PB84-232495
Toxicity Treatability of Iron and Steel
Plant Wastewaters: A Resource Document
Research Triangle Inst.
Research Triangle Park, NC
Prepared for
Industrial Environmental Research Lab,
Research Triangle Park, NC
Aug 84
U.S. DEPARTMENT OF COMMERCE
National Technical Information Service
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FB84-232495
EPA-600/2-84-137
August 1984
TOXICITY TREATABILITY
OF
IRON AND STEEL PLANT WASTEWATERS
A RESOURCE DOCUMENT
by
Ben H. Carpenter, M. R. Branscome,
C. Wayne Westbrook, W. F. Gutknecht,
and Alvia Gaskill
Contract No. 68-02-3125
EPA Project Officer: David Sanchez
Industrial Environmental Research Laboratory
Research Triangle Park, North Carolina 27711
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH'AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NC 27711
REPRODUCED BV
NATIONAL TECHNICAL
INFORMATION SERVICE
U.S. DEPARTMENr OF COMMERCE
SPRINGFIELD. VA. 22161
U.S. EPA-NEIC LIBRARY
Denver Federal Center
Building 25, Ent. El-3
P.O. Box 25227
Denver, CO 8022(5-0227
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ierl-rtp-1665
TECHNICAL REPORT DATA
(Please read laslructions on the reverse before completing)
1. REPORT NO.
EPA-600/2-84-137
2.
3. RECIPIENT'S ACCESSION NO.
P58* 232 A 9 5
4. TITLE AND SUBTITLE
Toxicity Treatability of Iron and Steel Plant
Wastewaters: a Resource Document
5. REPORT DATE
August 1984
6. PERFORMING ORGANIZATION CODE
?. AUTHORISIB. H. Carpenter, M. R. Branscome, C. W. West-
brook, W. F. Gutknecht, and A. Gaskill
8. PERFORMING ORGANIZATION REPORT NO.
^PERFORMING ORGANIZATION NAME AND ADDRESS
Research Triangle Institute
P. O. Box 12194
Research Triangle Park, North Carolina 27709
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-02-3125
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PE
Final; 4/82 - 8/83
PERIOD COVERED
14. SPONSORING AGENCY COOI:
EPA/600/13
^.SUPPLEMENTARY NOTES jERL-RTP project officer is David C. Sanchez, Mail Drop 54,
919/541-2979.
16. ABSTRACTTne repOrt gives results of an assessment of the toxicity treatability of
wastewaters from eight steelmaking subcategories, all considered assessable under
the somewhat low production levels of the study period. Tests were conducted using
prescribed procedures for conventional water contaminants, toxic organics, and
static bioassay. Samples were collected before and after units of the wastewater
treatment systems. All tests were done under the 'auspices of a quality assurance
program. Efforts were made to ensure representativeness of all samples; e. g.,
if the production facilities were operating only one turn, samples were collected only
during that turn. Results show the relative toxicity and variability of wastewaters
from the different manufacturing subcategories and the reductions in toxicity. Rela-
tionships between pollutant content and toxicity are examined with cognizance of the
possible site uniqueness of the data.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSAT: Field/Croup
Pollution Bioassay
Iron and Steel Industry
Waste Water
Water Treatment
Toxicity
Assessments
Pollution Control
Stationary Sources
13 B
11F
06T
14B
06A
13. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
111
20. SECURITY CLASS (Thispage)
Unclassified
22. PRIC
EPA Form 2220-1 (9-73)
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DISCLAIMER AND PEER REVIEW NOTICE
The information in this document has been funded wholly or in part by the
United States Environmental Protection Agency under contract number 68-02-3125.
It has been subject to the Agency's peer and administrative review, and it has
been approved for publication as an EPA document. Mention of trade names or
commercial products does not constitute endorsement or recommendation for use.
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ABSTRACT
As part of its toxic pollutant control program, the Environmental Protec-
tion Agency (EPA) has gathered information about priority toxic pollutants in
wastewaters discharged by the iron and steel industry (46 FR 1858). Little
information is available, however, on the effects of these pollutants and
their combinations on bioassay (toxicity) test species. Nor is it known how
effective the treatment processes identified in model treatment systems may be
in reducing their concentrations and the toxic effects.
Because a bioassay can simultaneously assess the effects of numerous
toxic pollutants, it is a useful test of overall toxicity and of toxicity
reduction resulting from various wastewater treatments. Bioassay data, together
with toxic pollutant data and the relevant parameters of the industrial process,
can guide the formulation of regulatory strategy and help in the selection of*
effective treatments that will reduce toxic impacts oh receiving waters.
This study assessed the toxicity treatability of wastewaters from eight
steelmaking subcategories. The study was limited to those treatment systems
considered assessable under the somewhat low production levels of the study
period.
Testing programs were conducted using prescribed procedures for conven-
tional water contaminants, toxic organics, and static bioassay. Samples were
collected before and after units of the wastewater treatment systems. All
testing was done under the auspices of a quality-assurance program. Efforts
were made to insure representativeness of all samples. For example, if the
production facilities were operating only one turn, samples were collected
only during that turn.
The results show the relative toxicity and variability of wastewaters
from the different manufacturing subcategories and the reductions in toxicity.
Relationships between pollutant content and toxicity are examined with cognizance
of the possible site uniqueness of the data.
iii
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TABLE OF CONTENTS
Section Page
Abstract
List of Figures V11
List of Tables .viii
Acknowledgment x
List of Abbreviations for Wastewater Treatments xi
1.0 INTRODUCTION 1
2.0 SELECTION OF TREATMENT SYSTEMS FOR STUDY 2
3.0 SAMPLING AND ANALYSIS 4
4.0 RESULTS AND DISCUSSION 6
4.1 Cokemaking . 6
4.2 Ironmaking • 18
4.3 Steelmaking 21
4.4 Continuous Casting 27
4.5 Hot Strip and Cold Rolling Mills 31
4.6 Slabbing Mills 36
4.7 Section Mills 40
4.8 Pickling 45
4.9 Cold Forming 48
4.10 Hot Coating 52
4. 11 .Central Treatment 52
5.0 QUALITY 'ASSURANCE 56
5.1 Quality Assurance Project Plan 56
5.2 Objectives and Standards 58
5.3 Precision 58
5.4 Accuracy 58
5.5 Precision and Accurate Methods 624 and 625 61
5.6 Tuning the GC/MS • 63
5.7 Calibration 63
5.8 Reagent Blanks 64
5.9 Surrogate Spikes and Extraction Controls 64
5.10 Metals 66
5.11 Bioassay Quality Assurance, Accuracy, and Precision 66
5.12 Comparability 68
5.13 Completeness 68
Preceding page blank
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TABLE OF CONTENTS (continued)
Section Page
6.0 SUMMARY OF EFFLUENT TOXICITY DATA 72
6.1 Iron and Steel Process Wastewaters 72
6.2 Summary of Existing Toxicity Data 75
6.2.1 Coke-Plant Effluent Toxicity 76
6.2.2 Ironmaking Wastewater Toxicity 82
6.2.3 Steelmaking Effluent Toxicity 87
6.2.4 Hot-Forming Effluent Toxicity 90
6.2.5 Acid Pickling Wastewater Toxicity 93
6.2.6 Cold-Forming Effluent Toxicity 96
6.2.7 Hot-Coating Effluent Toxicity . 99
6.2.8 Combined Effluent Toxicity 99
7.0 REFERENCES 101
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LIST OF FIGURES
Number Page
Cokemaking 9
Ironmaking—wastewater treatments and sampling 19
Steelmaking—wastewater treatments and sampling 23
Continuous casting—treatments and sampling 28
Hot forming, hot-strip mills,—treatments and sampling 32
Hot forming, slabbing mills,—treatments and sampling 38
Hot forming section mills treatments and sampling 41
Pick!ing--treatments and sampling 46
Cold forming--treatments and sampling 50
Hot coating galvanizing—treatments and sampling 53
Central treatment, systems and sampling 55
vii
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LIST OF TABLES
Number Page
3-1 Methods of Analysis 5
4-1 . Bioassay Results, Daphnia 7
4-2 . Bioassay Results, Minnows 8
4-3 Cokemaking: Pollutant Reduction, Plant C 11
4-4 Water Quality Criteria and Toxicity Limits 12
4-5 Cokemaking: Pollutant Reduction, Plant D 14
4-6 Cokemaking: Pollutant Reduction, Plant G 16
4-7 Cokemaking: Comparative Tests of Resamples Physical
Chemical System 17
4-8 Ironmaking: Pollutant Reduction, Plant A 20
4-9 Ironmaking: Pollutant Reduction, Plant D 22
4-10 Steelmaking, Suppressed Combustion: Pollutant Reduction,
Plant A 25
4-11 Steelmaking: Semi-Wet Open, Plant A 26
4-12 Continuous Casting: Pollutant Reduction, Plant B 29
4-13 Continuous Casting: Pollutant Reduction, Plant E 30
4-14 Hot Forming, Hot Strip, Cold Rolling: Pollutant Reduction,
Plant A 33
4-15 Hot Forming: Pollutant Reduction, Plant D 35
4-16 Hot Forming: Pollutant Reduction, Plant F ' 37
4-17 Hot Forming, Slab Mill, Hot Strip Mill, and Central Treatment:
Pollutant Reduction, Plant A 39
4-18 Hot Forming Slab Mill: Primary Pollutant Reduction,
Plant B 42
4-19 Hot Forming Bar Mill: Pollutant Reduction, Plant A 43
4-20 Hot Forming Section Mill: Pollutant Reduction, Plant E 44
4-21 Pickling: Pollutant Reduction, Plant F, Combination 47
4-22 Pickling and Cold Rolling: Pollutant Reduction,
Plant B, HC1 . 49
4-23 Cold Forming, Once-Through Tandem Mill:
Pollutant Reduction, Plant A 51
4-24 Hot Coating, Galvanizing: Pollutant Reduction, Plant C 54
5-1 Specifications for Analytical Results 59
5-2 Analyses of PedCo, EPA, and In-house QA Samples at RTI 60
5-3 Decafluorotriphenylphosphine, Key Ions, and Ion Abundance 62
5-4 Bromofluorobenzene, Key Ions, and Ion Abundance 62
5-5 Bioassay Test Precision 69
5-6 Comparative Analytical Results 70
viii
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LIST OF TABLES (continued)
Number Page
6-1 Iron and Steelmaking Raw Wastewater Characteristics 73
6-2 Regulated Pollutant List, Iron and Steel Industry 75
6-3 Toxicity Data, Cokemaking Wastewater 77
6-4 Toxicity Data, Ironmaking Wastewater 83
6-5 Toxicity Data, Steelmaking Wastewater 88
6-6 Toxicity Data, Hot-Forming Wastewater 91
6-7 Toxicity Data, Acid Pickling Wastewater 94
6-8 Toxicity Data, Cold-Forming Wastewater 97
6-9 Toxicity Data, Combined Effluent from
Integrated Plant . 100
IX
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ACKNOWLEDGMENT
This study was supported by the Industrial Environmental Research Labora-
tory of the U.S. Environmental Protection Agency under Contracts No. 68-02-3152
and No. 68-02-3173, Robert McCrillis, project manager. The experimental work
was conducted by RTI and by PedCo Environmental Inc. under separate work
assignments. PedCo work was carried out under the direction of Mr. Gopal
Annamraju.
The authors wish to thank Mr. David Sanchez, the EPA project officer, for
his guidance and support during all phases of the work. Also, we are grateful
for the support of Mr. Bruce Newton, Office of Water Enforcement and Permits,
EPA-Washington, during the study.
We wish to thank Dr. William Peltier and Ms. Kay Lamotte of EPA's Region
IV Environmental Services Division, Messrs. H. R. Preston and James Green of
EPA's Region III Field Office, and Dr. William Horning of EPA's Newtown Fish
Toxicology Station at Cincinnati for the bioassays performed. Much of the
existing toxicity data was supplied from EPA Regional Offices and State Agencies.
Their assistance is greatfully acknowledged.
Several iron and steel companies cooperated in this study by providing
access to their treatment systems. Although these companies are not identi-
fied, their cooperation is gratefully acknowledged.
Thanks are also extended to the Regional Offices, and therein in par-
ticular to Messrs. Terry Oda and Gary Amandola, for their assistance in survey-
ing the available data and in arranging for treatment system studies.
Mr. Oda and Dr. Peltier reviewed the draft report and offered helpful
suggestions which were incorporated in the final report.
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LIST OF ABBREVIATIONS FOR WASTEWATER TREATMENTS
A acidification
AF air flotation
AO air oxidation
ASF free ammonia still
ASFF-L free and fixed ammonia still-lime addition
BOA-1 one-stage biological reactor
BOA-2 two-stage biological reactor
CAG carbon adsorption, granular
CL clarifier
CLA alkaline chlorination
CNT central treatment
CRT chrome pretreatment
CT cooling tower
CYPT cyanide pretreatment
DP dephenolization
DS desulfurization
E equalization
FDMMG deep filtration, mixed media, gravity
FDMMP deep filtration, mixed media, pressure
FDS deep sand filter
FDSP deep sand filter, pressure
FDW deep walnut shell filter
FM-A flash mixture - alum.
FLF flocculation with ferric chloride
FLL flocculation with lime
FLP flocculation with polymer
FP pressure filtration
HOD hot oil decanter
N neutralization
NA neutralization with acid
NC neutralization with caustic
NL neutralization with lime
OWS oil-water separator
PSP . primary scale pit
RC( ) recycle (percent)
SB settling basin
SL settling lagoon
SL-U settling lagoon for underflow
ST-CL scalping tank, with chlorination
SS surface skimmer
SSP secondary scale pit
T . thickener
VF vacuum filtration
VF-S vacuum filtration of sludge
XI
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1.0 INTRODUCTION
Raw wastewaters from iron and steel manufacturing processes have been
shown to contain potentially toxic pollutants [1]. Wastewater treatment
techniques have been assessed for their effectiveness in removing identified
and regulated pollutants from wastewaters generated by eight manufacturing
process subcategories. The effectiveness of various treatment techniques in
reducing biotoxicity has not been assessed, however. Outfall compliance data
identify toxicities that persist, after currently applied treatments, in waste-
waters from cokemaking, ironmaking, and steelmaking [2-12]. Available data for
cold-forming effluents show low toxicity. No data are available for hot-coating
and continuous coating effluents. Effluents from centralized treatment of
combined wastewaters from several processes showed a range from an LC50 of
19.5 percent dilution to no mortality. (LC50 is the concentration, expressed
as volume percent, lethal to 50 percent of the organisms.) •
As part of the toxic pollutant control program, the U.S. Environmental
Protection Agency is developing industry-specific toxicity information. This
study develops data on wastewater toxicity, its treatability and its variabil-
ity in treated effluent for eight iron and steelmaking subcategories: coke-
making, ironmaking, steelmaking, continuous coating, hot forming, pickling,
cold forming, and hot coating. In addition, effluent data existing prior to
the study are summarized.
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2.0 SELECTION OF TREATMENT SYSTEMS FOR STUDY
Treatment technologies were selected and tested as parts of systems
operated in seven different plants identified by letters A through G. Criteria
applied in the selection of 24 systems for study were:
Technologies representative to some extent of BPT, BAT, or NSPS
systems [1]
Toxic pollutants generated and wastewaters discharged
Potential for treatment problems
Steel production rate at test time reasonably representative.
Wastewater treatment systems in steel plants are each somewhat unique.
While the 24 selected treatment systems offer many of the unit processes
inherent in BPT and BAT models [1], a complete match, process by process,
seldom exists. Systems selected do include unit processes that have been
shown to decrease pollutant loadings.
One of the selected treatments systems for ironmaking represents BAT-4
technology, except for emission of dechlorination and final filtering. The
system for suppressed combustion steelmaking was operated essentially as a BPT
system. The wet combustion treatment system was BAT, except for moderate
blowdown. One continuous casting system was BPT with addition of recycle; the
other had blowdown from the scale pit to a municipal sewer. Plant A's hot
strip mill treatment system lacked the filtration step of BPT, but used alter-
natives including flocculation with polymer and alum, and central treatment
along with slabbing mill wastewaters. Plant D processed hot strip mill waste-
water along with slabbing mill wastewaters, using filtration prior to discharge.
Plant F used settling tanks for clarification, thus closely approximating BPT,
then filtered the combined waters from the hot-strip, universal, and blowing
mill;;. Plant B applied polymer treatment and oil skimming before directly
discharging slabbing mill wastewaters.
-------
The bar mill treatment system did not include filtration, but added
flocculation and clarification, followed by recycle as does BAT-1.
Plant E's section mill wastewaters are treated by oil skimming, neutral-
ization and flocculation with polymers before discharge.
Plant F's pickling treatment system is BPT, except that air flotation is;
lacking. Plant B combines pickling wastewaters with those from cold forming
for treatment somewhat better than BPT-BAT-1.
Plant A combines cold rolling mill wastewaters with hot strip mill waters
for treatment. Its tandem mill wastewater is processed in a central treatment
system. Plant B's cold rolling wastewater treatment system is equivalent to
BPT.
The hot coating system at Plant C resembles BPT without chromium reduction.
One central treatment system involves settling with chlorination and
recycle. The other receives a more varied loading, requiring pretreatment for
cyanide and chromium, followed by neutralization, flocculation with polymer,
and clarification with skimming.
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3.0 SAMPLING AND ANALYSIS
Sampling sites were selected upstream and downstream of treatment unit
processes. Composite samples were obtained using Isco Model 2100 automatic
samplers at all locations except those in designated hazardous areas. Com-
posites in such areas were made from a corresponding set of grab samples.
Composite sample increments were taken automatically every 15-30 minutes
depending on the length of the sampling period, or by hand every 3 or 4 hours.
Sampling periods for compositing were coordinated with production schedules.
Thus, where 24-hour operation occurred (as in cokemaking, ironmaking, and
steelmaking), sampling continued over that period. Where operation was limited
in the number of turns (shifts) per week (as in many finishing operations), the
sampling was similarly limited to avoid collection of wastewaters which were
not receiving raw loadings from the production lines.
Sample containers were packed in coolers with ice. Bioassay samples were
delivered immediately by the fastest possible means to EPA testing laboratories.
Chemical analysis samples were transported, preserved with ice, under a chain
of custody, and were analyzed within the prescribed limited holding periods
[13]. To prevent losses of cyanide, volatile organics, and oil and grease
through sample degradation that might occur during composite sampling, grab
samples were taken for these constituents, Grab samples were also taken for
onsite determination of pH, dissolved oxygen, and residual chlorine.
Table 3-1 identifies the methods of chemical analysis employed [13-16].
Test detection limits, standard deviations, and percent recovery are given in
the references indicated. When limits had not previously been set, those
obtained in this study are included.
During this study, 10 percent of the composite samples taken were split
for chemical analysis by both laboratories for quality control purposes. The
volatile organics and extractable organics analyses (Methods 624 and 625)
yielded spectra which were screened for toxic and priority organics, pesticides,
and PCB's, with detection limits typically less than 10 ug/L.
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TABLE 3-1. METHODS OF ANALYSIS'
Constituent
Antimony
Arsenic
Chromium
Copper0
Iron
Lead
Nickel0
Selenium
Zinc
Total cyanide
Ammonia
Fluoride
Oil and grease
pH
Phenol ics (4AAP)
Chlorine residual
Total suspended solids
Volatile organics
Extractable organics
(base/neutral and acids)
Toxicological
Method
number
204.2
206.2
218.2
220.2
236.1
239.2
249.2
270.2
289.1
335.2
350.2
340.2
413.1
150.1
420.1
330.3
160.2
624
625
--
Recovery %
NAb
85-88
97-102
97
1.8 B
85-95
100
94-112
56.6 B
85-102
-5.5 B
—
93
±0.. 16 unit
--
--
NA
NA
NA
--'
Detection limit
(Mg/L)
3
1
1
1
30
1
1
2
5
20
50
100
--
--
5
1 mg/L
NA
10
10
--
Standard
deviation
(Mg/L)
NA
±9% R
±0.8
±3.8
±173
±3.7
±10
14% R
18
±620
±122
±30
±900
±0.12 unit
±4.2
±0.09 mg/L
NA
NA
NA
--
R = Relative standard deviation.
B = Percent bias.
NA — Not applicable.
.Reference 16.
Not available according to method.
Limits from analysis of all samples during this study.
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4.0 RESULTS AND DISCUSSION
Analytical results indicate that, in general, the wastewaters sampled are
representative of their respective subcategories. While some raw wastewater
values are markedly different from median values developed by EPA [1], the
overall characterizations show typical subcategory trends. Results presented
here, of course, represent only one 24-hour period, while subcategory data
represent years of operation.
Bioassay result are summarized in Tables 4-1 and 4-2. Details of pollutant
and toxicity reduction are discussed for each process subcategory. The tabu-
lated results are limited to the regulated pollutants plus total organics and
metals, compiled as the sum of all identified priority toxic pollutants.
4.1 COKEMAKING
Figure 4-1 indicates the succession of treatments and sampling points for
the three cokemaking wastewater treatment 'systems studied.
Plant C treats combined flows of excess ammonia liquor from the free and
fixed ammonia still, benzol plant wastewaters, and desulfurization wastewaters.
The first two flows are continuous, under 24-hour operation, to the equaliza-
tion tanks; the last flow is intermittent. Equalization tank holding capacity
is 2,650 m3. Influent to the biooxidation reactor (BOA-1) is drawn from the
equalization tanks at a design rate of 1.14 m3/min, first passed through a
cooling tower, and diluted with river water at a design ratio of 75/300 by
volume (75 m3 of dilution water to 300 m3 of wastewater). Phosphoric acid is
added as a nutrient.
The BOA-1 has two basins, each with 136 submerged aerators. It was
designed for single-stage parallel operation. Its effluent flows to clarifiers
where solids separation is assisted by addition of polymer. The overflow is
discharged to the river.
During the study, flow to the bioreactors was 0.83 m3/min (73 percent of
design)- Coke production average 3,671 MTD (90 percent of rated capacity).
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TABLE 4-1. BIOASSAY RESULTS, DAPHNIA
Cokemaking BOA-1 C
BOA-1 0
Phys/Chem G
Ironmaking A
D
Continuous Casting B
E
Toxicity,
Raw
wastewater
0.4
1.6
2.1
7.1
55.2
100% killed 65%
6.2
ECSO
Treated
wastewater
1.5
1.6 - 31
5.3
6.8
42.1
100% killed 60%
6.6
Hot Forming Section
Slab (B)
Bar (A)
Hot strip (F)
Slab hot strip
Bar (A)
Steelmaking (Sup. Comb.)
(Semi. Wet Open)
Hot Coating
Central treatment3
80% survived in 100%
NT
Could not calculate
a NT
(A)a NT
Could not calculate
Pickling
Comb.
HC1
4.1
4.3
90% killed in 6.3
60% survived in 100%
NT
Could not calculate
NT
(Central tr)
Could not calculate
58.6
<32
100% survived in 100%
<32
75% survived in 100%
100% killed in 95% w.
NT = Nontoxic.
To central treatment.
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TABLE 4-2. BIOASSAY RESULTS, MINNNOWS
Cokemaking BOA-1 C
BOA-1 D
Phys/Chem G
Ironrnaking A
D
Continuous Casting B
E
Hot Forming (section)
(slab), (bar)
(hot strip) F
(hot strip) D
Central Treatment A
E
Steelmaking (Sup. Comb.)
(Semi Wet Open)
Hot Coating
Pickling (comb)
(HC1)
Toxicity,
Raw
wastewater
0.61
4.4
0.85
21.5
22.6
NT
2.4
NT
NT
NT
NT
.
2.4 - NTb 65%
—
NT
3.9
6.9
8.8
LCSO
Treated
wastewater
3.8
8.9
71.5
32.6
NTa
NT
2.8
NT
NT
NT
35.4 - NT
NT
survived
in 100%
71 •
NT
NT
NT
NT
aNT = Nontoxic
Range for different wastewaters treated.
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Plant
Ammonia still s
fixed • • •
free *s * *
Dephenolizer • •
Hot oil decanter »s
Desulfurizer «s
Dissolved air flotation «s «s
Cooling tower *s
Light oil and final •
cooler condensate •
Equalization • «s
Dilution •
BOA-1 • •§
Clarifier «s *s
Thickener «s
Filtration (Dual Med) «s
Carbon ads. «s
Alkaline chlorination *s
Dilution
Discharge • • •
s = Sample point
Figure 4-1. Cokemaking.
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Grab composite samples were taken representative of the excess ammonia
liquor, the phenol plant wastewaters, the diluted feed to the bioreactors, and
the clarifier effluent.
The toxicity reduction, shown in Table 4-3, through the BOA-1 and clarifiers
(LC5(,:0.61 to 3.8) for minnows is certainly statistically significant, when
compared to the coefficients of variation for the test (37-93 percent). Nor
could it have resulted from dilution alone. For dilution after the cooling
tower, the ratio of LC50's would be no lower than 0.8, by:
\/i LCsn, 1 1.14 mVmin n ft
V2 LCSO, 2 1.42 m3/min u'° '
The toxicity ratio is in fact 0.16 (0.61 •=• 3.8).
The treated wastewater remained very toxic to minnows, even at final
discharge. Several pollutants could have contributed to the toxicity.
Tablo 4-4 shows water quality criteria and lethal limits which gu'ide the
assessment of sources of toxicity. By comparison, the treated effluent and
the LC5o dilution exceeded these limits for ammonia, cyanide, and benzo(a)-
pyrene. The increase in cyanide across the treatment systems is unusual.
Biotreatment systems tend to remove free cyanide efficiently, except for
complex rnetal cyanides [19].
Plant D collects only pretreated ammonia liquor in a holding tank of
757 in3 capacity. This is fed at 45 m3/h to the bioreactors, with light oil
and final cooler condensate waters added on the way. Plant D's holding time
is 14 hours; plant C's, 53 hours.
Plant D's bioreactor has four aeration cells, each with one surface
aerator. The total aeration (air flow) rate was 142 kg/h (it was 12,270 kg/h
at Plant C). Retention time in the reactor was 32 hours. Phosphoric acid was
added as a nutrient, and bay water was added to dilute the wastewater (up to
25 percent) and lower the thiocyanate concentration.
Overflow from the final thickener was discharged to receiving waters;
sludge was recycled to the aeration tanks.
Samples were taken of the raw ammonia liquor, the light-oil condensate,
the final cooler condensate, the mixed feed to the BOA-1, and the thickener
effluent,
10
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TABLE 4-3. COKEMAKING: POLLUTANT REDUCTION, PLANT C
Component
Flow
PH
Ammonia
Oil and grease
Phenol (4AAP)
Residual chlorine
Total suspended solids
Benzene
Naphthalene
Benzo(a)pyrene
Tetrachl oroethyl ene
Cyanide
Total organics
Lead
Nickel
Zinc
Total metals
Toxicity, minnow, 96 h
Toxicity, daphnia, 48 h
Units
'mVmin
S.U.
mg/L
mg/L
mg/L
mg/L
mg/L
pg/L
pg/L
pg/L
mg/L
pg/L
pg/L
pg/L
pg/L
pg/L
LC50
LC50
ASFF;DS;DP ;.
A A .
10 5
1,420 67.5
14.4 10.85
1,060 50.8
28 <2
4.2 58,500
9,500
: :
_
- .
1,910 500
4,294 804
0.61 0.61
0.4 <1.0
E ;
A
0.83
9
1,002
26.3
831
80
11,600
783
ND
<0.02
73,233
.
650
2,694
CT;Dilution:BOA-l;CL
A
1.1
7.8
612a
6.4
0.23
216
<2
136a
20. 2a
916
-
310a
1,679
3.8
1.5
Percent
reduction
(39)
(76)
(99.9)
-
99.7
_
99.9
-
52.3
38
Exceeds toxicity limits, Table 4-4.
-------
TABLE 4-4. WATER QUALITY CRITERIA AND TOXICITY LIMITS
Limits
Poiilutcint
Criteria0
Toxicity
Ammonia, mg/L
Arsenic, mg/L
Cadmium, pg/L
Chromium, trivalent, pg/L
Copper, pg/L
Lead, pg/L
Nick&l, pg/L
Zinc, pg/L
Cyanide, pg/L
Chlorine, pg/L
Phenols, pg/L
Benzene, pg/L
Benzo(a)pyrene, pg/L
Naphthalene, pg/L
Tetrachloroethylene, pg/L
0.4 - 10.5C (0.09 - 2.24)d
0.14 (0.072)
2-10
870 - 2,700 (42 - 130)
8.4 - 29 (5.8 - 20)
25 - 160 (1 - 64)
56 - 96e
47e
22
14 (8.3)
500e
h
478
0.028
8'
0.1 - 2
17.8
300
20 - 180
330 - 2,500
100 - 1,000
300 - 500
40 - 100f
30 - 1,500°
1,000 - 2,000
620'
Maximum cone., EPA, published in Federal Register 49, 26, February 7, 1984,
4551-4554.
Lowest cone, at which toxicity to minnows has been found [17].
cRange depends on pH for ammonia; on hardness for others.
Thirty-day average, or limit other than maximum, in parentheses.
ePrior standard.
Dodge and Reams [18].
^Varies with species.
To limit risk of cancer.
Effluent guidelines.
12
-------
During the tests several upsets in operation of the system occurred. In
the first hours, the holding tank was bypassed, and ammonia liquor after
distillation was fed directly to the BOA-1. No waste was fed from the light-
oil sump. At midnight of the 24-hour test, the holding tank was allowed to
overflow to the BOA-1, carrying over accumulated lime solids. A high pH
developed in the BOA-1, and bioreactivity was affected adversely. The data
reflect these upsets. The bioassay only was repeated at a later date when
these upsets did not occur.
During the study, flow to the BOA-1 was approximately 1.0 mVmin (70% of
design). Coke production was 2,120 MTD (70% of capacity).
Table 4-5 shows the higher biotoxicities obtained during the upsets. As
might be expected from the shorter treatment times and upsets, phenol reduction,
is only 25%, compared to 99.9% for Plant C. Here again cyanide removal is. not
estimable. Ammonia removal is higher than for Plant C (78% vs. 39%).
The remaining toxicity of the treated effluent coincides with concentra-
tions of ammonia, phenol, benzo(a)pyrene, cyanide, and zinc that exceeded
toxic limits.
Plant G uses a physical/chemical treatment system. Wastewaters were fed
to an equalization tank from four sources: the hot oil decanter, the phenolate
storage area, the light-oil separator and the final cooler. The phenolate
wastewaters passed through a free ammonia still, a dephenolyzer, and a fixed
ammonia still prior to mixing for equalization. The succession of treatments
applied thereafter were: clarification, filtration, carbon adsorption, and
alkaline chlorination. By adsorbing organics prior to chlorination, formation
of chlorinated organics is avoided. Also, if toxics break through from the
adsorbers, they can be subsequently chlorinated.
During the study, flow through the equalization tank was 0.67 mVmin (52%
of design). Detention (holding) time was 24 hours. At this flow, other
important process parameters differed from design, as follows:
13
-------
Component
Flow
PH
Ammonia
Oil and grease
Phenol (4AAP)
Residual chlorine
Total suspended solids
Benzene
Naphthalene
Benzo(a)pyrene
Tetrachloroethylene
Cyanide
Total organics
Lead
Nickel
Zinc
Total metals
Toxicity, minnow, 96 h
Toxicity, daphnia, 48 h
IMDLC H~;
3. OUIML.1HM.ML,:
rULLUIHINI KtUUL. 1 1UN
fLHINI U
Light oil + final cooler condensate Percent
Units 4- Raw NH3 Liquor -» ASFF-L •* ; E; 4- BOA-1; T reduction
A A A . A
m3/min
S.U.
mg/L
mg/L
mg/L
mg/L
mg/L
pg/L
pg/L
pg/L
mg/L
pg/L
pg/L
pg/L
pg/L
pg/L
EC50
—
8.0
119
235
48.9
-
19
286,000
56,300
NO
-
<0.02
446,971
-
640
683
9.1
2,710
80.2
589
-
66
8,950
56,000
NO
-
<0.02
483,817
-
120
1,214
0.17
0.16
1.0
11.9
107
11.1
149
-
1,040
3,570
4,130
0.1
129,867
-
240
899
4.42
1.6
0.9-1.25
12.2
22. 7a 78
14.6
1113 25
-
529 49
212 94
392 90.5
-------
Value
Treatment unit Parameter Design Test
Clarifier Overflow, mV(m2 x min) 0.0072 . 0.0037
Filter Flow-through rate, m3/(m2 x min) 0.09 0.045
Adsorber Flow-through rate, m3/(m2 x min) 0.18 0.09
Chlorinator Detention time, h 1.5 2.8
Samples were taken before and after dissolved air flotation (hot-oil
decanter wastewater), after equalization, after clarification, after filtra-
tion, after carbon adsorption, and after the alkaline chlorination.
Table 4-6 shows an LC50 for minnows of 71.5%, and the reduction of ammonia
and phenols to below detection limits. Priority pollutants were reduced 99.9%
to a residual 30 ug/L. Residual chlorine in the effluent exceeded toxic
limits (9,100 ug/L vs. 1,500). Cyanides, although reduced 87%, remained above
toxic limits at the LC50 dilution, and copper, at 3,460 ug/L, also exceeded
toxic limits. The buildup of concentration of this metal across the adsorber
was confirmed by subsequent sampling and testing by four different labora-
tories. The presence of phenols (4AAP) after the adsorber was not confirmed
by the results of GC/MS analyses. In resamples, the phenol concentration was
much lower (34 ug/L by AAP) and was consistent with the GC/MS results (Table 4-7).
Tests made by the four laboratories, shown in Table 4-7, do not check as
well as those made under the QA plan. The larger differences are due to lack
of uniformity in the methods used, e.g., three of the phenol results shown
were obtained by the 4AAP method; one is by GC/MS.
Conclusions
The physical-chemical treatment system reduced biotoxicity much more than
did the biosystems.
The physical-chemical treatment effected greater reduction of zinc, but
showed copper buildup across the adsorber which apparently formed complex
metal cyanides that resisted chlorination.
Causes to toxicity after biotreatment appear to be insufficient removal
of ammonia, benzo(a)pyrene, phenols, cyanides and zinc. Causes after physical/
15
-------
TABLE 4-6. COKEMAKING: POLLUTANT REDUCTION, PLANT G
cr>
Component
Flow
PH
Ammonia
Oi 1 and grease
Phenol (4AAP)
Residual chlorine
Total suspended solids
Benzene
Naphthalene
Benzo(a)pyrene
Tetrachloroethylene
Benzo(a)anthracene
Cyanide
Total organics
Lead
Nickel
Zinc
Total metals
Toxicity, minnow, 96 h
Toxicity, daphnia, 48 h
24 h
Units
m3/min
S.U.
mg/L
mg/L
mg/L
mg/L
mg/L
pg/L
pg/l
M9/L
pg/L
P9/L
mg/L
pg/L
pg/L
pg/l
P9/L
pg/L
LC50
ECSO
HOD;
A
0.08
6.8
1.4
-
87
21
880
1,200
-
-
BDL
0.07
13,085
16.7
NO
39
70.6
12.5
2.1
Arrr . nn .
n.>i i ,L/I ,
AF +
A
0.08
6.6
1.4
12.6
745
2
1,200
720
-
-
BDL
0.066
13,445
2.9
ND
22
• 27
25
50
E ; CL ; FDMMP
A A
0.67
8.4
17
1.37
390
159
18,000 15
250 1
-
-
^24
54.2
32,333' 26
19
35.2
870
1,499 :
0.85
60% survived
in 5%
0.67
8.4
16.7 (2)a
28.9 (-2,000)
601 (-54)
107 (33)
,000 (17)
,700 (-580)
-
-
14 (41)
44.0 (19)
,873
16.7 (12)
29.2 (17)
107 (87.)
591
0.72
75% survived
in 2%
t
A
0.67
8.2
16.8 (2)
15.4 (48)
82 (86)
33 (79)
9,000 (50)
1,100 (35)
ND
ND
BDL
43.3 (20)
19,034
ND (>99)
13.3 (62)
72 (92)
414
0.67
1.3
CAG ; CLA
A
0.67
8.4
16.8 (2)
ND (>99)
22 (95)
5 (97)
BDLb
BOL (98)
ND
ND
BDL
31.2 (42)
BDL
9.2 (51)
32.1 (9)
15 (98)
3,800
1.0
1.5
A
0.69
8.8
ND
8.8
ND
9.1C
16
BOL
' BDL
ND
ND
BDL
6.8C
30
9.2
37.2
17
3,841C
71.5
5.3
Percent
reduction
99
70
>99
90
100
98
-
-
(>60)
(87)
99.9
51
-6
98
-156
ND = None detected.
BDL = Below detection limits.
a
Values are cumulative % reduction across the intermediate processes.
b<10 pg/L.
Exceeds toxicity limits, Table 4-4.
-------
TABLE 4-7. COKEMAKING: COMPARATIVE TESTS OF RESAMPLES
PHYSICAL CHEMICAL SYSTEM
Component
analyst
Phenols mg/L
Rll
S*
Mead
Plant G
Copper M9/L
RTI
S
Mead
Lead M9/L
RTI
S
Mead
Nickel H9/L
RTI
S
Mead
Iron mg/L
. RTI
S
Mead
Hot-oil
decanter
59.7
'55
60
53.9
68.2
<50
<100
5.7
—
<200
2.7
0.68
0.55
0.48
Air
flotation
48.8
42
40
42.7
7.5
<50
<100
ND
55
<200
39.7
0.85
0.75
0.55
E
82.8
75
80
72.6
534
300
230
NO
100
<200
29.1
22.6
2.5
2
CL
79.6
80
80
70.2
315
150
<100
NO
—
<200
39.7
3.6
3.6
2.3
FDMMP
75
75
80
64.7
104
50
<100
6.2
—
<200
18.5
0 to <50
<100
2.4
2.5
1.8
CAG
<.05
0.015
0.3
0.034
4,604
1,700
940
3.8
--
<200
18.5
3.9
3.6
2.7
CLA
<.05
0.02
<.01
0.017
2,424
2,000
1,000
5.8
<50
<200
44.9
3.9
• 3.8
2.9
ND = None detected.
aS = Supplier of carbon.
17
-------
chemical treatment appear to be insufficient removal of residual chlorine,
extrcineous copper, and cyanides.
Cyanide removal in both systems was apparently constrained by the presence
of complex metal cyanides. One reason for low effluent cyanides from the
biosystems is the low influent concentration.
4.2 IRONMAKING
Figure 4-2 shows the wastewater treatments and sampling points for the
two plants studied (A and D).
Plant A recycles 96% of the treated water and quenches slag with the
blowdown. Spent scrubber water flows via a splitter box to two thickeners.
Upstream of the box, anionic polymer assists in settling the carbon particu-
lates. At the splitter .box, cationic polymer is added to improve settling of
solids in the thickeners. Sludge from the thickeners is recycled until the
solids become 10-15% by volume, whereupon the sludge is hauled by truck to
landfill.
During the study, flow through each thickener was 15 nrVmin (holding
time, 3.6 h).
Waters flow from the thickeners to a hot well; thence to a cooling tower
where makeup water is added as required. Blowdown, from the hot well, was
1.1 m3/min. This was sent through a surge tank to a clarifier with' a capacity
of 946 m3 (holding time, 14 h). Clarified water passed to chlorinators, pH
was adjusted with lime, and the waters were chlorinated to breakthrough.
Samples were taken at the splitter box, after the thickener, and after
the chlorinator. Analyses are given in Table 4-8.
Toxicities for minnows and daphnia were not significantly different in
the raw wastewaters and the final effluent, although 99% of the organics and
metals were removed. Raw waters exceeded toxic concentration limits for
ammonia and zinc, while final effluent waters exceeded limits for chlorine and
zinc. Since the metals would be mostly in particulate form, the excess chlorine
is the likely factor in final effluent toxicity.
Plant D uses a once-through treatment system. Scrubber waters, slag pit
waters, and dekishing station wastewaters flow to a flocculation tank of
341 m3 capacity. During the study, flow was 56.8 m3/min (79% of design)
equivalent to a holding time of 6 min. Production was 6,350 MTD (64% of
capacity for four blast furnaces).
18
-------
Plant
Primary scale pit
Splitter box
Flocculation with polymer
Thickener
Cooling tower
Recycle
Slowdown to
Clarifier
Alkaline chlorination
To quench
Discharge
Dekishing wastewater
*s
(96%)
s = Sample point
Figure 4-2. Ironmaking—wastewater treatments and sampling,
19
-------
TABLE 4-8. IRONMAKING: POLLUTANT REDUCTION, PLANT A
ro
o
Component
Flow
PH
Ammonia
Oil and grease
Phenol (4AAP)
Residual chlorine
Total suspended solids
Benzene
Naphthalene
Benzo(a)pyrene
Tetrachl oroethyl ene
Cyanide
Total organics
Lead
Nickel
Zinc
Total metals
Toxicity, minnow (96 h)
Toxicity, daphnia (48 h)
Units
m3/min
S.U.
mg/L
mg/L
mg/L
mg/L
mg/L
M9/L
ug/L
ug/L
ug/L
mg/L
M9/L
pg/L
pg/L
ug/L
Mg/L
LC50
EC50
Feed;
Splitter A
30.3
7.1
79
9.5
0.25
9,604
ND
10
ND
ND
c
23
73,967
119
349,340
427,833
21.5
7.1
FLP; T; CT; RC(96) -» CL;
A
30.3
7.0
57.8 (27)a'b
2.7 (71)
<0.06 (76)
29 (99.7)
ND
ND
ND
ND
0.042
ND
533 (99.3)
20.5 (83)
24,790 (93)b
25,384 (94)
18.4
5.1
CLA -» Quench
A
1.1
7.6
<0.4
5.6
<0.06
26. 5b
203
ND
ND
ND
ND
<0.02
ND
32.8
<19
4,100b
4,172
22.6
6.8
Percent
reduction
99.5
41
76
97.9
—
.99
—
—
52.4
99
99.9
84
98.8
99
ND = None detected.
a
Values in parentheses are cumulative percent reduction.
Exceeds toxicity limits, Table 4-4.
"Not quantified due to sample turbidity.
-------
Overflow from flocculation was fed to a 48 m dia. thickener (surface
area: 1,867 m2, depth 6.1 m). Overflow rate was 0.030 m3/m2 x min, vs a
design rate of 0.041. Polymer was added to the thickener to aid settling.
Underflow from the thickener passed through vacuum filters. The solids were
stored for future processing. Overflow from the thickeners is discharged to
receiving waters.
Samples were taken of the separate dekishing wastewater, the combined
waters into the flocculation tank, and the overflow from the thickener.
Table 4-9 shows no toxicity to minnows for the raw waters or the treated
effluent. Ammonia exceeded slightly the toxic limits, and zinc exceeded
limits in the raw waters. These may account for the toxicity shown in the
daphnia.
Conclusions
Blast furnace waters tested were nontoxic to minnows when the total
metals concentration was below 2,000 ug/L.
These wastewaters were more toxic to daphnia than to minnows.
Excess chlorine contributed to the toxicity of the final effluent so
treated.
4.3 STEELMAKING
Figure 4-3 shows the wastewater treatments and sampling points for the
two plants studied (suppressed combustion and wet open combustion at Plant. A).
The Suppressed Combustion treatment system had no blowdown during the
study because of the extent of evaporative loss in the quencher. Water from
the venturi scrubbers passed to the quenching tank, was used in the quench
circuit, and then returned through hydroclones and classifiers, along with
water from a secondary ventilation scrubber, to a "distribution box" where
polymer was added to induce settling in the two following thickeners. Flow
rates were 11.4 mVmin from the classifiers and 3.7 mVmin from the secondary
ventilation system. Holding time was 6.6 h vs. a design value of 5.0 h.
Thickener overflow was sent to a holding tank, from which it is usually
recycled with a 5% blowdown. Thickener underflow passed to a sludge holding
tank.
21
-------
TABLE 4-9. IRONMAKING: POLLUTANT REDUCTION, PLANT D'
ro
IXJ
Component
Flow
PH
Ammonia
Oil and grease
Phenol (4AAP)
Residual chlorine
Total suspended solids
Benzene
Naphthalene
Benzo(a)pyrene
Tetrachloroethylene
Cyanide
Total organics
Lead
Nickel
Zinc
Total metals
Toxicity, minnow, 96 h
Toxicity, daphnia, 48 h
Units
m3/min
S.U.
mg/L
mg/L
mg/L
mg/L
mg/L
Mg/L
Mg/L
Mg/L
Mg/L
mg/L
Mg/L
Mg/L •
Mg/L
Mg/L
LC50
EC50
Dekishing
water
1.7
12 •
2.6
8.2
0.09
133
ND
ND
ND
ND
<0.02
ND
<1.9
174
<30
291
A
56.8
7.1
5.5
4.2
0.12
<0.02
847
ND
ND
ND
ND
<0.02
ND
329
193
l,570a
2,164
100% survival
in 100%
55.2
FLP; T
56.8
6.9
3.6a
2.2
0.07
<0.02
38
ND
ND
ND
ND
0.05
ND
61.2
13
300
380
100% survival
in 100% .
42.1
Percent
reduction
35
47.6
41.7
—
95.5
81.4
93.3
80.9
82.4
ND = None detected.
Exceeds toxicity limits, Table 4-4.
-------
Suppressed Semi-Wet
Combustion Open
Classifier »s Surge Tank
Secondary vent «s s
Flocculation with polymer «s »s
Thickener «s •
Acidification • «s
Recycle •(100%)a
Slowdown to
Clarifier •
Discharge • •
s = Sample point
a = Actual value, design value = 95%
Figure 4-3. Steelmaking—wastewater treatments and sampling.
23
-------
Production was 1,950 MTD (72% of capacity).
Sampling was conducted from 11 p.m. to 7 a.m. on successive days. Samples
were taken from the classifier inlet (quencher water), from the secondary vent
return, and from the holding tank before recycle. The inlet to the thickeners
was calculated from the results of the first two samples.
Table 4-10 shows low remaining toxicity for both minnnows and daphnia.
The residual toxicity appears to be related to the levels of phenol, lead, and
zinc, all of which are above some of the limits of Table 4-4. . The ammonia
level at 0.4 mg/L cannot be discounted as a possible contributor to toxicity
at the pH values shown..
The Wet Open Combustion system collects waters from the scrubbers in a
surgo tank and passes them to one of two thickeners, adding polymer to aid
settling. The thickener effluent is pH adjusted with sulfuric acid, passed to
a holding tank, and recycled, with blowdown to a second thickener, which also
receives water from the process spark box. Blowdown and spark-box waters are
sewered after passing through this thickener. Makup water is added at the
scrubbers. Sludges from both thickeners are landfilled.
Production was 9,253 MTD (73% of capacity). Wastewater flow was at the
full 22.7 m3/min rate. Holding time in the main thickener was thus 1.2 h;
in the blowdown thickener, 10 h.
Samples were taken at the surge tank, the influent to the blowdown
thickener, and at the effluent from this thickener.
Table 4-11 shows that the minnows survived in 64% wastewater, treated or
untreated. Had stronger dilutions been tested, they would, perhaps, have
yielded LC5o values close to the 71 obtained for the suppressed combustion
system. The toxicity to daphnia may relate to concentrations of lead and
zinc, which exceeded limits. Ammonia is within the toxic range for the pH
given.
Conclusions
Steelmaking raw wastewaters were moderately toxic, and so were the
treated wastewaters. The simple flocculation and clarification treatments
removed 97-99% of the metals. Remaining concentrations of lead and zinc are
within the toxic range for daphnia as was the concentration of ammonia.
24
-------
TABLE 4-10. STEELMAKING, SUPPRESSED COMBUSTION: POLLUTANT REDUCTION, PLANT A
r\>
en
Component
Flow
PH
Ammonia
Oil and grease
Phenol (4AAP)
Residual chlorine
Total suspended solids
Benzene
Naphthalene
Benzo(a)pyrene
Tetrachloroethylene
Cyanide
Total organics
Lead
Nickel
Zinc
Total metals
Toxi city, minnow (96 h)
Toxicity, daphnia (48 h)
Units
mVmin
S.U.
mg/L
mg/L
mg/L
mg/L
mg/L
Mg/L
Mg/L
Mg/L
Mg/L
mg/L
Mg/L
Mg/L
Mg/L
Mg/L
Mg/L
LC50
EC50
Classifier
A
11.4
12.4
1
10.9
0.52
<0.2
9,644
ND
ND
ND
ND
<0.02
ND
102,000
4,180
194,000
304,424
Secondary vent
A
3.7
—
0.8
6.5
0.79
--
931 7
4.5
4.4
ND
ND
<0.02
8.9
8,240. 79
1,280 3
23,200 152
33,582 238
Sample lost
lab accident
Sample lost
lab accident
15.1
0.95
9.8
0.59
,509
1.1
1.07
<0.02
2.2
,026
,469
,148
,059
T; RC; CL
A
15.1
11.6
0.4
5.1
0.6b
<0.2
73
ND
2
ND
ND
<0.02
2
811b
6
852b
1,700
71
58.6
Percent
reduction
99
--
9
99
99.8
99.4
99.3
ND = None detected.
Constructed from classifier and secondary vent.
Exceeds toxicity limits.
-------
TABLE 4-11. STEELMAKING: SEMI-WET OPEN, PLANT A
(S3
CTl
Component
Flow
PH
Ammonia
Oil and grease
Phenol (4AAP)
Residual chlorine
Total suspended solids
Benzene
Naphthalene
Benzo(a)pyrene
Tetrachl oroethylene
Cyanide
Total organics
Lead
Nickel
Zinc
Total metals
Toxicity, minnow (96 h)
Toxicity, daphnia (48 h)
Units
m3/min
S.U.
mg/L
mg/L
mg/L
mg/L
mg/L
pg/L
pg/L
pg/L
pg/L
mg/L
pg/L
pg/L
pg/L
pg/L
pg/L
LC50
EC50
Scrubber
surge tank
A
--
10.3
1.7
3.1
<0.06
' ND
1,894
ND
ND
ND
ND
<0.02
ND
10,147
178
158,110
159,500
100% sur-
vival in 64%
>16
FLP;
A
22.7
10.9
0.5
3.1
<0.06
ND
1,302
ND
ND
ND
ND
<0.02
ND
2,589a
50.4
57,950
61,059
100% sur-
vival in 64%
>16
T; A; RC
A
22.7
9.3
0.6a
5.6
<0.06
ND
19.5
ND
ND
ND
ND
<0.02
ND
191. 4a
<19
1.4303
1,666
100% sur-
vival in 64%
>32
Percent
reduction
98.5
93
62
98
97.3
ND = None detected.
Exceeds toxicity limits.
-------
4.4 CONTINUOUS CASTING
Figure 4-4 shows the wastewater treatment systems and sampling points for
the two plants studied (Plants B and E).
Plant B's system passed machine cooling water, which is also used for
direct spraying of the strand of steel below the mold to a scale pit for
removal of heavy scale and oil. The water flowed from the scale pit through
two deep bed filters of walnut shells operated in parallel, and to a cooling
tower from which, after addition of makeup water, it was recycled... Slowdown
from the scale pit and filter backwash were discharged to the slabbing mill
stream.
Production was 789 MT per turn during the tests (42% of rate capacity).
Wastewater flow was at the normal 13.25 mVmin.
Samples were taken (only during active production) after the scale pit
and surface skimmer, and after filtration.
Table 4-12 shows that the raw and treated waters were nontoxic to minnows,
and that all pollutants were at relatively low concentration. The toxicity to
daphnia (100% waste killed 60%) may have been due to the zinc levels, or
the oil and grease.
Plant E requested that descriptions of its wastewater treatment system
supplied for this study be treated as confidential. Therefore, the unit
operations studied are identified from published sources [1], and only the
analytical data obtained in this study are presented. The wastewaters pass
through a scale pit, a deep sand filter, a cooling tower, and are then recycled.
Slowdown is from the scale pit.
Samples were taken after the scale pit and after filtration. Flows were
at normal rates. Production was an estimated two-thirds of normal.
Table 4-13 shows high toxicity to both organisms, in both raw and treated
waters. Nickel, zinc, and copper (at 47.9 pg/L) all exceeded toxic limits in
the samples of raw and treated waters.
Conclusions
Continuous casting wastewaters studied herein contained no toxic levels
of organics, ammonia, phenols, or cyanides. Treatment consisted of filtration,
after preliminary settling and removal of debris. The resulting biotoxicity
varied as the residual concentration of metals from very low to very high.
27
-------
Plant
B E
Primary scale pit • • •
Surface skimmer »s »s
Deep filter •s(walnut shell) »s(sand)
Coolin
-------
TABLE 4-12. CONTINUOUS CASTING: POLLUTANT REDUCTION, PLANT B
ro
Component
Flow
PH
Ammonia
Oil and grease
Phenol (4AAP)
Residual chlorine
Total suspended solids .
Benzene
Naphthalene
Benzo(a)pyrene
Tetrachl oroethyl ene
Cyanide
Total organics
Lead
Nickel
Zinc
Total metals
Toxicity, minnow (96 h)
Toxicity, daphnia (48 h)
Units
ma/min
S.U.
mg/L
mg/L
mg/L
mg/L
mg/L
M9/L
M9/L
H9/L
ug/L
mg/L
M9/L .
M9/L
M9/L
ug/L
M9/L
LC5o
EC50
Percent
PSP; SS; / FDW; CT: RC reduction
A A
13.25
6.0
<0.4
25.7
0.05
<0.2.
29 '
ND
ND
ND
ND
<0.02
ND
8.0
<4.6
96
157.8
100% survival
in 100% waste
100% waste
killed 65%
13.25
5.0
<0.4
27.7
<0.02 76
<0.2
30
ND
ND
ND
ND
<0.02
ND
6.5 18.8
<4.6
66a 31.3
117.2 26
100% survival
in 100% waste
100% waste
killed 60%
ND = None detected.
Exceeds toxicity limits, Table 4-4.
-------
/* R r~ HT T »!/•»
i J.UM , r unM i n
Component
Flow
PH
Ammonia
Oil and grease
Phenol (4AAP)
Residual chlorine
Total suspended solids
Benzene
Naphthalene
Benzo(a)pyrene
Tetrachl oroethyl ene
Cyanide
Total organics
Lead
Nickel
Zinc
Total metals
Toxicity, minnow (96 h)
Toxicity, daphnia (48 h)
Units
m3/min
S.U.
mg/L
mg/L
mg/L
mg/L
mg/L
H9/L
H9/L
M9/L
M9/L
mg/L
H9/L
M9/L
M9/L
M9/L
pg/L
LC5o
EC50
T
PSP; SS;
A
2.27
7.8
2.3
<1.0
•
0.03
<0.2
77
NO
ND
ND
ND
<0.02
ND
5.4
1.2803
360a
' 4.9503
2.4
j
6.2
Percent
FDS ; RC reduction
A
2.27
7.7
<0.4 83
<1.0
0.03
<0.2
10 87
ND
ND
ND
ND
<0.02 0
ND
5.4 0
l,190a 7
3003 17
4,885a 1.2
2.75
6.6
ND = Not detected.
Exceeds toxicity limits, Table 4-4.
-------
Metals removal by the treatments was low (17-26%). The high toxicity at
Plant E may possibly have been due, in part, to the addition of biocides,
corrosion inhibitors, or dispersants that were not detected in the analysis.
However, at Plant E, nickel, zinc, and copper all exceeded toxic limits.
4.5 HOT STRIP AND COLD ROLLING MILLS
Figure 4-5 shows the treatment systems studied at three plants. Plant A's
system also handles cold rolling. Waters flow from roughing and finishing
stands, runout tables and coilers to scale pits with oil skimmers. The flow
continues to a "flash mixing tank" where the streams are mixed with cold
rolling waters and treated with alum and polymer, then pumped to parallel
clarifiers. Retention time therein was 1.6 h (90% of design) at the 75.3 mV
min flow rate during the study. Overflow from the clarifiers was mixed with
hot strip mill noncontact cooling waters, the rest of the wastewaters from the
scale pits, and slabbing mill wastewaters. The final combined streams went to
central treatment.
Central treatment included scalping tanks with chlorination, cooling
towers, and settling basins. Total flow-through was an estimated 568 m3/min.
Equivalent holding time in the scalping tanks was. 5 min;-in the settling .
basins, 1.4 h. Water from the settling basins is recycled to several mills.
Samples were taken after the scale pit for the finishing strand and
run-out table waters; after the cold rolling mill sump, and its scalping pit;
after the clarifier for the combined waters; and after the settling basins for
central treatment.
Table 4-14 provides a basis for several comparisons, none involving just
hot forming or just cold rolling. Minnows survived in 64% raw wastewaters of
the scale pit, which were only from hot forming. Daphnia showed an EC50 of
>32%. Grab samples from other pits showed similar chemical content but were
not tested by bioassay. Residual chlorine may have contributed to the observed
toxicity.
The cold rolling raw wastewater was more toxic, with a minnow LC50 of 45
and a daphnia EC50 of 8.3. This sample showed much more oil and grease, and
concentrations of lead, nickel, and zinc exceeded limits. Further increase in
toxicity after the cold rolling scalping relates to the combining of the sump
waters with water from another cold rolling mill. The latter is the source of
31
-------
Plant
Primary scale pit(s) «
Settling basin
Surface skimmer «
Cold rolling mill; sump and
sealing pit
Rocculation with polymer
Flocculation with aluminum
Clarifier
Surface skimmer
Other wastewaters added
Scalp tank with chlorination
Cooling tower
Settling basin
Recycle
Filtration
Discharge
*s *s(three) *s(two)
•
's *
s
s
s -'''.••..
s *s
•FDMMPS «FDSPS
• •
s = Sample point
Figure 4-5. Hot forming hot-strip mills—treatments and sampling.
32
-------
TABLE 4-14. HOT FORMING, HOT STRIP, COLO ROLLING: POLLUTANT REDUCTION, PLANT A
CO
CO
Component
Flow
PH
Ammonia
Oil and grease
Phenol (4AAP)
Residual chlorine
Total suspended solids
Benzene
Naphthalene
Benzo(a)pyrene
Tetrachl oroethyl ene
Cyanide
Total organics
Lead
Nickel
Zinc
Total metals
Toxicity, minnow, 96 h
Toxicity, daphnia, 48 h
Units
mVmin
S.U.
mg/L
mg/L
mg/L
mg/L
. mg/L
M9/L
pg/L
pg/L
ng/L
mg/L
pg/L
pg/L
pg/L
pg/L
pg/L
LC50
EC50
Scale
Pit ;
3a
75.7
7.7
<0.4
<0.4
<0.06
<0.2
54
NO
NO
NO
NO
<0.02
NO
17.9
<19
<28
105
100 % survived
in 64%
>32
Cold
roll ;
sump
0.15
7.7
-
•8,109
•
-
203
NO
NO
NO
NO
-
NO
41C
82C
52C
602
45
8.3
Cold
roll
scalp -> FLP;FLA;
2.3 78
5.6
-
5,158 153 (88)
-
209 58.9
NO
ND
NO
62.7
-
' 79.7
596° 35
272C 25.6
170C 32.3
2,376 173
17.7
<1.0
Other wastewater
. 4. Percent
CL;CNT;SS SB;RC reduction
78b
7.5
1.2
18
<0.06
<0.2
16 (73)
ND
ND
ND
ND
<0.02
ND
12.2 (65)
24 (6)
<28 (13)
96.5 (44)
100% survived
in 64%
>32
416
7.7
<0.4
17.8 88.4
<0.06
0.2
9 84.7
ND
ND
ND
ND
<0.02
ND
13 63
.<19 26
<28 13
123 29
100% survived
in 64%
>32
ND = None detected.
Wastewaters from finishing stands and runout tables.
h-
Lstimates Tor combined wastewaters subjected Lu buubequent treatments.
Exceeded toxicity limits, Table 4-4.
Dilution accounts for part of the reduction.
-------
tetrachloroethylene and of increased lead, nickel, and zinc loadings, all of
which may have contributed to the toxicity.
The combined wastewater toxicity was reduced substantially after passage
through the clarifiers, partly due to dilution, since the hot-forming waste-
water, at 75.7 mVmin, was 31 times the sum of the other sources.
Central treatment applied to these plus other wastewaters did not alter
the toxicity beyond the limits of test precision.
Plant D collects hot forming wastewaters in scale pits: two for the
roughing stand; one for the finishing stand, mill run-out tables and coilers;
one for the slabber and scarfer. These were combined for treatment with those
from hot forming. Oil was removed at the finishing stand scale pit. Combined
waters were filtered using sand and anthracite coal. The filtrate was discharged
to receiving waters.
During the study, total flow to the filters was 102 mVmin. Total filter
surface area was 291 m2. The filtration rate was slightly below the design
rate of 0.5 mVmin x m2. Production was 6,532 MTD (normal capacity).
Samples were taken after the slabber scale pit, after the finish stand
scale pit, after the roughing stand scale pit, and after filtration.
Table 4~15 shows the slabber and finish stand wastewaters to be nontoxic
to minnows. The LC50 was 35.4 for filtered waters, which included an additional
waste stream. This stream was not separately tested for biotoxicity. Ammonia,
nicked, or zinc may have contributed to the toxicity. A repeat sample showed
100% survival, but metals and ammonia were not determined.
Plant F collected wastewaters from its universal mill (roughing stand of
the hot strip mill) and from the blooming mill flume flushing into a single
scale pit, to which are also added noncontact cooling waters from both mills.
During the test only noncontact water was received from the blooming mill,
which was not in operation and thus not yielding contact waters. Scale pit
effluent flowed to a collection pump where it combined with hot strip mill
finishing strand effluent. The combined mill discharge flowed to two settling
tanks for solids and oil removal. Overflow passed to 12 deep-bed filters (six
for each tank). Filtrate was discharged to receiving waters.
Hot strip mill production was 1,474 MTD (97% of capacity). Wastewater
flow was 41.6 m3/min. Filter loading was 0.31 mVmin x m2 vs a design level
of 0.55.
34
-------
TABLE 4-15. HOT FORMING: POLLUTANT REDUCTION, PLANT D
CO
en
Component
Flow
pH
Ammonia
Oil and grease
Phenol (4AAP)
Residual chlorine
Total suspended solids
Benzene
Naphthalene
Benzo(a)pyrene
Tetrachl oroethyl ene
Cyanide
Total organics
Lead
Nickel
Zinc
Total metals
Toxicity, minnow, 96 h
Toxicity, daphnia, 48 h
Units
m3/min
S.U.
mg/L
mg/L
mg/L
mg/L
mg/L
Mg/L
Mg/L
Mg/L
Mg/L
mg/L
Mg/L
Mg/L
Mg/L
Mg/L
Mg/L
LC50
EC50
Slabber
PSP;
A
24.6
8.6
h
2.5b
12.6
0.07
<0.2 •
117
ND
ND
ND
ND
<0.02
ND
8.6
h
75°
<30
173
100% survived
in 100%
100% killed
in 60%
Finish
stand
PSP;
A
67
7.95
h
3.4°
7.8
. / 0.08
<0.2
203
ND
ND
ND
ND
<0.02
ND
25.5
h
179°
<30
265
100% survived
in 100%
100% survived
in 100%
Rough
stand
PSP;
A
10.6
-
h
2.0°
8.4
0.04
NA
. 28
ND
ND
ND
ND
<0.02
2.2
6.6
h
83°
30
152
-
Percent
SS; FDMMG; reduction3
A
102.2
8.05
h
1.8° 41
7.0 22.3
0.07 4.7
<0.2
23 86
ND
ND
ND
ND
<0.02
ND
10.6 45.6
h
71 50.7
60b
171
35. 4C
H
5.7°
ND = None detected.
Based on comnosite of slabber, finish train, and rounh stand, all combined for treatment-.
Exceeds toxicity limits, Table 4-4.
Repeat sample, March 7, 1983 showed >100 percent survival in 100 percent. Original tests were run
November 30, 1982.
Repeat sample, March 7, 1983 showed 52.9 percent.
-------
Table 4-16 shows that neither the raw nor treated wastewaters were bio-
toxic. Concentrations of ammonia, lead, nickel, and zinc slightly exceeded
some of the toxic limits, however.
Conclusions
Raw hot-forming wastewaters have shown low biotoxicities, while raw cold
rolling waters have shown fairly high biotoxicity. Treatments applied to
combined hot forming and cold rolling wastewaters appear to have had little
effect on toxicity.
4.6 SLABBING MILLS
Figure 4-6 shows the wastewater treatment systems and sampling points for
the two systems studied. Plant A's slabbing mill wastewaters from work roll
cool ing and scarfing fume control were collected into a primary scale pit and
passud to the hot strip mill treatment system (Figure 4-5). Flows during the
study were 37.9 mVmin (normal rate), while production was 6,196 MTD (62% of
capacity).
Water from the scale pit,' mixed with that from the hot strip mill rough-
«
ing strands, scale pit waters from the runout tables and coilers of the hot-
strip mill, and pretreated combined waters- from the hot strip mill finishing
strand and cold rolling mill (Aa in Table 4-17), flows to the central treat-
ment plant previously described. Samples were taken at the primary scale pit
and the roughing strand scale pit.
Test results, Table 4-17, indicated that the raw wastewaters from this
slab mill were only slightly toxic to minnows, with 100% survival in a 64%
dilution. The LC50 for daphnia could not be calculated due to an inappropriate
choice of dilutions for the test.
Plant B collects slabbing mill roll cooling wastewater and fume control
wasteiwater in a scale pit. These flow along with other waters from the opera-
tion to a mixer where polymer is added, then to a treatment basin. There oil
is skimmed and the effluent is discharged to receiving waters.
During the study, wastewater flow was 18.9 mVmin (713» of average).
Production was 2,726 MTD (85% of average). Retention time in the basin was
4.5 h vs. 2.5 at maximum design flow.
36
-------
TABLE 4-16. HOT FORMING: POLLUTANT REDUCTION, PLANT F
U>
Component
Flow
PH
Ammonia
Oil and grease
Phenol (4AAP)
Residual chlorine
Total suspended solids
Benzene
Naphthalene
Benzo(a)pyrene
Tetrachloroethylene
Cyanide
Total organics
Lead
Nickel
Zinc
Total metals
Toxicity, minnow, 96 h
Toxicity, daphnia, 48 h
Units
nrVmin
S.U.
mg/L
mg/L
mg/L
mg/L
mg/L
pg/L
pg/L
pg/L
pg/L
mg/L
pg/L
pg/L
pg/L
pg/L
LC50
LC50
Universal
mill
PSP;
A
13.2
7.35
<0.04
19.9
<0.06
<0.5
28
ND
ND
ND
ND
<0.02
ND
13.7
691b
28
1,419
Nontoxic
Nontoxic
Hot strip
finish stand
PSP;
A
28.4
7.34
0.6b
14.0
<0.06
<0.5
41
ND
ND
ND
ND
<0.02
2.3
50. 9b
635b
77b
1,621
Nontoxic
Nontoxic
SB; SS;
A
41.6
7.35
15.9
<0.06
<0.5
37
ND
ND
ND
ND
<0.02
ND
39.1
653b
61.4
1,556
FDSP
A
41. 63
7.26
<0.4
8.0
<0.06
<0.5
7
ND
ND
ND
ND
<0.02
ND
10.4
71. 2b
44
185
Percent
reduction
_
49.7
-
-
81.1
-
-
-
-
73.4
89.1
28.3
88
ND = None detected.
Weighted combined universal mill and hot strip mill wastewaters.
Exceeds toxicity limits, Table 4-4.
-------
Plant
B
Primary scale pit
To hot strip mill system
Equalization
Flocculation with
polymer
Surface skimmer
Discharge
s = Sample point
Figure 4-6. Hot forming slabbing mills—treatments and sampling.
38
-------
TABLE 4-17. HOT FORMING, SLAB MILL, HOT STRIP MILL, AND CENTRAL TREATMENT: POLLUTANT REDUCTION, PLANT A
00
10
Component
Flow
PH
Ammonia
Oil and grease
Phenol (4AAP)
Residual chlorine
Total suspended solids
Benzene
Naphthalene
Benzo(a)pyrene
Tetrachl oroethyl ene
Cyanide
Total organics
Lead
Nickel
Zinc
Total metals
Toxicity, minnow, 96 h
Units
mVmin
S.U.
mg/L
mg/L
mg/L
mg/L
mg/L
pg/L
pg/L
pg/L
pg/L
mg/L
pg/L
pg/L
pg/L
pg/L
pg/L
LCSO
Slab
mill
PSP -»
37.9
7.9
1.2C
51.5
<0.06
<0.2
94
ND
ND
ND
ND
<0.02
ND
67C
178C
57C
601
100% sur-
Pretreated
hotmi-1 1 ,
cold
roll mill ->
78
153
58.9 .
<0.02
35C
25.6
32.3
173
Hot
strip mill
PSP23; PSP4;
A A
102.2
7.6
<0.4
23.7
<0.06
—
76
ND
ND
ND
ND
<0.02
ND
8.9
24
<28
118
65.9
7.6
<0.4
11.5
<0.06
—
15
ND
ND
ND
ND
<0.02
ND
67°
178C
57C
600
Central treatment _ .
ST-CL; CT; SB; RC reduction
A A
284 416
7.7
.396 <0.4 Nil
60.1 17.8 70
<0.06
0.2
59.6 9 85
ND
ND
ND
ND
<0.02
ND
37. 3C 13 65
80. 7C <19 76
39.8 <28 30
309 123 60
100% sur-
Toxicity, daphnia, 48 h
viva! in 64%
Could not
calculate
vival in 64%
>32
NO = None
.PSP2 collects wastewater from the roughing strands of the plants' hot strip mill
Total from these sources to control treatment.
Exceeds toxicity limits, Table 4-4.
-------
Samples were taken after the scale pit and after final treatment.
Table 4-18 shows no toxicity for minnows in both the raw and treated waters.
Lead and nickel were slightly above toxic limits in the raw and treated
waters, and zinc exceeded limits in the raw wastewater.
Conclusions
Wastewaters from slabbing mills tested were nontoxic to minnows and from
only moderately toxic to nontoxic to daphnia.
4.7 SECTION MILLS
Figure 4-7 shows the treatment systems and sampling points for the sec-
tion mill wastewaters studied. Plant A recycled 98% of its treated wastewater.
Treatment consisted of collection of process waters in a scale pit, with oil
skimming; clarification, dilution with noncontact cooling water from various
mills, cooling and recycle. Makeup, if needed, was added at the cooling
tower. A 2% blowdown was discharged.
Production was 562 MTD during the tests (44% of capacity). Flow was
3.8 mVmin (50% of design).
Samples were taken after the primary scale pit and after the clarifiers.
Test results shown in Table 4-19 indicate no toxicity for minnows for both raw
and treated waters. Very slight toxicity for daphnia was reported, in limited
fashion, as "could not calculate."
Plant €'s section mill wastewater treatment system collects process water
in a primary scale pit where oil is skimmed off. The effluent is sent to a
cooling tower and thence to recycle. A blowdown from the scale pit goes to
central treatment, where collected waters from many plant sources are received,
some after preliminary treatment. The central treatment proceeds through
equalization,-neutralization, flocculation with polymers, and clarification
with surface skimming.
Samples were taken at the equalization basin and after the final clarifier.
Table 4-20 shows that the section mill raw wastewaters were not toxic to
minnows before or after oil skimming. Toxicity to daphnia was very low. The
central treatment total influent was very toxic with an LD50 of 2.4 for minnows
and an LC50 of 0.1 for daphnia. Ammonia, residual chlorine, lead, nickel, and
zinc all exceeded the toxic limits. Considerable reduction in toxicity occurred
40
-------
Plant
Bar Mill
A
Section Mill
E
Primary scale pit
Surface skimmer
Central treatment, equalization
Flocculation with polymer
Flocculation with aluminum
Flocculation with lime
Acidification
Clarifier
Cooling tower
Recycle
Discharge
s
's
s = Sample point
Figure 4-7. Hot forming section mills—treatment and sampling.
41
-------
TABLE 4-18. HOT FORMING SLAB MILL: PRIMARY POLLUTANT REDUCTION, PLANT B
Component
Flow
PH
Ammonia •
Oil and grease
Phenol (4AAP)
Residual chlorine
Total suspended solids
Benzene
Naphthalene
Benzo(a)pyrene
Tetrachl oroethyl ene
Cyanide
Total organics
Lead
Nickel
Zinc
Total metals
Toxicity, minnow, 96 h
Toxicity, daphnia, 48 h
Units
m3/min
S.U.
mg/L
mg/L
mg/L
mg/L
mg/L
Mg/L
Mg/L
Mg/L
Mg/L
mg/L
Mg/L
Mg/L
Mg/L
Mg/L
LC50
EC50
PSP E
A
18.9
6.0
<0.4
134
<0.02
<0.2
250
ND
ND
ND
ND
<0.02
ND
116a
157a
131a
792
100% sur-
vival in
100% effluent
100% survival
in 100% effluent
FLP SS
A
18.9
6.0
<0.4
73.4
<0.02
<0.2
22
ND
ND
ND
ND
<0.02
ND
37. 9a
101a
198.6
100% survival
in 100% effluent
100% survival
in 100% effluent
Percent
reduction
-
48.2
-
-
91.2
67
36
92
75
ND = None detected.
a
Exceeds toxicity limits, Table 4-4.
-------
TABLE 4-19. HOT-FORMING BAR MILL: POLLUTANT REDUCTION, PLANT A
Component
Flow
pH
Ammonia
Oil and grease
Phenol (4AAP)
Residual chlorine
Total suspended solids
Benzene
Naphthalene
Benzo(a)pyrene
Tetrachl oroethyl ene
Cyanide
Total organics
Lead
Nickel
Zinc
Total metals
Toxicity, minnow (96 h)
Units
m3/min
s.u. •
mg/L
mg/L
mg/L
mg/L
mg/L
pg/L
pg/L
pg/L
pg/L
mg/L
pg/L
pg/L
pg/L
pg/L
pg/L
LC50
PSP; FLP; FLA; FLL;
A
3.8
8.1
<0.4
57
<0.02
0.2
110
ND
ND
ND
ND
<0.02
ND
112a
74a
<28
284
100% sur-
t
A; CL; CT;
A
3.8
8.0
<0.4
17.2
0.03
<0.2
24
ND
ND
ND
ND
<0.02
ND
20
15
<28
97
100% sur-
Percent
RC reduction
70
78
82
80
66
Toxicity, daphnia (48 h)
vival in 100%
Could not
calculate
vival in 100%
Could not
calculate
ND = None detected.
Exceeds toxicity limits, Table 4-4.
-------
TABLE 4-2U. HUl-FUKMlNG, SbCliON MILL; POLLUlANl KtDUClION, PLANT E
Central treatment n ...
Component
Flow
PH
Ammonia
Oil and grease
Phenol (4AAP)
Residual chlorine
Total suspended solids
Benzene
Naphthalene
Benzo(a)pyrene
Tetrachl oroethyl ene
Cyanide
Total organics
Lead
Nickel
Zinc
Total metals
Toxicity, minnow, 96 h
Toxicity, daphnia, 48 h
Units
mVmin
"S.U.
mg/L
mg/L
mg/L
mg/L
mg/L
Mg/L
Mg/L
M9/L
Mg/L
mg/L
Mg/L
Mg/L
Mg/L
Mg/L
Mg/L
LC50
EC50
PSP;
- A
7.6
7.9
1.8b
16.6
0.03
<0.2b
101
ND
NO
ND
ND
<0.02
ND
31b
9,350b
350b
10,333
Nontoxic
80% survi
in 100%
SS ; RC; CNT CPT
A
7.6
7.8
<0.4 (78)a
3.2 (88)
<0.02 (33)
<0.2b
61 (40)
ND
ND
ND
ND
<0.02
ND
24.1 (22)
5,840 (38)b
270 (21)b
6,488 (37)
Nontoxic
ved 60% survived
in 100%
;CYPT; E; NC
tA
2.6
10.9
4.6b
34.1
0.11
<0.2b
1,046
ND
76.3
ND
ND
0.04
83.7
66. 6b
62,500b
90b
232,746
2.4
0.1%
;NA;FLP;CL;SS reduction
A
2.6
7.51
5.8b
<1 97
0.07 36
<0.2b
11 98
ND
ND
ND
ND
0.04
11.9
<1.9 >97
326b 99.5
<20 78
492 99.8
65% survival in
100% sample
38%
ND = None detected.
a
Values in parentheses are cumulative reductions.
Exceeds toxicity limits, Table 4-4.
-------
through the system, and the final effluent showed 65% survival for minnows in
pure wastewaters, plus an LC50 of 38% for daphnia. Ammonia, chlorine, and
nickel are suspected sources of this toxicity.
Conclusions
Section mill raw wastewaters tested were not shown to be toxic to minnows.
They were slightly toxic to daphnia. Treatments applied included settling,
skimming, clarification, and central treatment (along with other wastewaters).
No reduction in toxicity was observed for central treatment, of course, under
the circumstances.
4.8 PICKLING
Figure 4-8 shows the treatment systems studied and the sampling points
for pickling operations. Plant F used a combination of sulfuric, nitric, and
hydrofluoric acids in these operations. Acidic rinse waters and fume scrubber
waters flow to an agitated equalization tank for treatment with lime to a pH
of 8-9. This was followed by: clarification after polymer addition, dilutian
with noncontact waters, and discharge.
During the study production exceeded rated capacity for the combined
acids lines and equaled 15% of capacity for the sulfuric acid line. The
overall production was 1,232 MTD. Wastewater flow was 2.3 m3/min (retention
time 8 h in each clarifier).
Samples were taken at the equalization tank and after the clarifier.
Table 4-21 shows the raw wastewaters to be very toxic to both minnnows and
daphnia. Ammonia, nickel, and zinc concentrations were excessive and pH was
low in the raw waters.
Treated waters were nontoxic to minnows, and 75% of the daphnia survived
in 100% sample. Metals content was reduced 99.7%. Ammonia was somewhat high
as was nickel.
Plant B used only hydrochloric acid in pickling operations. Collected
wastewaters from rinses, fume scrubbing, and miscellaneous process usage were
pumped to the cold rolling wastewater treatment system. Flows during the
study were 3.8 mVmin (67% of normal). Production averaged 1,361 MT per turn.
The cold rolling treatment system received waters from temper mills,
slitters, grinders, and the pickling units. The combined waters were subjected
45
-------
Plant
Combination HCI
F B
Surface skimmer Pickling wastewater s
Cold rolling wastewater s
•s(waters combined)
Equalization. «s •
Air oxidation •
Neutralization with lime • •
Flocculation with polymer •
Clarifier «s «s
Thickener •
Discharge • •
s = Sample) point
Figure 4-8. Pickling—treatments and sampling.
46
-------
TABLE 4-21. PICKLING: POLLUTANT REDUCTION, PLANT F, COMBINATION
Component
Flow
PH
Ammonia
Oi 1 and grease
Phenol (4AAP)
Residual chlorine
Total suspended solids
Benzene
Naphthalene
Benzo(a)pyrene
Tetrachloroethylene
Cyanide
•
Total organics
Lead
Nickel
Zinc
Total metals
Toxicity, minnow, 96 h
Toxicity, daphnia, 48 h
Units
mVmin
S.U.
mg/L
mg/L
mg/L
mg/L
mg/L
H9/L
H9/L
(jg/L
M9/L
mg/L
H9/L
H9/L
M9/L
M9/L
M9/L
LCso
EC50
E;
A
2.3
2.45
1.9a
1.5
<0.06
<0.5
169
ND
ND
ND
ND
0.02
2.8
8.2
14,900a
72a
56,881
6.9
4.3
NL; CL '
A
2.3
7.45
1.93
2.4
<0.06
<0.5
6
ND
ND
ND
ND
<0.02
ND
2.4
65. 2a
17
190
Nontoxic
75% survived
in 100% sample
Percent
reduction
96.4
71
99.6
76.4
99.7
ND = None detected.
a
Exceeds toxicity limits, Table 4-4.
-------
to oil skimming, air oxidation of ferrous ions to ferric ions, neutralization
with lime, clarification after polymer addition, and discharge to receiving
waters. Samples were taken of the raw pickling wastewater, the cold rolling
mill discharge after the surface skimmer, and combined streams after clarifica-
tion. Production was above average at 1,430 MTD. Wastewater flow was 1.9 m3/
min (83% of average). Holding time in the clarifiers was 48 min.
Table 4-22 shows low toxicity for the raw cold rolling wastewaters and
the final treated waters. Eighty to 100 percent of the minnows survived. . All
the claphnia were killed in 95% waste, probably due to additives that were not
determined in the analysis, although nickel was excessively high and and pH
was low in the raw waters, as was ammonia.
Conclus ions
Raw wastewaters from pickling showed high biotoxicity to both test organisms.
Treatment with lime and clarification reduced the toxicity substantially in
one system. Blending the cold rolling wastewaters and flocculation by inter-
nally generated ferric ions, addition of lime, and clarification practically
eliminated the toxicity of the combined wastes to minnows.
4.9 COLD FORMING
Figure 4-9 shows the treatment systems and sampling points for the cold
forming wastewaters studied. Plant A's recycle system has already been described.
Pretreatment of the wastewater prior to passage to the hot forming treatment
systesm of this plant included a primary scale pit with oil skimming.
Plant A's once-through system is separate. Collected waters from roll
cooling and lubrication with animal tallow are sent to an oil separation
basin. Oil is skimmed, and the waters flow to a central treatment system and
discharge.
Samples were taken at the inlet and outlet of the oil separation basin.
Performance of the central treatments was not assessed.
Production was 753 MTD (60% of capacity). Total water flow was estimated
at 0.56 m3/min (75% of normal).
Table 4-23 shows the raw waters to be nontoxic to minnows. The toxicity
to daphnia was indeterminate on the raw waters and high at 4.2 on the skimmed
sample. Suspected causes are the high oil and grease and other organics.
48
-------
TABLE 4-22. PICKLING AND COLD ROLLING: POLLUTANT REDUCTION, PLANT B, HC1
ID
Component
Flow
PH
Ammonia
Oil and grease
Phenol (4AAP)
Residual chlorine
Total suspended solids
Benzene
Naphthalene
Benzo(a)pyrene
Tetrachl oroethy 1 ene
Cyanide
Total organics
Lead
Nickel
Zinc
Total metals
Toxicity, minnow, 96 h
Toxicity, daphnia, 48 h
Units
m3/min
S.U.
mg/L
mg/L
mg/L
mg/L
mg/L
M9/L
M9/L
M9/L
M9/L
mg/L
M9/L
M9/L
M9/L
M9/L
M9/L
LC50
EC50
Pickl ing
rinse and
scrubber
A
3.8
1
2.5a
27.7
0.04
<0.2a
7
ND
ND
-
ND
<0.02
ND
15.1
375a
126a
1,900
8.84
90% killed
in 6.25%
Cold
rol 1 ing
discharge
A
1.9
6.5
885
;
55
ND
ND
ND
ND
•
2.2
7.6
98. 2a
46
365
. 80% sur-
vival in
100% waste
100% killed
in 95% waste
SS; FLF; A; AO; NL;
A
5.3
_
-
;
-
ND
ND
ND
ND
-
3.2
17.2
199a
91a
835
Percent
FLP; CL reduction
A
5.3
5.0
4.3 98.6
_ _
9 60
ND
ND
ND
ND
-
3.9 .
<1.9 85
12.3 96
<10 90
84 90
100% sur-
vived in
100% waste
100% killed
in 95% waste
ND = None detected.
Exceeds toxicity limits, Table 4-4.
-------
Plant
Recycle Once Through
A A
Once Through
B
Primary scale pit
Settling basin
Surface skimmer
To hot forming hot strip mill
system at floculation with
polymer
Central treatment
Flocculation with lime chloride
Air oxidation
Neutralization with lime
Flocculation with polymer
Clarifier
Central treatment settling basin
Discharge
s
's
Raw wastewater
Pickling wastewater
added
s
i
s
s = Sample point
Figure 4-9. Cold forming—treatments and sampling.
50
-------
TABLE 4-23. COLD FORMING, ONCE-THROUGH TANDEM MILL: POLLUTANT REDUCTION, PLANT A
en
Component
Flow
PH
Ammonia
Oil and grease
Phenol (4AAP)
Residual chlorine
Total suspended solids
Benzene
Naphthalene
Benzo(a)pyrene
Tetrachloroethylene
Cyanide
Total organics
Lead
Nickel
Zinc
Total metals
Toxicity, minnow, 96 h
Toxicity, daphnia, 48 h
Units
m3/min
S.U.
mg/L
mg/L
mg/L
mg/L
mg/L
pg/L
M9/L
pg/L
pg/L
mg/L
pg/L
pg/L
pg/L
pg/L
pg/L
LC5o
EC50
SB;
A
0.6
8.0
-
566
ND
30
ND
3.6
-
80.1
42b
37.3
<28
206
100% sur-
vival in
100% waste
could not
be cal-
culated
Percent
SS; CNTa reduction
A
0.6
7.7
-
217 62
ND
32.4
ND
5.1
-
88.9
10 76
11 71
<28
87 58
100% survival
in 100% waste
4.2
ND = None detected.
Not the central treatment system sampled, see Table 4-18.'
Exceeds toxic limits, Table 4-4.
-------
Plant B's cold rolling wastewater treatment was discussed in Section 4.8,
Pickling.
4.10 HOT COATING
Figure 4-10 shows the treatment system and sampling points for the hot
coating v/astewaters studied. Waters from rinsing acid-, alkali, and electro-
lytic cleaner were collected along with fume hood scrubber waters, and sent to
equalization, where spent pickling solution was added. Overflow passed to a
blending tank where recycled underflow from the clarifier and effluent from
the vacuum filter were added. The mixed waters passed to neutralization where
lime and polymer were added, then to a clarifier (holding time 3 h). The
overflow was discharged. At equalization, the pH was held at 4.5 by lime
addi tion.
During the study, flow was 4.9 mVmin (80% of normal). Production averaged
1,172 MTD (69% of average).
Samples were taken after equalization and after clarification.
Table 4-24 shows that the raw waters were highly toxic to minnows and to
daphnia. The treated waters were nontoxic, although the ammonia and zinc
concentrations exceeded toxicity limits,
Conclusions
The flocculation with lime and clarification effectively reduced waste-
water toxicity of hot coating wastewaters studied. There were no organics
present.
4.11 CENTRAL TREATMENT
The systems studied have been described in Section 4.5, Hot Strip and
Cold Rolling Mills, and Section 4.7, Section Mills. The processes employed
are summarized in Figure 4-11.
52
-------
Plant
C
Equalization »s
Neutralization with lime •
Flocculation with polymer •
Clarifier «s
Discharge ••''"' •
s = Sample point
Figure 4-10. Hot coating galvanizing—treatments and sampling.
53
-------
TABLE 4-24. HOT COATING, GALVANIZING: POLLUTANT REDUCTION, PLANT C
Component
Flow
pH
Ammonia
Oil and grease
Phenol (4APP)
Residual chlorine
Total suspended solids
Benzene
Naphthalene
Benzo(a)pyrene
Tetrachl oroethyl ene
Cyanide
Total organics
Lead
Nickel
Zinc
Total metals
Toxicity, minnow, 96 h
Toxicity,- daphnia, 48 h
Units
mVmin
S.U.
mg/L
mg/L
mg/L
mg/L
mg/L
pg/L
pg/L
pg/L
pg/L
mg/L
pg/L
pg/L
pg/L
pg/L
LC50
EC50
E; NL;
A
4.9
21. 93
1.4
<0.02'
<0.2
115
ND
ND
ND
ND
0.07
ND
1493
65a
99,000a
100,816
3.9
4.1
VF
FLP; CL
A
4.9
7.5
18. 5a
1.4
<0.02
<0.2
2
ND
ND
ND
ND
0.03
ND
<2
10
2,330a
2,422
100% survival in
100% waste
100% survival in
100% waste
Percent
reduction
15.5
98.3
57.1
98
85
97.6
ND = None detected.
Exceeds toxicity limits, Table 4-4.
-------
Plant
Scalp tank with chlorination
Cooling tower
Settling basin
Recycle
Chrome pretreatment
Cyanide pretreatment
Equalization
Neutralization with caustic
Neutralization with acid
Flocculation with polymer
Clarifier
Surface skimmer
Discharge
s = Sample point
Figure 4-11. Central treatment—systems and sampling.
55
-------
5.0 QUALITY ASSURANCE
5.1 QUALITY ASSURANCE PROJECT PLAN
The approved QA Project Plan prepared by PedCo Environmental for sampling
and analysis of iron and steel industry wastewaters under Contract No. 68-02-
3173 was, by mutual agreement, also used by RTI also in the collection,
analysis, and reporting of data.
5.2 OBJECTIVES AND STANDARDS
Quality assurance (QA) objectives were established for measurement data
in terms of precision, accuracy, completeness, representativeness, and com-
parability [14]. Accuracy was determined by analysis of Standard Reference
Samples (SRS), by spike samples and blanks, and by assessment of specific
steps in the methods of analysis. Precision was determined on the basis of
replicate results and comparative results on 10 percent of the samples which
were exchanged between both laboratories. Completeness was assessed in terms
of the percentage of the total proposed samples which were analyzed and met
the precision and accuracy requirements of the program.
Systems audits were conducted to insure compliance with the sampling and
analysis requirements set forth in the QA plan and any applicable reference
procedures contained therein. Personnel who collected and analyzed the
samples were interviewed prior to sampling and before initiation of the
analyses. In addition, the analysts were spot-checked on a random basis
during the course of their work. The proposed sample collection and analysis
procedures were reviewed, and the sampling equipment was inspected and found
to be acceptable prior to undertaking the field work. Particular attention
was given to the dissolved oxygen meter, and replacement of the membrane
therein was required. Thereafter, the meter performed acceptably.
Sample custody forms and labels were reviewed and found to be acceptable,
the proposed packaging and icing of samples in sample storage arrangements
were found to be acceptable. Sample collection, preservation, and field
56
-------
analysis procedures were also reviewed and found to be acceptable. Procedures
for collection of volatile organic samples were evaluated by requiring one of
the field personnel to collect dummy VOA samples from a laboratory tap. The
procedure was observed to be acceptable.
Audits of chemical analyses at RTI were conducted for phenol, ammonia,
oil and grease, and metals. Corrective actions were implemented when control
limits on precision or accuracy were exceeded. Whenever unacceptable QA
sample results were reported, reviews of the entire procedure and data reduc-
tion process were conducted. For example, the initially reported results for
the ammonia performance evaluation sample were unacceptable. Discussions with
the analyst disclosed an error in the reading of concentrations obtained from
a graph of the ammonia electrode response versus concentration. A rereading
of the graph and subsequent recalculation resulted in a value within the
acceptable range.
Prior to preparation of the final report, data were reviewed for reasona-
bleness with respect to the stream sampled, the procedures used, and the
results obtained. Calculation and reporting errors identified at this time
were corrected and, where necessary, laboratory notebooks were reviewed for
confirmation of data quality. Audits of analyses for organics by Mead
CompuChem were conducted by that firm. These are described in the Precision
Section.
Bioassays were audited by examination of the notebook records and
personal interviews with the EPA laboratories at Athens and Wheeling.
Performance audits of analyses were based on the results of testing of
Standard Reference Solutions (SRS) from PedCo Environmental, and from EPA at
Cincinnati. The SRS's were, to the extent possible, samples prepared and used
by PedCo for previous and current analyses of iron and steel industry waste-
waters. PedCo samples were used for total suspended solids, fluorides,
chromium, lead, iron, cadmium, copper, arsenic, nickel, selenium, zinc, and
antimony. Ammonia data quality was evaluated using two EMSL-C Nutrient
Quality Control Samples. Oil and grease test results audits were evaluated by
analyses of an aliquot of sunflower oil taken through the analyses procedure.
Phenol and cyanide performances were assessed based on recoveries obtained in
the distillation step of the prescribed methods.
57
-------
5.3 PRECISION
Precision was defined, except for GO/MS methods, by the coefficient of
variation (CV) of analytical test results:
h
• CV = - =
X K + X
2
where Xi and X2 = values of the replicate test results,
S = the estimated standard deviation of the replicates,
and
X = the mean of the replicates.
The value of the CV must have been within the 99.5 percentile (upper
control limit = 2.28 x CV), or the analysis was voided and the entire batch of
samples reanalyzed. Values of the upper control limit, developed from repli-
cate analysis of wastewater samples and standard reference solutions (SR.S's)
are given in Table 5-1 together with the CV's obtained at RTI during metals
analyses.
5.4 ACCURACY
The accuracy of the analyses was assessed, based on whether the results
obtained for the performance evaluation samples were within the 2a control
limits set forth in the PedCo QA Plan. The results are summarized in Table
5-2. Results for all metals, fluoride, total suspended solids, and ammonia
were within the acceptable 2a limits, except for Sb which was slightly lower
than the acceptable limit. The impact of this on the test results for the
wastewater stream is unclear since all of the reported Sb results were con-
siderably lower than the SRS concentration and near the detection limit by
electrothermal atomization atomic absorption.
Results for oil and grease were 5 percent higher than expected for a
large spike of 1.59 g. Spikes of 15 and 19 mg were used and also gave results
5 percent higher than expected.
58
-------
TABLE 5-1. SPECIFICATIONS FOR ANALYTICAL RESULTS
Upper control CV obtained
limit, 2.8 CV, during study ,
Constituent fraction fraction
Antimony
Arsenic
Copper
Cadmium
Selenium
Zinc
Chromium
Lead
Iron
Nickel
Total cyanide
Ammonia
Fluoride
Oil and grease
pH
Phenol ics (4AAP)
Residual chlorine
Total suspended solids
0.196 0.003 - 0.235b
0.389 0.009 - 0.18
0.129 0.005 - 0.076
0.216 0.101 - 0.67b
0.154 0.004 - 0.136
0.064
0.123 . 0.003 - 0.046
0.095 0.019 - 0.20b
0.050
0.109 0.025 - 0.134b
0.269
0.059
0.232
c , c . .
0.036d ' -
0.078 0.013 - 1.2b
c
0.202
RTI
detection
limits, ng/L
5
3
1
0.1
10
1
2
3
10
5
4
20
50
1000
30
-
Replicate analyses of prepared sample.
DSet of analyses was rerun when CV exceeded the indicated upper limit.
"Insufficient data to establish a value.
Single laboratory precision taken from Methods for Chemical Analysis of
Water and Wastes EPA 600/4-79-020.
59
-------
TABLE 5-2. ANALYSES OF PedCo, EPA AND IN-HOUSE QA SAMPLES AT RTI
(|jg/L unless otherwise noted)
Expected
Analyte concentration
Sb
Cd
Cr
As
Cu
Fe
Pb
Ni
Se
Zn
Phenol ics
F
TSS
CNb
Oil and grease
Ammonia
150
7.5
50
75
75
6000
150
150
50
1500
-
1600
135,000
1-59 g
150
1500
2a
control limits
120-180
6.3-8.7
44.4-55.6
65.6-84.6
67.4-82.6
5800-6200
129-171
130-180
46-54
1370-1630
.
1340-1860
134,600-145,400
-
-
~
Reported
concentration
113
7.31
47.7
81.9
78.9
6100
147
159
54.7
1551
-
1610
141,000
l.Slg
155
1530
a!04 percent recovery obtained.
92-95 percent recovery obtained.
60
-------
Results for ammonia were well within the EMSL-C acceptance limits for
these samples.
A phenol standard was analyzed at RTI with and without the distillation
step of the prescribed method (4-AAP). This was done to evaluate the effect
of the sample distillation on phenol recovery. A recovery of 104 percent was;
obtained and was accepted under the limits set by PedCo (±10 percent). Subse-
quent standards were shown to have the same photometer response.
Cyanide recovery was evaluated by analysis of two distilled water samples
spiked with cyanide at 50 and 100 ug/L, respectively. These spiked samples
were then carried through the distillation procedure. Recoveries of 92 and 95
percent were obtained. These are considered acceptable.
5.5 PRECISION AND ACCURACY METHODS 624 AND 625
Aliquots of collected samples were analyzed for priority pollutants by
RTI's subcontractor, Mead CompuChem, or by PedCo if that firm did the sampling.
Detection limits ranged above the minimum (usually ~ 10 ug/L) for some samples
and pollutant categories because the samples were diluted to avoid saturation
of the mass spectrometer's detection system by other compounds present at hicjh
concentrations, or because the responses were obtained at lowered sensitivity.
Complete analytical reports, including chromatograms, mass spectra,
calibration, and quality-control data, are available for the data from each
plant involved.
At this time, good estimates of the accuracy and precision of Methods 624
and 625 are not available (Quality Assurance Plan, June 1982, and CFR 40-136).
Results by these GC/MS methods are judged by the absence of interference and
contamination and by the percent recovery and standard deviation of surrogate
spikes and matrix spikes, and by replicate analyses.
The quality control measures employed during this study included:
instrument tuning and calibration three times daily; reagent blanks; surrogate
spikes in all samples, matrix spikes, method blanks at least every 20 samples,
and duplicate analyses.
When volatile organics were analyzed, DFTPP could not be used because of
its low volatility. Bromofluorobenzene (BFB) was used instead. Tables 5-3
and 5-4 show specified ion abundancies for these standard compounds.
61
-------
TABLE 5-3. DECAFLUOROTRIPHENYLPHOSPHINE, KEY IONS AND ION ABUNDANCE
Mass • DFTPP specs
51 30 to 60 percent of mass 198
68 Less than 2 percent of mass 69
70 Less than 2 percent of mass 69
127 " 40 to 60 percent of mass 198
197 Less than 1 percent of mass 198
198 Base peak 100 percent relative abundance
199 5 to 9 percent of mass 198
275 10 to 30 percent of mass 198
365 Greater than 1 percent of mass 198
441 Present but less than mass 443
442 Greater than 40 percent or mass 198
443 17 to 23 percent of mass 442
TABLE 5-4. BROMOFLUOROBENZENE, KEY IONS, AND ION ABUNDANCE
Mass BFB specs
50 20 to 40 percent of mass 95.
75 50 to 70 percent of mass 95.
95 Base peak, 100 percent relative abundance.
96 5 to 9 percent of mass 95.
173 Less than 1 percent of mass 95.
174 70 to 90 percent of mass 95.
175 5 to 9 percent of mass 95.
176 70 to 90 percent of mass 95.
177 5 to 9 percent of mass 95.
62
-------
5.6 TUNING THE GC/MS
Once per 8-hour shift, the instrument was fine-tuned using decafluorotri-
phenylphosphine (DFTPP) or bromofluorobenzene (BFB). The mass spectrum ob-
tained for DFTPP met the criteria described by Harris et al. [20]; or adjust-
ments were made until a match was obtained.
5.7 CALIBRATION
After the instrument met the key ion and ion abundance criteria for the
above-mentioned compounds, it was calibrated. Calibration curves were gener-
ated from the results of analyses of at least three solutions of known concen-
trations of pure chemicals or standards. These standard concentrations were
evenly distributed throughout the range of the method corresponding to nomin-
ally 10, 40, and 200 M9/L.
D10-anthracene (the internal standard) was also injected at a constant
amount, nominally 100 ng. From these data, external and internal standard
libraries were generated. For the internal calibration method, response
factors versus concentrations versus the integrated heights were plotted.
After the master set of instrument calibration curves had been established,
they were verified daily by injecting at least one standard solution. If
significant drift had occurred, a new calibration curve was constructed.
For volatile organic analysis, 100 ng each of bromochloromethane, 2-bromo-
1-chloropropane, and 1,4-dichlorobutane were used as internal standards. A
calibration curve was prepared. The response factor (RF) was plotted against
the standard concentration using a minimum of three concentrations over the
range of interest. Once this calibration curve had been determined, it was
verified daily by introducing at least one standard solution containing the
appropriate internal standard with each sample. If significant drift were
observed, a new calibration curve was constructed.
The response factor, RF, is the ratio of the calibration factors for the
standard solution and the internal standard:
area of the characteristic ion of the standard used
concentration of the standard
RF =
area of the characteristic ion of the internal standard
concentration of the internal standard
63
-------
After calibration was completed, sample analysis began. A typical run log
sequence was as follows:
Standard
Blank Organic-free water
Sample 1
2
3
4
5
6
Blank Organic-free water
Sample 7
8
9
10
11
12
Standard
Blank
Sample 13
This cycle was continued until the run was completed. However, if there was a
shift overlap in running these samples, a new DFTPP sample was inserted at the
beginning of each 8-hour shift.
Duplicates and spikes were processed approximately one in every 20 samples
to further monitor the performance of the GC/MS. In addition, surrogate stan-
dards were used with each sample processed.
Blind samples were routinely sent to the laboratory for analysis. These
consisted of replicates as well as external quality control samples. These
samples were obtained from outside sources and contained known concentrations
of specific compounds. They were submitted to the laboratory on a regular
basis. This was done at least once a month for every shift.
5.8 REAGENT BLANKS
With each new lot of reagents, a reagent blank was prepared and analyzed
to assure that the reagents did not introduce contaminants or interferences.
5.9 SURROGATE SPIKES AND EXTRACTION CONTROLS
Each extraction batch had at least one quality assurance sample included
(blank, spike, or replicate). Method blanks were generated by passing a clean
matrix through the entire analytical scheme. At least one method blank was
64
-------
run for every 20 samples and whenever reagent lots changed. Replicates were
utilized to determine the precision of the procedure under real operating cir-
cumstances.
Before each sample was extracted, a minimum of two surrogate standards
were added at concentrations of 100 ug/L. These surrogate standards were
quantitatively analyzed in the GC/MS phase. Historical records were main-
tained on the percent recovery of the surrogate standards for each sample.
These data form the statistical basis upon which.the extraction technique is
monitored.
The controls specified for surrogates, duplicates, blanks and matrix
samples are shown below. Any sample for which surrogate recoveries fell out-
side two standard deviations (which is tighter than the recommended three)
were reviewed by the Quality Control Board. This Board, which consists of the
Vice President-Operations, the Chief Chemist, and the Quality Control Officer,
reviewed all relevant quality control information for any sample outside con-
trol and made recommendations to the President. If there were any uncertainty
as to the validity.of the data, the sample was re-analyzed and this additional
information reviewed by the Board.
' SURROGATE SPIKE CONTROLS
Recovery Duplicates (Relative Percent Difference)
d6-benzene 80-130 < 35
d8-toluene 80-140 < 20
ds-nitrobenzene 20-85 < 60
2-fluorophenol 35-110 < 60
d8-naphthalene 30-105 < 45
2-fluordphenol 15-80 < 55
d6-phenol 10-50 < 60
MATRIX AND BLANK SPIKE CONTROLS
Matrix Blank
heptachlor 65-125 80-120
aldrin 70-115 80-115
dieldrin 80-110 80-115
1,4-dichlorobenzene 20-105 0-110
1,2,4-trichlorobenzene 20-100 25-100
2,4-dinitrotoluene 20-70 20-70
pyrene 65-130 65-140
acenaphthene 45-95 50-100
2-chlorophenol 40-90 30-100
65
-------
. . MATRIX AND BLANK SPIKE CONTROLS (con.)
Matrix Blank
phenol 10-40 15-40
p-chloro-m-cresol 30-90 35-95
pentachlorophenol 45-135 45-140
benzene 70-125 90-130
chlorobenzene 90-135 95-135
toluene 85-130 90-125
(N-nitrosodi-n-propylamine and 4-nitrophenol are also monitored, but due to
well-known capricious nature of these compounds it has not yet been possible
to establish meaningful controls).
5.10 METALS
Samples were analyzed for metals using flame and furnace atomic absorp-
tion spectrophotometry. The analysis procedure involved two steps: sample
digestion with nitric acid and subsequent instrumental analysis.
For each batch of samples in the digestion process, a method blank was
included. This blank was analyzed along with the samples to assure that no
contaminants were introduced by the reagents or laboratory procedures.
For each element analyzed, a five-point calibration curve was prepared
using standard solutions covering the concentration range of interest. System
blanks, method blanks, and a standard solution were also run every 10 samples
during the analysis sequence. The accuracy and precision of these measure-
ments fell within the guidelines found in "Methods for Chemical Analysis of
Water and Wastes (EPA-600/4-79-020)" if available for the element in question.
If that guideline was absent, the manufacturer's literature was used to establish
limits.
5.11 BIOASSAY QUALITY ASSURANCE, ACCURACY, AND PRECISION
Bioassays were conducted by exposing organisms (fathead minnows and
daphnia) to several different concentrations of the samples in dilution water
and observing the number of survivals daily for up to 4 days (fathead minnows)
or up to 2 days (daphnia). The test protocols were essentially those pre-
scribed by Peltier and Weber [15]. Replicate tests were run using 10 organisms
for each test.
Test organisms at Athens were exposed to a standard toxic substance,
sodium pentachlorophenate, using the test protocol. The results for April and
May were as follows:
66
-------
5-9 day-old 24-hour-old Daphrria
Date fathead minnows pulex
4/14-15/83 LC50 0.16 mg/L LC50 1.5 mg/L
5/12-3/83 LC50 0.215 mg/L LC50 1.5 mg/L
The Wheeling Laboratory maintained "Precision Control Charts" on normalized
toxicity tests, that is, one of the test results was assigned the value "100"
and the other was ratioed: (X2/X!) x 100. An UCL was established for this
normalized range at 39.6 percent. The results reported were within the labora-
tory's control range.
During the tests of wastewater samples, controls were run using only
dilution water. If more than 20 percent of the organisms died in the controls,
the tests were considered invalid. The mortalities for Athens and Wheeling
were well below this limit.
For each toxicity test, the LC50 and, if possible, the 95-percent confi-
dence interval are calculated on the basis of the volume percent of the efflu-
ent in the test solutions. The "volume percent" equals (100 x volume of
effluent)/(volume of effluent + volume of dilution water). A wide variety of
methods are available to calculate a LC50 and EC50, including the.log-concen-
tration-versus-percent-survival, probit, and Litchfield-Wilcoxon methods. Use
of the Litchfield-Wilcoxon and probit methods require partial mortalities at
dilutions above and below the LC50- Most of the samples of this study did rot
yield this kind of data, there being a rapid fall in survival to 0 after a few
partial mortalities. As is frequent in effluent toxicity tests, there were
for some samples no partial mortalities at any effluent concentration. In
these cases, survival fell from 100 percent at one or more lower effluent
concentrations to 0 at the next highest concentration. When this occurs, it
is not possible to calculate a confidence interval, and the log-concentration-
versus-percent-survival method must be used. The log-concentration-versus-
percent-survival method was adopted for use with data for this study.
While accuracy was controlled by checks on the culture of the organisms,
by a toxicity control sample, and by blanks, precision was not calculable via
the Litchfield-Wilcoxon procedure for 95-percent confidence limits because of
the lack of sufficient partial mortalities above and below the 50-percent sur-
vival level.
67
-------
RTI has therefore assessed the test precision by the coefficient of vari-
ation of the two estimates of LC50 obtainable by the log-concentration plots.
These are given in Table 5-5. In a few cases, where both replicates were
needed to identify an LC50 value, no estimate of CV was obtainable.
5.12 COMPARABILITY
Several samples were analyzed both at PedCo and at RTI during the study.
These "split samples" provide a comparison between the two laboratories.
The results are given in Table 5-6.
5.13 COMPLETENESS .
All samples were carried through the analyses as planned, except for one
sample submitted to EPA-Newtown for bioassay which was accidently lost when
the container broke, three unacceptable metals analyses, and one split sample
that was delayed too long in shipment to qualify for analysis. The complete-
ness was well over the 90-percent goal set for the study.
68
-------
TABLE 5-5. BIOASSAY TEST PRECISION
LC50 and coefficient of variation, %
Minnow
Sample
Hot oil decanter
Adsorber inlet
Adsorber outlet
Dissolved air
flotation
Clarifier outlet
Laboratory
Athens
Athens
Athens
Wheeling
Wheeling
LCso
12.2, 12.5
0.6, 0.35
1.8, 0.37
18, 33
63,80
CV,%
1.7
37
93
42
17
Daphnia
EC50 CV
2.0, 2.3 9.8
1.3, 1.3 0
1.3, 1.7 19
a
3.5, 7.0 47
EC50 determined by use of combined data and did not yield a CV.
69
-------
TABLE 5-6. COMPARATIVE ANALYTICAL RESULTS
January 1983
Raw flushing
liquid, Plant B
Constitutent
Antimony (ug/L)
Arsenic
Cadmium
Copper
Lead
Zinc
Chromium
Selenium
Nickel
Cyanide
Phenol (4-AAP) (mg/L)
Fluorides
Ammonia
Residual chlorine
Total suspended solids
Iron
Oil and grease
Acrylonitrile. (pg/L)
Benzene
Chloroform
RTI
(Mead)
ND
77
—
12
156
—
2,790
<20
919
—
3,970
--
31
--
428
--
11,000
—
PedCo
<5
50
--
19.5
120
—
1,020
<20
589
--
3,291
—
66
—
80.2
16.6
8,950
ND
November 1982
Equal
tank,
RTI
(Mead)
50
154
0.
354
76.
1.
163
1,850
36.
---
812
65
665
—
—
10.
102
b
-'-
ization
Plant C
PedCo
180
320
53 ND
244
7
3 650
--
1,300
2
<0.02
831
—
1,010
--
85/75
-i — _
26.3
11,600
ND
Section
mill , Plant A
RTI
(Mead)
3.8
9
0.03
52.2
93.5
0.02
34.6
ND
67.8
. 1.0
958
0.2
3.9
--
30/33
18.5
77
PedCo
ND
ND
1.1
43.6
112
<28
25.2
ND
74
<0.02
<0.02
0.21
<0.4
0.2
110
—
57
QA samples
RTI
(Mead)
88a
73a
7.3a
73. la
110a
180a
45. 9a
43. 4a
149. 5a
--
19,230
1.6
54
—
135
5.9
14.9
PedCo
120-180
66-85
6.3-8.7
67-83
129-171
137-163
44-56
46-54
130-180
—
18,490
1.6
60
—
135
—
(104%
recovery)
See footnotes at end of table.
(continued)
-------
TABLE 5-6 (continued)
Constitutent
Ethyl benzene
Toluene
Xylene
Acenaphthene
Anthracene
3 ,4-Benzof 1 uoranthene
Benzo(k)fluoranthene
Phenol
2, 4-Dimethyl phenol
Fl uoranthene
Fluorene
2,1,1-Trichloroethyelene
Naphthalene
Phenanthrene
Tetrachl oroethy 1 ene
1,2-Transdichloroethylene
Chrysene
Acenaphthyl.ene
Pyrene
January 1983
Raw flushing
liquid, Plant B
RTI
(Mead) PedCo
20.3
2,000 5,230
— 1,820
2,500 ND
800 ND
700 ND
700 ND
200,000 404,000
2,400 ND
1,600 ND
1,800 ND
__
40,000 56,000
3,100 ND
__
—
775
3,600 . 6,400
1,000 1,340
November 1982
Equalization Section
tank, Plant C mill, Plant A QA samples
RTI RTI RTI
(Mead) PedCo (Mead) PedCo (Mead) PedCo
9
— 1,010
825
.
— 1,860
12.2
ND
53 49.6
783
25 57.4
11 ND
ND
ND
8.7
ND = None detected.
NBS SRM 1643a, trace elements in water used as performance evaluation sample.
Priority pollutants not determined because split sample was delayed in shipment.
-------
6.0 SUMMARY OF EFFLUENT TOXICITY DATA
6.1 IRON AND STEEL PROCESS WASTEWATERS
Raw wastewaters from iron and steel manufacturing have been characterized
chemically using historical data from a broad range of manufacturers [1].
Pollutant concentrations, based on loadings for model plants, were developed
for process subcategories. These are summarized in Table 6-1 for the eight
subcategories chosen for biotoxicity evaluation: cokemaking, ironmaking,
steelmaking, continuous casting, hot forming, pickling, cold forming, and hot
coating. Most of the toxic pollutants are found in cokemaking and cold form-
ing; although, as shown, potentially toxic pollutants .are present in all eight
wastewaters. All these model processes except cold rolling include some
recycling of wastewaters. Water recycle, while reducing overall discharge,
would be expected by itself to concentrate wastewaters and increase toxicity.
Control of regulated pollutants, listed in Table 6-2, and other toxic
pollutants known to be present, has been assessed for these subcategories, in
each of which treatment technologies have been examined as to their demonstra-
tion status, application and performance in reducing pollutant concentration.
This assessment does not include effectiveness in reducing biotoxicity; hence
there is no basis for relating the reductions in toxic chemical content to
reductions in biotoxicity. The information gained, however, provides the
basis for selection of subcategories for biotoxicity assessment.
The effectiveness of wastewater treatment technologies in reducing bio-
toxicity is not inherent in outfall compliance data. Nor can these data pro-
vide a basis for relating reduction in toxic chemical content to reductions in
biotoxicity. Outfalls represent the results of accumulative treatment and
collection. These data nevertheless do identify toxicities that persist after
currently applied treatments. Therefore, available bioassay test results are
summarized in Section 6.2 to identify the current status of treated waste-
waters.
72
-------
TABLE 6-1. IRON AND STEEL MAKING RAW WASTEWATER CHARACTERISTICS
a,b
Coke Iron Steelmakingc Contin. • Hot
Characteristics making making S.C. W.O. Cast. Forming
Flow, 1/kkg 676 13353 1172 4590 14188 14188
pH, SU 7-10 6-9 7-12 8-11 6-9
-------
TABLE 6-1 (continued)
Characteristics
72
73
76
77
78
80
81
84
85
86
87
114
115
117
118
119
120
121
122
123
124
125
126
127
128
130
Coke Iron
making making
Steelmakinqc Contin.
S.C.
W.O. Cast.
Benzo(a)anthracene 0.3g
Benzo(a)pyrene "'^o 0.01
Chrysene 0.4® 0.01
Acenaphthylene 3.5
Anthracene
Fluorene 0.6
Phenanthrene
Pyrene 0.6 0.05
Tetrachloroethylene
Toluene 25e
Hot
Pickling
Forming H2S04
o
HC1
Trichloroethylene „ „
Antimony
Arsenic
Beryll ium
Cadmium
Chromium
Copper
Cyanide
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Xylene
Tin
0.2 0.04
2* O.I3
O.le
0.5
0.25
50e 126
5
O.le
0.2 0.06
0.2e 20e
12
0.06
0.6 „
0.15e
8
0.3e
0.02
6.8e
0.06e
0.4
0.65
5.2e 0.11
3.9e 0.08
0.02
0.4
0.02 0.08
0.08
0.03
14e 0.7
0.
0.
1.3 6.
5.7 1.
6.5 0.
5.7 2.
0.
3.1 5.
17e
°i
9«
3e
p
2e
4e
02
6
0.54C
O.lle
Q.OI
Q.72e
p
2.6e
1.5e
7e
Comb.
p
0.38e
0.01
76%
3.8e
0.05
95e
0.64
Comb.
0.18
0.98
5.1
0.05
0.02
0.16e
0.03e
0.89e
0.1
0.21e
0.15e
Cold forming Hot coating
Reel re.
0.16
0.11
0.14
0.14
3.5
0.91
0.3
0.036
0.012
0.009
0.031
0.26e
O.^6
5:ie
p
2.9e
3.3e
3.7e
Once Thru Galv. Terne
0.014
0.02
0.69
0.02 0.25 0.15
0.01
°e3
0.04 2e 5e
0.17e 0.08e 0.6
P P
0.39 2 1.2
0.2e 0.5e le
0.098 1.0e 1.5e
3
From Development Document for Effluent Guidelines and Standards
All concentrations are in mg/L unless otherwise noted.
S.C. = suppressed combustion W.O. = wet open combustion.
Primary carbon with scarfers.
Pollutant found in all samples
-------
TABLE 6-2. REGULATED POLLUTANT LIST, IRON AND STEEL INDUSTRY [1]
4 Benzene
55 Naphthalene
73 Benzo(a)pyrene
85 Tetrachloroethylene
119 Chromium
121 Cyanide
122 Lead
124 Nickel
128 Zinc
Ammonia
Oil and Grease
PH
Phenol (4AAP)
Chlorine Residual
Total Suspended Solids
Hexavalent Chromium
Persistent toxicity is evident in outfalls from cokemaking and ironmaking,
steelmaking, and certain central treatment systems processing combined waste-
waters from several processes. Cold-forming effluents tested do not show much
toxicity; the treatments need investigation to determine their effectiveness
and the loadings involved. No data are available for Hot Coating and Contin-
uous Casting. Three effluents from central treatment showed a range from an
LC50 of 19.5 percent dilution to no mortality. (LC5o is the concentration
expressed as volume percent, lethal to 50 percent of the organisms. EC50 is
the concentration that causes an adverse effect other than mortality to 50
percent of the organisms.)
6.2 SUMMARY OF EXISTING TOXICITY DATA
Existing data generally represent process wastewaters after treatment
and/or dilution with noncontact cooling water, and they often are the combined
effluents from several processes. The toxicity tests are often accompanied by
chemical analyses of the discharged waters. Included are existing data from
compliance tests and data submitted with permit applications.
75
-------
The summaries given in Tables 6-3 to 6-9 are arranged according to
process category so that the information may be readily related to that
supplied in the guidelines development documents.
6.2.1 Coke-Plant Effluent Toxicity
Much of the existing data on the toxicity of coke-plant wastewaters are
for final (treated) effluent, but these data are supplemented by a pilot-plant
study and influent/effluent testing at two plants. The data are summarized in
Table 6-3 and include various combinations of wastewater streams:
• Process wastewater from cokemaking
• Noncontact water from cokemaking
• Process water diluted with non-contact water
• Wastewater from cokemaking combined with process water from other
sources
Chemical analyses of the water are available for most of these toxicity sam-
ples. Treatment technologies were taken from the referenced reports when
available and supplemented with plant data from Reference 1.
Both the Koppers and Alabama By-Products outfalls were from a single-
stage biological treatment of coke-plant wastewaters. Noncontact cooling
water is not included in the Koppers effluent.' These data show LC50 concen-
trations that range from less than 10 to 56.5 percent, depending on the
organism. The fathead minnow appeared to be most sensitive to the Koppers
effluent; the bluegill, to the Alabama By-Products effluent.
The third sampled outfall was from the Jim Walters Resources Plant.
Wastewater from a chemical plant, a coke plant, and a pipe-lining plant are
given biological treatment and then combined with all other wastewaters (blast
furnace, mineral wool plant), and sent to a polishing lagoon. The sample was
taken from the lagoon.
At the Republic Steel Plant, the coke-plant wastewater, noncontact water,
and surface runoff are combined in an aerated lagoon with a retention time of
30 to 35 days. The sample taken from the outfall of the lagoon in 1981 showed
no mortality to minnows or waterfleas. However, samples taken in 1978 show a
significant mortality to bluegill sunfish in a static 96-hour test.
76
-------
TABLE 6-3. TOXICITY DATA, COKEMAKING WASTEWATER
No.
1
2
3
4
5
6
7
8
Plant Outfall From3
Koppers Company A
Woodward, AL
Alabama By- A
Products
Tarrant, AL
Jim Walters A,P,0
Resources
Birmingham, AL
Republic Steel A,N,0
Thomas, AL
Great Lakes Af,C,M,N
Steel
Zug Island, MI
Ford Motor Co. Af,C,M
River Rouge, MI
U.S. Steel A
Clairton, PA
A1
EDI/USS Pilot A
Plant
Clairton, PA
Treatment
ASF.BOA1
ASF.BOA1
BOA1.SL
ASF.BOA1
CL,T,VF,(FLP)
T,VF,(FLP,CT,
FP)
Untreatedh
ASF.DP.BOAl
ASF.DP.BOAl
ASF.DP.BOAl,
CA
Date
8/78
8/81
8/81
3/78
8/81
8/81
4/78
3/81
8/81
2/78
2/78
8/81
8/81
12/78
6/81
10/79
8/77
8/77
1981
1981
9/80
10/80
9/80
10/80
Test0
CF-96
S-24
S-24
S-96
S-24
S-24
CF-96
S-96
S-24
S-96
S-96
S-24
S-24
S-48
CF-96
S-48
S-24
S-24
7
?
CF-96
CF-96
CF-96
CF-96
• d
Organism
LM
PP
DP
LM
PP
DP
LM
LM
PP
LM
LM
PP
DP
DM
PP
DM
PP
PP
PP
DM
PP
PP
PP
PP
LC50 (%)6
32.0
<10.0
14.5
28.5
44.0
56.5
42.3
24.0
15% Mort.
6.6
12.9
NM
NM
NSM
10% Mort.9
NM
0.06
27
SI. Toxic
Mod. Toxic
65% Mort.
15% Mort.
20% Mort.
100% Mort.
Reference
2
2,3
2,3
2,3
2,3
2,3
2,3
2,3
2,3
2,3
2,3
2,3
2,3
4
5
6
7
7,8
9
9
10
10
10
10
See footnotes at end of table.
(continued)
-------
TABLE 6-3. (continued)
00
No.
9
10
11
12
Plant Outfall From3
J&L Steel A
Pittsburgh, PA
National Steel A
Wierton, WV
Bethlehem Steel A
Sparrows Point,
MD
Shenango A
Neville Island, Am
PA
Treatment
Untreated!}
Untreated
ASF, DP
ASF.BOA2
BOA1
CLA.CAG
aProcesses are coded as prescribed in Reference 1
A: By-product cokemaking
C: Ironmaking
M: Boiler and/or compressor
N: Noncontact cooling water
0: Surface runoff, drainage
P: Chemical plant and pipe 1
house
ining
Date
9/77
9/77
9/77
9/77
9/77
9/77
1977
1977
1981
1981
(Volume 1,
Test
S-24
S-24
S-24
S-24
S-24
S-24
S-24
S-24
?
?
pg.338)
Organism
PP
DM
PP
DM
PP
DM
DM
PP
?
?
LC50 (%)e
0.46
0.65
4.6H
3'3k
2'8k
3.9K
NM
<20
V. Toxic
V. Toxic
Reference
7,11
11
7,11
11
7,11
11
8
8
9
9
with additions:
Treatments
ASF: Free-ammonia still
BOA1: Single-stage biological oxidation
BOA2: Two-stage biological oxidation
-------
TABLE 6-3. (continued)
Treatments: (continued)
CA: Carbon adsorption
CL: Clarifier
CLA: Alkaline chlorination . ,
CT: Cooling tower
DP: Dephenolization
FLP: Flocculation with polymer
FP: Pressure filtration
SL: Settling lagoon
T: Thickener
VF: Vacuum filtration
Type of test:
S-n: Static test for n hours
CF-n: Continuous flow test for n hours
j • *
Type of test organism:
CV: Cyprinodon variegatus (sheepshead minnow)
DM: Daphnia magna (waterflea)
DP: Daphnia pulex (waterflea)
LM: Leopomis machrochirus (bluegill sunfish)
MB: Mysidopsis bahia (shrimp)
NA: Notropis atherinoides (emerald shiner)
PP: Pimephales promelas (fathead minnow)
£
LC50 = Effluent concentration lethal to 50 percent of the test organisms and is the way most
toxicity tests were reported. Other units used to report test results are:
n% Mortality: Percent mortality in 100 percent effluent reported when LC50 cannot be calculated
NM: No mortality
NSM: No significant mortality
Mod. Toxic: Moderately toxic
SI. Toxic: Slightly toxic
V. Toxic: Very toxic
Wastewater from cokemaking is noncontact only.
-------
TABLE 6-3. (continued)
9Low mortality, but fish were lethargic in concentrations > 25 percent. Suspect volatile organic
compounds. • >'
Untreated influent to wastewater pi ant-was sampled.
nOutfall No. 8107271045
•^Effluent from Treatment Plant 1
k
Effluent from Treatment Plant 2
]0utfall No. 8107271455
mOutfall No. 8107281518
00
o
-------
The data from Great Lakes Steel include noncontact cooling water from the
coke plant. (Process water from the coke plant is discharged to the Detroit
wastewater treatment plant.) The sample represents treated wastewater from
the blast furnace combined with untreated noncontact water from the blast fur-
nace and coke plant. No significant mortality was observed. The sample taken
at Ford Motor Company includes noncontact cooling water and steam condensate
from the coke plant which combines with treated effluent from the blast fur-
naces. The process water from cokemaking is discharged to the sanitary sewer
except for final cooler water, which is injected into deep wells.
The U.S. Steel samples from References 7 and 8 were taken to measure
the efficiency of Clairton's physical-chemical and biological treatment sys-
tems for cokemaking wastewaters. In August 1977, influent to the coke plant
and final effluent after dilution were sampled. The final effluent was mixed
with 34.4 percent dilution water; therefore, the LC50 of the treated process
effluent is estimated as "17.7 percent (0.656 x 27) which is approximately 290
times less toxic than the untreated water. The influent to the treatment
plant was extremely toxic with an LC50 of 0.061 percent. Reference 9 presen-
ted some qualitative data on Clairton's effluent and stated that toxicity was
slight to moderate.
Plant No. 8 includes samples taken during a pilot-scale study of the U.S.
Steel, Clairton Works biotreatment system conducted by Environmental Dynamics,
Inc. (EDI) in 1980-81 [10]. The system was operated during the tests at con-
ditions selected from bench-scale tests: a hydraulic retention time of 2
days; a volume ratio of dilution water to process water 700/2000; a control
target temperature of 30°C (20°-30°C); a dissolved oxygen'target level of 4
mg/L (3-5 mg/L); and a pH controlled at 6.8. The results shown are for two
separate tests of each system using 100 percent effluent. On the second test,
the PAC-containing unit showed toxicity associated with nitrification upsets,
presumed to have arisen from oil and grease shock in early October. Effluent
ammonia increased substantially at that time. The non-PAC-containing unit,
run in parallel, recovered more quickly, and the toxicity test showed 15 per-
cent affected minnows. The LC50 for the PAC unit was estimated at 49 percent.
The increased toxicity may have been due to abnormally high effluent thiocya-
nate from the PAC unit. Thiocyanate rose from a norm of 1.0 mg/L to a high of
160 mg/L at the conclusion of the run. Evidently desorption of materials from
81
-------
the PAC inhibited thiocyanate-metabolizing organisms. Other toxic substances
that were detected at higher concentrations from the PAC unit were: fluoran-
thene, 820 ug/L vs. 70 ug/L for the control unit operated in parallel; benzo(a)-
pyrene, 20 mg/L vs. nil in the control.
Data from the Pittsburgh Works of J&L Steel also provide an analysis of
the treatment system's effectiveness. Wastewaters are subjected to free-
ammonia stripping and dephenolization by solvent extraction. The coke-plant
wastewater is given a physical-chemical treatment in two different treatment
plants. The LC50 for the untreated water was 0.46 and 0.65 percent for fat-
head minnows and waterfleas, respectively. Treatment Plant 1 reduced the
toxicity by factors of 10 and 5 for the minnows and waterfleas, respectively.
The second treatment plant reduced toxicity by a factor of 6 for both organ-
isms. A comparison of physical-chemical treatment at J&L with the biological
treatment at Clairton led the investigators to the following conclusion: the
biological treatment at Clairton is much more efficient at reducing toxicity
than physical-chemical treatment at J&L. The final effluent at J&L was more
toxic, even though the influent at Clairton was much more toxic than J&L's in-
fluent [7]. These comparisons must be regarded a applicable at the time tests
were made.
The remaining data are for three plants with at least BPT treatment of
cokemaking wastewaters. The National Steel data showed no toxicity from a
biological oxidation treatment system with two aeration basins operated in
parallel, but data for the other two plants suggest a toxicity problem [8,9].
The Shenango plant uses carbon adsorption and alkaline chlorination (the
latter to convert cyanides to cyanates), but the resulting effluent was classi-
fied "very toxic" [9].
6.2.2 Ironmaking Wastewater Toxicity
The available toxicity data for blast-furnace effluent are summarized in
Table 6-4. These data include blowdown from the recycle system alone and in
combination with dilution water from noncontact cooling. No tests were con-
ducted on the untreated water; therefore, it is difficult to assess the treat-
ment's effectiveness at reducing toxicity. Chemical analyses are available
for many of the samples. Treatment methods were obtained from the referenced
reports and supplemented with data reported in Reference 1.
82
-------
TABLE 6-4. TOXICITY DATA, IRONMAKING WASTEWATER
00
CO
No. Plant Outfall From3
1 Ford Motor Co. Af,C,M
River Rouge, MI ' C.N.O
Cd
2 Great Lakes C,0h
Steel C,0
Zug Island, MI C,N
Cf
A ,C,M,N
CfM
AT,C,M,N
3 U.S. Steel Pilot C
Plant
South Chicago, IL
4 McLouth Steel C.D1.D3
Trenton, MI G1,I1J
Treatment
T,VF,(FLP,CT,
FP)
CL,T,VF,(FLP)
CL.FLL.CLB,
FDSG.CA
SL,PSP,SS,
FLF.FLL.CL,
FLP
Processes are coded as prescribed in Reference 1 (Vpl
A: By-product cokemaking
C: Ironmaking
Dl: Basic oxygen furnace
D3: Electric arc furnace
Gl: Hot forming
11: Acid pickling
M: Boiler and/or compressor
N: Noncontact cooling water
0: Surface runoff, drainage
P: Chemical plant and pipe 1
house
ining
Date
10/79
10/79
10/80
12/78
12/78
12/78
12/78
12/78
6/81
6/81
8/78
8/78
8/78
9/80
ume 1,
Testc
S-48
S-48
S-24
S-48
S-48
S-48
S-48
S-48
CF-96
CF-96
CF-96
CF-96
CF-96
S-24
pg.338)
Organism
DM
DM
DM
DM
DM
DM
DM
DM
PP
PP
LM
NA
PP
DM
LC50 (%)e
NM
NM
82
< 6
NM
NM
60% Mort.
NM
<43
10% Mort.
NM
NM
5% Mort.
NM
Reference
6
6
12
4
4
4
4
4
5
5
13
13
13
14
with additions:
-------
TABLE 6-4. (continued)
Treatments
ASF: Free-ammonia still
BOA1: Single-stage biological oxidation
BOA2: Two-stage biological oxidation
CA: Carbon adsorption
CL: Clarifier
CLA: Alkaline chlorination
CLB: Breakpoint chlorination
CT: Cooling tower
DP: Dephenolization
FDSG: Filter, deep, sand, gravity
FLF: Flocculation with ferric chloride
FLL: Flocculation with lime
FLP: Flocculation with polymer
FP: Pressure filtration
oo SL: Settling lagoon
* T: Thickener
VF: Vacuum filtration
cType of test:
S-n: Static test for n hours
CF-n: Continuous flow test for n hours
Type of test organism:
CV: Cyprinodon variegatus (sheepshead minnow)
DM: Daphnia magna (waterflea)
DP: Daphnia pulex (waterflea)
LM: Leopomis machrochirus (bluegill sunfish)
MB: Mysidopsis bahia (shrimp)
NA: Notropis atherinoides (emerald shiner)
PP: Pimephales promelas (fathead minnow)
eLC50 = Effluent concentration lethal to 50 percent of the test organisms:
n% Mortality: Percent mortality in 100-percent effluent reported when LC50 cannot be calculated
NM: No mortality
-------
TABLE 6-4. (continued)
(continued)
NSM: No significant mortality
Mod. Toxic: Moderately toxic
SI. Toxic: Slightly toxic
V. Toxic: Very toxic
Noncontact water from the coke plant
%last furnace blowdown
Includes equipment blowdown
Low mortality, but fish were lethargic in concentrations over 25 percent. Suspect volatile organic
compounds.
JEffluent from a central treatment plant
00
in
-------
The first Ford Motor Company sample represents treated blast-furnace
water from the thickener overflow after mixing with noncontact water from the
coke plant and boiler house. The second sample represents treated blast-fur-
nace water combined with noncontact cooling water from several processes and
storm water. No'significant toxicity was observed in either sample. The
third sample represents only the blowdown from the blast-furnace treatment
plant before any dilution. The LC50 concentration was reported as 82 percent.
The seven samples from Great Lakes Steel represent several combinations
of blast-furnace water with water from miscellaneous sources. The first
sample includes treated blast-furnace water, sump drainage, gas-line drips,
equipment blowdown, yard runoff, and drainage from the stockhouse and slag
pits. This effluent was very toxic with an LC50 concentration less than 6
percent. The analyst noted higher than normal pH in this sample (8.6 to 10)
and also reported a distinct hydrogen sulfide odor. Chemical analyses were 88
mg/L sulfide and 0.92 mg/L cyanide.
The second Great Lakes sample represents contaminated cooling water from
the blast furnaces and yard drainage. The third sample includes miscellaneous
process water from the blast furnace after combining with noncontact cooling
water and storm runoff. No toxicity was observed in these two samples. The
fourth sample includes water from the gas washers, gas coolers, and wet pre-
cipitators from all of the b.last furnaces after it passes through the clari-
fiers and thickeners. No mortality was observed at a concentration of 50 per-
cent, and a mortality of 60 percent was observed in the undiluted effluent.
The fifth and seventh Great Lakes samples represent two different toxic-
ity tests on the same outfall at different dates. This outfall includes
treated process water from the blast furnace after the clarifier, noncontact
water from the coke plant and blast furnace, and boiler-house water. The
sixth sample includes only the treated blast-furnace water from the clarifier
and some boiler-house blowdown. An LC50 of less than 43 percent was observed
in a 96-hour continuous flow test of fathead minnows. The analyst believed
un-ionized ammonia (NH3-N) was probably responsible for the toxicity. Un-
ionized ammonia estimates ranged from 0.1 mg/L for 6 percent effluent to 3
mg/L for 50-percent effluent. The seventh sample (labeled A,C,M,N) represents
the blast furnace effluent after dilution. Although a mortality of only 10
percent was observed in the 100-percent effluent, increasing lethargy was ob-
86
-------
served in the fish for concentrations greater than 25 percent. The analyst
noted that several volatile organic compounds not found in the process water
from the blast furnace appeared in the diluted stream and was probably respon-
sible for the developed lethargy [5].
Reference 13 is a study of a pilot-plant process to treat blast-furnace
blowdown at U.S. Steel's South Chicago Works. Wastewater from the gas scrub-
bers is directed to a grit pit for settling of gross dirt, to a clarifier, and
then to the hot well of the cooling tower. The water for the pilot system
study was removed from the hot well, pH adjusted to 10.7 to precipitate calci-
um, enriched to contain 5 ppm phenol, and clarified. This process water was;
subjected to breakpoint chlorination, filtered through a mixed media of
anthracite and sand, and then passed through a column of activated carbon.
The treated effluent showed no significant mortality to the test organisms.
The contractor also conducted bioconcentration studies of the bluegill
sunfish. Chemical analyses of the tissues of the control and exposed fish
revealed no significant differences. An egg and fry test was also conducted
and yielded a minimum threshold concentration (MTC) of 42 to 65 percent. The
MTC is an.estimate of the highest effluent concentration tested that did not
cause any significant effect on the embryo and fry during the early stages of
development [13].
The sample taken at McLouth Steel represents the effluent from the waste-
water treatment plant that treats process water from several sources. The
treatment plant receives water from the blast-furnace blowdown, basic oxygen
furnace, electric arc furnace, hot forming, and acid pickling. The process.
water is treated initially by some oil and solids removal in scale pits and
settling basins at each process. At the wastewater treatment plant, the fol-
lowing processes are used: primary sedimentation, mechanical oil removal,
ferric chloride and lime addition, clarification, and anionic polymer addition.
No mortality was observed in the treated final effluent.
6.2.3 Steelmaking Effluent Toxicity
The existing data on the toxicity of steelmaking effluent are summarized
in Table 6-5. Some of the treated effluent samples represent a combination of
process streams. Chemical analyses are available for most of these toxicity
samples. Treatment technologies were taken from the referenced reports when
87
-------
TABLE 6-5. TOXICITY DATA, STEELMAKING WASTEWATER
00
00
No. Plant Outfall From3 Treatment Date
1 Georgetown Steel D3f,F,Gl SSP,CT,FDSP, 3/78
Georgetown, SC SS
2 Ford Motor Co. D3f,N9 CL.FLP.SL 10/79
River Rouge, MI
3 Great Lakes Dlf,D3f Untreated 11/79
Steel D3,I1,J1,M E,SS,AO,FLF, 11/79
Ecorse, MI A.CL 6/80
9/81
Processes are coded as prescribed in Reference 1 (Volume 1,
Dl: Basic oxygen furnace
D3: Electric arc furnace
F: Continuous casting
Gl: Hot forming
11: Sulfuric acid pickling
Jl: Cold forming
M: Boiler and/or compressor house
N: Noncontact cooling water
Treatments
A: Acidification .
AO: Air oxidation
CL: Clarifier
CLA: Alkaline chlori nation
CT: Cooling tower
E: Equilization of flow
FDSP: Deep-sand filter pressure
Test0
CF-96
S-96
CF-96
S-96
S-48
S-48
S-48
CF-96
S-48
p. 338)
• d
Organism
CV
CV
MB
MB
DM
DM
DM
DM
DM
LC50 (%)e
NM
NM
20% Mort.
NM
NM
NM
10% Mort.
NM
NM
Reference
15
15
15
15
6
16
16
17
18
with additions:
-------
TABLE 6-5. (continued)
Treatments: (continued)
FLF: Flocculation with ferric chloride
FLP: Flocculation with polymer
FP: Pressure filtration
SL: Settling lagoon
SS: Surface skimming (oil)
SSP: Secondary scale pit
Type of test:
S-n: Static test for n hours
CF-n: Continuous flow test for n hours
Type of test organism:
CV: Cyprinodon variegatus (sheepshead minnow)
oo DM: Daphnia magna (waterflea)
^ DP: Daphnia pulex (waterflea)
LM: Leopomis machrochirus (bluegill sunfish)
MB: Mysidopsis bahia (shrimp)
NA: Notropis atherinoides (emerald shiner)
PP: Pimephales promelas (fathead minnow)
LC50 = Effluent concentration lethal to 50 percent of the test organisms:
n% Mortality: Percent mortality in 100-percent effluent reported when LCSO cannot be calculated
NM: No mortality
NSM: No significant mortality
Mod. Toxic: Moderately toxic
SI. Toxic: Slightly toxic
V. Toxic:. Very toxic
Noncontact cooling water from the steelmaking furnace.
^Also includes overflow from the slag pits and cooling water from miscellaneous sources.
Approximate breakdown is 25-30% from pickling, 20% from the EAF, and 50-55% from cold rolling.
-------
available and supplemented with data from Reference 1. In general, the treated
steel making effluent showed little'or no toxicity to the test organisms.
The Georgetown Steel plant uses electric arc furnaces to produce steel
wire and rod. The wastewater sample is from the steel manufacturing process,
cooling water, and runoff before discharge. Potential pollutants include
iron, chromium, manganese, grease, and oil. The wastewater from noncontact
cooling of the electric arc furnace (dry system), process water from continu-
ous casting, and hot forming are directed to a central treatment plant. Water
treatment includes scale pits and settling basins, a cooling tower, deep-sand
filters with pressure, and surface skimming for oil removal. The toxicity
tests showed a 20-percent mortality for shrimp in the continuous flow test at
a 100-percent concentration, but no shrimp mortality was observed for the
static test.
The Ford Motor Company sample is also for noncontact cooling from the EAF
(dry system), noncontact cooling water from several sources, and overflow from
the slag pits. Treatment includes chlorine addition, clarification with poly-
mer addition, and a settling lagoon. No mortality was observed in this sam-
ple.
The first sample from Great Lakes Steel is noncontact cooling water from
the electric furnace shop and basic oxygen process shop which is discharged
untreated. No mortality was observed. The remaining samples from Great Lakes
Steel represent the outfall from a central treatment plant which handles
wastewater from the electric arc furnace spray chamber, boiler blowdown,
filter backwash, pickling rinse water, and cold-rolling wastewater. The
breakdown is approximately 20 percent from the EAF, 25-30 percent from pick-
ling, and 50-55 percent from cold rolling. Treatment includes flow equaliza-
tion, surface skimming, ferrous ion and HC1 addition, aeration tanks to oxi-
dize the ferrous ion, acid addition, and clarification. Toxicity tests of
this effluent showed no significant mortality.
6.2.4 Hot-Forming Effluent Toxicity
Toxicity data for hot-forming effluent from other sources are summarized
in Table 6-6. These data are from two plants, and both cases represent the
effluent from the treatment of a combination of process streams. Chemical
90
-------
TABLE 6-6. TOXICITY DATA, HOT-FORMING WASTEWATER
No.
Plant
Outfall From
Treatment
Date Test Organism LC50
Reference
1
2
Ford Motor Co.
River Rouge, MI
Great Lakes
Steel
Ecorse, MI
G.I1
F,G,M,R
G.N.O.R
G,N
PSP.FDO.CL,
SS,NC,SL
FLP.SB.SS
SB.SS
SB.SL.SS.FLP
10/79
11/79
11/79
4/80
S-48
S-48
S-48
S-48
DM
DM
DM
DM
NM
NM
NM
10% Mort.
6
16
16
19
Processes are coded as prescribed in Reference 1 (Volume 1, p. 338) with additions:
F: Continuous casting
Gl: Hot forming
II: Sulfuric acid pickling
M: Boiler and/or compressor house
N: Noncontact cooling water
0: Surface runoff, drainage
R: Soaking pit drainage
Treatments
CL:
FDD:
FLP:
NC:
PSP:
SB:
SL:
SS:
"Type of test:
S-n:
CF-n:
Clarifier
Deep filter with walnut shells
Flocculation with polymer
Neutralization with caustic
Primary scale pit
Settling basin
Settling lagoon
Surface skimming (oil)
Static test for n hours
Continuous flow test for n hours
-------
TABLE 6-6. (continued)
j *
Type of test organism:
CV: Cyprinodon variegatus (sheepshead minnow)
DM: Daphnia magna (waterflea)
DP: Daphnia pulex (waterflea)
LM: Leopomis machrochirus (bluegill sunfish)
MB: Mysidopsis bahia (shrimp)
NA: Notropis atherinoides (emerald shiner)
PP: Pimephales promelas (fathead minnow)
el_C50 = Effluent concentration lethal to 50 percent of the test organisms:
n% Mortality: Percent mortality in 100-percent effluent reported when LC50 cannot be calculated
NM: No mortality
NSM: No significant mortality
Mod. Toxic: Moderately toxic
SI. Toxic: Slightly toxic
V. Toxic: Very toxic
-------
analyses of the water sample are available for both of these plants. The des-
criptions of treatment technology were taken from the referenced reports when
available and supplemented with data from Reference 1.
The sample from Ford Motor Company includes treated wastes from the slab-
bing mill, blooming mill, hot-roll ing mill, pickling operations, and a few
miscellaneous plant sources. Scale-removal water and contact-cooling water
from the wet scrubber on the scarfing operations is discharged to scale pit:;,
filtered, and recycled with blowdown to the treatment plant.- Water from the
scrubber on the pickling baths and pickle liquor rinse water are neutralized
with caustic and sent to the treatment plant. At the treatment plant, the
wastewater passes through grit chambers, clarifiers, and oil-polishing lagoons
equipped with oil skimmers. The effluent from this treatment plant showed no
mortality to waterfleas.
The first Great Lakes Steel sample is treated wastewater from a soaking
pit, slab mill, blowdown from the continuous caster and boiler house, and floor
drainage from service shops. Polymer is added to the wastewater prior to set-
tling in basins, and floating oils are removed mechanically before the under-
flow is discharged. No mortality was observed in this effluent.
The secorrd sample listed for Great Lakes Steel includes wastewater from •
the blooming mill, noncontact cooling water, area drainage from the blooming
mill, and drainage from a soaking pit. The wastewater drains to an oil skim-
mer basin before discharge. No mortality was observed in a 48-hour static
test of waterfleas.
The third sample for Great Lakes Steel represents treated process waste-
water from contact cooling in the hot-strip mill after the treated water has
been diluted with noncontact cooling water. The process wastewater is treated
in scale pits, settling basins, settling lagoons with oil skimmers, and floc-
culated with polymer. Ten-percent mortality of waterfleas in 100-percent
effluent was observed for this sample.
6.2.5 Acid Pickling Wastewater Toxicity
The existing data for toxicity of pickling wastewater are summarized in
Table 6-7. The data for Ford Motor Company and Great Lakes Steel have been
presented previously because they represent a combination of process waste-
93
-------
TABLE 6-7. TOXICITY DATA, ACID PICKLING WASTEWATER
No.
Plant
Outfall From3 Treatment Date Testc Organism LC50 (%)e Reference
1
2
3
McLouth Steel I2,J,M
Gibraltar, MI
Ford Motor Co. G.I1
River Rouge, MI
Great Lakes D3,I1,J1,M
Steel
Ecorse, MI
NC.SL
PSP.FDO.CL,
SS.NC.SL
E,SS,AO,FLF,
A.CL
3/78
10/79
11/79
6/80
9/81
S-48
S-48
S-48
CF-96
S-48
DM
DM
DM
DM
DM
NM
NM
10% Mort.
NM
NM
20
6
16
17
18
Processes are coded as prescribed in Reference 1 (Volume 1, p. 338) with additions:
D3:
G:
II:
12:
J2:
M:
^Treatments
A:
AO:
CL:
E:
FDO:
FLF:
NC:
SL:
SS:
"Type of test:
Electric arc furnace
Hot forming
Sulfuric acid pickling
Hydrochloric acid pickling
Cold forming
Boiler and/or compressor house
Acid addition
Air oxidation
Clarifier
Flow equalization
Deep filter with walnut shells
Flocculation with ferric chloride
Neutralization with caustic
Settling lagoon
Surface skimming (oil)
S-n: Static test for n hours
CF-n: Continuous flow test for n hours
-------
TABLE 6-7. (continued)
Type of test organism:
CV: Cyprinodon variegatus (sheepshead minnow)
DM: Daphnia magna (waterflea)
DP: Daphnia pulex (waterflea)
LM: Leopomis machrochirus (bluegill sunfish)
MB: Mysidopsis bahia (shrimp)
NA: Notropis atherinoides (emerald shiner)
PP: Pimephales promelas (fathead minnow)
Q
LC50= Effluent concentration lethal to 50 percent of the test organisms:
n% Mortality: Percent mortality in 100-percent effluent reported when LC50 cannot be.calculated
NM: No mortality
NSM: No significant mortality
Mod. Toxic: Moderately toxic
SI. Toxic: Slightly toxic
V. Toxic: Very toxic
-------
waters. The data are listed again in this section because pickling wastewater
comprises a significant portion of the treated stream.
The sample from McLouth Steel represents treated water from the pickling
rinse, boiler blowdown, acid regeneration scrubber, floor drains, pickling
tower scrubber, and pond water from the tandem mill. The treatment consists
of neutralization in two stages and settling in lagoons. No mortality to
waterfleas was observed in the effluent from this lagoon.
The samples from Ford Motor Company were described in the previous section
and include treated wastewater from hot forming, water from the scrubbers on
the pickling baths, and pickle liquor rinse water.
The pickling wastewater is neutralized with caustic and delivered to a
central treatment of grit chambers, clarifiers, and oil-polishing lagoons with
oil skimmers. The treated effluent from the combined processes showed no mor-
tality.
The sample from Great Lakes Steel was previously described in Section
6.2.3, and includes treated water from pickling (25-30 percent), electric arc
furnace (20 percent), and cold rolling (50-55 percent). No significant mor-
tality was observed.
6.2.6 Cold-Forming Effluent Toxicity
Some of the data in Table 6-8 have been presented previously because a
combination of processes was involved. The sample from McLouth Steel was des-
cribed in Section 6.2.5. Wastewater from the cold mill is an oil/water solu-
tion which is pumped to a pond where acid is added to aid oil/water separation.
The pond water is then sent to a central treatment which includes neutraliza-
tion and settling lagoons. No mortality was observed.
The Ford Motor Company sample includes noncontact cooling water from both
the cold-rolling operation and from powerhouse cooling. No treatment is pro-
vided, and no mortality to waterfleas was observed. However, daphnids in all
test concentrations except the control were observed floating on the surface.
The analyst suspected oils in the wastewater (9 to 29 mg/L) caused the test
organisms to float.
The sample from Great Lakes Steel was discussed in detail in Section
6.2.3. Approximately 50-55 percent of the process wastewater originates from
96
-------
TABLE 6-8. TOXICITY-DATA, COLD-FORMING WASTEWATERS
No. Plant Outfall From3 Treatment6 Date Testc Organismd LC50 (%)e
1 ' McLouth Steel I2.J.M NC.SL 3/78 S-48 DM NM
Gibraltar, MI
2 Ford Motor Co. Jf,M None 10/80 S-24 DM NM9
River Rouge, MI
3 Great Lakes D3,I1,J,M E,SS,AO,FLF, 11/79 S-48 DM 10% Mort.
Steel A.CL 6/80 CF-96 DM NM
Ecorse, MI 9/81 S-48 DM NM
Processes are coded as prescribed in Reference 1 (Volume 1, p. 338) with additions:
D3: Electric arc furnace
11: Sulfuric acid pickling
12: Hydrochloric acid pickling
J: Cold forming
M: Boiler and/or compressor house
Treatments
A: Acid addition
AO: Air oxidation
CL: Clarifier
E: Flow equalization
FLF: Flocculation with ferric chloride
NC: Neutralization with caustic
SL: Settling lagoon
SS: Surface skimmer (oil)
cType of test:
S-n: Static test for n hours
CF-n: Continuous flow test for n hours
Reference
20
12
16
17
18
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TABLE 6-8. (continued)
Type of test organism:
CV: Cyprinodon variegatus (sheepshead minnow)
DM: Daphnia magna (waterflea)
DP: Daphnia pulex (waterflea)
LM: Leopomis machrochirus (bluegill sunfish)
MB: Mysidopsis bahia (shrimp)
NA: Notropis atherinoides (emerald shiner)
PP: Pimephales promelas (fathead minnow)
eLC50 = Effluent concentration lethal to 50 percent of the test organisms:
n% Mortality: Percent mortality in 100-percent effluent reported when LC50 cannot be calculated
NM: No mortality
NSM: No significant mortality
Mod. Toxic: Moderately toxic
SI. Toxic: Slightly toxic
V. Toxic: Very toxic
Noncontact cooling water from cold rolling.
^Daphnids floated on surface; suspect oil in the water.
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the cold-rolling operation, and the balance is from the electric arc furnace .
and pickling operations. No significant mortality was observed in the treated
effluent.
6.2.7 Hot-Coating Effluent Toxicity
No data were found that evaluated the toxicity of effluent from hot-
coating operations.
6.2.8 Combined Effluent Toxicity
Table 6-9 summarizes data on the toxicity of the final combined effluent
from three steelmaking facilities. Process streams from all major processes.
are combined for discharge after various types of treatment. Treatment tech-
niques include some initial treatment at the specific process followed by
additional treatment in a central location or dilution with noncontact water
after treatment. Samples taken in 1975 at Republic Steel show significant
mortality with LC50 concentrations of 19.5 and 34.5 percent. The samples
taken in 1980-81 at U.S. Steel and McLouth Steel show much lower toxicity in
the final treated effluent.
99
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TABLE 6-9. TOXICITY DATA, COMBINED EFFLUENT FROM INTEGRATED PLANT
o
o
No. Plant Outfall From Treatment Date Test3 Organismb LC50 (%)C Reference
1 U.S. Steel All Processes Various 8/81 S-24 PP NM
Fairfield, AL 8/81 S-24 DP 89.5
2 Republic Steel All Processes Various 5/75 S-48 DM 19.5
Gadsden, AL 5/75 S-96 LM NM
5/75 CF-96 LM 34.5
3 McLouth Steel All Processes Various 9/80 S-24 DM NM
Trenton, MI
Type of test:
S-n: Static test for n hours
CF-n: Continuous flow test for n hours
Type of test organism:
CV: Cyprinodon variegatus (sheepshead minnow)
DM: Daphnia magna (waterflea)
DP: Daphnia pulex (waterflea)
LM: Leopomis machrochirus (bluegill sunfish)
MB: Mysidopsis bahia (shrimp)
NA: Notropis atherinoides (emerald shiner)
PP: Pimephales promelas (fathead minnow)
CLC50 = Effluent concentration lethal to 50 percent of the test organisms:
n% Mortality: Percent mortality in 100-percent effluent reported when LC50 cannot be
NM: No mortality
NSM: No significant mortality
Mod. Toxic: Moderately toxic
SI. Toxic: Slightly toxic
V. Toxic: Very toxic
2
2
21
21
21
14
calculated
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7.0 REFERENCES
1. Development Document for Effluent Limitation, Guidelines, and Standards
for the Iron and Steel Manufacturing Points Source Category. Volumes 1-6.
EPA-440/1-82-024.
2. Weldon, R., and M. McGhee. Static Bioassay Tests Conducted on Birmingham,
Alabama, Area Industries. S&A Division, College Station Road, Athens, GA,
August 26, 1981.
3. Branscome, M. Conversation with Mr. Rod Hames. Alabama State Pollution
Control Agency, (205)7277-3630, November'23, 1981.
4. Rock, M., et al. Industrial Wastewater Survey Conducted at Great Lakes
Steel Corporation Blast Furnace Division, Zug Island, Wayne County, MI.
Michigan Department of Natural Resources, Environmental Protection Bureau,
Point Source Studies Section, December 1978.
5. White, B.E. Report of On-Site Toxicity Evaluation at Great Lakes Steel
Corporation Blast Furnace Division, Zug Island, Wayne County, River
Rouge, MI. Michigan Department of Natural Resources, Environmental
Protection Bureau, Point Source Studies Section, June 1981.
6. White, LaBonnie, et al. Industrial Wastewaters Survey Conducted at Ford
Motor Company, Rouge Plant, Green County, Dearborn, MI, October 2-3,
1979. Michigan Department of Natural Resources, Environmental Protection
Bureau, Point Source Studies Section, December 19, 1979.
7. Preston, H.R. Toxicity Results of Selected Steel Industry Discharges.
U.S. Environmental Protection Agency, Region III, Wheeling Field Ofice,
January 11, 1978.
8. Preston, H.R. Coke Effluent Toxicity. U.S. Environmental Protection
Agency, Region III, Wheeling Field Office, August 16, 1978.
9. Preston, H.R. Special Effluent Analysis Request. U.S. Environmental
Protection Agency, Region III, Western Regional Laboratory and Environ-
mental Center, Wheeling, West Virginia, November 5, 1981.
10. Clairton Research Program - Bench-Scale Tests. Environmental Dynamic;;,
Inc., for U.S. Steel Corporation, September 1980.
11. Oda, T.N. Memo to B.H. Carpenter. Results of J&L Steel, Pittsburgh
Works Toxicity Tests Conducted in 1976 and 1977. November 24, 1982.
101
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12. Waybrant, R., and B. White. Report of Toxicity Screening Tests - Ford
Motor Company Rouge Complex, Dearborn, MI. Michigan Department of
Natural Resources, Environmental Protection Bureau, Point Sources Study
Section, October 1980.
13. Guidelines Establishing Test Procedures for the-Analysis of Pollutants,
Federal Register, 44, 233, Monday, Dec. 3, 1979, pages 69501-69559.
14. Quality Assurance Project Plan for the Toxicity Treatability Assessment
of Iron and Steel Industry Wastewaters, U.S. Environmental Protection
Agency, Ind. Envir. Res. Lab., Research Triangle Park, North Carolina,
prepared by PedCo Environmental, Inc., under EPA contract 68-02-3173-72,
June 1982.
15. Peltier, W., and C. I. Weber, Methods for Measuring the Acute Toxicity of
Effluents to Aquatic Organisms, U.S. EPA/EMSL, Cincinnati, Ohio.
EPA-600/4-78-012, July 1978.
16. Guidelines Establishing Test Procedures for the Analysis of Pollutants,
Environmental Protection Agency, 40 CFR Part 136, Federal Register/
44 No. 233/December 3, 1979/Proposed Rules, pp. 69464-69575.
17. Klein, Lewis. River Pollution II. Causes and Effects, London, Butter-
worths, 1961.
18. Dodge, B. F., and Reams, D. C. Critical Review of the Literature Pertain-
ing to Disposal of Waste Cyanide Solutions, Amer. Electropolaters Soc.
Res. Rept. 14: 1, 1949.
19. Treatability Manual, Office of Research and Development, U.S. Environ-
mental Protection Agency, Washington, D.C., EPA-600/2-82-001A, September
1981.
20. Harris, J., et al. Analyt. Chem., 47, 995 [1975].
102
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