes." Public Works. 100:11.
pp 66-67 and 142. November 1969.
53. Jones, R. H., 1970. "Lime Treatment and In-Flant Reuse of an Activated
Sludge Plant Effluent in the Citrus Processing Industry." IN: Pro-
ceedings: First National Symposium on Food Processing Wastes.
FWQA, WPCRS 12060:04/70:177-188.
54. Lambou, V., 1970. "Hazards of Mercury in the Environment with
Particular Reference1 to the Aquatic Environment." Unpublished.
55. Lambou, V., and B. Lim, 1970. "Hazards of Arsenic in the Environment
with particular reference to the Aquatic Environment." Unpublished.
56. Lambou, V., and B. Lim, 1970. "Hazards of Lead in the Environment
with particular reference to the Aquatic Environment." Unpublished.
57. Lawton, G. W., 1967. "Detergents in Wisconsin Waters." Jour. AWWA.
59:10:1327-1334. October 1967.
58. Linstedt, K. D., Houck, C. P., and J. T. O'Connor, 1971. "Traces
Element Removals in Advanced Waste Water Treatment Processes."
JWPCF 43:7:1507-1513:1971.
59. Arthur D. Little, Inc., ed. Water Quality Criteria Data Book
Volume 1 Organic Chemical Pollution of Freshwater. EPA, WPCRS;
18010DPV.
60. Little, A. D., 1971. Draft copy of - Industrial Waste Studies
Program Textile Mill Products. WOO, EPA. May 1971.
A-5
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REFERENCES (CONT.)
61. Lund, H. E. ed., 1971. Industrial Pollution Control Handbook. "
McGraw-Hill 1971. 26 Chapt.
62. Lyons, D. N., and W. W. Eckenfelder, Jr., 1971. "Optimizing a Kraft •
Mill Water Reuse System." IN: Water-1970; Chemical Engineering
Progress Symposium Series 107: Vol 67:1971. L. K. Cecil, ed. g
pp 381-387. •
63. Massey, A., and J. Robinson, 1971. "A Review of the Factors Limit-
ing the Growth of Nuisance Algae." Water _& Sewage Works. 118:11: •
352-355. November 1971. •
64. McDonough, W. P., and F. A. Steward, 1971. "The Use of the Integrated •
Waste Treatment Approach in the Large Electroplating Shop." IN: •
Water-1970: Chemical Engineering Progress Symposium Series 107:
Vol 67:1971. pp 428-431. ^
65. McGaruey, F. X., Tenhoor, R. E., and R. P. Nevers, 1959. "Brass *
and Copper Industry: Cation Exchanges for Metals Concentration
from Pickle Rinse Waters." Ind. & Engr. Chem. 44:3:534-541. •
March 1952. •
66. McKee, J. E. , and H. W. Wolf, ed. Water Quality Criteria, 2nd ed., tm
1963. State Quality Control Board, California. Pub. No. 3-A. •
548pp.
67. Menar, A. B., and D. Jenkins, 1970. "Fate of Phosphorus in Waste •
Treatment Processes: Enhanced Removal of Phosphate by Activated •
Sludge." Environ. Sci^ & Tech. 4:12:1115-1121. December 1970.
68. Merrill, W. H., 1970. "Treatment Plant Designed for Frozen Meat
Wastes." Water & Waste Eng., 7:5:C-5, May 1970.
69. Michel, R. L., 1970. "Cost and Manpower for Municipal Waste Water I
Treatment Plant Operation and Maintenance, 1965-1968." JWPCF.
42:1883 (1970).
70. Mulbarger, M. C. and D. G. Shifflett, 1971. "Combined Biological •
and Chemical Treatment for Phosphorus Removal." IN: Water-1970:
ChemicalEngineering Progress Symposium Series 107:Vol 67:1971.
L. K. Cecil, ed. pp 107-116.
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71. Nemerow, H. L., 1963. Theories and Practices of Industrial Waste ^
Treatment. Addison-Wesley Publication Company, Inc., Reading, •
Massachusetts, 557p.
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REFERENCES (CONT.)
72. Nemero^, H. L., 1971. Liquid Waste of Industry: Theories, Practices,
and Treatment. Addison-Wesley 1971. 584pp.
73. Nesbitt, J. B., 1969. "Phosphorus Removal the State of the Art."
JWPCF. 41:5:701-713. May 1969.
74. O'Connor, J. T., 1972. Professor of Sanitary Engineering, University
of Illinois, Urbana, Illinois. (Personal Communication)
75. Parker, C. E., 1970. Anaerobic-Aerobic Lagoon Treatment for Vegetable
Tanning Wastes. EPA, WPCRS 12120 DIK 12/70.
76. Patterson, J. W., and R. A. Minear, 1971. Waste Water Treatment
Technology. Illinois Institute of Environmental Qaulity, August
1971. 279pp.
77. Raabe, E. W., 1968. Biochemical Oxygen Demand and Degradation of
Lignin in Natural Waters." JWPCF, 40:R145-R150, May 1968.
78. Rich, L. G., 1961. Unit Operations of Sanitary Engineering. John
Wiley & Sons, Inc., New York. 308p.
79. Rich, L. G., 1963. Unit Processes of Sanitary Engineering. John
Wiley & Sons, Inc., New York. 190p.
80. Salutsky, M. L. Et al., 1971 "Ultimate Disposal of Phosphate from
Waste Water by Recoveiy as Fertilizer." IN: Water—1970:
Chemical Engineering Progress Symposium Series 107:Vol 67:1971, L.
K. Cecil, ed. pp 44-62.
81. Sawyer, C. N., and P. L. McCarty, 1967. Chemistry for Sanitary
Engineers. McGraw-Hill, New York. 518p.
82. Schmid, L. A. and R. E. McKinney, 1969. "Phosphate Removal by a
Lime-Biological Treatnent Scheme." JWPCF, 41:7:1259-1276.
July 1969.
83. Schneider, R. F., 1971. "The Impact of Various Heavy Metals on
the Aquatic Environment." EPA, WQP. Tech. Report No. 2,
February 1971.
84. Schulze, K. L., 1955. "Experiences with a New Type of Daily Waste
Treatment." JSWS, ASCE 81"847:12-55:1-3.
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REFERENCES (CONT.)
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85. Selikoff, I. J., ed., 1971. Hazards of Mercury. Environmental
Research, Academic Press, New York. Vol 4:1 March 1971. 69p. •
86. Smith, R. , 1968. "Cost of Conventional and Advanced Treatment of.
Waste Waters." JWPCF, 40:9:1546. September 1968.
87. Soderguist, M. R., Et al., 1970. Current Practice in Seafood ™
Processing Waste Treatment. EPA, WQO, WPCRS 12060 ECF 04/70 120pp.
88. Spiegel, M. and T. H. Forrest, 1969. "Phosphate Removal: Summary of |
Papers." Jour. SED, ASCE, SA5:6807:803-815. October 1969.
89. Spohr, G. and A. Talts, 1970. "Phosphate Removal by pH Controlled I
Lime Dosage." Public Works. 101:7, pp 63-67. July 1970.
90. Stanier, R. Y., Doudoroff, M., and E. A. Adelberg, 1963. The ft
Microbial World, 2nd ed. Prentice-Hall, Inc., Englewood Cliffs, ft
N. J. 753p.
91. Stanley Consultants, Inc., 1971. Draft copy of-Effluen t Requirements |
for the Leather Tanning and Finishing Industry. WQP, EPA,
September 1971. _
92. Stewart, M. J., 1964. "Activated Sludge Process Varations: The *
Complete Spectrum." W & SW, Reference Number - 1964: R-241-262.
93. Thomas, A. A. and W. H. Brown, 1968. "Closed-Loop Chlorination for ft
Waste Waters." JWPCF, 40:4:684, April 1968.
94. U. S. Public Health Service. Drinking Water Standards. Revised I
1962. Pub. No. 956. Washington, D. C. 1962.
95. Van Den Berg, L. A., Personal communication, January 1972. •
96. Volco Brass and Copper Company, 1971. Brass Wire Mill Pro cess
Changes and Waste Abatementv Recovery and Reuse. EPA, WPCRS •
12010 DPF 11/71:44 pp. ft
97. Weston, R. F., 1971. "Testimony Presented to the Illinois Pollution £
Control Board." October 1, 1971. I
98. Wieferig, T., 1969. "Practical Experience with the Purification of
Sewage from Poultry Slaughterhouses." Muechner, Beitr. Abwasser I
Fish. Flussbiol. (Ger.), 16:282: Chem. Abs. 72:47182n (1970) ft
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REFERENCES (CONT.)
99. Wilmoth, R. C., and R. D. Hill, 1970. Neutralization of High
Ferric Iron Acid Mine Drainage. WPCRS 14010 ETV 08/70.
100. Anom. Current Events, "Biochemical Role of Selenium described"
C & E News May 1, 1972 p.16.
101. Clarkson, T. W. "Recent Advances in the Toxicology of Mercury
with Emphasis on the Alkylmercurials" CRC Critical Reviews in
Toxicology 203-234, March 1970.
102. Jernelov, A. "Conversion of Mercury Compounds", (in Miller, M. W.,
ed., Chemical Fallout, Thomas, Illinois, 1969, Chapter 4, p.68).
103. Johnson, W. F. and Hindin, E. 1972 "Bioconcentration of Arsenic
vy Activated Sludge Biomass" Water and Sewage Works, Vol 119
No. 10 pp. 95-97 (Oct. 1972).
104. Lakin, H. W. 1971 "The Geochemical, Cycle of Selenium in our
Environment", (ACS Meeting, Washington, D.C., Sept. 1971, un-
published) .
105. Little, A. D., Walter Quality Criteria Data Book, Vol. 2., Inor-
ganic Chemical Pollution of Freshwater.
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WATER QUALITY CRITERIA RECOMMENDATIONS FOR TOTAL RESIDUAL
CHLORINE IN RECEIVING WATERS FOR THE PROTECTION OF
1
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FRESHWATER AQUATIC LIFE
by
William A. Brungs ,Ph.D.
and Staff (20)
National Water Quality Laboratory
Duluth , Minnesota
The recommendations are:
RECOMMENDATION FOR TOTAL
TYPE OF CRITERIA RESIDUAL CHLORINE
continuous 0.01 mg/liter
continuous 0.002 mg/liter
intermittent A. 0.1 mg/liter not
to exceed 30 minutes
per day.
B. 0.05 mg/liter not
to exceed 2 hours
per day.
LEVEL OF PROTECTION
This level would pro-
bably not protect trout
reproduction, some im-
portant fish food organisms
and could be partially
lethal to sensitive life
stages of sensitive fish
species.
This level should pro-
tect most aquatic
organisms.
These levels should not
result in significant
kills of aquatic organ-
isms or adversely
affect the aquatic ecology.
The above recommendations in clean water require the use of the
amperometric titration method that is among the most
determination of free or combined available chlorine
accurate for the
. The method is
largely unaffected by the presence of common oxidizing agents , temperature
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variations, and turbidity and color, which interfere with the accuracy •
of the other methods. Simpler methods, such as orthotolidine, are
best suited for the routine measurement of total residual chlorine, •
but are commonly affected by the above interferences and provided appre- •
ciably lower values than actually occur (Standard Methods, 1971).
These colorimetric methods may provide a measure as low as 10% or less •
than the real level depending upon interferences.
Despite the fact th.it there are several significant studies in |
progress to evaluate the effects of total residual chlorine in waste M
and cooling waters, theri are available sufficient data to make rather
accurate estimates of criteria to protect freshwater aquatic life. Studies •
are being conducted by the National Water Quality Laboratory on sewage
plant effluent, the City of Wyoming, Michigan on domestic and combined |
sewage plant effluent (EPA Demonstration Grant, 17060 HJB), the Michigan _
Water Resources Commission on chlorinated power plant condenser cooling
waters, and the University of California, Berkeley, on the toxicity of •
treated municipal effluents. It is probably that the results of these
studies will either confirm or necessitate more stringent criteria re- |
commendations.
The recommendations for continuous total residual chlorine levels
are based on the maximum levels that would provide for the successful •
completion of life cycles, including reproduction, of aquatic organisms
and the relative persistence of total residual chlorine in the environ- •
ment (Table 1). Obviously the persistence of chlorine is greater than
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commonly thought and it clearly does not disappear in minutes as is
often stated. The Michigan Water Resources Commission observed fish
mortality in cages up to one mile below a sewage outfall (Basch, 1971).
«
In other studies by the same organization, during which total residual
• chlorine was not measured, fish were killed in cages up to 4 miles
downstream (Fetterolf, 1970).
| Many of the recent investigations of chlorine toxicity have in-
M eluded analytical determinations of total residual chlorine to which
" the test organisms were exposed. These more recent studies have also
• utilized continuous flow procedures which alleviate the problem of
gradually declining total residual chlorine concentrations characteris-
I tic of static, or standing volume, bioassays. Despite the fact that
^ nearly 120 publications, reports, etc., were read and evaluated prior
* to making the above recommendations, 15-20 of these papers provided
B the basis for the recommendations. A summary of these data is shown
in Table 2.
• Trout and salmon appear to be the most sensitive fish species
(Holland, et al. , 1960; Merkens, 1958; Arthur, 1971; Basch, 1971; Conventry
™ et al., 1935; Sprague and Drury, 1969; Taylor and James, 1928; and
• Tsai, 1971). Some fish food organisms such as scuds, cladocerans, and
protozoans are also rather sensitive (Arthur, 1971; Arthur and Eaton,
• 1972; Hale, 1930; Biesinger, 1971). Smallmouth bass are almost as
sensitive as trout (Tasi, 1971 and Pyle, 1960) while crayfish, snails,
• mussels, bullfrog tadpoles, oligochaetes , algae, and stoneflies are
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generally more resistant (Sinclair, 1964; Kott, et al, 1966; Learner
and Edwards, 1968; Panikkar, 1960; Arthur, 1971; and Coventry, et al, •
1935).
The recommendations for discontinuous total residual chlorine
in fresh water are on less firm ground due to the scarcity of data on •
toxic effects during a few minutes to a few hours of exposure. Pro-
bably the most pertinent data, again developed by the Michigan Water •
Resources Commission, observed in a power plant discharge canal erratic •
swimming by fish of several within 6 minutes of the initiation of
chlorination by the plant. At this time the total residual chlorine •
was 0.09 mg/liter (Truchan, 1971). After 15 minutes there were dead
fish at a total chlorine residual of 0.28 mg/liter. Other studies have £
shown rainbow trout killed in 2 hours at 0.3 mg/liter (Taylor and James, •
1928), brook trout median mortality was 90 minutes at 0.5 mg/liter
and smallmoutn bass median mortality was 15 hours at 0.5 mg/liter (Pyle, •
1960). Trout fry were killed instantly at 0.3 mg/liter (Coventry, et al,
1935). Chinook salmon, which have been introduced into Lake Michigan, ||
started to die in 2.2 hours at 0.25 mg/liter in salt water (Holland, et al, _
1960). Arthur (1971) has shown that the 1-hour median tolerance limit *
was slightly above 0.7 mg/liter for fathead minnows, yellow perch, and •
largemouth bass although the 12-hour median tolerance limits for these
species is between 0.3 and 0.5 mg/liter. Unfortunately, no extensive |
studies have been conducted to determine the fate of aquatic organisms _
upon returning to water containing no total residual chlorine following *
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a brief exposure to lethal concentrations. Preliminary studies with
• Daphnia Magna, a cladoceran, indicate that they did not recover from
a 4-hour exposure to what would have been a lethal concentration
| (0.125 mg/liter), after being returned to uncontaminated water (Natlon-
M al Water Quality Laboratory, 1971). In this latter study some fathead
minnows were killed in 2 hours at 0.45 mg/liter and 20% were killed in
I 7 hours at 0.2 mg/liter.
These data indicate the chlorination of cooling water should be
| avoided whenever possible to reduce undue stress or risk to the aquatic
« environment resulting from commonly-occuring excessive use of chlorine.
When chlorine is added to water for the purposes of disinfection,
• reduction of biochemical demand or antifouling, the dissolved materials
in the water acted upon are oxidized or combine with chlorine. The
• addition of chlorine to compounds slows the degradation rate of the
_ compound and is in part responsible for lower or reduced biochemical
™ oxygen demand of a chlorinated waste. Chlorine residual is commonly
• stabilized by the addition of ammonia and the resulting chloramines
persist for much longer periods of time than does the hypochlorite ion.
I Chlorine is known to combine with organoamines , phenols, lipids, thio-
cyanate, aromatic hydrocarbons, several perticides and carcinogens,
• terpenes and humates.
• Experiments are currently underway in several laboratories to assess
the extent of the hazards of these organochlorine compounds and to
• identify them.
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Decline in Total Residual Chlorine with Time in Static
Bioassay Chambers*
TOTAL RESIDUAL CHLORINE
(mg/liter)
INITIAL
2.10
1.02
0.50
0.26
0.13
2HOURS
1.90
0.96
0.41
0.18
0.07
7 HOURS
1.66
0.83
0.32
0.15
0.035
24 HOURS
1.09
0.42
0.18
0.04
0.001
48 HOURS
0.47
0.12
0.001
0.001
0.001
72 HOURS
0.10
0.001
0.001
0.001
0.001
secondary sewage plant effluent and the mixture was split and then
chlorinated to the initial concentrations.
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We further realize that our recommendations run counter to the
minimal recommendations for total residual chlorine in municipal
seqage effluent (usually 0.5 to 1.0 mg/liyer). For this reason it is
advisable that our Agency seriously consider the feasibility of al- •
ternate disinfection procedures to avoid the problem of toxicity and
the formation of potentially harmful organochlorine compounds. |
TABLE 1 |
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* Nine volumes of Lake Superior water were mixed with one volume
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1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
TABLE II
Selected Summary of Toxic Effects of Total Residual Chlorine
on Aquatic Life.
SPECIES
trout fry
rainbow trout
rainbow trout
rainbow trout
rainbow trout
brook trout
coho salmon
pink salmon
coho salmon
pink salmon
coho salmon
brook trout
brown trout
fathead minnow
fathead minnow
walleye
black bullhead
white sucker
yellow perch
largemouth bass
smallmouth bass
scud
scud
cladoceran
fish species
diversity
protozoa
fathead minnow
aTLSO = median
RESIDUAL CHLORINE
CONCENTRATION ,
EFFECT ENDPOINT MG/LITER
lethal (2 day) 0.06
96-hr. TL50 a 0.14-0.29
7-day TL50 0.08
lethal (12 day) 0.01
avoidance 0.001
7-day TL50 0.083
7-day TL50 0.083
100% kill (1-2 day) 0.08-0.10
100% kill (1-2 day) 0.13-0.20
max. non-lethal 0.05
max. non-lethal 0.05
not found in streams 0.015
not found in streams 0.015
96-hr. TL50 0.05-0.16
7-day TL50 0.082-0.115
7-day 0.15
96-hr. TL50 0.099
7-day TL50 0.132
7-day TL50 0.205
7-day TL50 0.261
not found in streams 0.1
safe concentration 0.0034
safe concentration 0.012
0.001
50% reduction 0.01
lethal 0.1
safe concentration 0.0165
tolerance limit
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BRUNGS '
REFERENCES
Coventry et al, 1935
Basch, 1971
Merkens, 1958
Sprague & Drury, 1969
Sprague & Drury, 1969
Arthur, 1971
Arthur, 1971
Holland et al, 1960
Holland et al, 1960
Holland et al, 1960
Holland et al, 1960
Tsai, 1971
Tsai, 1971
Zillich, 1969 & Zillich
& Wuerthele, 1969
Arthur, 1971
Arthur, 1971
Arthur, 1971
Arthur, 1971
Arthur, 1971
Arthur, 1971
Tsai, 1971
Arthur & Eaton, 1972
Arthur, 1971
Biesinger, 1971
Tsai, 1971
Hale, 1930
Arthur & Eaton, 1972
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CITED REFERENCES
American Public Health Association, 1971. Standard methods for the
examination of water and wastewater. 13th Ed., APHA, New York, •
N.Y., pp. 874. I
Arthur, J.W., 1971. Quarterly Progress Reports. National Water _
Quality Laboratory, Duluth, Minnesota. I
Arthur, J.W., and J.G. Eaton, 1972. "Toxicity of Chloramines to the
Amphipod, Gammarus Pseudolimnaeus Sousfield, and the Fathead I
Minnow, Pimephales Promelas Rafinesque". Accepted for publica- •
tion in J. Fish. Res. Bd. Canada.
Basch, R.W., 1971. "In-situ Investigations of the Toxicity of Chlori- I
nated Municipal Wastewater Treatment Plant Effluents to Rainbow
Trout (Salmo Gairdneri) and Fathead minnows (Pimephales Promelas)" _
Bureau of Water Management, Michigan Department of Natural Re- I
sources, Lansing, Michigan 48926, pp. 50. •
Biesinger, K.E., 1971. Personal communication. National Water Quality •
Laboratory, Duluth, Minnesota. |
Coventry, F.L., V.E. Shelford, and L.F. Miller, 1935. "The Conditioning «
of a Chloramine Treated Water Supply for Biological Purposes". I
Ecology 16: 60-66.
Fetterolf, G., 1970. "Summary of Staff Investigations into the Toxicity I
of Chlorine to Fish". Presented to the Water Resources Commission, •
June 25-26, 1970. Muskegon, Michigan, pp. 5.
Hale, F.E., 1930. "Control of Microscopic Organisms in Public Water |
Supplies with Particular Reference to New York City". New England
Water Works Asjsociation 44: 361-385. g
Holland, G.A., J.E. Lasater, E.D. Neumann, W.E. Eldridge, 1960. "Toxic •
Effects of Organic and Inorganic Pollutants on Yound Salmon and
Trout". State of Washington, Department of Fisheries, Research I
Bulletin No. 5, pp. 186-214. •
Kott, Y., G. Hershkovitz, A. Shemtob, and J.B. Sless, 1966. "Algicidal •
Effect of Bromine and Chlorine on Chorella Pyrenoidosa". Appl. |
Microbiol. 14 (1): 8-11.
Learnei, M.A., and R.W. Edwards, 1968. "The Toxicity of Some Substances I
to Nais (Oligochaeta)". Society for Water Treatment and Examina- •
12 (3): 161-168.
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Merkens, J.C., 1958. "Studies on the Toxicity of Chlorine and Chlora-
mine to the Rainbow Trout". Water and Waste Treatment Journal
7: 150-151.
National Water Quality Laboratory, 1971. Unpublished data.
Panikkar, B.M., 1960. "Low Concentrations of Calcium Hypochlorite as
a Fish and Tadpole Poison Applicable for Use in Partly Drained Ponds
and Other Small Bodies of Water". Progressive Fish-Culturist
22: 117-120.
Pyle, E.A., 1960. "Neutralizing Chlorine in City Water for Use in Fish-
distribution Tanks". Progressive Fish-Culturist 22: 30-33.
Sinclair, R.M., 1964. "Clam Pests inTennessee Water Supplies". JAWWA
56 (5): 592-599.
Sprague, J.B., and D.E. Drury, 1969. "Avoidance Reactions of Salmonid
Fish to Representative Pollutants". Advances in Water Pollution
Research, Proceedings of the 4th International Conference.
pp. 169-179.
Taylor, R.S., and M.C. James, 1928. "Treatment for Removal of Chlorine
from City Water for use in Aquaria". U.S. Bur. Fish Doc. #1045.
Rept. U.S. Comm. Fish App. 7: 322-327.
Truchan, J., 1971. Personal communication. Michigan Water Resources
Commission.
Tsai, C., 1971. "Water Quality and Fish Life Below Sewage Outfalls".
University of Maryland.
Zillich, J.A. "The Toxicity of the Wyoming Wastewater Treatment Plant
Effluent to the Fathead Minnow , December 8-12, 1969". 7 p.
Zillich, J.A., and M. Wuerthele. "The Toxic Effects of the Grandville
Wastewater Treatment Plant Effluent to the Fathead Minnow, Pimep-
hales Promelas". November 17-21, 1969. pp. 4.
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CAPITAL AND OPERATING COSTS
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Indiv dual cost data are presented in the individual sections
• when such data exist. However, in the treatment of municipal and
• industrial effluents, a finite number of unit operations are
required for the treatment of the wastewater.
• Cost data have been prepared by Burns and Roe (23), Datagraphics
Inc. (28), Smith (86) and Mitchel (69). These published data include
• capital, operation, and maintenance costs for the individual processes.
• Also the total costs, including debt service for the process, are
presented. Most of the data were prepared over a different period
• of time. Hence the cost index is not the same for all of the
charts. When the costs for a plant are compared, care must be
• taken to assure that the same cost index is used for all comparisons.
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