United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Cincinnati OH 45268
EPA-600/ 2-80-019
January 1980
Research and Development
&ER&
Characterization of
Priority Pollutants
from an Airplane
Parts Manufacturing
Facility
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development. U S Environmental
Protection Agency, have been grouped into nine series These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields
The nine series are:
1 Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5 Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8 "Special" Reports
9, Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-80-019
January 1980
Characterization of
Priority Pollutants from an
Airplane Parts Manufacturing Facility
by
A. K. Reed, M. A. Eischen, M. M. McKown, and G. R. Smithson, Jr.
Battelle's Columbus Laboratories
Columbus, Ohio 43201
Contract No. 68-03-2552
Project Officer
A. B. Craig, Jr.
Industrial Pollution Control Division
Industrial Environmental Research Laboratory
Cincinnati, Ohio 45268
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
-------
DISCLAIMER
This report has been reviewed by the Industrial Environmental Research
Laboratory, U.S. Environmental Protection Agency, and approved for publication.
Approval does not signify that the contents necessarily reflect the views and
policies of the U.S. Environmental Protection Agency, nor does mention of
trade names or commercial products constitute endorsement or recommendation
for use.
ii
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FOREWORD
When energy and material resources are extracted, processed, converted,
and used, the related pollutional impacts on our environment and our health
often require that new and increasingly more efficient pollution control
methods be used. The Industrial Environmental Research Laboratory - Cincinnati
(lERL-Ci) assists in developing and demonstrating new and improved methodo-
logies that will meet these needs both efficiently and economically.
This report contains an assessment of waterborne emissions from a
facility in which airplane parts are produced. The study has been conducted
to provide a better understanding of the sources, nature, and control of
emissions from such facilities. Particular attention has been given to the
presence and control of the priority pollutants. Further information on this
subject may be obtained from the Metals and Inorganic Chemicals Branch,
Industrial Pollution Control Division.
David G. Stephan
Director
Industrial Environmental Research Laboratory
Cincinnati
ill
-------
ABSTRACT
Wastewater from an airplane parts manufacturing plant was sampled using
the U.S. EPA screening protocol for the 129 priority pollutants. The waste-
water treatment facilities at this site include batch systems to destroy
cyanides, remove oil, and reduce hexavalent chromium to the trivalent state
before it is discharged to a system where heavy metals are removed by pH
adjustment and settling.
The results of the study show that the treatment practiced at this site
removes about 90 percent of the chromium, zinc and 70 percent of the copper.
The system is slightly less effective for cadmium because of its low concen-
tration in the influent to the treatment plant. Nevertheless, in excess of
60 percent of the cadmium is removed. Because of the extremely low concen-
trations of other metals in the influent to the treatment plant, the effect-
iveness' Of the treatment for their removal could not be evaluated with any
degree of confidence.
Although the treatment system was not designed for the removal of the
priority organic constituents, some are removed during the treatment. This
could be due to evaporation or sorption on the solids formed during the
precipitation of the metallic components of the wastewater.
iv
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CONTENTS
Foreword ill
Abstract lv
Figures vi
Tables vi
1. Introduction 1
2. Summary 2
3. Source Description 4
Process description 4
4. Sampling and Analytical Approach for Screening
Testing of Priority Pollutants 8
Sampling procedures 8
Flow measurement 10
Analytical procedures and quality assurance 11
5. Discussions of Effectiveness of the Continuous
Treatment System for the Removal of Priority Pollutants . . 24
Waste loads per 24-hour period , 24
Removal efficiencies 24
Conclusion 24
Bibliography 26
Appendices
A. Sample log 27
B. Summary of analytical procedures for
the priority organic pollutants 29
Extraction procedure 29
GC/MS analysis 30
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FIGURES
Number Page
1 Diagram of water flow, airplane parts fabrication
plant, showing sampling locations 6
2 Scheme for analysis of wastewater 14
TABLES
Number Page
1 Efficiency of the Removal of Metals from Wastewater
Produced in An Airplane Parts Fabrication Plant 2
2 Results of Atomic Absorption Analyses 11
3 Quality Assurance for Metal Analyses , 12
4 Quality Assurance Data for Total Cyanide Analyses 13
5 Volatile Halogenated Hydrocarbons 16
6 Summary of the Results from the Analyses of
Standard Samples 16
7 Results of the Base Neutral Extractables and
Phenolics Analyses 17
8 Percent Recovery of Priority Pollutants Spiked
in Water 20
9 Results of Benzidine Analyses 22
10 Waste Load of Priority Pollutants in a 24-Hour Period 24
A-l Sample Log 26
B-l GC/MS Data Used for Determining Semivolatile
Priority Pollutants 31
vi
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SECTION 1
INTRODUCTION
The Effluent Guidelines Division (EGD), Office of Water Planning and
Standards, of the U.S. Environmental Protection Agency (EPA) has been charged
with the responsibility for conducting tests to determine the presence of
129 priority pollutants in wastewater from facilities which manufacture non-
ferrous metals. Specifically, the EPA is obligated to identify toxic priority
pollutants and the effectiveness of various treatment processes for removing
them from wastewaters generated in the various types of manufacturing facil-
ities, including airplane parts plants. The EGD is required to review the
effectiveness of various technologies and to propose and promulgate effluent
limitations.
Battelle's Columbus Laboratories (BCL) and Centec Consultants, Inc. under-
took the preliminary evaluation of facilities and conducted the sampling and
analyses of waste streams at one facility. The data were collected for the
Metals and Inorganic Chemicals Branch (MICB), Office of Research and Develop-
ment, in support of the EGD. The information developed herein is to be used
to augment the existing data base. These data also will be used by the MICB
to substantiate a metals precipitation manual which is under preparation.
Plant operating data are to be used to quantify the performance of the system
and to identify factors influencing the characteristics of the samples col-
lected. The activity for this task deals with wastewater discharges from a
facility in which airplane parts are fabricated.
This report describes the process, the wastewater treatment facility,
and the sampling and analytical protocol, and presents the results and conclu-
sions. The conclusions are based on the sampling program, which showed how
effective the wastewater treatment was in removing not only the priority
pollutants, but also those tentatively listed as pollutants.
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SECTION 2
SUMMARY
A plant site at which airplane parts are fabricated was sampled using
EPA screening protocol procedures for the priority pollutants.' ' Before
discharging wastewater into a stream, the plant uses an alkaline chlorination
treatment to remove cyanides, chemical de-emulsification and settling to
remove oil, and sulfur dioxide to reduce hexavalent chromium. (The reduced
chromium and other metals are precipitated as hydroxides.) All of the waste
streams discharging into the continuous treatment plant were sampled (according
to protocol) upstream and downstream of any specific batch treatment used.
The influent as well as the effluent of the wastewater treatment plant was
sampled during two 7-hour periods of plant operation. The samples were
analyzed for the priority pollutants.
The daily waste loads calculated for the metallic priority pollutants
and the efficiencies of their removal are shown in Table 1. The other metallic
priority pollutants were not detectable.
TABLE 1. EFFICIENCY OF THE REMOVAL OF METALS
FROM WASTEWATER PRODUCED IN AN AIRPLANE
PARTS FABRICATION PLANT
Influent
Priority load concentration
pollutant
Cadmium (Cd)
Chromium (Cr)
Copper (Cu)
Nickel (Ni)
Zinc (Zn)
kg/day
0.055
18.88
0.27
0.055
0.236
mg/Jl
0.03
10.4
0.15
0.03
0.13
Effluent
load concentration
kg/day
0.02
0.436
0.082
0.055
0.027
mg/«,
<0.01
0.24
0.045
<0.03
0.015
Removal
efficiency,
%
63.6
97.7
70.0
—
88.6
Based on these results, it is concluded that the treatment as practiced in
this facility is very effective in removing zinc and chromium, and slightly
less effective for cadmium and copper because of the low concentrations
encountered. The effectiveness of this method in removing the other priority
metals could not be evaluated with confidence because the low concentrations
in the effluent to the treatment plant are probably near solubility limits at
pH 8.5.
-------
In general, about 40 percent of the phenol was removed during the treat-
ment of the wastewater in the continuous system. Essentially complete
(99.8 percent) removal of the total cyanide was effected in a separate, batch
treatment system. There was no appreciable removal of the purgeable halo-
genated hydrocarbons. Finally, no clear pattern emerged regarding the
effectiveness of the treatment for removing other organic priority pollutants.
Removal of specific organic components ranged from 0 to more than 99 percent.
Although the mechanism of organic removal was not determined, these materials
may have been eliminated from the wastewater through evaporation or by
sorption on the precipitated metal hydroxides.
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SECTION 3
SOURCE DESCRIPTION
PROCESS DESCRIPTION
The plant whose waste treatment facilities were sampled is a parts fabri-
cation and supply center for aircraft assembly plants. Water is used in this
plant for sanitary purposes, cooling air compressors and other machinery,
rinsing after chemical processing, and preparing coolants for use in machining
operations. The cooling water (which is recycle) and the sanitary wastewaters
are not included in the scope of the current sampling program. Only the last
two categories—the process wastewaters—are included.
The wastewater destined for the process wastewater treatment plant is
generated as follows:
o Pickling aluminum, steel and titanium
o Plating chromium, cadmium, nickel, and copper
o Surface conversion coating of chromium on aluminum and phosphate
on steel
o Anodizing
o Alodining
o Hot Sealing
o Etching
o Stripping
o Chemical Machining
o Passivating
o Descaling
o Penetrant inspection (Zyglo) of aluminum
o Magnaflux of steel
o Mechanical Machining of aluminum and steel
o Heat Treating
The wastewater is treated in the industrial wastewater facility. The
facility has sixteen production chemical process tank lines. Ranging in
length from six feet to one hundred and fourteen feet. Total tank volume is
over 1.3 million gallons of solution with double counter-current flows in all
rinse tanks and most rinse tanks contain air agitation. Other innovative
procedures include the installation of plastic spheres which float on the
surface of process tanks that require elevated temperatures. These spheres
conserve heat and chemicals by lowering evaporation rates. Fresh water is
supplied by the city, averaging 1.3 million gallons per day. This plant
produces around one and one-half million parts per month; principal products
-------
include aircraft skins and wing spars for commercial and military aircraft.
Principle raw materials used at the facility are aluminum, steel, titanium,
and a wide variety of alloys. Other materials used include:
o Aliphatic Hydrocarbon Petroleum Solvent
o Magnaflux ZL60B Penetrent
o Sherwin D-113A Developer
o Oakite 60 Descaler
o Pace SP-112
o Turco Jet Clean
o Pennwalt DP1131 - Cutting Compound
o Oakcut - Drawing Compound
o Cool Lube 21 (Pacific Chemical Co.) Cutting Compound
o Pace N-136-B Cutting Compound
o HO Cut-237 (Houghton) Cutting Compound
o Velocite 416 (Mobil) Lube Oil
o DTE-25 Lube Oil
o CX-305-(Cincinnati Milacron) Cutting Compound
o CX-305 Cutting Compound
o Gin Cool C-305 and 202 Lube Oil
o Grindtex 410 Lube Oil
o Mobil 45 Lube Oil
o Mask Coat #2 (Western Coating) - Chemical Mill Maskant
o 1, 1, 1, - Trichlorethane - Degreaser
o Various Paints and Common Plating Chemicals
Wastewater Treatment
By far the largest volume of wastewater is produced by chemical processes
such as anodizing. Most of the chrome wastewater is generated in the anodizing
area from double countercurrent rinse tanks. The chemical processing area
generates about 1,515 mj/day (400,000 gal/day) of wastewater.
The volumes of wastewaters produced in the other operations are signifi-
cantly smaller. About 6 nrVday (1,600 gal/day) of rinsewaters are generated
by the electroplating operations in which cyanide baths are used. In addition,
about 23 m /day (6,000 gal/day) of oily wastes are generated by machining
operations, and about 115 mj/day (30,000 gal/day) of wastewater by nondes-
tructive testing of structural parts (dye penetrant inspection rinsewater—
Zyglo).
The relationship of the various manufacturing operations to wastewater
loading and treatment are shown in Figure 1. The coding used for identifying
the component samples also is shown in Figure 1. As shown there, both the
cyanide wastes and the oily wastes are treated in batches prior to being dis-
charged into a lagoon.
Approximately two batches of cyanide wastewater are treated each week,
using conventional alkaline chlorination to detoxify the wastewater by
destroying the cyanide. In addition, two batches of oily wastewater are
treated each day, using chemical de-emulsification, settling, and decantation
to remove the oil and other pollutants.
-------
The Zyglo rinsewater and the chrome surge tank overflow flow intermit-
tently into the spills lagoon. Wastewater from both the chrome surge tank and
the spills lagoon is pumped into the continuous treatment system where the
hexavalent chromium is reduced to the trivalent state with sulfur dioxide.
Excess sulfur dioxide ( 10 mg/ ) is used to ensure complete reduction of the
hexavalent chromium. The metallic components are precipitated as hydroxides
by adjusting the pH of the wastewater with lime.
The underflow from the clarifier is centrifugally dewatered to remove
the solids and the solid residue is transported to a landfill. The clarified
effluent flows through a storm sewer which discharges into Stuck Creek.
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ChcBlcal Processing
Vastes (Acid and -
Be«-Chro«* Uastevater-
— 1.515 «Vday*
(-400.000 gal/day)
DT« Penctrant
Inspection
Unsewater
(Zyglo)
Hastevater
-115 mVday
MO.OOO gal/day)
0-5
Chemical Processing
Haste* Surge Tank
(Acid and Hex-throw)
—379 m3
(-1000.000 gal)
006>0
007 J
*-D
90. Reduction
* and
Neutralization
Overflow
-1,032 •J/d*y
f-272,600
Chrome
Treatment
Tank.
-24 m3
f-6.500 gal)
"627 • /day
t~16S.OOO gal/day)
Retention
Tank
~87 i?
r»23,000 gal)
Filtrate
Filter
T
Cyanide
Plating
Oastes
•^ » /day
t"1.600 gal/d«y)
x - 5
Oily Hast
-23 m3/d
stes
3/day
(-6,000 Ml/day)
1
Cyanide Waste
Surge Tank
-507 a3
(-13.MO gal)
Alkaline
Chlorlnatlon
Oily Haste
Surge Tank
-23 «3
(-6,100 gal)
Batch
Cyanide Haste
Treatncnc Tank
-15 n3
t-«.000 gal)
OO9
Solid* to
Landfill
•Plows shown are
nominal flows.
Final
Effluent ,
—1.659 • /day
t-437,600 gal/day)
FIGURE 1.
Batch
Oily Haste
Treatment Tank
-23 m5
<-6.100 gal)
X - 5
"«-«ulslflcatlon
Settling and Ocean-
tatlon
- 5
Lagoon
—2.045 m3
(-5*0,000 gal)
Diagram of water flow, airplane parts
fabrication plant, showing sampling locations.
0 - Composite samples. 3 total
Q - Grab samples. 1 per day
'* - Crab samples, once only
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SECTION 4
SAMPLING AND ANALYTICAL APPROACH FOR
SCREENING TESTING OF PRIORITY POLLUTANTS
To determine the presence or absence of priority pollutants in wastewater
discharges from an airplane parts fabrication plant, the approach described
in this section was developed for sampling, analysis, and screening testing.
Because of the separate pretreatment of portions of the waste stream, waste
streams were sampled at two stages—not only as commingled effluent, but also
before commingling.
The precautions taken to meet stringent quality assurance guidelines in
the sampling procedure, field flow measurements, and analytical procedures
(i.e., sampling and analytical protocol) are described in this section of the
report.
SAMPLING PROCEDURES
Fresampling Preparation
All presampling activity was directed at assembling, cleaning, and
storing sample containers to be used in the field according to the procedures
outlined in "Appendix III, Collection of Samples for Screening Analysis," in
Sampling and Analysis Procedures for Screening Industrial Effluents for
Priority Pollutants.^Sample containers were cleaned, rinsed with organic-
free water, drained, and air- or oven-dried at 100°C as appropriate.
Sampling Sites
During an initial survey of the plant, sampling sites were chosen.
Sampling points were located at the influent to the treatment plant (between
the chrome surge tank and the continuous treatment system and between the
lagoon and the continuous treatment system). The effluent being discharged
from the continuous treatment system also was sampled. Upstream sampling
points of the wastewater from the industrial operations are noted in Figure 1.
The sampling sites and the coding used in the field to identify the samples
and record information on the progress of the sampling in a permanent record
book* are shown in Figure 1. Organic-free distilled water supplied by BCL
was used as a blank.
Collection Techniques
Three areas assumed to be critical in the overall wastewater collection
and treatment facility were sampled as composites:
BCL Log Book No. 33888
8
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• The influents to the treatment plant (002 and 003; 006 and 007) were
composited manually over two 7-hour periods. The manual collection
took place every 2 hours using a 600-mX, beaker filled to 300 m£.
All composites were collected in 10,000-m£ bottles (glass) and kept
at ice temperature.
• Two 10,000-mJl composites of treatment plant effluent (001 and 004)
were collected manually in the same two 7-hour periods using the
same technique described above. Again, all samples were kept iced
during and after the sampling period.
• Duplicate composites of both influents and the continuous treatment
plant effluent also were collected manually during the second 7-hour
period.
A continuous sampling unit was not used because of delays by the airline during
the shipment of the equipment.
Grab samples for phenols, cyanide, metals, and organics were taken once.
These samples were taken before and after the continuous treatment system as
well as before and after each of the pretreatment units.
• Each sample for cyanide analysis was collected in a 1-liter amber
polyethylene bottle and preserved with 0.6 gram of ascorbic acid
and at least 2 mi of ION NaOH; final pH = 10.0.
• Each sample for phenol was collected in a 1-liter glass bottle
and preserved with 2 m£ H_SO, (cone.), if pH was greater than 4.
• Samples for benzene (volatile organics) were collected in 8-oz
glass bottles with extra precautions taken during filling to
eliminate entrapped air bubbles at the Teflon/silicone septa cap.
• Samples for metals were collected in 8-oz glass bottles. Preser-
vatives were not added.
• Each set of grab samples had its own blank of organic-free distilled
water sample prepared.
All sampling events were recorded in a permanent record book and specially
prepared labels were marked with waterproof markers and affixed with waterproof
tape. A log of the grab samples and composites was prepared and is appended
to this report.
Sample Shipping
The collected samples were kept at ice temperature while being transported
from the plant site to BCL by air. Once at BCL, the samples were stored in a
cooler set at 4°C until they were split.
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Sample Splitting
The composited samples were split according to the recommendations cited ,-.
in the "Collections of Samples for Screening Analyses of Priority Pollutants;"
that is, by syphoning into five clean bottles after magnetic stirring of the
composite using a Teflon stirring bar. Polyethylene tubing equipped with a
Viton rubber tip was used to make the transfers. The system was washed thor-
oughly and rinsed with organic-free distilled water between uses. The bottles
were cleaned using IN HNO and at least triple rinsed with "blank" water
(Milli-Q-Water), drained, heated to 200°C, and cooled to room temperature in
a dust-free area. Caps also were cleaned and lined with close-fitting Teflon
liners. The bottles were labeled and coded in sets of five (one 16-oz bottle
and four 32-oz bottles), to match the composite being split. The five samples
were to be used for the following purposes and were identified as such:
Metals (MET)
Pesticides, PCB, and asbestos (P&P)
Gas chromatography/mass spectroscopy (GC/MS)
Classic parameters (CP)
Company's sample.
The remainder of the composite was stored at 4°C for further use if needed.
The coding used to identify the split samples matched that used to
identify the streams sampled in the field (i.e., 000 through 009).
All of the samples split from the composite were stored at 4°C until
their submission for analysis. Custody of these samples was transferred for-
mally to the analytical team with a list of their identity, origin, and
analyses required.
FLOW MEASUREMENT
The flow rate of the effluent from the treatment plant is metered. The
influent from the holding tank and from the lagoon are pumped to the treatment
plant. Flows from these sources were estimated on the basis of the flow control
valve settings and the duration of the pumping periods. On the basis of the
material effluent, the volumes for the sampling period waste load calculations
are based on 1,815 m3/day (480,000 gal/day).* The materials from the Zyglo
holding tank, the cyanide batch treatment system, and the oily waste treatment
materials were discharged in batches into the lagoons. Their daily volumes
were estimated on the basis of the levels of liquids in the respective tanks.
The total influent from the chromium holding tank and from the lagoon to the
treatment plant consisted of <-l,190 m3/day (315,000 gal/day) and ~625 m3/day
(165,000 gal/day), respectively.
The flows during the sampling period were slightly different from the
nominal flows shown in Figure 1, e.g., a total effluent of 1,815 m vs
1,659 m3.
10
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ANALYTICAL PROCEDURES AND QUALITY ASSURANCE
The analytical procedures and quality assurance methodologies were those
set forth in the U.S. EPA screening protocol(1) except where specifically
noted. The analytical results are summarized in each of the sections related
to specific elements or compounds. The sample numbers in the tables of analy-
tical data are the base numbers recorded in Battelle Report Book No. 33888 (see
section on sample splitting). Quality assurance information is given in the
sections relevant to these materials.
Metals
Samples for all metal determinations with the exception of mercury were
concentrated by acidifying 200 ml with nitric acid and evaporating to 50 ml.
Perkin-Elmer Models 305B and 603 atomic absorption spectrophotometers were
used for the metal analysis. The conventional air-acetylene flame method
was used for the determination of Ag, Cd, Pb, Cu, Zn, Cr, and Ni, while Be
was determined using a nitrous oxide-acetylene flame. The HGA Graphite Furnace
technique was used for determining Sb and Tl. Analyses for Se and As were
carried out using the hydride generation-flame method in which the metal is
converted to a volatile hydride and introduced into a hydrogen-nitrogen air
entrained flame. Mercury was determined on an aliquot of the original samples
by a cold vapor technique in which the mercury is reduced, amalgamated onto
silver wool, and then released into an absorption cell by heating the silver
wool.
Results of the atomic absorption analyses are given in Table 2.
To provide quality assurance, measured amounts of the elements being
determined were added to the blank, which was acidified for further confirmation
of the accuracy of the procedures. The spike and recovery data are presented
in Table 3. Not enough sample was available for duplicate analyses.
Total Cyanides
The influents to and effluents from the continuous treatment plant were
analyzed for total cyanide using the procedures set forth in the U.S. EPA
screening protocolw. The results of these analyses are given in Table 2.
In addition, samples of the influent to and effluent from the batch cyanide
treatment system for 6/22/78 were analyzed for total cyanides. The results
of these analyses also are given in Table 2.
Quality assurance for the total cyanide analysis was provided by analyzing
two standard samples as well as a spiked sample of the influent to the contin-
uous treatment plant. Further quality assurance was provided by analyzing
these samples both colorimetrically and volumetrically. The quality assurance
data are presented in Table 4.
Organic Constituents
The general procedure used for the determination of the priority organic
pollutants is outlined in Figure 2. The compounds which were sought included
11
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TABLE 2. RESULTS OF ATOMIC ADSORPTION AND TOTAL CYANIDE ANALYSES (rag/*,)
(a)
Sample
no. (b) Se
001 <-001
002 <.001
003 < . 001
004 <.001
004-005
006 < . 001
008 <.001
008-009
032
037
(a) Analyses
(b) Sample No
001
002
003
004-005
006
007
008-009
032
037
As Hg Sb Be Tl Ag Cd Pb Cu
.0006 <.0002 <.005 <.005 <.003 <.01 <.01 <.05 0.05
.001 <.0002 <.005 <.005 <.003 <.01 <.01 <.05 0.13
.0009 <.0002 <.005 <.005 <.003 <.01 .03 <.05 0.18
.0004 <.0002 <.005 <.005 <.003 <.01 <.01 <.05 0.04
.001 <.0002 <.005 <.005 <.003 <.01 .07 <.05 0.16
.0006 <.0002 <.005 <.005 <.003 <.01 .02 <.05 0.14
were completed July 7, 1978.
Sample site ,_,.
Treatment plant effluent V:?
Treatment plant effluent ^ ' from wood tank
Influent from lagoon ^ ' .
Treatment plant effluent
Treatment plant influent from wood tank ^e?
Treatment plant influent from wood tank.
Treatment plant influent from lagoon ^e'
Influent to cyanide treatment f ,
Effluent from cyanide treatment
Zn Cr Ni CN^
.01 .28 <.03 .05(d)
.12 12 <.03
.15 8.9 .03 .05(d)
.02 .20 <.03
05(e)
• \J J
•14 11 .03
.12 7.8 .03
0.15(e)
22.0(e)
.05(e)
See page 26-27 for complete sample listing
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TABLE 3. QUALITY ASSURANCE FOR METAL ANALYSES
Spike recovery data
Sample
Acid blank
Acid blank
Reagents blank
Acid blank
Acid blank
Acid blank
Acid blank
Acid blank
Acid blank
Acid blank
Acid blank
Acid blank
Acid blank
Element
Se
As
Hg
Sb
Be
Tl
Ag
Cd
Pb
Cu
Zn
Cr
Ni
Amount
present,
mg
<0.001
< 0.0001
0.016
<0.005
<0.005
<0.003
<0.01
<0.01
<0.05
<0.01
2.5
6.5
2.8
Amount
added,
mg
10.0
10.0
0.100
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0
Amount
found, Percent
mg recovery
10.3
9.4
0.117
9.5
10.0
9.0
9.4
10.0
10.0
9.5
10.0
16.5
12.5
103
94
101
95
100
90
94
100
100
95
80(a)
100
98
(a)
Discrepancy in recovery in excess of the + 15 percent permitted by the
T>T*ofnfn1 v-^/
13
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TABLE 4. QUALITY ASSURANCE DATA FOR TOTAL CYANIDE ANALYSES
Sample
Standard
003 ^
Standard
CN
present,
mg
<0.05
<0.05
O.05
CN~
added,
mg
1.281
0.128
0.640
CN found ,
mg
Colorimetric
1.230
0.111
0.640
Volumetric
1.273
0.127
0.658
Percent
Colorimetric
96.0
86.7
100
recovery
Volumetric
99.4
99.2
102.8
-------
25 ml Wastewater
Purge with helium
(15 min at 40 ml/min)
1500 ml Wastewater
5 g KHSO
75 g NaCr
1 ml cone. H_SO,
Trap Organ!cs Using Tenax
Desorb by Heating
Analyze by GC with
Electron Capture Detector
Extract with CH.Cl-
(150 ml + 50 ml 4 50 ml)
I
Extract CH,C12 layer
with 0.2 N RaOH
(200 ml + 200 ml)
500 ml Wastewater
Adjust to pH /"7
Using 1 M Na.PO.
"I 3 4
Extract with CHC1
Preserved with Ethanol
(50 ml + 30 ml)
I
Wash CHC1 Layer with
Water
VOLATILES
Aqueous Layer
Acidify to pH -1
(20 ml of 6 N. HC1)
Extract with CH Cl
(50 ml -I- 50 ml + 50 ml)
Dry CH,C1_ Layer Over
*Na,SO,
I2 '
Concentrate to 1 ml
Methylate with
Add 1 ml Benzene
and 20 yg HEB
(Int. Std.)
Concentrate to 0.4 ml
Analyze by GC/MS
Using Glass Capillary
Column
ACIDS
Add 20 ml Methanol
CH-C1- Layer
Concentrate to 0.4 ml
I
Add 1 ml of CHC1,
Wash with 0.1 N HC1
(100 ml) Extract with 2N^ H SO
I (1 ml + 1 ml)
Dry Over Na_SO, |
Neutralize Aquaeous Extracts
to pH 6-7 Using 1 M Na P04
Concentrate to 1 ml |
I
Add 1 ml Benzene
and 20 yg HEB
(Int. Std.)
I Add 1 ml Methanol
Concentrate to 0.4 ml to CHC13 Extract
Extract with CHC1,
(2 ml + 2 ml) J
Analyze by GC/MS Concentrate to 0.4 ml
Using Glass Capillary
Column Dilute to 1.0 ml with
0.1 M pH 4.7 Acetate Buffer
NEUTRALS I
Analyze by I:PLC Using
Electrochemical Detector
(Including PCBs and
Pesticides)
BENZIDINES
Figure 2. Scheme for Analysis of Wastewater.
15
-------
volatile organic compounds, base-neutral extractables, phenolic compounds, and
benzidines. In general, the U.S. EPA screening protocol' ' in effect at that
time was followed during the performance of these analyses. A summary of the
specific procedures which were used is included as Appendix B.
Volatile Organic Compounds—
Battelle was asked to analyze six composite samples from the Boeing,
Seattle, Washington plant for organics. The "Purge and Trap Gas Chromatography"
method was used for determining the volatile organic compounds. This method
includes the use of a Tekmar liquid sample concentrator (LSC-1) to concentrate
the water samples and a Packard, Series 800, gas chromatography instrument
with an electron capture detector for analysis. The results obtained are
shown in Table 5.
The most volatile compounds, such as vinyl chloride, chloroethane, and
methylene chloride were not detected; therefore, if present, they would be at
a level of less than 0.01 yg per liter. The compounds reported appear to be
the compounds frequently detected in chlorinated water supplies.
Several standards were used for these analyses. The "Purgeable A"
standard was purchased from Supelco, Inc. (Catalog 13, Cat. No. 4-8815) and
contained the following compounds at a concentration of 0.2 mg/m£ in methanol:
Methylene chloride Trichloroethylene
1,1-dichloroethylene 1,1,2-trichloroethylene
1,1-dichloroethane Dibromochloromethane
Chloroform Tetrachloroethylene
Carbon tetrachloride Chlorobenzene
1,2-dichloropropane
This base standard was added to boiled and purged water, to form a solution
containing 10 yg/£ of each compound listed above.
Battelle-prepared standards were of two different concentrations and
contained chloroform, carbon tetrachloride, and trichloroethylene. One
standard was at the 3 yg/fc level, and the other at 8 yg/fc. The Battelle
standards gave essentially the same detector response as the purchased
standard and served as a cross-check on the validity of the method. A summary
of the results of the analyses of the standards is given in Table 6.
The reproducibility of the method based on the Battelle standards was
approximately 10 percent relative. The Battelle standards compared to the
Supelco A standard indicated that an error as high as 41 percent might exist
for the Supelco A standard for carbon tetrachloride. Blank water used to make
the standards was also sparged and no interferences detected. This three-
point cross-check to verify the validity of the purchased standard, which was
used in this work, shows an agreement for the three components of 5 to 40
percent.
Base Neutral Extractables and Phenolic Compounds—
The initial attempt to determine the non-volatile organics was made in
July, 1978. However, the results obtained then were discarded because of
16
-------
TABLE 6. VOLATILE HALOGENATED HYDROCARBONS
(Reported as Mlcrograms/Llter)
Sample designation
Compounds 001 (b) 002 (c) 003(d' 004-5(e) 006-7 (f)
Chloroform 1.2 1.2 1.0 0.8 0.6
1,1-dichloroethane 0.4 <0.01 0.9 0.6 0.01
1,1,1-trichloroe thane
(methyl chloroform) 1.9 2.1 1.6 2.0 2.0
Carbon tetrachloride 2.3 1.9 1.7 1.5 1.7
1,2-dichloropropane 1.3 1.8 0.6 1.2 1.3
1,3-dichloropropene 0.2 <0.01 0.6 0.2 <0.01
Trlchloroethylene 0.8 0.9 0.8 0.7 0.7
Trichloroethane 0.9 1.4 0.5 0.7 1.1
Tetrachloroethyiene or ..*
tetrachloroethane <0.01 <0.01 0.05 0.02 --
(a) Analyses were completed on July 8, 1978
(b) Plant effluent 6/21/78
(c) Wood tank influent 6/21/78
(d) Lagoon influent 6/21/78
(e) Plant effluent 6/22/78
(f) Wood tank influent 6/22/78
(g) Lagoon influent 6/22/78
(h) Chromatograph stopped before reaching this compound.
TABLE 7. SUMMARY OF THE RESULTS FROM THE ANALYSES
OF STANDARD SAMPLES
Carbon
Chloroform tetrachloride
Battelle std. 11
Concentration, ug/1 2.81 3.19
Integrator counts per ug/1 23,181 90,958
Battelle std. 12
Concentration, ug/1 7.03 7.98
Integrator counts per ug/1 29,182 72,671
Counts average 26,182 81,815
Supelco std. A
Concentration, ug/1 10.0 10.0
Integrator counts per ug/1 27,604 58,190
008-9 (8)
1.2
0.7
1.3
1.5
0.6
0.4
0.4
0.1
0.05
Trichloro-
ethylene
6.19
78,595
7.98
83,750
81,143
10.0
123,680
Z deviation from Battelle stds. 5.2 40.6 34.5
17
-------
TABLE 8. RESULTS OF THE BASE NEUTRAL EXTRACTABLES AND PHENOLICS ANALYSES
(Analyses completed on December 16, 1978)
00
Amount found in sample. ue/S.
Compound
Bis - (2 chloroethyl) ether
1,3 - dichlorobenzene
1,4 - dichlorobenzene
1,2 - dichlorobenzene
Bis - (2 chloroisopropyl) ether
N-nitrosodlpropylamine
Hexachloroethane
Nitrobenzene
Isophorone
Bis (2-chloroethoxy) methane
1,2,4 - trichlorobenzene
Naphthalene
Hexachlorobutadlene
Hexachlorocyclopentadiene
2-chloronaphthalene
2 , 6-d inl t r o t o luene
Dimethyl phthalate
Acenaphthylene
Acenaphthene
2, 4-dinitro toluene
Oiethylphthalate
Fluorene
4— chlorophenyl phenyl ether
N-nltrosodiphenylamine
4— bromophenyl phenyl ether
Hexachlorobenzene
001
a
a
a
a
a
a
a
a
a
a
0.5
a
a
a
a
<0.1
1.7
a
0.2
a
a
a
002
a
a
a
a
a
a
a
a
a
a
0.7
a
a
a
a
<0.1
a
a
0.2
a
a
a
003
a
a
a
a
a
a
a
a
a
a
1.7
a
a
a
a
a
a
a
2.6
a
a
a
004-
005
a
a
a
a
a
a
a
a
a
a
1.5
a
a
a
a
<0.1
a
a
0.1
0.4
a
a
005
a
a
a
a
a
a
a
a
a
a
0.6
a
a
a
a
0.1
1.0
a
0.1
a
a
a
006-
007
a
a
a
a
a
a
a
a
a
a
0.3
a
a
a
a
0.1
<0.1
a
0.1
a
a
a
007
a
a
a
a
a
a
a
a
a
a
0.9
a
a
a
a
0.1
a
a
a
a
8
a
a
008-009
Phenols
a
a
a
a
a
a
a
a
a
a
a
10.1
a
a
a
a
a
a
a
a
a
a
a
a
a
a
008-009
Comp.
a
a
a
a
a
a
a
a
a
a
a
2.3
a
a
a
a
a
a
a
a
a
a
a
a
a
a
(Continued)
-------
TABLE 8. (Continued)
vo
Amount found
Compound
Phenanthrene
Anthracene
Di-n-butyl phthalate
Fluoranthene
Pyrene
Butyl benzyl phthalate
Chrysene
Beazo (a) anthracene
Bis - (2 ethylhexyl) phthalate
Di-n-octyl phthalate
Benzo (b) fluoranthene
Benzo (k) fluoranthene
Benzo (a) pyrene
Benzo (g,h,i) perylene
Indeno (1,2,3-cd) pyrene
Dlbenzo (a,h) anthracene
Phenol
2-chlorophenol
2,4— dime thy Iphenol
2 ,4-dichlorophenol
2,4,6-trichlorophenol
2-nitrophenol
4-chloro— 3-methyl phenol
4-nitrophenol
4,6-dlnitro-o-cresol
Pentachlorophenol
2 ,4-dinltrophenol
001
0.1
a
2.4
2.9
a
0.1
a
a
0.1
a
a
a
a
a
a
a
2.4
a
a
a
a
a
g
a
a
a
002
<0.1
a
1.2
a
a
0.2
a
a
0.8
a
a
a
a
a
a
a
1.6
a
a
a
a
a
a
a
a
a
003
0.6
a
1.6
42.
a
a
a
a
0.7
a
a
a
a
a
a
a
11.6
a
a
a
a
a
a
a
a
004-
005
0.1
a
0.2
5.4
a
0.4
a
a
a
a
a
a
a
a
a
a
1.7
a
a
a
a
a
a
a
a
005
a
a
0.5
0.1
a
0.3
a
a
0.4
a
a
a
a
a
a
a
1.3
a
a
a
a
a
a
a
a
in sample, ug/£
006-
007
a
a
2.6
a
a
1.2
a
a
1.3
a
a
a
a
a
a
a
1.6
a
a
a
a
a
a
a
a
007
a
a
3.5
a
a
3.4
a
a
3.3
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
008-009
Phenols
1.0
a
a
120.
a
a
a
a
0.8
a
a
a
a
a
a
a
a
a
a
a
a
a
a
&
a
a
a
008-009
Comp.
a
a
a
155.
a
a
a
a
4.3
a
a
a
a
a
a
a Neutrals
, „ Phenols
a
a
a
a
a
a
a
a
<0.1
a
(a) Not detected. Detection limit~1 ug/1.
-------
difficulties encountered with a newly-instailed GC/MS system. The analyses
were repeated in December, 1978, and the results of the base neutral extract-
ables are presented in Table 7. Of the 42 base neutral extractable compounds
sought, only 10 were above the detection limits of the GC/MS procedure which
was used in analyzing the influents to and effluents from the continuous
treatment system: included in these 10 were 5 phthalates, naphthalene,
acenaphthene, fluorene, phenanthrene, and fluoranthene. Of the 11 phenolics,
only phenol was present in the samples analyzed except for a trace (<0.1 ug/£)
of pentachlorophenol in the composite treatment plant influent from the lagoon.
The quality control procedures which were used during analysis of the
nine wastewater samples for the semivolatile priority pollutants were as
follows:
• Two process blanks were extracted along with the wastewater
samples. One blank consisted of distilled water and the
other blank was received with the wastewater samples. These
blanks were analyzed by GC/MS.
• The percentage recoveries for the semivolatile priority
pollutants were determined by spiking two distilled water
samples with the priority pollutant semivolatile compounds
and then extracting them along with the wastewater samples.
The spiked samples were also analyzed by GC/MS. The results
of these recovery studies are shown in Table 8.
• Strict performance criteria were followed to ensure that the
GC/MS/DS were providing the highest quality chromatograms and
mass spectra possible as described previously.
Benzidines—
Nine influent and effluent samples from the continuous waste treatment
system were analyzed for benzidines and dichlorobenzidines using high pressure
liquid chromatography and an electrochemical detector. The results of these
analyses are given in Table 9.
20
-------
TABLE 8. PERCENT RECOVERY OF PRIORITY POLLUTANTS SPIKED IN WATER
Compound
Neutrals
Bis-(2-chloroethyl) ether
1 , 3-Dichlorobenzene
1,4-Dichlorobenzene
1 , 2-Dichlorobenzene
Bis-(2-chloroisopropyl) ether
N-Nitrosodipropylamine
Hexachloroe thane
Nitrobenzene
Isophorone
Bis-(2-chloroethoxy) methane
1,2, 4-Tr ichlorobenzene
Naphthalene
Hexachlorobutadiene
Hexachlorocyclopentadiene
2-Chloronaphthalene
2 ,6-Dinitrotoluene
Dimethyl phthalate
Acenaphthalene
Acenaphthene
2 ,4-Dinitrotoluene
Diethyl phthalate
Fluorene
4-Chlorophenyl phenyl ether
N-Nitrosodiphenylamine
4-Bromophenyl phenyl ether
Hexachlorobenzene
Phenanthrene
Anthracene
Di-n-butyl phthalate
Fluoranthene
Pyrene
Butylbenzyl phthalate
Chrysene
Benzo (a) anthracene
Bis(2-ethylhexyl) phthalate
Di-n-octyl phthalate
Benzo (b) f luoranthene
Benzo (k) f luoranthene
Run 1
116
92
92
96
124
120
92
132
(a)
112
100
108
56
(a)
108
116
128
84
80
100
56
80
60
112
116
148
108
104
140
88
80
124
80
80
116
64
48
48
Run 2
108
67
67
84
112
91
87
119
(a)
87
88
89
60
(a)
73
94
116
59
67
72
53
65
55
91
81
107
79
85
163
42
40
56
11
11
48
22
22
22
Average
112
80
80
90
118
106
90
126
(a)
100
94
99
58
(a)
91
105
122
72
74
86
55
73
57
102
99
128
94
95
152
65
60
90
46
46
82
43
35
35
21
-------
TABLE 8. (Continued)
Compound
Run 1
Run 2
Average
Benzo(a)pyrene
Benzo(g,h,l)perylene
Indeno (1 , 2 , 3-cd)pyrene
Dibenzo (a ,h) anthracene
Phenol
2-Chlorophenol
2 , 4-Dimethylphenol
2 , 4-Dichlorophenol
2,4, 6-Trichlorophenol
2-Nitrophenol
4-Chloro-3-methylphenol
4-Nitrophenol
4 , 6-Dinitro-o-cresol
Pentachlorophenol
2 , 4-Dinitrophenol
48
24
32
(b)
136
90
36
20
84
20
76
48
150
78
114
16
11
16
(b)
108
67
30
24
92
34
90
44
150
94
140
32
18
24
(b)
122
79
33
22
88
27
83
46
150
86
127
(a) Compound not contained in standard used to spike samples.
(b) Level of compound below detection limits.
22
-------
TABLE 9. RESULTS OF BENZIDINE ANALYSES
(a)
Sample
no.
Analytical results
Sample site
Benzidine,
Dichlorobenzidine,
Vg/l
001
002
Treatment plant effluent
(6/21/78) (b)
Influent from, wood tank to..
treatment plant (6/21/78)l
<1
003
(Phenol)
004/005
005
006/007
007
008
008/009
(Phenol)
Influent from lagoon to , x <1 <1
treatment plant (6/21/78) QcJ
Treatment P1/^ effluent
(6/22/78) W <1 <1
Treatment plant effluent
(6/22/78) (d) <1 <1
Influent from wood tank to,x
treatment plant (6/22/78)* ' <1 <3-
Influent from wood tank to. >
treatment olflnt (6/22/78)* <:L <:L
Influent from lagoon to
treatment olant (6/22/78) ( <1 <:L
Influent from lagoon to ...
treatment plant (6/22/78) v <1 <1
(a) Analyses were completed on December 16, 1978.
(b) Aliquots of composite samples prepared and preserved expecially for
organic analyses.
(c) Grab samples preserved for phenol analyses.
(d) Grab samples preserved for organic analyses.
23
-------
SECTION 5
DISCUSSIONS OF EFFECTIVENESS OF THE CONTINUOUS
TREATMENT SYSTEM FOR THE REMOVAL OF PRIORITY POLLUTANTS
WASTE LOADS PER 24-HOUR PERIOD
The analytical results and the average dally flow rates measured for the
sampling period were used to calculate the waste loads of the priority
pollutants for the influent and the effluent waste streams related to the
continuous treatment system.
Priority Pollutant Loads
The mass flow of the priority pollutants entering and leaving the waste-
water treatment plant daily are given in Table 10. The compounds and elements
whose concentrations were below detection limits were assumed to be absent
and were not included in the loading calculations.
REMOVAL EFFICIENCIES
The efficiency for the removal of the priority pollutants by the tech-
nique of lime and settle (pH = 8.5) is also given in Table 10. The efficiency
was calculated by the following method:
[(kg/day)1 f - (kg/day)eff]
x 100 = Removal efficiency, percent.
(kg/day)
Of the priority pollutants, 97 percent of the chromium was removed, or
better. More than 88 percent of the zinc and fluoranthene was removed, and
more than 78 percent of the base neutral organics was removed. Copper and
cadmium removals were about 70 and 64 percent, respectively.
CONCLUSION
The technique used for the removal of metals at this airplane parts
olant removes 97 percent of the chromium, 88 percent of the zinc, and
about 70 percent of the copper. It also is effective for removing the base
neutral organic compounds (>78 percent). Cyanide is almost completely removed
in a batch pretreatment system. The volatile organic compounds are not removed
to a detectable extent.
24
-------
TABLE 10. WASTE LOAD OF PRIORITY POLLUTANTS IN A
24-HOUR PERIOD
Metals:
Cadmium
Chromium
Copper
Nickel
Zinc
Volatile organics
Base neutral organics
Fluoranthene
Phenol
Influent
kg/day
0.055
18.88
0.27
0.055
0.236
0.016
0.065
0.06
0.005
Effluent Removal
kg/day efficiency, %
0.02
0.436
0.082
0.055
0.027
0.016
0.014
0.007
0.003
63.6
97.7
70.0
—
88.6
—
78.5
88.3
40.0
25
-------
BIBLIOGRAPHY
(1) Sampling and Analysis Procedures for Screening Industrial Effluents for
Priority Pollutants. Staff of the Environmental Monitoring and Support
Laboratories, U.S. EPA, Cincinnati, Ohio, March, 1977 (rev. April, 1977)
26
-------
APPENDIX A
SAMPLE LOG
Following is a list of samples collected at the facility June 21-22, 1978.
TABLE A-l. SAMPLE AND ANALYTICAL LOG
Sample no.
Location
Type
Date of
collection
001
Plant effluent
002
Wood tank influent
(to treatment plant)
003
Lagoon influent
(to treatment plant)
004
005*
004-005
006
007*
006-007
Plant effluent
Plant effluent
II
II
II
Wood tank influent
(to treatment plant)
Wood tank influent
(to treatment plant)
3-gal composite
grab-cyanide
grab-phenol
grab-oil & grease
grab-organics
distilled H20 blank
3-gal composite
grab-cyanide
grab-phenol
grab-oil & grease
grab-orpanics
distilled H20 blank
3-gal composite
grab-cyanide
grab-phenol
grab-oil & grease
grab-organics
distilled H20 blank
3-gal composite
3-gal composite
grab-cyanide
grab-phenol
grab-oil & grease
grab-organics
3-gal composite
3-gal composite
grab-cyanide
grab-phenol
grab-oil & grease**
grab-organics
6-21-78
6-22-78
M
It
II
If
II
II
27
(continued)
-------
TABLE A-l. (Continued)
Sample no.
008
009*
008-009
010
Oil
012
013
014
015
016
017
018
019
020
021
022
023
024
025
026
030
031
032
033
034
035
036
037
038
039
046
047**
048
049
050
051
052
053
* Duplicate
** Broken in
Location
Lagoon influent
(to treatment plant)
Lagoon influent
(to treatment plant)
ii
n
ii
ii
Oil system influent
n
n
n
ii
Zyglo influent
n
n
ii
n
it
Oil system treated
it
n
n
it
n
Chrome tank influent
Cyanide input
n
it
n
n
Cyanide output
n
it
n
it
Cyanide - after Cl_
Cyanide - after Cl-
Boeing source water
Zyglo
n
n
it
n
sample
shipping
Type
3-gal composite
3-gal composite
grab-cyanide
grab-phenols
grab-oil & grease
grab-organics
grab-cyanide
grab-organics
grab-oil & grease
grab-phenols
distilled H00 blank
2
grab-cyanide
grab-phenol
grab-metals
grab-organics
grab-oil & grease
distilled H00 blank
2
grab-cyanide
grab-organics
grab-oil & grease
grab-phenols
grab-metals
distilled H00 blank
2
grab-metals
grab-metals
grab-phenols
grab-cyanide
grab-oil & grease
grab-organics
grab-metals
grab-phenols
grab-cyanide
grab-oil & grease
grab-organics
grab-cyanide
grab-metals
2-gal grab
grab-oil & grease
grab-cyanide
grab-phenols
grab-metals
grab-organics
Date of
collection
6-22-78
n
n
it
n
n
6-21-78
n
n
n
n
n
n
ii
ti
it
it
n
ii
n
ii
n
n
ii
6-22-78
n
n
it
it
n
tt
ii
it
it
ii
n
n
ii
it
ii
n
it
28
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APPENDIX B
SUMMARY OF ANALYTICAL PROCEDURES FOR
THE PRIORITY ORGANIC POLLUTANTS
The general scheme used for the analysis of the organic constituents of
the wastewater samples is given in Figure 2. Volatile components are deter-
mined by a purge-and-trap technique. Semivolatile components are initially
extracted with dichloromethane under acidic conditions. Acidic conditions
yield better recovery efficiencies and fewer emulsion problems than alkaline
conditions. The acidic components in the initial extracts are separated from
the neutral components by extraction into 0.2 N[ NaOH.
Benzidines are separated from neutral and acidic compounds present in a
separate chloroform extract of a neutral water sample by extracting the
chloroform with 2 _N H-SO,. The exceptionally strong acidic conditions are
necessary for the extraction of 3,3'-dichlorobenzidine. Ethanol or methanol
must be present during the solvent concentration steps to avoid decomposition
of the benzidine.
The benzidines are quantified by high pressure liquid chromatography
(HPLC) using an electrochemical detector which is a highly sensitive and
selective system. All other separation, identification, and quantification
is achieved by combined gas chromatography-mass spectrometry-data system
using high resolution glass capillary columns. Some of the details of the
analytical procedure are given below.
EXTRACTION PROCEDURE
Half-gallon jugs containing 1,500 m£ of water sample, 5 g of KHSO,, and
75 g of NaCl are treated with 150 mi of dichloromethane and 1 mi of concen-
trated H-SO,. The mixture is then stirred in the jug with a magnetic stirrer
for 2 hours. The rate of stirring is such that a slight vortex is formed at
the water-dichloromethane interface but not fast enough to form emulsions.
After the solution is stirred for 2 hours, the dichloromethane layer is trans-
ferred with a 50-m£ syringe to a 500-m£ separatory funnel with a Teflon stop-
cock. The aqueous solution is re-extracted two times with 50 mi of dichloro-
methane for 30 minutes and the dichloromethane layers are combined with the
first extract (about 210 mi of dichloromethane is recovered).
The combined dichloromethane extract, containing the acidic and neutral
compounds, is extracted twice with 200-mi aliquots of 0.2 N NaOH with vigorous
shaking for 2 minutes and washed with 0.1 Jl HC1. The resulting dichloromethane,
containing only the neutrals, is dried with —5 g MgSO, and concentrated to
29
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1 m£ using a Kuderna-Danish apparatus. Then 1 mJl of benzene and a solution
containing 20 yg of hexaethylbenzene (HEB) as an internal standard are added
and the solution is concentrated to 0.4 mJl for GC and GC/MS analysis.
The 0.2 II NaOH extracts containing the sodium salts of acid compounds
are combined in a 500-m£ separatory funnel, acidified with 20 ml of 6 N_ HC1
(pH 1.0-1.5) and extracted three times with 50 m£ of dichloromethane. The
combined dichloromethane layers are dried over MgSO, and concentrated to 1 m£.
This extract, containing the acids, is methylated with diazomethane. Then
1 m£ of benzene and a solution containing 20 pg of the internal standard,
hexaethylbenzene (HEB), are added and the solution is concentrated to 0.4 m£
for GC and GC/MS analysis.
GC/MS ANALYSIS
Capillary Column GC/MS Instrumentation
The GC/MS/DS used is a Finnigan Model 9500 gas chromatograph directly
interfaced to a Finnigan Model 3200 quadrupole mass spectrometer. Data acqui-
sition and manipulation are controlled by a Systems Industries Model 150 data
system. The column used for all the analyses is a 30 m x 0.2 mm I.D. glass
capillary coated with SE-30 and supplied by J & W Scientific. Samples
(2.0 p£) are injected through a Grob injector operated in the splitless mode.
Following injection the column is held for 5 minutes at 60°C, then temperature
programmed at 4°/min. to 270°C and held at 270°C for 15 minutes. The computer
retention time clock is started during injection. Data acquisition is started
at the end of about six minutes. The sensitivity of the MS is generally 10
amp/volt at an electron multiplier setting of 1800 volts.
Strict performance criteria are followed to ensure that the GC/MS/DS is
providing the highest quality chromatograms and mass spectra possible. Prior
to each day's GC/MS data acquisition, a test mixture is analyzed to test the
complete GC/MS system for the following characteristics:
MS tune-up
Splitless injection system
Capillary column efficiency
Capillary column acidity or basicity
Presence of adsorptive sites on the column
Detection limit
GC/MS transfer line losses.
The compounds in the test mixture include:
1-naphthylamine Tridecylbenzene
2-methylnaphthol n-eicosane
1-pentadecanol Pyrene
Decafluoretriphenylphosphine n-heneicosane
3-methylnonadecane Methyl stearate
2-methyleicosane
30
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Computerized Compound Search Routine
The computerized compound search is used on all the semivolatile extract-
able pollutant standard solutions and wastewater extracts.
The first step in using the computer to search for specific compounds is
to enter the compounds and search parameters into a queue editor computer
program. The search program parameters are chosen to minimize false negative
responses at the expense of the possible production of false positives. The
GC/MS data for each of the priority pollutants is listed in Table B-l. It
must be emphasized that the mass spectrum of each "hit" is manually examined
before the presence of a specific compound is reported. The search parameters
are determined by analyzing standard solutions containing all the priority
pollutants of concern and hexaethylbenzene (HEB) internal standard. The mass
spectrum of each of the compounds in the standard mixture is identified by
comparison to published spectra and the retention time of each of the compounds
is recorded. Separate samples are analyzed containing the neutrals and methy-
lated phenols. The search parameters for each of these groups of compounds
are entered into a separate editor program. The search parameters include the
compound name, the retention time, and two or three chemically significant
fragment masses. In order to enhance search selectivity, a threshold may be
assigned. The threshold value directs the search program to sum the set of
ions only if each ion intensity is equal to or greater than the specified
percentage of the highest intensity. The value one was used for all the
searches for this study. One of the masses in the search program may also
be selected as the base peak (most intense ion) which directs the search
program to perform the summation only if the indicated mass exhibits the
largest intensity of the selected ions.
Following GC/MS analysis of a sample, the data file is transferred to the
search disc containing the search parameters and the search program. Once the
program is initiated, the user enters the spectrum data file name and the
queue editor file name containing the search data for the compounds of interest.
The program then requests from the user the retention time of the internal
standard. If a value is entered, the program searches on the basis of relative
retention time; if no value is entered, the search proceeds on the basis of
retention time. The program then requests a search window (e.g., 300 scans)
to be used for each specific compound search.
Four different output modes are available with the program. For this
study the output consisted of a CRT image of the reconstructed gas chromato-
gram (RGC) of the search window on the lower half of the screen and the
selected ion summation mass chromatogram of the compound searched for on the
top half of the screen. Following the appearance of the RGC and SIS (Selected
Ion Summation) plot on the screen a hardcopy list of the results is printed.
If the user has selected the CRT graphic option, the program allows a pause
for the RGC and SIS plot to appear on the screen until the RETURN key is
pressed. When the pause occurs during the search the user is provided with
several options such as horizontal expansion, vertical amplication, area
determination for quantification as described in the next section, and also
queuing of the spectrum for later printout. If areas are determined, these
data are included in the hardcopy list.
31
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TABLE B-l. GC/MS DATA USED FOR OETF.RMINING SEMIVOLATILE PRIORITY POLLUTANTS
K)
Compound
Bis-(2-chloroethyl) ether
1 , 3-dichlorobenzene
1 ,4-dichlorobenzene
1 , 2-dichlorobenzene
Bis-(2-chloroisopropyl) ether
N-nitrosodipropylamine
Hexachlo roe thane
Nitrobenzene
Isophorone
Bis-(2-chloroethoxy)methane
1,2,4-trichlorobenzene
Naphthalene
Hexachlorobutadiene
Hexachlorocyclopentadiene
2-chloronaphthalene
2, 6-din it ro toluene
Dimethyl phthalate
Acenaphthalene
Acennphthene
2,4-dinitrotoluene
Diethyl phthalate
Fluorene
4-chlorophenyl phenyl ether
N-nltrosodiphenylamine'*-)
4-bromophenyl phenyl ether
Hexachlo robenzene
Phenanthrene
Anthracene
Di-n-butyl phthalate
Fluoranthene
Pyrene
Approx.
retention
index (a)
975
994
999
1017
1025
1035
1050
1065
1100
1125
1150
1158
1200
1315
1330
1370
1415
1420
1445
1475
1550
1555
1570
1590
1650
1675
1740
1750
1920
2020
2060
Approx.
retention
time,min. *•'
Neutrals
10.5
10.6
10.6
11.2
11.7
12.6
13.0
13.4
14.6
15.5
16.8
17.1
18.8
22.7
24.0
25.5
26.3
27.0
27.2
27.9
30.4
30.5
30.6
31.4
33.0
33.4
35.6
35.9
40.1
42.5
43.7
() M.W.
142
146
146
146
170
130
234
123
138
180
180
128
258
270
162
150
194
152
154
150
222
166
204
198
248
282
178
178
278
202
202
Ions used for quantification,
m/e (intensity)
93(100), 63(99),
146(100), 148(65),
146(100), 148(65),
146(100), 148(65),
45(100), 77(19),
70(100), 130(30)
201(100), 117(90)
77(100), 123(50)
82(100), 138(15)
93(100), 95(32),
180(100), 182(97)
128(100), 127(15)
225(100), 227(60)
237(100), 235(63),
162(100), 127(40)
165(100), 89(80)
163(100), 77(21)
152(100), 151(23)
153(100), 154(90)
165(100), 63(60)
149(100), 173C25)
166(100), 165(90)
204(100), 141(75)
169(100), 168(72)
748(100), 250(95)
282(100), 284(77)
178(100). 176(17)
178(100), 176(17)
149(100), 104(10)
202(100), 101(25)
202(100). 101(25)
95(31)
111(35)
111(35)
111(35)
79(12)
123(21)
272(12)
(Continued)
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TABLE B-l. CONTINUED
u>
Compound
Butylbenzyl phthalace
Chrysene
Benzo (a) anthracene
Bis(2-ethylhexyl) phthalate
Di-n-octyl phthalace
Benzo(b) fluoranthene
Benzo(k) fluoranthene
Benzo(a)pyrene
Benzo(g,h, i)perylene
Indeno ( 1 , 2 , 3-cd ) py rene
Dibenzo (a, h) anthracene
2-chlorophenol(free)
Phenol
2-chlorophenol (Me)
2,4-dimethylplienol
2,4-dichlorophenol
2,4-dichlorophenol (Me)
2,4, 6-trichlorophenol (Me)
2-nitrophenol(Me)
4-chloro-3-methylphenol(f ree)
4-nit rophenol (;ie)
4 , 6-dint ro-o-crosol (Me)
Pentachlorophenol (He)
2 ,4-dinit rophenol (Me)
Hexaethyl benzene
Approx. Approx.
retention retention
index
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Occasionally several peaks may appear on the SIS output above the RGC,
any one of which could be the searched compound. However, the peak should
occur near the center of the search window. The user can then move the vertical
cursor to select a spectrum and a background for entry into a Queue file.
At the end of the search the spectra can then all be printed out automatically
for manual inspection to determine if the searched compound was actually
present.
Quantification
The method for quantification of the priority pollutants in the wastewater
extracts is based on the GC/MS analysis using area counts under the extracted
ion current profiles (EICP) from the SIS portion of the computer program.
The ions used for quantification are the same ions used to search for the
compound in the search routine. The area reported is independent of the
amplification of the trace, allowing the user to amplify low intensity chroma-
tographic peaks for the purpose of properly delimiting the peak. Although the
dual display format individually normalizes the selected ion and total ion
traces, the program maintains internally their true relationship used for area
determinations. Areas may be determined either by tangential "skimming" of a
smaller peak on the tail of a larger one or by a perpendicular drop to the
x-axis of the display simply by proper positioning of the crosshairs.
Quantification of wastewater samples is based on the area counts of the
compound compared to the area counts of the hexaethylbenzene (HEB) internal
standard. However, the mass spectrometric response is somewhat different for
each compound because of differing degrees of fragmentation and ionization
efficiencies. Therefore, standard solutions were analyzed containing all
extractable priority pollutants at three different concentrations, but each
containing 50 ng/y£ of HEB. This same quantity of HEB is then added to each
of the wastewater extracts just prior to GC/MS analysis. For each of the
standard solutions, the area counts of the priority pollutant are divided by
the area counts of the internal standard. This value is then multiplied by
a factor to bring the concentration of the priority pollutant equal to that
of the internal standard. For example, when the concentration of the priority
pollutant is 10 ng/y£ and the concentration of the internal standard is
50 ng/p£, the value is multiplied by 5. This number represents the relative
mass spectrometric response factor between the two compounds. For quantifi-
cation of the priority pollutants in the wastewater extracts, an adjusted
response factor was used based on the results of the three standards.
The amount of priority pollutant in each extract is calculated using the
following equation:
, _ yig _ Area Counts Compound Amount HEB (yg) x MS Response Factor
PP = £ = Area Counts HEB X Amount of Water (£)
The early-eluting compounds did not yield quite as precise peak area
ratios as the later-eluting compounds due to the relatively small number of
scans across the peak (e.g., 3 or 4 scans) and also because of some tailing
for a few of the more polar compounds. From the results of the GC/MS analyses
of the priority pollutant standards, we estimate that the maximum relative
error is ± 50 percent, although the results should be somewhat better for the
later eluting compounds.
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/2-80-019
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Characterization of Priority Pollutants from an
Airplane Parts Manufacturing Facility
REPORT DATE
January 1980 issuing date
6. PERFORMING ORGANIZATION COOE
G-6617-Q601
7. AUTHOR(S)
A. K. Reed, M. A. Eischen, M. M. McKown & G. R. Smithson
8. PERFORMING ORGANIZATION REPORT NO.
Jr.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Battelle's Columbus Laboratories
505 King Avenue
Columbus, Ohio 43201
10. PROGRAM ELEMENT NO.
A33B1B
11. CONTRACT/GRANT NO.
68-03-2552 (T2006)
12. SPONSORING AGENCY NAME AND ADDRESS
Industrial Environmental Research Lab.
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
- Cinn, OH
13. TYPE OF REPORT AND PERIOD COVERED
Final; January-December 1978
14. SPONSORING AGENCY CODE
EPA/600/12
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Wastewater from an airplane parts manufacturing plant was sampled using the U.S. EPA
screening protocol for the 129 priority pollutants. The wastewater treatment facilities
at this site include batch systems to destroy cyanides, remove oil, and reduce hexavalent
chromium to the trivalent state before it is discharged to a system where heavy metals
are removed by pH adjustment and settling.
The results of the study show that the treatment practiced at this site removes more than
90 percent of the chromium, zinc and 70 percent of the copper. The system is slightly
less effective for cadmium because of its low concentration in the influent to the treat-
ment plant. Nevertheless, in excess of 60 percent of the cadmium is removed. Because
of the extremely low concentrations of other metals in the influent to the treatment
plant, the effectiveness of the treatment for their removal could not be evaluated with
any degree of confidence.
Although the treatment system was not designed for the removal of the priority organic
constituents, some are removed during the treatment. This could be due to evaporation
or sorption on the solids formed during the precipitation of the metallic components of
the wastewater.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Pollution Alkaline chlorination
Aircraft treatment
Airplane parts manufacturing
Wastewater
Treatment
Lime and settle treatment
Sulfur dioxide reduction & neutralization
b.IDENTIFIERS/OPEN ENDED TERMS
Pollution control
Stationary source
COSATI Field/Group
68D
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (This Report)
UNCLASSIFIED
21. NO. OF PAGES
41
20. SECURITY CLASS (This page)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (R*v. 4-77) PREVIOUS COITION is OBSOLETE
35
t, US GOVERNMENT PRINTING Of FICf I960 -657-146/5547
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